CN101475734B - Completely biodegradable polyhydroxyalkanote / polycarbonate blending alloy and preparation thereof - Google Patents
Completely biodegradable polyhydroxyalkanote / polycarbonate blending alloy and preparation thereof Download PDFInfo
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- CN101475734B CN101475734B CN2008102181646A CN200810218164A CN101475734B CN 101475734 B CN101475734 B CN 101475734B CN 2008102181646 A CN2008102181646 A CN 2008102181646A CN 200810218164 A CN200810218164 A CN 200810218164A CN 101475734 B CN101475734 B CN 101475734B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention discloses a full biodegradable N-poly-ester/polycarbonate blending alloy, which is characterized in that the blending alloy is prepared from polyhydroxy alkyl esters, polycarbonate, compatibilizer and auxiliaries. The blending alloy is added with the compatiblizer to enhance the compatibility of the polyhydroxy alkyl esters and the polycarbonate so as to make full use of respective advantages, and the physical property of the blending alloy is promoted remarkably. The invention also discloses a method for preparing the blending alloy; and the method is simple, efficient and can be applied in large-scale industrial production.
Description
[technical field]
The present invention relates to the material field, more particularly, relate to PHA/polycarbonate blending alloy of a kind of fully biodegradable and preparation method thereof.
[background technology]
The petroleum-based energy that the consumption of conventional plastic industry is a large amount of and " white pollution " that bring have been subjected to increasing concern, since eighties of last century 60, the seventies, people have begun the research and development to biodegradable plastic, there has been multiple biodegradable material (Biodegradable material) to come out at present, after the biodegradable material biological degradation, become water and carbonic acid gas, can not produce harm environment.
PHA (PHAs) be a class by microorganism synthetic macromolecule polyester, its molecular weight generally several ten thousand between millions of, extensively is present in the natural multiple microbe.Its some physical properties and traditional petroleum-based plastics polypropylene-base are seemingly, PHA is synthetic by the reproducible energy, it is a kind of thermoplastics of fully biodegradable, can be in soil, seawater complete biodegradable, have broad prospects in fields such as agricultural, medicine, food product pack, but most PHAs fragility are big, shock strength is low, thereby limited being extensive use of of it.
Polycarbonate (PPC) is a kind of synthetic macromolecule, and one of its main synthesis material is CO
2, in environment, be easy to degraded and hydrolysis, have the toughner that good toughness, transparency and good processing properties can be used as above-mentioned PHA.
Publication number is that patent of invention that CN1226348C, name are called the preparation method of carbon dioxide-epoxy propane copolymer and poly-3-hydroxy alkanoic acid ester blend has utilized PHBV (poly 3-hydroxy butyrate-3-hydroxyl valerate) to the enhancement of PPC and the PPC toughening effect to PHBV, but the consistency of PPC and PHBV is very poor, the poor-performing of blend.And the amorphism characteristics of publication number to be publication that CN1436812A, name are called the mixture of a kind of PHA and polypropylene carbonate utilize polypropylene carbonate, cooperate softening agent, improve the toughness of PHA, polypropylene carbonate is used as toughner, but still there is the very poor problem of consistency between PHA and the polypropylene carbonate, can not give full play to the advantage of each component, cause physicals and processing characteristics all not ideal enough.
Therefore, improve the consistency between polycarbonate and the PHA, thereby the intermingling material that obtains more satisfactory over-all properties is present urgent problem.
[summary of the invention]
In order to overcome above-mentioned technological deficiency, the invention discloses a kind of novel completely biodegradable polyhydroxyalkanote ester/polycarbonate blending alloy, this blend alloy has excellent especially processing characteristics and good physicals.
The invention also discloses the preparation method of above-mentioned blend alloy.
The technical scheme of completely biodegradable polyhydroxyalkanote ester/polycarbonate blending alloy of the present invention is as described below:
A kind of completely biodegradable polyhydroxyalkanote ester/polycarbonate blending alloy mainly is prepared from by PHA, polycarbonate, compatilizer and auxiliary agent.
By weight, the poly (hydroxyalkanoate) ester content is 53%-90%, and polycarbonate content is 5%-40%, and compatilizer is 1%-5%, and auxiliary agent is 0.1%-2%.
Described compatilizer is the polyhydroxy alkanoates graft polymer that is prepared from by PHA, grafted monomer, initiator.
Further, each the composition weight umber for preparing described compatilizer is, PHA is that 1.0 parts, grafted monomer 0.01-0.1 part, initiator are 0.01-0.1 part.
Wherein, described grafted monomer is that one or more are selected from maleic anhydride and ester, fumaric acid anhydride and ester thereof, vinylbenzene and derivative thereof, vinylformic acid and ester thereof, methacrylic acid and ester fat thereof, propylene is fine and derivative, long-chain unsaturated carboxylic acid and ester thereof are formed grafted monomer group.
Described initiator is one or more mixtures in peroxide initiator, azo-initiator, the redox class initiator.
Described initiator is dicumyl peroxide or benzoyl peroxide or the two mixture.
Described auxiliary agent is one or more mixtures in oxidation inhibitor, lubricant, stablizer, the nucleator.
Preferably, the composite assistant formed by oxidation inhibitor, stablizer of described auxiliary agent or the composite assistant of forming by oxidation inhibitor, stablizer, lubricant.
Described PHA is one or more mixtures among PHB, P3HB4HB, PHBV, the PHBH.
Wherein said P3HB4HB, PHBV, PHBH are meant respectively poly--3-butyric ester-4 hydroxybutyric acid ester, polyhydroxybutyrate valerate, poly--the 3-butyric ester-altogether-the 3-hydroxycaproic ester.
The preparation method of completely biodegradable polyhydroxyalkanote ester/polycarbonate blending alloy comprises the steps,
(1) preparation compatilizer: PHA, grafted monomer and initiator are mixed in proportion, then with the reaction of twin screw extruder melting mixing, extruding pelletization;
(2) preparation blend alloy: compatilizer and PHA, polycarbonate, the auxiliary agent of preparation in the step (1) are mixed in proportion, melt extrude granulation with twin screw then.
Extrusion temperature is 110-160 ℃ in the described step (1), and extrusion temperature is 100-160 ℃ in the step (2).
Beneficial effect of the present invention is: (1) has added compatilizer in preparation blend alloy of the present invention, strengthened the consistency between PHA and the polycarbonate, and can make full use of separately advantage, prepared blend alloy is compared with the common mixture that is formed by PHA and polycarbonate that does not add compatilizer, and its physicals significantly is improved; (2) compatilizer that adds among the present invention has also been accelerated the biodegradability of blend alloy, has also improved the consistency between auxiliary agent and PHA, the polycarbonate simultaneously, has given full play to the function of auxiliary agent, has bigger practical value; (3) preparation method of blend alloy disclosed by the invention, simple, efficient, be fit to a large amount of suitability for industrialized production.
[embodiment]
To describe technical scheme of the present invention and beneficial effect in detail by some embodiment and Comparative Examples below.
Embodiment 1:
At first prepare compatilizer: with 100g poly 3-hydroxy butyrate (PHB), 2.0g maleic anhydride and the blend of 1.0g dicumyl peroxide, use the twin screw extruder extruding pelletization, extrusion temperature is 110 ℃, and the compatilizer that obtains is poly 3-hydroxy butyrate graftomer (PHB-g-MAH).
Prepare completely biodegradable polyhydroxyalkanote ester/polycarbonate blending alloy then: get 90%PHB, 3.5%PHB-g-MAH, 5%PPC, 0.2% antioxidant four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, 0.3% lubricant PE wax (polyethylene wax), 1% stearate stablizer mix with high-speed mixer, use the twin screw extruder extruding pelletization then, extrusion temperature is 130 ℃, obtains the PHB/PPC blend alloy.
PHB/PPC blend alloy performance is tested, and its tensile strength is 24.64MPa, and elongation at break is 60.93%.
Comparative Examples 1:
Do not add compatilizer in this Comparative Examples 1, PHB content is 93.5%, and all the other components and preparation method are identical with embodiment 1.Product performance to preparation are tested, and its tensile strength is 16.80MPa, and elongation at break is 50.40%.
Embodiment 2:
At first prepare compatilizer: with 100g poly 3-hydroxy butyrate-4 hydroxybutyric acid ester (P3HB4HB, comonomer 4HB molar content is 10%) and the 2.8g acrylic amine, 2.0g dibenzoyl peroxide blend, use the twin screw extruder extruding pelletization, extrusion temperature is 140 ℃, and the compatilizer that obtains is poly 3-hydroxy butyrate-4 hydroxybutyric acid ester graftomer (P3HB4HB-g-GMA).
Prepare completely biodegradable polyhydroxyalkanote ester/polycarbonate blending alloy then: get 85%P3HB4HB (the 4HB molar content is 10%), 4%P3HB4HB-g-GMA, 10%PPC, 0.2% antioxidant 2-tertiary butyl-6-(3-tertiary butyl-2-hydroxyl-5 methyl-benzyl)-4 aminomethyl phenyl acrylate, 0.3% lubricant stearic acid, 0.5% stearate stablizer and mix with high-speed mixer, use the twin screw extruder extruding pelletization then, extrusion temperature is 120 ℃, obtains the P3HB4HB/PPC blend alloy.
P3HB4HB/PPC blend alloy performance is tested, and its tensile strength is 24.51MPa, and elongation at break is 200%.
Comparative Examples 2:
Do not add compatilizer in this Comparative Examples 2, P3HB4HB (the 4HB molar content is 10%) content is 89%, and all the other components and preparation method are identical with embodiment 2.Product performance to preparation are tested, and its tensile strength is 16.70MPa, and elongation at break is 69%.
Embodiment 3:
At first be the preparation of compatilizer: with the poly-3-hydroxybutyric acid valerate (PHBV of 100g, comonomer 3-hydroxypentanoic acid (HV) molar content is 5%) and the 4.0g acrylic amine, 5.0g dibenzoyl peroxide blend, use the twin screw extruder extruding pelletization, extrusion temperature is 150 ℃, and the compatilizer that obtains is poly-3-hydroxybutyric acid valerate graftomer (PHBV-g-GMA).
Prepare completely biodegradable polyhydroxyalkanote ester/polycarbonate blending alloy then: get 75%PHBV (the HV molar content is 5%), 2%PHBV-g-GMA, 22%PPC, 0.5% antioxidant 2-tertiary butyl-6-(3-tertiary butyl-2-hydroxyl-5 methyl-benzyl)-4 aminomethyl phenyl acrylate, 0.5% lubricant stearic acid and mix with high-speed mixer, use the twin screw extruder extruding pelletization then, extrusion temperature is 150 ℃, obtains the PHBV/PPC blend alloy.
PHBV/PPC blend alloy performance is tested, and its tensile strength is 32MPa, and elongation at break is 250%.
Comparative Examples 3:
Do not add compatilizer in this Comparative Examples 3, PHBV (the HV molar content is 5%) content is 89%, and all the other components and preparation method are identical with embodiment 3.Product performance to preparation are tested, and its tensile strength is 22MPa, and elongation at break is 70%.
Embodiment 4:
At first be the preparation of compatilizer: with the poly-3-hydroxybutyric acid of 100g-3-hydroxycaproic ester (PHBH, comonomer 3-hydroxycaproic acid (HH) molar content is 7%) and the 8g acrylic amine, the blend of 6g dibenzoyl peroxide, use the twin screw extruder extruding pelletization, extrusion temperature is 150 ℃, and the compatilizer that obtains is poly-3-hydroxybutyric acid-3-hydroxycaproic ester graftomer (PHBH-g-GMA).
Prepare completely biodegradable polyhydroxyalkanote ester/polycarbonate blending alloy then: get 64%PHBH (the HH molar content is 7%), 5%PHBH-g-GMA, 30%PPC, 0.5% antioxidant 2-tertiary butyl-6-(3-tertiary butyl-2-hydroxyl-5 methyl-benzyl)-4 aminomethyl phenyl acrylate, 0.5% stearate stablizer and mix with high-speed mixer, use the twin screw extruder extruding pelletization then, extrusion temperature is 160 ℃, obtains the PHBH/PPC blend alloy.
PHBH/PPC blend alloy performance is tested, and its tensile strength is 25.26MPa, and elongation at break is 123.53%.
Comparative Examples 4:
Do not add compatilizer in this Comparative Examples 4, PHBH (the HH molar content is 7%) content is 69%, and all the other components and preparation method are identical with embodiment 4.Product performance to preparation are tested, and its tensile strength is 15MPa, and elongation at break is for being 40%.
Embodiment 5:
The compatilizer of present embodiment is got the compatilizer of preparation among the embodiment 1.
Prepare completely biodegradable polyhydroxyalkanote ester/polycarbonate blending alloy then: get 55%P3HB4HB (the 4HB molar content is 17%), 3%PHB-g-MAH, 40%PPC, 2% antioxidant 2-tertiary butyl-6-(3-tertiary butyl-2-hydroxyl-5 methyl-benzyl)-4 aminomethyl phenyl acrylate and mix with high-speed mixer, use the twin screw extruder extruding pelletization then, extrusion temperature is 110 ℃, obtains the P3HB4HB/PPC blend alloy.
P3HB4HB/PPC blend alloy performance is tested, and its tensile strength is 25.35MPa, and elongation at break is 134.57%.
Comparative Examples 5:
Do not add compatilizer in this Comparative Examples 5, P3HB4HB (the 4HB molar content is 17%) content is 58%, and all the other components and preparation method are identical with embodiment 5.Product performance to preparation are tested, and its tensile strength is 17.8MPa, and elongation at break is 50.6%.
Embodiment 6:
The compatilizer of present embodiment is got the compatilizer of preparation among the embodiment 4.
Prepare completely biodegradable polyhydroxyalkanote ester/polycarbonate blending alloy then: get 75%P3HB4HB (the 4HB molar content is 9%), 2%PHBH-g-GMA, 22%PPC, 0.5% antioxidant 2-tertiary butyl-6-(3-tertiary butyl-2-hydroxyl-5 methyl-benzyl)-4 aminomethyl phenyl acrylate, 0.5% nucleator titanium dioxide and mix with high-speed mixer, use the twin screw extruder extruding pelletization then, extrusion temperature is 150 ℃, obtains the P3HB4HB/PPC blend alloy.
P3HB4HB/PPC blend alloy performance is tested, and its tensile strength is 26.45MPa, and elongation at break is 153%.
Comparative Examples 6:
Do not add compatilizer in this Comparative Examples 6, P3HB4HB (the 4HB molar content is 9%) content is 77%, and all the other components and preparation method are identical with embodiment 6.Product performance to preparation are tested, and its tensile strength is 15.6MPa, and elongation at break is 65%.
By above embodiment 1-6 and Comparative Examples 1-6 as can be seen, its tensile strength of blend alloy and the elongation at break that have added compatilizer all have bigger lifting.
To PHA/polycarbonate blending alloy biodegrade test of above each embodiment preparation, all can be in seawater and soil in half a year complete biodegradable, be unusual ideal biological plastics.
More than the PHA/polycarbonate blending alloy of each embodiment preparation all possess excellent physicals and processing characteristics; can be widely used in products such as extrusion board, sheet material, preparation film and injection moulding; on non-returnable container material, refuse bag, shopping bag, can extensively utilize especially especially, have great social value for the environment protection aspect.
Simultaneously; also need to prove; the present invention prepares the used PHA of compatilizer and the preparation PHA raw material that blend alloy utilized can be with a kind of PHA; as described in embodiment 1-4; it can also be PHA inequality; as described in embodiment 5-6, which kind of situation no matter is all within protection scope of the present invention.
In sum; although the specific embodiment of the present invention is described in detail the present invention; but persons skilled in the art should be understood that; the foregoing description only is the description to the preferred embodiments of the present invention; but not limiting the scope of the invention; persons skilled in the art are in the disclosed technical scope of the present invention, and the variation that can expect easily is all within protection scope of the present invention.
Claims (9)
1. completely biodegradable polyhydroxyalkanote ester/polycarbonate blending alloy, described blend alloy is by PHA, polycarbonate, compatilizer and auxiliary agent are prepared from, described compatilizer is by PHA, grafted monomer, the polyhydroxy alkanoates graft polymer that initiator is prepared from, it is characterized in that: content meter by weight, PHA is 53%-90%, polycarbonate is 5%-40%, compatilizer is 1%-5%, auxiliary agent is 0.1%-2%, and described grafted monomer is to be selected from fumaric acid anhydride and ester thereof, vinylbenzene and derivative thereof, vinylformic acid and ester thereof, methacrylic acid and ester thereof, vinyl cyanide and derivative thereof, one or more mixtures in long-chain unsaturated carboxylic acid and the ester thereof.
2. completely biodegradable polyhydroxyalkanote ester/polycarbonate blending alloy as claimed in claim 1, it is characterized in that: each the composition weight umber for preparing described compatilizer is, PHA is that 1.0 parts, grafted monomer 0.01-0.1 part, initiator are 0.01-0.1 part.
3. completely biodegradable polyhydroxyalkanote ester/polycarbonate blending alloy as claimed in claim 1 is characterized in that: described initiator is one or more mixtures in peroxide initiator, azo-initiator, the redox class initiator.
4. completely biodegradable polyhydroxyalkanote ester/polycarbonate blending alloy as claimed in claim 3 is characterized in that: described initiator is dicumyl peroxide or benzoyl peroxide or the two mixture.
5. completely biodegradable polyhydroxyalkanote ester/polycarbonate blending alloy as claimed in claim 1 is characterized in that: described auxiliary agent is one or more mixtures in oxidation inhibitor, lubricant, stablizer, the nucleator.
6. completely biodegradable polyhydroxyalkanote ester/polycarbonate blending alloy as claimed in claim 5 is characterized in that: composite assistant that described auxiliary agent is made up of oxidation inhibitor, stablizer or the composite assistant of being made up of oxidation inhibitor, stablizer, lubricant.
7. completely biodegradable polyhydroxyalkanote ester/polycarbonate blending alloy as claimed in claim 1 is characterized in that: described PHA is one or more mixtures among PHB, P3HB4HB, PHBV, the PHBH.
8. the preparation method of completely biodegradable polyhydroxyalkanote ester/polycarbonate blending alloy as claimed in claim 1 comprises the steps,
(1) preparation compatilizer: PHA, grafted monomer and initiator are mixed in proportion, then with the reaction of twin screw extruder melting mixing, extruding pelletization;
(2) preparation blend alloy: compatilizer and PHA, polycarbonate, the auxiliary agent of preparation in the step (1) are mixed in proportion, melt extrude granulation with twin screw then.
9. the preparation method of completely biodegradable polyhydroxyalkanote ester/polycarbonate blending alloy as claimed in claim 9 is characterized in that: extrusion temperature is 110-160 ℃ in the described step (1), described step
(2) extrusion temperature is 100-160 ℃ in.
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| CN101475734B true CN101475734B (en) | 2011-10-12 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20140016548A (en) * | 2012-07-30 | 2014-02-10 | 삼성정밀화학 주식회사 | Resin composition for foaming comprising biodegradable rresin and foamed article made thereof |
| CA2982717A1 (en) * | 2015-04-17 | 2016-10-20 | Repsol, S.A. | Polyalkylencarbonate and polyhydroxyalkanoate blends |
| CN105001611A (en) * | 2015-08-03 | 2015-10-28 | 金宝丽科技（苏州）有限公司 | Scratch-resistant polycarbonate composite material and preparation method thereof |
| CN115594957B (en) * | 2021-06-28 | 2023-10-03 | 青岛周氏塑料包装有限公司 | High-barrier degradable material, high-barrier degradable film and preparation method thereof |
| CN114196182B (en) * | 2022-01-28 | 2023-05-30 | 唐山师范学院 | Polylactic acid-based biomass composite material and preparation method thereof |
| CN114230993B (en) * | 2022-01-28 | 2023-06-16 | 唐山师范学院 | Biodegradable PHBH-based composite material and preparation method thereof |
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| CN1441001A (en) * | 2003-03-28 | 2003-09-10 | 中国科学院长春应用化学研究所 | Prepn of poly(3-hydroxy phytanate)/polypropylene carbonate reaction blend |
| WO2005078018A1 (en) * | 2004-02-11 | 2005-08-25 | Michigan State University | Anhydride functionalized polyhydroxyalkanoates, preparation and use thereof |
| CN1226348C (en) * | 2002-03-04 | 2005-11-09 | 中国科学院长春应用化学研究所 | Process for preparing carbon dioxide, epoxy propene copolymer and polytri-hydroxy alkanoic ester comixer |
-
2008
- 2008-12-15 CN CN2008102181646A patent/CN101475734B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1226348C (en) * | 2002-03-04 | 2005-11-09 | 中国科学院长春应用化学研究所 | Process for preparing carbon dioxide, epoxy propene copolymer and polytri-hydroxy alkanoic ester comixer |
| CN1441001A (en) * | 2003-03-28 | 2003-09-10 | 中国科学院长春应用化学研究所 | Prepn of poly(3-hydroxy phytanate)/polypropylene carbonate reaction blend |
| WO2005078018A1 (en) * | 2004-02-11 | 2005-08-25 | Michigan State University | Anhydride functionalized polyhydroxyalkanoates, preparation and use thereof |
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