CN102108194B - Polylactic acid/fatty dibasic acid and diol polyester composite - Google Patents
Polylactic acid/fatty dibasic acid and diol polyester composite Download PDFInfo
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Abstract
The invention discloses a polylactic acid/fatty dibasic acid and diol polyester composite, which mainly comprises 40 to 98 weight parts of polylactic resin, 10 to 50 weight parts of fatty dibasic acid and diol polyester, 10 to 30 weight parts of plasticizer, 0.1 to 2 weight parts of capping agent, 0.1 to 2 weight parts of crosslinking agent and 0.01 to 0.1 weight part of crosslinking catalyst. The composite disclosed by the invention has higher mechanical performance and high impact strength, can completely degrade and can be used to make lunch boxes, plastic bags, agricultural thin films, food and medical packages, automobile interior ornaments and other products, and has a bright application prospect.
Description
Technical field
The invention belongs to polymeric material field, relate to a kind of poly(lactic acid)/aliphatic diacid diol polyester composition, be specifically related to the poly(lactic acid) aliphatic diacid diol polyester composition with excellent mechanical properties of a kind of plasticizer-containing, end-capping reagent, linking agent, crosslinking catalyst.
Background technology
Plastics are high with its light weight, intensity, good endurance, painted and forming process are easy etc. a bit is widely used.But due to the harm that the good endurance of plastics has also caused plastic refuse that environment is caused, the conventional plastic waste can't decompose in physical environment, thereby makes rivers, ocean, soil be subject to grievous injury, and becomes gradually serious social concern.For this reason, to utilizing microorganism in water or in soil can decompose, form, can day by day not become outline to the research of the Biodegradable material of environment by occurring in nature material capable of circulation.
Poly(lactic acid) is the polymkeric substance that obtains as the main raw material polymerization take lactic acid, and raw material sources fully and can regenerate.The production process of poly(lactic acid) is pollution-free, and product can biological degradation, realizes the circulation at occurring in nature, is therefore desirable Green Polymer Material.Yet poly(lactic acid) causes product frangible, easily broken because the mechanical property of its goods is not strong.In order to address this problem, the macromolecular material with soft character is used to and polylactic acid blend or copolymerization.
Polymer, Vol.35,2233 (1994) disclose the technology of a kind of polyhydroxycarboxyliacid acid and polycaprolactone blend, but because the consistency of its molecular scale is poor, can make material become soft though the content of polycaprolactone increases, thermotolerance can obviously descend, and mechanical property is not good.
US Patent No. P5202413 discloses the blend of a kind of poly(lactic acid) and aliphatic diacid diol polymer, because the molecular weight of polyester is lower, can't be met the blend of flexibility, physical strength, thermotolerance, forming process.
The clear 63-145661 of Japanese Patent Laid-Open discloses the multipolymer of a kind of poly(lactic acid) and polycaprolactone, and the flexibility of this multipolymer is better, but thermotolerance is not good, and opaque, and physical strength is low, it is used be restricted.
Japanese patent laid-open 9-95603 discloses the blend of a kind of poly(lactic acid), aliphatic diacid diol polyester, chainextender, utilize chainextender to improve the molecular weight of goods, thereby obtain mechanical property and flexibility preferably, simultaneously, by adding sequestrant, the metal complex that contains in its chainextender is lost activity, extend the work-ing life of product, still, the reaction efficiency of chainextender is lower, and the lifting of physical strength is limited.
Summary of the invention
The object of the invention is to address the above problem, a kind of soft poly(lactic acid) with superior mechanical intensity of biodegradable/aliphatic diacid diol polyester composition is provided.
The present invention is achieved by the following scheme:
A kind of poly(lactic acid)/aliphatic diacid diol polyester composition, said composition contains following ingredients:
Polylactic resin (A) 10～98 weight parts; Aliphatic diacid diol polyester (B) 1～90 weight part; Softening agent (C) 1～50 weight part; End-capping reagent (D) 0.01～5 weight part; Linking agent (E) 0.01～5 weight part; Crosslinking catalyst (F) 0.001～0.5 weight part.
Poly(lactic acid) belongs to bio-based materials by the lactic acid polymerizes that amylofermentation forms, and the content that increases the poly(lactic acid) composition helps to reduce Carbon emission; Plasticizer loading is less than 10 weight parts, and may soft effect to occur not obvious, causes cost to rise greater than 30 weight parts; End-capping reagent be less than 0.1 weight part, linking agent be less than 0.1 weight part, crosslinking catalyst content be less than 0.01 weight part may the unconspicuous situation of appearance effect, cross and may cause at most molecular weight too high, processing difficulties.Therefore, above-mentioned poly(lactic acid)/aliphatic diacid diol polyester composition preferably mainly contains following ingredients: polylactic resin (A) 40～98 weight parts; Aliphatic diacid diol polyester (B) 10～50 weight parts; Softening agent (C) 10～30 weight parts; End-capping reagent (D) 0.1～2 weight part; Linking agent (E) 0.1～2 weight part; Crosslinking catalyst (F) 0.01～0.1 weight part.
Poly(lactic acid) of the present invention/aliphatic diacid diol polyester composition is except above-mentioned main component, still can add other known additive, for example, thermo-stabilizer, antioxidant, photostabilizer, lubricant, tinting material, various mineral filler, fire retardant, crystallization nucleating agent, opening agent.
In above-mentioned poly(lactic acid)/aliphatic diacid diol polyester composition, described poly(lactic acid) is poly (l-lactic acid), poly-D-ALPHA-Hydroxypropionic acid or PDLLA or both above blends; Perhaps poly (l-lactic acid), gather both above multipolymers in D-ALPHA-Hydroxypropionic acid, PDLLA; Perhaps poly (l-lactic acid), the blend of both above multipolymers in poly-D-ALPHA-Hydroxypropionic acid, PDLLA.The weight-average molecular weight of this polylactic resin is 5～50w.
In above-mentioned poly(lactic acid)/aliphatic diacid diol polyester composition, described aliphatic diacid diol polyester (B) is one or both in poly butylene succinate or poly-succinic acid-butanediol adipic acid ester.Wherein the weight-average molecular weight of poly butylene succinate and poly-succinic acid-butanediol adipic acid ester is 5～50w.
In above-mentioned poly(lactic acid)/aliphatic diacid diol polyester composition, described softening agent (C) is one or more in citric acid ester plasticizer, polyalcohols derivative softening agent, fatty acid ester plasticiser or Reoplex.
Above-mentioned citric acid ester plasticizer is one or more in triethyl citrate, tri-n-butyl citrate, Triethyl citrate acetate, the positive butyl ester of citric acid acetyl three, acetyl tributyl citrate three (2-ethyl hexyl) ester; in view of cost and market popularity, optimization citric acid tri-n-butyl.
polyalcohols derivative softening agent is diethylene glycol dibenzoate, triethylene glycol dibenzoate, triglycol two (2 Ethylbutanoic acid) ester, triglycol (2 ethyl hexanoic acid) ester, triethylene glycol dieaprylate, Tetraglycol 99 two (2 ethyl hexanoic acid) ester, diethylene glycol dipelargonate, triethylene glycol dipelargonate, triethylene glycol diheptylate, the di-alcohol diacetate esters, triethylene-glycol diacetate, glyceryl monoacetate, glyceryl diacetate, triacetin, tributyrin, one or more in glycerin tripropionate, in view of cost and market popularity, the preferably glycerine triacetate, tributyrin, one or more in glycerin tripropionate, more preferably tributyrin.
fatty acid ester plasticiser is the acetyl methyl ricinoleate, acetyl ricinoleic acid butyl ester, single ricinoleic acid glyceryl ester, single ricinoleic acid glycol ether ester, glycerine three (acetyl ricinoleic acid) ester, single acetyl hydrogenated castor oil alkyd two glycerol mono acetate bulks, methyl ricinoleate, the ricinoleic acid butyl ester, single ricinoleic acid propylene glycol ester, ethanoyl ricinoleic acid methoxyl group ethyl ester, Wickenol 111, iso-octyl palmitate, Isopropyl myristate, n-butyl myristate, the tetradecanoic acid Wickenol 111, sucrose octaacetate, sucrose benzoate, the dibenzoic acid monooctyl ester, the tall oil acid methyl esters, the different monooctyl ester of tall oil acid, methyl abietate, hydrogenated methyl abietate, hydroabietyl alcohol, 2,2,4-trimethylammonium-1,3 pentanediol diisobutyrate, diisodecyl glutarate, dibutoxyethyl glutarate, didecyl glutarate, pentanedioic acid two (butoxy oxyethyl group second) ester, Zerol, glyceryl monooleate, glycerine list linolenate, Glyceryl monobehenate, sorbitan mono-laurate, the anhydrous sorbitol monopalmitate, sorbitan monostearate, the anhydrous sorbitol tristearate, sorbitan monooleate, one or more in Witconol AL 69-66, in view of cost and market popularity, preferred single ricinoleic acid glyceryl ester, single ricinoleic acid glycol ether ester, glycerine three (acetyl ricinoleic acid) ester, single acetyl hydrogenated castor oil alkyd two glycerol mono acetate bulks, the tetradecanoic acid Wickenol 111, the different monooctyl ester of tall oil acid, hydrogenated methyl abietate, Zerol, glyceryl monooleate, glycerine list linolenate, the anhydrous sorbitol tristearate, one or more in Witconol AL 69-66, more preferably single acetyl hydrogenated castor oil alkyd two glycerol mono acetate bulks, Zerol, one or more in the anhydrous sorbitol tristearate.
Reoplex is that molecular weight is that 3000～20000 polyoxyethylene glycol, molecular weight are 800～8000 poly-hexanodioic acid-1,3-fourth diester, molecular weight are that poly-hexanodioic acid-Isosorbide-5-Nitrae of 800～8000-Ding diester, molecular weight are that 800～8000 poly-pentanedioic acid diester in the last of the ten Heavenly stems, molecular weight are one or more in 800～8000 poly-suberic acid second diester.
In above-mentioned poly(lactic acid)/aliphatic diacid diol polyester composition, described end-capping reagent (D) for the compound of Ju You oxazoline functional group, have carbodiimide functionality compound, have isocyanate functional group's compound＞, wherein be preferably the compound with carbodiimide functionality, further preferred Stabaxol1LF, Stabaxol P, LA-1, HMV-8CA, DCC (N, N '-dicyclohexylcarbodiimide).
in above-mentioned poly(lactic acid)/aliphatic diacid diol polyester composition, described linking agent (E) is the compound that Ju You oxazoline palace can be rolled into a ball, compound with multi-functional epoxy's group, compound with isocyanate functional group, wherein be preferably the compound with multi-functional epoxy's group, further preferred epoxy equivalent (weight) is the compound with multi-functional epoxy's group of 5～5000g/mol, the too low meeting of epoxy equivalent (weight) causes excessively crosslinked, processibility descends, the too high meeting of epoxy equivalent (weight) causes cross-linking effect not obvious, therefore more preferably epoxy equivalent (weight) is the compound with multi-functional epoxy's group of 50～500g/mol.
In above-mentioned poly(lactic acid)/aliphatic diacid diol polyester composition, described crosslinking catalyst (F) is one or more in metal salts of organic acids, metal complex.
above-mentioned metal salts of organic acids is that backbone structure is alkane, alkene, the monobasic of aromatic hydrocarbon or polycarboxylic acid and potassium, calcium, sodium, magnesium, aluminium, zinc, iron, tin, plumbous, lithium, manganese, one or more in the metal salts of organic acids that cobalt or barium metal ion form, preferred backbone structure is alkane, alkene, the monobasic of aromatic hydrocarbon or polycarboxylic acid and magnesium, zinc, one or more in the metal salts of organic acids that iron or barium metal ion form, more preferably Magnesium Stearate, Zinic stearas, iron stearate, barium stearate, magnesium oleate, zinc oleate, iron oleate, barium oleate, magnesium benzoate, Zinc dibenzoate, phenylformic acid iron, Barium dibenzoate, magnesium citrate, zinc citrate, ironic citrate, barium citrate, terephthalic acid magnesium, terephthalic acid zinc, one or more in terephthalic acid iron or terephthalic acid barium, further preferred Zinic stearas, barium stearate, one or more in zinc citrate.
Metal complex is one or more in the complex compound that forms of acetylacetonate compound and potassium, calcium, sodium, magnesium, aluminium, zinc, iron, tin, lead, lithium, manganese, cobalt or barium metallic element, one or more in preferred magnesium acetylacetonate, zinc acetylacetonate, ferric acetyl acetonade or acetylacetone barium, more preferably zinc acetylacetonate.
Above-mentioned poly(lactic acid)/aliphatic diacid diol polyester composition melt blending is made the products formed of poly (lactic acid) composition by overmolding processing.The forming process means can adopt conventional extruding, injection moulding, foaming, blowing, curtain coating, mold pressing etc.
Be significantly improved via poly(lactic acid) of the present invention/aliphatic diacid diol polyester composition physical strength, this advantage obviously improves confirmation by the mold pressing sample shock strength of composition.The simple molecular weight of linking agent raising goods and then the method for raising physical strength used can only make the Charpy shock strength of goods reach 150～200kJ/m
2, and the poly(lactic acid) in the present invention/aliphatic diacid diol polyester composition is tested its shock strength through similarity condition and can be reached 300kJ/m
2Above.The products formed of poly(lactic acid) of the present invention/aliphatic diacid diol polyester composition can be made the products such as cutlery box, plastics bag, agricultural film, food medical packaging, automotive trim, is with a wide range of applications.
Embodiment
For further illustrating purpose of the present invention, feature and advantage, illustrated below by specific embodiment.
Extruding pelletization:
Under vacuum environment, with dry 5 hours of poly(lactic acid) particle.By formula, various raw materials are carried out melt blending by twin screw extruder and extrude, generate composition mother particle after melt is cooling through tank, 180 ℃ of forcing machine feed zone temperature, 190 ℃ of second segments, all the other sections are 200 ℃.
Compression molding:
With composition mother particle under 80 ℃, vacuum environment dry 5 hours, by vulcanizing press, master batch is pressed into the thick diaphragm of 0.2mm, on vulcanizing press, plate temperature is 200 ℃, 200 ℃ of lower plate temperatures, sample melted 3 minutes, exhaust 3 times, exhaust pressure 10～12MPa, pressurize 30 seconds, dwell pressure 10MPa.
Shock strength is measured:
The sample diaphragm is made the batten of 5mm * 50mm, tested its shock strength by the Charpy shock-testing machine, pendulum energy 1J, initial angle 135 degree.Each sample test seven times is averaged after the removal maximin.
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 6251D processed, weight-average molecular weight 7～13w.
A-3: the positive REVODE 101 processed of biotech firm in sea, weight-average molecular weight 10w.
(2) aliphatic diacid diol polyester (B)
B-1: clear and polymer PBSA processed, trade mark 3001G, weight-average molecular weight 15～20W.
B-2: the PBS processed of Mitsubishi Chemical, trade mark AZ91T, weight-average molecular weight 15～20W.
B-3: prosperous rich medicine company PBS processed, trade mark 1803F, weight-average molecular weight 15～20W.
B-4: and Xinghua work PBS processed, trade mark film-grade, weight-average molecular weight 15～20W.
(3) softening agent (C)
C-1: traditional Chinese medicines reagent tri-n-butyl citrate processed.
C-2:Eastman Chem glycerine tri-n-butyl processed.
C-3:Danisco single acetyl hydrogenated castor oil processed alkyd two glycerol mono acetate bulks.
C-4: ancient cooking vessel additive Zerol processed in the Zhangjiagang.
C-5:Danisco anhydrous sorbitol tristearate processed.
C-6: traditional Chinese medicines reagent PEG20000 processed.
(4) end-capping reagent (D)
D-1: Lay mattress chemistry Stabaxol 1LF processed.
D-2: Nisshinbo LA-1 processed.
D-3: Nisshinbo HMV-8CA processed.
D-4: Shanghai covalent chemical DCC processed.
(5) linking agent (E)
E-1: Beijing lean work TGIC processed that refines, epoxy equivalent (weight) 99g/mol.
E-2:BASF Joncryl ADR-4368 processed, epoxy equivalent (weight) 285g/mol.
E-3:BASF Joncryl ADR-4380 processed, epoxy equivalent (weight) 450g/mol.
(6) crosslinking catalyst (F)
F-1: traditional Chinese medicines reagent Zinic stearas processed.
F-2: traditional Chinese medicines reagent barium stearate processed.
F-3: traditional Chinese medicines reagent zinc citrate processed.
F-4: traditional Chinese medicines reagent zinc acetylacetonate processed.
Embodiment 1～3, Comparative Examples 1 (the every weight part of following examples is 100 grams)
Table 1
Embodiment 4～6, Comparative Examples 2.
Table 2
Embodiment 7～9, Comparative Examples 3.
Table 3
Embodiment 10～12, Comparative Examples 4.
Table 4
Embodiment 13～15, Comparative Examples 5.
Table 5
Embodiment 16,17, Comparative Examples 6,7.
Table 6
Claims (10)
1. poly(lactic acid)/aliphatic diacid diol polyester composition, is characterized in that, said composition contains following ingredients:
Polylactic resin (A) 10～98 weight parts; Aliphatic diacid diol polyester (B) 1～90 weight part; Softening agent (C) 1～50 weight part; End-capping reagent (D) 0.01～5 weight part; Linking agent (E) 0.01～5 weight part; Crosslinking catalyst (F) 0.001～0.5 weight part; Wherein, softening agent (C) is one or more in citric acid ester plasticizer, polyalcohols derivative softening agent, fatty acid ester plasticiser or Reoplex, and crosslinking catalyst (F) is one or more in organic metal salt, metal complex.
2. poly(lactic acid) according to claim 1/aliphatic diacid diol polyester composition, is characterized in that, said composition contains following ingredients:
Polylactic resin (A) 40～98 weight parts; Aliphatic diacid diol polyester (B) 10～50 weight parts; Softening agent (C) 10～30 weight parts; End-capping reagent (D) 0.1～2 weight part; Linking agent (E) 0.1～2 weight part; Crosslinking catalyst (F) 0.01～0.1 weight part.
3. poly(lactic acid) according to claim 1 and 2/aliphatic diacid diol polyester composition, is characterized in that, described aliphatic diacid diol polyester (B) is one or both in poly butylene succinate or poly-succinic acid-butanediol adipic acid ester.
4. poly(lactic acid) according to claim 1/aliphatic diacid diol polyester composition, it is characterized in that, described citric acid ester plasticizer is one or more in triethyl citrate, tri-n-butyl citrate, Triethyl citrate acetate, the positive butyl ester of citric acid acetyl three, acetyl tributyl citrate three (2-ethyl hexyl) ester, described polyalcohols derivative softening agent is diethylene glycol dibenzoate, triethylene glycol dibenzoate, triglycol two (2 Ethylbutanoic acid) ester, triglycol (2 ethyl hexanoic acid) ester, triethylene glycol dieaprylate, Tetraglycol 99 two (2 ethyl hexanoic acid) ester, diethylene glycol dipelargonate, triethylene glycol dipelargonate, triethylene glycol diheptylate, the di-alcohol diacetate esters, triethylene-glycol diacetate, glyceryl monoacetate, glyceryl diacetate, triacetin, tributyrin, one or more in glycerin tripropionate, described fatty acid ester plasticiser is the acetyl methyl ricinoleate, acetyl ricinoleic acid butyl ester, single ricinoleic acid glyceryl ester, single ricinoleic acid glycol ether ester, glycerine three (acetyl ricinoleic acid) ester, single acetyl hydrogenated castor oil alkyd two glycerol mono acetate bulks, methyl ricinoleate, the ricinoleic acid butyl ester, single ricinoleic acid propylene glycol ester, ethanoyl ricinoleic acid methoxyl group ethyl ester, Wickenol 111, iso-octyl palmitate, Isopropyl myristate, n-butyl myristate, the tetradecanoic acid Wickenol 111, sucrose octaacetate, sucrose benzoate, the dibenzoic acid monooctyl ester, the tall oil acid methyl esters, the different monooctyl ester of tall oil acid, methyl abietate, hydrogenated methyl abietate, hydroabietyl alcohol, 2,2,4-trimethylammonium-1,3 pentanediol diisobutyrate, diisodecyl glutarate, dibutoxyethyl glutarate, didecyl glutarate, pentanedioic acid two (butoxy oxyethyl group second) ester, Zerol, glyceryl monooleate, glycerine list linolenate, Glyceryl monobehenate, sorbitan mono-laurate, the anhydrous sorbitol monopalmitate, sorbitan monostearate, the anhydrous sorbitol tristearate, sorbitan monooleate, one or more in Witconol AL 69-66, described Reoplex is that molecular weight is that 3000～20000 polyoxyethylene glycol, molecular weight are 800～8000 poly-hexanodioic acid-1,3-fourth diester, molecular weight are that poly-hexanodioic acid-Isosorbide-5-Nitrae of 800～8000-Ding diester, molecular weight are that 800～8000 poly-pentanedioic acid diester in the last of the ten Heavenly stems, molecular weight are one or more in 800～8000 poly-suberic acid second diester.
5. poly(lactic acid) according to claim 1 and 2/aliphatic diacid diol polyester composition, is characterized in that, the compound of described end-capping reagent (D) for having carbodiimide functionality.
6. poly(lactic acid) according to claim 1 and 2/aliphatic diacid diol polyester composition, it is characterized in that, described linking agent (E) is for having the compound of multi-functional epoxy's group, and wherein, the epoxy equivalent (weight) with compound of multi-functional epoxy's group is 5～5000g/mol.
7. poly(lactic acid) according to claim 1/aliphatic diacid diol polyester composition, it is characterized in that, described metal salts of organic acids is that backbone structure is one or more in the metal salts of organic acids that forms of the monobasic of alkane, alkene, aromatic hydrocarbon or polycarboxylic acid and potassium, calcium, sodium, magnesium, aluminium, zinc, iron, tin, lead, lithium, manganese, cobalt or barium metal ion.
8. poly(lactic acid) according to claim 1/aliphatic diacid diol polyester composition, it is characterized in that, described metal salts of organic acids is one or more in Magnesium Stearate, Zinic stearas, iron stearate, barium stearate, magnesium oleate, zinc oleate, iron oleate, barium oleate, magnesium benzoate, Zinc dibenzoate, phenylformic acid iron, Barium dibenzoate, magnesium citrate, zinc citrate, ironic citrate, barium citrate, terephthalic acid magnesium, terephthalic acid zinc, terephthalic acid iron or terephthalic acid barium.
9. poly(lactic acid) according to claim 1/aliphatic diacid diol polyester composition, it is characterized in that, described metal complex is one or more in the complex compound that forms of acetylacetonate compound and potassium, calcium, sodium, magnesium, aluminium, zinc, iron, tin, lead, lithium, manganese, cobalt or barium metallic element.
10. poly(lactic acid) according to claim 9/aliphatic diacid diol polyester composition, is characterized in that, described metal complex is one or more in magnesium acetylacetonate, zinc acetylacetonate, ferric acetyl acetonade or acetylacetone barium.
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| CN102352094A (en) * | 2011-09-20 | 2012-02-15 | 奇瑞汽车股份有限公司 | High-toughness and highly heat-resistant polylactic acid (PLA) alloy material and preparation method thereof |
| CN102532833A (en) * | 2011-12-16 | 2012-07-04 | 奇瑞汽车股份有限公司 | Nanometer high polymer polylactic acid composite material and preparation method thereof |
| KR101460399B1 (en) * | 2012-04-09 | 2014-11-10 | (주)엘지하우시스 | Biodegradable resin composition having eco plasticizer and biodegradable product using the same |
| CN103819884A (en) * | 2012-11-16 | 2014-05-28 | 上海载和实业投资有限公司 | Novel heat-resistant high-toughness polylactic acid composite material and preparation method thereof |
| CN105086969A (en) * | 2015-07-13 | 2015-11-25 | 中国石油大学(北京) | Degradable resin material for operation of oil and gas field and preparation method thereof |
| CN105802155A (en) * | 2016-05-12 | 2016-07-27 | 江西禾尔斯环保科技有限公司 | Preparation method and application of PBAT modified material |
| CN106380856A (en) * | 2016-09-29 | 2017-02-08 | 东至绿洲环保化工有限公司 | Organic silicon plasticizer capable of reducing fracture rate of agricultural films |
| CN112409647A (en) * | 2020-10-16 | 2021-02-26 | 安徽省怀宁县希望纸塑有限责任公司 | Biodegradable material for preparing tableware and preparation method thereof |
| CN115028899A (en) * | 2022-04-18 | 2022-09-09 | 高邮市恒昌泡沫制品有限公司 | Degradable environment-friendly antibacterial tableware and preparation process thereof |
| CN115044179A (en) * | 2022-06-15 | 2022-09-13 | 贵州省材料产业技术研究院 | Plasticized polylactic acid composite material and preparation method thereof |
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| CN1973227A (en) * | 2004-02-12 | 2007-05-30 | 帕诺拉马实验室有限公司 | Device, method, and computer program product for substrated waveguide including recursion regions |
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