CN107573502B - Preparation method of long carbon chain nylon 1211 - Google Patents
Preparation method of long carbon chain nylon 1211 Download PDFInfo
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- CN107573502B CN107573502B CN201710676108.6A CN201710676108A CN107573502B CN 107573502 B CN107573502 B CN 107573502B CN 201710676108 A CN201710676108 A CN 201710676108A CN 107573502 B CN107573502 B CN 107573502B
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Abstract
The invention discloses a preparation method of long carbon chain nylon 1211. The process comprises the steps of synthesizing nylon 1211 salt in an alcohol solvent by using dodecanediamine and undecanedioic acid as main raw materials, adding a catalyst and an antioxidant into the dried nylon salt, heating and pressurizing, and carrying out polymerization reaction to obtain the nylon 1211. The product of the invention is superior to nylon 11 in structural performance, and has good mechanical and thermodynamic properties; the method is used for preparing the composite material under high pressure, effectively shortens the molding period, improves the production efficiency, can meet the requirements of people on the automobile industry, the aerospace industry, the electronic and electrical industry and the like, and has good market prospect.
Description
Technical Field
The invention relates to a preparation method of nylon, in particular to a preparation method of long carbon chain nylon 1211.
Background
The polyamide is one of five engineering plastics, and is a thermoplastic engineering plastic which is widely applied at home and abroad due to the excellent characteristics of toughness, wear resistance, impact resistance, corrosion resistance, fatigue resistance, oil resistance and the like. The nylon containing less than 10 carbon chains (including 10 carbon chains) is called short carbon chain nylon internationally, mainly comprises nylon 6 and nylon 66, and accounts for about 90 percent of the total amount of the nylon; the nylon containing more than 10 carbon chains is changed into long-carbon-chain nylon, mainly comprising nylon 11 and nylon 12, and the total yield of the nylon is about 10 percent.
Long carbon chain nylons have many unique advantages over conventional nylons, and have been of particular interest in industry, such as: the paint has the advantages of low water absorption, good flexibility, good dimensional stability, wear resistance, corrosion resistance, good low-temperature impact resistance, good electrical insulation property and the like, is widely applied to the fields of automobiles, machinery, aviation, aerospace, electronics, electricity, information, buildings, textiles and the like, and is a key research field at home and abroad at present; the long carbon chain nylon resin is used as a base to develop a reinforced and flame-retardant modified material, so that the characteristics of high strength, wear resistance, heat resistance and the like of common nylon are reserved, and the modified material has excellent low-temperature flexibility. Therefore, the long carbon chain nylon is the current nylon with the important research and development direction in the world.
Nylon 1010 is the long carbon chain nylon with the best industrialization performance in China at present, a plurality of researchers develop modified materials based on the nylon 1010 at present, and Chinese patents CN1491990A, CN101899153A and CN103483813A disclose that the nylon 1010 is respectively made into composite materials with montmorillonite, nano silicon dioxide and nano titanium dioxide to modify the physical and mechanical properties. In order to research nylon materials with better performance, zheng zhou university develops nylon 1111 and nylon 1212 materials, and the existing literature and patent search finds that Chinese patents CN101880458B and CN1095479C disclose the preparation process of nylon 1212, and nylon 1212 belongs to even nylon, so nylon 1212 has high hydrogen bond content, so that nylon 1212 has higher water absorption in long carbon chain nylon family.
Disclosure of Invention
In order to solve the problems in the background art, the invention aims to provide a preparation method of long carbon chain nylon 1211, which obtains a new type of long carbon chain nylon 1211, has good mechanical properties and low water absorption rate, and has no related patent report at present.
As shown in fig. 1, the technical scheme adopted by the invention comprises the following specific steps:
a. adding undecane dibasic acid into alcohol at normal temperature, heating to 40-60 ℃, adding dodecane diamine for reaction until the pH value is 7.0-8.0, and continuing to react for 1-1.5 hours at constant temperature to obtain a nylon salt solution;
b. purifying the nylon 1211 salt by using a suction filter, separating and purifying the nylon 1211 salt from the nylon salt solution to obtain a purified nylon 1211 salt, and drying the purified nylon 1211 salt at the temperature of 50-60 ℃ for 10-24 hours to obtain a dry white powdery nylon 1211 salt.
The separation and purification of the nylon salt solution to obtain the refined nylon 1211 salt specifically utilizes the technical characteristics that the nylon 1211 salt has low solubility in alcohol and impurities have high solubility in alcohol.
The refined nylon 1211 salt has higher purity, and is favorable for synthesizing high-purity nylon.
c. The dry white powder nylon 1211 salt, water, the anti-aging agent and the molecular weight regulator are processed together to prepare the finished nylon 1211.
In the step a, the molar ratio of the undecanedioic acid to the dodecanediamine is as follows: 1: 1.0-1: 1.2.
The nylon salt solution prepared in the step a contains a molecular formula of H3 +N(CH2)12N+H3 -OOC(CH2)9COO-A salt.
The step c comprises the following steps:
c.1, mixing dry white powdery nylon 1211 salt, water, an anti-aging agent and a molecular weight regulator, adding the mixture into a polymerization reaction kettle, vacuumizing until oxygen in the kettle is exhausted, filling inert gas into the polymerization reaction kettle until the pressure is 0.01-0.5 MPa, and heating to control the temperature to be 120-150 ℃ for reaction for 0.5-1 hour;
c.2, heating to 190-200 ℃, keeping the pressure in the polymerization kettle at 1.1-1.7 MPa, keeping the temperature for 1-1.5 hours, and then discharging gas to normal pressure, wherein the gas discharging time is controlled to be 200-300 minutes;
c.3, heating to 250-260 ℃, and then vacuumizing, wherein the vacuum degree is 0.01-50 KPa, and the pumping time is 30-50 min;
c.4, finally discharging, cooling and granulating to obtain the material containing the molecular formula of- [ -HN (CH)2)12NHOC(CH2)9CO-]-nN is 60-300.
In the step c, the ratio of the salt of nylon 1211, water, the anti-aging agent and the molecular weight regulator is 1: 0.5-2: 0.01% -0.4%: 0.1 to 1 percent by weight.
In the step c, the water is distilled water or deionized water.
In the step c, the anti-aging agent is phosphorous acid or potassium chloride or stannous chloride or copper acetate.
In the step c, the molecular weight regulator is undecane dicarboxylic acid or adipic acid or acetic acid.
The product of the invention is superior to nylon 11 and nylon 12 in comprehensive performance, and has good mechanical and thermodynamic properties; the nylon of the invention is characterized by lower water absorption and flexibility than long carbon chain nylon sold in the market. The preparation is carried out under high pressure, so that the polymerization reaction period is effectively shortened, and the production efficiency is improved.
The raw materials of the nylon 1211 synthetic material, namely the undecanedioic acid and the dodecanediamine, are obtained from a byproduct light wax of petroleum refining after microbial fermentation, and the raw material source is wide.
The nylon 1211 can be widely applied to the fields of electronic and electric appliance elements, precision equipment, medical equipment, automobile industry and the like.
The invention has the beneficial effects that:
compared with other existing industrialized nylon materials, the invention prepares and obtains the new type nylon 1211. Nylon 1211 has a lower CONH/CH relative to nylon 10102The molecular chain has better fluidity, so better flexibility is obtained. Nylon 1212CONH/CH tube only2The ratio of (A) is lower than that of nylon 1211, but nylon 1212 belongs to coupling nylon, so that the coupling nylon has higher crystallinity and reduces the flexibility of the coupling nylon. At the same time, the high hydrogen bond density of nylon 1212 increases its water absorption, which decreases dimensional stability in humid environments.
Compared with the existing process method of other types of nylon, the one-step method is adopted to polymerize the nylon 1211. Compared with other nylon processes, the process flow of the invention is short, and the purity of the polymer is high under the process condition.
The preparation method of the invention effectively accelerates the polymerization of the polymer monomer by the preparation at the early stage through high temperature and high pressure. And further heating and raising the temperature in the later reaction stage, and removing the small-molecular polymer in the polymer under the vacuum condition to increase the molecular weight of the polymer, so that the overall performance of the discharged polymer is more excellent.
Drawings
FIG. 1 is a diagram of the steps of the method of the present invention.
Detailed Description
The invention is further illustrated by the following figures and examples.
The examples of the invention are as follows:
example 1
a. Firstly, 54 kg of undecanedioic acid (molecular formula is HOOC- (CH)) is added at normal temperature2)9-COOH) in alcohol, heating to 40 deg.C, adding 50 kg of dodecadiamine (molecular formula H)2N-(CH2)12-NH2) Adding into reaction, adjusting pH to 7.0 with undecanedioic acid, stirring at 40 deg.C for 1.5 hr to obtain a mixture containing molecular formula H3 +N(CH2)12N+H3 -OOC(CH2)9COO-Nylon salt solution.
b. Purification of the nylon 1211 salt with a suction filter: the method comprises separating and purifying nylon 1211 salt to obtain refined nylon 1211 salt, and drying the refined nylon 1211 salt at 60 deg.C for 10 hr to obtain 103.5 kg of white powder nylon 1211 salt.
c. Mixing dry white powdery nylon 1211 salt, water, an anti-aging agent and a molecular weight regulator according to the weight ratio of 1:2: 0.01% to 0.1%, adding the mixture into a polymerization reaction kettle, vacuumizing until the pressure in the kettle reaches-0.1 MPa, filling high-purity nitrogen gas to 0.01MPa, vacuumizing again until the pressure in the kettle reaches-0.1 MPa, filling the high-purity nitrogen gas, and repeating the steps for 5 times; heating, controlling the temperature at 120 ℃, reacting for 1 hour, heating to 190 ℃, keeping the pressure in the polymerization kettle at 1.1MPa, slowly exhausting to normal pressure after keeping the temperature for 1 hour, controlling the exhausting time at 200 minutes, heating to 250 ℃, starting to vacuumize, controlling the reaction vacuum degree at 0.01KPa, and extracting for 30 minutes. Discharging, cooling, granulating, and oven drying to obtain powder with molecular formula of- [ -HN (CH)2)12NHOC(CH2)9CO-]-n94 kg of nylon 1211 finished product, and the yield is 91.4%.
Example 2
a. Firstly, at normal temperature, the86 kg of undecanedioic acid (molecular formula HOOC- (CH))2)9-COOH) in alcohol, heating to 50 deg.C, adding 80 kg of dodecadiamine (molecular formula H)2N-(CH2)12-NH2) Adding into the mixture for reaction, adjusting the pH value to 7.5 by using undecanedioic acid, stirring for 1.5 hours at the constant temperature of 50 ℃ to obtain a molecular formula H3 +N(CH2)12N+H3 -OOC(CH2)9COO-Nylon salt solution.
b. Purification of the nylon 1211 salt with a suction filter: the method utilizes the characteristics that the solubility of the nylon 1211 salt in alcohol is low and the solubility of impurities in alcohol is high, the nylon 1211 salt is separated and purified to obtain refined nylon 1211 salt, and the refined nylon 1211 salt is dried at the temperature of 60 ℃ for 18 hours to obtain 165.5 kg of dried white powdery nylon 1211 salt.
c. Mixing dry white powdery nylon 1211 salt, water, an anti-aging agent and a molecular weight regulator according to the weight ratio of 1:1: 0.1% to 0.5%, adding the mixture into a polymerization reaction kettle, vacuumizing until the pressure in the kettle reaches-0.1 MPa, filling high-purity nitrogen gas to 0.01MPa, vacuumizing again until the pressure in the kettle reaches-0.1 MPa, filling the high-purity nitrogen gas, and repeating the steps for 5 times; heating, controlling the temperature at 140 ℃, reacting for 0.5 hour, heating to 195 ℃, keeping the pressure in the polymerization kettle at 1.5MPa, slowly exhausting to normal pressure after keeping the temperature for 1.5 hours, controlling the exhausting time at 240 minutes, heating to 255 ℃, starting to vacuumize, controlling the reaction vacuum degree at 30KPa, and extracting for 40 min. Discharging, cooling, granulating, and oven drying to obtain powder with molecular formula of- [ -HN (CH)2)12NHOC(CH2)9CO-]-n148 kg of nylon 1211 finished product, and the yield is 90.1%.
Example 3
a. Firstly, 108 kg of undecane diacid (molecular formula of HOOC- (CH)) is added at normal temperature2)9-COOH) in alcohol, heating to 50 deg.C, adding 100 kg of dodecadiamine, reacting with undecanedioic acid (molecular formula H)2N-(CH2)12-NH2) Adjusting pH value to 8, 60 deg.CStirring for 1 hour to obtain a molecular formula H3 +N(CH2)12N+H3 -OOC(CH2)9COO-Nylon salt solution.
b. Purification of the nylon 1211 salt with a suction filter: the method utilizes the characteristics that the solubility of the nylon 1211 salt in alcohol is low and the solubility of impurities in alcohol is high to separate and purify the nylon 1211 salt to obtain refined nylon 1211 salt, and the refined nylon 1211 salt is dried for 24 hours at the temperature of 60 ℃ to obtain 207 kg of the dried white powdery nylon 1211 salt.
c. Mixing dry white powdery nylon 1211 salt, water, an anti-aging agent and a molecular weight regulator according to the weight ratio of 1:1: 0.4% to 1%, adding the mixture into a polymerization reaction kettle, vacuumizing the polymerization reaction kettle until the pressure in the kettle reaches-0.1 MPa, filling high-purity nitrogen gas into the polymerization reaction kettle, vacuumizing the polymerization reaction kettle until the pressure in the kettle reaches-0.1 MPa, and filling the high-purity nitrogen gas into the polymerization reaction kettle, and repeating the steps for 5 times; heating, controlling the temperature at 150 ℃, reacting for 0.5 hour, heating to 200 ℃, keeping the pressure in the polymerization kettle at 1.7MPa, keeping the temperature for 1.5 hours, slowly exhausting to normal pressure, controlling the exhausting time at 300 minutes, heating to 260 ℃, starting to vacuumize, controlling the reaction vacuum degree at 50KPa, and extracting for 50 min. Discharging, cooling, granulating, and oven drying to obtain powder with molecular formula of- [ -HN (CH)2)12NHOC(CH2)9CO-]-n186 kg of nylon 1211 finished product and 89.5 percent of yield.
The obtained product nylon 1211 is tested for the saturation water absorption and the mechanical property of nylon according to national standards, and the comparison refers to data of nylon 11, nylon 12, nylon 1010 and nylon 1212, and the test of the conditions is as follows:
as can be seen from the above examples, the nylon 1211 of the invention has low water absorption and better flexibility than nylon 1010 and nylon 1212.
The above embodiments are merely preferred examples to illustrate the present invention, and it should be apparent to those skilled in the art that any obvious variations and modifications can be made without departing from the spirit of the present invention.
Claims (6)
1. The preparation method of the long carbon chain nylon 1211 is characterized by comprising the following specific steps of:
a. adding undecane dibasic acid into alcohol at normal temperature, heating to 40-60 ℃, adding dodecane diamine for reaction until the pH value is 7.0-8.0, and continuing to react for 1-1.5 hours at constant temperature to obtain a nylon salt solution;
b. purifying the nylon 1211 salt by using a suction filter, separating and purifying the nylon 1211 salt solution to obtain a refined nylon 1211 salt, and drying the refined nylon 1211 salt at the temperature of 50-60 ℃ for 10-24 hours to obtain a dry white powdery nylon 1211 salt;
c. processing dry white powdery nylon 1211 salt, water, an anti-aging agent and a molecular weight regulator together to prepare a nylon 1211 finished product;
the step c comprises the following steps:
c.1, mixing dry white powdery nylon 1211 salt, water, an anti-aging agent and a molecular weight regulator, adding the mixture into a polymerization reaction kettle, vacuumizing until oxygen in the kettle is exhausted, filling inert gas into the polymerization reaction kettle until the pressure is 0.01-0.5 MPa, and heating to control the temperature to be 120-150 ℃ for reaction for 0.5-1 hour;
in the step c, the ratio of the salt of nylon 1211, water, the anti-aging agent and the molecular weight regulator is 1: 0.5-2: 0.01% -0.4%: 0.1 to 1 percent by weight;
c.2, heating to 190-200 ℃, keeping the pressure in the polymerization kettle at 1.1-1.7 MPa, keeping the temperature for 1-1.5 hours, and then discharging gas to normal pressure, wherein the gas discharging time is controlled to be 200-300 minutes;
c.3, heating to 250-260 ℃, and then vacuumizing, wherein the vacuum degree is 0.01-50 KPa, and the pumping time is 30-50 min;
c.4, finally discharging, cooling and granulating to obtain the material containing the molecular formula of- [ -HN (CH)2)12NHOC(CH2)9CO-]-nN is 60-300.
2. The method of claim 1, wherein the long carbon chain nylon 1211 is prepared by: in the step a, the molar ratio of the undecanedioic acid to the dodecanediamine is as follows: 1: 1.0-1: 1.2.
3. The method of claim 1, wherein the long carbon chain nylon 1211 is prepared by: the nylon salt solution prepared in the step a contains a molecular formula of H3 +N(CH2)12N+H3 -OOC(CH2)9COO-A salt.
4. The method of claim 1, wherein the long carbon chain nylon 1211 is prepared by: in the step c, the water is distilled water or deionized water.
5. The method of claim 1, wherein the long carbon chain nylon 1211 is prepared by: in the step c, the anti-aging agent is phosphorous acid or potassium chloride or stannous chloride or copper acetate.
6. The method of claim 1, wherein the long carbon chain nylon 1211 is prepared by: in the step c, the molecular weight regulator is undecane dicarboxylic acid or adipic acid or acetic acid.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1353129A (en) * | 2001-11-29 | 2002-06-12 | 巴陵石化岳阳石油化工总厂 | Process for preparing copolymerized nylon 613 or 1013 |
| CN1580094A (en) * | 2003-08-07 | 2005-02-16 | 上海杰事杰新材料股份有限公司 | Process for producing long carbon chain nylon salt |
| CN101210071A (en) * | 2006-12-25 | 2008-07-02 | 上海凯赛生物技术研发中心有限公司 | Technique for synthesizing nylon from long chain dicarboxylic acid grown based on biological method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1353129A (en) * | 2001-11-29 | 2002-06-12 | 巴陵石化岳阳石油化工总厂 | Process for preparing copolymerized nylon 613 or 1013 |
| CN1580094A (en) * | 2003-08-07 | 2005-02-16 | 上海杰事杰新材料股份有限公司 | Process for producing long carbon chain nylon salt |
| CN101210071A (en) * | 2006-12-25 | 2008-07-02 | 上海凯赛生物技术研发中心有限公司 | Technique for synthesizing nylon from long chain dicarboxylic acid grown based on biological method |
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Effective date of registration: 20220119 Address after: 310018 928, 2 Avenue, Xiasha Higher Education Park, Jianggan District, Hangzhou, Zhejiang. Patentee after: ZHEJIANG SCI-TECH University Patentee after: BEIJING University OF CHEMICAL TECHNOLOGY Patentee after: INSTITUTE OF QUARTERMASTER ENGINEERING TECHNOLOGY, INSTITUTE OF SYSTEMS ENGINEERING, ACADEMY OF MILITARY SCIENCES Address before: No.928, No.2 street, Jianggan Economic Development Zone, Hangzhou City, Zhejiang Province, 310018 Patentee before: ZHEJIANG SCI-TECH University Patentee before: Beijing University of Chemical Technology |
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