CN101045810A - Flexible modified method for poly beta-hydroxybutyric butyrate and poly beta-hydroxybutyric butyrate-beta hydroxyl valerate - Google Patents
Flexible modified method for poly beta-hydroxybutyric butyrate and poly beta-hydroxybutyric butyrate-beta hydroxyl valerate Download PDFInfo
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- CN101045810A CN101045810A CN 200710039380 CN200710039380A CN101045810A CN 101045810 A CN101045810 A CN 101045810A CN 200710039380 CN200710039380 CN 200710039380 CN 200710039380 A CN200710039380 A CN 200710039380A CN 101045810 A CN101045810 A CN 101045810A
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Abstract
This invention relates to a toughness modify method of e. Poly-beta-hydroxybutyric acid ester and poly-beta-hydroxybutyric acid ester-beta-hydroxy valerate and poly- succinic acid butanediol ester or poly- lactic acid carry out vacuum drying, then according to a certainty weight proportion add to Banbury mixer for fusion and blending, after several minutes, add cross-linking agent to carry out dynamic co crosslinking. This materials breaking elongation rate can reach 425%, fracture strength can reach 33.5 MPa, notch impact strength reach 64 joule/m.
Description
Technical field
The present invention relates to a kind of method of modifying of polyester type biodegradable material, the toughening modifying method of particularly a kind of poly-beta-hydroxy-butanoic acid ester and poly-beta-hydroxy-butanoic acid ester-beta-hydroxy valerate.
Background technology
Poly-beta-hydroxy-butanoic acid ester (PHB) and poly-beta-hydroxy-butanoic acid ester-beta-hydroxy valerate (PHBV) are the thermoplasticity aliphatic poly ester materials that is used for carbon source and energy storage that generates by fermentation using bacteria, have favorable biological degradability and biocompatibility, better gas barrier and heat resistance.PHB that biological fermentation process obtains and PHBV purity and tacticity height, therefore easily crystallization has very high degree of crystallinity, and crystalline size and crystal growth rate are big.But the PHBV spherocrystal cracked in big spherocrystal inside in cause different with the circumferential direction shrinkage coefficient of radius in the fusion process of cooling, when material is subjected to reactive forces such as quick stretching, crackle will constantly increase, thereby cause PHB to become a kind of extremely crisp material (Polymer.1996,37 (15): 3241-3246).When beta-hydroxy valerate (HV) among PHBV when molar content is higher, the snappiness of material improves, but produces the PHBV material cost height of high HV content, and practical commercial value is low; The HV molar content is lower than at 20% o'clock, and the PHBV material still has very high fragility.
Both at home and abroad PHB and the toughness reinforcing main method of PHBV are had at present: in PHB or PHBV, add elastomerics, softening agent, nucleator and with other biological degradable material blend etc.The personnel of Changchun applied chemistry institute adopt the crosslinked PHBV of dicumyl peroxide (DCP) that its toughness is made moderate progress, elongation be up to 14% (Polymer International.2004,53:93%943).But these results can not be satisfactory, thereby limited the application of PHBV material in producing and living greatly.
US Patent 4427614 discloses a kind of cold roll-in method that passes through, and controls the PHB spherulitic crystal structure, and the mechanical property of PHB is necessarily improved.But the actual comparison difficulty that implements of this method, not having can be by wide popularization and application.Disclose among the Chinese patent CN 1312305A and a kind ofly reached the novel method of medical materials such as toughness reinforcing PHB, made the PHB elongation be increased to 17.2% by 8.2% by Co radiation grafting isoprene on PHB.Chinese patent ZL 02156420.5 discloses a kind of toughness reinforcing PHBV of method by interpolation phenolic compound in PHBV, and material modified elongation maximum is brought up to about 200%, and PHBV toughness is greatly improved; But the PHBV tensile strength of material that this method of modifying obtains is not high, and the second component phenolic compound (10-30wt%) that adds contains a large amount of aromatic groups.
Summary of the invention
The toughening modifying method that the purpose of this invention is to provide a kind of poly-beta-hydroxy-butanoic acid ester (PHB) and poly-beta-hydroxy-butanoic acid ester-beta-hydroxy valerate (PHBV).The present invention is directed to that poly-beta-hydroxy-butanoic acid ester and poly-beta-hydroxy-butanoic acid ester-beta-hydroxy valerate fragility are big, the problem of poor mechanical property, adopt dynamic co-crosslinking technology, proposed the simple method of modifying of a kind of complete processing, the PHBV that has prepared good-toughness is material modified.
The toughening modifying method of a kind of poly-beta-hydroxy-butanoic acid ester of the present invention and poly-beta-hydroxy-butanoic acid ester-beta-hydroxy valerate is as follows:
Poly-beta-hydroxy-butanoic acid ester or poly-beta-hydroxy-butanoic acid ester-beta-hydroxy valerate and poly butylene succinate or poly(lactic acid) were 40～100 ℃ of following vacuum-dryings 0.5～2 day, wherein poly-beta-hydroxy-butanoic acid ester or poly-beta-hydroxy-butanoic acid ester-beta-hydroxy valerate and poly butylene succinate or poly(lactic acid) are 98/2～40/60 according to weight ratio, join then and carry out melt blending in the Banbury mixer, blending temperature is 160～190 ℃, 30～80 rev/mins of rotor speeds, after the blend 2～15 minutes, add 0.01～5 part of linking agent again, carry out dynamic co-crosslinking 1～10 minute, and obtained the toughness-increasing modified material of a kind of poly-beta-hydroxy-butanoic acid ester and poly-beta-hydroxy-butanoic acid ester-beta-hydroxy valerate.
Poly-beta-hydroxy-butanoic acid ester or poly-beta-hydroxy-butanoic acid ester-beta-hydroxy valerate viscosity-average molecular weight that the present invention uses are 1.0 * 10
5～1.0 * 10
6, beta-hydroxy valerate molar content is less than 30% in poly-beta-hydroxy-butanoic acid ester-beta-hydroxy valerate.
Poly butylene succinate or poly(lactic acid) viscosity-average molecular weight that the present invention uses are 1.0 * 10
5～5.0 * 10
5
The linking agent that the present invention uses is dicumyl peroxide or benzoyl peroxide.
In the toughening modifying method of a kind of poly-beta-hydroxy-butanoic acid ester of the present invention and poly-beta-hydroxy-butanoic acid ester-beta-hydroxy valerate, owing to adopted dynamic co-crosslinking technology, co-crosslinking by poly-beta-hydroxy-butanoic acid ester or poly-beta-hydroxy-butanoic acid ester-beta-hydroxy valerate and poly butylene succinate or poly(lactic acid) under the molten state, having remedied poly-beta-hydroxy-butanoic acid ester under the processing conditions or molecular weight that poly-beta-hydroxy-butanoic acid ester-degraded of beta-hydroxy valerate causes reduces, increased the process compatibility of two components, reduce the degree of crystallinity of material, thereby given material modified excellent flexibility.A kind of poly-beta-hydroxy-butanoic acid ester that the present invention obtains and poly-beta-hydroxy-butanoic acid ester-beta-hydroxy valerate excellent performance: shock strength can reach 64J/m, improves about 5 times than pure PHBV material; Elongation at break improves about 80 times up to 425% than pure PHBV material, improves 1～4 times than Chinese patent ZL 02156420.5 disclosed modification result; Tensile strength reaches 33.5MPa, improves 35.6% than pure PHBV, improves 50%～184% than the disclosed modification result of Chinese patent ZL02156420.5.
Second component is that phenolic compound (10-30wt%) contains a large amount of aromatic groups in the Chinese patent ZL 02156420.5 disclosed method of modifying, and the toughening modifying method of a kind of poly-beta-hydroxy-butanoic acid ester of the present invention and poly-beta-hydroxy-butanoic acid ester-beta-hydroxy valerate has overcome this shortcoming, and the poly-beta-hydroxy-butanoic acid ester that the present invention adopts, poly-beta-hydroxy-butanoic acid ester-beta-hydroxy valerate, poly butylene succinate and poly(lactic acid) are all universally acknowledged environmental friendliness and Biodegradable Materials.
The toughening modifying method of a kind of poly-beta-hydroxy-butanoic acid ester of the present invention and poly-beta-hydroxy-butanoic acid ester-beta-hydroxy valerate is easy to operate, technology is simple, the starting material wide material sources, poly-beta-hydroxy-butanoic acid ester that obtains and poly-beta-hydroxy-butanoic acid ester-beta-hydroxy valerate toughness-increasing modified material, over-all properties is good, and stable performance can be used as daily necessities, packing film, disposable tableware etc., and prospects for commercial application is wide.
Embodiment:
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
The poly-beta-hydroxy-butanoic acid ester (PHB) that uses in following examples is produced by Ningbo Tianan Biological Material Co., Ltd., and viscosity-average molecular weight is 2.7 * 10
5Poly-beta-hydroxy-butanoic acid ester-beta-hydroxy valerate (PHBV) is produced by Ningbo Tianan Biological Material Co., Ltd., and beta-hydroxy valerate (HV) content is 12mol%, and viscosity-average molecular weight is 2.3 * 10
5Poly butylene succinate (PBS) material is provided by Physical Chemistry Technology Inst., Chinese Academy of Sciences, and viscosity-average molecular weight is 2.0 * 10
5Linking agent is dicumyl peroxide (DCP).
Embodiment 1-5
Poly-beta-hydroxy-butanoic acid ester or poly-beta-hydroxy-butanoic acid ester-beta-hydroxy valerate and poly butylene succinate were 50 ℃ of following vacuum-dryings 24 hours, then according to prescription in the table-1, join and carry out melt blending in the Banbury mixer, blending temperature is 175 ℃, 40 rev/mins of rotor speeds, blend add crosslink agent DCP according to prescription in the table-1 after 4 minutes again, carry out dynamic co-crosslinking 2 minutes, and obtained PHB and PHBV toughness-increasing modified material.
Material modified test bars is tested its performance park 24 hours in 23 ℃ of environment after.Tensile property is gone up according to the ISO.178 standard testing at universal electrical puller system (Instron 4465), 23 ℃ of probe temperatures, and rate of extension is 10mm/min; Notched Izod impact strength is pressed ASTM D256 standard, and (RAY-RANTest Equipment Ltd. UK) goes up test, 23 ℃ of probe temperatures at the impact experiment instrument; Fusing point is by differential scanning calorimeter (Pyris1; Perkin Elmer, Inc., USA) test, 10 ℃/min of scanning speed.
Comparative Examples 1
In the Comparative Examples 1, the poly-beta-hydroxy-butanoic acid ester of use-beta-hydroxy valerate (PHBV) is produced by Ningbo Tianan Biological Material Co., Ltd., and beta-hydroxy valerate (HV) content is 12mol%, and viscosity-average molecular weight is 2.3 * 10
5Poly-beta-hydroxy-butanoic acid ester-beta-hydroxy valerate according to prescription in the table-1, joins and carries out melt blending in the Banbury mixer then 50 ℃ of following vacuum-dryings 24 hours, and blend is identical with embodiment 1-5 with test condition.
Table-1
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 |
| Prescription, g PHB PHBV PBS DCP dihydroxyphenyl propane (BPA) p-tert-butylphenol (TBP) HV content, mol% physical and mechanical properties shock strength, the J/m tensile strength, the MPa elongation at break, the % flexural strength, the MPa modulus in flexure, MPa fusing point (PHBV), ℃ | 56 14 0.35 0 40 28.5 115 34.5 720 172 | 56 14 0.014 12 25.0 25.4 20.3 38.6 1226 169.7 | 56 14 0.14 12 36 33.5 186 43 1391 166.9 | 56 14 0.35 12 49 30.8 406 31.9 684 164.8 | 56 14 0.7 12 64 28.2 425 29.1 598 160.5 | 70 12 11.0 24.7 5.3 39.1 2600 160.5 | 49 21 12 -- 11.8 85 -- -- 124 | 56 14 5 -- 22.3 220 -- -- 158 |
In the table-1, Comparative Examples 1 is some performance of pure PHBV material, and the data of Comparative Examples 2-3 are from Chinese patent ZL:02156420.5, and embodiment 1-5 is some material modified performance.Relatively know by data in the table-1: poly-beta-hydroxy-butanoic acid ester and poly-beta-hydroxy-butanoic acid ester-beta-hydroxy valerate that the toughening modifying method by a kind of poly-beta-hydroxy-butanoic acid ester of the present invention and poly-beta-hydroxy-butanoic acid ester-beta-hydroxy valerate obtains are material modified, its shock strength can reach 64J/m, improves about 5 times than pure PHBV material; Elongation at break improves about 80 times up to 425% than pure PHBV material, improves 1～4 times than Chinese patent ZL 02156420.5 disclosed modification result; Tensile strength reaches 33.5MPa, improves 35.6% than pure PHBV, improves 50%～184% than the disclosed modification result of Chinese patent ZL02156420.5.
The poly-beta-hydroxy-butanoic acid ester of the modification that toughening modifying method by a kind of poly-beta-hydroxy-butanoic acid ester of the present invention and poly-beta-hydroxy-butanoic acid ester-beta-hydroxy valerate obtains and poly-beta-hydroxy-butanoic acid ester-beta-hydroxy valerate material, have excellent mechanical properties such as very high elongation at break, good impelling strength and higher draw tensile strength, have broad prospect of application.
Claims (4)
1. the toughening modifying method of a poly-beta-hydroxy-butanoic acid ester and poly-beta-hydroxy-butanoic acid ester-beta-hydroxy valerate is characterized in that method of modifying is as follows:
Poly-beta-hydroxy-butanoic acid ester or poly-beta-hydroxy-butanoic acid ester-beta-hydroxy valerate and poly butylene succinate or poly(lactic acid) were 40～100 ℃ of following vacuum-dryings 0.5～2 day, wherein poly-beta-hydroxy-butanoic acid ester or poly-beta-hydroxy-butanoic acid ester-beta-hydroxy valerate and poly butylene succinate or poly(lactic acid) are 98/2～40/60 according to weight ratio, join then and carry out melt blending in the Banbury mixer, blending temperature is 160～190 ℃, 30～80 rev/mins of rotor speeds, after the blend 2～15 minutes, add 0.01～5 weight part linking agent again, carry out dynamic co-crosslinking 1～10 minute, and obtained the toughness-increasing modified material of a kind of poly-beta-hydroxy-butanoic acid ester and poly-beta-hydroxy-butanoic acid ester-beta-hydroxy valerate.
2. the toughening modifying method of a kind of poly-beta-hydroxy-butanoic acid ester according to claim 1 and poly-beta-hydroxy-butanoic acid ester-beta-hydroxy valerate is characterized in that poly-beta-hydroxy-butanoic acid ester or poly-beta-hydroxy-butanoic acid ester-beta-hydroxy valerate viscosity-average molecular weight are 1.0 * 10
5～1.0 * 10
6, beta-hydroxy valerate molar content is less than 30% in poly-beta-hydroxy-butanoic acid ester-beta-hydroxy valerate.
3. the toughening modifying method of a kind of poly-beta-hydroxy-butanoic acid ester according to claim 1 and poly-beta-hydroxy-butanoic acid ester-beta-hydroxy valerate is characterized in that poly butylene succinate or poly(lactic acid) viscosity-average molecular weight are 1.0 * 10
5～5.0 * 10
5
4. the toughening modifying method of a kind of poly-beta-hydroxy-butanoic acid ester according to claim 1 and poly-beta-hydroxy-butanoic acid ester-beta-hydroxy valerate is characterized in that linking agent is dicumyl peroxide or benzoyl peroxide.
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| WO2010008447A1 (en) * | 2008-06-25 | 2010-01-21 | Metabolix, Inc. | Methods for branching pha using thermolysis |
| CN101977641A (en) * | 2008-03-24 | 2011-02-16 | 泰尔茂株式会社 | Medical instrument, medical material, and method for production of the medical instrument and medical material |
| CN101157793B (en) * | 2007-09-20 | 2011-06-08 | 浙江海正生物材料股份有限公司 | Heat-proof polylactic acid blend and preparation method thereof |
| WO2011071666A1 (en) * | 2009-12-08 | 2011-06-16 | International Paper Company | Thermoformed articles made from reactive extrusion products of biobased materials |
| CN101475735B (en) * | 2008-12-15 | 2012-02-15 | 山东省意可曼科技有限公司 | Completely biodegradable polyhydroxyalkanote / poly(butylene succinate) blending alloy |
| CN103571165A (en) * | 2013-11-06 | 2014-02-12 | 江南大学 | Polylactic acid 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 |
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| US10669417B2 (en) | 2013-05-30 | 2020-06-02 | Cj Cheiljedang Corporation | Recyclate blends |
| WO2024029492A1 (en) * | 2022-08-01 | 2024-02-08 | Dic株式会社 | Copolyester comprising 3-hydroxybutyric acid and method for producing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101157793B (en) * | 2007-09-20 | 2011-06-08 | 浙江海正生物材料股份有限公司 | Heat-proof polylactic acid blend and preparation method thereof |
| CN101977641A (en) * | 2008-03-24 | 2011-02-16 | 泰尔茂株式会社 | Medical instrument, medical material, and method for production of the medical instrument and medical material |
| WO2010008447A1 (en) * | 2008-06-25 | 2010-01-21 | Metabolix, Inc. | Methods for branching pha using thermolysis |
| US9034989B2 (en) | 2008-06-25 | 2015-05-19 | Metabolix, Inc. | Branched PHA compositions, methods for their production, and use in applications |
| CN101475735B (en) * | 2008-12-15 | 2012-02-15 | 山东省意可曼科技有限公司 | Completely biodegradable polyhydroxyalkanote / poly(butylene succinate) blending alloy |
| CN102648234A (en) * | 2009-12-08 | 2012-08-22 | 国际纸业公司 | Thermoformed articles made from reactive extrusion products of biobased materials |
| US8231954B2 (en) | 2009-12-08 | 2012-07-31 | International Paper Co. | Thermoformed articles made from reactive extrusion products of biobased materials |
| WO2011071666A1 (en) * | 2009-12-08 | 2011-06-16 | International Paper Company | Thermoformed articles made from reactive extrusion products of biobased materials |
| US10030135B2 (en) | 2012-08-17 | 2018-07-24 | Cj Cheiljedang Corporation | Biobased rubber modifiers for polymer blends |
| US10669417B2 (en) | 2013-05-30 | 2020-06-02 | Cj Cheiljedang Corporation | Recyclate blends |
| CN103571165A (en) * | 2013-11-06 | 2014-02-12 | 江南大学 | Polylactic acid composite material and preparation method thereof |
| US10611903B2 (en) | 2014-03-27 | 2020-04-07 | Cj Cheiljedang Corporation | Highly filled polymer systems |
| CN106147171A (en) * | 2016-07-16 | 2016-11-23 | 宁波联华汽车部件有限公司 | A kind of shape memory automobile baffle 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 |
| WO2024029492A1 (en) * | 2022-08-01 | 2024-02-08 | Dic株式会社 | Copolyester comprising 3-hydroxybutyric acid and method for producing same |
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