CN103724209A - Preparation method of long-carbon-chain semi-aromatic nylon salt - Google Patents
Preparation method of long-carbon-chain semi-aromatic nylon salt Download PDFInfo
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- CN103724209A CN103724209A CN201410019451.XA CN201410019451A CN103724209A CN 103724209 A CN103724209 A CN 103724209A CN 201410019451 A CN201410019451 A CN 201410019451A CN 103724209 A CN103724209 A CN 103724209A
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- 150000003839 salts Chemical class 0.000 title claims abstract description 142
- 229920006012 semi-aromatic polyamide Polymers 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
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- 238000003756 stirring Methods 0.000 claims abstract description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000011261 inert gas Substances 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 21
- 150000004985 diamines Chemical class 0.000 claims abstract description 15
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 6
- 239000000376 reactant Substances 0.000 claims abstract description 5
- 239000000706 filtrate Substances 0.000 claims abstract description 4
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- 238000005119 centrifugation Methods 0.000 claims description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 150000007520 diprotic acids Chemical class 0.000 claims description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 14
- 235000011089 carbon dioxide Nutrition 0.000 claims description 14
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- ZCILODAAHLISPY-UHFFFAOYSA-N biphenyl ether Natural products C1=C(CC=C)C(O)=CC(OC=2C(=CC(CC=C)=CC=2)O)=C1 ZCILODAAHLISPY-UHFFFAOYSA-N 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000001307 helium Substances 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- UFMBOFGKHIXOTA-UHFFFAOYSA-N 2-methylterephthalic acid Chemical compound CC1=CC(C(O)=O)=CC=C1C(O)=O UFMBOFGKHIXOTA-UHFFFAOYSA-N 0.000 claims description 4
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 claims description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 4
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- GWZCCUDJHOGOSO-UHFFFAOYSA-N diphenic acid Chemical compound OC(=O)C1=CC=CC=C1C1=CC=CC=C1C(O)=O GWZCCUDJHOGOSO-UHFFFAOYSA-N 0.000 claims description 4
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
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- 239000004677 Nylon Substances 0.000 description 101
- 229920001778 nylon Polymers 0.000 description 101
- 229910052799 carbon Inorganic materials 0.000 description 57
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- 239000002904 solvent Substances 0.000 description 13
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- 150000001412 amines Chemical class 0.000 description 10
- 238000002425 crystallisation Methods 0.000 description 9
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- 230000006911 nucleation Effects 0.000 description 8
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- 239000000243 solution Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 4
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
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- 229920006119 nylon 10T Polymers 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 229920000007 Nylon MXD6 Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
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- 239000000463 material Substances 0.000 description 1
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- 239000000178 monomer Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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- 239000007787 solid Substances 0.000 description 1
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Landscapes
- Polyamides (AREA)
Abstract
The invention discloses a preparation method of a long-carbon-chain semi-aromatic nylon salt, belonging to the technical field of synthesis of high polymer materials. The preparation method comprises the following steps: (1) adding long-carbon-chain aliphatic diamine and aromatic binary acid or aromatic diamine and long-carbon-chain aliphatic binary acid into water according to a molar ratio of 1: 1, and uniformly stirring in an autoclave, wherein the mass fraction of the reactants is 20-80 percent; (2) under the protection atmosphere of inert gas, heating to 100-200 DEG C, preserving the pressure in the autoclave to 0.2-2Mpa, then adding a proper amount of corresponding diamine or binary acid to adjust the pH value of the solution, and when the pH value of the solution is 7.0-7.5, preserving heat for 0-5 hours and beginning to cool; (3) cooling at 5-50 DEG C/h, and when the temperature is reduced to room temperature, centrifugally separating to obtain the long-carbon-chain semi-aromatic nylon salt; (4) adding the centrifugally separated filtrate into the step (1) for recycling. According to the preparation method disclosed by invention, the molar ratio of the binary acid to the diamine can be accurately controlled, and the prepared semi-aromatic nylon salt is high in purity; in addition, the long-carbon-chain semi-aromatic nylon salt is prepared with water as a medium, the preparation method is simple to operate, the raw materials can be sufficiently reacted, and the salifying efficiency is high; the preparation method is environment-friendly and low in cost.
Description
Technical field
The present invention relates to a kind of preparation method who grows carbochain semi-aromatic nylon salt, belong to synthesis of polymer material technical field.Be particularly related to a kind of method of preparing long carbochain semi-aromatic nylon salt take water as solvent.
Background technology
Conventionally by the standby chemical reaction of nylon, distinguish, can be divided into two classes: a class is to be made by amino acid or lactan ring-opening polymerization, is commonly referred to AB type nylon; Another kind of is to be made by diprotic acid and diamine polycondensation, is commonly referred to AABB type nylon.It is to prepare the most frequently used method of AABB type nylon that diprotic acid and diamine are made to nylon salt, and the method can effectively be controlled the mol ratio of diprotic acid and diamine, thereby controls the molecular weight of nylon.
Nylon 66 is as the earliest and be topmost nylon kind so far, and the preparation of its salt can be divided into aqua-solution method and organic solvent crystallization process according to the difference of solvent.About Monsanto Chemicals, E.I.Du Pont Company and French Luo Na-Rhone-Poulenc adopts aqua-solution method to produce, and is characterized in not adopting organic solvent, and convenient and easy, safe and reliable, technique is simple, and cost is low, but high to raw material midbody specification of quality.Britain ICI company, German BASF AG adopt organic solvent crystallization process to produce, and are characterized in that salify is convenient, flexible, good product quality, but strong to temperature, humidity, light and oxygen sensitivity, and adopting methyl alcohol and ethanol to make solvent, cost is higher.Along with the increase of carbon chain lengths, diprotic acid, diamine and the salt solubleness in water reduces gradually, adopts aqua-solution method to carry out the increase of salify difficulty, and therefore the long carbon chain nylon such as nylon 1010, nylon 1212 adopts organic solvent crystallization process salify mostly.
Semi-aromatic nylon is by aliphatic diamine (acid) and the diprotic acid (amine) with aromatic nucleus, through polycondensation, makes.Nylon 6T salt, nylon 9 T salt, nylon MXD 6 salt adopt water as solvent conventionally, and nylon 10T salt is because the solubleness in water is lower, generally adopts dimethyl formamide to make solvent.Patent US20130172521A1 has announced a kind of preparation method of semi-aromatic nylon salt, adopt solventless method to prepare semi-aromatic nylon salt, diprotic acid is heated to the fusing point of diamine above and keep the pulverulence of diprotic acid, liquid diamine is joined and in pulverous diprotic acid, prepares semi-aromatic nylon salt.Purity and the salifying process conditional request of this method to monomer is higher, in addition, cannot accurately control reaction end.Patent CN101456804A has announced a kind of preparation method of semi-aromatic nylon salt, adopting N-Methyl pyrrolidone or dimethyl formamide etc. is solvent, at 100 ℃ ~ 140 ℃, neutralization reaction is made semi-aromatic nylon salt, uses the fusing point of nylon salt to judge reaction end.Patent CN101880235A has announced a kind of preparation method who grows carbochain semi-aromatic nylon salt, and employing methyl-sulphoxide is solvent, 60 ℃ ~ 80 ℃ neutralization reactions, prepares semi-aromatic nylon salt, with pH value, judges reaction end.Clearly, with an organic solvent salify, not only can increase production cost, also can cause environmental pollution, is unfavorable for large-scale industrial production.Patent EP0411790A1 has announced a kind of method of preparing semi-aromatic nylon salt, specifically take water as medium, at temperature when water seethes with excitement, prepare nylon salt, then adopt suitable cooling conditions to obtain nylon salt, the aqueous solution massfraction of the nylon salt that this patent is announced is along with the increase of diamines carbon chain lengths, and the concentration of gained nylon salt reduces, and particularly the concentration of nylon 12T salt is only 5% mass fraction, productive rate also only has 3.8%, obviously cannot meet the needs of large-scale industrial production.Patent CN1887841A has announced a kind of preparation method of heat resistant nylon salt, and the diprotic acid of heating and the mixture of the mixture of water and the diamine of heating and water are prepared to semi-aromatic nylon salt 60 ℃ ~ 95 ℃ neutralization reactions.
Obviously, selecting water is that solvent is prepared nylon salt and possessed environmental protection and the advantage such as cheap and easy to get, is the ideal solvent of preparing nylon salt.The more important thing is while preparing nylon salt using water as solvent, can accurately judge by pH value the terminal of salt-forming reaction, realize instant on-line Control.Along with the raising of people's environmental consciousness and the great attention to health of human body, organic solvent will be substituted by the water of environmental protection more etc. gradually in the mankind's life.But the solubleness of semi-aromatic nylon salt in water can sharply reduce with the increase of carbochain, if the solubleness of 6T salt in the water of 80 ℃ is 68g, and 12T salt only has 2.6g, even the solubleness of 12T salt also only has 5g in boiling water.The solubleness of aromatic acid (amine) in water is less compared with salt simultaneously, as the solubleness in the water of 80 ℃ is less than 1g.When adopting aforesaid method to prepare long carbochain semi-aromatic nylon salt take water as solvent, when large percentage in reaction system of raw material aromatic acid (amine) and aliphatic diamine (acid), the rapid crystallization of salt generating, and unreacted and do not have dissolve aromatic acid (or amine) will be covered by the crystal of salt, make the aromatic acid (or amine) being wrapped by just cannot participate in salt-forming reaction, and then cause and in salt, include aromatic acid (amine), make product mol ratio uncontrollable, can not prepare high quality nylon salt, thereby cause polymer molecular weight not high, poor-performing.
Summary of the invention
The object of the present invention is to provide a kind of preparation method who realizes the online instant long carbochain semi-aromatic nylon salt of controlling mol ratio take water as solvent, under High Temperature High Pressure, by the accurate control to nylon salification process, thereby for growing the synthetic nylon salt that high-quality is provided of carbochain semi-aromatic nylon.
For realizing object of the present invention, during the present invention carries out the long carbochain aliphatic diamine after refining and aromatic acid or aromatic diamine and long carbochain aliphatic dibasic acid under High Temperature High Pressure and salify, by controlling the methods such as rate of temperature fall and stir speed (S.S.), obtain and expect the long carbochain semi-aromatic nylon salt of crystalline sizes.Simultaneously add a small amount of amine or acid to adjust the pH value of system being neutralized in reactant salt process, obtain and expect the long carbochain semi-aromatic nylon salt of mol ratio.
Principle is: the present invention adopts in elevated pressures, is greater than under 100 ℃ of temperature condition, and aromatic acid (amine) reacts salify with aliphatic diamine (acid), and cooling makes the method for the nylon salt crystallization generating prepare semi-aromatic nylon salt.Because under high pressure conditions, the elevation of boiling point, the density of water reduces, surface tension diminishes, dissolving power strengthens, the solubleness in water such as diprotic acid, diamine, nylon salt all increases, thus the problem of wrapping up unreacted aromatic acid (amine) while having solved nylon salt crystallization.Meanwhile, adopt the method, the salt-forming reaction time is short, and efficiency is high.Therefore, by improving the temperature and pressure of water, can be under higher solids content state, the long carbochain semi-aromatic nylon of the high quality salt of efficient preparation expection mole proportioning.
In addition, by processing condition such as the rate of temperature fall after being controlled to reactant salt and finishing, stir speed (S.S.)s, control crystalline size and the crystallization rate of generated salt, improve the yield of nylon salt.Crystallisation process comprises nucleation and crystal two stages of growth.Nucleation stage is divided into again homogeneous nucleation and heterogeneous nucleation.This reaction system is homogeneous nucleation.Homogeneous nucleation is to disturb without other tramp material, relies on the fluctuation of strength of solution and molecular thermalmotion energy to form crystallization nuclei, is characterized in that high temperature nucleation rate is slow, low temperature nucleation rate is fast.Therefore can control crystalline size by controlling rate of temperature fall, lower the temperature faster, crystalline size is less; Otherwise crystalline size is larger.By stir speed (S.S.) processed, also can control crystalline size.Stir speed (S.S.) is larger, and crystalline size is less, otherwise crystalline size is larger.So can control by controlling rate of temperature fall and stir speed (S.S.) the size of long carbochain semi-aromatic nylon salt crystal in the process of solution cooling.
The preparation method of this length carbochain semi-aromatic nylon salt specifically comprises the steps:
(1) will grow carbochain aliphatic diamine and aromatic acid, or aromatic diamine and long carbochain aliphatic dibasic acid, under stirring, according to the mol ratio of 1:1, being added to the water, the massfraction of reactant is 20% ~ 80%;
(2) under protection of inert gas, be heated to 100 ℃ ~ 200 ℃, keeping still internal pressure is 0.2MPa ~ 2MPa, add again appropriate corresponding diamine or diprotic acid, adjust the pH value of solution, stir, when the pH of solution value is 7.0 ~ 7.5, be incubated 0 ~ 5 hour, start cooling;
(3), with 5 ℃ ~ 50 ℃/h cooling, when being down to room temperature, centrifugation obtains long carbochain semi-aromatic nylon salt.
(4) filtrate after centrifugation is joined in step (1) and recycled.
Described aromatic acid is terephthalic acid, m-phthalic acid, 2-methyl terephthalic acid, 1,4-naphthalic acid, 2,6-naphthalic acid, 4,4 '-biphenyl dicarboxylic acid, 2,2 '-biphenyl dicarboxylic acid, 4,4 '-dicarboxyl sulfobenzide, 4, one or more in 4 '-dicarboxylate biphenyl ether.Aliphatic dibasic acid is one or more in straight chain aliphatic dibasic acid or the side chain aliphatic dibasic acid that contains 10 ~ 18 carbon atoms in molecular backbone chain.
Described aromatic diamine is Ursol D, mphenylenediamine, p dimethylamine, m-xylene diamine, 2-dimethyl-p-phenylenediamine, 4,4 '-benzidine ether, 4, one or more in 4'-diamino diphenyl sulfone.Aliphatic diamine is one or more in straight chain aliphatic diamine or the side chain aliphatic diamine that contains 10 ~ 18 carbon atoms in molecular backbone chain.
Step (1), (2) stirring velocity are 15 ~ 200r/min.
Described water is one or more in the filtrate after the centrifugation described in distilled water, deionized water, step (4).
Described rare gas element is the one in carbonic acid gas, nitrogen, argon gas or helium.
The present invention utilizes diprotic acid, diamine and the dissolubility difference of semi-aromatic nylon salt in the water of High Temperature High Pressure and in normal temperature and pressure water to carry out the preparation of nylon salt, by regulating stir speed (S.S.), cooling method to control the crystalline size of nylon salt.Have the following advantages:
(1) solvent using water as salt-forming reaction, green, economy, environmental protection, little to harm.
(2) salify under high-temperature and high-pressure conditions, has increased substantially raw material and the nylon salt solubleness in water, can make the massfraction of nylon salt reach 80%.
(3) can on-line Control diprotic acid by pH value and the mol ratio of diamine, judge salt-forming reaction terminal, simple to operate, workable, significantly improve long carbon chain nylon salt preparation efficiency.
(4) separating mother liquor can reuse.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1
30.53kg decamethylene diamine, 29.47kg terephthalic acid and 43.73kg water are joined in reactor, with 20r/min speed, stir.Under carbonic acid gas protection of inert gas, heat to 140 ℃, with 20r/min speed, stir.Under carbonic acid gas protection of inert gas, still internal pressure 0.4MPa, with decamethylene diamine, adjusting pH is 7.3, stirs 50 minutes.Be cooled to rapidly nylon salt and separated out, then with the speed of 20 ℃/h, be cooled to room temperature, centrifugation, the dry nylon 10T salt that to obtain.Gained nylon salt yield is 92%.Carry out polymerization with the 10T salt of gained, obtaining melting point polymer is 315 ℃.
Embodiment 2
29.08kg 11 carbon diamines, 25.92kg terephthalic acid and 41.35kg water are joined in reactor, with 200r/min speed, stir.Under carbonic acid gas protection of inert gas, heat to 145 ℃, still internal pressure 0.4MPa, with 11 carbon diamines, adjusting pH is 7.3, stirs 60 minutes.Be cooled to rapidly nylon salt and separated out, then with the speed of 30 ℃/h, be cooled to room temperature, centrifugation, the dry nylon 11 T salt that to obtain.Gained nylon salt yield is 92%.
Embodiment 3
35.48kg 12 carbon diamines, 29.47kg terephthalic acid and 43.73kg water are joined in reactor, with 100r/min speed, stir.Under nitrogen protection of inert gas, heat to 150 ℃, still internal pressure 0.5MPa, with 12 carbon diamines, adjusting pH is 7.2, stirs 70 minutes.Be cooled to rapidly nylon salt and separated out, then with the speed of 40 ℃/h, be cooled to room temperature, centrifugation, the dry nylon 12T salt that to obtain.Gained nylon salt yield is 93%.Carry out polymerization with the 12T salt of gained, obtaining melting point polymer is 310 ℃.
Embodiment 4
28.17kg 13 carbon diamines, 21.83kg terephthalic acid and 45.25kg water are joined in reactor, with 50r/min speed, stir.Under nitrogen protection of inert gas, heat to 150 ℃, still internal pressure 0.5MPa, with 13 carbon diamines, adjusting pH is 7.2, stirs 90 minutes.Be cooled to rapidly nylon salt and separated out, then with the speed of 30 ℃/h, be cooled to room temperature, centrifugation, the dry nylon 13T salt that to obtain.Gained nylon salt yield is 93%.
Embodiment 5
30.68kg 14 carbon diamines, 22.32kg terephthalic acid and 41.36kg water are joined in reactor, with 150r/min speed, stir.Under nitrogen protection of inert gas, heat to 155 ℃, still internal pressure 0.5MPa, with 14 carbon diamines, adjusting pH is 7.2, stirs 120 minutes.Be cooled to rapidly nylon salt and separated out, then with the speed of 40 ℃/h, be cooled to room temperature, centrifugation, the dry nylon 14T salt that to obtain.Gained nylon salt yield is 94%.
Embodiment 6
18.95kg 18 carbon diamines, 11.05kg terephthalic acid and 69.32kg water are joined in reactor, with 50r/min speed, stir.Under argon gas protection of inert gas, heat to 190 ℃, still internal pressure 1.8MPa, with 18 carbon diamines, adjusting pH is 7.2, stirs 240 minutes.Be cooled to rapidly nylon salt and separated out, then with the speed of 15 ℃/h, be cooled to room temperature, centrifugation, the dry nylon 18T salt that to obtain.Gained nylon salt yield is 97%.
Embodiment 7
11.87kg Ursol D, 28.13kg DC14 and 58.35kg water are joined in reactor, with 100r/min speed, stir.Under nitrogen protection of inert gas, heat to 160 ℃, still internal pressure 0.8MPa, with Ursol D, adjusting pH is 7.0, stirs 90 minutes.Be cooled to rapidly nylon salt and separated out, then with the speed of 35 ℃/h, be cooled to room temperature, centrifugation, the dry nylon salt that obtains.Gained nylon salt yield is 93%.
Embodiment 8
16.07kg mphenylenediamine, 33.93kg SL-AH and 47.87kg water are joined in reactor, with 50r/min speed, stir.Under helium protection of inert gas, heat to 150 ℃, still internal pressure 0.7MPa, with mphenylenediamine, adjusting pH is 7.1, stirs 120 minutes.Be cooled to rapidly nylon salt and separated out, then with the speed of 45 ℃/h, be cooled to room temperature, centrifugation, the dry nylon salt that to obtain.Gained nylon salt yield is 90%.
Embodiment 9
By 13.61kg 4,4 '-benzidine ether, 16.39kg 16-dicarboxylic acid and 65.23kg water join in reactor, with 90r/min speed, stir.Under helium protection of inert gas, heat to 190 ℃, still internal pressure 1.7MPa, with 4, it is 7.2 that 4 '-benzidine ether is adjusted pH, stirs 200 minutes.Be cooled to rapidly nylon salt and separated out, then with the speed of 30 ℃/h, be cooled to room temperature, centrifugation, the dry nylon salt that to obtain.Gained nylon salt yield is 97%.
Embodiment 10
Mixing acid and the 50.67kg water of 27.34kg 12 carbon diamines, 22.66kg terephthalic acid and m-phthalic acid are joined in reactor, with 90r/min speed, stir.Under helium protection of inert gas, heat to 160 ℃, still internal pressure 0.7MPa, with 12 carbon diamines, adjusting pH is 7.2, stirs 30 minutes.Be cooled to rapidly nylon salt and separated out, then with the speed of 10 ℃/h, be cooled to room temperature, centrifugation, the dry nylon salt that to obtain.Gained nylon salt yield is 92%.
Embodiment 11
11.74kg decamethylene diamine, 13.67kg 12 carbon diamines, 22.66kg terephthalic acid and 50.84kg water are joined in reactor, with 120r/min speed, stir.Under helium protection of inert gas, heat to 170 ℃, still internal pressure 1.0MPa, with 12 carbon diamines, adjusting pH is 7.2, stirs 50 minutes.Then with the speed of 50 ℃/h, be cooled to room temperature, centrifugation, the dry nylon salt that to obtain.Gained nylon salt yield is 93%.
Embodiment 12
By 20.97kg 14 carbon diamines, 8.42kg terephthalic acid, 10.61kg 4,4 '-dicarboxylate biphenyl ether and 61.84kg water join in reactor, with 60r/min speed, stir.Under nitrogen protection of inert gas, heat to 190 ℃, still internal pressure 1.9MPa, with 14 carbon diamines, adjusting pH is 7.0, stirs 150 minutes.Be cooled to rapidly nylon salt and separated out, then with the speed of 40 ℃/h, be cooled to room temperature, centrifugation, the dry nylon salt that to obtain.Gained nylon salt yield is 92%.
Embodiment 13
11.27kg 13 carbon diamines, 8.73kg terephthalic acid, 6.17kg Ursol D, 13.83kg tridecanyldicarboxylic acid and 61.34kg water are joined in reactor, with 30r/min speed, stir.Under nitrogen protection of inert gas, heat to 180 ℃, still internal pressure 1.6MPa, with 13 carbon diamines, adjusting pH is 7.0, stirs 200 minutes.Be cooled to rapidly nylon salt and separated out, then with the speed of 20 ℃/h, be cooled to room temperature, centrifugation, the dry nylon salt that to obtain.Gained nylon salt yield is 93%.
Embodiment 14
11.94kg mphenylenediamine, 13.57kg SL-AH, 14.49kg 16-dicarboxylic acid and 55.46kg water are joined in reactor, with 80r/min speed, stir.Under nitrogen protection of inert gas, heat to 150 ℃, still internal pressure 0.9MPa, with mphenylenediamine, adjusting pH is 7.1, stirs 60 minutes.Be cooled to rapidly nylon salt and separated out, then with the speed of 40 ℃/h, be cooled to room temperature, centrifugation, the dry nylon salt that to obtain.Gained nylon salt yield is 95%.
Embodiment 15
21.06kg 12 carbon diamines, 18.94kg 2-methyl terephthalic acid and 61.34kg water are joined in reactor, with 40r/min speed, stir.Under nitrogen protection of inert gas, heat to 170 ℃, still internal pressure 1.0MPa, with 12 carbon diamines, adjusting pH is 7.2, stirs 40 minutes.Be cooled to rapidly nylon salt and separated out, then with the speed of 20 ℃/h, be cooled to room temperature, centrifugation, the dry nylon 12M salt that to obtain.Gained nylon salt yield is 95%.
Embodiment 16
By 16.92kg 14 carbon diamines, 18.08kg 4,4 '-biphenyl dicarboxylic acid and 65.32kg water join in reactor, with 80r/min speed, stir.Under carbonic acid gas protection of inert gas, heat to 160 ℃, still internal pressure 0.8MPa, with 14 carbon diamines, adjusting pH is 7.2, stirs 160 minutes.Be cooled to rapidly nylon salt and separated out, then with the speed of 25 ℃/h, be cooled to room temperature, centrifugation, the dry nylon 14B salt that to obtain.Gained nylon salt yield is 96%.
Embodiment 17
By 13.84kg 12 carbon diamines, 21.16kg 4,4 '-dicarboxyl sulfobenzide and 67.15kg water join in reactor, with 80r/min speed, stir.Under carbonic acid gas protection of inert gas, heat to 170 ℃, still internal pressure 1.0MPa, with 12 carbon diamines, adjusting pH is 7.2, stirs 50 minutes.Be cooled to rapidly nylon salt and separated out, then with the speed of 20 ℃/h, be cooled to room temperature, centrifugation, the dry nylon 12S salt that to obtain.Gained nylon salt yield is 94%.
Embodiment 18
By 15.29kg 12 carbon diamines, 19.71kg 4,4 '-dicarboxylate biphenyl ether and 64.36kg water join in reactor, with 50r/min speed, stir.Under carbonic acid gas protection of inert gas, heat to 160 ℃, still internal pressure 0.8MPa, with 12 carbon diamines, adjusting pH is 7.2, stirs 30 minutes.Be cooled to rapidly nylon salt and separated out, then with the speed of 15 ℃/h, be cooled to room temperature, centrifugation, the dry nylon 12O salt that to obtain.Gained nylon salt yield is 92%.
Embodiment 19
By 14.96kg 16 carbon diamines, 15.04kg 4,4 '-dicarboxylate biphenyl ether and 69.58kg water join in reactor, with 120r/min speed, stir.Under carbonic acid gas protection of inert gas, heat to 180 ℃, still internal pressure 1.3MPa, with 16 carbon diamines, adjusting pH is 7.1, stirs 200 minutes.Be cooled to rapidly nylon salt and separated out, then with the speed of 25 ℃/h, be cooled to room temperature, centrifugation, the dry nylon 16O salt that to obtain.Gained nylon salt yield is 95%.
Embodiment 20
By 13.52kg 12 carbon diamines, 16.48kg 2,2 '-biphenyl dicarboxylic acid and 68.74kg water join in reactor, with 80r/min speed, stir.Under carbonic acid gas protection of inert gas, heat to 170 ℃, still internal pressure 1.1MPa, with 12 carbon diamines, adjusting pH is 7.2, stirs 120 minutes.Be cooled to rapidly nylon salt and separated out, then with the speed of 15 ℃/h, be cooled to room temperature, centrifugation, the dry nylon 12D salt that to obtain.Gained nylon salt yield is 95%.
Embodiment 21
14.43kg 12 carbon diamines, 15.57kg Isosorbide-5-Nitrae-naphthalic acid and 69.31kg water are joined in reactor, with 180r/min speed, stir.Under carbonic acid gas protection of inert gas, heat to 160 ℃, still internal pressure 0.8MPa, with 12 carbon diamines, adjusting pH is 7.1, stirs 150 minutes.Be cooled to rapidly nylon salt and separated out, then with the speed of 25 ℃/h, be cooled to room temperature, centrifugation, the dry nylon 12N salt that to obtain.Gained nylon salt yield is 94%.
Embodiment 22
16.84kg 12 carbon diamines, 18.16kg NDA and 69.31kg water are joined in reactor, with 80r/min speed, stir.Under carbonic acid gas protection of inert gas, heat to 170 ℃, still internal pressure 1.0MPa, with 12 carbon diamines, adjusting pH is 7.1, stirs 140 minutes.Be cooled to rapidly nylon salt and separated out, then with the speed of 20 ℃/h, be cooled to room temperature, centrifugation, the dry nylon 12N salt that to obtain.Gained nylon salt yield is 94%.
Embodiment 23
35.48kg 12 carbon diamines, 29.47kg terephthalic acid and 43.73kg water are joined in reactor, with 80r/min speed, stir.Under carbonic acid gas protection of inert gas, heat to 140 ℃, still internal pressure 0.4MPa, with 12 carbon diamines, adjusting pH is 7.3, with 50r/min speed, stirs 50 minutes.Then under identical stirring velocity, with the speed of 10,20,30,40 ℃/h, be cooled to room temperature, centrifugation, the dry nylon 12T salt that to obtain.The particle diameter of gained nylon salt is greater than 160 object parts by weight and is respectively: 71%, 63%, 57%, 48%.
Embodiment 24
35.48kg 12 carbon diamines, 29.47kg terephthalic acid and 43.73kg water are joined in reactor, with 80r/min speed, stir.Under carbonic acid gas protection of inert gas, heat to 140 ℃, still internal pressure 0.4MPa, with 12 carbon diamines, adjusting pH is 7.3, stirs 50 minutes respectively with 30r/min, 50r/min, 70r/min, 90r/min speed.Then with the speed of 30 ℃/h, be cooled to room temperature, centrifugation, the dry nylon 12T salt that to obtain.The particle diameter of gained nylon salt is greater than 160 object parts by weight and is respectively: 66%, 57%, 52%, 45%.
By the present invention, producing the long carbochain semi-aromatic nylon of the part salt obtaining sees the following form:
| Embodiment | Diamine | Diprotic acid | Productive rate (%) |
| 1 | Decamethylene diamine | Terephthalic acid | 92 |
| 2 | 11 carbon diamines | Terephthalic acid | 92 |
| 3 | 12 carbon diamines | Terephthalic acid | 93 |
| 4 | 13 carbon diamines | Terephthalic acid | 93 |
| 5 | 14 carbon diamines | Terephthalic acid | 94 |
| 6 | 18 carbon diamines | Terephthalic acid | 97 |
| 7 | Ursol D | DC14 | 93 |
| 8 | Mphenylenediamine | SL-AH | 90 |
| 9 | 4,4 '-benzidine ether | 16-dicarboxylic acid | 97 |
| 10 | 12 carbon diamines | Terephthalic acid, m-phthalic acid | 92 |
| 11 | Decamethylene diamine, 12 carbon diamines | Terephthalic acid | 93 |
| 12 | 14 carbon diamines | Terephthalic acid, 4,4 '-dicarboxylate biphenyl ether | 92 |
| 13 | 13 carbon diamines, Ursol D | Tridecanyldicarboxylic acid, terephthalic acid | 93 |
| 14 | Mphenylenediamine | SL-AH, 16-dicarboxylic acid | 95 |
| 15 | 12 carbon diamines | 2-methyl terephthalic acid | 95 |
| 16 | 14 carbon diamines | 4,4 '-biphenyl dicarboxylic acid | 96 |
| 17 | 12 carbon diamines | 4,4 '-dicarboxyl sulfobenzide | 94 |
| 18 | 12 carbon diamines | 4,4 '-dicarboxylate biphenyl ether | 92 |
| 19 | 16 carbon diamines | 4,4 '-dicarboxylate biphenyl ether | 95 |
| 20 | 12 carbon diamines | 2,2 '-biphenyl dicarboxylic acid | 95 |
| 21 | 12 carbon diamines | Isosorbide-5-Nitrae-naphthalic acid | 94 |
| 22 | 12 carbon diamines | NDA | 94 |
| 23 | 12 carbon diamines | Terephthalic acid | 93~95 |
| 24 | 12 carbon diamines | Terephthalic acid | 92~94 |
More than can find out, the present invention utilizes and under High Temperature High Pressure, carries out salt-forming reaction, increased the solubleness of raw material and nylon salt, improved the dissolution equilibrium speed of acid and amine, raw material reaction is abundant, improved long carbochain semi-aromatic nylon salt output and productive rate, reduced water consumption, reduced energy consumption, improved production efficiency.
Claims (6)
1. a preparation method for long carbochain semi-aromatic nylon salt, is characterized in that, comprises the steps:
(1) will grow carbochain aliphatic diamine and aromatic acid, or aromatic diamine and long carbochain aliphatic dibasic acid, under stirring, according to the mol ratio of 1:1, being added to the water, reactant quality mark is 20% ~ 80%;
(2) under protection of inert gas, be heated to 100 ℃ ~ 200 ℃, keeping still internal pressure is 0.2MPa ~ 2MPa, add again appropriate corresponding diamine or diprotic acid, adjust the pH value of solution, stir, when the pH of solution value is 7.0 ~ 7.5, be incubated 0 ~ 5 hour, start cooling;
(3), with 5 ℃ ~ 50 ℃/h cooling, when being down to room temperature, centrifugation obtains long carbochain semi-aromatic nylon salt.
2. according to the preparation method of the long carbochain semi-aromatic nylon salt described in claim 1, it is characterized in that, aromatic acid described in step (1) is terephthalic acid, m-phthalic acid, 2-methyl terephthalic acid, Isosorbide-5-Nitrae-naphthalic acid, NDA, 4,4 '-biphenyl dicarboxylic acid, 2,2 '-biphenyl dicarboxylic acid, 4,4 '-dicarboxyl sulfobenzide, 4, one or more in 4 '-dicarboxylate biphenyl ether; Described long carbochain aliphatic dibasic acid is one or more in straight chain aliphatic dibasic acid or the side chain aliphatic dibasic acid that contains 10 ~ 18 carbon atoms in molecular backbone chain.
3. according to the preparation method of the long carbochain semi-aromatic nylon salt described in claim 1, it is characterized in that, aromatic diamine described in step (1) is Ursol D, mphenylenediamine, p dimethylamine, m-xylene diamine, 2-dimethyl-p-phenylenediamine, 4,4 '-benzidine ether, 4, one or more in 4'-diamino diphenyl sulfone; Described long carbochain aliphatic diamine is one or more in straight chain aliphatic diamine or the side chain aliphatic diamine that contains 10 ~ 18 carbon atoms in molecular backbone chain.
4. the preparation method of the long carbochain semi-aromatic nylon salt described in one of them according to claim 1-3, is characterized in that, step (1), (2) stir speed (S.S.) are 15 ~ 200r/min.
5. the preparation method of the long carbochain semi-aromatic nylon salt described in one of them according to claim 1-3, is characterized in that, the filtrate after centrifugation is joined in step (1) and recycled.
6. the preparation method of the long carbochain semi-aromatic nylon salt described in one of them according to claim 1-3, is characterized in that, the rare gas element described in step (2) is the one in carbonic acid gas, nitrogen, argon gas or helium.
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| CN105712888A (en) * | 2014-12-01 | 2016-06-29 | 中国石油化工股份有限公司 | Preparation method of long-chain nylon salt |
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