CN105778452A - Biodegradable heat shrinking film - Google Patents
Biodegradable heat shrinking film Download PDFInfo
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- CN105778452A CN105778452A CN201610361470.XA CN201610361470A CN105778452A CN 105778452 A CN105778452 A CN 105778452A CN 201610361470 A CN201610361470 A CN 201610361470A CN 105778452 A CN105778452 A CN 105778452A
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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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
- 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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- 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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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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
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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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
- C08L2205/02—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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- 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
- 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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
Abstract
The invention relates to a biodegradable heat shrinking film, and belongs to the technical field of high polymer materials. The heat shrinking film is prepared through the steps that dialdehyde starch, polyvinyl alcohol, chitosan and sodium carboxymethylcellulose are added into a reaction kettle and subjected to a reaction on the sealed condition to obtain modified dialdehyde starch; a stirring mixer is adopted for stirring polylactic acid, high density polyethylene, polybutylene adipate, the modified dialdehyde starch, polypropylene glycol, a plasticizer, a cross-linking agent, a bulking agent, a surface active agent, a photo-decomposing agent, an inorganic filler, a nucleating agent and a coupling agent to be uniform; the mixed raw materials are placed into a double-screw extruder for extrusion granulation. The heat shrinking film has the good biodegradability and the good physical performance.
Description
Technical field
The present invention relates to a kind of biodegradable heat shrink films, belong to technical field of polymer materials.
Background technology
Heat-shrinkable film (abbreviation shrink film) adopts the Process blow molding of hurried cooling and shaping, the production technology of this quenching designs according to high polymer orientation principle, after resin is plastified be extruded into embryophoric membrane completely, polymer carries out along two directions in length and breadth forcing to stretch between vitrification point and glutinous stream temperature, make the strand of polymer along draw direction orientation, at this moment by hurried for thin film cooling, freeze straining produced by stretch orientation.When thin film is reheated to thaw point, stress relaxation will be produced, namely oriented strand generation disorientation, now, it is forced in the drawing chain of tense situation, then returns to the folded chain of relaxed state before orientation, therefore give the shrinkage that shrink film is good.Especially at packaging industry, shrink film, with the feature of its super quality and competitive price, is replacing other packaging material.
Heat shrink films is widely used in: food, medicine, sterilizing dinnerware, stationery sports goods, process gift, leaflet, five metals plastic, telephone set, the outer package of the various product of electronic apparatus etc., combination type (boundling) packaging aspect particularly in anomalistic object article or commodity, the protection against the tide that can meet commodity is dust-proof, touch-proof substitute for another surreptitiously, the functions such as transparent display, product appearance captivation can be increased again, can also be used for replacing all kinds of carton, not only save packing cost, and meet packaging trend shrink film (bag) and can be processed into: flat mouth bag, circular arc bag, trapezoidal bag, the abnormity sack such as stereoscopic bag.
It can be largely classified into: PE shrink film, POF shrink film, OPS shrink film, PET shrink film etc..
PE heat shrink films is widely used in the one integral piece assembly package of the products such as drinks, pop can class, mineral water class, various beverage class, cloth, and this product pliability is good, and impact resistance, tear resistance are strong, not cracky, not to be afraid of tide, shrinkage factor big.
PVC film has that transparency height, glossiness be good, shrinkage factor high；
POF surface gloss height, good toughness, tearing toughness is big, thermal contraction is uniform and the feature such as applicable fully automatic high-speed packaging, is the regeneration product of tradition PVC heat shrink films.POF is exactly the meaning of heat shrink films, the multi-layer co-extruded Polyolefin Heat Shrinkable Film of POF full name, it is as intermediate layer (LLDPE) using linear low density polyethylene, co-polypropylene (pp) is as inside and outside layer, by three extruder plasticizing extrusions, process then through special process such as die head molding, bubble blown
OPS shrink film (oriented polystyrene) heat-shrinkable film is a kind of novel patch ops thermal contraction film body packaging material meeting environmental requirement, and OPS heat-shrinkable film has intensity height, and rigidity is big, dimensionally stable, and has good glossiness and transparency.Easy to process, it is easy to painted, printing performance is good, has high printed resolution, for constantly pursuing the trade mark of exquisite printing, is entirely the progress of a kind of material.This high shrinkage and intensity due to OPS thin film, can fit tightly with various difform containers, so it can not only print out the pattern of fineness, the use of the totally different novel package container of various profile can also be met, this nonpoisonous and tasteless, can grease resistance, the thin film meeting food hygienic standard can allow designer adopt noticeable color, realize the label design of 360 °, give full play of creativity and imaginative power, so that beverage and other commodity pattern in label uses is more lively, highlight the image on shelf, produce a kind of beyond thought counter effect.
The feature of PET thermal contraction type mylar: it is stable at normal temperatures, shrinks during heating (more than vitrification point), and be the thermal contraction of generation more than 70% in one direction.The advantage of heat shrinkable polyester film packaging is: 1. fit transparent, embodies commodity image.2. tightly restrainting packing material, anti-scattered property is good.3. rainproof, moistureproof, mildew-resistant.4. without restoration, there is certain antiforge function.It is its topmost application that heat shrinkable polyester film is usually used in instant food, beverage market, electronic apparatus, metallic article, particularly shrink label.Because along with the fast development of PET, as the carafe such as cola, sprite, various fruit juice are required for the matched heat-sealing label that does of PET heat shrink films, they belong to polyesters, are environment-friendly materials, it is easy to recovery and reusing and recycling.
CN102718951B discloses the preparation technology of a kind of chemical products, particularly a kind of bisgallic acid one alcohol modification by copolymerization PET-A and unidirectional heat shrink film preparation technology thereof, preparation method is to carry out the modified prepared PET-A polyester of ternary polymerization with p-phthalic acid (PTA), M-phthalic acid (IPA) and ethylene glycol (MEG) for primary raw material, its unidirectional heat shrink film preparation technology includes two kinds of preparation technologies of vertical and horizontal, the unidirectional heat shrink film that the method prepares after vertical or horizontal stretching percent thermal shrinkage 95～130 DEG C, reach 45～80% in 2～3s.The open a kind of high transparency polyvinyl chloride heat shrinkable film composition and method of making the same of CN103524916B, the weight portion of compositions consists of: Corvic 100 parts, stabilizer 1.5～3.5 parts, plasticizer 3～7 parts, toughener 1.0～4.0 parts, lubricant 1.0～2.0 parts, Transparence modifier 0.8～5.0 part, mainly through the problem that the use of Transparence modifier solves heat shrink films jaundice.But being as abandoning the concern of problem for plastic material, above-mentioned heat shrink films is difficult to biodegradation and becomes problem to be solved.
Summary of the invention
It is an object of the invention to: a kind of heat shrink films with good biological degradability is provided, and needs that there is good physical property.
Technical scheme is:
A kind of biodegradable heat shrink films, it prepares as follows:
1st step, by weight, in dialdehyde starch 10～20 parts, polyvinyl alcohol 4～7 parts, chitosan 3～5 parts and 1～3 part of addition reactor of sodium carboxymethyl cellulose, under air-proof condition after reaction, will obtain modified dialdehyde starch；
2nd step, adopt stirring mixer, by polylactic acid 150～200 parts by weight, high density polyethylene (HDPE) 15～25 parts, poly adipate succinic acid ester 15～25 parts, modified dialdehyde starch 10～30 parts, polypropylene glycol 5～15 parts, plasticizer 1～4 part, cross-linking agent 1～4 part, bulking agent 1～4 part, 1～4 part of surfactant, photolysis agent 1～4 part, inorganic filler 4～6 parts, nucleator 1～4 part, coupling agent 1～4 part stirring to uniformly；
3rd step, puts into the raw material mixed in double screw extruder and carries out extruding pelletization, to obtain final product.
In the 1st described step, response time 40～60min, reaction temperature 80～90 DEG C.
Described high density polyethylene (HDPE) weight average molecular weight is 4～500,000, and 200 DEG C is 0.02～50g/10min with the melt flow rate (MFR) under 2.16kg.
The weight average molecular weight of described polylactic acid is 3～300,000.
The weight average molecular weight 6000～100000 of poly adipate succinic acid ester.
The molecular weight of described polypropylene glycol is 1000～2000, and degree of functionality is 2.
Described plasticizer can be one or several in ethylene glycol, propylene glycol, sorbitol or glycerol.
Described cross-linking agent can be one or several in formaldehyde, paraformaldehyde, acetaldehyde, Metaldehyde or epoxychloropropane.
Described bulking agent is the one in ethylene acrylic acid co polymer, ethylene ethyl acrylate, ethylene-vinylacetate grafting maleic anhydride copolymer.
Described surfactant can adopt one or more mixture in sodium lauryl sulphate, diethanolamine of fat acyl, AESA, polyoxyethylenated alcohol sodium sulfate.
Photolysis agent is the mixture in any proportion of one or more in benzophenone, aromatic ketone, aromatic amine, acetophenone, ferric acetyl acetonade, 2-hydroxy-4-methyl acetophenone oxime ferrum, ferric stearate.
Described inorganic filler is the mixture in any proportion of one or more in calcium carbonate, Pulvis Talci, silicon oxide, calcium silicates.
Described nucleator one in amide-type organic nucleating agent, hydrazides class organic nucleating agent, terres rares nucleator.
Described coupling agent is selected from N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane; γ-(methacryloxypropyl) propyl trimethoxy silicane; γ-glycidyl ether oxygen propyl trimethoxy silicane; r-chloropropyl trimethoxyl silane; ethyl trimethoxy silane, the mixture in any proportion of one or more in isopropyl two (methylacryloyl) isostearoyl base titanate esters.
In the 3rd described step, extrusion condition is: one section of feeding section 100～140 DEG C, 150～180 DEG C, two, three sections of compression sections, four sections of melt zones 170～190 DEG C, five sections of conversion zones 170～190 DEG C, six sections of metering sections 170～190 DEG C, seven sections of heads 175～185 DEG C.
Beneficial effect
Heat shrink films provided by the invention has good biological degradability, and has good physical property.
Detailed description of the invention
Embodiment 1
A kind of biodegradable heat shrink films, it prepares as follows:
1st step, by weight, in dialdehyde starch 10 parts, polyvinyl alcohol 4 parts, chitosan 3 parts and 1 part of addition reactor of sodium carboxymethyl cellulose, under air-proof condition after reaction, will obtain modified dialdehyde starch, response time 40min, reaction temperature 80 DEG C；
2nd step, adopt stirring mixer, by the polylactic acid 150 parts that weight average molecular weight by weight is 3～300,000, weight average molecular weight is the high density polyethylene (HDPE) 15 parts of 4～500,000, the poly adipate succinic acid ester of weight average molecular weight 6000～100,000 15 parts, modified dialdehyde starch 10 parts, molecular weight is the polypropylene glycol 5 parts of 1000～2000, plasticizer ethylene glycol 1 part, 1 part of cross-linking agent acetaldehyde, bulking agent ethylene acrylic acid co polymer 1 part, surfactant AESA 1 part, photolysis agent aromatic ketone 1 part, inorganic filler calcium carbonate 4 parts, amide-type organic nucleating agent 1 part, coupling agent r-chloropropyl trimethoxyl silane 1 part stirring is to uniformly；
3rd step, puts into the raw material mixed in double screw extruder and carries out extruding pelletization, to obtain final product, extrusion condition is: one section of feeding section 100 DEG C, 150 DEG C, two, three sections of compression sections, four sections of melt zones 170 DEG C, five sections of conversion zones 170 DEG C, six sections of metering sections 170 DEG C, seven sections of heads 175 DEG C.
Embodiment 2
A kind of biodegradable heat shrink films, it prepares as follows:
1st step, by weight, in dialdehyde starch 20 parts, polyvinyl alcohol 7 parts, chitosan 5 parts and 3 parts of addition reactors of sodium carboxymethyl cellulose, under air-proof condition after reaction, will obtain modified dialdehyde starch, response time 60min, reaction temperature 90 DEG C；
2nd step, adopt stirring mixer, by the polylactic acid 200 parts that weight average molecular weight by weight is 3～300,000, weight average molecular weight is the high density polyethylene (HDPE) 25 parts of 4～500,000, the poly adipate succinic acid ester of weight average molecular weight 6000～100,000 25 parts, modified dialdehyde starch 30 parts, molecular weight is the polypropylene glycol 15 parts of 1000～2000, plasticizer ethylene glycol 4 parts, 4 parts of cross-linking agent acetaldehyde, bulking agent ethylene acrylic acid co polymer 4 parts, surfactant AESA 4 parts, photolysis agent aromatic ketone 4 parts, inorganic filler calcium carbonate 6 parts, amide-type organic nucleating agent 4 parts, coupling agent r-chloropropyl trimethoxyl silane 4 parts stirring is to uniformly；
3rd step, puts into the raw material mixed in double screw extruder and carries out extruding pelletization, to obtain final product, extrusion condition is: one section of feeding section 140 DEG C, 180 DEG C, two, three sections of compression sections, four sections of melt zones 190 DEG C, five sections of conversion zones 190 DEG C, six sections of metering sections 190 DEG C, seven sections of heads 185 DEG C.
Embodiment 3
A kind of biodegradable heat shrink films, it prepares as follows:
1st step, by weight, in dialdehyde starch 15 parts, polyvinyl alcohol 5 parts, chitosan 4 parts and 2 parts of addition reactors of sodium carboxymethyl cellulose, under air-proof condition after reaction, will obtain modified dialdehyde starch, response time 50min, reaction temperature 85 DEG C；
2nd step, adopt stirring mixer, by the polylactic acid 170 parts that weight average molecular weight by weight is 3～300,000, weight average molecular weight is the high density polyethylene (HDPE) 20 parts of 4～500,000, the poly adipate succinic acid ester of weight average molecular weight 6000～100,000 20 parts, modified dialdehyde starch 20 parts, molecular weight is the polypropylene glycol 10 parts of 1000～2000, plasticizer ethylene glycol 2 parts, 2 parts of cross-linking agent acetaldehyde, bulking agent ethylene acrylic acid co polymer 2 parts, surfactant AESA 3 parts, photolysis agent aromatic ketone 3 parts, inorganic filler calcium carbonate 3 parts, amide-type organic nucleating agent 3 parts, coupling agent r-chloropropyl trimethoxyl silane 3 parts stirring is to uniformly；
3rd step, puts into the raw material mixed in double screw extruder and carries out extruding pelletization, to obtain final product, extrusion condition is: one section of feeding section 120 DEG C, 170 DEG C, two, three sections of compression sections, four sections of melt zones 180 DEG C, five sections of conversion zones 180 DEG C, six sections of metering sections 180 DEG C, seven sections of heads 180 DEG C.
Reference examples 1
It is distinctive in that with embodiment 3: dialdehyde starch is without modification.
1st step, adopt stirring mixer, by the polylactic acid 170 parts that weight average molecular weight by weight is 3～300,000, weight average molecular weight is the high density polyethylene (HDPE) 20 parts of 4～500,000, the poly adipate succinic acid ester of weight average molecular weight 6000～100,000 20 parts, dialdehyde starch 20 parts, molecular weight is the polypropylene glycol 10 parts of 1000～2000, plasticizer ethylene glycol 2 parts, 2 parts of cross-linking agent acetaldehyde, bulking agent ethylene acrylic acid co polymer 2 parts, surfactant AESA 3 parts, photolysis agent aromatic ketone 3 parts, inorganic filler calcium carbonate 3 parts, amide-type organic nucleating agent 3 parts, coupling agent r-chloropropyl trimethoxyl silane 3 parts stirring is to uniformly；
2nd step, puts into the raw material mixed in double screw extruder and carries out extruding pelletization, to obtain final product, extrusion condition is: one section of feeding section 120 DEG C, 170 DEG C, two, three sections of compression sections, four sections of melt zones 180 DEG C, five sections of conversion zones 180 DEG C, six sections of metering sections 180 DEG C, seven sections of heads 180 DEG C.
Reference examples 2
It is distinctive in that with embodiment 3: do not add polypropylene glycol.
1st step, by weight, in dialdehyde starch 15 parts, polyvinyl alcohol 5 parts, chitosan 4 parts and 2 parts of addition reactors of sodium carboxymethyl cellulose, under air-proof condition after reaction, will obtain modified dialdehyde starch, response time 50min, reaction temperature 85 DEG C；
2nd step, adopt stirring mixer, by the polylactic acid 170 parts that weight average molecular weight by weight is 3～300,000, weight average molecular weight is the high density polyethylene (HDPE) 20 parts of 4～500,000, the poly adipate succinic acid ester of weight average molecular weight 6000～100,000 20 parts, modified dialdehyde starch 20 parts, molecular weight is the polypropylene glycol 10 parts of 1000～2000, plasticizer ethylene glycol 2 parts, 2 parts of cross-linking agent acetaldehyde, bulking agent ethylene acrylic acid co polymer 2 parts, surfactant AESA 3 parts, photolysis agent aromatic ketone 3 parts, inorganic filler calcium carbonate 3 parts, amide-type organic nucleating agent 3 parts, coupling agent r-chloropropyl trimethoxyl silane 3 parts stirring is to uniformly；
3rd step, puts into the raw material mixed in double screw extruder and carries out extruding pelletization, to obtain final product, extrusion condition is: one section of feeding section 120 DEG C, 170 DEG C, two, three sections of compression sections, four sections of melt zones 180 DEG C, five sections of conversion zones 180 DEG C, six sections of metering sections 180 DEG C, seven sections of heads 180 DEG C.
Performance test
Being put into by the granular materials that above example and reference examples prepare in single screw rod inflation film manufacturing machine of draw ratio 40～60:1, extrude blown film and get final product, the thickness of described thin film is 6 microns.The performance of this thin film is tested, and result is referring to table 1.
Table 1
As can be seen from the table, heat shrink films provided by the invention has good biological degradability, and has good physical property.Hot strength can reach more than 60Mpa, and stretching ratio can reach more than 35%, and when 100, shrinkage factor can reach more than 51%.It addition, contrasted by embodiment 3 and reference examples 1 it can be seen that by dialdehyde starch can be improved shrinkage factor through modification, contrasted by embodiment 3 and reference examples 2 it can be seen that the hot strength of material can be improved by adding polypropylene glycol.
Claims (10)
1. a biodegradable heat shrink films, it is characterised in that it prepares as follows:
1st step, by weight, in dialdehyde starch 10～20 parts, polyvinyl alcohol 4～7 parts, chitosan 3～5 parts and 1～3 part of addition reactor of sodium carboxymethyl cellulose, under air-proof condition after reaction, will obtain modified dialdehyde starch；
2nd step, adopt stirring mixer, by polylactic acid 150～200 parts that weight average molecular weight by weight is 3～300,000, high density polyethylene (HDPE) 15～25 parts, poly adipate succinic acid ester 15～25 parts, modified dialdehyde starch 10～30 parts, polypropylene glycol 5～15 parts, plasticizer 1～4 part, cross-linking agent 1～4 part, bulking agent 1～4 part, 1～4 part of surfactant, photolysis agent 1～4 part, inorganic filler 4～6 parts, nucleator 1～4 part, coupling agent 1～4 part stirring to uniformly；
3rd step, puts into the raw material mixed in double screw extruder and carries out extruding pelletization, to obtain final product.
2. biodegradable heat shrink films according to claim 1, it is characterised in that: in the 1st described step, response time 40～60min, reaction temperature 80～90 DEG C.
3. biodegradable heat shrink films according to claim 1, it is characterised in that: described high density polyethylene (HDPE) weight average molecular weight is 4～500,000, and 200 DEG C is 0.02～50g/10min with the melt flow rate (MFR) under 2.16kg.
4. biodegradable heat shrink films according to claim 1, it is characterised in that: the weight average molecular weight of described polylactic acid is 3～300,000；The weight average molecular weight 6000～100000 of poly adipate succinic acid ester；The molecular weight of described polypropylene glycol is 1000～2000, and degree of functionality is 2.
5. biodegradable heat shrink films according to claim 1, it is characterised in that: described plasticizer can be one or several in ethylene glycol, propylene glycol, sorbitol or glycerol.
6. biodegradable heat shrink films according to claim 1, it is characterised in that: described cross-linking agent can be one or several in formaldehyde, paraformaldehyde, acetaldehyde, Metaldehyde or epoxychloropropane.
7. biodegradable heat shrink films according to claim 1, it is characterised in that: described bulking agent is the one in ethylene acrylic acid co polymer, ethylene ethyl acrylate, ethylene-vinylacetate grafting maleic anhydride copolymer.
8. biodegradable heat shrink films according to claim 1, it is characterised in that: described surfactant can adopt one or more mixture in sodium lauryl sulphate, diethanolamine of fat acyl, AESA, polyoxyethylenated alcohol sodium sulfate.
9. biodegradable heat shrink films according to claim 1, it is characterised in that: photolysis agent is the mixture in any proportion of one or more in benzophenone, aromatic ketone, aromatic amine, acetophenone, ferric acetyl acetonade, 2-hydroxy-4-methyl acetophenone oxime ferrum, ferric stearate.
10. biodegradable heat shrink films according to claim 1, it is characterised in that: described inorganic filler is the mixture in any proportion of one or more in calcium carbonate, Pulvis Talci, silicon oxide, calcium silicates；Described nucleator one in amide-type organic nucleating agent, hydrazides class organic nucleating agent, terres rares nucleator；Described coupling agent is selected from N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane; γ-(methacryloxypropyl) propyl trimethoxy silicane; γ-glycidyl ether oxygen propyl trimethoxy silicane; r-chloropropyl trimethoxyl silane; ethyl trimethoxy silane, the mixture in any proportion of one or more in isopropyl two (methylacryloyl) isostearoyl base titanate esters；In the 3rd described step, extrusion condition is: one section of feeding section 100～140 DEG C, 150～180 DEG C, two, three sections of compression sections, four sections of melt zones 170～190 DEG C, five sections of conversion zones 170～190 DEG C, six sections of metering sections 170～190 DEG C, seven sections of heads 175～185 DEG C.
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| CN201610361470.XA CN105778452A (en) | 2016-05-27 | 2016-05-27 | Biodegradable heat shrinking film |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106432814A (en) * | 2016-09-30 | 2017-02-22 | 华南理工大学 | Starch/polyvinyl alcohol composite material and preparation method thereof |
| CN108159901A (en) * | 2018-01-16 | 2018-06-15 | 东华理工大学 | Nylon fiber screen cloth enhances the compound membrane preparation method of modification of chitosan/calcium-base bentonite |
| CN109867819A (en) * | 2019-01-11 | 2019-06-11 | 安徽鼎正包装材料有限公司 | Polylactic acid-starch-PVA composite degradable packaging film and preparation method thereof |
| CN111040255A (en) * | 2019-12-26 | 2020-04-21 | 深圳市虹彩新材料科技有限公司 | Bio-based polyethylene/starch blending modified blown film material and preparation method thereof |
| KR20210062197A (en) * | 2019-11-21 | 2021-05-31 | 이종현 | Eco-friendly plastic composite material containing starch and silica |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101240086A (en) * | 2008-03-14 | 2008-08-13 | 上海悦仕生物材料有限公司 | Total-biodegradation plastic film and preparation method thereof |
| CN102627841A (en) * | 2012-03-21 | 2012-08-08 | 清华大学 | Preparation method of degradation-controllable polylactic acid/starch total biodegradable plastic |
| CN105440606A (en) * | 2014-09-02 | 2016-03-30 | 允友成(宿迁)复合新材料有限公司 | Preparation method of fully biodegradable starch/polylactic acid base resin |
-
2016
- 2016-05-27 CN CN201610361470.XA patent/CN105778452A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101240086A (en) * | 2008-03-14 | 2008-08-13 | 上海悦仕生物材料有限公司 | Total-biodegradation plastic film and preparation method thereof |
| CN102627841A (en) * | 2012-03-21 | 2012-08-08 | 清华大学 | Preparation method of degradation-controllable polylactic acid/starch total biodegradable plastic |
| CN105440606A (en) * | 2014-09-02 | 2016-03-30 | 允友成(宿迁)复合新材料有限公司 | Preparation method of fully biodegradable starch/polylactic acid base resin |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106432814A (en) * | 2016-09-30 | 2017-02-22 | 华南理工大学 | Starch/polyvinyl alcohol composite material and preparation method thereof |
| CN108159901A (en) * | 2018-01-16 | 2018-06-15 | 东华理工大学 | Nylon fiber screen cloth enhances the compound membrane preparation method of modification of chitosan/calcium-base bentonite |
| CN109867819A (en) * | 2019-01-11 | 2019-06-11 | 安徽鼎正包装材料有限公司 | Polylactic acid-starch-PVA composite degradable packaging film and preparation method thereof |
| KR20210062197A (en) * | 2019-11-21 | 2021-05-31 | 이종현 | Eco-friendly plastic composite material containing starch and silica |
| KR102370368B1 (en) * | 2019-11-21 | 2022-03-04 | 이종현 | Eco-friendly plastic composite material containing starch and silica gel |
| CN111040255A (en) * | 2019-12-26 | 2020-04-21 | 深圳市虹彩新材料科技有限公司 | Bio-based polyethylene/starch blending modified blown film material and preparation method thereof |
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