CN101215375B - Long carbon chain condensed ring semi-fragrant nylon and synthesis technique thereof - Google Patents
Long carbon chain condensed ring semi-fragrant nylon and synthesis technique thereof Download PDFInfo
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- CN101215375B CN101215375B CN2008100490452A CN200810049045A CN101215375B CN 101215375 B CN101215375 B CN 101215375B CN 2008100490452 A CN2008100490452 A CN 2008100490452A CN 200810049045 A CN200810049045 A CN 200810049045A CN 101215375 B CN101215375 B CN 101215375B
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Abstract
The invention discloses a novel long carbon-chain fused-ring semi-aromatic PA13N and a process for synthesis, which comprises the following repeat structure unit, n=2-200. The invention utilizes aliphatic diamine 1 with long carbon chain, 13-thirteen carbon diamine, fused-ring aromatic dibasic acid 2 and 6-naphthalic acid to be raw material, which is prepared through salt forming, prepolymerization, and polymerization after solid phase. The invention has low energy consumption and environment friendly, PA13N which is prepared by the invention has excellent performance, which is easy to be processed, and the invention particularly has an excellent market prospects to the field such as electron, electric appliance, automobile and the like.
Description
Technical field
The present invention relates to nylon and synthetic method thereof, be specifically related to a kind of long carbon chain condensed ring semi-aromatic nylon and synthetic method thereof.
Background technology
Semi-aromatic nylon is by the diacid or the diamines of aliphatie diamine or diacid and band aromatic nucleus, makes through polycondensation, and be a kind of of aromatic nylon.Because the nylon molecular backbone chain has been introduced aromatic ring structure, thereby the resistance toheat of nylon product and mechanical property are improved, water-intake rate also has reduction in various degree simultaneously, and cost performance is preferably arranged, be the high heat resistance resin between general engineering plastic nylon and thermostability engineering plastic PEEK, be mainly used in automobile and electric and electronic industry.According to the product performance requirement, each manufacturer develops the semi-aromatic nylon product of the multiple trade mark, and along with the needs with environmental protection cause of developing rapidly of new and high technology, its market requirement is in rising trend, and application and development also has new progress.Semi-aromatic nylon mainly contains nylon 6T, nylon 9 T and nylon MXD 6 etc., compares with nylon 66, and the characteristics of semi-aromatic nylon maximum are fine heat-resisting performance.Simultaneously, compare with all aromatic nylon, semi-aromatic nylon has easy machining characteristics.
According to the difference of synthetic method, the semi-aromatic nylon synthesis technique can be divided into following four kinds: High Temperature High Pressure solution polycondensation, low-temperature solution polycondensation, interfacial polycondensation, direct melt polycondensation method.Traditional High Temperature High Pressure solution polycondensation process using water has reduced production cost, thereby has obtained widespread use as solvent.But be subjected to the influence of factors such as temperature of reaction, pressure and reactor whipped form, the prepolymer molecular weight of this method preparation is relatively low, need further melt phase polycondensation or solid phase polycondensation to remove low-boiling-point substance wherein, make the polyamide product of high molecule mass, further the devolatilization operation has increased production cost.
Compare with traditional High Temperature High Pressure solution polycondensation, the temperature of reaction of cryogenic fluid method decreases, and can under normal pressure, operate, but because the cryogenic fluid method has adopted the solvent system of the more expensive organic solvent of price as reaction, the gas dissolving that produces in the reaction process simultaneously can produce corrosive nature to reactor in solvent, and adopt this method production cost higher, again can not the continuous production operation.Therefore, cryogenic fluid method and be not suitable for the large-scale industrialization production application.
Interface polycondensation requires at first will become acyl chlorides to diacid, then diacid chloride and diamines is dissolved in respectively in the different solvents, carries out interfacial polycondensation again, and monomer whose cost and solvent cost are all higher, therefore is not suitable for large-scale industrial production.
The direct melt polycondensation method is carried out under condition of no solvent, has not only improved the molecular weight of polymerisate, can also carry out operate continuously, has therefore significantly reduced production cost.Compare with other polymerization techniques, the direct melt polycondensation method has clear superiority.But direct melting copolymerization can not directly synthesize the higher polymkeric substance of molecular weight in semi-aromatic nylon is synthetic.
Thereby seek to develop new synthesis route and become one of focus of present semi-aromatic nylon research field.
Summary of the invention
The object of the invention is to provide a kind of novel long carbon chain condensed ring semi-aromatic nylon PA13N, and it is a kind of energy-efficient that another purpose is to provide, and is fit to the novel process of synthetic this kind long carbon chain condensed ring semi-aromatic nylon PA13N of suitability for industrialized production.
Long carbon chain condensed ring semi-aromatic nylon PA13N has following repeated structural unit:
Its molecular backbone chain is by the aromatic series 2 that contains condensed ring, and 6-naphthalene diformyl is rolled into a ball and long carbochain aliphatics 1, and 13-13 carbon diamine group are alternately formed.
Research by experiment, the present invention improves traditional High Temperature High Pressure solution polycondensation technology, synthesizes PA13N by following concrete steps:
(1) be 1 with mol ratio: 2 of 0.96-1.02,6-naphthalic acid and 1,13-13 carbon diamines are put into water, are warming up to 65-95 ℃ under whipped state, react 2-5 hour, by continuing to add 1, the pH value that 13-13 carbon diamines are adjusted solution is 7.0-7.5, treats to continue reaction 2-3 hour behind the pH value stabilization, cools off 2-3 hour under 0～10 ℃ of condition then, throw out is filtered, dries, obtain the PA13N nylon salt;
(2) the PA13N nylon salt that step (1) is obtained is made into the aqueous solution of 55%-85%, put into airtight polymeric kettle, go out air in the still with carbon dioxide replacement, and to keep pressure be that the carbonic acid gas of 0.1-0.4MPa is as shielding gas, reactor was warming up to 190-240 ℃ in 2-3 hour, pressure remains 1.2-2.0MPa, reacts 1-2 hour, slowly exitted in 1-2 hour then to normal pressure, 210-240 ℃ is continued the performed polymer that reaction obtained PA13N in 1-3 hour under normal pressure;
(3) the PA13N performed polymer that step (2) is obtained is ground into the particle that particle diameter is the 0.2-2.5mm size, at 100-150 ℃ of following vacuum-drying 10-24 hour, be 0.5-0.8kPa at pressure then, temperature is solid phase post polymerization 10-20 hour under 220-240 ℃ the condition, obtains semi-aromatic nylon PA13N.
Semi-aromatic nylon is as a kind of high performance engineering plastics, can the key issue of its synthesis technique be to make di-carboxylic acid monomer and the diamine monomer mixed effect in mol ratios such as the prepolymerization process stage reach as far as possible, and reach devolatilization effect as well as possible to satisfy desired higher molecular weight in the polymerization technique stage.Therefore, the mixing in polyreaction early stage and the devolatilization effect in later stage become the key that influences quality product, and the present invention inquires into its synthetic technological condition.Compared with prior art, the present invention has following advantage:
1. use among the present invention 1,13-13 carbon diamines are to be made by the petroleum fermentation method, with the light wax (C of byproduct of refining of petroleum
10-C
14Normal alkane) be raw material,, contain a large amount of wax, and paraffin must be taken off again when refining oil product because CNPC mostly is paraffinic base (alkyl) oil, so raw material sources are very abundant, relative low price.And the successful development and application of new polyester PEN (PEN) resin has quickened 2, and the suitability for industrialized production of this starting monomer of 6-naphthalic acid is for this condensed ring aromatics dicarboxylic acid monomer's widespread use lays a solid foundation.
2. the polymerization technique taked of this paper, reaction polymerization in the aqueous solution in early stage, temperature is far below the temperature of conventional melt polymerization, the solid phase post polymerization in later stage is to carry out below the performed polymer fusing point, and energy consumption reduces greatly, has reduced cost, improve benefit, be fit to suitability for industrialized production.
3. synthetic PA13N of the present invention had both had the advantage of semi-aromatic nylon, long carbon chain nylon is arranged (as nylon 1212 again, Ni Long11 11) excellent in toughness and weathering resistance are a kind of novel materials that better application prospect is arranged, and in electronics, electrical equipment, automobile and other industries better market prospect are arranged especially.
Embodiment
Below in conjunction with embodiment the present invention is further described.
Embodiment 1
The first step: accurately the weighing mol ratio be 1: 12,6-naphthalic acid and 1,13-13 carbon diamines amount to 150g, add in the 400ml distilled water, be 80 ℃ and reaction 4 hours are arranged under the stirring condition in water temperature, add 1 then, 13-13 carbon diamines are regulated the pH=7.0 of the aqueous solution, treat the pH value stabilization after constant temperature continue reaction 1.5 hours.This system is placed under 5 ℃ of temperature cooling 2 hours, with throw out filter, oven dry obtains the PA13N nylon salt, the fusing point of this salt is 254 ℃.
Second step: it is 75% aqueous solution that the PA13N nylon salt that obtains in the first step is made into concentration, is put in the 1500ml polymerization reaction kettle, displaces air in the still with carbon dioxide, and to keep pressure be that the carbonic acid gas of 0.2MPa is as shielding gas.Reactor slowly heats, 2.5 hour internal heating to 206 ℃, pressure remains on 2.0MPa, and kept this state 2 hours, begin slow venting subsequently, put to normal pressure through 1.5 hours, this moment, temperature reached 230 ℃, 230 ℃ are continued the performed polymer that reaction obtained PA13N in 2 hours, 270 ℃ of the fusing points of performed polymer under normal pressure.
The 3rd step: the PA13N performed polymer that obtains in second step is ground into the particle that particle diameter is 1-2.5mm, 120 ℃ of following vacuum-dryings 10 hours, then at 800Pa, the solid phase post polymerization is 12 hours under 230 ℃ of conditions, obtain semi-aromatic nylon PA13N, its fusing point is 275 ℃, and the physical and mechanical properties test result is listed in table 1.
Table 1, semi-aromatic nylon PA13N physical and mechanical properties test result
| PA13N | Testing standard | |
| Fusing point | 275℃ | The DSC method |
| Second-order transition temperature | 110℃ | The DSC method |
| Tensile strength MPa | 84 | GB/T 1040 |
| Tensile modulus MPa | 1483 | GB/T 1040 |
| Elongation at break % | 56 | GB/T 1040 |
| Shock strength (breach) KJ/m 2 | 4.9 | GB/T 1843 |
| Flexural strength MPa | 48 | GB/T 1042 |
| Modulus in flexure MPa | 1625 | GB/T 1042 |
Embodiment 2
The first step: accurately the weighing mol ratio be 1: 0.96 2,6-naphthalic acid and 1,13-13 carbon diamines amount to 100g, add in the 300ml distilled water, are 65 ℃ and reaction are arranged under the stirring condition 2 hours in water temperature, add 1,13-13 carbon diamines are regulated the pH=7.2 of the aqueous solution, treat the pH value stabilization after constant temperature continue reaction 2 hours, this system was put under 9 ℃ of temperature cooling 3 hours, with throw out filter, oven dry the PA13N nylon salt, the fusing point of this salt is 254 ℃.
Second step: it is 55% aqueous solution that the PA13N nylon salt that obtains in the first step is made into concentration, is put in the 1500ml polymerization reaction kettle, displaces air in the still with carbon dioxide, and to keep pressure be that the carbonic acid gas of 0.1MPa is as shielding gas.Reactor slowly heats, 2 hours internal heating to 190 ℃, pressure remains on 1.2MPa, and kept this state 1 hour, begin slow venting subsequently, put to normal pressure through 1 hour, this moment, temperature reached 210 ℃, 210 ℃ are continued the performed polymer that reaction promptly got PA13N in 1 hour under normal pressure, and the fusing point of performed polymer is 270 ℃.
The 3rd step: the PA13N performed polymer that obtains in second step is ground into the particle that particle diameter is 0.2-1.5mm, 100 ℃ of following vacuum-dryings 15 hours, be put under 500Pa, the 220 ℃ of conditions solid phase post polymerization then 10 hours, and promptly got semi-aromatic nylon PA13N, its fusing point is 275 ℃.
Embodiment 3
The first step: accurately the weighing mol ratio be 1: 1.02 2,6-naphthalic acid and 1,13-13 carbon diamines amount to 200g, add in the 500ml distilled water, are 95 ℃ and reaction are arranged under the stirring condition 5 hours in water temperature, add 1,13-13 carbon diamines are regulated the pH=7.5 of the aqueous solution, treat the pH value stabilization after constant temperature continue reaction 3 hours, then this system was put under 0 ℃ of temperature cooling 2 hours, with throw out filter, oven dry the PA13N nylon salt, the fusing point of this salt is 254 ℃.
Second step: it is 85% aqueous solution that the PA13N nylon salt that obtains in the first step is made into concentration, is put in the 1500ml polymerization reaction kettle, displaces air in the still with carbon dioxide, and keeps the 0.4MPa carbonic acid gas as protection gas.Reactor slowly heats, 3 hours internal heating to 220 ℃, pressure remains on 2.0MPa, and kept this state 2 hours, begin slow venting subsequently, put to normal pressure through 2 hours, this moment, temperature reached 215 ℃, 215 ℃ are continued the performed polymer that reaction promptly got PA13N in 3 hours, 270 ℃ of the fusing points of performed polymer under normal pressure.
The 3rd step: the PA13N performed polymer that obtains in second step is ground into the particle that particle diameter is 1.5-2.5mm, vacuum-drying is 15 hours under 150 ℃ of conditions, be put under 800Pa, the 240 ℃ of conditions solid phase post polymerization then 10 hours, and promptly got semi-aromatic nylon PA13N, its fusing point is 275 ℃.
Claims (1)
1. the long carbon chain condensed ring semi-aromatic nylon synthesis technique with following repeated structural unit is characterized in that,
Adopt fatty clan elder's carbochain diamine 1,13-13 carbon diamines and condensed nucleus aromatic di-carboxylic acid 2,6-naphthalic acid condensation polymerization forms, and specifically makes as follows:
(1) be 1 with mol ratio: 2 of 0.96-1.02,6-naphthalic acid and 1,13-13 carbon diamines are put into water, are warming up to 65-95 ℃ under whipped state, react 2-5 hour, by continuing to add 1, the pH value that 13-13 carbon diamines are adjusted solution is 7.0-7.5, treats to continue reaction 2-3 hour behind the pH value stabilization, cools off 2-3 hour under 0-10 ℃ of condition then, throw out is filtered, dries, obtain the PA13N nylon salt;
(2) the PA13N nylon salt that step (1) is obtained is made into the aqueous solution of 55%-85%, put into airtight polymeric kettle, go out air in the still with carbon dioxide replacement, and to keep pressure be that the carbonic acid gas of 0.1-0.4MPa is as shielding gas, reactor was warming up to 190-240 ℃ in 2-3 hour, pressure remains 1.2-2.0MPa, reacts 1-2 hour, slowly exitted in 1-2 hour then to normal pressure, 210-240 ℃ is continued the performed polymer that reaction obtained PA13N in 1-3 hour under normal pressure;
(3) the PA13N performed polymer that step (2) is obtained is ground into the particle that particle diameter is the 0.2-2.5mm size, at 100-150 ℃ of following vacuum-drying 10-24 hour, be 0.5-0.8kPa at pressure then, temperature is solid phase post polymerization 10-20 hour under 220-240 ℃ the condition, obtains long carbon chain condensed ring semi-aromatic nylon.
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| CN103539935B (en) * | 2012-07-03 | 2016-06-15 | 金发科技股份有限公司 | A kind of method improving polymeric amide whiteness |
| CN103539937B (en) * | 2012-07-03 | 2016-05-25 | 金发科技股份有限公司 | The application of a kind of polyamide, its synthetic method and this polyamide |
| CN103539936B (en) * | 2012-07-03 | 2016-04-20 | 金发科技股份有限公司 | A kind of polymeric amide and synthetic method thereof and application and polyamide article |
| CN106928452A (en) * | 2015-12-31 | 2017-07-07 | 上海杰事杰新材料(集团)股份有限公司 | A kind of semi-aromatic nylon material of Long carbon chain containing naphthalene nucleus and preparation method thereof |
| CN107446130B (en) * | 2017-09-08 | 2020-07-07 | 中央军委后勤保障部军需装备研究所 | Nylon 126 and preparation method thereof |
| CN113881036B (en) * | 2020-07-01 | 2023-10-31 | 中国石油化工股份有限公司 | Preparation method of long carbon chain nylon and nylon obtained by preparation method |
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| US20030050376A1 (en) * | 2001-06-05 | 2003-03-13 | Kuraray Co. Ltd, | Polyamide composition |
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| US20030050376A1 (en) * | 2001-06-05 | 2003-03-13 | Kuraray Co. Ltd, | Polyamide composition |
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| JP特开2005-233319A 2005.09.02 |
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