CN111825964A - Degradable PBST/P34HB blend and preparation method thereof - Google Patents
Degradable PBST/P34HB blend and preparation method thereof Download PDFInfo
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- CN111825964A CN111825964A CN202010791219.3A CN202010791219A CN111825964A CN 111825964 A CN111825964 A CN 111825964A CN 202010791219 A CN202010791219 A CN 202010791219A CN 111825964 A CN111825964 A CN 111825964A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention discloses a degradable PBST/P34HB blend and a preparation method thereof, wherein the blend comprises the following components in parts by weight: 10-90 parts of PBST resin, 2-10 parts of P34HB90, 2-10 parts of plasticizer, 1-5 parts of inorganic filler, 0.1-1 part of antioxidant and 0.1-0.5 part of lubricant. The PBST/P34HB blend is prepared by uniformly mixing the PBST, the P34HB and other auxiliary agents, the process flow is simple and easy to operate, the prepared blend is degradable, the comprehensive performance is excellent, and the use requirements of a plurality of fields can be met.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a degradable PBST/P34HB blend and a preparation method thereof.
Background
PBS enters the field of material research in the 90 s of the 20 th century and quickly becomes one of hot materials for research on general completely biodegradable plastics which can be widely popularized and applied, and compared with degradable plastics such as PCL, PHB, PHA and the like, PBS has the characteristics of low price, excellent mechanical property and the like; compared with PLA with a similar price, PBS has the characteristics of convenient processing, adaptability to the conventional plastic processing technology at present and good heat resistance, and the heat distortion temperature can exceed 100 ℃ (the heat resistance temperature of PLA is only about 60 ℃). In addition, the raw material source for PBS synthesis can be either petroleum resource or biomass resource, and therefore, the method has attracted high attention in science and technology and industry.
However, the further use of PBS is limited by the disadvantages of low molecular weight, poor flowability, high crystallinity, low melt strength, and poor toughness. In recent years, a series of relevant laws and regulations have been developed at home and abroad to require the content of a biological base in a plastic product, and the trend is more obvious, so that the biodegradable polymer material has important significance in modifying and researching the performance of the PBS while ensuring that the biodegradability of the PBS is not damaged.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide a degradable PBST/P34HB blend and a preparation method thereof.
In order to solve the practical problems in the prior art, the PBS is modified by copolymerizing 1, 5-glutaric acid, succinic acid and 1, 4-butanediol through a chemical modification means, a series of PBST copolyesters are synthesized, the impact resistance of the PBS is improved, and good biodegradability is maintained. On the basis, P34HB is selected for further physical blending modification. The P34HB is a novel material which is produced by microbial fermentation and can be completely biodegraded, is a type of aliphatic polyester which is formed by accumulation in a prokaryotic microorganism body, has wide application in various industries such as agriculture, the packaging field, the medicine field and the like, has good performance, excellent biocompatibility and biodegradability, can be completely degraded in a natural environment within 3-5 months, is an environment-friendly material, and has good application prospect. P34HB is commonly applied to modification of PLA, reports are less in modification of PBS, and the research on the modification and performance influence of PBS has important significance.
The purpose of the invention is realized by the following technical scheme:
the invention provides a degradable PBST/P34HB blend, which comprises the following components in parts by weight:
preferably, the degradable PBST/P34HB blend comprises the following components in parts by weight:
preferably, the P34HB resin is produced by Tianjin national rhyme biomaterial, Inc.
Preferably, the preparation method of the PBST comprises the following steps:
adding a certain amount of succinic acid, 1, 5-glutaric acid and butanediol (the molar ratio of acid to alcohol is 1:1.2, and the mass ratio of the succinic acid to the 1, 5-glutaric acid is 90: 10) into a closed stainless steel 100ml reaction kettle provided with a stirring device, introducing nitrogen, starting stirring and heating under the atmosphere of the nitrogen, raising the temperature to 180 ℃ and starting constant temperature, starting the first-stage esterification reaction, distilling off a large amount of water in the esterification reaction process, and ending the first-stage reaction for about 2 hours when the first-stage reaction is finished; and adding 3 wt% of tetrabutyl titanate after the esterification is finished, stopping introducing nitrogen, continuing stirring, sealing the reaction kettle, raising the temperature to 220 ℃, pumping the pressure in the reaction kettle to be below-0.1 MPa by using a vacuum oil pump, keeping the vacuum degree, starting the second-stage polycondensation reaction, and ensuring that the reaction time is about 2 hours. And after the reaction is finished, cooling to 60 ℃ to obtain the product PBST.
Preferably, the plasticizer is one or more of citrate plasticizers.
Preferably, the inorganic filler is one or a mixture of calcium carbonate and talcum powder.
Preferably, the antioxidant is one or a mixture of two of antioxidant 1076 and antioxidant 168.
Preferably, the lubricant is pentaerythritol stearate.
The invention also provides a preparation method of the degradable PBST/P34HB blend, which comprises the following steps: PBST and P34HB resin are mixed, and then are fully mixed with a plasticizer, an inorganic filler, an antioxidant and a lubricant, and then are melted and blended to obtain the blend.
Preferably, the melt blending temperature is 140 ℃.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention introduces modified monomer 1, 5-glutaric acid to PBS molecular chain to carry out chemical copolymerization modification, so as to prepare degradable modified copolyester PBST, and then adds P34HB as a main modified component to further carry out physical blending modification on PBST. The PBS is modified by the means of combining the chemical modification and the physical modification to prepare the degradable PBST/P34HB blend, and the modified material not only maintains good biodegradability, but also greatly improves the mechanical property, thereby having very important significance.
2. The PBST/P34HB blend is prepared by uniformly mixing the PBST, the P34HB and other auxiliary agents, the process flow is simple and easy to operate, the prepared blend is degradable, the comprehensive performance is excellent, and the use requirements of a plurality of fields can be met.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The following example provides a degradable PBST/P34HB blend comprising the following components in parts by weight:
the P34HB resin is produced by Tianjin national rhyme biomaterial Co.
The preparation method of the PBST comprises the following steps:
adding a certain amount of succinic acid, 1, 5-glutaric acid and butanediol (the molar ratio of acid to alcohol is 1:1.2, and the mass ratio of the succinic acid to the 1, 5-glutaric acid is 90: 10) into a closed stainless steel 100ml reaction kettle provided with a stirring device, introducing nitrogen, starting stirring and heating under the atmosphere of nitrogen, starting constant temperature when the temperature is increased to 180 ℃, starting esterification reaction at the first stage, distilling off a large amount of water in the esterification reaction process, and ending the esterification reaction until no water is distilled off, wherein 2 hours are needed after the first-stage reaction is finished; and adding 3 wt% of tetrabutyl titanate after the esterification is finished, stopping introducing nitrogen, continuing stirring, sealing the reaction kettle, raising the temperature to 220 ℃, pumping the pressure in the reaction kettle to be below-0.1 MPa by using a vacuum oil pump, keeping the vacuum degree, starting the second-stage polycondensation reaction, and ensuring that the reaction time is about 2 hours. And after the reaction is finished, cooling to 60 ℃ to obtain the product PBST.
The plasticizer is one or more of citric acid ester plasticizers.
The inorganic filler is one or a mixture of calcium carbonate and talcum powder.
The antioxidant is one or a mixture of two of antioxidant 1076 and antioxidant 168.
The lubricant is pentaerythritol stearate.
The preparation method of the degradable PBST/P34HB blend comprises the following steps: PBST and P34HB resin are mixed, and then are fully mixed with a plasticizer, an inorganic filler, an antioxidant and a lubricant, and then are melted and blended to obtain the blend.
The melt blending temperature was 140 ℃.
Examples 1 to 5
The embodiment provides a degradable PBST/P34HB blend, the weight parts of the components are shown in Table 1, and the preparation method comprises the following steps:
PBST and P34HB resin are mixed, and then are fully mixed with a plasticizer, an inorganic filler, an antioxidant and a lubricant, and then are melted and blended to obtain the blend.
Wherein, the plasticizer adopted in the embodiment 1-2 is tributyl citrate, the inorganic filler is calcium carbonate, the antioxidant is antioxidant 1076, and the lubricant is pentaerythritol stearate.
The plasticizer used in examples 3-5 was acetyl tributyl citrate, the inorganic filler was talc, the antioxidant was antioxidant 168, and the lubricant was pentaerythritol stearate.
Comparative example 1
The components and the preparation method of the comparative example are basically the same as those of the example 2, and the components and the contents are shown in the table 1.
Comparative example 2
The components and the preparation method of the comparative example are basically the same as those of the example 1, and the components and the contents are shown in the table 1.
Comparative example 3
The components and the preparation method of the comparative example are basically the same as those of the example 3, and the components and the contents are shown in the table 1.
Comparative example 4
The components and the preparation method of the comparative example are basically the same as those of the example 1, and the components and the contents are shown in the table 1.
TABLE 1
| PBST | P34HB | Plasticizer | Inorganic filler | Antioxidant agent | Lubricant agent | |
| Example 1 | 90 | 10 | 10 | 1 | 0.5 | 0.1 |
| Example 2 | 85 | 15 | 2 | 5 | 0.1 | 0.2 |
| Example 3 | 88 | 12 | 5 | 3 | 1 | 0.5 |
| Example 4 | 80 | 20 | 7 | 4 | 0.7 | 0.3 |
| Example 5 | 75 | 25 | 10 | 2 | 1 | 0.5 |
| Comparative example 1 | 85 | 15 | - | 5 | 0.1 | 0.2 |
| Comparative example 2 | 90 | 10 | 0.5 | 10 | 0.5 | 0.1 |
| Comparative example 3 | 88 | 12 | 5 | - | 1 | 0.5 |
| Comparative example 4 | 95 | 5 | 10 | 1 | 0.5 | 0.1 |
Comparative example 5
This comparative example is essentially the same as example 1 in terms of components and preparation, except that: this comparative example used PBS instead of PBST, and the resulting product was a PBS/P34HB blend. The preparation method of the PBS comprises the following steps:
putting a certain amount of succinic acid and 1, 4-butanediol (the molar ratio of acid to alcohol is 1:1.2) into a reaction kettle, starting stirring under the atmosphere of nitrogen, keeping the temperature constant and carrying out esterification reaction at 180 ℃ until anhydrous distillation is finished, wherein the reaction time is about 2 hours; then adding 3 wt% of catalyst tetrabutyl titanate, and carrying out polycondensation reaction at 220 ℃ and under the pressure of-0.1 MPa, wherein the reaction time is about 2 hours. And after the reaction is finished, cooling to 60 ℃ to obtain the product PBS.
Comparative example 6
This comparative example is essentially the same as example 1 in terms of components and preparation, except that: the procedure for the preparation of PBST used in this comparative example was as follows:
mixing succinic acid, 1, 4-butanediol and 1, 5-pentanediol according to an acid-alcohol molar ratio of 1:1.2, the mass percentage of 1, 4-butanediol and 1, 5-pentanediol is 80 percent and 20 percent, and the reaction is carried out in a reaction kettle in two stages: the esterification reaction temperature of the first stage is 200 ℃, and the reaction time is 2 hours; and the second-stage polycondensation reaction is carried out at the temperature of 200 ℃ for 2h to obtain the PBST.
Effect verification:
the blends prepared in each example and comparative example were subjected to performance tests, and the results are shown in table 2.
The testing method of the mechanical property adopts standard methods of GBT1843-2008 (plastic cantilever beam impact strength measurement) and GB/T1040-; the method for testing the degradability is GB/T19277-2013 (determination of the final aerobic biological decomposition capacity of the material under the controlled composting condition).
TABLE 2
Note: in Table 2, comparative example 1 is PBS prepared by the method of comparative example 5 of the present invention; comparative example 2 is PBST prepared using the method of the present invention example.
The invention has many applications, and the above description is only a preferred embodiment of the invention. It should be noted that the above examples are only for illustrating the present invention, and are not intended to limit the scope of the present invention. It will be apparent to those skilled in the art that various modifications can be made without departing from the principles of the invention and these modifications are to be considered within the scope of the invention.
Claims (9)
1. A degradable PBST/P34HB blend, characterized by: the paint comprises the following components in parts by weight:
2. the degradable PBST/P34HB blend of claim 1, wherein: the paint comprises the following components in parts by weight:
3. the degradable PBST/P34HB blend according to claim 1, characterized in that: the P34HB resin is produced by Tianjin national rhyme biomaterial Co.
4. The degradable PBST/P34HB blend according to claim 1, characterized in that: the plasticizer is one or more of citric acid ester plasticizers.
5. The degradable PBST/P34HB blend according to claim 1, characterized in that: the inorganic filler is one or a mixture of calcium carbonate and talcum powder.
6. The degradable PBST/P34HB blend according to claim 1, characterized in that: the antioxidant is one or a mixture of two of antioxidant 1076 and antioxidant 168.
7. The degradable PBST/P34HB blend according to claim 1, characterized in that: the lubricant is pentaerythritol stearate.
8. A method of making the degradable PBST/P34HB blend according to any one of claims 1-7, characterized in that: the method comprises the following steps: PBST and P34HB resin are mixed, and then are fully mixed with a plasticizer, an inorganic filler, an antioxidant and a lubricant, and then are melted and blended to obtain the blend.
9. The method of making the degradable PBST/P34HB blend of claim 8, wherein: the melt blending temperature was 140 ℃.
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| CN2019107340897 | 2019-08-09 | ||
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070880A (en) * | 2010-12-24 | 2011-05-25 | 金发科技股份有限公司 | Biodegradable resin composition and product thereof |
| CN102421819A (en) * | 2009-04-06 | 2012-04-18 | 梅塔玻利克斯公司 | Method of improving film processing and injection molding of polyhydroxyalkanoate polymers |
| CN102977566A (en) * | 2012-12-31 | 2013-03-20 | 江苏华信塑业发展有限公司 | Degradable PHA/PBS (Polyhydroxyalkanoates/Polybutylene Succinate) blend sheet and preparation method thereof |
| WO2015092257A1 (en) * | 2013-12-17 | 2015-06-25 | Université De Reims Champagne-Ardenne | Composition based on agro-based biodegradable polymers |
| US20180334564A1 (en) * | 2015-11-17 | 2018-11-22 | Cj Cheiljedang Corporation | Polymer blends with controllable biodegradation rates |
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- 2020-08-07 CN CN202010791219.3A patent/CN111825964B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102421819A (en) * | 2009-04-06 | 2012-04-18 | 梅塔玻利克斯公司 | Method of improving film processing and injection molding of polyhydroxyalkanoate polymers |
| CN102070880A (en) * | 2010-12-24 | 2011-05-25 | 金发科技股份有限公司 | Biodegradable resin composition and product thereof |
| CN102977566A (en) * | 2012-12-31 | 2013-03-20 | 江苏华信塑业发展有限公司 | Degradable PHA/PBS (Polyhydroxyalkanoates/Polybutylene Succinate) blend sheet and preparation method thereof |
| WO2015092257A1 (en) * | 2013-12-17 | 2015-06-25 | Université De Reims Champagne-Ardenne | Composition based on agro-based biodegradable polymers |
| US20180334564A1 (en) * | 2015-11-17 | 2018-11-22 | Cj Cheiljedang Corporation | Polymer blends with controllable biodegradation rates |
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