CN110684190B - Preparation method of bio-based high-temperature nylon - Google Patents
Preparation method of bio-based high-temperature nylon Download PDFInfo
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- CN110684190B CN110684190B CN201910764330.0A CN201910764330A CN110684190B CN 110684190 B CN110684190 B CN 110684190B CN 201910764330 A CN201910764330 A CN 201910764330A CN 110684190 B CN110684190 B CN 110684190B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
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Abstract
The invention discloses a preparation method of bio-based high-temperature nylon, which comprises the following steps: (1) adding mixed diacid, pentanediamine, an alcohol solvent, a catalyst and an end-capping reagent into a reaction kettle, replacing air in the kettle with nitrogen, opening and heating, keeping the temperature for 1-2h at the temperature of 170-200 ℃, cooling, filtering or centrifuging, and recovering the solvent to obtain a white powdery prepolymer; (2) putting the white powdery prepolymer obtained in the step (1) into a vacuum drum, adding a heat stabilizer, vacuumizing, opening and heating, and reacting at the temperature of 220-; cooling and discharging to obtain the white polymer, namely the bio-based high-temperature nylon. According to the invention, mixed diacid and pentanediamine are selected as reaction raw materials, and a specific reaction solvent (alcohol solvent) is combined, so that the bio-based high-temperature nylon with more excellent performance can be prepared under the condition of lower requirements.
Description
Technical Field
The invention relates to the field of preparation of high-temperature nylon, in particular to a preparation method of bio-based high-temperature nylon.
Background
The high-temperature nylon is high-heat-resistance resin between general engineering plastic nylon and high-temperature-resistant engineering plastic PEEK, and is widely applied to the fields of electronic and electrical industry, automobile industry and the like. The material has excellent comprehensive properties, such as: short-term and long-term heat resistance, high rigidity, creep resistance at high temperature, outstanding toughness, excellent fatigue resistance, good chemical resistance.
Domestic and foreign patents such as CN102153741A, CN101289535A, CN1012153751A, CN102477219A, US4603166, US4076664, US4762910, US6518341, US6747120, US4246395 and the like disclose preparation methods of high-temperature nylon, and methods of prepolymerization and then polymerization are mostly adopted, and a solid-phase or reactive screw extruder is generally adopted for the post polymerization to improve the molecular weight, wherein the prepolymerization process is the most critical and influences the final quality of products. In addition, most of domestic and foreign related enterprises still adopt petroleum-based raw materials to prepare high-temperature nylon, and sustainable development is not achieved.
After the twenty-first century, human beings are puzzled by energy and environmental problems, and in order to realize sustainable, green and environment-friendly development of macromolecules and related fine chemical industries, bio-based raw materials capable of replacing the existing petroleum are searched globally, so that the dependence on the petroleum is reduced, the national energy safety is improved, the pollution of the petroleum industry to the environment is reduced, and the common 'home' and earth are protected.
In recent years, the increase of the content of the bio-based materials is a new trend of being environment-friendly high polymer materials, and the preparation of the bio-based nylon by using biomass as a raw material, especially the bio-based high temperature nylon, is a hot point of domestic and foreign research and is a direction of future development of the high temperature nylon. China is in the same starting line with the renewable bio-based high-temperature nylon at abroad, and if the China actively advances, the situation that the current monopoly of petroleum-based high-temperature-resistant nylon is broken is expected to break, and the China is in the international leading level.
The bio-based pentanediamine is produced by renewable raw materials and a biological fermentation process, and compared with the existing production process of hexanediamine, the production process of the pentanediamine can obviously reduce the carbon footprint. At present, the domestic production is realized, the yield is sufficient, the price is equivalent to that of hexamethylene diamine, and the biogenic amine has excellent cost performance. The pentamethylene diamine is used as the matrix to prepare the novel high-performance bio-based high-temperature nylon.
Disclosure of Invention
The invention provides a preparation method of bio-based high-temperature nylon, which takes pentanediamine as a substrate to prepare the bio-based high-temperature nylon through copolymerization. Provides a new idea and a new method for preparing the high-temperature nylon resin, and is suitable for industrialization.
A preparation method of bio-based high-temperature nylon comprises the following steps:
(1) adding mixed diacid, pentanediamine, an alcohol solvent, a catalyst and an end-capping reagent into a reaction kettle, replacing air in the kettle with nitrogen, filling nitrogen to keep the pressure in the kettle at 0.05-0.1MPa, opening and heating, raising the temperature in the kettle to 170-200 ℃, keeping the temperature at 170-200 ℃ for 1-2h, cooling, filtering or centrifuging, and recovering the solvent to obtain a white powdery prepolymer;
(2) putting the white powdery prepolymer obtained in the step (1) into a vacuum drum, adding a heat stabilizer, vacuumizing, opening and heating, raising the temperature to 260 ℃ of 220-; cooling and discharging to obtain the white polymer, namely the bio-based high-temperature nylon.
According to the invention, mixed diacid and pentanediamine are selected as reaction raw materials, and a specific reaction solvent (alcohol solvent) is combined, so that the bio-based high-temperature nylon with more excellent performance can be prepared under the condition of lower requirements.
In the step (1), the mixed diacid is at least two of terephthalic acid, adipic acid, isophthalic acid and furandicarboxylic acid.
The alcohol solvent is ethanol.
The catalyst is sodium hypophosphite, potassium hypophosphite, sodium hypophosphite, magnesium hypophosphite, calcium hypophosphite or zinc hypophosphite, and preferably sodium hypophosphite.
The end-capping reagent comprises any one of benzoic acid, naphthoic acid, methylnaphthoic acid and phenylacetic acid, and preferably benzoic acid.
The mixed diacid, the pentanediamine, the alcohol solvent, the catalyst, the end-capping agent and the heat stabilizer comprise the following components in percentage by mass: 40-80 parts of mixed diacid: 30-50 parts of pentamethylene diamine: 200-500 parts of an alcohol solvent: 0.1-5 parts of a catalyst: 0.1-5 parts of end-capping agent: 0.1-5 parts of a heat stabilizer.
More preferably, the mixed diacid, the pentanediamine, the alcohol solvent, the catalyst, the end-capping agent and the heat stabilizer are in mass fraction: 50-70 parts of mixed diacid: 35-45 parts of pentamethylene diamine: 200-400 parts of an alcohol solvent: 0.1-5 parts of a catalyst: 0.1-5 parts of end-capping agent: 0.1-5 parts of a heat stabilizer.
The air in the kettle was replaced with nitrogen three times.
Still more preferably, the temperature in the vessel is raised to 190 ℃ and maintained at 190 ℃ for 1 hour.
The reaction formula is as follows:
in the step (2), the vacuum is pumped to 0-50 Pa, and preferably to 20 Pa.
The temperature is increased to 230 ℃, and the reaction is carried out for 6h at 230 ℃;
the heat stabilizer comprises any one of copper chloride, copper bromide, copper iodide, copper dichloride, copper dibromide, copper diiodide and copper phosphate, and preferably copper iodide.
In the preparation method (1), the prepolymerization temperature is controlled to be between 170 ℃ and 220 ℃ and lower than 170 ℃, the reaction monomers cannot be effectively converted into prepolymers, the temperature is too high, the pressure in the reactor is too high, the requirement on equipment is high, and side reactions are easy to occur.
Compared with the prior art, the invention has the following advantages:
firstly, the bio-based reaction monomer pentanediamine is used as a substrate to prepare the bio-based high-temperature nylon with a novel chemical structure through copolymerization, and the prepared bio-based high-temperature nylon has more excellent performance.
Secondly, alcohol is used as a reaction solvent, and a specific reactant (mixed diacid and 1, 5-pentanediamine) is combined, so that a chemical reaction can be carried out at a low temperature (below 200 ℃), a prepolymer is promoted to be generated, the requirement on equipment is not high, the energy consumption of the reaction is low, the alcohol solvent can be mutually dissolved with water generated in the reaction, the polycondensation reaction is accelerated to be carried out in the positive direction, the obtained prepolymer is powdery, and the discharge is convenient.
Drawings
FIG. 1 is an infrared spectrum of bio-based high temperature nylon obtained in example 1;
FIG. 2 is a DSC (Differential Scanning calorimetry) curve of the bio-based high temperature nylon obtained in example 1;
FIG. 3 is a DSC curve of high temperature nylon PA6T prepared using 1, 6-hexanediamine.
Detailed Description
The following examples and comparative examples illustrate the present invention by way of illustration and explanation of the synthetic process, but do not limit the scope of the invention.
1. Intrinsic viscosity [ eta ]
The nylon tested was dissolved in concentrated sulfuric acid to give concentrations of 1g/dl, 0.8g/dl, 0.6g/dl, 0.4g/dl, 0.2g/dl, respectively, and the logarithmic viscosity η inh of the solution was measured at 25 ℃:
ηinh＝[ln(t1/t0)]/C
where t0 represents the time(s) of solvent outflow, t1 represents the time(s) of sample solution outflow, C represents the concentration (g/dl) of the sample solution, and η inh represents the logarithmic viscosity number (dl/g).
Extrapolating the data of η inh to a concentration of 0 to obtain the intrinsic viscosity of the sample.
2. Melting Point
The melting point of the sample was measured using a Mettler-Toriledo DSC1 apparatus, and the temperature was raised from room temperature to 330 ℃ at 10 ℃/min under nitrogen atmosphere for 5min, then cooled at 10 ℃/min to room temperature, and then raised at 10 ℃/min to 330 ℃ at which the endothermic peak temperature was the polymer melting point.
3. Mechanical properties
The prepared nylon injection molding test sample bar is tested for tensile strength according to the GB/T1040.2 standard, bending strength and bending modulus according to the GB/T9341-2008 standard, and impact strength of a simply supported beam according to the GB/T1043.1 standard.
Example 1
Preparation of prepolymer: adding 100 parts of reaction monomers (37.16 parts of terephthalic acid, 23.55 parts of adipic acid and 39.29 parts of 1, 5-pentanediamine), 300 parts of ethanol and 1.28 parts of auxiliaries (0.4 part of sodium hypophosphite and 0.88 part of benzoic acid) into a high-temperature high-pressure reaction kettle, replacing tertiary air with nitrogen, and filling nitrogen, wherein the initial pressure in the kettle is 0.1 MPa; starting heating and stirring, and reacting for 1h at the temperature of 190 ℃ when the internal temperature is stabilized; cooling, filtering or centrifuging, and recovering the solvent to obtain the white powdery prepolymer.
Preparation of the polymer: adding the white powdery prepolymer and 0.5 part of copper iodide into a vacuum rotary drum, and keeping the pressure in the rotary drum at 20 Pa; raising the temperature to 230 ℃, and reacting for 6 hours at the temperature; cooling and discharging to obtain the white polymer, namely the bio-based high-temperature nylon.
FIG. 1 is an infrared spectrum of the polymer obtained in example 1, from FIG. 1, it can be seen that N-H absorption peak of stretching vibration is at 3308 cm-1; the 2935cm-1 and 2867cm-1 are stretching vibration absorption peaks of methylene (-CH 2-); a stretching vibration absorption peak of C ═ O at 1626 cm-1; 1542cm-1 of N-H bending vibration absorption peak; the deformation vibration absorption peaks at 1497cm-1 and 1438cm-1 are (-CH 2-); the C-N stretching vibration absorption peak at 1291cm < -1 > indicates nylon; from the DSC curve of FIG. 2, it can be seen that the melting point of the polymer is 312 ℃ and the glass transition temperature is 100.3 ℃.
PA6T polymer was prepared by changing 1, 5-pentanediamine to 1, 6-hexanediamine and the other conditions were the same as in example 1, and FIG. 3 shows the DSC curve of PA6T, the melting point was 320 ℃ and the glass transition temperature was 92 ℃.
Compared with PA6T, PA5T (the bio-based high-temperature nylon prepared by 1, 5-pentanediamine in the invention) has the advantages that the flexibility of a molecular chain is reduced and the difficult movement of the chain segment is increased due to the shortening of the carbon chain, so that the glass transition temperature of PA5T is increased.
Example 2
The prepolymer synthesis process is the same as that of example 1, except that the amount of the reaction monomers is 30.23 parts of furandicarboxylic acid, 30.97 parts of terephthalic acid and 38.8 parts of 1, 5-pentamethylenediamine in example 2.
The polymer preparation process was the same as in example 1.
Example 3
The prepolymer synthesis process was the same as in example 1, except that the amount of the reaction monomers was changed, and in example 3, 40.25 parts of terephthalic acid, 21.67 parts of isophthalic acid and 38.08 parts of 1, 5-pentanediamine were used.
The polymer preparation process was the same as in example 1.
Comparative example 1
The prepolymer synthesis was the same as in example 1, except that the amount of the reactive monomers charged was 37.16 parts terephthalic acid, 23.55 parts adipic acid and 39.29 parts 1, 6-hexanediamine in comparative example 1.
The polymer preparation process was the same as in example 1.
Comparative example 2
The prepolymer synthesis process was the same as in example 1, except that 300 parts of deionized water was used as the reaction solvent instead of 300 parts of ethanol in example 1.
The polymer preparation process was the same as in example 1.
Table 1: EXAMPLES comparative Properties of the obtained Nylon resin
Comparative example 1 adopts 1, 6-hexanediamine, and the high-temperature nylon prepared by the method has unsatisfactory performance due to the fact that the temperature of reaction conditions is not high enough. The comparative example 2 adopts deionized water to react in a water reaction system, the performance of the high-temperature nylon prepared under the condition is not ideal enough, and the water reaction system and the lower temperature condition are mainly not beneficial to the generation of the high-temperature nylon with excellent performance. In embodiments 1 to 3, the bio-based high-temperature nylon with better performance can be prepared under the condition of lower temperature requirement by using mixed diacid and 1, 5-pentanediamine as reaction raw materials and combining a specific reaction solvent (alcohol solvent, namely ethanol).
Claims (8)
1. The preparation method of the bio-based high-temperature nylon is characterized by comprising the following steps:
(1) adding mixed diacid, pentanediamine, an alcohol solvent, a catalyst and an end-capping reagent into a reaction kettle, replacing air in the kettle with nitrogen, filling nitrogen to keep the pressure in the kettle at 0.05-0.1MPa, opening and heating, raising the temperature in the kettle to 170-200 ℃, keeping the temperature at 170-200 ℃ for 1-2h, cooling, filtering or centrifuging, and recovering the solvent to obtain a white powdery prepolymer;
(2) putting the white powdery prepolymer obtained in the step (1) into a vacuum drum, adding a heat stabilizer, vacuumizing, opening and heating, raising the temperature to 260 ℃ below 220-;
the heat stabilizer is any one of copper chloride, copper bromide, copper iodide, copper dichloride, copper dibromide, copper diiodide and copper phosphate;
in the steps (1) and (2), the mixed diacid, the pentanediamine, the alcohol solvent, the catalyst, the end-capping reagent and the heat stabilizer are prepared from the following components in parts by weight: 40-80 parts of mixed diacid: 30-50 parts of pentamethylene diamine: 200-500 parts of an alcohol solvent: 0.1-5 parts of a catalyst: 0.1-5 parts of end-capping agent: 0.1-5 parts of a heat stabilizer.
2. The method for preparing bio-based high temperature nylon according to claim 1, wherein in step (1), the mixed diacid is at least two of terephthalic acid, adipic acid, isophthalic acid and furandicarboxylic acid.
3. The method for preparing bio-based high temperature nylon according to claim 1, wherein in the step (1), the alcohol solvent is ethanol.
4. The method as claimed in claim 1, wherein in step (1), the catalyst is sodium hypophosphite, potassium hypophosphite, sodium hypophosphite, magnesium hypophosphite, calcium hypophosphite or zinc hypophosphite.
5. The method for preparing bio-based high temperature nylon according to claim 1, wherein in the step (1), the end-capping reagent is any one of benzoic acid, naphthoic acid, methylnaphthoic acid and phenylacetic acid.
6. The method for preparing bio-based high temperature nylon according to claim 1, wherein in the step (1), the air in the autoclave is replaced with nitrogen three times.
7. The method for preparing bio-based high temperature nylon according to claim 1, wherein in the step (1), the temperature in the kettle is raised to 190 ℃ and is maintained at 190 ℃ for 1 h.
8. The method for preparing bio-based high temperature nylon according to claim 1, wherein in the step (2), the temperature is raised to 230 ℃ and the reaction is carried out for 6h at 230 ℃.
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| CN113214471B (en) * | 2020-01-21 | 2023-11-17 | 上海凯赛生物技术股份有限公司 | Polyamide 5X resin, preparation method thereof and high-strength high-modulus fiber |
| CN111471297B (en) * | 2020-05-11 | 2022-12-16 | 浙江新力新材料股份有限公司 | Preparation method and application of bio-based transparent polyamide |
| CN113896886B (en) * | 2021-09-24 | 2023-07-25 | 珠海万通特种工程塑料有限公司 | Furandioic acid-based polyamide, preparation method thereof and furandioic acid-based polyamide composition |
| CN113930070B (en) * | 2021-09-28 | 2023-10-20 | 浙江新力新材料股份有限公司 | Preparation method and application of low-dielectric-constant bio-based high-temperature nylon |
| CN113999388B (en) * | 2021-12-30 | 2022-04-08 | 富海(东营)新材料科技有限公司 | Preparation method of bio-based high-temperature-resistant nylon PA5T/5I copolymer |
| CN117209751A (en) * | 2022-06-02 | 2023-12-12 | 中国科学院化学研究所 | Preparation method of all-bio-based polyamide |
| CN115505120A (en) * | 2022-10-31 | 2022-12-23 | 中国五环工程有限公司 | High-performance bio-based copolymerized nylon and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768266A (en) * | 2009-12-25 | 2010-07-07 | 郑州大学 | Method for preparing semi-aromatic nylon |
| CN103387667A (en) * | 2013-07-31 | 2013-11-13 | 上海凯赛生物技术研发中心有限公司 | Semi-aromatic nylon and preparation method thereof |
| JP2015034276A (en) * | 2013-07-08 | 2015-02-19 | 宇部興産株式会社 | Polyamide resin |
| CN104710613A (en) * | 2015-03-12 | 2015-06-17 | 中国科学院理化技术研究所 | Solvent-thermal preparation method for semi-aromatic polyamide |
| CN109575277A (en) * | 2018-12-06 | 2019-04-05 | 浙江新力新材料股份有限公司 | A kind of preparation method of high-fire resistance nylon |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768266A (en) * | 2009-12-25 | 2010-07-07 | 郑州大学 | Method for preparing semi-aromatic nylon |
| JP2015034276A (en) * | 2013-07-08 | 2015-02-19 | 宇部興産株式会社 | Polyamide resin |
| CN103387667A (en) * | 2013-07-31 | 2013-11-13 | 上海凯赛生物技术研发中心有限公司 | Semi-aromatic nylon and preparation method thereof |
| CN104710613A (en) * | 2015-03-12 | 2015-06-17 | 中国科学院理化技术研究所 | Solvent-thermal preparation method for semi-aromatic polyamide |
| CN109575277A (en) * | 2018-12-06 | 2019-04-05 | 浙江新力新材料股份有限公司 | A kind of preparation method of high-fire resistance nylon |
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Denomination of invention: A Preparation Method of Biobased High Temperature Nylon Effective date of registration: 20220930 Granted publication date: 20220408 Pledgee: Industrial and Commercial Bank of China Limited Rui'an sub branch Pledgor: ZHEJIANG SHINY NEW MATERIAL CO.,LTD. Registration number: Y2022330002415 |
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