CN103709399A - Technology for preparing nylon 11 by 11-aminoundecanoic acid normal-pressure melt polymerization - Google Patents
Technology for preparing nylon 11 by 11-aminoundecanoic acid normal-pressure melt polymerization Download PDFInfo
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- CN103709399A CN103709399A CN201310617769.3A CN201310617769A CN103709399A CN 103709399 A CN103709399 A CN 103709399A CN 201310617769 A CN201310617769 A CN 201310617769A CN 103709399 A CN103709399 A CN 103709399A
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Abstract
The invention relates to a technology for preparing nylon 11 by 11-aminoundecanoic acid normal-pressure melt polymerization. The technology comprises the following steps of mixing 11-aminoundecanoic acid and a fluxing agent which comprises one or more organic solvents having any ratio and multiple boiling points of 185-220 DEG C, carrying out heating under normal pressure so that the mixture is melted, sequentially carrying out heating to a temperature of 230-270 DEG C so that the fluxing agent and reaction product water are evaporated, after the normal-pressure melting reaction, continuously keeping the temperature in a range of 230-270 DEG C, carrying out vacuum pumping, carrying out a vacuum reaction process in vacuum, after the vacuum reaction process, stopping the vacuum pumping, recovering a normal pressure state and discharging nylon 11. The technology can reduce an equipment cost and reduce 11-aminoundecanoic acid monomer loss.
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 is prepared nylon 11, belong to nylon technology for making field.
Background technology
Nylon 11 is the soft nylon of a kind of long carbochain, and its methene chain is longer, and amide group density is low, compare with other nylon, it has very low water-absorbent, good dimensional stability, mechanical property, chemical resistant properties and electrical insulation capability, low temperature (40 ℃) excellent shock resistance; Have elastic memory benefit, when external force is removed, 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, can meet the injection moulding of various melt viscosity scopes and extrude processing, be usually used in manufacturing oil pipe, the flexible pipe of 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 be take 11-aminoundecanoic acid and is prepared from as raw material.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 as ε-caprolactam, make the aqueous solution and process, and its fusing point is 187 ℃, is thick after melting, when being heated to fusing point, will start the polycondensation of dewatering.Owing to being accompanied by the generation of polycondensation at solid in the phase transition process of molten state, as controlled, badly will cause coking, decomposition, caking, do not reach the object of making high molecular weight nylon 11.
On general industry, all adopt moisture 11-aminoundecanoic acid heating and pressurizing melting at present, required pressure generally, more than 1MPa, is let out to atmospheric pressure state after the fusing point that surpasses 11-aminoundecanoic acid until temperature, then continues melt polymerization and finally obtain nylon 11.In pressure leak process, when water vapour is discharged, a large amount of 11-aminoundecanoic acids also can, along with water vapour is taken out of, cause monomer loss.
Summary of the invention
The present invention is intended to solve the nylon 11 of prior art to be needed 11-aminoundecanoic acid to carry out pressurizing melting in synthetic, higher to equipment requirements, need high-tension apparatus, and in pressure leak process, in water vapour discharge, aminoundecanoic acid also can be along with water vapour is taken out of after melting, cause the problem of monomer loss, provide a kind of 11-aminoundecanoic acid normal pressure melt polymerization to prepare the technique of nylon 11, can under normal pressure, carry out the synthetic of nylon 11, reduce equipment cost, and can reduce the loss of 11-aminoundecanoic acid monomer.
In order to realize foregoing invention object, its concrete technical scheme is as follows:
11-aminoundecanoic acid normal pressure melt polymerization is prepared a technique for nylon 11, it is characterized in that: 11-aminoundecanoic acid and fusing assistant are mixed, and described fusing assistant is a kind of or the multiple boiling point of arbitrary proportion is the organic solvent of 185～220 ℃; Under atmospheric pressure state, heating makes material melting, then continues to be heated to 230～270 ℃, and the water of fusing assistant and reaction generation is evaporated; After normal pressure frit reaction completes, continuing to keep temperature is 230～270 ℃, then vacuumizes, and carries out vacuum reaction under vacuum state; After vacuum reaction completes, stop vacuumizing, recover atmospheric pressure state, discharging obtains nylon 11; In preparing the technique of nylon 11, described 11-aminoundecanoic acid normal pressure melt polymerization also adds 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 to refer to that described catalyzer and 11-aminoundecanoic acid and fusing assistant are mixed together, or adds after material melting; Described auxiliary agent and 11-aminoundecanoic acid and fusing assistant are mixed together, or add after material melting.
Fusing assistant of the present invention is that the boiling point of this area routine is the organic solvent of 185～220 ℃, 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 ℃.
The consumption of fusing assistant of the present invention is that the weight ratio of 11-aminoundecanoic acid and fusing assistant is 1:0.05～1, and the weight ratio that is preferably 11-aminoundecanoic acid and fusing assistant is 1:0.1～0.6.
Catalyzer of the present invention at least comprises a kind of material: phosphoric acid, phosphorous acid, ortho phosphorous acid, acetic acid, its consumption is that the weight ratio of 11-aminoundecanoic acid and catalyzer is 1:0.0001～0.03, and the weight ratio that is preferably 11-aminoundecanoic acid and catalyzer is 1:0.0002～0.01.
Auxiliary agent of the present invention at least comprises a kind of material: hexanodioic acid, SA, inclined to one side benzoic anhydride, hexanediamine, certain herbaceous plants with big flowers diamines, hexanolactam, Stearyl Amine, dioctyl phthalate (DOP), dimethyl phthalate, diethyl phthalate, its consumption is that the weight ratio of 11-aminoundecanoic acid and auxiliary agent is 1:0.0005～0.1, and the weight ratio that is preferably 11-aminoundecanoic acid and auxiliary agent is 1:0.001～0.05.
Of the present inventionly continue to be heated to 230～270 ℃, be evaporated reaction times of this process of the water that fusing assistant and reaction are generated 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 use Ubbelohde viscometer under 25 ℃ of water bath condition, measure its relative viscosity η r, by formula calculating below, obtain the intrinsic viscosity (dl/g) of nylon 11
[η]=[2（ηsp-lnηr）]
1/2/c
η sp=η r-1 in formula;
C is strength of solution.
The present invention brings useful technique effect:
1, the present invention is intended to solve the nylon 11 of prior art needs 11-aminoundecanoic acid to carry out pressurizing melting in synthetic, higher to equipment requirements, need high-tension apparatus, and in pressure leak process, in water vapour discharge, aminoundecanoic acid also can be along with water vapour is taken out of after melting, cause the problem of monomer loss, provide a kind of 11-aminoundecanoic acid normal pressure melt polymerization to prepare the technique of nylon 11, can under normal pressure, carry out the synthetic of nylon 11, reduce equipment cost, and can reduce the loss of 11-aminoundecanoic acid monomer.11-aminoundecanoic acid of the present invention melting under atmospheric pressure state, and owing to there being the existence of fusing assistant, greatly improved 11-aminoundecanoic acid heat and mass condition in melting process, there will not be coking, decomposition, the caking phenomenon of 11-aminoundecanoic acid.Owing to being normal pressure melting, do not need high pressure reactor, reduced the requirement to equipment.In polycondensation process after the melting of 11-aminoundecanoic acid, fusing assistant can be distilled out of, and can not exert an influence to the polycondensation process of 11-aminoundecanoic acid, and fusing assistant can Reusability.
2, method of the present invention can also be for normal pressure melt phase polycondensation techniques such as nylon 9, nylon 12, nylon 1010, nylon 8 10, nylon 11 11, nylon 1212s.The present invention is by adding fusing assistant, improved 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 that is 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 on the not impact of the performance of nylon 11, 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 adding of fusing assistant is to promote 11-aminoundecanoic acid 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, after material melting, needs it can steam very soon disengaging reaction system, and the increase of add-on, can increase energy consumption, slows down the temperature rise rate of material, increase production cost.In above-mentioned preferable range, the add-on of fusing assistant can guarantee 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 catalyzer add-on can be conducive to control molecular weight and the performance of 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 the nylon 11 that makes is better.
Embodiment
embodiment 1
11-aminoundecanoic acid normal pressure melt polymerization is prepared the technique of nylon 11:
11-aminoundecanoic acid and fusing assistant are mixed, and described fusing assistant is a kind of or the multiple boiling point of arbitrary proportion is the organic solvent of 185～220 ℃; Under atmospheric pressure state, heating makes material melting, then continues to be heated to 230 ℃, and the water of fusing assistant and reaction generation is evaporated; After normal pressure frit reaction completes, continuing to keep temperature is 230 ℃, then vacuumizes, and carries out vacuum reaction under vacuum state; After vacuum reaction completes, stop vacuumizing, recover atmospheric pressure state, discharging obtains nylon 11; In preparing the technique of nylon 11, described 11-aminoundecanoic acid normal pressure melt polymerization also adds catalyzer and auxiliary agent.
embodiment 2
11-aminoundecanoic acid normal pressure melt polymerization is prepared the technique of nylon 11:
11-aminoundecanoic acid and fusing assistant are mixed, and described fusing assistant is a kind of or the multiple boiling point of arbitrary proportion is the organic solvent of 185～220 ℃; Under atmospheric pressure state, heating makes material melting, then continues to be heated to 270 ℃, and the water of fusing assistant and reaction generation is evaporated; After normal pressure frit reaction completes, continuing to keep temperature is 270 ℃, then vacuumizes, and carries out vacuum reaction under vacuum state; After vacuum reaction completes, stop vacuumizing, recover atmospheric pressure state, discharging obtains nylon 11; In preparing the technique of nylon 11, described 11-aminoundecanoic acid normal pressure melt polymerization also adds catalyzer and auxiliary agent.
embodiment 3
11-aminoundecanoic acid normal pressure melt polymerization is prepared the technique of nylon 11:
11-aminoundecanoic acid and fusing assistant are mixed, and described fusing assistant is a kind of or the multiple boiling point of arbitrary proportion is the organic solvent of 185～220 ℃; Under atmospheric pressure state, heating makes material melting, then continues to be heated to 250 ℃, and the water of fusing assistant and reaction generation is evaporated; After normal pressure frit reaction completes, continuing to keep temperature is 250 ℃, then vacuumizes, and carries out vacuum reaction under vacuum state; After vacuum reaction completes, stop vacuumizing, recover atmospheric pressure state, discharging obtains nylon 11; In preparing the technique of nylon 11, described 11-aminoundecanoic acid normal pressure melt polymerization also adds catalyzer and auxiliary agent.
embodiment 4
11-aminoundecanoic acid normal pressure melt polymerization is prepared the technique of nylon 11:
11-aminoundecanoic acid and fusing assistant are mixed, and described fusing assistant is a kind of or the multiple boiling point of arbitrary proportion is the organic solvent of 185～220 ℃; Under atmospheric pressure state, heating makes material melting, then continues to be heated to 260 ℃, and the water of fusing assistant and reaction generation is evaporated; After normal pressure frit reaction completes, continuing to keep temperature is 260 ℃, then vacuumizes, and carries out vacuum reaction under vacuum state; After vacuum reaction completes, stop vacuumizing, recover atmospheric pressure state, discharging obtains nylon 11; In preparing the technique of nylon 11, described 11-aminoundecanoic acid normal pressure melt polymerization also adds 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 to refer to that described catalyzer and 11-aminoundecanoic acid and fusing assistant are mixed together, or adds after material melting; Described auxiliary agent and 11-aminoundecanoic acid and fusing assistant are mixed together, or add after material melting.
Preferably, described fusing assistant is that boiling point is the organic solvent of 190～200 ℃.
Preferably or further, the consumption of described fusing assistant is that the weight ratio of 11-aminoundecanoic acid and fusing assistant is 1:0.1.
Preferably or further, described catalyzer at least comprises a kind of material: phosphoric acid, phosphorous acid, ortho phosphorous acid, acetic acid, its consumption is that the weight ratio of 11-aminoundecanoic acid and catalyzer is 1:0.0002.
Preferably or further, described auxiliary agent at least comprises a kind of material: hexanodioic acid, SA, inclined to one side benzoic anhydride, hexanediamine, certain herbaceous plants with big flowers diamines, hexanolactam, Stearyl Amine, dioctyl phthalate (DOP), dimethyl phthalate, diethyl phthalate, its consumption is that the weight ratio of 11-aminoundecanoic acid and auxiliary agent is 1:0.001.
Preferably, described continuing is heated to 230 ℃, and be evaporated reaction times of this process of the water that fusing assistant and reaction are generated 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 to refer to that described catalyzer and 11-aminoundecanoic acid and fusing assistant are mixed together, or adds after material melting; Described auxiliary agent and 11-aminoundecanoic acid and fusing assistant are mixed together, or add after material melting.
Preferably, described fusing assistant is that boiling point is the organic solvent of 190～200 ℃.
Preferably or further, the consumption of described fusing assistant is that the weight ratio of 11-aminoundecanoic acid and fusing assistant is 1:0.6.
Preferably or further, described catalyzer at least comprises a kind of material: phosphoric acid, phosphorous acid, ortho phosphorous acid, acetic acid, its consumption is that the weight ratio of 11-aminoundecanoic acid and catalyzer is 1:0.01.
Preferably or further, described auxiliary agent at least comprises a kind of material: hexanodioic acid, SA, inclined to one side benzoic anhydride, hexanediamine, certain herbaceous plants with big flowers diamines, hexanolactam, Stearyl Amine, dioctyl phthalate (DOP), dimethyl phthalate, diethyl phthalate, its consumption is that the weight ratio of 11-aminoundecanoic acid and auxiliary agent is 0.05.
Preferably, described continuing is heated to 270 ℃, and be evaporated reaction times of this process of the water that fusing assistant and reaction are generated 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 to refer to that described catalyzer and 11-aminoundecanoic acid and fusing assistant are mixed together, or adds after material melting; Described auxiliary agent and 11-aminoundecanoic acid and fusing assistant are mixed together, or add after material melting.
Preferably, described fusing assistant is that boiling point is the organic solvent of 190～200 ℃.
Preferably or further, the consumption of described fusing assistant is that the weight ratio of 11-aminoundecanoic acid and fusing assistant is 1:0.35.
Preferably or further, described catalyzer at least comprises a kind of material: phosphoric acid, phosphorous acid, ortho phosphorous acid, acetic acid, its consumption is that the weight ratio of 11-aminoundecanoic acid and catalyzer is 1:0.0051.
Preferably or further, described auxiliary agent at least comprises a kind of material: hexanodioic acid, SA, inclined to one side benzoic anhydride, hexanediamine, certain herbaceous plants with big flowers diamines, hexanolactam, Stearyl Amine, dioctyl phthalate (DOP), dimethyl phthalate, diethyl phthalate, its consumption is that the weight ratio of 11-aminoundecanoic acid and auxiliary agent is 1:0.0255.
Preferably, described continuing is heated to 250 ℃, and be evaporated reaction times of this process of the water that fusing assistant and reaction are generated 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 to refer to that described catalyzer and 11-aminoundecanoic acid and fusing assistant are mixed together, or adds after material melting; Described auxiliary agent and 11-aminoundecanoic acid and fusing assistant are mixed together, or add after material melting.
Preferably, described fusing assistant is that boiling point is the organic solvent of 190～200 ℃.
Preferably or further, the consumption of described fusing assistant is that the weight ratio of 11-aminoundecanoic acid and fusing assistant is 1:0.5.
Preferably or further, described catalyzer at least comprises a kind of material: phosphoric acid, phosphorous acid, ortho phosphorous acid, acetic acid, its consumption is that the weight ratio of 11-aminoundecanoic acid and catalyzer is 1:0.002.
Preferably or further, described auxiliary agent at least comprises a kind of material: hexanodioic acid, SA, inclined to one side benzoic anhydride, hexanediamine, certain herbaceous plants with big flowers diamines, hexanolactam, Stearyl Amine, dioctyl phthalate (DOP), dimethyl phthalate, diethyl phthalate, its consumption is that the weight ratio of 11-aminoundecanoic acid and auxiliary agent is 1:0.04.
Preferably, described continuing is heated to 260 ℃, and be evaporated reaction times of this process of the water that fusing assistant and reaction are generated 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 N-Methyl pyrrolidone of the 11-aminoundecanoic acid of 150kg and 60kg is put in reactor, after the deoxygenation of vacuum nitrogen filling gas, start, after normal heating to 190 ℃, to add phosphorous acid 45g and adipic acid 300g, continue to be heated to 240 ℃ of reactions 2.5 hours, then, closed reactor vacuumizes, and vacuum degree control is at 0.085MPa, continuation is reacted 1 hour at 240 ℃, stopped reaction discharging, obtains 131kg nylon 11, and its intrinsic viscosity is 1.32dl/g.
In said process, can also add oxidation inhibitor, anti-aging agent etc.
embodiment 10
The dimethyl sulfoxide (DMSO) of the 11-aminoundecanoic acid of 150kg and 30kg is put in reactor, after the deoxygenation of vacuum nitrogen filling gas, started after normal heating to 190 ℃, add acetic acid 120ml, SA 600g, hexanediamine 200g, antioxidant 1010 750g, continues to be heated to 250 ℃ of reactions 1 hour, then, closed reactor vacuumizes, vacuum degree control is at 0.08MPa, and at 260 ℃, reacts stopped reaction discharging 1 hour, obtain 132kg nylon 11, its intrinsic viscosity is 0.95dl/g.
In said process, can also add oxidation inhibitor, anti-aging agent etc.
embodiment 11
The methyl-silicone oil of the 11-aminoundecanoic acid of 150kg and 45kg is put in reactor, after the deoxygenation of vacuum nitrogen filling gas, start after normal heating to 190 ℃, add phosphatase 11 00ml, hexanolactam 5kg, diamines 200g, continue to be heated to 250 ℃ of reactions 2 hours, then, closed reactor vacuumizes, and vacuum degree control is at 0.08MPa, and at 270 ℃, react 0.75 hour, stopped reaction discharging, obtains 138kg nylon 11, and its limiting viscosity is 1.6dl/g.
In said process, can also add oxidation inhibitor, anti-aging agent etc.
embodiment 12
Vacuum nitrogen filling gas for getting rid of after the oxygen of reactor, starts heating, reactor Yu Yu ambient atmosphere UNICOM in heat-processed, with guarantee whole heat-processed at reactor in atmospheric pressure state.
After material melting, continue heating, make temperature of charge reach 230～270 ℃, in this process, reactor still with ambient atmosphere UNICOM, reactor is in atmospheric pressure state, and guarantees to surpass the fusing assistant of boiling point and water that reaction generates can be steamed in time in this process, and this process reaction time is 1～3 hour.
Continuation remains on 230～270 ℃ by temperature of charge, closed reactor, start reaction to vacuumize, under the vacuum state that makes material be 0.08MPa～0.1MPa in vacuum tightness, react after 0.5～1.5 hour stop pumping vacuum fill gas to normal pressure, then discharging, after Cast Strip, cooling, pelletizing, obtain nylon 11 resin.
The catalyzer and the auxiliary agent that react required can together add with 11-aminoundecanoic acid and fusing assistant, also can after the melting of 11-aminoundecanoic acid, add; Its auxiliary agent is as oxidation inhibitor, anti-aging agent, staining agent etc. can together add with 11-aminoundecanoic acid and fusing assistant, after also can adding after the melting of 11-aminoundecanoic acid, also can synthesis under normal pressure completing or can add after vacuum reaction completes.
Claims (9)
1. 11-aminoundecanoic acid normal pressure melt polymerization is prepared a technique for nylon 11, it is characterized in that: 11-aminoundecanoic acid and fusing assistant are mixed, and described fusing assistant is a kind of or the multiple boiling point of arbitrary proportion is the organic solvent of 185～220 ℃; Under atmospheric pressure state, heating makes material melting, then continues to be heated to 230～270 ℃, and the water of fusing assistant and reaction generation is evaporated; After normal pressure frit reaction completes, continuing to keep temperature is 230～270 ℃, then vacuumizes, and carries out vacuum reaction under vacuum state; After vacuum reaction completes, stop vacuumizing, recover atmospheric pressure state, discharging obtains nylon 11; In preparing the technique of nylon 11, described 11-aminoundecanoic acid normal pressure melt polymerization also adds catalyzer and auxiliary agent.
2. a kind of 11-aminoundecanoic acid normal pressure melt polymerization according to claim 1 is prepared 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 to refer to that described catalyzer and 11-aminoundecanoic acid and fusing assistant are mixed together, or adds after material melting; Described auxiliary agent and 11-aminoundecanoic acid and fusing assistant are mixed together, or add after material melting.
3. a kind of 11-aminoundecanoic acid normal pressure melt polymerization according to claim 1 is prepared the technique of nylon 11, it is characterized in that: described fusing assistant is that boiling point is the organic solvent of 190～200 ℃.
4. according to a kind of 11-aminoundecanoic acid normal pressure melt polymerization described in claim 1 or 3, prepare the technique of nylon 11, it is characterized in that: the consumption of described fusing assistant is that 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 is prepared the technique of nylon 11, it is characterized in that: described catalyzer at least comprises a kind of material: phosphoric acid, phosphorous acid, ortho phosphorous acid, acetic acid, its consumption is that 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 and 2 is prepared the technique of nylon 11, it is characterized in that: described auxiliary agent at least comprises a kind of material: hexanodioic acid, SA, inclined to one side benzoic anhydride, hexanediamine, certain herbaceous plants with big flowers diamines, hexanolactam, Stearyl Amine, dioctyl phthalate (DOP), dimethyl phthalate, diethyl phthalate, its consumption is that the weight ratio of 11-aminoundecanoic acid and auxiliary agent is 1:0.001～0.05.
7. a kind of 11-aminoundecanoic acid normal pressure melt polymerization according to claim 1 is prepared the technique of nylon 11, it is characterized in that: described continuing is heated to 230～270 ℃, be evaporated reaction times of this process of the water that fusing assistant and reaction are generated is 1～3 hour.
8. a kind of 11-aminoundecanoic acid normal pressure melt polymerization according to claim 1 is prepared the technique of nylon 11, it is characterized in that: the vacuum tightness of described vacuum state is 0.08～0.1MPa.
9. according to a kind of 11-aminoundecanoic acid normal pressure melt polymerization described in claim 1 or 8, prepare 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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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104710613A (en) * | 2015-03-12 | 2015-06-17 | 中国科学院理化技术研究所 | Solvothermal preparation method of semi-aromatic polyamide |
| CN111303408A (en) * | 2020-03-16 | 2020-06-19 | 珠海派锐尔新材料有限公司 | Preparation method of high-temperature nylon |
| CN114917856A (en) * | 2022-05-31 | 2022-08-19 | 中国五环工程有限公司 | Process system and method for preparing nylon 11 by polymerizing 11-aminoundecanoic acid |
| CN115536853A (en) * | 2022-10-28 | 2022-12-30 | 中国五环工程有限公司 | Method for preparing PA11 elastomer from 11-aminoundecanoic acid |
| CN116693843A (en) * | 2023-06-27 | 2023-09-05 | 中国科学院微生物研究所 | Preparation method of nylon 11 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104710613A (en) * | 2015-03-12 | 2015-06-17 | 中国科学院理化技术研究所 | Solvothermal preparation method of semi-aromatic polyamide |
| CN111303408A (en) * | 2020-03-16 | 2020-06-19 | 珠海派锐尔新材料有限公司 | Preparation method of high-temperature nylon |
| CN114917856A (en) * | 2022-05-31 | 2022-08-19 | 中国五环工程有限公司 | Process system and method for preparing nylon 11 by polymerizing 11-aminoundecanoic acid |
| 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 |
| CN115536853A (en) * | 2022-10-28 | 2022-12-30 | 中国五环工程有限公司 | Method for preparing PA11 elastomer from 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 |
| CN116693843A (en) * | 2023-06-27 | 2023-09-05 | 中国科学院微生物研究所 | Preparation method of nylon 11 |
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| CN103709399B (en) | 2016-04-27 |
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