CN1749316A - A kind of ternary built poly lactic acid type composite material and application thereof - Google Patents
A kind of ternary built poly lactic acid type composite material and application thereof Download PDFInfo
- Publication number
- CN1749316A CN1749316A CN 200510017206 CN200510017206A CN1749316A CN 1749316 A CN1749316 A CN 1749316A CN 200510017206 CN200510017206 CN 200510017206 CN 200510017206 A CN200510017206 A CN 200510017206A CN 1749316 A CN1749316 A CN 1749316A
- Authority
- CN
- China
- Prior art keywords
- lactic acid
- composite material
- type composite
- pla
- poly lactic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to poly lactic acid type composite material of a kind of ternary built completely biological degradation and uses thereof.This matrix material % meter each component by weight is: poly(lactic acid) (PLA): 45.0-80.0, and polypropylene carbonate (PPC): 4.0-40.0, poly 3-hydroxy butyrate (PHB): 4.0-40.0, all the other are various auxiliary agents.Ternary built poly lactic acid type composite material of the present invention has improved the dimensional stability of forming process, thermotolerance, tear strength and the goods of polylactic acid article as the thermoplastic composite of masterbatch preparation; Ternary built poly lactic acid type composite material blow molding provided by the invention can prepare the membrane product of physical chemistry excellent property.The membrane product biodegradation rate that is obtained is controlled, is widely used in packaging industry and product for agriculture.
Description
Technical field
The present invention relates to a kind of ternary built completely biological degradation poly lactic acid type composite material and application thereof.
Background technology
In order to solve " white pollution " problem that plastics cause, environment for use close friend's complete biodegradable polymkeric substance substitutes traditional petroleum-based plastics, has become the current research hot of research and development.In numerous biodegradable polymers, aliphatic polyester, as poly(lactic acid) (PLA), PHA (PHAs), poly-epsilon-caprolactone (PCL), polypropylene carbonate (PPC) etc., demonstrate excellent performance, and have wide application field and significant social economic benefit.Poly(lactic acid) (PLA) is the thermoplasticity aliphatic polyester by synthetic, and synthetic its monomer lactic acid is by fermentations such as reproducible corn, cereal.PLA has excellent biodegradability and biocompatibility, finally is decomposed into carbonic acid gas and water in environment, and environment is not polluted, and therefore becomes one of research focus of degradable material.Just begun synthesizing and applied research as far back as the fifties to poly(lactic acid), begun to synthesize the PLA that high-molecular weight has the D type or the L type of opticity from the seventies, and be used for the research of aspects such as pharmaceutical preparation and medical surgery, for overcoming the limitation that PLA depends merely on molecular weight and distributes and regulate degradation speed, begin synthetic each analog copolymer simultaneously based on PLA.After entering the eighties,, the synthetic and applied research of the multipolymer of synthesis mechanism, different structure and composition is enlarged day by day along with the continuous expansion of the Application Areas of PLA and multipolymer thereof.Along with deepening continuously of research aspect medical and application, the application of poly(lactic acid) more and more widely, for example: it can be used as suture line, nail, bone rod, medicine sustained release carrier; The research of PLA simultaneously also begins to develop to the degradative plastics aspect.
From the nineties so far, the PLA of five kinds of trades mark has appearred in world market in succession, is respectively (the Dainippon Ink ﹠amp of big Japanese ink of (1) CPLA-and chemical company; Chemical) product; (2) LACEA-Mitsui Chemicals company (Mitsui Toatsu) product; (3) LACTY-Shimadzu Corp product; (4) Ecopla-Cargill Dow company product; (5) Heplon-U.S. Chronopol company product.Wherein the throughput maximum of Cargill Dow company has reached 140,000 tons/year.Along with PLA enters the industrialized production phase, will equally be applied to the every field of the development of the national economy with other general-purpose plastics, will become the favorable substitutes of existing general-purpose plastics.Poly(lactic acid) is a kind of have good biocompatibility, Biodegradable Polymers, compares with polyolefine, and from the environmental protection aspect, it has unrivaled characteristic.Poly(lactic acid) is applied to packaging field, also has a lot of technical barriers to overcome.For example thermolysis or transesterification reaction take place in the ester group instability of PLA easily in molding process, make PLA that hydrolysis in use take place easily, cause jaundice, become fragile, even still lose use properties.Poly(lactic acid) belongs to polar material, easily suction, and its water content is to the highly significant that influences of processing characteristics.The elongation at break of pure poly(lactic acid) is low, toughness is not good enough, as the just necessary disadvantageous effect of selecting suitable plasticising, toughened system and suitable metal passivator with catalyzer remaining in the elimination poly(lactic acid) melt process to be produced of this softish wrapping material of film.
No matter poly(lactic acid) is by the rac-Lactide ring-opening polymerization or directly by the lactic acid monomer condensation, all is typical simple linear polymer.Compare with polyolefine, its melt elasticity is poor, and it is embodied in has lower die swell ratio.This specific character is at extrusion process, and as casting films, paper applies, and can produce in the blown film manufacturing processed and reach " the film bubble is unstable " such as " constriction ".This than low melt elasticity can be interpreted as molecular chain twine degree lower reason caused.The most effectual way that the raising molecular chain twines the degree of connecing is to make polylactic acid molecule chain formation side chain.U.S. Pat 5,539, graft reaction is carried out with a small amount of epoxidized vegetable oil and poly(lactic acid) in 026 (1994), and the molecular weight distribution of poly(lactic acid) is widened, and melt strength increases like this, and " constriction " reach " film bubble instability " phenomenon and improves.
The binary formulation of poly(lactic acid) and aliphatic polyester has constituted the theme of a lot of patents, particularly European patent EP-0 980894 A1 (Mitsui Chemical) mixture of having described poly(lactic acid) and poly-succinic fourth diester adds the film tear resistance for preparing under a kind of condition of softening agent and the obvious improvement of balance of mechanical properties aspect, but the intensity of goods is quite low, and the more crisp shortage flexibility of film.
US patent 5 883 199 has been described the binary formulation of poly(lactic acid) and polyester, and wherein the content of poly(lactic acid) is 10-90%, and polyester forms external phase or common external phase, but the tear resistance of formulation described here is very poor.
Summary of the invention
One of purpose of the present invention provides a kind of poly lactic acid type composite material of ternary built completely biological degradation, solves the problem of the aspects such as forming process, goods heat-resistant stability, dimensional stability and physical and chemical performance difference of the single resin of poly(lactic acid).The poly lactic acid type composite material of ternary built completely biological degradation of the present invention has improved the dimensional stability of processibility, thermotolerance, tear strength and the goods of polylactic acid based resin.
A kind of ternary built completely biological degradation poly lactic acid type composite material that the present invention relates to, its matrix resin comprises:
(A) poly(lactic acid) (PLA)
(B) polypropylene carbonate (PPC)
(C) poly--3 butyric esters (PHB)
When poly(lactic acid) (PLA) is carried out forming process as first component, poor heat stability, fragility is big, and tear strength is poor, shortcoming such as easily shrinks, wrinkling during the blown film goods, has limited its use range.Use polypropylene carbonate, poly 3-hydroxy butyrate and poly(lactic acid) to carry out melt blending among the present invention and prepare the matrix resin alloy, adjustment by each component ratio, and select suitable thermostability, composite Plasticising system and nucleator for use, improved the heat-resistant stability of resin alloy, regulate and control its crystallization rate, improve flow rate, melt viscosity and the intensity of melt in the molding process, thereby obtained the preferable matrix material of performance.
Matrix material polycomponent weight % content of the present invention is as follows:
(A) poly(lactic acid) (PLA) 45-80
(B) polypropylene carbonate (PPC) 4-40
(C) poly 3-hydroxy butyrate (PHB) 4-40
Softening agent 3-15
Heat-resisting stabilizing agent 1.0-6.5
Oxidation inhibitor 0.5-2.0
Nucleator 0.05-1.0
Lubricant 0.35-1.0
Opening agent 0.1-1.0
Photolysis agent 0.1-1.0
Biodegradation agent promotor 0.1-1.0
Light (ultraviolet ray) stablizer 0.1-1.0
Antistatic agent 0.5-1.0
Weighting agent 1.0-15.0
Tinting material 0.05-1.0
Described softening agent is: dioctyl phthalate (DOP), diethyl phthalate, dimixo-octyl phthalate, tributyl citrate, acetyl tributyl citrate three (2-ethylhexyl), hexanoyl tributyl citrate, hexanodioic acid two (2-ethylhexyl), polyoxyethylene glycol, polypropylene glycol oxalic acid ester, epoxy soybean wet goods epoxy resin softening agent, can select a kind of or two or more, if select the two or more gross weight % that should keep constant;
Heat-resisting stabilizing agent is: polynite, silicon-dioxide, kaolin, zinc oxide, magnesium oxide, calcium stearate, maleic dibutyl tin, can select a kind of or two or more, if select the two or more gross weight % that should keep constant;
Oxidation inhibitor is: any one of dihydroxyphenyl propane, triphenyl phosphite, phosphorous acid ethyl ester or phosphorous acid dihydroxyphenyl propane ester;
Lubricant is: any one of stearylamide, amine hydroxybenzene, erucicamide, Zinc Stearate, ethylenebisstearamide, alkylidene group two fatty amides;
Nucleator is: dibenzylidene sorbitol, terephthalic acid, aluminium hydroxide, aluminum oxide, aluminium carbonate, talcum powder;
Photolysis agent is: any one of benzene idol alkyl oxide, benzophenone, phenyl methyl ketone, anatase-type titanium oxide;
Photolysis promotor is: any one of citric acid, tartrate, oxysuccinic acid, oxalic acid, propanedioic acid, Succinic anhydried, activated coco nut charcoal;
Weighting agent is: lime carbonate, talcum, mica, fine silica powder, white carbon black, asbestos, clay, glass fibre, xylon, cotton fibriia, kaolinic any one;
Uv-absorbing agent is: 1,2,2, and 4-four (4-ketonic oxygen base-2,2,6,6-four-pipecoline)-amine (HALS), 2 benzotriazole-ethyl-4,6-DI-tert-butylphenol compounds, benzoic ether are any one of uv-absorbing agent;
Static inhibitor is: any one of aliphatic amide, dodecyl sodium sulfonate ester, glyceryl monolaurate, GLYCERYL DILAURATE;
Tinting material is: any one of carbon black, titanium white, pthalocyanine blue, transparent violet.
The preparation method of ternary built completely biological degradation poly lactic acid type composite material of the present invention is as follows:
With starting material in baking oven 45-65 ℃ of dry 6-10 hour, in high-speed mixer stirring at low speed 5-10 minute then, the recurrence high-speed stirring went out after 3-5 minute, enters in the parallel dual-screw extruding machine, and be to carry out the product that extruding pelletization gets final product under the 65-195 ℃ of condition in temperature.
The purposes of the poly lactic acid type composite material of described ternary built completely biological degradation, this matrix material carries out blow molding as master batch can make film article.
The described poly lactic acid type composite material that utilizes ternary built completely biological degradation is blow molded into and makes film article, and the film article thickness that utilizes this matrix material to make is 10 μ m-50 μ m.
Utilize the matrix material of above-mentioned preparation method's preparation to carry out blow molding, make film article as masterbatch.Its blowing complete processing is as follows:
Utilize SJDD-260 type Electromagnetic Dynamic extrusion-blown modling unit to carry out blow molding
Forcing machine length-to-diameter ratio: 24: 1
Temperature is provided with as follows:
One district: 105-115 ℃
Two districts: 145-170 ℃
Three districts: 165-180 ℃
Junctor: 165-180 ℃
Die head D
1: 175-190 ℃
Die head D
2: 175-190 ℃
From the hopper blanking, pellet is expressed into D from a district
1, D
2Upwards extrusion moulding is compressed into row by air and is blown into cylindric film bubble, forms film article.
Film master pulling speed: 15Hz-30Hz
Mouth die clearance: 0.5-2.0mm
Film is wide: 100-450mm
Thickness: 10 μ m-50 μ m:
Blow-up ratio: 1.5-5.5
Stretch ratio: 3-40
The Mechanics Performance Testing of the goods of the matrix material of ternary built of the present invention:
The matrix material masterbatch of ternary built of the present invention is cut into batten with the standard cutting knife through the vulcanizing press compacting in flakes again.Film article directly cuts sample with the dumbbell shape cutting knife, film is die-cut to carry out from MD, TD both direction, and tension test is at room temperature tested on Instron Model-1211 section bar material trier, and wherein rate of extension is 10mm/min, test number (TN) n=5 time, the result represents with its mean value.
The tear strength test of film:
Film article is cut growth (MD direction) 100mm, the batten of wide 25mm, in width one side from the centre, engrave the cut channel of 30mm along its length, at room temperature with the test of Instron Model-1211 section bar material trier, wherein rate of extension is 10mm/min, test number (TN) n=3 time then, the result represents that with its mean value it is as follows that test bars is intuitively passed judgment on benchmark:
Best: tear strength is big, oblique segmentation, cracking face have wrinkle
Good: tear strength is big, the cracking face linearly, the cracking face has wrinkle
Generally: tear strength is little, the cracking face linearly
Difference: tear strength is very little, the cracking face linearly, the cracking face do not have wrinkle
Hand tear test:
Add upper cut at the polyethylene film (inflation formed film) that is widely used as general purpose film at present, the sensation during its passive tearing is divided into full marks as benchmark 10, tears sense according to the film hand separately of each composition and carries out sensory evaluation.The judging criterion of this moment is the ripple situation etc. that is delivered to resistance on hand when being torn by hand or tears mode (having or not rectilinearity), tear face: the tearing property to integral body except that simple intensity is carried out sensory evaluation.
The metewand of sensory test is as follows:
◎: cracking ground roll shape, oblique segmentation in addition, tearing resistance is big.
Zero: the cracking face is in line, and a little waveform is also arranged, but tearing resistance is big.
*: the cracking face is in line, and tearing resistance is little.
* *: ratio * tearing resistance is little, easily spreads in the crack
The thermostability of goods: select differential scanning calorimeter (perkin-Elmer TGA-TC) for use, heat-up rate is 20 ℃/min.
Ternary built completely biological degradation poly lactic acid type composite material of the present invention, reach the film article that obtains by its blowing, has preferable physical and chemical performance, the processing of more single resin in aspect such as the stability of its course of processing, the thermotolerance of goods and dimensional stability and binary complex has clear improvement, thereby has enlarged the use range of this complete biodegradable polyester of poly(lactic acid) on agricultural, food and packaging industry.
Embodiment:
Following examples are used to illustrate the present invention, but do not limit the present invention.
Embodiment 1:
Press column weight amount % and take by weighing each component:
PLA 45.0
PPC 38.0
PHB 6.0
Polynite (MMT) 1.0
PEG 3.0
Tributyl acetylcitrate 4.2
Triphenyl phosphite 0.5
Erucicamide 0.4
Two inferior Bian Ji sorbyl alcohols 0.05
Benzophenone 0.1
Oxalic acid 0.1
HALS 0.1
Glyceryl monolaurate 0.5
Fine silica powder 1.0
Phthalein blue or green blue 0.05
Preparation technology is as follows:
With starting material in baking oven 45-65 ℃ of dry 6-10 hour, in high-speed mixer stirring at low speed 5-10 minute then, the recurrence high-speed stirring went out after 3-5 minute, entered and carried out extruding pelletization in the parallel dual-screw extruding machine, and processing conditions is as follows:
Length-to-diameter ratio: 44: 1
Two districts: liquid filling feeding
Seven districts: vacuumizing and exhausting
Screw combinations is arranged: banburying element, kneading member, high-shear unit construction are arranged
Temperature is provided with:
One district: 65-75 ℃
Two districts: 115-125 ℃
Three districts: 135-140 ℃
Four districts: 160-170 ℃
Five districts: 165-175 ℃
Six districts: 180-195 ℃
Seven districts: 170-185 ℃
Head: 165-175 ℃
The traction tie rod enters the dicing machine pelletizing and promptly obtains product.
Utilize the matrix material master batch of above-mentioned prepared to carry out blow molding, obtain the film article of 10 μ m-50 μ m, the blowing complete processing is as follows:
Blow-moulding process:
Utilize SJDD-260 type Electromagnetic Dynamic extrusion-blown modling unit to carry out blow molding
Forcing machine length-to-diameter ratio: 22: 1
Temperature is provided with as follows:
One district: 105-115 ℃
Two districts: 145-170 ℃
Three districts: 165-180 ℃
Junctor: 165-180 ℃
Die head D
1: 175-190 ℃
Die head D
2: 175-190 ℃
From the hopper blanking, pellet is expressed into D from a district
1, D
2Upwards extrusion moulding is compressed into row by air and is blown into cylindric film bubble, forms film article.
The performance that obtains goods sees Table 1.
Table 1:
| Hand tear test is estimated | 10 stages were estimated | 8 | ||
| Sensory evaluation | Good | |||
| Tear strength (MD direction) | g/20μm | 110 | ||
| Sensory evaluation | ◎ | |||
| Stretching experiment | The MD direction | Tensile strength | Mpa | 29 |
| Elongation at break | ％ | 190 | ||
| The TD direction | Tensile strength | Mpa | 22 | |
| Elongation at break | ％ | 150 | ||
Embodiment 2:
Press column weight amount % and take by weighing each component:
PLA 45.0
PPC 6.0
PHB 38.0
Polynite (MMT) 1.0
PEG 3.0
Tributyl acetylcitrate 4.2
Triphenyl phosphite 0.5
Erucicamide 0.4
Two inferior Bian Ji sorbyl alcohols 0.05
Benzophenone 0.1
Oxalic acid 0.1
HALS 0.1
Glyceryl monolaurate 0.5
Fine silica powder 1.0
Phthalein blue or green blue 0.05
Complete processing is seen embodiment 1.
The performance that obtains goods sees Table .2.
Table 2:
| Hand tear test is estimated | 10 stages were estimated | 7 | ||
| Sensory evaluation | Good | |||
| Tear strength (MD direction) | g/20μm | 85 | ||
| Sensory evaluation | ○ | |||
| Stretching experiment | The MD direction | Tensile strength | Mpa | 27 |
| Elongation at break | ％ | 140 | ||
| The TD direction | Tensile strength | Mpa | 20 | |
| Elongation at break | ％ | 180 | ||
Embodiment 3:
Press column weight amount % and take by weighing each component:
PLA 75.0
PPC 5.0
PHB 8.0
Polynite (MMT) 2.0
PEG 5.0
Epoxy soybean oil 1.9
Triphenyl phosphite 0.7
Zinic stearas 0.5
Sorbitol dibenzal 0.05
Benzophenone 0.1
Oxalic acid 0.1
HALS 0.1
Glyceryl monolaurate 0.5
Fine silica powder 1.0
Phthalein blue or green blue 0.05
Complete processing is seen embodiment 1.
The performance that obtains goods sees Table 3:
Table 3:
| Hand tear test is estimated | 10 stages were estimated | 7 | ||
| Sensory evaluation | Good | |||
| Tear strength (MD direction) | g/20μm | 85 | ||
| Sensory evaluation | ○ | |||
| Stretching experiment | The MD direction | Tensile strength | Mpa | 25 |
| Elongation at break | ％ | 160 | ||
| The TD direction | Tensile strength | Mpa | 16 | |
| Elongation at break | ％ | 130 | ||
Embodiment 4: press column weight amount % and take by weighing each component:
PLA 80.0
PPC 4.0
PHB 5.0
Polynite (MMT) 1.0
Tributyl acetylcitrate 5.0
Epoxy soybean oil 1.9
Triphenyl phosphite 0.7
Stearylamide 0.5
Two inferior Bian Ji sorbyl alcohols 0.05
Phenyl methyl ketone 0.1
Tartrate 0.1
HALS 0.1
Glyceryl monolaurate 0.5
Fine silica powder 1.0
Transparent violet 0.05
Complete processing is seen embodiment 1.
The performance that obtains goods sees Table 4:
Table 4:
| Hand tear test is estimated | 10 stages were estimated | 7 | ||
| Sensory evaluation | Good | |||
| Tear strength (MD direction) | g/20μm | 90 | ||
| Sensory evaluation | ○ | |||
| Stretching experiment | The MD direction | Tensile strength | Mpa | 27 |
| Elongation at break | ％ | 168 | ||
| The TD direction | Tensile strength | Mpa | 22 | |
| Elongation at break | ％ | 186 | ||
Embodiment 5:
Press column weight amount % and take by weighing each component:
PLA 45.0
PPC 22.0
PHB 22.0
Polynite (MMT) 1.0
PEG 3.0
Tributyl acetylcitrate 4.2
Triphenyl phosphite 0.5
Erucicamide 0.4
Two inferior Bian Ji sorbyl alcohols 0.05
Benzophenone 0.1
Oxalic acid 0.1
HALS 0.1
Glyceryl monolaurate 0.5
Fine silica powder 1.0
Phthalein blue or green blue 0.05
Complete processing is seen embodiment 1.
The performance that obtains goods sees Table 5:
Table 5:
| Hand tear test is estimated | 10 stages were estimated | 6 | ||
| Sensory evaluation | Generally | |||
| Tear strength (MD direction) | g/20μm | 70 | ||
| Sensory evaluation | × | |||
| Stretching experiment | The MD direction | Tensile strength | Kgf/cm 3 | 19 |
| Elongation at break | ％ | 90 | ||
| The TD direction | Tensile strength | Kgf/cm 3 | 15 | |
| Elongation at break | ％ | 130 | ||
Embodiment 6:
Press column weight amount % and take by weighing each component:
PLA 80.0
PPC 5.0
PHB 4.0
Polynite (MMT) 1.0
PEG 3.0
Tributyl acetylcitrate 4.2
Triphenyl phosphite 0.5
Erucicamide 0.4
Two inferior Bian Ji sorbyl alcohols 0.05
Benzophenone 0.1
Oxalic acid 0.1
HALS 0.1
Glyceryl monolaurate 0.5
Fine silica powder 1.0
Phthalein blue or green blue 0.05
Complete processing is seen embodiment 1.
The performance that obtains goods sees Table 6:
Table 6:
| Hand tear test is estimated | 10 stages were estimated | 8 | ||
| Sensory evaluation | Good | |||
| Tear strength (MD direction) | g/20μm | 90 | ||
| Sensory evaluation | ○ | |||
| Stretching experiment | The MD direction | Tensile strength | Mpa | 26 |
| Elongation at break | ％ | 148 | ||
| The TD direction | Tensile strength | Mpa | 22 | |
| Elongation at break | ％ | 167 | ||
Embodiment 7:
Press column weight amount % and take by weighing each component:
PLA 55.0
PPC 15.0
PHB 5.0
Polynite (MMT) 2.0
PEG 10.0
Epoxy soybean oil 5.0
Triphenyl phosphite 0.5
Zinic stearas 1.0
Two inferior Bian Ji sorbyl alcohols 1.0
Benzophenone 1.0
Oxalic acid 1.0
HALS 1.0
Glyceryl monolaurate 1.0
Fine silica powder 1.0
Phthalein blue or green blue 0.5
Complete processing is seen embodiment 1.
The performance that obtains goods sees Table 7:
Table 7:
| Hand tear test is estimated | 10 stages were estimated | 7 | ||
| Sensory evaluation | Generally | |||
| Tear strength (MD direction) | g/20μm | 110 | ||
| Sensory evaluation | ○ | |||
| Stretching experiment | The MD direction | Tensile strength | Mpa | 19 |
| Elongation at break | ％ | 170 | ||
| The TD direction | Tensile strength | Mpa | 14 | |
| Elongation at break | ％ | 163 | ||
Embodiment 8:
Press column weight amount % and take by weighing each component:
PLA 55.0
PPC 15.0
PHB 5.0
Polynite (MMT) 2.0
Tributyl acetylcitrate 9.0
Acetyl triethyl citrate 6.0
Triphenyl phosphite 0.5
Zinic stearas 1.0
Two inferior Bian Ji sorbyl alcohols 1.0
Benzophenone 1.0
Oxalic acid 1.0
HALS 1.0
Glyceryl monolaurate 1.0
Fine silica powder 1.0
Phthalein blue or green blue 0.5
Complete processing is seen embodiment 1.
The performance that obtains goods sees Table 8:
Table 8:
| Hand tear test is estimated | 10 stages were estimated | 7 | ||
| Sensory evaluation | Generally | |||
| Tear strength (MD direction) | g/20μm | 100 | ||
| Sensory evaluation | ○ | |||
| Stretching experiment | The MD direction | Tensile strength | Mpa | 21 |
| Elongation at break | ％ | 146 | ||
| The TD direction | Tensile strength | Mpa | 19 | |
| Elongation at break | ％ | 133 | ||
Embodiment 9:
Press column weight amount % and take by weighing each component:
PLA 65.0
PPC 19.0
PHB 5.0
Polynite (MMT) 1.0
Tributyl acetylcitrate 5.0
Acetyl triethyl citrate 2.1
Triphenyl phosphite 0.5
Erucicamide 0.5
Terephthalic acid 0.05
Benzophenone 0.1
Oxalic acid 0.1
HALS 0.1
Glyceryl monolaurate 0.5
Fine silica powder 1.0
Phthalein blue or green blue 0.05
Complete processing is seen embodiment 1.
The performance that obtains goods sees Table 9:
Table 9:
| Hand tear test is estimated | 10 stages were estimated | 9 | ||
| Sensory evaluation | Best | |||
| Tear strength (MD direction) | g/20μm | 115 | ||
| Sensory evaluation | ◎ | |||
| Stretching experiment | The MD direction | Tensile strength | Mpa | 29 |
| Elongation at break | ％ | 188 | ||
| The TD direction | Tensile strength | Mpa | 26 | |
| Elongation at break | ％ | 175 | ||
Embodiment 10:
Press column weight amount % and take by weighing each component:
PLA 80.0
PPC 6.0
PHB 3.0
Polynite (MMT) 1.0
PEG 4.0
Epoxy soybean oil 3.1
Triphenyl phosphite 0.5
Zinic stearas 0.5
Two inferior Bian Ji sorbyl alcohols 0.05
Benzophenone 0.1
Oxalic acid 0.1
HALS 0.1
Glyceryl monolaurate 0.5
Fine silica powder 1.0
Phthalein blue or green blue 0.05
Complete processing is seen embodiment 1.
The performance that obtains goods sees Table 10:
Table 10:
| Hand tear test is estimated | 10 stages were estimated | 5 | ||
| Sensory evaluation | Difference | |||
| Tear strength (MD direction) | g/20μm | 50 | ||
| Sensory evaluation | ×× | |||
| Stretching experiment | The MD direction | Tensile strength | Mpa | 21 |
| Elongation at break | ％ | 55 | ||
| The TD direction | Tensile strength | Mpa | 16 | |
| Elongation at break | ％ | 76 | ||
Embodiment 11:
Press column weight amount % and take by weighing each component:
PLA 71.0
PPC 12.0
PHB 3.0
Polynite (MMT) 1.0
PEG 4.0
Epoxy soybean oil 3.1
Triphenyl phosphite 0.5
Zinic stearas 0.5
Two inferior Bian Ji sorbyl alcohols 0.05
Benzophenone 0.1
Oxalic acid 0.1
HALS 0.1
Glyceryl monolaurate 0.5
Fine silica powder 1.0
Transparent violet 0.05
Complete processing is seen embodiment 1.
The performance that obtains goods sees Table 11:
Table 11:
| Hand tear test is estimated | 10 stages were estimated | 5 | ||
| Sensory evaluation | Difference | |||
| Tear strength (MD direction) | g/20μm | 46 | ||
| Sensory evaluation | × | |||
| Stretching experiment | The MD direction | Tensile strength | Mpa | 23 |
| Elongation at break | ％ | 66 | ||
| The TD direction | Tensile strength | Mpa | 17 | |
| Elongation at break | ％ | 86 | ||
Embodiment 12:
Press column weight amount % and take by weighing each component:
PLA 65.0
PPC 19.0
PHB 5.0
Polynite (MMT) 1.0
PEG 4.0
Epoxy soybean oil 3.1
Triphenyl phosphite 0.5
Erucicamide 0.5
Terephthalic acid 0.05
Benzophenone 0.1
Oxalic acid 0.1
HALS 0.1
Glyceryl monolaurate 0.5
Fine silica powder 1.0
Phthalein blue or green blue 0.05
Complete processing is seen embodiment 1.
The performance that obtains goods sees Table 12:
Table 12:
| Hand tear test is estimated | 10 stages were estimated | 9 | ||
| Sensory evaluation | Good | |||
| Tear strength (MD direction) | g/20μm | 105 | ||
| Sensory evaluation | ○ | |||
| Stretching experiment | The MD direction | Tensile strength | Mpa | 27 |
| Elongation at break | ％ | 157 | ||
| The TD direction | Tensile strength | Mpa | 19 | |
| Elongation at break | ％ | 122 | ||
Claims (16)
1, a kind of poly lactic acid type composite material of ternary built completely biological degradation is characterized in that % meter each component is by weight:
Poly(lactic acid) (PLA) 45.0-80.0
Polypropylene carbonate (PPC) 4.0-40.0
Poly 3-hydroxy butyrate (PHB) 4.0-40.0
Softening agent 3.0-15.0
Heat-resisting stabilizing agent 1.0-6.5
Oxidation inhibitor 0.5-2.0
Nucleator 0.05-1.0
Lubricant 0.35-1.0
Opening agent 0.1-1.0
Photolysis agent 0.1-1.0
Biodegradation agent promotor 0.1-1.0
Light (ultraviolet ray) stablizer 0.1-1.0
Antistatic agent 0.5-1.0
Weighting agent 1.0-15.0
Tinting material 0.05-3.014.
2, a kind of poly lactic acid type composite material of ternary built completely biological degradation as claimed in claim 1 is characterized in that:
Described softening agent is: dioctyl phthalate (DOP), diethyl phthalate, dimixo-octyl phthalate, tributyl citrate, acetyl tributyl citrate three (2-ethylhexyl), hexanoyl tributyl citrate, hexanodioic acid two (2-ethylhexyl), polyoxyethylene glycol, polypropylene glycol oxalic acid ester, epoxy soybean wet goods epoxy resin softening agent, can select a kind of or two or more, if select the two or more gross weight % that should keep constant;
Heat-resisting stabilizing agent is: polynite, silicon-dioxide, kaolin, zinc oxide, magnesium oxide, calcium stearate, maleic dibutyl tin, can select a kind of or two or more, if select the two or more gross weight % that should keep constant;
Oxidation inhibitor is: any one of dihydroxyphenyl propane, triphenyl phosphite, phosphorous acid ethyl ester or phosphorous acid dihydroxyphenyl propane ester;
Lubricant is: any one of stearylamide, amine hydroxybenzene, erucicamide, Zinc Stearate, ethylenebisstearamide, alkylidene group two fatty amides;
Nucleator is: dibenzylidene sorbitol, terephthalic acid, aluminium hydroxide, aluminum oxide, aluminium carbonate, talcum powder;
Photolysis agent is: any one of benzene idol alkyl oxide, benzophenone, phenyl methyl ketone, anatase-type titanium oxide;
Photolysis promotor is: any one of citric acid, tartrate, oxysuccinic acid, oxalic acid, propanedioic acid, Succinic anhydried, activated coco nut charcoal;
Weighting agent is: lime carbonate, talcum, mica, fine silica powder, white carbon black, asbestos, clay, glass fibre, xylon, cotton fibriia, kaolinic any one;
Uv-absorbing agent is: 1,2,2, and 4-four (4-ketonic oxygen base-2,2,6,6-four-pipecoline)-amine (HALS), 2 benzotriazole-ethyl-4,6-DI-tert-butylphenol compounds, benzoic ether are any one of uv-absorbing agent;
Static inhibitor is: any one of aliphatic amide, dodecyl sodium sulfonate ester, glyceryl monolaurate, GLYCERYL DILAURATE;
Tinting material is: any one of carbon black, titanium white, pthalocyanine blue, transparent violet.
The poly lactic acid type composite material of 3 a kind of ternary built completely biological degradations as claimed in claim 1 or 2 is characterized in that:
PLA 75.0
PPC 5.0
PHB 8.0
Polynite (MMT) 2.0
PEG 5.0
Epoxy soybean oil 1.9
Triphenyl phosphite 0.7
Zinic stearas 0.5
Sorbitol dibenzal 0.05
Benzophenone 0.1
Oxalic acid 0.1
HALS 0.1
Glyceryl monolaurate 0.5
Fine silica powder 1.0
Phthalein blue or green blue 0.05.
4, the poly lactic acid type composite material of claim 1 or 2 described a kind of ternary built completely biological degradations is characterized in that % meter each component is by weight:
PLA 80.0
PPC 4.0
PHB 5.0
Polynite (MMT) 1.0
Tributyl acetylcitrate 5.0
Epoxy soybean oil 1.9
Triphenyl phosphite 0.7
Stearylamide 0.5
Two inferior Bian Ji sorbyl alcohols 0.05
Phenyl methyl ketone 0.1
Tartrate 0.1
HALS 0.1
Glyceryl monolaurate 0.5
Fine silica powder 1.0
Transparent violet 0.05.
5, the poly lactic acid type composite material of claim 1 or 2 described ternary built completely biological degradations is characterized in that % meter each component is by weight:
PLA 45.0
PPC 38.0
PHB 6.0
Polynite (MMT) 1.0
PEG 3.0
Tributyl acetylcitrate 4.2
Triphenyl phosphite 0.5
Erucicamide 0.4
Two inferior Bian Ji sorbyl alcohols 0.05
Benzophenone 0.1
Oxalic acid 0.1
HALS 0.1
Glyceryl monolaurate 0.5
Fine silica powder 1.0
Phthalein blue or green blue 0.05.
6, the poly lactic acid type composite material of claim 1 or 2 described a kind of ternary built completely biological degradations is characterized in that % meter each component is by weight:
PLA 45.0
PPC 6.0
PHB 38.0
Polynite (MMT) 1.0
PEG 3.0
Tributyl acetylcitrate 4.2
Triphenyl phosphite 0.5
Erucicamide 0.4
Two inferior Bian Ji sorbyl alcohols 0.05
Benzophenone 0.1
Oxalic acid 0.1
HALS 0.1
Glyceryl monolaurate 0.5
Fine silica powder 1.0
Phthalein blue or green blue 0.05.
7, the poly lactic acid type composite material of a kind of ternary built completely biological degradation as claimed in claim 1 or 2 is characterized in that % meter each component is by weight:
PLA 45.0
PPC 22.0
PHB 22.0
Polynite (MMT) 1.0
PEG 3.0
Tributyl acetylcitrate 4.2
Triphenyl phosphite 0.5
Erucicamide 0.4
Two inferior Bian Ji sorbyl alcohols 0.05
Benzophenone 0.1
Oxalic acid 0.1
HALS 0.1
Glyceryl monolaurate 0.5
Fine silica powder 1.0
Phthalein blue or green blue 0.05
8, the poly lactic acid type composite material of claim 1 or 2 described a kind of ternary built completely biological degradations is characterized in that % meter each component is by weight:
PLA 80.0
PPC 5.0
PHB 4.0
Polynite (MMT) 1.0
PEG 3.0
Tributyl acetylcitrate 4.2
Triphenyl phosphite 0.5
Erucicamide 0.4
Two inferior Bian Ji sorbyl alcohols 0.05
Benzophenone 0.1
Oxalic acid 0.1
HALS 0.1
Glyceryl monolaurate 0.5
Fine silica powder 1.0
Phthalein blue or green blue 0.05.
9, the poly lactic acid type composite material of a kind of ternary built completely biological degradation as claimed in claim 1 or 2 is characterized in that % meter each component is by weight:
PLA 55.0
PPC 15.0
PHB 5.0
Polynite (MMT) 2.0
PEG 10.0
Epoxy soybean oil 5.0
Triphenyl phosphite 0.5
Zinic stearas 1.0
Two inferior Bian Ji sorbyl alcohols 1.0
Benzophenone 1.0
Oxalic acid 1.0
HALS 1.0
Glyceryl monolaurate 1.0
Fine silica powder 1.0
Phthalein blue or green blue 0.5.
10, profit requires the poly lactic acid type composite material of 1 or 2 described a kind of ternary built completely biological degradations, it is characterized in that % meter each component is by weight:
PLA 55.0
PPC 15.0
PHB 5.0
Polynite (MMT) 2.0
Tributyl acetylcitrate 9.0
Acetyl triethyl citrate 6.0
Triphenyl phosphite 0.5
Zinic stearas 1.0
Two inferior Bian Ji sorbyl alcohols 1.0
Benzophenone 1.0
Oxalic acid 1.0
HALS 1.0
Glyceryl monolaurate 1.0
Fine silica powder 1.0
Phthalein blue or green blue 0.5.
11, the poly lactic acid type composite material of claim 1 or 2 described a kind of ternary built completely biological degradations is characterized in that % meter each component is by weight:
PLA 65.0
PPC 19.0
PHB 5.0
Polynite (MMT) 1.0
PEG 4.0
Epoxy soybean oil 3.1
Triphenyl phosphite 0.5
Erucicamide 0.5
Terephthalic acid 0.05
Benzophenone 0.1
Oxalic acid 0.1
HALS 0.1
Glyceryl monolaurate 0.5
Fine silica powder 1.0
Phthalein blue or green blue 0.05.
12, the poly lactic acid type composite material of claim 1 or 2 described a kind of ternary built completely biological degradations is characterized in that % meter each component is by weight:
PLA 65.0
PPC 19.0
PHB 5.0
Polynite (MMT) 1.0
Tributyl acetylcitrate 5.0
Acetyl triethyl citrate 2.1
Triphenyl phosphite 0.5
Erucicamide 0.5
Terephthalic acid 0.05
Benzophenone 0.1
Oxalic acid 0.1
HALS 0.1
Glyceryl monolaurate 0.5
Fine silica powder 1.0
Phthalein blue or green blue 0.05.
13, the poly lactic acid type composite material of claim 1 or 2 described a kind of ternary built completely biological degradations is characterized in that % meter each component is by weight:
PLA 80.0
PPC 6.0
PHB 3.0
Polynite (MMT) 1.0
PEG 4.0
Epoxy soybean oil 3.1
Triphenyl phosphite 0.5
Zinic stearas 0.5
Two inferior Bian Ji sorbyl alcohols 0.05
Benzophenone 0.1
Oxalic acid 0.1
HALS 0.1
Glyceryl monolaurate 0.5
Fine silica powder 1.0
Phthalein blue or green blue 0.05.
14, the poly lactic acid type composite material of claim 1 or 2 described a kind of ternary built completely biological degradations is characterized in that % meter each component is by weight:
PLA 71.0
PPC 12.0
PHB 3.0
Polynite (MMT) 1.0
PEG 4.0
Epoxy soybean oil 3.1
Triphenyl phosphite 0.5
Zinic stearas 0.5
Two inferior Bian Ji sorbyl alcohols 0.05
Benzophenone 0.1
Oxalic acid 0.1
HALS 0.1
Glyceryl monolaurate 0.5
Fine silica powder 1.0
Transparent violet 0.05.
15, as the purposes of the poly lactic acid type composite material of the described ternary built completely biological degradation of any one claim of claim 1, it is characterized in that this matrix material carries out blow molding as masterbatch can make film article.
16, the poly lactic acid type composite material that utilizes ternary built completely biological degradation as claimed in claim 15 is blow molded into and makes film article, it is characterized in that the film article thickness that utilizes this matrix material to make is 10 μ m-50 μ m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100172066A CN100406518C (en) | 2005-10-21 | 2005-10-21 | Ternary built poly lactic acid type composite material and its use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100172066A CN100406518C (en) | 2005-10-21 | 2005-10-21 | Ternary built poly lactic acid type composite material and its use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1749316A true CN1749316A (en) | 2006-03-22 |
| CN100406518C CN100406518C (en) | 2008-07-30 |
Family
ID=36604981
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100172066A Expired - Fee Related CN100406518C (en) | 2005-10-21 | 2005-10-21 | Ternary built poly lactic acid type composite material and its use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100406518C (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101557708A (en) * | 2006-12-11 | 2009-10-14 | 3M创新有限公司 | Biocompatible antimicrobial compositions |
| WO2011079492A1 (en) * | 2009-12-28 | 2011-07-07 | 天津国韵生物材料有限公司 | Fully biodegradable multi-component film material and preparing method thereof |
| CN102153838A (en) * | 2011-03-09 | 2011-08-17 | 江苏兴业塑化股份有限公司 | Biodegradable polycarbonate butylene terephthalate composite material and preparation method of biodegradable polycarbonate butylene terephthalate composite material |
| CN101392069B (en) * | 2007-09-19 | 2012-01-18 | 东丽纤维研究所（中国）有限公司 | Additive agent mixture and preparation method |
| CN102341455A (en) * | 2009-03-03 | 2012-02-01 | 巴斯夫欧洲公司 | Method for producing polymer mixtures |
| CN102391635A (en) * | 2011-08-26 | 2012-03-28 | 南阳中聚天冠低碳科技有限公司 | Biological degradation foamed plastic and preparation method thereof |
| CN102796361A (en) * | 2012-08-10 | 2012-11-28 | 中国科学院长春应用化学研究所 | Biodegradable carbon dioxide-epoxypropane copolymer foamed plastic and preparation method thereof |
| CN102892820A (en) * | 2009-12-28 | 2013-01-23 | 3M创新有限公司 | Plasticized polylactide |
| CN103788601A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | Polylactic acid resin suitable for rapid injection moulding and preparation method thereof |
| CN104231582A (en) * | 2014-10-17 | 2014-12-24 | 中国科学院长春应用化学研究所 | Polylactic acid base composite material and preparation method thereof |
| CN106046729A (en) * | 2016-08-22 | 2016-10-26 | 广西南宁智翠科技咨询有限公司 | Novel environment-friendly plastic |
| US9487893B2 (en) | 2009-03-31 | 2016-11-08 | 3M Innovative Properties Company | Dimensionally stable nonwoven fibrous webs and methods of making and using the same |
| CN106336636A (en) * | 2016-10-14 | 2017-01-18 | 西南大学 | Preparation method of polylactic acid/epoxy soybean oil resin alloy and product |
| CN106467657A (en) * | 2016-10-20 | 2017-03-01 | 上海弘睿化工产品有限公司 | High heat-resisting PLA/PHA composite and preparation method thereof |
| CN107459794A (en) * | 2017-09-15 | 2017-12-12 | 贵州通汇塑料科技有限公司 | A kind of degradation plastic particle |
| US10138576B2 (en) | 2008-06-12 | 2018-11-27 | 3M Innovative Properties Company | Biocompatible hydrophilic compositions |
| CN111484650A (en) * | 2020-04-27 | 2020-08-04 | 包头稀土研究院 | Composite nucleating agent and composition for polylactic acid and preparation method of composite nucleating agent |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4323023B2 (en) * | 1999-09-22 | 2009-09-02 | リケンテクノス株式会社 | Resin composition and biodegradable draining bag |
-
2005
- 2005-10-21 CN CNB2005100172066A patent/CN100406518C/en not_active Expired - Fee Related
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101557708A (en) * | 2006-12-11 | 2009-10-14 | 3M创新有限公司 | Biocompatible antimicrobial compositions |
| CN101392069B (en) * | 2007-09-19 | 2012-01-18 | 东丽纤维研究所（中国）有限公司 | Additive agent mixture and preparation method |
| US10138576B2 (en) | 2008-06-12 | 2018-11-27 | 3M Innovative Properties Company | Biocompatible hydrophilic compositions |
| CN102341455A (en) * | 2009-03-03 | 2012-02-01 | 巴斯夫欧洲公司 | Method for producing polymer mixtures |
| US9487893B2 (en) | 2009-03-31 | 2016-11-08 | 3M Innovative Properties Company | Dimensionally stable nonwoven fibrous webs and methods of making and using the same |
| WO2011079492A1 (en) * | 2009-12-28 | 2011-07-07 | 天津国韵生物材料有限公司 | Fully biodegradable multi-component film material and preparing method thereof |
| CN102892820A (en) * | 2009-12-28 | 2013-01-23 | 3M创新有限公司 | Plasticized polylactide |
| CN102153838A (en) * | 2011-03-09 | 2011-08-17 | 江苏兴业塑化股份有限公司 | Biodegradable polycarbonate butylene terephthalate composite material and preparation method of biodegradable polycarbonate butylene terephthalate composite material |
| CN102153838B (en) * | 2011-03-09 | 2012-04-25 | 江苏兴业塑化股份有限公司 | Biodegradable polycarbonate butylene terephthalate composite material and preparation method of biodegradable polycarbonate butylene terephthalate composite material |
| CN102391635A (en) * | 2011-08-26 | 2012-03-28 | 南阳中聚天冠低碳科技有限公司 | Biological degradation foamed plastic and preparation method thereof |
| CN102796361A (en) * | 2012-08-10 | 2012-11-28 | 中国科学院长春应用化学研究所 | Biodegradable carbon dioxide-epoxypropane copolymer foamed plastic and preparation method thereof |
| CN103788601A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | Polylactic acid resin suitable for rapid injection moulding and preparation method thereof |
| CN104231582A (en) * | 2014-10-17 | 2014-12-24 | 中国科学院长春应用化学研究所 | Polylactic acid base composite material and preparation method thereof |
| CN104231582B (en) * | 2014-10-17 | 2016-06-01 | 中国科学院长春应用化学研究所 | A kind of polylactic acid-base composite material and its preparation method |
| CN106046729A (en) * | 2016-08-22 | 2016-10-26 | 广西南宁智翠科技咨询有限公司 | Novel environment-friendly plastic |
| CN106336636A (en) * | 2016-10-14 | 2017-01-18 | 西南大学 | Preparation method of polylactic acid/epoxy soybean oil resin alloy and product |
| CN106336636B (en) * | 2016-10-14 | 2018-06-29 | 西南大学 | The preparation method and product of a kind of polylactic acid/epoxy soybean oil resin alloy |
| CN106467657A (en) * | 2016-10-20 | 2017-03-01 | 上海弘睿化工产品有限公司 | High heat-resisting PLA/PHA composite and preparation method thereof |
| CN107459794A (en) * | 2017-09-15 | 2017-12-12 | 贵州通汇塑料科技有限公司 | A kind of degradation plastic particle |
| CN111484650A (en) * | 2020-04-27 | 2020-08-04 | 包头稀土研究院 | Composite nucleating agent and composition for polylactic acid and preparation method of composite nucleating agent |
| CN111484650B (en) * | 2020-04-27 | 2021-09-14 | 包头稀土研究院 | Composite nucleating agent and composition for polylactic acid and preparation method of composite nucleating agent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100406518C (en) | 2008-07-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1749316A (en) | A kind of ternary built poly lactic acid type composite material and application thereof | |
| CN1749318A (en) | The poly lactic acid type composite material preparation method of ternary built completely biological degradation | |
| CN1749315A (en) | Quaternary built completely biological degradation polylactic acid type composite material and application | |
| CN1290817C (en) | Ester compound, plasticizer for biodegradable aliphatic polyester resin, and biodegradable resin composition | |
| CN1749317A (en) | Preparation technology's method of quaternary built completely biological degradation polylactic acid type composite material | |
| CN1123593C (en) | Process for increasing melt strength of polypropylene | |
| CN1264899C (en) | Filler concentrates for use in thermoplastic mateirals | |
| CN1119364C (en) | Propylene ethylene copolymer compositions and process for the production thereof | |
| CN101040003A (en) | Flowable thermoplastics with halogen flame retardancy system | |
| CN1471546A (en) | Block copolymer, composition thereof, and film made thereof | |
| CN1993423A (en) | Flowable polyester molding compounds comprising ASA/ABS and SAN | |
| CN1018458B (en) | The preparation method of the linear low density polyethylene of graft modification | |
| CN1662603A (en) | Polylactic acid base polymer composition molding thereof and film | |
| CN1906248A (en) | Matte film | |
| CN1227853A (en) | Novel polyester pellets and process for preparing the same | |
| CN1239490A (en) | Polyester resin compsn. and bottle produced from resin compsn. | |
| CN1649951A (en) | Agent for suppressing transfer of odor and taste originating from a diacetal, a diacetal composition comprising the agent for suppressing transfer of odor and taste, a polyolefin nucleating agent comp | |
| CN1333714A (en) | Method for producing foamed-mold product of aromatic polyester based resin | |
| CN1159462A (en) | Legradable thermoplastics from lactides | |
| CN1033517C (en) | Degradable thermoplastics from lactides bio-degradable lactides plastics | |
| CN1424338A (en) | Alkyd resin and molded products | |
| CN1922264A (en) | Vinyl chloride resin composition | |
| CN1028762C (en) | Ethylene/ pentene-1 copolymer composition | |
| CN1946801A (en) | Thickener for thermoplastic polyester resin and thermoplastic polyester resin composition wherein such thickener is blended | |
| CN1491986A (en) | Completely biological degradable fatty polyester composite material and its preparing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Xiamen Xiehe Environmental Protection Technology Co., Ltd. Assignor: Changchun Institue of Applied Chemistry, Chinese Academy of Sciences Contract record no.: 2011220000050 Denomination of invention: Ternary built poly lactic acid type composite material and its use Granted publication date: 20080730 License type: Exclusive License Open date: 20060322 Record date: 20110926 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080730 Termination date: 20151021 |
|
| EXPY | Termination of patent right or utility model |