CN106893275A - A kind of degradable recovery poly-lactic acid material and preparation method thereof - Google Patents
A kind of degradable recovery poly-lactic acid material and preparation method thereof Download PDFInfo
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- CN106893275A CN106893275A CN201510949306.6A CN201510949306A CN106893275A CN 106893275 A CN106893275 A CN 106893275A CN 201510949306 A CN201510949306 A CN 201510949306A CN 106893275 A CN106893275 A CN 106893275A
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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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- 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
- 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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Abstract
The invention provides degradable recovery poly-lactic acid material of one kind and preparation method thereof, belong to technical field of biological materials.Molecular weight decay is larger when it solves polylactic acid sheet material melt-processed, and the material of 35% or so one-level can not directly reclaim participation and use, and price is high, the problem promoted and be limited using scope.This degradable recovery poly-lactic acid material, including by the composition extrusion molding of following weight portion：Poly-lactic acid in high molecular weight resin：50 ~ 90 parts；Low molecular weight resin：10 ~ 50 parts；Processing aid：0.2~10 part；The number-average molecular weight of poly-lactic acid in high molecular weight resin is 9~150,000 dalton, and the number-average molecular weight of low molecular weight resin is 5~90,000 dalton.Low cost of the invention, mechanical property is good, and durable usability is good, there is good post forming, and method technological process is simple, workable.
Description
Technical field
The present invention relates to a kind of biodegradated polymer materal and preparation method thereof, more particularly to a kind of degradable recovery poly-lactic acid material and preparation method thereof, belong to technical field of biological materials.
Background technology
The discarded object of macromolecular material has caused the extensive concern of people to the negative effect that environment brings, and solving serious " white pollution " problem turns into the problem of many country's concerns.Under these circumstances, the research and development of biodegradated polymer materal are valued by people, and part biological degraded family macromolecule material is had started to for industrialized production.The various physical properties of its existing common plastics, can widely use, again can be free from environmental pollution after use is discarded, and it can be completely decomposed into carbon dioxide and water by the microorganism collective effect of certain temperature, humidity and nature.Biodegradated polymer materal is widelyd popularize, can effectively alleviate problem of environmental pollution, also comply with current macromolecular material development trend.
PLA (PLA) is referred to as " green plastic " as the macromolecular material of Wholly-degradable, with good biodegradability, can be degradable by microorganism in nature after use, and carbon dioxide and water are ultimately generated, it is free from environmental pollution.PLA has good physical property, suitable for various processing methods such as blowing, injections, be made fiber, film, block, plate etc. for being processed into from industry to civilian various plastic products, packaging for foodstuff, fast food lunch-box, non-woven fabrics, geotextile, health care fabric, rag, amenities, outdoor Uvr Protective Fabric, tent cloth, ground pad etc., market prospects are very good.
The initial raw material of PLA is the crops of various high-content of starch, and starch is milled into by driving away, and lactic acid is changed into by biofermentation, and lactic acid aggregates into PLA through dehydration.It can be seen that PLA is totally different from other plastics, its essence is using reproducible plant resources；And it have with common plasticses identical physical property and processing characteristics, therefore use poly-lactic acid material, can effectively alleviate the exhaustion of non-renewable resources.As U.S. Jia Ji (Cargill) company has the annual productions such as 50,000 tons of abilities of poly-lactic acid material of annual output, the positive biomaterial limited company in state inland sea to progressively reach the level of the advanced countries such as America and Europe.
Chinese patent application (publication number：CN1732228A) it is related to the poly lactic acid polymerized compositions for thermoforming, for the polylactic acid polymer sheet material of thermoforming, and the thermoformed articles obtained by it.Wherein described polylactic acid sheet material is formed by amorphous polylactic acid polymer and crystalline polylactic acid polymer composition, described amorphous polylactic acid polymer and crystalline polylactic acid polymer include the Pfansteihl and D-ALPHA-Hydroxypropionic acid of certain content ratio, on the basis of the amorphous polylactic acid polymer of wherein 100 weight portions, the amount of the crystalline polylactic acid polymer is 10~200 weight portions.Although the polylactic acid sheet material represents the intrinsic impact resistance and heat resistance of crystalline polylactic acid polymer, and with the pliability of amorphous polylactic acid polymer.But due to the thermal degradation of polylactic acid sheet material, the decay of melt-processed middle-molecular-weihydroxyethyl is larger；The rim charge produced in the forming process of polylactic acid sheet material, and leftover pieces after sheet material post forming can account for 35% or so of material total amount, this partial material can not unlimited number of direct recovery participation use, otherwise the physical property of sheet material can be influenceed by very big.The feed back of this 35% or so one-level is not used in the middle of sheet material, and the price that this just directly results in polylactic acid sheet material is higher, is limited its popularization yet and is used scope.
The content of the invention
It is an object of the invention to the defect being directed to existing for prior art, there is provided a kind of cost is relatively low, the preferable full-biodegradable polylactic acid sheet material of mechanical strength.
Above-mentioned technical purpose of the invention is carried out by the following technical programs：A kind of degradable recovery poly-lactic acid material, it is characterised in that：The polylactic acid sheet material is included by the composition extrusion molding of following weight portion：
Poly-lactic acid in high molecular weight resin：50 ~ 90 parts；Low molecular weight resin：10 ~ 50 parts；Processing aid：0.2~10 part；The number-average molecular weight of described poly-lactic acid in high molecular weight resin is 9~150,000 dalton, and the number-average molecular weight of described low molecular weight resin is 5~90,000 dalton.
Poly-lactic acid in high molecular weight resin of the present invention is that virgin material polylactic resin can be polymerized by polycondensation, ring-opening polymerisation or other known method.In polycondensation reaction, polylactic resin is obtained by dehydration/polycondensation reaction by directly making Pfansteihl, D-ALPHA-Hydroxypropionic acid or their mixture.
In ring-opening polymerization, hand over fat to obtain polylactic acid polymer by polymerization third in the presence of a catalyst, hand over fat, D- third to hand over fat and DL- third to hand over fat wherein the third described friendship fat can be L- third.
The low molecular weight resin that the present invention is used is the low molecular weight resin processed by one or many, creative is prepared two kinds of polylactic resin compositions, it is polylactic acid sheet material to add a certain amount of processing aid extrusion molding, the polylactic acid sheet material has obvious low-cost advantage, and complete biodegradable is able to ensure that after use, with good suitability for secondary processing.
In above-mentioned degradable recovery poly-lactic acid material, described processing aid is one or more in heat stabilizer, lubricant, plasticizer and hydrolysis agent.Because pure polylactic resin does not have price or performance advantage, frangible and very low-heat denaturation temperature and low melt strength, processing aid are indispensable to improving processing and final use performance and allowing that polylactic acid sheet material meets its potential.Some processing aids such as lubricant and hydrolysis agent that the present invention is used etc. can improve the melt strength and melt elasticity of polylactic resin, can also improve polylactic resin transparency and recyclability.
In above-mentioned degradable recovery poly-lactic acid material, described sheet material is nontransparent polylactic acid sheet material, the nontransparent polylactic acid sheet material by following weight portion composition extrusion molding：
Poly-lactic acid in high molecular weight resin：50 ~ 90 parts；Low molecular weight resin：10 ~ 50 parts；Coupling agent：1.0~3.0 parts；0.5~3.0 part of plasticizer；Lubricant：1.0~3.0 parts；Hydrolysis agent：0.1~2.0 part.
In order to increase molecular weight, a small amount of chain extender such as epoxide, acid anhydrides, chain extender ADR-4370S etc. can also be used in transparent or nontransparent polylactic acid sheet material, it is recovered by the inherent viscosity of adjustment and control polylactic resin and improves mechanical performance, hot property, processing characteristics and optical balance.
It is another object of the present invention to provide the preparation method of above-mentioned polylactic acid sheet material, the method is comprised the following steps：
A, drying：Poly-lactic acid in high molecular weight resin and low molecular weight resin are weighed according to above-mentioned weight portion to be dried under the conditions of 90 DEG C~120 DEG C of temperature, the moisture of polylactic resin is less than 200ppm after drying；
B, melting：Processing aid or processing aid and filler are added in polylactic resin after the drying, is well mixed by after high-speed stirred, making each composition, melted under conditions of being 180 DEG C~210 DEG C in temperature；
C, extrusioning shaping：By the melt extrusion sheet blank of above-mentioned melting, cooling and shaping under conditions of being 40 DEG C~65 DEG C in temperature by sheet blank；
D, traction, post processing：By the sheet blank after cooling and shaping after draw-gear draws, surface electrostatic is eliminated, and polylactic acid sheet material is obtained final product to winding after the coating of surface.
The present invention is by low molecular weight resin (the pure polylactic resin of low-molecular-weight processed by one or many) by stirring at low speed cold crystallization, mix uniform through moderate-speed mixer with poly-lactic acid in high molecular weight resin (i.e. virgin material polylactic resin) again, the moisture dried in hot-air is removed again, material is dried again, the moisture of mixed material is less than 150ppm.
Various composition fusion plastification under conditions of temperature is for 180 DEG C~210 DEG C, makes various composition mix under molecular state, and certain chemical reaction occurs.The stabilization for ensureing melt pressure and flow is also needed to ensure the stabilization of polylactic acid sheet material production in melting process.Melt is uniformly extruded during extrusion sheet.
Polylactic acid sheet material blank can play press polish, cooling, sizing and the progressively function of release sheet internal stress during cooling and shaping.It is to ensure that polylactic acid sheet material remains smooth in process of production to be drawn by draw-gear.
In sum, the present invention has advantages below：
1st, degradable recovery poly-lactic acid material of the invention, cost of material is relatively low, and cost is compared with existing polylactic acid sheet material can reduce 20-40%, and can meet the demand of different product such as food container and shell-type packing container completely.
2nd, degradable recovery poly-lactic acid material of the invention is used cooperatively using multicomponent, it is ensured that complete biodegradable, and with outstanding mechanical property, tensile strength can reach 30-55MDa, tension fracture elongation rate 5-30%；With good durable usability.
3rd, the degradable recovery poly-lactic acid material preparation method of the present invention, the method has outstanding plasticizing plasticating capacity, and melt viscosity stabilization can prepare the polylactic acid sheet material of 0.2mm-1.5mm different sizes.And with good post forming.
4th, the degradable recovery poly-lactic acid material preparation method of the present invention, the method technological process is simple, workable.
Specific embodiment
Below by specific embodiment, technical scheme is described in further detail；But the present invention is not limited to these embodiments.
Embodiment 1：The making of nontransparent polylactic acid sheet material
Weigh 30 parts of low molecular weight resin, after stirring at low speed cold crystallization, again with 70 parts of poly-lactic acid in high molecular weight resin, mixing is uniform through moderate-speed mixer, first pass through molecular sieve system and remove the moisture dried in hot-air, it is dried under the conditions of 90 DEG C of closed circulations of temperature again, the moisture of polylactic resin is less than 200ppm after drying；
3 parts of coupling agent, 3 parts of lubricant, 1 part of plasticizer, 0.5 part of hydrolysis agent are added in polylactic resin after the drying, by after high-speed stirred, it is well mixed each composition, material fusion plastification under conditions of temperature is for 180 DEG C, various raw materials is sufficiently mixed under molecular state, and certain chemical reaction occurs；Pass through to vacuumize in melting process to spin off the moisture in melt with other small molecules using negative pressure, and the various magazines that can not be melted in melt are separated by filtration, ensure the stabilization of melt pressure and flow by Melt Pump in melting process.
The uniform extrusion sheet blank of the melt of above-mentioned melting, cooling and shaping under conditions of being 40 DEG C in temperature by sheet blank are determined into wide cut and trimming, and the progressively internal stress of release sheet blank.
Sheet blank after cooling and shaping is remained smooth after draw-gear draws in distraction procedure, surface electrostatic is eliminated, and nontransparent polylactic acid sheet material is obtained final product to winding after the coating of surface.
30 ~ 55Mpa of tensile strength, tension fracture elongation rate 5 ~ 30%, durable practicality 3 years.
Embodiment 2：The making of transparent polylactic acid sheet material
Weigh 40 parts of low molecular weight resin, after stirring at low speed cold crystallization, again with 60 parts of poly-lactic acid in high molecular weight resin, mixing is uniform through moderate-speed mixer, first pass through molecular sieve system and remove the moisture dried in hot-air, it is dried under the conditions of 100 DEG C of closed circulations of temperature again, the moisture of polylactic resin is less than 200ppm after drying；
3 parts of coupling agent, 3 parts of lubricant, 1 part of plasticizer, 0.5 part of hydrolysis agent are added in polylactic resin after the drying, by after high-speed stirred, it is well mixed each composition, material fusion plastification under conditions of temperature is for 190 DEG C, various raw materials is sufficiently mixed under molecular state, and certain chemical reaction occurs；Pass through to vacuumize in melting process to spin off the moisture in melt with other small molecules using negative pressure, and the various magazines that can not be melted in melt are separated by filtration, ensure the stabilization of melt pressure and flow by Melt Pump in melting process.
The uniform extrusion sheet blank of the melt of above-mentioned melting, cooling and shaping under conditions of being 50 DEG C in temperature by sheet blank are determined into wide cut and trimming, and the progressively internal stress of release sheet blank.
Sheet blank after cooling and shaping is remained smooth after draw-gear draws in distraction procedure, surface electrostatic is eliminated, and transparent polylactic acid sheet material is obtained final product to winding after the coating of surface.
30 ~ 55Mpa of tensile strength, tension fracture elongation rate 5 ~ 30%, durable practicality 2 years.
Claims (7)
1. a kind of degradable recovery poly-lactic acid material, it is characterised in that：The polylactic acid sheet material is included by the composition extrusion molding of following weight portion：Poly-lactic acid in high molecular weight resin：50 ~ 90 parts；Low molecular weight resin：10~50 parts；Processing aid：0.2~10 part；The number-average molecular weight of described poly-lactic acid in high molecular weight resin is 9~150,000 dalton, and the number-average molecular weight of described low molecular weight resin is 5~90,000 dalton.
2. degradable recovery poly-lactic acid material according to claim 1, it is characterised in that：Described processing aid is one or more in heat stabilizer, lubricant, plasticizer and hydrolysis agent.
3. degradable recovery poly-lactic acid material according to claim 2, it is characterised in that：Described heat stabilizer is one or more in tetraalkyl tin, tribasic lead sulfate, pentaerythritol ester.
4. degradable recovery poly-lactic acid material according to claim 2, it is characterised in that：Described lubricant is one or more in zinc stearate, calcium stearate, polyethylene glycol, Tissuemat E.
5. degradable recovery poly-lactic acid material according to claim 2, it is characterised in that：Described plasticizer is one or more in ethylene acrylic, tricresyl phosphate, dibutyl phthalate.
6. degradable recovery poly-lactic acid material according to claim 2, it is characterised in that：Described hydrolysis agent is one or more in carbodiimides, siloxanes, calcium chloride, silica gel.
7. the preparation method of a kind of degradable recovery poly-lactic acid material as described in claim 1 ~ 6,
The method is comprised the following steps：
A, drying：Poly-lactic acid in high molecular weight resin and low molecular weight resin are weighed according to above-mentioned weight portion to be dried under the conditions of 90 DEG C~120 DEG C of temperature, the small 200ppm of moisture of polylactic resin is made after drying；
B, melting：Processing aid or processing aid and filler are added in polylactic resin after the drying, is well mixed by after high-speed stirred, making each composition, melted under conditions of being 180 DEG C~210 DEG C in temperature；
C, extrusioning shaping：By the melt extrusion sheet blank of above-mentioned melting, cooling and shaping under conditions of being 40 DEG C~65 DEG C in temperature by sheet blank；
D, traction, post processing：By the sheet blank after cooling and shaping after draw-gear draws, surface electrostatic is eliminated, and polylactic acid sheet material is obtained final product to winding after the coating of surface.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107299413A (en) * | 2017-07-05 | 2017-10-27 | 浙江理工大学 | The preparation method and product of a kind of height molecular weight PLLA blended fiber |
| CN107974062A (en) * | 2017-11-03 | 2018-05-01 | 金发科技股份有限公司 | A kind of polylactic acid 3D printing material and wire rod prepared therefrom |
| TWI636860B (en) * | 2017-07-14 | 2018-10-01 | 寀呈股份有限公司 | Pla composition and manufacturing method of pla product |
| CN109161973A (en) * | 2018-09-21 | 2019-01-08 | 浙江汇隆新材料股份有限公司 | The production technology of acid fiber by polylactic |
| CN113956763A (en) * | 2021-11-16 | 2022-01-21 | 深圳市思尚科技有限公司 | Coating for preventing marine organism adhesion and preparation method thereof |
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| CN101362853A (en) * | 2008-09-12 | 2009-02-11 | 浙江海正生物材料股份有限公司 | Low cost full-biodegradable polylactic acid sheet material and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107299413A (en) * | 2017-07-05 | 2017-10-27 | 浙江理工大学 | The preparation method and product of a kind of height molecular weight PLLA blended fiber |
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| TWI636860B (en) * | 2017-07-14 | 2018-10-01 | 寀呈股份有限公司 | Pla composition and manufacturing method of pla product |
| CN107974062A (en) * | 2017-11-03 | 2018-05-01 | 金发科技股份有限公司 | A kind of polylactic acid 3D printing material and wire rod prepared therefrom |
| CN109161973A (en) * | 2018-09-21 | 2019-01-08 | 浙江汇隆新材料股份有限公司 | The production technology of acid fiber by polylactic |
| CN113956763A (en) * | 2021-11-16 | 2022-01-21 | 深圳市思尚科技有限公司 | Coating for preventing marine organism adhesion and preparation method thereof |
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Application publication date: 20170627 |