CN1366004A - Biodegradable aliphatic polyester composite material - Google Patents
Biodegradable aliphatic polyester composite material Download PDFInfo
- Publication number
- CN1366004A CN1366004A CN02104174A CN02104174A CN1366004A CN 1366004 A CN1366004 A CN 1366004A CN 02104174 A CN02104174 A CN 02104174A CN 02104174 A CN02104174 A CN 02104174A CN 1366004 A CN1366004 A CN 1366004A
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- CN
- China
- Prior art keywords
- aliphatic polyester
- composite material
- nucleator
- polyhydroxyalkanoate
- polyester composite
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- 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.)
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Classifications
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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
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
A biodegradable aliphatic polyester composite material is prepared from one or several aliphatic polyesters (100 Wt. portions), primary nucleator (0.01-10), auxiliary nucleator (0.01-20), and one or several thermal stabilizers through premixing in high-speed mixer, extruding in screw extruder and granulating. Its advantages are simple preparing process, and high crystallizing speed, productivity and thermal stability.
Description
Technical field: the present invention relates to a kind of biodegradable aliphatic polyester composite material
Background technology:, all be devoted to exploitation both at home and abroad and both had the plastics advantageous property, simultaneously degradable again plastic prod of new generation for reducing the white pollution that plastic prod causes.Wherein a class is to utilize general-purpose plastics such as polyethylene, polypropylene etc. as matrix, again the biodegradable plastic that is mixed and made into mutually under certain condition with degradable macromolecular materials such as starch.Existing many patents of this series products such as CN1049671 etc.But this series products can only the part degraded, as disposable food packing film or plastic film for agricultural use, its resistates will destroy Soil structure, influences plant growth.Another kind of aliphatic polyester by chemosynthesis, as polycaprolactone, though degradable, fusing point is lower, and range of application is restricted.
Poly-hydroxy fatty acid fat (the PHA) (CN1190674 that is developing both at home and abroad with biological fermentation process or chemical synthesis preparation; Pool R., Science, 1989,245:1187), be a kind of thermoplastic plastics, can make film, injection-molded item, foam article and extrusion moulding with traditional plastic working method; This product can be in soil, seawater complete biodegradable, free from environmental pollution; Having excellent biocompatibility simultaneously, is the ideal material of aspects such as medicament slow release controlled release, operating sutures, bone surgery be fixing.Because These characteristics, PHA is in agricultural, medicine, and the food product pack field has broad prospects.
But, the PHA poor heat stability, as PHB, temperature is higher than fusing point and just begins degraded; Crystallization velocity is slow, the PHB goods of machine-shaping under the high temperature, if be quenched under the room temperature, just the meeting crystallization is complete to place 600 hours.These two factors have caused very big difficulty for the machine-shaping of material, and goods need long crystalline forming; Blown film is difficult for opening.
Summary of the invention: the purpose of this invention is to provide a kind of biodegradable aliphatic polyester composite material.Shortcoming at polyhydroxyalkanoate class biodegradable polymer poor processability, choose properly mixed nucleator, thermo-stabilizer, and, prepare the biodegradable aliphatic polyester composite material that has Heat stability is good, crystalline forming speed is fast and has actual production to be worth in conjunction with complete processing.The nucleator that the present invention selects for use joins its crystallization velocity is significantly improved, and prevents that effectively polyhydroxyalkanoate from cracking in crystallisation process, increases its toughness.The thermo-stabilizer that the present invention selects for use can hinder the formation of the six-ring in the polyhydroxyalkanoate thermal degradation process, thereby improves its thermostability.
A kind of biodegradable aliphatic polyester composite material provided by the invention is made up of one or more aliphatic polyesters of 100 parts of parts by weight, the main nucleator of 0.01-10 part, the auxiliary nucleator of 0.01-20 part, one or more thermo-stabilizers of 0.01-5 part.
Aliphatic polyester is a polyhydroxyalkanoate, and its structure is:
Wherein R is an alkyl, m=1; When R is methyl, polyhydroxyalkanoate be poly-(the 3-butyric ester) used always (PHB); When R is ethyl, polyhydroxyalkanoate be poly-(3-hydroxypentanoic acid fat) (PHV); When R was methyl and ethyl, polyhydroxyalkanoate was butyric ester and hydroxypentanoic acid resin copolymer (PHBV);
Main nucleator is the compound with following array structure:
R wherein
1And R
2Be H, COOH, NH
2, OH, R
1And R
2Can be the same or different, but cannot be H simultaneously;
Auxiliary nucleator is talcum powder, potter's clay or lime carbonate;
Thermo-stabilizer be four [3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] wherein one or both of pentaerythritol ester (antioxidant 1010), three (2, the 4-di-tert-butyl-phenyl) phosphorous acid esters (oxidation inhibitor 168), two (octadecyl) pentaerythritol diphosphites (oxidation inhibitor 618), MALEIC ANHYDRIDE.
Cooperate suitable nucleator and thermo-stabilizer in high-speed mixer, to carry out pre-mixing earlier aliphatic polyester, carry out extruding pelletization with twin screw extruder or single screw extrusion machine then.The temperature of forcing machine is set at: feeding section 50-120 degree, 100-155 ℃ of mixing section temperature, 115-170 ℃ of fluxing zone temperature, head temperature 100-160 ℃.
The nucleator that uses among the present invention can improve the Tc of polyhydroxyalkanoate PHA 20 to 50 degree, accelerates its crystallization rate greatly.Thereby in the actual production of PHA goods, the machine-shaping time can shorten greatly, and productivity obviously improves.The thermo-stabilizer that uses among the present invention can improve the thermostability of PHA, thereby widens the process window of PHA.
Advantage of the present invention is: the raw material of processing aid is easy to get, and complete processing is simple; Obviously improve the crystallization velocity of aliphatic polyester, solved the very slow problem of its moulding, improved the production efficiency of its goods greatly; Improve the thermostability of aliphatic polyester, thereby widened its process window.
Embodiment is as follows: embodiment 1: take by weighing each component by following prescription (weight part):
PHBV(8％V) 100
Terephthalic acid 0.01
Talcum powder 20
MALEIC ANHYDRIDE 0.01 was carried out pre-mixing 5 minutes with each component with high-speed mixer earlier then, more mixed material was joined extruding pelletization in the forcing machine.The temperature setting of forcing machine is: 70 ℃ of feeding sections, 100 ℃ of mixing sections, 160 ℃ of fluxing zones, 150 ℃ of heads.Screw speed is 50 rev/mins.110 ℃ of the Tcs of material, tensile strength 31MPa.Embodiment 2: take by weighing each component by following prescription (weight part):
PHBV(V8％) 100
Resorcinol 1
Potter's clay 10
Antioxidant 1010 0.5
MALEIC ANHYDRIDE 1.5 obtains matrix material by mixing expressing technique and the condition granulation of embodiment 1.109 ℃ of the Tcs of material, tensile strength 33MPa.Embodiment 3: take by weighing each component by following prescription (weight part):
PHB 90
PHBV(V8％) 10
Phenylformic acid 10
Lime carbonate 10
Oxidation inhibitor 168 0.1
MALEIC ANHYDRIDE 4.9 was carried out pre-mixing 5 minutes with each component with high-speed mixer earlier, more mixed material was joined extruding pelletization in the forcing machine.The temperature setting of forcing machine is: 80 ℃ of feeding sections, 150 ℃ of mixing sections, 170 ℃ of fluxing zones, 160 ℃ of heads.Screw speed is 50 rev/mins.113 ℃ of the Tcs of material, tensile strength 38MPa.Embodiment 4: take by weighing each component by following prescription (weight part):
PHB 100
Para-amino benzoic acid 5
Talcum powder 5
Oxidation inhibitor 618 1
MALEIC ANHYDRIDE 1 was carried out pre-mixing 5 minutes with each component with high-speed mixer earlier, more mixed material was joined extruding pelletization in the forcing machine.The temperature setting of forcing machine is: 120 ℃ of feeding sections, 150 ℃ of mixing sections, 170 ℃ of fluxing zones, 160 ℃ of heads.Screw speed is 50 rev/mins.114 ℃ of the Tcs of material, tensile strength 39MPa.Embodiment 5: take by weighing each component by following prescription (weight part):
PHV 100
P-hydroxybenzoic acid 1
Talcum powder 10
Oxidation inhibitor 618 1
MALEIC ANHYDRIDE 1.5 was carried out pre-mixing 5 minutes with each component with high-speed mixer earlier, more mixed material was joined extruding pelletization in the forcing machine.The temperature setting of forcing machine is: 50 ℃ of feeding sections, 100 ℃ of mixing sections, 115 ℃ of fluxing zones, 100 ℃ of heads.Screw speed is 50 rev/mins.90 ℃ of the Tcs of material, tensile strength 29MPa.
Claims (8)
1, a kind of biodegradable aliphatic polyester composite material, be to cooperate nucleator and thermo-stabilizer in high-speed mixer, to carry out earlier pre-mixing aliphatic polyester, carry out extruding pelletization with twin screw extruder or single screw extrusion machine then, the temperature of forcing machine is set at: feeding section 50-120 degree, 100-155 ℃ of mixing section temperature, 115-170 ℃ of fluxing zone temperature, head temperature 100-160 ℃, it is characterized in that selecting one or more aliphatic polyesters of 100 parts of parts by weight, 0.01-10 the main nucleator of part, 0.01-20 the auxiliary nucleator of part, 0.01-5 one or more thermo-stabilizers of part are formed;
Aliphatic polyester is a polyhydroxyalkanoate, and its structure is:
Wherein R is an alkyl, m=1; When R was methyl, polyhydroxyalkanoate was poly-(the 3-butyric ester) used always; When R was ethyl, polyhydroxyalkanoate was poly-(3-hydroxypentanoic acid fat); When R was methyl and ethyl, polyhydroxyalkanoate was butyric ester and hydroxypentanoic acid resin copolymer;
Main nucleator is the compound with following array structure:
R wherein
1And R
2Be H, COOH, NH
2, OH, R
1And R
2Can be the same or different, but cannot be H simultaneously;
Auxiliary nucleator is talcum powder, potter's clay or lime carbonate;
Thermo-stabilizer be four [3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] wherein one or both of pentaerythritol ester, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, two (octadecyl) pentaerythritol diphosphites, MALEIC ANHYDRIDE.
2. biodegradable aliphatic polyester composite material as claimed in claim 1 is characterized in that aliphatic polyester is a polyhydroxyalkanoate, and its structure is:
Wherein R is an alkyl, m=1; R is a methyl.
3. biodegradable aliphatic polyester composite material as claimed in claim 1 is characterized in that aliphatic polyester is a polyhydroxyalkanoate, and its structure is:
Wherein R is an alkyl, m=1; R is an ethyl.
4. biodegradable aliphatic polyester composite material as claimed in claim 1 is characterized in that aliphatic polyester is a polyhydroxyalkanoate, and its structure is:
Wherein R is an alkyl, m=1; R is methyl and ethyl.
5. biodegradable aliphatic polyester composite material as claimed in claim 1 is characterized in that main nucleator is the compound with following array structure:
R wherein
1Be H, COOH, NH
2, OH.
6. biodegradable aliphatic polyester composite material as claimed in claim 1 is characterized in that main nucleator is the compound with following array structure:
R wherein
2Be H, COOH, NH
2, OH.
7. biodegradable aliphatic polyester composite material as claimed in claim 1 is characterized in that main nucleator is the compound with following array structure:
R wherein
1Be COOH, NH
2, OH and R
2
8. biodegradable aliphatic polyester composite material as claimed in claim 1 is characterized in that main nucleator is the compound with following array structure:
R wherein
2Be COOH, NH
2, OH and R
1
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021041741A CN1215122C (en) | 2002-03-15 | 2002-03-15 | Biodegradable aliphatic polyester composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021041741A CN1215122C (en) | 2002-03-15 | 2002-03-15 | Biodegradable aliphatic polyester composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1366004A true CN1366004A (en) | 2002-08-28 |
| CN1215122C CN1215122C (en) | 2005-08-17 |
Family
ID=4740018
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021041741A Expired - Fee Related CN1215122C (en) | 2002-03-15 | 2002-03-15 | Biodegradable aliphatic polyester composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1215122C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1308395C (en) * | 2002-11-08 | 2007-04-04 | 株式会社钟化 | Aqueous dispersion of biodegradable polyester and method for production thereof |
| CN101495572A (en) * | 2006-07-26 | 2009-07-29 | 三井化学株式会社 | Polylactic acid resin composition and molded body thereof |
| CN102002222A (en) * | 2010-10-21 | 2011-04-06 | 中国科学院宁波材料技术与工程研究所 | Halogen-free flame retardant polylactic acid composite material |
| CN102558580A (en) * | 2012-01-13 | 2012-07-11 | 中国印刷科学技术研究所 | Dissoluble light-cured resin and dissoluble ultraviolet (UV) printing ink and preparing method thereof |
| CN104662088A (en) * | 2012-08-03 | 2015-05-27 | 株式会社钟化 | Polyester resin composition and molded body containing this resin composition |
| CN105482397A (en) * | 2016-01-26 | 2016-04-13 | 苏州羽帆新材料科技有限公司 | Biodegradable weather-proof composite material and preparation method thereof |
| CN110128804A (en) * | 2019-06-03 | 2019-08-16 | 北京化工大学 | A method of improving polyhydroxyalkanoate melt-processable and mechanical property |
| CN115572470A (en) * | 2016-10-18 | 2023-01-06 | 梅雷迪安股份有限公司 | Crystal nucleating agent for polyhydroxyalkanoate |
| CN116277593A (en) * | 2023-05-23 | 2023-06-23 | 北京微构工场生物技术有限公司 | Method for granulating and molding polyhydroxyalkanoate and molded body thereof |
-
2002
- 2002-03-15 CN CNB021041741A patent/CN1215122C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1308395C (en) * | 2002-11-08 | 2007-04-04 | 株式会社钟化 | Aqueous dispersion of biodegradable polyester and method for production thereof |
| CN101495572A (en) * | 2006-07-26 | 2009-07-29 | 三井化学株式会社 | Polylactic acid resin composition and molded body thereof |
| CN101495572B (en) * | 2006-07-26 | 2012-09-19 | 三井化学株式会社 | Polylactic acid resin composition and molded body thereof |
| CN102002222A (en) * | 2010-10-21 | 2011-04-06 | 中国科学院宁波材料技术与工程研究所 | Halogen-free flame retardant polylactic acid composite material |
| CN102558580A (en) * | 2012-01-13 | 2012-07-11 | 中国印刷科学技术研究所 | Dissoluble light-cured resin and dissoluble ultraviolet (UV) printing ink and preparing method thereof |
| CN102558580B (en) * | 2012-01-13 | 2013-09-18 | 中国印刷科学技术研究所 | Dissoluble light-cured resin and dissoluble ultraviolet (UV) printing ink and preparing method thereof |
| CN104662088A (en) * | 2012-08-03 | 2015-05-27 | 株式会社钟化 | Polyester resin composition and molded body containing this resin composition |
| CN105482397A (en) * | 2016-01-26 | 2016-04-13 | 苏州羽帆新材料科技有限公司 | Biodegradable weather-proof composite material and preparation method thereof |
| CN115572470A (en) * | 2016-10-18 | 2023-01-06 | 梅雷迪安股份有限公司 | Crystal nucleating agent for polyhydroxyalkanoate |
| CN110128804A (en) * | 2019-06-03 | 2019-08-16 | 北京化工大学 | A method of improving polyhydroxyalkanoate melt-processable and mechanical property |
| CN116277593A (en) * | 2023-05-23 | 2023-06-23 | 北京微构工场生物技术有限公司 | Method for granulating and molding polyhydroxyalkanoate and molded body thereof |
| CN116277593B (en) * | 2023-05-23 | 2023-10-20 | 北京微构工场生物技术有限公司 | Method for granulating and molding polyhydroxyalkanoate and molded body thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1215122C (en) | 2005-08-17 |
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Granted publication date: 20050817 Termination date: 20110315 |