CN1995137A - Biodegradable high polymer foaming material, foam article and its production method - Google Patents
Biodegradable high polymer foaming material, foam article and its production method Download PDFInfo
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- CN1995137A CN1995137A CN 200610130557 CN200610130557A CN1995137A CN 1995137 A CN1995137 A CN 1995137A CN 200610130557 CN200610130557 CN 200610130557 CN 200610130557 A CN200610130557 A CN 200610130557A CN 1995137 A CN1995137 A CN 1995137A
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- lactic acid
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Abstract
The invention discloses a making method of biological degraded macromolecular foaming material and foamer, which comprises the following parts: 1) emulsion polymer: aliphatic-aromatic block copolyester, coring agent and raw material system; 2) foaming agent, wherein the raw material is added in the screw squeezer separately and continuously, which is squeezed out of screw-squeezing machine head after blending, plastifying and or fusing.
Description
Technical field
The invention belongs to biodegradated polymer materal and make forming field, relate to the manufacture method of a kind of biodegradable material or moulding product, but particularly the biodegradable polymer foam material, thing and manufacture method thereof foam.
Background technology
At present, domestic plastic packing article annual production is more than 2000 kilotons, the non-returnable container goods account for 30%, about 600 kilotons of the plastic garbage that produces, about 300 kilotons of agripast mulch film output, about 200 kilotons of disposable plastic medical treatment product, the annual plastic garbage that produces reaches more than 1000 kilotons, is one of the important source of " white pollution ".
Using degradable high polymer material is one of effective way that reduces the conventional plastic pollution.Although the degradable high polymer material of exploitation does not thoroughly solve serious day by day " white pollution " problem as yet at present, it remains an effective way that alleviates the problems.Its appearance has not only enlarged the function of macromolecular material, has alleviated the mankind and environmental relation, and has showed the power and the prospect of biotechnology from synthetic technology, will be the key areas of 21 century new material development.
But poly(lactic acid) is one of fully bio-degradable macromolecular material that attracts people's attention, and poly(lactic acid) is nontoxic, have excellent biological compatibility, good protection against the tide, grease resistance and stopping property.The production of poly(lactic acid) mainly is by biological process starch/glucose to be changed into lactic acid, and then carries out macromolecular polymerization reaction by chemical method, generates poly(lactic acid).Poly(lactic acid) is stable performance at normal temperatures, but degraded automatically under high temperature or oxygen enrichment and action of microorganisms.It can be degraded fully by the occurring in nature microorganism to use the back, finally generates carbonic acid gas and water, and is free from environmental pollution, is very beneficial for developing green manufacturing industry and environment protection.
Prepare foam material and goods thereof with fully bio-degradable macromolecular materials such as poly(lactic acid); and replace the foam material of traditional chemical industry thermoplastics such as nondegradable polystyrene and goods thereof with it and have unusual realistic meaning, be very beneficial for developing green manufacturing industry and environment protection.
Chinese patent prospectus CN200310115826.4 discloses a kind of biodegradable poly(lactic acid) plastics preparation method, these plastics are the percentage ratio meter by weight, poly(lactic acid) by 60-97%, the superoxide of 1-10%, the whipping agent of 1-20% and the nucleator of 1-5% are formed, and wherein used whipping agent is a chemical foaming agent; This plastic raw materials system through mix in Banbury mixer or mill mixing after, compression molding on thermocompressor in oil bath, is foamed in the baking oven or on the thermocompressor after crosslinked.
Chinese patent prospectus CN200310110047.5 discloses a kind of biodegradable polylactic acid foam plastic of chainextender and preparation method thereof that contains, prepared porous plastics is 3-100 ten thousand by the molecular weight of 75-97.5%, Tg is 40-60 ℃ a poly(lactic acid), the chainextender of 1-10%, the chemical foaming agent of 0.5-10%, the nucleator of 1-5% is formed; Its preparation process is: earlier starting material are mixed in a container in proportion, the back is mixing in Banbury mixer, then with the compression molding on thermocompressor of this pre-composition, carries out free foaming at last in oil bath or in the baking oven.
The major defect of these two parts of disclosed technology of patent disclosure specification sheets is that the product foaming is even inadequately.
Chinese patent prospectus CN03160150.2 discloses a kind of foaming method and its foam of poly(lactic acid), being characterised in that of this method, this method comprises at least: mix multipolymer, nucleator, the interior lubrication prescription and outer lubrication prescription of poly(lactic acid), aliphatic-aromatic polyester, make it form a foaming precursor; This precursor is added an extruding machine, it is carried out the extrusion molding step, and add whipping agent simultaneously, to obtain polylactic acid foam, this poly(lactic acid), the multipolymer of this aliphatics-aromatic polyester, this nucleator, lubrication prescription in being somebody's turn to do, the weight isodisperse that is somebody's turn to do outer lubrication prescription and this whipping agent is 60-95,1-40,0.2-3.0,0,2-3.0 and 1-12.Yet this patent disclosure specification sheets is not determined the position that whipping agent adds.
Summary of the invention
But an object of the present invention is to provide biodegradable polymer foam material, foaming raw material component formation, overcome existing fully bio-degradable foaming raw material component and constitute the defective that exists.
But another object of the present invention provides the manufacture method of biodegradable polymer foam material, foaming thing, overcomes the defective that existing fully bio-degradable foaming thing manufacturing technology exists.
A distinguishing feature of the present invention is, the distribution of cells of the macromolecule foaming thing that produces according to the present invention is even, and the foaming thing has good thermal deformation resistant, permeability resistance, physical strength and/or flexibility, fully biodegradable.
Another distinguishing feature of the present invention is: the macromolecule foaming thing that produces according to the present invention does not have the chemicals osmotic phenomena, can be widely used in based food packing, medicine, medicine equipment or vessel manufacturing field fully.
But the biodegradable polymer foam material that the present invention relates to, foaming thing are by weight percentage by raw material system 1): lactic acid polymer 1-96.9%, aliphatic-aromatic blocked copolyester 0-96.9%, nucleator 1-10% and raw material system 2): whipping agent 0.1-20% constitutes.
But the manufacture method of the biodegradable polymer foam material that the present invention relates to, foaming thing comprises the following steps:
A) with raw material system 1) drop into the mixing device uniform mixing after, or without the direct opening for feed (main opening for feed) that measures screw extrusion press first district that adds preheating continuously respectively of mixing device mixing, make raw material system 1) under the screw rod turning effort, towards the motion of cross-head direction, experience be heated mixing, plasticizing and/or fusion;
B) with raw material system 2) after mixing or without mixing directly metering respectively, be added to partially or completely fused raw material system 1 in the motion continuously by the opening for feed (secondary opening for feed) that is arranged on this machine fusion section) in and/or on the surface;
C) make whole raw material system after mixing under the screw rod turning effort, plasticizing, fusion homogenizing, extrude, become to foam thing or foaming thing immediately by the screw extrusion press head;
D) make the thing that to foam become pellet, slitting material or sheet stock by fervent granulation, cooling granulation, slitting or slicing device, make foaming thing cooling and shaping, folded flat, shear, become plate and/or rolling, or make the foaming thing directly or become to enter rolling press, thermoforming machine, press-forming machine and/or corresponding supplementary unit after the plate and produce various foam articles.
Wherein, the screw extrusion press head comprises the head with an annular gap and has the head in a rectangle gap (T type head), becomes tubulose foaming thing after the former can make whole raw material system melt be extruded immediately; After can making whole raw material system melt be extruded, the latter becomes en plaque foaming thing immediately.Be preferably and adopt the former.
The screw extrusion press head comprises that also profiled material forms head and line, bar, hollow piece form head.
But foaming granule material, slitting material or section material can and adopt prior art to make foaming line bar, single or multiple lift composite foamed plate sheet material, hollow foaming product, thermoforming foaming product, molding foaming product or press foaming product for existing molding device.
Lactic acid polymer of the present invention is a L-type lactic acid polymer, D-type lactic acid polymer, one or more in L/D-type lactic acid polymer or their mixture; Wherein, the weight ratio of L-type lactic acid and D-type lactic acid is 95 in the L/D-type lactic acid polymer: 5-60: 40 or 5: 95-40: 60.
Aliphatic-aromatic blocked copolyester of the present invention comprises the copolyesters that aliphatic diol and aliphatics and aromatic series dihydroxy acid form.
Nucleator of the present invention is one or more in general purpose grade or nano level talcum powder, carbonic acid powder, lime carbonate, zinc oxide, calcium oxide, silicon-dioxide, aluminum oxide, wood powder, the cellulose powder.
Whipping agent of the present invention comprises nitrogen, carbonic acid gas, butane, pentane, hexane, Trimethylmethane, ethanol, one or more in water or their mixture.They can be measured respectively, are added to partially or completely fused raw material system 1 in the motion continuously by the one or more opening for feeds (secondary opening for feed) that are arranged on machine plasticizing, fusion/homogenizing section) in and/or on the surface; Be preferably by the one or more opening for feeds (secondary opening for feed) that are arranged on machine fusion section and be added to partially or completely fused raw material system 1 in the motion continuously) in and/or on the surface.Wherein, the best is to adopt butane, pentane, and hexane, Trimethylmethane, one or more in ethanol or their mixture are made the thing that can foam, and adopt nitrogen, and carbonic acid gas or their mixture are made the foaming thing.
But the biodegradable polymer foam material that the present invention relates to, foaming thing and manufacture method thereof allow those skilled in the art according to concrete manufacturing shaped device situation and product requirement, at raw material system 1) in or at an amount of stablizer of opening for feed (main opening for feed) adding in screw extrusion press first district, keep away in mouse agent, weighting agent, fire retardant, properties-correcting agent, processing aid, coupling agent, emulsifying agent, urea and derivative thereof, tinting material or other polymkeric substance one or more.
The screw extrusion press that adopts according to the present invention can be a single screw extrusion machine, twin screw extruder or multiple screw extruder; Be preferably twin screw extruder.The length-to-diameter ratio of screw extrusion press is more than or equal to 19, screw extrusion press can not comprise vacuum extractor, but preferably adopt plasticizing, the fusion screw extrusion press that comprises at least one vacuum orifice and be connected with corresponding vacuum extractor, and its working vacuum degree is controlled at 50MPa-0.01MPa.
The main charging oral region working temperature of the screw extrusion press that adopts according to the present invention is lower than 100 ℃; Other respectively distinguishes working temperature is 130-245 ℃; Head temperature is 120-240 ℃.
According to the present invention adopt make foaming thing cooling and shaping, folded flat, to shear, become the device of plate and/or rolling be roll squeezer, the supplementary unit in the extrusion moulding unit, the supplementary unit in rolling press, thermoforming machine or the compression moulding unit.
The various foam article shaped devices that adopt according to the present invention comprise rolling press, thermoforming machine, press and supplementary unit thereof.Calendering formation, thermoforming or the compression moulding temperature of foaming thing are 50-190 ℃.Foam article comprises profiled material, ripple type plate material and the container etc. of various configurations.
Embodiment
Further specify the present invention below by embodiment, but the present invention is not limited in these embodiment declared ranges.
Embodiment 1:
By weight percentage, with lactic acid polymer 1-96.9%, aliphatic-aromatic blocked copolyester 0-96.9%, nucleator, as talcum powder 1-10%, after dropping into the mixing device uniform mixing, or without the direct opening for feed (main opening for feed) that measures screw extrusion press first district that adds preheating continuously respectively of mixing device mixing, make the raw material system under the screw rod turning effort,, experience be heated mixing, plasticizing and/or fusion towards the motion of cross-head direction.When this system arrives the fusion section of twin screw extruder/after,
With whipping agent, as nitrogen, carbonic acid gas 0.1-20% is after mixing or without mixing directly metering respectively, be added to partially or completely fused raw material system 1 in the motion continuously by the opening for feed (secondary opening for feed) that is arranged on this machine fusion section) in and/or on the surface, whole raw material system is mixed under the screw rod turning effort, plasticizing, after the fusion homogenizing, extrude by the screw extrusion press head, become the foaming thing immediately, the foaming thing is through cooling and shaping, folded flat, shear the back and become the plate material, or make the plate material and then enter thermoforming machine, press-forming machine and supplementary unit thereof produce various foam articles; Or make the foaming thing directly enter rolling press, and thermoforming machine, press-forming machine and supplementary unit thereof produce various foam articles.
Embodiment 2 (embodiment 1):
It with 3.5 kilogram molecular weights 170,000 poly(lactic acid), 2 kilogram molecular weights are 150,000 aliphatic-aromatic blocked copolyester, 0.1 the kilogram talcum powder drops into high-speed mixer, under 2000 rev/mins of stirrings of rotating speed, mix after 7 minutes, discharging is input to twin screw extruder (German JP industrial technology equipment company limited continuously, model JSK26, screw slenderness ratio: in district's charging opening 30), ethanol with 10% is added in the partially or completely fused raw material system in the motion by the opening for feed (secondary opening for feed) that is arranged on this machine fusion section and/or on the surface continuously, whole raw material system is mixed under the screw rod turning effort, plasticizing, after the fusion homogenizing, leave forcing machine by extrusion die, but in air-cooled, be cut into cylindrical foaming granule material with 2 circular passages.Twin screw extruder charging opening (district) temperature is 40 ℃, and other respectively distinguishes working temperature is 140-210 ℃, and head temperature is 180 ℃.
Embodiment 3 (embodiment 2):
It with 4 kilogram molecular weights 170,000 poly(lactic acid), 2 kilogram molecular weights are 150,000 aliphatic-aromatic blocked copolyester, 0.12 the kilogram talcum powder drops into high-speed mixer, under 2000 rev/mins of stirrings of rotating speed, mix after 8 minutes, discharging is input to twin screw extruder (German JP industrial technology equipment company limited continuously, model JSK26, screw slenderness ratio: in district's charging opening 30), nitrogen with 0.3% and 2.2% carbonic acid gas are without mixing metering respectively, be added in the partially or completely fused raw material system in the motion continuously and/or on the surface by two opening for feeds (secondary opening for feed) that are arranged on this machine fusion section, whole raw material system is mixed under the screw rod turning effort, plasticizing, after the fusion homogenizing, be extruded by head, become tubulose foaming thing immediately with an annular gap.Charging opening (district) temperature is 40 ℃, and other respectively distinguishes working temperature is 140-210 ℃, and head temperature is 170 ℃.
Embodiment 4 (embodiment 3):
It with 5 kilogram molecular weights 170,000 poly(lactic acid), 2 kilogram molecular weights are 150,000 aliphatic-aromatic blocked copolyester, 0.15 the kilogram talcum powder drops into high-speed mixer, under 2000 rev/mins of stirrings of rotating speed, mix after 8 minutes, discharging is input to twin screw extruder (German JP industrial technology equipment company limited continuously, model JSK26, screw slenderness ratio: in district's charging opening 30), nitrogen with 0.4% and 2% carbonic acid gas measure respectively, be added in the partially or completely fused raw material system in the motion continuously and/or on the surface by two opening for feeds (secondary opening for feed) that are arranged on this machine fusion section, whole raw material system is mixed under the screw rod turning effort, plasticizing, after the fusion homogenizing, be extruded by a T type head, become en plaque foaming thing immediately, this foaming thing enters one two roller tabletting machine through overcooling, through compressing tablet, after the shearing, become sheet material.The distribution of cells of this macromolecule foaming sheet material is even, has good thermal deformation resistant, permeability resistance and physical strength.
Claims (9)
- But 1, biodegradable polymer foam material, foaming thing and manufacture method thereof, it is characterized in that but this polymer foam material, foaming thing are by weight percentage by raw material system 1): lactic acid polymer 1-96.9%, aliphatic-aromatic blocked copolyester 0-96.9%, nucleator 1-10% and raw material system 2): whipping agent 0.1-20% constitutes; Its manufacture method comprises:With raw material system 1) drop into the mixing device uniform mixing after, or without the direct opening for feed (main opening for feed) that measures screw extrusion press first district that adds preheating continuously respectively of mixing device mixing, make raw material system 1) under the screw rod turning effort, towards the motion of cross-head direction, experience be heated mixing, plasticizing and/or fusion;With raw material system 2) after mixing or without mixing directly metering respectively, be added to partially or completely fused raw material system 1 in the motion continuously by the opening for feed (secondary opening for feed) that is arranged on this machine fusion section) in and/or on the surface;Make whole raw material system after mixing under the screw rod turning effort, plasticizing, fusion homogenizing, be extruded as to foam thing or foaming thing by the screw extrusion press head;Make the thing that to foam become pellet, slitting material or sheet stock by fervent granulation, cooling granulation, slitting or slicing device, make foaming thing cooling and shaping, folded flat, shear, become plate and/or rolling, or make the foaming thing directly or become to enter rolling press, thermoforming machine, press-forming machine and/or corresponding supplementary unit after the plate and produce various foam articles.
- But 2, biodegradable polymer foam material according to claim 1, foaming thing and manufacture method thereof, it is characterized in that: described lactic acid polymer is a L-type lactic acid polymer, D-type lactic acid polymer, one or more in L/D-type lactic acid polymer or their mixture; Wherein, the weight ratio of L-type lactic acid and D-type lactic acid is 95 in the L/D-type lactic acid polymer: 5-60: 40 or 5: 95-40: 60.
- But 3, biodegradable polymer foam material according to claim 1, foaming thing and manufacture method thereof is characterized in that: described aliphatic-aromatic blocked copolyester comprises the copolyesters that aliphatic diol and aliphatics and aromatic series dihydroxy acid form.
- But 4, biodegradable polymer foam material according to claim 1, foaming thing and manufacture method thereof, it is characterized in that: described nucleator is one or more in general purpose grade or nano level talcum powder, carbonic acid powder, lime carbonate, zinc oxide, calcium oxide, silicon-dioxide, aluminum oxide, wood powder or the cellulose powder.
- But 5, biodegradable polymer foam material according to claim 1, foaming thing and manufacture method thereof, it is characterized in that: described whipping agent comprises nitrogen, carbonic acid gas, butane, pentane, hexane, Trimethylmethane, one or more in ethanol or their mixture.
- But 6, biodegradable polymer foam material according to claim 1, foaming thing and manufacture method thereof, it is characterized in that: described screw extrusion press is a single screw extrusion machine, twin screw extruder or multiple screw extruder.
- But 7, according to claim 1 or 6 described biodegradable polymer foam materials, foaming thing and manufacture method thereof, it is characterized in that: described screw extrusion press does not comprise or comprises at least one for the vacuum orifice that connects vacuum extractor.
- 8, but according to claim 1 or 6 described biodegradable polymer foam materials, foaming thing and manufacture method thereof, it is characterized in that: the main charging oral region working temperature of described screw extrusion press is lower than 100 ℃; Other respectively distinguishes working temperature is 130-245 ℃; Head temperature is 120-240 ℃.
- But 9, biodegradable polymer foam material according to claim 1, foaming thing and manufacture method thereof, it is characterized in that: the calendering formation of described foaming thing, thermoforming or compression moulding temperature are 50-190 ℃.
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| CN 200610130557 CN1995137A (en) | 2006-12-25 | 2006-12-25 | Biodegradable high polymer foaming material, foam article and its production method |
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| CN 200610130557 CN1995137A (en) | 2006-12-25 | 2006-12-25 | Biodegradable high polymer foaming material, foam article and its production method |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101955638A (en) * | 2010-09-21 | 2011-01-26 | 浙江大学宁波理工学院 | Plant fiber-reinforced polylactic acid foam material and preparation method thereof |
| CN101717475B (en) * | 2008-10-09 | 2011-09-14 | 中国科学院化学研究所 | Biodegradable foam plastic and preparation method thereof |
| CN102618001A (en) * | 2012-03-29 | 2012-08-01 | 浙江大学宁波理工学院 | Poly fatty acid ester microcellular foaming material containing nanometer celluloses and preparing method thereof |
| CN104327471A (en) * | 2014-11-18 | 2015-02-04 | 中国科学院长春应用化学研究所 | Polylactic acid three-dimensional complex |
| CN105793337A (en) * | 2013-10-09 | 2016-07-20 | 巴斯夫欧洲公司 | Method for producing expanded polyester foam particles |
| CN110483962A (en) * | 2018-05-15 | 2019-11-22 | 湖北文理学院 | A kind of expanded polylactic acid plastics of high intensity and preparation method thereof |
| CN111699945A (en) * | 2020-06-15 | 2020-09-25 | 长沙华脉新材料有限公司 | Porous composite material fused with soil-base matrix and preparation method thereof |
| CN112266616A (en) * | 2020-09-16 | 2021-01-26 | 宁波家联科技股份有限公司 | Heat-resistant polylactic acid polymer and thermoforming process thereof |
| CN115181362A (en) * | 2022-08-15 | 2022-10-14 | 中国科学院宁波材料技术与工程研究所 | Polyolefin foaming bead and preparation method thereof |
-
2006
- 2006-12-25 CN CN 200610130557 patent/CN1995137A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717475B (en) * | 2008-10-09 | 2011-09-14 | 中国科学院化学研究所 | Biodegradable foam plastic and preparation method thereof |
| CN101955638A (en) * | 2010-09-21 | 2011-01-26 | 浙江大学宁波理工学院 | Plant fiber-reinforced polylactic acid foam material and preparation method thereof |
| CN101955638B (en) * | 2010-09-21 | 2012-07-04 | 浙江大学宁波理工学院 | Plant fiber-reinforced polylactic acid foam material and preparation method thereof |
| CN102618001A (en) * | 2012-03-29 | 2012-08-01 | 浙江大学宁波理工学院 | Poly fatty acid ester microcellular foaming material containing nanometer celluloses and preparing method thereof |
| CN102618001B (en) * | 2012-03-29 | 2014-07-09 | 浙江大学宁波理工学院 | Poly fatty acid ester microcellular foaming material containing nanometer celluloses and preparing method thereof |
| CN105793337A (en) * | 2013-10-09 | 2016-07-20 | 巴斯夫欧洲公司 | Method for producing expanded polyester foam particles |
| CN105814126A (en) * | 2013-10-09 | 2016-07-27 | 巴斯夫欧洲公司 | Process for the production of expanded polyester foam beads |
| CN105793337B (en) * | 2013-10-09 | 2018-12-14 | 巴斯夫欧洲公司 | The method for preparing the polyester form particle of expansion |
| CN105814126B (en) * | 2013-10-09 | 2019-05-07 | 巴斯夫欧洲公司 | The method for preparing intumescent polyester form bead |
| CN104327471A (en) * | 2014-11-18 | 2015-02-04 | 中国科学院长春应用化学研究所 | Polylactic acid three-dimensional complex |
| CN104327471B (en) * | 2014-11-18 | 2017-02-22 | 中国科学院长春应用化学研究所 | Polylactic acid three-dimensional complex |
| CN110483962A (en) * | 2018-05-15 | 2019-11-22 | 湖北文理学院 | A kind of expanded polylactic acid plastics of high intensity and preparation method thereof |
| CN111699945A (en) * | 2020-06-15 | 2020-09-25 | 长沙华脉新材料有限公司 | Porous composite material fused with soil-base matrix and preparation method thereof |
| CN112266616A (en) * | 2020-09-16 | 2021-01-26 | 宁波家联科技股份有限公司 | Heat-resistant polylactic acid polymer and thermoforming process thereof |
| CN115181362A (en) * | 2022-08-15 | 2022-10-14 | 中国科学院宁波材料技术与工程研究所 | Polyolefin foaming bead and preparation method thereof |
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Open date: 20070711 |