CN108373560A - A kind of degradable polymeric packaging material of the transparency and preparation method thereof - Google Patents
A kind of degradable polymeric packaging material of the transparency and preparation method thereof Download PDFInfo
- Publication number
- CN108373560A CN108373560A CN201810108992.8A CN201810108992A CN108373560A CN 108373560 A CN108373560 A CN 108373560A CN 201810108992 A CN201810108992 A CN 201810108992A CN 108373560 A CN108373560 A CN 108373560A
- Authority
- CN
- China
- Prior art keywords
- packaging material
- polymeric packaging
- degradable polymeric
- preparation
- transparency
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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
-
- 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
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- 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
-
- 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
- C08J2323/08—Copolymers of ethene
-
- 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
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/04—Starch derivatives
- C08J2403/06—Esters
-
- 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
- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2461/16—Condensation polymers of aldehydes or ketones with phenols only of ketones with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/018—Additives for biodegradable polymeric composition
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- 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
-
- 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
-
- 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)
Abstract
A kind of degradable polymeric packaging material of the transparency and preparation method thereof, belongs to the preparing technical field of macromolecule new material.Polymeric packaging material of the present invention is made of following raw material：Polyethylene, sulfonated polyether-ether-ketone, sodium lignin sulfonate, Ethylene Glycol Methyl methyl acrylate copolymer, microbial nutrition additive, amyl-based polyol polyester, phosphorylation PASELLI EASYGEL, zinc stearate, methyl vinyl ether maleic acid anhydride copolymer, oligomerization polylactic acid, lactide, epoxy silane coupling, oxidized polyethylene wax and dolomite fines, it is modified by cold grinding, pass through one-step method melt modification polyethylene again, high-efficiency low energy consumption it is prepared for the degradable polymeric packaging material of the transparency, it has both transparent, intensity is good and readily degradable, simple production process, green non-pollution, it is easy to industrialized production.
Description
Technical field
The present invention relates to a kind of degradable polymeric packaging materials of the transparency and preparation method thereof, belong to macromolecule new material
Preparing technical field.
Background technology
Polyolefin is because its is inexpensive, good mechanical performance, so dosage is huge, but the time of its natural degradation is 200
~300 years, long-time service caused serious " white pollution " to China's ecological environment.Plastic products are according to using purpose not
Together, the degradative phase being divided into after different storage counter phases, validity period and use.Non-biodegradable plastics how are made to use
After obtain biodegradability, cheap, lightweight, high specific strength, health plastic products can be continuing with and keep away by being the mankind
Exempt from the key of white pollution.Degradable high polymer material, including Natural Degradation material and synthesis and degradation material, natural material change
Property, natural material and compound, novel hybride materials the preparations of synthetic material and the research of new bio degradable material etc..It is raw
Object degraded macromolecular material is also referred to as " green ecological high molecular material ", and ideal biodegradated polymer materal should have excellent
Good performance can be completely decomposed into carbon dioxide and water after discarded by environmental microorganism, can finally be entered by inorganic mineralising
Nature carbon recycles.Greatest problem existing for degraded macromolecular material, which is degradability and mechanical property, at present to get both
How problem obtains transparent, excellent mechanical property and degradable function equal especially in the occasion for needing transparent wrapper
Weighing apparatus property is the problem for restricting vinyon development and using.
Invention content
The purpose of the present invention is to overcome the deficiencies of the prior art, provides a kind of degradable macromolecule packing timber of the transparency
Material and preparation method thereof, by developing all kinds of New-type adjuvants, such as transparent high-quality nucleating agent, transparent photoinitiator, transparent compatible increasing
Tough dose, novel green plasticizer, photochemical catalyst, autoxidation catalyst, be aided with transparent fleut dolomite etc., and by cold
Mill is modified the step of with further melt modification, is prepared for high-efficiency low energy consumption transparent, degradable and good mechanical performance poly-
Vinyl packaging material.
Technical scheme of the present invention, a kind of degradable polymeric packaging material of the transparency and preparation method thereof, with poly- second
Alkene is macromolecule matrix, by adding novel transparent photoinitiator sulfonated polyether-ether-ketone, introduces Benzophenone base photosensitive group, and sulphur
Acidic group plays hydrophilic interaction；Sodium lignin sulfonate is added as transparent nucleater；Add ethylene glycol-methyl methacrylate copolymer
Object is as transparent compatilizer；Microbial nutrition additive is added to promote microbic resolvability；It is polynary to add amyl-based polyol
Ester is as green plasticization agent；Phosphorylation PASELLI EASYGEL and zinc stearate are added as thermal oxide accelerating agent；Add methyl second
Alkene ether-copolymer-maleic anhydride is light absorber；Oligomerization polylactic acid, lactide and epoxy silane coupling are added as parent
Water crosslinking modifying agent；Oxidized polyethylene wax is as stress release agent；The high dolomite fines of transparency are as transparent filler；Pass through
Cold grinding method is modified and melts the method that co-extrusion is further modified, and the degradable polymeric packaging material of the transparency is made.
A kind of degradable polymeric packaging material of the transparency, formula rate are counted as follows in mass ratio：Ju Yi Xi ︰ sulfonated polyethers
Ether ketone ︰ wood quality sulphur acid sodium ︰ ethylene glycol-methyl-prop e pioic acid methyl ester be total to poly- object ︰ microbial nutritions add plus agent ︰ amyl-based polyols it is more
Yuan Zhi ︰ phosphorylation Er Dian powder Lin Suan Zhi ︰ Ying resin acid Xin ︰ methyl vinyl ethers-maleic anhydride Wu ︰ oligomerization Ju Ru Suan ︰ third are handed over
Zhi ︰ epoxy radicals silicone hydride Ou Lian Ji ︰ Yangization Ju ethylene La ︰ dolomite fines ratios are：10~30 ︰, 0.001~0.002 ︰ 0.1~
0.5 ︰, 0.01~0.03 ︰, 0.001~0.002 ︰, 0.1~0.2 ︰, 1~5 ︰, 1~5 ︰, 0.1~0.5 ︰, 0.2~0.5 ︰, 0.2~0.8 ︰ 0.1
1 ︰ 3~8 of~0.3 ︰.
Further, the polyethylene is high density polyethylene (HDPE), low density polyethylene (LDPE) or linear low density polyethylene.
Further, the epoxy silane coupling is KH-560, i.e. γ-（The third oxygen of 2,3- epoxies）Propyl trimethoxy
Silane.
Further, the microbial nutrition additive is oleoyl glutamic acid, lauroyl glutamate, lauroyl paddy
Propylhomoserin sodium or oleic acid diethyl amide phosphate.
The preparation method of the degradable polymeric packaging material of the transparency, steps are as follows：
（1）The preparation of sulfonated polyether-ether-ketone：At 50 DEG C, industrial stage polyetheretherketoneresin is dissolved in the concentrated sulfuric acid, wherein polyether-ether-ketone：Quality
A concentration of 98% concentrated sulfuric acid mass ratio is 1：50~100,3~5h is stirred, is stood for 24 hours, it is 7 that sodium hydroxide, which is added, and is adjusted to pH, mistake
Filter, washing, vacuum degree be 5~20kPa, 50~70 DEG C vacuum drying 30~60min, obtain sulfonated polyether-ether-ketone；
（2）The preparation of modified high-molecular：By raw material proportioning dispensing, Ju Yi Xi ︰ sulfonation Ju Mi Mi Tong ︰ Mu quality Huang Suan Na ︰ second two
Alcohol-methyl-prop e pioic acid methyl ester is total to poly- object ︰ microbial nutritions and adds plus more two starch phosphates of member ester ︰ phosphorylations of agent ︰ amyl-based polyols
Zhi ︰ Ying resin acid Xin ︰ methyl vinyl ethers-maleic anhydride Wu ︰ oligomerization Ju Ru Suan ︰ Bing Jiao Zhi ︰ epoxy radicals silicone hydride Ou Lian Ji ︰ oxygen
Change Ju ethylene La ︰ dolomite fines mass ratio be：10~30 ︰, 0.001~0.002 ︰, 0.1~0.5 ︰, 0.01~0.03 ︰ 0.001
0.1~0.3 ︰ of~0.002 ︰ 0.1~0.2 ︰, 1~5 ︰, 1~5 ︰, 0.1~0.5 ︰, 0.2~0.5 ︰, 0.2~0.8 ︰, 1 ︰ 3~8；By raw material
Component is sufficiently mixed 10min in homogenizer, with 800~1000r/min, obtains mixture, adds mixture into planet
In ball mill, after carrying out 40~70min of vibration hybrid reaction under the rotating ratio of material ball ratio 1 ︰ 2~5 and 1 ︰ 2, it is made modified high
Molecule；
（3）The preparation of the degradable polymeric packaging material of the transparency：By step（2）Gained modified high-molecular is in double screw extruder
Middle carry out melt modification, operation temperature are 140~180 DEG C, under 50~70 r/min of screw speed, melt blending extruding pelletization,
Obtain composite master batch；By gained composite master batch feeding Single screw extrusion inflation film manufacturing machine, the hot-melt extruded Blown Film at 180~200 DEG C,
Obtain the degradable polymeric packaging material of the transparency.
Further, the degradable polymeric packaging material film thickness of the transparency is 30 μm.
Further, step（3）The a diameter of 20mm of double screw extruder, draw ratioL/D It is 36:1；Single screw rod is squeezed
Go out a diameter of 20mm of inflation film manufacturing machine, draw ratioL/DIt is 30:1.
Beneficial effects of the present invention：The present invention is by developing all kinds of New-type adjuvants, specially：Transparent high-quality nucleating agent, thoroughly
Photoinitiator, novel green plasticizer, photochemical catalyst, autoxidation catalyst, is aided with transparent powdery at transparent compatible toughening agents
Filler dolomite etc. is prepared for high-efficiency low energy consumption transparent easily drop by cold grinding modification and one-step method melt modification polyethylene
Polymeric packaging material is solved, has both that transparent, intensity is good and readily degradable, simple production process, green non-pollution are easy to industrial
Metaplasia is produced.
Specific implementation mode
With reference to embodiment, the invention will be further described, but the application of the present invention is without being limited thereto.Used in embodiment
Parallel dual-screw extruding machine：KS20, Kunshan Kesun Rubber ＆ Plastic Machinery Co., Ltd.（Diameter=20mm, draw ratioL/D=36:1）；Single spiral shell
Bar squeezes out inflation film manufacturing machine：Harbin Ha Pu electrical technologies Co., Ltd（Diameter=20mm, draw ratioL/D=30:1）；Planet ball
Grinding machine：XQM-2L types, Bei Jing Xin Biao rise experimental instruments and equipment limited；Universal testing machine：1185, Britain Instron are public
Department；
Polyethylene glycol methyl methacrylate diblock copolymer PEG-PMMA（PEG:10500, PMMA:18000, Xiamen
Yan Ke Bioisystech Co., Ltd）；Methyl vinyl ether-maleic acid copolymer（Mw 130000, the limited public affairs of lark prestige science and technology
Department）；Oligomerization polylactic acid（Mw:200,300,400, Aladdin reagent）；Oxidized polyethylene wax (trade mark PE wax OA2, Bath
Husband)；Amyl-based polyol polyester（Liaocheng Rui Jie Chemical Co., Ltd.s）；Oleoyl glutamic acid, lauroyl glutamate, bay
Acyl glutamic acid sodium, oleic acid diethyl amide phosphate, lactide, sodium lignin sulfonate, zinc stearate, dolomite etc. are purchased from
Chinese medicines group Shanghai Co., Ltd；KH-560（γ-（The third oxygen of 2,3- epoxies）Propyl trimethoxy silicane, the peaceful coupling agent of Nanjing product
Co., Ltd）；Polyether-ether-ketone（Trade mark D150GL30, Britain Wei Gesi）；Phosphorylation PASELLI EASYGEL（Jinan sage and chemical industry
Co., Ltd, the Jiangsu bio tech ltd Cai Wei）；Dolomite fines（2000 mesh, Changxing Qing Shenggai industry Co., Ltd）；It is high
Density polyethylene（The trade mark, DMDB-8916, Maoming Petrochemical）；Low density polyethylene (LDPE) (trade mark 2426H, orchidization)；Low density polyethylene (LDPE)
(trade mark 2426H, Daqing petrochemical)；Linear low density polyethylene（The trade mark 7042, Daqing petrochemical）；Linear low density polyethylene（Board
Numbers 7042, Jilin Petrochemical）；Unless otherwise instructed, it is other it is raw materials used be commercial goods.
The preparation of the 1 degradable polymeric packaging material of the transparency of embodiment
（1）The preparation of sulfonated polyether-ether-ketone：At 50 DEG C, industrial stage polyetheretherketoneresin is dissolved in the concentrated sulfuric acid, wherein polyether-ether-ketone：Quality
A concentration of 98% concentrated sulfuric acid mass ratio is 1：50,3h is stirred, is stood for 24 hours, it is 7 that sodium hydroxide, which is added, and is adjusted to pH, is filtered, washing,
Vacuum degree be 5kPa, 50 DEG C vacuum drying 30min, obtain sulfonated polyether-ether-ketone；
（2）The preparation of modified high-molecular：By raw material proportioning dispensing, high density polyethylene (HDPE)（The trade mark, DMDB-8916, Maoming Petrochemical）︰
It is polynary that the poly- ether ether ketone ︰ wood quality sulphur acid sodium ︰ ethylene glycol-methyl-prop e pioic acid methyl ester of sulfonation is total to poly- object ︰ oleoyls paddy ammonia acid ︰ neopentyls
Alcohol Duo Yuan Zhi ︰ phosphorylation Er Dian powder Lin Suan Zhi ︰ Ying resin acid Xin ︰ methyl vinyl ethers-maleic anhydride Wu ︰ oligomerization polylactic acid
（200）The mass ratio of ︰ Bing Jiao Zhi ︰ KH-560 ︰ Yangization Ju ethylene La ︰ dolomite fines is：10 ︰, 0.001 ︰, 0.1 ︰, 0.01 ︰
0.001 ︰, 0.1 ︰, 1 ︰, 1 ︰, 0.1 ︰, 0.2 ︰, 0.2 ︰, 0.1 ︰, 1 ︰ 3；By raw material components in homogenizer, it is sufficiently mixed with 800r/min
10 min, obtain mixture, add mixture into planetary ball mill, and vibration is carried out under the rotating ratio of material ball ratio 1 ︰ 2 and 1 ︰ 2
After hybrid reaction 40min, modified high-molecular is made；
（3）The preparation of the degradable polymeric packaging material of the transparency：By step（2）Gained modified high-molecular is in double screw extruder
Middle carry out melt modification, double screw extruder each section operation temperature are：140 DEG C, 150 DEG C, 160 DEG C, 180 DEG C, 170 DEG C, spiral shell
Under bar rotating speed 50r/min, melt blending extruding pelletization obtains composite master batch；Gained composite master batch is sent into Single screw extrusion blown film
The operation temperature of machine, each section is：Hot-melt extruded Blown Film at 180 DEG C, 190 DEG C, 200 DEG C, 180 DEG C, obtains the transparency
Degradable polymeric packaging material, 30 μm of film thickness.
The preparation of the 2 degradable polymeric packaging material of the transparency of embodiment
（1）The preparation of sulfonated polyether-ether-ketone：At 50 DEG C, industrial stage polyetheretherketoneresin is dissolved in the concentrated sulfuric acid, wherein polyether-ether-ketone：Quality
A concentration of 98% concentrated sulfuric acid mass ratio is 1：100,5h is stirred, is stood for 24 hours, it is 7 that sodium hydroxide, which is added, and is adjusted to pH, filtering, water
It washes, vacuum degree 20kPa, 70 DEG C of vacuum drying 60min obtain sulfonated polyether-ether-ketone；
（2）The preparation of modified high-molecular：By raw material proportioning dispensing, low density polyethylene (LDPE) (trade mark 2426H, orchidization) ︰ sulfonated polyethers
That methyl-prop e pioic acid methyl ester is total to the poly- month osmanthus object ︰ acyl group paddy ammonia acid ︰ amyl-based polyols to ether ketone ︰ wood quality sulphur acid sodium ︰ ethylene glycol-is polynary
Zhi ︰ phosphorylation Er Dian powder Lin Suan Zhi ︰ Ying resin acid Xin ︰ methyl vinyl ethers-maleic anhydride Wu ︰ oligomerization polylactic acid（300）︰ third
The mass ratio of Jiao Zhi ︰ KH-560 ︰ Yangization Ju ethylene La ︰ dolomite fines is：30 ︰, 0.002 ︰, 0.5 ︰, 0.03 ︰, 0.002 ︰, 0.2 ︰, 5 ︰
5 ︰, 0.5 ︰, 0.5 ︰, 0.8 ︰, 0.3 ︰, 1 ︰ 8；By raw material components in homogenizer, it is sufficiently mixed 10min with 1000 r/min, is obtained mixed
Material is closed, is added mixture into planetary ball mill, vibration hybrid reaction is carried out under the rotating ratio of material ball ratio 1 ︰ 5 and 1 ︰ 2
After 70min, modified high-molecular is made；
（3）The preparation of the degradable polymeric packaging material of the transparency：By step（2）Gained modified high-molecular is in double screw extruder
Middle carry out melt modification, double screw extruder each section operation temperature are：140 DEG C, 160 DEG C, 180 DEG C, 180 DEG C, 140 DEG C, spiral shell
Under bar rotating speed 70r/min, melt blending extruding pelletization obtains composite master batch；Gained composite master batch is sent into Single screw extrusion blown film
Machine, each section operation temperature are：Hot-melt extruded Blown Film at 180 DEG C, 200 DEG C, 200 DEG C, 190 DEG C obtains the transparency easily
Degraded macromolecular packaging material, 30 μm of film thickness.
The preparation of the 3 degradable polymeric packaging material of the transparency of embodiment
（1）The preparation of sulfonated polyether-ether-ketone：At 50 DEG C, industrial stage polyetheretherketoneresin is dissolved in the concentrated sulfuric acid, wherein polyether-ether-ketone：Quality
A concentration of 98% concentrated sulfuric acid mass ratio is 1：60,4h is stirred, is stood for 24 hours, it is 7 that sodium hydroxide, which is added, and is adjusted to pH, is filtered, washing,
Vacuum degree be 10kPa, 55 DEG C vacuum drying 40min, obtain sulfonated polyether-ether-ketone；
（2）The preparation of modified high-molecular：By raw material proportioning dispensing, linear low density polyethylene（The trade mark 7042, Daqing petrochemical）︰ sulphurs
Change poly- ether ether ketone ︰ wood quality sulphur acid sodium ︰ ethylene glycol-methyl-prop e pioic acid methyl ester and is total to poly- object ︰ oleoyls paddy ammonia acid ︰ amyl-based polyols
Duo Yuan Zhi ︰ phosphorylation Er Dian powder Lin Suan Zhi ︰ Ying resin acid Xin ︰ methyl vinyl ethers-maleic anhydride Wu ︰ oligomerization polylactic acid
（400）The mass ratio of ︰ Bing Jiao Zhi ︰ KH-560 ︰ Yangization Ju ethylene La ︰ dolomite fines is：20 ︰, 0.001 ︰, 0.2 ︰, 0.02 ︰
0.001 ︰, 0.2 ︰, 2 ︰, 3 ︰, 0.2 ︰, 0.4 ︰, 0.3 ︰, 0.2 ︰, 1 ︰ 4；It is fully mixed with 900 r/min by raw material components in homogenizer
10 min are closed, mixture is obtained, are added mixture into planetary ball mill, are shaken under the rotating ratio of material ball ratio 1 ︰ 3 and 1 ︰ 2
After grinding hybrid reaction 50min, modified high-molecular is made；
（3）The preparation of the degradable polymeric packaging material of the transparency：By step（2）Gained modified high-molecular is in double screw extruder
Middle carry out melt modification, double screw extruder each section operation temperature are：150 DEG C, 170 DEG C, 180 DEG C, 180 DEG C, 170 DEG C, spiral shell
Under 60 r/min of bar rotating speed, melt blending extruding pelletization obtains composite master batch；Gained composite master batch is sent into Single screw extrusion blown film
Machine, each section operation temperature are：Hot-melt extruded Blown Film at 190 DEG C, 200 DEG C, 200 DEG C, 190 DEG C obtains the transparency easily
Degraded macromolecular packaging material, 30 μm of film thickness.
The preparation of the 4 degradable polymeric packaging material of the transparency of embodiment
（1）The preparation of sulfonated polyether-ether-ketone：At 50 DEG C, industrial stage polyetheretherketoneresin is dissolved in the concentrated sulfuric acid, wherein polyether-ether-ketone：Quality
A concentration of 98% concentrated sulfuric acid mass ratio is 1：70,3.5h is stirred, is stood for 24 hours, it is 7 that sodium hydroxide, which is added, and is adjusted to pH, filtering, water
It washes, vacuum degree 15kPa, 65 DEG C of vacuum drying 50min obtain sulfonated polyether-ether-ketone；
（2）The preparation of modified high-molecular：By raw material proportioning dispensing, low density polyethylene (LDPE) (trade mark 2426H, Daqing petrochemical) ︰ sulfonation
It is polynary that poly- ether ether ketone ︰ wood quality sulphur acid sodium ︰ ethylene glycol-methyl-prop e pioic acid methyl ester is total to the poly- month osmanthus object ︰ acyl glutamic acid sodium ︰ neopentyls
Alcohol Duo Yuan Zhi ︰ phosphorylation Er Dian powder Lin Suan Zhi ︰ Ying resin acid Xin ︰ methyl vinyl ethers-maleic anhydride Wu ︰ oligomerization polylactic acid
（200）The mass ratio of ︰ Bing Jiao Zhi ︰ KH-560 ︰ Yangization Ju ethylene La ︰ dolomite fines is：15 ︰, 0.001 ︰, 0.3 ︰, 0.01 ︰
0.002 ︰, 0.1 ︰, 3 ︰, 4 ︰, 0.3 ︰, 0.4 ︰, 0.5 ︰, 0.2 ︰, 1 ︰ 7；By raw material components in homogenizer, it is sufficiently mixed with 800r/min
10min obtains mixture, adds mixture into planetary ball mill, and vibration is carried out under the rotating ratio of material ball ratio 1 ︰ 5 and 1 ︰ 2
After hybrid reaction 60min, modified high-molecular is made；
（3）The preparation of the degradable polymeric packaging material of the transparency：By step（2）Gained modified high-molecular is in double screw extruder
Middle carry out melt modification, double screw extruder each section operation temperature are：150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 160 DEG C, spiral shell
Under bar rotating speed 60r/min, melt blending extruding pelletization obtains composite master batch；Gained composite master batch is sent into Single screw extrusion blown film
Machine, each section operation temperature are：Hot-melt extruded Blown Film at 180 DEG C, 200 DEG C, 200 DEG C, 190 DEG C obtains the transparency easily
Degraded macromolecular packaging material, 30 μm of film thickness.
The preparation of the 5 degradable polymeric packaging material of the transparency of embodiment
（1）The preparation of sulfonated polyether-ether-ketone：At 50 DEG C, industrial stage polyetheretherketoneresin is dissolved in the concentrated sulfuric acid, wherein polyether-ether-ketone：Quality
A concentration of 98% concentrated sulfuric acid mass ratio is 1：80,4.5h is stirred, is stood for 24 hours, it is 7 that sodium hydroxide, which is added, and is adjusted to pH, filtering, water
It washes, vacuum degree 8kPa, 55 DEG C of vacuum drying 55min obtain sulfonated polyether-ether-ketone；
（2）The preparation of modified high-molecular：By raw material proportioning dispensing, linear low density polyethylene（The trade mark 7042, Jilin Petrochemical）︰ sulphurs
Change poly- ether ether ketone ︰ wood quality sulphur acid sodium ︰ ethylene glycol-methyl-prop e pioic acid methyl ester and is total to poly- object ︰ oleic acid diethyl amides phosphorus acid ester ︰ new penta
Polylol Duo Yuan Zhi ︰ phosphorylation Er Dian powder Lin Suan Zhi ︰ Ying resin acid Xin ︰ methyl vinyl ethers-maleic anhydride Wu ︰ oligomerizations are poly-
Lactic acid（400）The mass ratio of ︰ Bing Jiao Zhi ︰ KH-560 ︰ Yangization Ju ethylene La ︰ dolomite fines is：25 ︰, 0.002 ︰, 0.4 ︰, 0.03 ︰
0.001 ︰, 0.2 ︰, 4 ︰, 2 ︰, 0.3 ︰, 0.3 ︰, 0.7 ︰, 0.1 ︰, 1 ︰ 5；By raw material components in homogenizer, it is sufficiently mixed with 900r/min
10min obtains mixture, adds mixture into planetary ball mill, and vibration is carried out under the rotating ratio of material ball ratio 1 ︰ 4 and 1 ︰ 2
After hybrid reaction 45min, modified high-molecular is made；
（3）The preparation of the degradable polymeric packaging material of the transparency：By step（2）Gained modified high-molecular is in double screw extruder
Middle carry out melt modification, double screw extruder each section operation temperature are：150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 140 DEG C, spiral shell
Under bar rotating speed 50r/min, melt blending extruding pelletization obtains composite master batch；Gained composite master batch is sent into Single screw extrusion blown film
Machine, each section operation temperature are：Hot-melt extruded Blown Film at 180 DEG C, 190 DEG C, 200 DEG C, 180 DEG C obtains the transparency easily
Degraded macromolecular packaging material, 30 μm of film thickness.
The Mechanics Performance Testing of film article obtained by 1 Examples 1 to 5 of Application Example
The tensile strength of film presses GB/T 1040.3-2006, is tested using universal testing machine, test speed 10
Mm/min the results are shown in Table 1.
The mechanical property of 1 film of table
The translucency test of film obtained by 2 Examples 1 to 5 of Application Example
The light transmission of film is tested according to GB/T2410-80, the results are shown in Table 2.
The thermal oxide of film article obtained by 3 Examples 1 to 5 of Application Example and biodegradability test
It is carried out according to Unite States Standard ASTM D5988-03 standards, sample is simulated into refuse landfill or compost environment, is put into 70 DEG C
Thermal aging oven is handled 60 days, is carried out biodegradable test, be the results are shown in Table 2.
2 thermal oxide of table, biodegradability and light transmission
Exposure degradation property is tested under the outdoor natural conditions of film obtained by 4 Examples 1 to 5 of Application Example,
Concrete outcome is shown in Table 3.
Exposure degradation property under 3 natural conditions of table（Longitudinal tensile strength）
The above is only a preferred embodiment of the present invention, it is noted that for those skilled in the art,
Under the premise of not departing from present inventive concept, several improvements and modifications can also be made, these improvements and modifications also should be regarded as this hair
In bright protection domain.
Claims (7)
1. a kind of degradable polymeric packaging material of the transparency, it is characterised in that formula rate is counted as follows in mass ratio：Ju Yi Xi ︰
The poly- ether ether ketone ︰ wood quality sulphur acid sodium ︰ ethylene glycol-methyl-prop e pioic acid methyl ester of sulfonation is total to poly- object ︰ microbial nutritions and adds plus agent ︰ neopentyls
The poly- breast of polyalcohol Duo Yuan Zhi ︰ phosphorylation Er Dian powder Lin Suan Zhi ︰ Ying resin acid Xin ︰ methyl vinyl ethers-maleic anhydride Wu ︰ oligomerizations
Suan ︰ Bing Jiao Zhi ︰ epoxy radicals silicone hydride Ou Lian Ji ︰ Yangization Ju ethylene La ︰ dolomite fines ratios are：10~30 ︰, 0.001~0.002 ︰
0.1~0.5 ︰, 0.01~0.03 ︰, 0.001~0.002 ︰, 0.1~0.2 ︰, 1~5 ︰, 1~5 ︰, 0.1~0.5 ︰, 0.2~0.5 ︰ 0.2~
0.8 ︰, 0.1~0.3 ︰, 1 ︰ 3~8.
2. transparent degradable polymeric packaging material according to claim 1, it is characterised in that：The polyethylene is highly dense
Spend polyethylene, low density polyethylene (LDPE) or linear low density polyethylene.
3. transparent degradable polymeric packaging material according to claim 1, it is characterised in that：The epoxy radicals silicone hydride is even
Connection agent is KH-560, i.e. γ-（The third oxygen of 2,3- epoxies）Propyl trimethoxy silicane.
4. transparent degradable polymeric packaging material according to claim 1, it is characterised in that：The microbial nutrition adds
It is oleoyl glutamic acid, lauroyl glutamate, sodium lauroyl glutamate or oleic acid diethyl amide phosphate to add agent.
5. the preparation method of one of the claim 1-4 degradable polymeric packaging materials of the transparency, it is characterised in that step
It is as follows：
（1）The preparation of sulfonated polyether-ether-ketone：At 50 DEG C, industrial stage polyetheretherketoneresin is dissolved in the concentrated sulfuric acid, wherein polyether-ether-ketone：Quality
A concentration of 98% concentrated sulfuric acid mass ratio is 1：50~100,3~5h is stirred, is stood for 24 hours, it is 7 that sodium hydroxide, which is added, and is adjusted to pH, mistake
Filter, washing, vacuum degree be 5~20kPa, 50~70 DEG C vacuum drying 30~60min, obtain sulfonated polyether-ether-ketone；
（2）The preparation of modified high-molecular：By raw material proportioning dispensing, Ju Yi Xi ︰ sulfonation Ju Mi Mi Tong ︰ Mu quality Huang Suan Na ︰ second two
Alcohol-methyl-prop e pioic acid methyl ester is total to poly- object ︰ microbial nutritions and adds plus more two starch phosphates of member ester ︰ phosphorylations of agent ︰ amyl-based polyols
Zhi ︰ Ying resin acid Xin ︰ methyl vinyl ethers-maleic anhydride Wu ︰ oligomerization Ju Ru Suan ︰ Bing Jiao Zhi ︰ epoxy radicals silicone hydride Ou Lian Ji ︰ oxygen
Change Ju ethylene La ︰ dolomite fines mass ratio be：10~30 ︰, 0.001~0.002 ︰, 0.1~0.5 ︰, 0.01~0.03 ︰ 0.001
0.1~0.3 ︰ of~0.002 ︰ 0.1~0.2 ︰, 1~5 ︰, 1~5 ︰, 0.1~0.5 ︰, 0.2~0.5 ︰, 0.2~0.8 ︰, 1 ︰ 3~8；By raw material
Component is sufficiently mixed 10min in homogenizer, with 800~1000r/min, obtains mixture, adds mixture into planet
In ball mill, after carrying out 40~70min of vibration hybrid reaction under the rotating ratio of material ball ratio 1 ︰ 2~5 and 1 ︰ 2, it is made modified high
Molecule；
（3）The preparation of the degradable polymeric packaging material of the transparency：By step（2）Gained modified high-molecular is in double screw extruder
Middle carry out melt modification, operation temperature are 140~180 DEG C, under 50~70 r/min of screw speed, melt blending extruding pelletization,
Obtain composite master batch；By gained composite master batch feeding Single screw extrusion inflation film manufacturing machine, the hot-melt extruded Blown Film at 180~200 DEG C,
Obtain the degradable polymeric packaging material of the transparency.
6. the preparation method of transparent degradable polymeric packaging material according to claim 5, it is characterised in that：It is described
The bright degradable polymeric packaging material film thickness of property is 30 μm.
7. the preparation method of transparent degradable polymeric packaging material according to claim 5, it is characterised in that：Step
（3）The a diameter of 20mm of double screw extruder, draw ratioL/D It is 36:1；The a diameter of 20mm of Single screw extrusion inflation film manufacturing machine, it is long
Diameter ratioL/DIt is 30:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810108992.8A CN108373560A (en) | 2018-02-05 | 2018-02-05 | A kind of degradable polymeric packaging material of the transparency and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810108992.8A CN108373560A (en) | 2018-02-05 | 2018-02-05 | A kind of degradable polymeric packaging material of the transparency and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108373560A true CN108373560A (en) | 2018-08-07 |
Family
ID=63017212
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810108992.8A Pending CN108373560A (en) | 2018-02-05 | 2018-02-05 | A kind of degradable polymeric packaging material of the transparency and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108373560A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110330680A (en) * | 2019-07-08 | 2019-10-15 | 华南理工大学 | A kind of anti-fog properties SPEEK/PE controlled atmosphere composite membrane of high separability and preparation and application |
| CN112679203A (en) * | 2021-01-21 | 2021-04-20 | 清远市简一陶瓷有限公司 | Light-transmitting brick and preparation method thereof |
| CN114685961A (en) * | 2020-12-29 | 2022-07-01 | 中国石油化工股份有限公司 | Modified polylactic acid film material |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007044506A2 (en) * | 2005-10-06 | 2007-04-19 | Coating Excellence International Llc | Composite film bag for packaging bulk products |
| CN102040737A (en) * | 2010-11-11 | 2011-05-04 | 西北工业大学 | Polyetheretherketone-modified phenol formaldehyde resin and preparation method thereof |
| CN103408827A (en) * | 2013-08-29 | 2013-11-27 | 河北奥柯柏环保科技有限公司 | Degradable environmental-friendly mulching film and preparation method thereof |
| CN103410001A (en) * | 2013-07-05 | 2013-11-27 | 浙江理工大学 | Preparation method of self-cleaning cotton fabric based on light-induced polymer free radicals for degrading pollutants |
| CN104140582A (en) * | 2014-07-25 | 2014-11-12 | 杨建� | Non-starchy light-and bio-degradable plastic transparent master batch and preparation method thereof |
| US9056979B2 (en) * | 2012-11-15 | 2015-06-16 | Basf Se | Biodegradable polyester mixture |
| CN105954078A (en) * | 2016-05-11 | 2016-09-21 | 上海瀚海检测技术股份有限公司 | Method for quantitative analysis of polyether-ether-ketone in polyether-ether-ketone composite |
| CN106084748A (en) * | 2016-06-08 | 2016-11-09 | 东莞市雄林新材料科技股份有限公司 | A kind of biodegradable TPU film and preparation method thereof |
-
2018
- 2018-02-05 CN CN201810108992.8A patent/CN108373560A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007044506A2 (en) * | 2005-10-06 | 2007-04-19 | Coating Excellence International Llc | Composite film bag for packaging bulk products |
| CN102040737A (en) * | 2010-11-11 | 2011-05-04 | 西北工业大学 | Polyetheretherketone-modified phenol formaldehyde resin and preparation method thereof |
| US9056979B2 (en) * | 2012-11-15 | 2015-06-16 | Basf Se | Biodegradable polyester mixture |
| CN103410001A (en) * | 2013-07-05 | 2013-11-27 | 浙江理工大学 | Preparation method of self-cleaning cotton fabric based on light-induced polymer free radicals for degrading pollutants |
| CN103408827A (en) * | 2013-08-29 | 2013-11-27 | 河北奥柯柏环保科技有限公司 | Degradable environmental-friendly mulching film and preparation method thereof |
| CN104140582A (en) * | 2014-07-25 | 2014-11-12 | 杨建� | Non-starchy light-and bio-degradable plastic transparent master batch and preparation method thereof |
| CN105954078A (en) * | 2016-05-11 | 2016-09-21 | 上海瀚海检测技术股份有限公司 | Method for quantitative analysis of polyether-ether-ketone in polyether-ether-ketone composite |
| CN106084748A (en) * | 2016-06-08 | 2016-11-09 | 东莞市雄林新材料科技股份有限公司 | A kind of biodegradable TPU film and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 岳德茂: "《印刷科技实用手册 第3分册 印刷器材篇》", 30 April 2010, 北京：印刷工业出版社 * |
| 马春平等: "可降解聚乙烯材料的研究进展", 《塑料科技》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110330680A (en) * | 2019-07-08 | 2019-10-15 | 华南理工大学 | A kind of anti-fog properties SPEEK/PE controlled atmosphere composite membrane of high separability and preparation and application |
| CN110330680B (en) * | 2019-07-08 | 2021-11-23 | 华南理工大学 | High-separability antifogging SPEEK/PE air-conditioning composite membrane and preparation and application thereof |
| CN114685961A (en) * | 2020-12-29 | 2022-07-01 | 中国石油化工股份有限公司 | Modified polylactic acid film material |
| CN114685961B (en) * | 2020-12-29 | 2024-04-05 | 中国石油化工股份有限公司 | Modified polylactic acid film material |
| CN112679203A (en) * | 2021-01-21 | 2021-04-20 | 清远市简一陶瓷有限公司 | Light-transmitting brick and preparation method thereof |
| CN112679203B (en) * | 2021-01-21 | 2022-09-02 | 清远市简一陶瓷有限公司 | Light-transmitting brick and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xie et al. | Plasticizer combinations and performance of wood flour–poly (lactic acid) 3D printing filaments | |
| CN108373560A (en) | A kind of degradable polymeric packaging material of the transparency and preparation method thereof | |
| CN100572433C (en) | The production method of a kind of fully biodegradable Plastic Resin and film based article thereof | |
| CN113801350A (en) | Calcium carbonate filled PBAT/PLA biodegradable plastic film and preparation method thereof | |
| KR20110077642A (en) | Eco-friendly earphone cord | |
| CN1230466C (en) | Fully bio-degradable plastic master batch and preparing process thereof | |
| CN101948598A (en) | Method for preparing biodegradable membrane | |
| WO2018199494A1 (en) | Multi-degradable polyolefin-based resin composition and method for preparing same | |
| CN108263061A (en) | A kind of degradable green package film of high-barrier and preparation method thereof | |
| US11130259B1 (en) | Device and method for online preparation of modified polylactic acid material with polylactic acid melt | |
| CN109467791A (en) | A kind of high strength easy-to-degrade modified poly ethylene film and preparation method thereof | |
| CN108276644A (en) | A kind of toughening enhancing Fully-degradable ethylene master batch and preparation method thereof | |
| CN112391042A (en) | Biodegradable material for dental floss rod handle and preparation method thereof | |
| CN112625347A (en) | Low-odor, high-performance and environment-friendly polypropylene composite material and preparation method thereof | |
| CN109467793A (en) | A kind of transparent multiple-factor degradation modification polyethylene film and preparation method thereof | |
| CN102604308B (en) | Preparation method of blow molding type thermoplastic konjak glucomannan/poly-caprolactone composite resin | |
| CN101205314A (en) | Method for preparing thermoplastic starch material | |
| CN101921422B (en) | Ecologically degradable plastic garbage bags | |
| CN114805697A (en) | Compatibilizer for improving PLA/PBAT compatibility and high-filling full-biodegradable composite material | |
| CA2949145A1 (en) | Thermoformable polylactic acid | |
| CN108329563A (en) | Degradable polymeric packaging material and preparation method thereof under a kind of natural conditions | |
| CA2776948A1 (en) | Compositions comprising polylactic acid and gum arabic | |
| WO2011050479A1 (en) | Compositions comprising polylactic acid, bentonite, and gum arabic | |
| CN111057274A (en) | High-filling starch-based thermoplastic composite material and preparation method thereof | |
| CN111423703A (en) | CaCO for high-filling PBAT biodegradable film3Surface treatment method and preparation of film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180807 |
|
| RJ01 | Rejection of invention patent application after publication |