CN103709399B - A kind of 11-aminoundecanoic acid normal pressure melt polymerization prepares the technique of nylon 11 - Google Patents
A kind of 11-aminoundecanoic acid normal pressure melt polymerization prepares the technique of nylon 11 Download PDFInfo
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- CN103709399B CN103709399B CN201310617769.3A CN201310617769A CN103709399B CN 103709399 B CN103709399 B CN 103709399B CN 201310617769 A CN201310617769 A CN 201310617769A CN 103709399 B CN103709399 B CN 103709399B
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Abstract
The present invention relates to the technique that a kind of 11-aminoundecanoic acid normal pressure melt polymerization prepares nylon 11.The present invention is by 11-aminoundecanoic acid and fusing assistant mixing, and described fusing assistant is a kind of or the multiple boiling point of arbitrary proportion is the organic solvent of 185 ~ 220 DEG C; Under atmospheric pressure state, heating makes material melts, then continues to be heated to 230 ~ 270 DEG C, is evaporated by the water that fusing assistant and reaction generate; After normal pressure frit reaction completes, continue to keep temperature to be 230 ~ 270 DEG C, then vacuumize, carry out vacuum reaction under vacuum conditions; After vacuum reaction completes, stopping vacuumizes, and recover atmospheric pressure state, discharging obtains nylon 11.Method of the present invention can reduce equipment cost, and can reduce the loss of 11-aminoundecanoic acid monomer.
Description
Technical field
The present invention relates to a kind of preparation technology of nylon 11, more particularly, the present invention relates to the technique that a kind of 11-aminoundecanoic acid normal pressure melt polymerization prepares nylon 11, belong to nylon technology for making field.
Background technology
Nylon 11 is the soft nylon of a kind of Long carbon chain, and its methene chain is longer, and amide group density is low, compared with other nylon, it has very low water-absorbent, good dimensional stability, mechanical property, chemical resistant properties and electrical insulation capability, low temperature (-40 DEG C) excellent shock resistance; Have elastic memory benefit, when external force removes, it can return to original shape, and stress cracking resistance is good, embeds metal parts and not easy to crack; And be easy to machine-shaping, harmless, the injection moulding of various melt viscosity scope can be met and extrude processing, being usually used in the oil pipe, the flexible pipe that manufacture antivibration wear resistant, as automobile oil flexible pipe, transition pipeline, clutch tube, become the up-and-coming youngster of nylon-type engineering plastics.
Nylon 11 with 11-aminoundecanoic acid for raw material is prepared from.Easy dehydrating condensation during the heating of 11-aminoundecanoic acid, its polymerization principle is very simple, and its reaction equation is:
11-aminoundecanoic acid is insoluble in water, can not make aqueous solution process, and its fusing point is 187 DEG C as ε-caprolactam, in thick after melting, when being heated to fusing point, will start dehydrating polycondensation.Due to the generation along with polycondensation in the phase transition process of solid to molten state, as controlled badly will to cause coking, decomposition, caking, do not reach the object making high molecular weight nylon 11.
Current general industry all adopts by moisture 11-aminoundecanoic acid heating and pressurizing melting, required pressure, generally at more than 1MPa, is let out to atmospheric pressure state after the fusing point of temperature more than 11-aminoundecanoic acid, then continues melt polymerization and finally obtain nylon 11.In pressure leak process, while water vapour discharge, a large amount of 11-aminoundecanoic acids also can be taken out of along with water vapour, causes monomer loss.
Summary of the invention
The present invention is intended to need to carry out pressurizing melting to 11-aminoundecanoic acid in the nylon 11 synthesis of solution prior art, higher to equipment requirements, need high-tension apparatus, and after melting in pressure leak process water vapour discharge while aminoundecanoic acid also can be taken out of along with water vapour, cause the problem of monomer loss, a kind of 11-aminoundecanoic acid normal pressure melt polymerization is provided to prepare the technique of nylon 11, the synthesis of nylon 11 can be carried out at ambient pressure, reduce equipment cost, and the loss of 11-aminoundecanoic acid monomer can be reduced.
In order to realize foregoing invention object, its concrete technical scheme is as follows:
11-aminoundecanoic acid normal pressure melt polymerization prepares a technique for nylon 11, it is characterized in that: by 11-aminoundecanoic acid and fusing assistant mixing, described fusing assistant is a kind of or the multiple boiling point of arbitrary proportion is the organic solvent of 185 ~ 220 DEG C; Under atmospheric pressure state, heating makes material melts, then continues to be heated to 230 ~ 270 DEG C, is evaporated by the water that fusing assistant and reaction generate; After normal pressure frit reaction completes, continue to keep temperature to be 230 ~ 270 DEG C, then vacuumize, carry out vacuum reaction under vacuum conditions; After vacuum reaction completes, stopping vacuumizes, and recover atmospheric pressure state, discharging obtains nylon 11; Prepare in the technique of nylon 11 at described 11-aminoundecanoic acid normal pressure melt polymerization and also add catalyzer and auxiliary agent.
11-aminoundecanoic acid normal pressure melt polymerization of the present invention is prepared in the technique of nylon 11 and is also added catalyzer and auxiliary agent refers to that described catalyzer and 11-aminoundecanoic acid and fusing assistant are mixed together, or adds after material melts; Described auxiliary agent and 11-aminoundecanoic acid and fusing assistant are mixed together, or add after material melts.
Fusing assistant of the present invention to be the boiling point of this area routine the be organic solvent of 185 ~ 220 DEG C, such as long chain alkane, ethers, benzene class, ketone, ester class and other syntheticss: n-undecane, n-dodecane, benzyl toluene, isoamylbenzene, 9-bromine phenanthrene, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, diethylene glycol dimethyl ether, amyl ether, Propiophenone, methyl heptadiene ketone, methyl cyanoacetate, hydroacetic acid ethyl ester, oxalic acid diethyl ester, methyl-silicone oil etc., preferred above-mentioned organic solvent mid-boiling point is the organic solvent of 190 ~ 200 DEG C.
The consumption of fusing assistant of the present invention is the weight ratio of 11-aminoundecanoic acid and fusing assistant is 1:0.05 ~ 1, and the weight ratio being preferably 11-aminoundecanoic acid and fusing assistant is 1:0.1 ~ 0.6.
Catalyzer of the present invention at least comprises following a kind of material: phosphoric acid, phosphorous acid, ortho phosphorous acid, acetic acid, its consumption is the weight ratio of 11-aminoundecanoic acid and catalyzer is 1:0.0001 ~ 0.03, and the weight ratio being preferably 11-aminoundecanoic acid and catalyzer is 1:0.0002 ~ 0.01.
Auxiliary agent of the present invention at least comprises following a kind of material: hexanodioic acid, sebacic acid, partially benzoic anhydride, hexanediamine, decamethylene diamine, hexanolactam, Stearyl Amine, dioctyl phthalate (DOP), dimethyl phthalate, diethyl phthalate, its consumption is the weight ratio of 11-aminoundecanoic acid and auxiliary agent is 1:0.0005 ~ 0.1, and the weight ratio being preferably 11-aminoundecanoic acid and auxiliary agent is 1:0.001 ~ 0.05.
Of the present invention continuation is heated to 230 ~ 270 DEG C, and the reaction times of this process that is evaporated by the water that fusing assistant and reaction generate is 1 ~ 3 hour.
The vacuum tightness of vacuum state of the present invention is 0.08 ~ 0.1MPa.
The reaction times of vacuum reaction of the present invention is 0.5 ~ 1.5 hour.
The mensuration of the intrinsic viscosity of nylon 11 in the present invention:
Nylon 11 is dissolved in meta-cresol, then uses Ubbelohde viscometer under 25 DEG C of water bath condition, measure its relative viscosity η r, obtain the intrinsic viscosity (dl/g) of nylon 11 by formulae discovery below
[η]=[2（ηsp-lnηr）]
1/2/c
η sp=η r-1 in formula;
C is strength of solution.
The present invention brings Advantageous Effects:
1, the present invention is intended to need to carry out pressurizing melting to 11-aminoundecanoic acid in the nylon 11 synthesis of solution prior art, higher to equipment requirements, need high-tension apparatus, and after melting in pressure leak process water vapour discharge while aminoundecanoic acid also can be taken out of along with water vapour, cause the problem of monomer loss, a kind of 11-aminoundecanoic acid normal pressure melt polymerization is provided to prepare the technique of nylon 11, the synthesis of nylon 11 can be carried out at ambient pressure, reduce equipment cost, and the loss of 11-aminoundecanoic acid monomer can be reduced.11-aminoundecanoic acid of the present invention melting under atmospheric pressure state, and owing to there being the existence of fusing assistant, substantially increasing 11-aminoundecanoic acid heat and mass condition in melting process, there will not be the coking of 11-aminoundecanoic acid, decomposition, caking phenomenon.Owing to being normal pressure melting, do not need high pressure reactor, reduce the requirement to equipment.In polycondensation process after the melting of 11-aminoundecanoic acid, fusing assistant can be distilled out of, and can not have an impact, and fusing assistant can Reusability to the polycondensation process of 11-aminoundecanoic acid.
2, method of the present invention can also be used for the normal pressure melt phase polycondensation techniques such as nylon 9, nylon 12, nylon 1010, nylon 8 10, nylon 11 11, nylon 1212.The present invention is by adding fusing assistant, improve the heat and mass effect of 11-aminoundecanoic acid in melting process, 11-aminoundecanoic acid can be carried out in melting process under atmospheric pressure state, avoid conventional 11-aminoundecanoic acid pressurizing melting, need high-tension apparatus, and easily cause the problem of 11-aminoundecanoic acid loss.The organic solvent being chosen as fusing assistant of the present invention does not substantially react with 11-aminoundecanoic acid in 11-aminoundecanoic acid polycondensation process, can Reusability.
3, the fusing assistant that the present invention selects can not affect the polyreaction of 11-aminoundecanoic acid, further preferred fusing assistant remains in nylon 11, not only the performance of nylon 11 is not affected, even as useful in color and luster, thermostability and fluidity of molten to the performance of nylon 11.
4, the weight ratio of 11-aminoundecanoic acid of the present invention and fusing assistant is 1:0.1 ~ 0.6.The object added of fusing assistant promotes that 11-aminoundecanoic acid is at the heat and mass of melting process, makes 11-aminoundecanoic acid can be good at melting.Along with the increase of fusing assistant add-on, 11-aminoundecanoic acid also can increase at the heat and mass of melting process.But fusing assistant is after material melts, needs it can steam disengaging reaction system very soon, the increase of add-on, can energy consumption be increased, slow down the temperature rise rate of material, increase production cost.In above-mentioned preferable range, the add-on of fusing assistant can ensure the increase of the effective heat and mass of 11-aminoundecanoic acid melting, and production cost increases few.
5, the weight ratio of 11-aminoundecanoic acid of the present invention and catalyzer is 1:0.0002 ~ 0.01, and the scope of above-mentioned catalyst charge can be conducive to the molecular weight and the performance that control speed of response and final polymkeric substance.The weight ratio of 11-aminoundecanoic acid of the present invention and auxiliary agent is 1:0.001 ~ 0.05, and the scope of above-mentioned promoter addition can control effectively to reaction, and the performance of its speed of response and obtained nylon 11 is better.
Embodiment
Embodiment 1
11-aminoundecanoic acid normal pressure melt polymerization prepares the technique of nylon 11:
By 11-aminoundecanoic acid and fusing assistant mixing, described fusing assistant is a kind of or the multiple boiling point of arbitrary proportion is the organic solvent of 185 ~ 220 DEG C; Under atmospheric pressure state, heating makes material melts, then continues to be heated to 230 DEG C, is evaporated by the water that fusing assistant and reaction generate; After normal pressure frit reaction completes, continue to keep temperature to be 230 DEG C, then vacuumize, carry out vacuum reaction under vacuum conditions; After vacuum reaction completes, stopping vacuumizes, and recover atmospheric pressure state, discharging obtains nylon 11; Prepare in the technique of nylon 11 at described 11-aminoundecanoic acid normal pressure melt polymerization and also add catalyzer and auxiliary agent.
Embodiment 2
11-aminoundecanoic acid normal pressure melt polymerization prepares the technique of nylon 11:
By 11-aminoundecanoic acid and fusing assistant mixing, described fusing assistant is a kind of or the multiple boiling point of arbitrary proportion is the organic solvent of 185 ~ 220 DEG C; Under atmospheric pressure state, heating makes material melts, then continues to be heated to 270 DEG C, is evaporated by the water that fusing assistant and reaction generate; After normal pressure frit reaction completes, continue to keep temperature to be 270 DEG C, then vacuumize, carry out vacuum reaction under vacuum conditions; After vacuum reaction completes, stopping vacuumizes, and recover atmospheric pressure state, discharging obtains nylon 11; Prepare in the technique of nylon 11 at described 11-aminoundecanoic acid normal pressure melt polymerization and also add catalyzer and auxiliary agent.
Embodiment 3
11-aminoundecanoic acid normal pressure melt polymerization prepares the technique of nylon 11:
By 11-aminoundecanoic acid and fusing assistant mixing, described fusing assistant is a kind of or the multiple boiling point of arbitrary proportion is the organic solvent of 185 ~ 220 DEG C; Under atmospheric pressure state, heating makes material melts, then continues to be heated to 250 DEG C, is evaporated by the water that fusing assistant and reaction generate; After normal pressure frit reaction completes, continue to keep temperature to be 250 DEG C, then vacuumize, carry out vacuum reaction under vacuum conditions; After vacuum reaction completes, stopping vacuumizes, and recover atmospheric pressure state, discharging obtains nylon 11; Prepare in the technique of nylon 11 at described 11-aminoundecanoic acid normal pressure melt polymerization and also add catalyzer and auxiliary agent.
Embodiment 4
11-aminoundecanoic acid normal pressure melt polymerization prepares the technique of nylon 11:
By 11-aminoundecanoic acid and fusing assistant mixing, described fusing assistant is a kind of or the multiple boiling point of arbitrary proportion is the organic solvent of 185 ~ 220 DEG C; Under atmospheric pressure state, heating makes material melts, then continues to be heated to 260 DEG C, is evaporated by the water that fusing assistant and reaction generate; After normal pressure frit reaction completes, continue to keep temperature to be 260 DEG C, then vacuumize, carry out vacuum reaction under vacuum conditions; After vacuum reaction completes, stopping vacuumizes, and recover atmospheric pressure state, discharging obtains nylon 11; Prepare in the technique of nylon 11 at described 11-aminoundecanoic acid normal pressure melt polymerization and also add catalyzer and auxiliary agent.
Embodiment 5
On the basis of embodiment 1-4:
Preferably, described 11-aminoundecanoic acid normal pressure melt polymerization is prepared in the technique of nylon 11 and is also added catalyzer and auxiliary agent refers to that described catalyzer and 11-aminoundecanoic acid and fusing assistant are mixed together, or adds after material melts; Described auxiliary agent and 11-aminoundecanoic acid and fusing assistant are mixed together, or add after material melts.
Preferably, described fusing assistant to be boiling point the be organic solvent of 190 ~ 200 DEG C.
Preferably or further, the consumption of described fusing assistant is the weight ratio of 11-aminoundecanoic acid and fusing assistant is 1:0.1.
Preferably or further, described catalyzer at least comprises following a kind of material: phosphoric acid, phosphorous acid, ortho phosphorous acid, acetic acid, its consumption is the weight ratio of 11-aminoundecanoic acid and catalyzer is 1:0.0002.
Preferably or further, described auxiliary agent at least comprises following a kind of material: hexanodioic acid, sebacic acid, partially benzoic anhydride, hexanediamine, decamethylene diamine, hexanolactam, Stearyl Amine, dioctyl phthalate (DOP), dimethyl phthalate, diethyl phthalate, its consumption is the weight ratio of 11-aminoundecanoic acid and auxiliary agent is 1:0.001.
Preferably, described continuation is heated to 230 DEG C, and the reaction times of this process that is evaporated by the water that fusing assistant and reaction generate is 1 hour.
Preferably, the vacuum tightness of described vacuum state is 0.099MPa.
Preferably or further, the reaction times of described vacuum reaction is 0.5 hour.
Embodiment 6
On the basis of embodiment 1-4:
Preferably, described 11-aminoundecanoic acid normal pressure melt polymerization is prepared in the technique of nylon 11 and is also added catalyzer and auxiliary agent refers to that described catalyzer and 11-aminoundecanoic acid and fusing assistant are mixed together, or adds after material melts; Described auxiliary agent and 11-aminoundecanoic acid and fusing assistant are mixed together, or add after material melts.
Preferably, described fusing assistant to be boiling point the be organic solvent of 190 ~ 200 DEG C.
Preferably or further, the consumption of described fusing assistant is the weight ratio of 11-aminoundecanoic acid and fusing assistant is 1:0.6.
Preferably or further, described catalyzer at least comprises following a kind of material: phosphoric acid, phosphorous acid, ortho phosphorous acid, acetic acid, its consumption is the weight ratio of 11-aminoundecanoic acid and catalyzer is 1:0.01.
Preferably or further, described auxiliary agent at least comprises following a kind of material: hexanodioic acid, sebacic acid, partially benzoic anhydride, hexanediamine, decamethylene diamine, hexanolactam, Stearyl Amine, dioctyl phthalate (DOP), dimethyl phthalate, diethyl phthalate, its consumption is the weight ratio of 11-aminoundecanoic acid and auxiliary agent is 0.05.
Preferably, described continuation is heated to 270 DEG C, and the reaction times of this process that is evaporated by the water that fusing assistant and reaction generate is 3 hours.
Preferably, the vacuum tightness of described vacuum state is 0.08MPa.
Preferably or further, the reaction times of described vacuum reaction is 1.5 hours.
Embodiment 7
On the basis of embodiment 1-4:
Preferably, described 11-aminoundecanoic acid normal pressure melt polymerization is prepared in the technique of nylon 11 and is also added catalyzer and auxiliary agent refers to that described catalyzer and 11-aminoundecanoic acid and fusing assistant are mixed together, or adds after material melts; Described auxiliary agent and 11-aminoundecanoic acid and fusing assistant are mixed together, or add after material melts.
Preferably, described fusing assistant to be boiling point the be organic solvent of 190 ~ 200 DEG C.
Preferably or further, the consumption of described fusing assistant is the weight ratio of 11-aminoundecanoic acid and fusing assistant is 1:0.35.
Preferably or further, described catalyzer at least comprises following a kind of material: phosphoric acid, phosphorous acid, ortho phosphorous acid, acetic acid, its consumption is the weight ratio of 11-aminoundecanoic acid and catalyzer is 1:0.0051.
Preferably or further, described auxiliary agent at least comprises following a kind of material: hexanodioic acid, sebacic acid, partially benzoic anhydride, hexanediamine, decamethylene diamine, hexanolactam, Stearyl Amine, dioctyl phthalate (DOP), dimethyl phthalate, diethyl phthalate, its consumption is the weight ratio of 11-aminoundecanoic acid and auxiliary agent is 1:0.0255.
Preferably, described continuation is heated to 250 DEG C, and the reaction times of this process that is evaporated by the water that fusing assistant and reaction generate is 2 hours.
Preferably, the vacuum tightness of described vacuum state is 0.09MPa.
Preferably or further, the reaction times of described vacuum reaction is 1 hour.
Embodiment 8
On the basis of embodiment 1-4:
Preferably, described 11-aminoundecanoic acid normal pressure melt polymerization is prepared in the technique of nylon 11 and is also added catalyzer and auxiliary agent refers to that described catalyzer and 11-aminoundecanoic acid and fusing assistant are mixed together, or adds after material melts; Described auxiliary agent and 11-aminoundecanoic acid and fusing assistant are mixed together, or add after material melts.
Preferably, described fusing assistant to be boiling point the be organic solvent of 190 ~ 200 DEG C.
Preferably or further, the consumption of described fusing assistant is the weight ratio of 11-aminoundecanoic acid and fusing assistant is 1:0.5.
Preferably or further, described catalyzer at least comprises following a kind of material: phosphoric acid, phosphorous acid, ortho phosphorous acid, acetic acid, its consumption is the weight ratio of 11-aminoundecanoic acid and catalyzer is 1:0.002.
Preferably or further, described auxiliary agent at least comprises following a kind of material: hexanodioic acid, sebacic acid, partially benzoic anhydride, hexanediamine, decamethylene diamine, hexanolactam, Stearyl Amine, dioctyl phthalate (DOP), dimethyl phthalate, diethyl phthalate, its consumption is the weight ratio of 11-aminoundecanoic acid and auxiliary agent is 1:0.04.
Preferably, described continuation is heated to 260 DEG C, and the reaction times of this process that is evaporated by the water that fusing assistant and reaction generate is 2.5 hours.
Preferably, the vacuum tightness of described vacuum state is 0.095MPa.
Preferably or further, the reaction times of described vacuum reaction is 0.75 hour.
Embodiment 9
The 11-aminoundecanoic acid of 150kg and the N-Methyl pyrrolidone of 60kg are put in reactor, after the deoxygenation of vacuum nitrogen filling gas, after starting normal heating to 190 DEG C, add phosphorous acid 45g and adipic acid 300g, continue to be heated to 240 DEG C of reactions 2.5 hours, then, closed reactor vacuumizes, and vacuum degree control is at 0.085MPa, continue to react 1 hour at 240 DEG C, stopped reaction discharging, obtains 131kg nylon 11, and its intrinsic viscosity is 1.32dl/g.
Oxidation inhibitor, anti-aging agent etc. can also be added in said process.
Embodiment 10
The 11-aminoundecanoic acid of 150kg and the dimethyl sulfoxide (DMSO) of 30kg are put in reactor, after the deoxygenation of vacuum nitrogen filling gas, after starting normal heating to 190 DEG C, add acetic acid 120ml, sebacic acid 600g, hexanediamine 200g, antioxidant 1010 750g, continues to be heated to 250 DEG C of reactions 1 hour, then, closed reactor vacuumizes, vacuum degree control at 0.08MPa, and is reacted 1 hour, stopped reaction discharging at 260 DEG C, obtain 132kg nylon 11, its intrinsic viscosity is 0.95dl/g.
Oxidation inhibitor, anti-aging agent etc. can also be added in said process.
Embodiment 11
The 11-aminoundecanoic acid of 150kg and the methyl-silicone oil of 45kg are put in reactor, after the deoxygenation of vacuum nitrogen filling gas, after starting normal heating to 190 DEG C, add phosphatase 11 00ml, hexanolactam 5kg, diamines 200g, continue to be heated to 250 DEG C of reactions 2 hours, then, closed reactor vacuumizes, and vacuum degree control is at 0.08MPa, and react 0.75 hour at 270 DEG C, stopped reaction discharging, obtains 138kg nylon 11, and its limiting viscosity is 1.6dl/g.
Oxidation inhibitor, anti-aging agent etc. can also be added in said process.
Embodiment 12
Vacuum nitrogen filling gas, for after getting rid of the oxygen in reactor, starts heating, in heat-processed reactor with ambient atmosphere UNICOM, to ensure that whole heat-processed is in atmospheric pressure state at reactor.
After material melts, continue heating, temperature of charge is made to reach 230 ~ 270 DEG C, in the process, reactor still with ambient atmosphere UNICOM, reactor is in atmospheric pressure state, and ensures that the water of the fusing assistant and reaction generation exceeding boiling point in the process can be steamed in time, and this process reaction time is 1 ~ 3 hour.
Temperature of charge is continued to remain on 230 ~ 270 DEG C, closed reactor, start to vacuumize reaction, material is reacted under vacuum tightness is the vacuum state of 0.08MPa ~ 0.1MPa stop vacuumizing after 0.5 ~ 1.5 hour to be filled with gas to normal pressure, then discharging, after Cast Strip, cooling, pelletizing, namely obtain nylon 11 resin.
Catalyzer needed for reaction and auxiliary agent together can add with 11-aminoundecanoic acid and fusing assistant, also can add after the melting of 11-aminoundecanoic acid; Its auxiliary agent together can add with 11-aminoundecanoic acid and fusing assistant as oxidation inhibitor, anti-aging agent, staining agent etc., also can add after the melting of 11-aminoundecanoic acid, also can synthesis under normal pressure complete after or can add after vacuum reaction completes.
Claims (8)
1. 11-aminoundecanoic acid normal pressure melt polymerization prepares a technique for nylon 11, it is characterized in that: by 11-aminoundecanoic acid and fusing assistant mixing, described fusing assistant is a kind of or the multiple boiling point of arbitrary proportion is the organic solvent of 185 ~ 220 DEG C; Under atmospheric pressure state, heating makes material melts, then continues to be heated to 230 ~ 270 DEG C, is evaporated by the water that fusing assistant and reaction generate; After normal pressure frit reaction completes, continue to keep temperature to be 230 ~ 270 DEG C, then vacuumize, carry out vacuum reaction under vacuum conditions; After vacuum reaction completes, stopping vacuumizes, and recover atmospheric pressure state, discharging obtains nylon 11; Prepare in the technique of nylon 11 at described 11-aminoundecanoic acid normal pressure melt polymerization and also add catalyzer and auxiliary agent, described auxiliary agent at least comprises following a kind of material: hexanodioic acid, sebacic acid, partially benzoic anhydride, hexanediamine, decamethylene diamine, hexanolactam, Stearyl Amine, dioctyl phthalate (DOP), dimethyl phthalate, diethyl phthalate, its consumption is the weight ratio of 11-aminoundecanoic acid and auxiliary agent is 1:0.001 ~ 0.05.
2. a kind of 11-aminoundecanoic acid normal pressure melt polymerization according to claim 1 prepares the technique of nylon 11, it is characterized in that: described 11-aminoundecanoic acid normal pressure melt polymerization is prepared in the technique of nylon 11 and also added catalyzer and auxiliary agent refers to that described catalyzer and 11-aminoundecanoic acid and fusing assistant are mixed together, or adds after material melts; Described auxiliary agent and 11-aminoundecanoic acid and fusing assistant are mixed together, or add after material melts.
3. a kind of 11-aminoundecanoic acid normal pressure melt polymerization according to claim 1 prepares the technique of nylon 11, it is characterized in that: described fusing assistant to be boiling point the be organic solvent of 190 ~ 200 DEG C.
4. a kind of 11-aminoundecanoic acid normal pressure melt polymerization according to claim 1 or 3 prepares the technique of nylon 11, it is characterized in that: the consumption of described fusing assistant is the weight ratio of 11-aminoundecanoic acid and fusing assistant is 1:0.1 ~ 0.6.
5. a kind of 11-aminoundecanoic acid normal pressure melt polymerization according to claim 1 and 2 prepares the technique of nylon 11, it is characterized in that: described catalyzer at least comprises following a kind of material: phosphoric acid, phosphorous acid, ortho phosphorous acid, acetic acid, its consumption is the weight ratio of 11-aminoundecanoic acid and catalyzer is 1:0.0002 ~ 0.01.
6. a kind of 11-aminoundecanoic acid normal pressure melt polymerization according to claim 1 prepares the technique of nylon 11, it is characterized in that: described continuation is heated to 230 ~ 270 DEG C, the reaction times of this process that is evaporated by the water that fusing assistant and reaction generate is 1 ~ 3 hour.
7. a kind of 11-aminoundecanoic acid normal pressure melt polymerization according to claim 1 prepares the technique of nylon 11, it is characterized in that: the vacuum tightness of described vacuum state is 0.08 ~ 0.1MPa.
8. a kind of 11-aminoundecanoic acid normal pressure melt polymerization according to claim 1 or 7 prepares the technique of nylon 11, it is characterized in that: the reaction times of described vacuum reaction is 0.5 ~ 1.5 hour.
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| CN104710613B (en) * | 2015-03-12 | 2017-08-25 | 中国科学院理化技术研究所 | Solvothermal preparation method of semi-aromatic polyamide |
| CN111303408B (en) * | 2020-03-16 | 2022-11-01 | 珠海派锐尔新材料有限公司 | Preparation method of high-temperature nylon |
| CN114917856B (en) * | 2022-05-31 | 2023-12-19 | 中国五环工程有限公司 | Process system and method for preparing nylon 11 by polymerizing 11-aminoundecanoic acid |
| CN115536853B (en) * | 2022-10-28 | 2023-06-27 | 中国五环工程有限公司 | Method for preparing PA11 elastomer from 11-aminoundecanoic acid |
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| CN101289534A (en) * | 2008-06-12 | 2008-10-22 | 山西宏远科技股份有限公司 | Strand spinneret discharge process for polymerization reaction of 11-amino undecanoic acid monomer |
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