CN103171219A - Membrane consisting of inner-layer structure and outer-layer structure - Google Patents
Membrane consisting of inner-layer structure and outer-layer structure Download PDFInfo
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Abstract
The invention discloses a membrane consisting of an inner-layer structure and an outer-layer structure. The membrane is characterized in that an outer layer is a polyester composition I, and at least one layer in an inner layer contains a polyester composition II, wherein the polyester composition I contains 10-98 parts of polylactic resin (A), 5-90 parts of aliphatic polyesters or aliphatic-aromatic copolyesters (B) and 1-30 parts of polyether-polyester copolymer plasticizers (C) in parts by weight; and the polyester composition II contains 10-98 parts of the polylactic resin (A), 5-90 parts of the aliphatic polyesters or the aliphatic-aromatic copolyesters (B) and 1-30 parts of plasticizers (D) excepting the plasticizers (C) in parts by weight. According to the membrane, the seepage of the plasticizers normally used in the inner layer can be effectively restrained, and the performance of the membrane can be better maintained in a degradation time range; and the membrane can be applied to garbage bags, food bags, packaging material bags of various industrial products, agricultural membranes and the like.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of film of polymer blend preparation.
Background technology
In recent years, the consumption as the polyethylene of food, beverage-container, pallet etc. and commodity external packing box material, polypropylene, polyester, nylon etc. increases year by year.What accompany therewith is that after using, the amount of discarded object is also in continuous increase.Waste plastic class material is regarded as " white pollution " because it is difficult to collect reclaim, reason is that the plastics back to nature process (being biodegradation) that finally incorporates cyclic microorganism is very very long, need even more than one thousand years of centuries, the puzzlement that a large amount of discarded plastic products have brought " white pollution " because of its non-biodegradable.In causing the factors of environmental pollution, oneself has caused social extensive concern the public hazards that plastic refuse causes, and the development biodegradable plastic has become the task of top priority.
PLA is a kind of macromolecular material of complete biodegradable, and the enzyme effect by microorganisms in natural environment is degraded into inorganic substances such as water and carbon dioxide at last, and raw material sources fully and can regenerate.The production process of PLA is pollution-free, and product can biodegradation, realizes the circulation at occurring in nature, is therefore desirable Green Polymer Material.
PLA has higher fusing point, and higher glass transition temperature and mechanical strength are therefore there is heat resistance preferably.But, PLA exists hard and crisp, and the shortcoming such as cost of material is higher, be restricted in the field that requires the material softness degree, by improving significantly the plasticity of PLA with the plasticizer blend, improved the processing characteristics of PLA, and can be applied to extrude injection moulding, blowing, the multiple processing mode such as curtain coating, this will expand the application of PLA greatly.
Patent documentation CN101955639A discloses a kind of modified polylactic acid material and preparation method thereof, by add thermoplastic polyester elastomer, plasticizer and filler in PLA, improve the poly-lactic acid material pliability, material mechanical performance fracture extensibility through modification can reach 20-380%, but due to plasticizer and the polymeric system cohesive force relatively poor, after after a while, plasticizer more easily oozes out from system, thus the material mechanical performance variation.
Summary of the invention
The object of the invention is to address the above problem, a kind of film of polymer blend preparation is provided.
The present invention wraps in nexine by the film with plasticizer D plasticising, the outer film with the good plasticizer C plasticising of resin compatible by being difficult for oozing out consists of, this plasticizer C is degradation material simultaneously, ooze out thereby reduce by plasticizer D the impact on film performance decline that brings, make film still keep higher mechanical property after after a while.
Purpose of the present invention can reach by following measures:
A kind of film that is formed by internal layer and layer structure, skin is the polymer blend first, in internal layer at least one deck comprised polymer blend second;
In described polymer blend first, contain polylactic resin (A) 10～98 weight portions, aliphatic polyester or aliphatic aromatic copolyester (B) 5～90 weight portions, and weight average molecular weight is polyether polyester copolymer plasticizer (C) 1～30 weight portion of 300-100000;
In described polymer blend second, contain polylactic resin (A) 10～98 weight portions, aliphatic polyester or aliphatic aromatic copolyester (B) 5～90 weight portions, and plasticizer (D) 1～30 weight portion except plasticizer (C).
PLA belongs to bio-based materials by the lactic acid polymerizes that amylofermentation forms, and is renewable resource, enlarges to use PLA all to be of great importance for environmental protection and sustainable development.Add copolyesters to help to improve pliability and the dimensional stability of polylactic acid film, reduce modulus and increase elongation at break; Aliphatic polyester or aliphatic aromatic copolyester (B) content are preferably the 10-30 weight portion.Compatible DeGrain may occur when its content is less than 10 weight portions, cause cost to rise greater than 30 weight portions.Plasticizer can improve the pliability of PLA, improves plasticity, changes the hard and crisp characteristics of poly-lactic acid material.
Polylactic resin is the polymer take Pfansteihl construction unit and/or D-ALPHA-Hydroxypropionic acid construction unit as main component, what are relevant for the content that the crystal property of poly (l-lactic acid) adds along with poly-D-ALPHA-Hydroxypropionic acid, add abundant poly-D-ALPHA-Hydroxypropionic acid can cause gathering-the not even crystallization that greatly descends of L lactic acid crystal property; Vice versa.
Polylactic resin of the present invention (A) be crystallization type polylactic acid resin or non-crystalline type polylactic resin in one or both.Described crystallization type polylactic acid is measured with differential scanning calorimeter after referring to this PLA crystallization, can observe the polylactic resin of sharp melting point; Under differential scanning calorimeter scanning, do not observe the polylactic resin of sharp melting point during described armorphous polylactic resin.
For satisfying the mechanical property of goods, the weight average molecular weight of described polylactic resin (A) is preferably 10-40 ten thousand, and more preferably 10-30 ten thousand.The weight average molecular weight here is to adopt chloroform as solvent, the molecular weight that uses gel permeation chromatography (GPC) to measure.
Described aliphatic polyester is preferably one or both in poly butylene succinate or poly-adipic acid succinic acid-butanediol ester, and its weight average molecular weight is 5-40 ten thousand, further preferred 10-30 ten thousand; The aliphatic aromatic copolyester is preferably the poly terephthalic acid tetramethylene adipate, and its weight average molecular weight is 5-40 ten thousand, further preferred 10-30 ten thousand.
It is that 300～30000 polyethylene glycol and weight average molecular weight are one or more in 300～30000 the PLA homopolymers, random copolymer or the block copolymer that form that described polyether polyester copolymer plasticizer (C) is preferably weight average molecular weight.This plasticizer contains lactic component, therefore produce compatibility with polylactic resin (A), good compatibility is arranged.Lactic acid segment in plasticizer (C) is understood some and is inserted in polylactic resin (A), thereby well be bonded together, thereby to a great extent always plasticizer (C) ooze out from resin, but also played the effect that increases plasticity, improved the flexibility of resin.
described plasticizer (D) except plasticizer (C) is preferably glycerine, propane diols, macrogol ester, ATEC, triethyl citrate, ATBC, tri-n-butyl citrate, ATBC, single triacetin, two acetoglycerides, triacetyl glycerine, repefral, diethyl phthalate, dioctyl phthalate, diisononyl phthalate, diisooctyl phthalate, dibutyl phthalate, the adjacency pair toluenesulfonamide, ethylazelaate, dibutyl sebacate, decanedioic acid two (2-Octyl Nitrite), trimethylolpropane, N-ethyl adjacency pair toluenesulfonamide, N-butylbenzenesulfonamide, trioctyl trimellitate (TOTM), epoxidized soybean oil, coconut oil, castor oil, pentaerythritol tetrastearate, or one or more in n butyl oleate.
In order to meet the applicability of packaging for foodstuff, when perhaps being used for agriculture and forestry, consider the short-term compost and remain in undecomposed material in soil, as plasticizer (D), preferably select the plasticizer through the license of the sanitation associations such as U.S. food health bureau (FDA) or polyolefin.
Polymer blend first of the present invention or polymer blend second, except above-mentioned main component, still can add other known additive, for example, one or more in heat stabilizer, antioxidant, light stabilizer, lubricant, colouring agent, various inorganic filler, fire retardant, crystallization nucleating agent or opening agent.
Wherein, heat stabilizer is selected from one or more in tin stabilizing agent, lead stabilizer or zinc stabilizer; Antioxidant is selected from one or more in butylated hydroxy anisole, dibutyl hydroxy toluene, n-propyl gallate or ditert-butylhydro quinone; Light stabilizer is selected from organic complex or one or more in the hindered amines derivative of organic complex, the iron of organic complex, the cobalt of carbon black, zinc oxide, titanium dioxide, zinc oxide, barium monoxide, benzophenone compound, salicylic acid compounds, benzotriazole compound, nickel; Lubricant is selected from one or more in fatty acid metal salts, fatty acid amide or fatty acid ester; Colouring agent is painted one or more with additive that generally use in resin; Various inorganic fillers are selected from one or more in calcium carbonate, talcum powder, silica, diatomite, mica or zeolite powder; Fire retardant is selected from one or more in phosphorus flame retardant or halogenated flame retardant; Crystallization nucleating agent is selected from one or more in the additive with promotion crystallization that is widely used in resin forming; Opening agent is selected from one or more in various inorganic particles or metal salts of organic acids.
Film-forming method in the present invention is not particularly limited, and can use existing known manufacture method.For example, carry out extruder and carry out extruding pelletization, use inflation film manufacturing machine to carry out blown film.
(1) utilize the granulation of extruder melt blending, 100～170 ℃ of feed zone temperature, 170～220 ℃ of extruding zone temperature, extruder rotating speed 200～600rpm obtains particle through the press mold moulding, and the press mold temperature is similarly 170～220 ℃.
(2) blowfilm shaping, 100～170 ℃ of extruder feed zone temperature, 150～220 ℃ of extruding zone temperature, die temperature is similarly 150～220 ℃, extruder rotating speed 200～600rpm, regulate vane to suitable cooling air, adjust blow-up ratio and rolling speed according to required film thickness, control respectively the thickness of ectonexine film by the extrusion capacity of regulating each extruder.Here take three-layer co-extruded inflation film manufacturing machine as the example explanation.
Because oozing out of plasticizer has been subject to inhibition, have good durability by the three-layer co-extruded film that makes, this point is proved by initial stage tensile property and the variation of the tensile property after month of film.
The present invention can fully reduce the cost of polylactic acid film goods, improves film performance, and polylactic acid film can be used on farm-oriented mulch, shopping bag, refuse bag and various packing purposes.
The specific embodiment
Extruding pelletization:
Under vacuum environment, with dry 5 hours of PLA particle.By formula, various raw materials are carried out melt blending by double screw extruder and extrude, generate composition mother particle after melt is cooling through tank, 180 ℃ of extruder feed zone temperature, 190 ℃ of second segments, all the other sections are 200 ℃.
The blowing masking:
With composition mother particle under 80 ℃, vacuum environment dry 5 hours, by blow moulding machine, master batch is blow molded into the thick film of 0.02mm, for multilayer, its gross thickness is 0.020mm.The feed zone temperature of inflation film manufacturing machine is 140 ℃, and second segment, the 3rd section, die head district are 160 ℃, and mouthful mould district is 155 ℃.
Mechanics performance determining:
Film sample is made the batten of 10mm * 100mm, tested its elongation at break, fracture strength, modulus by the film stretching testing machine, jaw span is 50mm, and rate of extension is 200mm/min.Each sample test seven times is averaged after the removal maximin.Wherein, MD represents film along producer to being vertical performance, TD represent film perpendicular to producer to being lateral performance.
The raw material that embodiment, Comparative Examples are used:
(1) polylactic resin (A)
A-1:Natural Works 4032D processed, weight average molecular weight 18～22w.
A-2:Natural Works 4060D processed, weight average molecular weight 18～22w.
(2) copolyesters (B)
B-1:BASF PBAT processed, trade mark FBX7011.
B-2: prosperous rich medicine company PBS processed, trade mark 1903F.
B-3: prosperous rich medicine company PBSA processed, trade mark 1803Z.
B-4: prosperous rich medicine company PBAT processed, trade mark 2003F.
(3) plasticizer (C)
Sanyo's chemistry PEG6000-PLA LEP-850 processed.
(4) plasticizer (D)
D-1: traditional Chinese medicines reagent ATBC processed.
D-2: traditional Chinese medicines reagent tri-n-butyl citrate processed.
D-3: traditional Chinese medicines reagent di-n-octyl phthalate processed.
D-4: traditional Chinese medicines reagent phthalic acid two processed (2-Octyl Nitrite).
D-5: traditional Chinese medicines reagent decanedioic acid two processed (2-Octyl Nitrite).
D-6: traditional Chinese medicines reagent dibutyl sebacate processed.
Below embodiment and Comparative Examples
Embodiment 1-6, Comparative Examples 1: table 1;
Embodiment 7-12, Comparative Examples 2: table 2;
Embodiment 18-24, Comparative Examples 3: table 3;
Embodiment 25-30, Comparative Examples 4: table 4.
Claims (5)
1. film that is comprised of internal layer and layer structure is characterized in that: outerly be the polymer blend first, in internal layer at least one deck comprised polymer blend second;
In described polymer blend first, contain polylactic resin (A) 10～98 weight portions, aliphatic polyester or aliphatic aromatic copolyester (B) 5～90 weight portions, and weight average molecular weight is polyether polyester copolymer plasticizer (C) 1～30 weight portion of 300-100000;
In described polymer blend second, contain polylactic resin (A) 10～98 weight portions, aliphatic polyester or aliphatic aromatic copolyester (B) 5～90 weight portions, and plasticizer (D) 1～30 weight portion except plasticizer (C).
2. film according to claim 1, it is characterized in that: the weight average molecular weight of described polylactic resin (A) is 10～400,000.
3. film according to claim 1, it is characterized in that: described aliphatic polyester is one or both in poly butylene succinate or poly-adipic acid succinic acid-butanediol ester, and its weight average molecular weight is 5-40 ten thousand; The aliphatic aromatic copolyester is the poly terephthalic acid tetramethylene adipate, and its weight average molecular weight is 5-40 ten thousand.
4. film according to claim 1 is characterized in that: described polyether polyester copolymer plasticizer (C) is that 300～30000 polyethylene glycol and weight average molecular weight are one or more in 300～30000 the PLA homopolymers, random copolymer or the block copolymer that form for weight average molecular weight.
5. film according to claim 1, it is characterized in that: described plasticizer (D) except plasticizer (C) is glycerine, propane diols, macrogol ester, ATEC, triethyl citrate, ATBC, tri-n-butyl citrate, ATBC, single triacetin, two acetoglycerides, triacetyl glycerine, repefral, diethyl phthalate, dioctyl phthalate, diisononyl phthalate, diisooctyl phthalate, dibutyl phthalate, the adjacency pair toluenesulfonamide, ethylazelaate, dibutyl sebacate, decanedioic acid two (2-Octyl Nitrite), trimethylolpropane, N-ethyl adjacency pair toluenesulfonamide, N-butylbenzenesulfonamide, trioctyl trimellitate (TOTM), epoxidized soybean oil, coconut oil, castor oil, pentaerythritol tetrastearate, or one or more in n butyl oleate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN 201110455486 CN103171219A (en) | 2011-12-20 | 2011-12-20 | Membrane consisting of inner-layer structure and outer-layer structure |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201110455486 CN103171219A (en) | 2011-12-20 | 2011-12-20 | Membrane consisting of inner-layer structure and outer-layer structure |
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| CN103171219A true CN103171219A (en) | 2013-06-26 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105109165A (en) * | 2015-08-31 | 2015-12-02 | 浙江大学 | Controllable biodegradable mulch film |
| CN105416797A (en) * | 2015-12-15 | 2016-03-23 | 河南天仁生物材料研究所有限公司 | Biodegradation express delivery packaging bag and preparation technology thereof |
| WO2018072746A1 (en) * | 2016-10-21 | 2018-04-26 | 中国石油化工股份有限公司 | Polyester composition, preparation method therefor and application thereof |
| CN108948701A (en) * | 2018-07-31 | 2018-12-07 | 合肥浦邦农业科技有限公司 | A kind of environmental protection high-ductility agricultural film and preparation method thereof |
| CN111409344A (en) * | 2020-04-14 | 2020-07-14 | 四川汇利实业有限公司 | Medicine packaging film and preparation method thereof |
-
2011
- 2011-12-20 CN CN 201110455486 patent/CN103171219A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105109165A (en) * | 2015-08-31 | 2015-12-02 | 浙江大学 | Controllable biodegradable mulch film |
| CN105416797A (en) * | 2015-12-15 | 2016-03-23 | 河南天仁生物材料研究所有限公司 | Biodegradation express delivery packaging bag and preparation technology thereof |
| CN105416797B (en) * | 2015-12-15 | 2017-12-26 | 河南天仁生物材料研究所有限公司 | A kind of biodegradable express packaging bag and its preparation technology |
| WO2018072746A1 (en) * | 2016-10-21 | 2018-04-26 | 中国石油化工股份有限公司 | Polyester composition, preparation method therefor and application thereof |
| US11466151B2 (en) | 2016-10-21 | 2022-10-11 | China Petroleum & Chemical Corporation | Polyester composition, preparation method therefor and application thereof |
| CN108948701A (en) * | 2018-07-31 | 2018-12-07 | 合肥浦邦农业科技有限公司 | A kind of environmental protection high-ductility agricultural film and preparation method thereof |
| CN111409344A (en) * | 2020-04-14 | 2020-07-14 | 四川汇利实业有限公司 | Medicine packaging film and preparation method thereof |
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Application publication date: 20130626 |