CN1544514A - Biodegradable poly-lactic acid foam plastic containing chain extender and method for preparing the same - Google Patents
Biodegradable poly-lactic acid foam plastic containing chain extender and method for preparing the same Download PDFInfo
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- CN1544514A CN1544514A CNA2003101100475A CN200310110047A CN1544514A CN 1544514 A CN1544514 A CN 1544514A CN A2003101100475 A CNA2003101100475 A CN A2003101100475A CN 200310110047 A CN200310110047 A CN 200310110047A CN 1544514 A CN1544514 A CN 1544514A
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Abstract
The invention provides a complete biodegradable polylactic acid plastic containing chain extender and its preparing process, wherein the molecular weight of polylactic acid is 30-1000 thousand, the glass transition temperature is 40-60 deg. C, chain extending agent and core forming agent are charged to be blended uniformly in closed-smelting machine at 90 deg C. to 140 deg C, free foaming is carried out in oil bath or on vulcanizing press at 120 deg C. -170 deg C., the foaming time being 5 minutes. The invention can effectively alleviate the lowering down of polylactic acid molecular weight on one hand, but also can effectively improve the flux intensity for the polylactic acid.
Description
Technical field
The present invention relates to a kind of biodegradable polylactic acid foam plastic of chainextender and preparation method thereof that contains.
Background technology
Porous plastics be a kind of be basal component with plastics, contain the material of a large amount of bubbles.Therefore, also to can be described as with gas be the composite plastic of filler to porous plastics.It has light weight, material-saving, thermal conductivity is low, heat-proof quality good, can absorb shock load, have good shock-absorbing capacity, valuable performances such as sound-proofing properties is good, specific tenacity height.The purposes of porous plastics is very extensive, and output shared ratio in the plastics ultimate production constantly increases.Porous plastics occupies very large volume, and the offal treatment after the consumption is people's attention extremely.Usually the treating method to waste mainly is that soil buries and burns.Soil buries a large amount of soil of waste, and the country that some density of population are high is difficult to bear; Burn and then can produce deleterious compounds such as a large amount of carbonic acid gas and nitrogen, sulphur, phosphorus, halogen, encouraged the formation of Greenhouse effect and acid rain.The recycling of porous plastics theoretically, not only can solve environmental pollution but also can solve the problem of shortage of resources, but in implementation process, often be subjected to the restriction of the character of macromolecular material own, technology and cost.In order to address the above problem, research and develop the concern that biodegradable novel material is subjected to worldwide academia and industry member from the material self character.
Poly(lactic acid) (PLA) does not exist at nature, makes by synthetic.Monomer as synthesis material---lactic acid then is by biological fermentation.Poly(lactic acid) belongs to synthetic straight chain aliphatic polyester, by lactic acid cyclisation dipolymer---and the ring-opening polymerization of rac-Lactide or the direct polymerization of lactic acid obtain.Poly(lactic acid) has good biodegradability, and degraded product is carbonic acid gas and water, environment is not produced any problem.Poly(lactic acid) also has excellent biological compatibility and Bioabsorbable, has been considered to the most promising degradable high polymer material in medical field, and is very active to its research and development.But,, in recent years,, begun its exploration exploitation as the general-purpose plastics substitute products because environmental requirement makes people extraordinarily pay attention to poly(lactic acid) because the too high restriction of poly(lactic acid) production cost is being started late as general degradative plastics use.Though the price of PLA resin along with the input of great amount of manpower and financial resources, will produce breakthrough also than higher at present.
Among the U.S. Pat Patent 5348983 (1994), people such as Sterzel adopt the method for sneaking into pneumatogen in poly(lactic acid) to prepare the poly(lactic acid) structural foam, but this working method implements very difficult, can not be pushed wide application.In U.S. Pat Patent5763098 (1998), people such as Kameoka adopt and to sneak into the method that chemical foaming agent and pneumatogen directly extrude and prepare polylactic acid foam plastic, the porous plastics density of gained be 0.5g cm
3
Summary of the invention
The purpose of this invention is to provide a kind of biodegradable polylactic acid foam plastic of chainextender that contains;
Another object of the present invention provides a kind of preparation method who contains the biodegradable polylactic acid foam plastic of chainextender.
The poly(lactic acid) thermostability is bad, tends to cause comparatively serious thermal destruction in the course of processing, causes the decline significantly of molecular weight.The chainextender that uses among the present invention contains a plurality of isocyanate groups, the terminal hydroxy group of energy and poly(lactic acid) or end carboxyl reaction in the course of processing, thereby play the effect of chain extension, the reduction of polylactic acid molecule amount can be effectively alleviated on the one hand, the melt strength of poly(lactic acid) can be effectively improved on the other hand.
The present invention adds the polylactic acid molecule amount in the course of processing be 3-100 ten thousand, second-order transition temperature is 40-60 ℃, the weight percentage that adds is 75-97.5%, chainextender is tolylene diisocyanate (TDI), hexamethylene-diisocyanate (HDI), xylylene diisocyanate (XDI), poly methylene poly phenyl poly isocyanate (PAPI), isophorone diisocyanate (IPDI), diphenylmethanediisocyanate (MDI), dicyclohexyl methane diisocyanate (HMDI), hexahydrotoluene vulcabond (HTDI) or trimethyl cyclohexane vulcabond (TMDI), the weight percentage of adding is 1-10%; Chemical foaming agent is Cellmic C 121 (AC), 2,2 '-Diisopropyl azodicarboxylate (AZDN), diisopropyl azodiformate (DIPA), two azoanilines (DAB), N, N-dinitroso five methyne tetramines, N, N-dimethyl-N, N '-dinitroso is to benzene, benzol sulfohydrazide (BSH), 4,4 '-OBSH (OBSH), 3,3 '-disulfonyl hydrazide sulfobenzide, 1,3 '-benzene disulfohydrazide, diazobenzeneanilide, oxaluria, nitro urine, the mixture of the mixture of yellow soda ash and citric acid or lime carbonate and citric acid, the weight percentage that adds is 0.5-10%, nucleator is a zinc oxide, calcium oxide, silicon-dioxide, aluminum oxide, talcum powder or lime carbonate, the weight percentage that adds is 1-5%, makes through moulded from foam then.
The melt blending process: after starting material were mixed in homemade plastic containers in proportion in advance, mixing in Banbury mixer then, melting temperature was 90 ℃-140 ℃, and mixing time is 3-5 minute;
Behind 100 ℃ of-140 ℃ of die formings on the thermocompressor, 120 ℃-170 ℃ are carried out free foaming in oil bath or in baking oven with the pre-composition of gained, and foamed time is 5 minutes.
Embodiment
Below will come further detailed explanation the present invention by representing example of the present invention.In example, mark and per-cent are all by weight except as otherwise noted.But the present invention is not limited to these examples.
Embodiment 1
Molecular weight is 160,000 poly(lactic acid), AC whipping agent, talcum powder, zinc oxide by following proportioning 96.5: 1: 2: 0.5 in Banbury mixer 140 ℃ mixing 5 minutes down.The mixture that obtains under 140 ℃ after being pressed into sheet material on the vulcanizing press, in 170 ℃ of oil baths, carried out free foaming 5 minutes.The molecular weight that records poly(lactic acid) is 80,000.The density of the porous plastics that obtains is 0.5g/cm
3Mechanical property: Young's modulus is 300MPa, and tensile strength is 4.20MPa, and elongation at break is 4.4%.The biological degradation experiment can be degraded fully.
Embodiment 2
Molecular weight is 160,000 poly(lactic acid), tolylene diisocyanate, AC whipping agent, talcum powder, zinc oxide by following proportioning 95.5: 1: 1: 2: 0.5 in Banbury mixer 140 ℃ mixing 5 minutes.The mixture that obtains is pressed into sheet material on 140 ℃ of vulcanizing presses, carried out free foaming 5 minutes in 170 ℃ of oil baths.The molecular weight that records poly(lactic acid) is 140,000, and the density of the porous plastics that obtains is 0.5g/cm
3Mechanical property: Young's modulus is 311MPa, and tensile strength is 4.20MPa, and elongation at break is 4.4%.The biological degradation experiment can be degraded fully.
Embodiment 3
Molecular weight is 30,000 poly(lactic acid), hexamethylene-diisocyanate, N, N-dinitroso five methyne tetramines, talcum powder, by following proportioning 97.5: 1: 0.5: 1: in Banbury mixer 140 ℃ mixing 5 minutes.The mixture that obtains carried out free foaming 5 minutes in 170 ℃ of vulcanizing presses after being pressed into sheet material on 140 ℃ of vulcanizing presses.The molecular weight that records poly(lactic acid) is 2.5 ten thousand.The density of the porous plastics that obtains is 0.7g/cm
3, mechanical property: Young's modulus is 340MPa, and tensile strength is 5.10MPa, and elongation at break is 5.0%.The biological degradation experiment can be degraded fully.
Embodiment 4
Molecular weight is 160,000 poly(lactic acid), diphenylmethanediisocyanate, 4,4 '-OBSH, silicon-dioxide, by following proportioning 92: 5: 1: 2 in Banbury mixer 140 ℃ mixing 5 minutes.The mixture that obtains carried out free foaming 5 minutes in 160 ℃ of vulcanizing presses after being pressed into sheet material on 140 ℃ of vulcanizing presses.The molecular weight that records poly(lactic acid) is 14.3 ten thousand.The density of the porous plastics that obtains is 0.45g/cm
3Mechanical property: Young's modulus is 300MPa, and tensile strength is 4.10MPa, and elongation at break is 4.0%.The biological degradation experiment can be degraded fully.
Embodiment 5
Molecular weight is 160,000 poly(lactic acid), poly methylene poly phenyl poly isocyanate, diisopropyl azodiformate, lime carbonate, by following proportioning 92: 5: 1: 2, in Banbury mixer 140 ℃ mixing 5 minutes.The mixture that obtains is pressed into sheet material on 140 ℃ of vulcanizing presses, carried out free foaming 5 minutes in 170 ℃ of vulcanizing presses.The molecular weight that records poly(lactic acid) is 130,000.The density of the porous plastics that obtains is 0.5g/cm
3Mechanical property: Young's modulus is 330MPa, and tensile strength is 4.50MPa, and elongation at break is 4.5%.The biological degradation experiment can be degraded fully.
Embodiment 6
Molecular weight is 50,000 poly(lactic acid), isophorone diisocyanate, 2,2 '-Diisopropyl azodicarboxylate, lime carbonate, by following proportioning 75: 10: 10: 5, in Banbury mixer 100 ℃ mixing 3 minutes.The mixture that obtains carried out free foaming 5 minutes in 120 ℃ of following vulcanizing presses after being pressed into sheet material on 100 ℃ of vulcanizing presses.The molecular weight that records poly(lactic acid) is 2.5 ten thousand.The density of the porous plastics that obtains is 0.30g/cm
3Mechanical property: Young's modulus is 224MPa, and tensile strength is 3.60MPa, and elongation at break is 5.0%.The biological degradation experiment can be degraded fully.
Embodiment 7
Molecular weight is 50,000 poly(lactic acid), isophorone diisocyanate, 2,2 '-Diisopropyl azodicarboxylate, lime carbonate, by following proportioning 92: 5: 1: 2, in Banbury mixer 100 ℃ mixing 3 minutes.The mixture that obtains is pressed into sheet material on 100 ℃ of vulcanizing presses, carried out free foaming 5 minutes in 120 ℃ of vulcanizing presses.The molecular weight that records poly(lactic acid) is 4.1 ten thousand.The density of the porous plastics that obtains is 0.51g/cm
3Mechanical property: Young's modulus is 320MPa, and tensile strength is 5.50MPa, and elongation at break is 5.5%.The biological degradation experiment can be degraded fully.
Embodiment 8
Molecular weight is 50,000 poly(lactic acid), diphenylmethanediisocyanate, two azoanilines, lime carbonate, by following proportioning 92: 5: 1: 2, in Banbury mixer 90 ℃ mixing 3 minutes.The mixture that obtains is pressed into sheet material on vulcanizing press under 100 ℃, carried out free foaming 5 minutes in 120 ℃ of following vulcanizing presses.The molecular weight that records poly(lactic acid) is 3.5 ten thousand.The density of the porous plastics that obtains is 0.60g/cm
3Mechanical property: Young's modulus is 340MPa, and tensile strength is 6.50MPa, and elongation at break is 5.0%.The biological degradation experiment can be degraded fully.
Embodiment 9
Molecular weight is 50,000 poly(lactic acid), dicyclohexyl methane diisocyanate, benzol sulfohydrazide, lime carbonate, by following proportioning 92: 5: 1: 2, in Banbury mixer 90 ℃ mixing 3 minutes.The mixture that obtains is pressed into sheet material on 100 ℃ of vulcanizing presses, carried out free foaming 5 minutes in 120 ℃ of vulcanizing presses.The molecular weight that records poly(lactic acid) is 3.5 ten thousand.The density of the porous plastics that obtains is 0.50g/cm
3Mechanical property: Young's modulus is 309MPa, and tensile strength is 5.50MPa, and elongation at break is 5.1%.The biological degradation experiment can be degraded fully.
Embodiment 10
Molecular weight is 50,000 poly(lactic acid), hexahydrotoluene vulcabond, 1,3 '-benzene disulfohydrazide, lime carbonate, by following proportioning 92: 5: 1: 2, in Banbury mixer 90 ℃ mixing 3 minutes.The mixture that obtains carried out free foaming 5 minutes in 120 ℃ of following vulcanizing presses after being pressed into sheet material on 100 ℃ of vulcanizing presses.The molecular weight that records poly(lactic acid) is 3.0 ten thousand.The density of the porous plastics that obtains is 0.48g/cm
3Mechanical property: Young's modulus is 313MPa, and tensile strength is 5.34MPa, and elongation at break is 5.5%.The biological degradation experiment can be degraded fully.
Embodiment 11
Molecular weight is 50,000 poly(lactic acid), trimethyl cyclohexane vulcabond, oxaluria, lime carbonate, by following proportioning 92: 5: 1: 2, in Banbury mixer 90 ℃ mixing 3 minutes.The mixture that obtains carried out free foaming 5 minutes in 130 ℃ of vulcanizing presses after being pressed into sheet material on 100 ℃ of vulcanizing presses.The molecular weight that records poly(lactic acid) is 3.8 ten thousand.The density of the porous plastics that obtains is 0.55g/cm
3Mechanical property: Young's modulus is 301MPa, and tensile strength is 4.14MPa, and elongation at break is 5.0%.The biological degradation experiment can be degraded fully.
Embodiment 12
Molecular weight is 50,000 poly(lactic acid), diphenylmethanediisocyanate, nitric acid urine, calcium oxide, by following proportioning 92: 5: 1: 2, in Banbury mixer 90 ℃ mixing 3 minutes.The mixture that obtains is pressed into sheet material on vulcanizing press under 100 ℃, carried out free foaming 5 minutes in 130 ℃ of vulcanizing presses.The molecular weight that records poly(lactic acid) is 3.5 ten thousand.The density of the porous plastics that obtains is 0.60g/cm
3Mechanical property: Young's modulus is 330MPa, and tensile strength is 4.40MPa, and elongation at break is 5.3%.The biological degradation experiment can be degraded fully.
Embodiment 13
Molecular weight is mixture, the calcium oxide of 50,000 poly(lactic acid), diphenylmethanediisocyanate, yellow soda ash and citric acid, by following proportioning 92: 5: 1: 2, in Banbury mixer 90 ℃ mixing 3 minutes.The mixture that obtains is pressed into sheet material on 100 ℃ of vulcanizing presses, carried out free foaming 5 minutes in 130 ℃ of following vulcanizing presses.The molecular weight that records poly(lactic acid) is 3.6 ten thousand.The density of the porous plastics that obtains is 0.70g/cm
3Mechanical property: Young's modulus is 341MPa, and tensile strength is 7.40MPa, and elongation at break is 3.3%.The biological degradation experiment can be degraded fully.
Embodiment 14
Molecular weight is mixture, the calcium oxide of 1,000,000 poly(lactic acid), diphenylmethanediisocyanate, lime carbonate and citric acid, by following proportioning 92: 5: 1: 2, in Banbury mixer 90 ℃ mixing 3 minutes.The mixture that obtains is pressed into sheet material on 100 ℃ of vulcanizing presses, carried out free foaming 5 minutes in 130 ℃ of following vulcanizing presses.The molecular weight that records poly(lactic acid) is 840,000.The density of the porous plastics that obtains is 0.73g/cm
3Mechanical property characterizes: Young's modulus is 444MPa, and tensile strength is 12.80MPa, and elongation at break is 4.3%.The biological degradation experiment can be degraded fully.
Claims (5)
1. one kind contains the biodegradable polylactic acid foam plastic of chainextender, and the polylactic acid molecule amount is 3-100 ten thousand, and second-order transition temperature is 40-60 ℃.
2. prepare the described method that contains the biodegradable polylactic acid foam plastic of chainextender of claim 1, it is characterized in that chainextender is tolylene diisocyanate, hexamethylene-diisocyanate, xylylene diisocyanate, poly methylene poly phenyl poly isocyanate, isophorone diisocyanate, diphenylmethanediisocyanate, dicyclohexyl methane diisocyanate, hexahydrotoluene vulcabond or trimethyl cyclohexane vulcabond, weight percentage is 1-10%.
3. prepare the described method that contains the biodegradable polylactic acid foam plastic of chainextender of claim 1, it is characterized in that the whipping agent that uses is Cellmic C 121,2,2 '-Diisopropyl azodicarboxylate, diisopropyl azodiformate, two azoanilines, N, N-dinitroso five methyne tetramines, N, N-dimethyl-N, N '-dinitroso is to benzene, benzol sulfohydrazide, 4,4 '-OBSH, 3,3 '-disulfonyl hydrazide sulfobenzide, 1,3 '-benzene disulfohydrazide, diazobenzeneanilide, oxaluria, nitro urine, the mixture of the mixture of yellow soda ash and citric acid or lime carbonate and citric acid, weight percentage are 0.5-10%.
4. prepare the described method that contains the biodegradable polylactic acid foam plastic of chainextender of claim 1, it is characterized in that nucleator is zinc oxide, calcium oxide, silicon-dioxide, aluminum oxide, talcum powder or lime carbonate, weight percentage is 1-5%.
5. prepare the described method that contains the biodegradable polylactic acid foam plastic of chainextender of claim 1, it is included in and adds chainextender, nucleator in the course of processing, mixing even in 90 ℃-140 ℃ in Banbury mixer, carry out free foaming in 120 ℃-170 ℃ on oil bath or vulcanizing press, foamed time is 5 minutes.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2007147290A1 (en) * | 2006-06-15 | 2007-12-27 | Sichuan Yibin Wuliangye Group Co., Ltd. | Biodegrable grating sheet and its article, and preparing method thereof |
| CN101245175B (en) * | 2007-05-21 | 2010-09-08 | 肖望东 | Biodegradation expanded plastic |
| WO2010108383A1 (en) * | 2009-03-23 | 2010-09-30 | 伟盟工业股份有限公司 | Biodegradable two-liquid type foaming composition |
| CN1810877B (en) * | 2005-01-25 | 2010-12-01 | 株式会社Jsp | Expandable polylactic acid resin particles, expanded polylactic acid resin beads and molded article obtained from expanded polylactic acid resin beads |
| CN101899139A (en) * | 2010-07-23 | 2010-12-01 | 同济大学 | Method for preparing polylactic acid-based high-elasticity copolymer |
| CN101768334B (en) * | 2008-12-29 | 2011-12-14 | 中国林业科学研究院木材工业研究所 | Wood-plastic composite material and forming plate made of wood-plastic composite material |
| CN101362833B (en) * | 2008-09-25 | 2012-08-22 | 上海交通大学 | Method for preparing polylactic acid foam material |
| CN103509316A (en) * | 2012-06-18 | 2014-01-15 | 北京化工大学 | High-thermal-conductivity insulation polyester composite material and preparation method thereof |
| CN104245808A (en) * | 2012-03-30 | 2014-12-24 | 乐金华奥斯有限公司 | Foam sheet using polylactic acid having extended chain and method for preparing same |
| CN105001605A (en) * | 2015-07-27 | 2015-10-28 | 郑州大学 | Green and environment-friendly toughened strong-antibacterial degradable polylactic acid composite and preparation method thereof |
| CN106810677A (en) * | 2017-03-01 | 2017-06-09 | 中国科学院长春应用化学研究所 | The preparation method of poly-lactic acid in high molecular weight, the preparation method of polymer grade lactide |
| CN110713583A (en) * | 2019-10-14 | 2020-01-21 | 西南大学 | In-situ synthesis method of polylactic acid nucleating agent |
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- 2003-11-17 CN CN 200310110047 patent/CN1260279C/en not_active Expired - Fee Related
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1810877B (en) * | 2005-01-25 | 2010-12-01 | 株式会社Jsp | Expandable polylactic acid resin particles, expanded polylactic acid resin beads and molded article obtained from expanded polylactic acid resin beads |
| WO2007147290A1 (en) * | 2006-06-15 | 2007-12-27 | Sichuan Yibin Wuliangye Group Co., Ltd. | Biodegrable grating sheet and its article, and preparing method thereof |
| CN101245175B (en) * | 2007-05-21 | 2010-09-08 | 肖望东 | Biodegradation expanded plastic |
| CN101362833B (en) * | 2008-09-25 | 2012-08-22 | 上海交通大学 | Method for preparing polylactic acid foam material |
| CN101768334B (en) * | 2008-12-29 | 2011-12-14 | 中国林业科学研究院木材工业研究所 | Wood-plastic composite material and forming plate made of wood-plastic composite material |
| WO2010108383A1 (en) * | 2009-03-23 | 2010-09-30 | 伟盟工业股份有限公司 | Biodegradable two-liquid type foaming composition |
| CN101845207B (en) * | 2009-03-23 | 2012-04-04 | 伟盟工业股份有限公司 | Biodegradable two-fluid foaming composition |
| CN101899139A (en) * | 2010-07-23 | 2010-12-01 | 同济大学 | Method for preparing polylactic acid-based high-elasticity copolymer |
| CN104245808B (en) * | 2012-03-30 | 2017-02-22 | 乐金华奥斯有限公司 | Foam sheet using polylactic acid having extended chain and method for preparing same |
| CN104245808A (en) * | 2012-03-30 | 2014-12-24 | 乐金华奥斯有限公司 | Foam sheet using polylactic acid having extended chain and method for preparing same |
| CN103509316A (en) * | 2012-06-18 | 2014-01-15 | 北京化工大学 | High-thermal-conductivity insulation polyester composite material and preparation method thereof |
| CN105001605A (en) * | 2015-07-27 | 2015-10-28 | 郑州大学 | Green and environment-friendly toughened strong-antibacterial degradable polylactic acid composite and preparation method thereof |
| CN105001605B (en) * | 2015-07-27 | 2017-03-01 | 郑州大学 | A kind of green environmentally friendly toughened strong antibacterial degradable lactic acid composite material and preparation method thereof |
| CN106810677A (en) * | 2017-03-01 | 2017-06-09 | 中国科学院长春应用化学研究所 | The preparation method of poly-lactic acid in high molecular weight, the preparation method of polymer grade lactide |
| CN106810677B (en) * | 2017-03-01 | 2019-04-26 | 中国科学院长春应用化学研究所 | Preparation method, the preparation method of polymer grade lactide of poly-lactic acid in high molecular weight |
| CN110713583A (en) * | 2019-10-14 | 2020-01-21 | 西南大学 | In-situ synthesis method of polylactic acid nucleating agent |
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