CN116003266A - Preparation method and application of long carbon chain nylon salt - Google Patents
Preparation method and application of long carbon chain nylon salt Download PDFInfo
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- CN116003266A CN116003266A CN202111233441.2A CN202111233441A CN116003266A CN 116003266 A CN116003266 A CN 116003266A CN 202111233441 A CN202111233441 A CN 202111233441A CN 116003266 A CN116003266 A CN 116003266A
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- 239000004677 Nylon Substances 0.000 title claims abstract description 68
- 229920001778 nylon Polymers 0.000 title claims abstract description 68
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 150000003839 salts Chemical class 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 60
- 239000003960 organic solvent Substances 0.000 claims abstract description 32
- 239000002253 acid Substances 0.000 claims abstract description 27
- 150000004985 diamines Chemical class 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000012266 salt solution Substances 0.000 claims abstract description 16
- -1 carbon chain diamine Chemical class 0.000 claims abstract description 13
- 150000002148 esters Chemical class 0.000 claims abstract description 9
- 238000004064 recycling Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 141
- 238000004090 dissolution Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- UUGLJVMIFJNVFH-UHFFFAOYSA-N Hexyl benzoate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1 UUGLJVMIFJNVFH-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 9
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 9
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 claims description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 2
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 claims description 2
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 claims description 2
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 22
- 239000002904 solvent Substances 0.000 abstract description 20
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- 230000002411 adverse Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 44
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 34
- 239000000463 material Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 10
- 150000007513 acids Chemical class 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 206010059866 Drug resistance Diseases 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- JMLPVHXESHXUSV-UHFFFAOYSA-N dodecane-1,1-diamine Chemical compound CCCCCCCCCCCC(N)N JMLPVHXESHXUSV-UHFFFAOYSA-N 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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Abstract
The invention discloses a preparation method and application of long carbon chain nylon salt, wherein the method comprises the steps of dissolving long carbon chain diamine in a first organic solvent to obtain diamine solution; dissolving long carbon chain dibasic acid in a second organic solvent to obtain a dibasic acid solution; and mixing the diamine solution with the dibasic acid solution for reaction to obtain a nylon salt solution, and separating to obtain long carbon chain nylon salt, wherein the first organic solvent and the second organic solvent are the same or different and are respectively and independently selected from ester organic solvents. The method of the invention avoids the adverse effect on nylon polymerization reaction caused by using ethanol as solvent, has mild condition, obviously improves the yield and bulk density of the obtained nylon salt, is more beneficial to recycling the solvent, can shorten the process flow and reduce the production cost.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation method and application of a long carbon chain nylon salt.
Background
The long carbon chain nylon salt is usually a salt obtained by neutralization reaction of diamine with methylene length of more than 10 carbons in chain segments and dibasic acid, and is a precursor of a polymerized long carbon chain nylon material. The methylene in the macromolecular chain is longer and the density of amide groups is low from the chain structure of the long carbon chain nylon resin. Therefore, compared with the conventional nylon 6 and nylon 66, the long carbon chain nylon has the characteristics of high toughness, softness, low water absorption, high dimensional stability and the like. Nylon 1212 is one of long carbon chain nylon, has the characteristics of low density, low water absorption, good dimensional stability, excellent drug resistance, corrosion resistance, wear resistance, fatigue resistance, good low-temperature impact resistance and the like, can be used in industries such as automobiles, electronic appliances, machinery, packaging, military industry and the like, such as coil frameworks, insulating layers of wires and cables, fuel oil pipelines, oil pressure system pipelines, conduits and the like, and has stronger competitiveness. Nylon 1212 is synthesized from dodecanedioic acid obtained by microbial fermentation of petroleum light wax.
The nylon salt is used as a precursor for nylon polymerization, so that the equimolar ratio of diamine to diacid can be controlled, and the process of polymerization reaction can be controlled and the repeatability can be improved. At present, two main methods for preparing nylon 1212 salts exist. The alcohol solvent crystallization process includes dissolving dodecyl diamine and dodecyl diacid in alcohol solvent at certain temperature, dropping diamine solution into diamine solution in certain molar ratio, neutralizing to separate out solid, filtering and drying to obtain nylon salt powder. Under the condition, dibasic acid and ethanol can generate acid ester, which can have adverse effect on nylon polymerization reaction, and recovery of ethanol needs rectification, so that energy consumption and cost are increased. The other is water as solvent, but the solubility of the dodecadiamine and the dodecadiacid in water is extremely small at normal temperature and normal pressure, so the method needs to be carried out at high temperature and high pressure, and a large amount of energy is consumed, and side reactions possibly occur at high temperature and high pressure to influence the subsequent nylon polymerization reaction.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a novel preparation method of long carbon chain nylon salt, which uses an ester organic solvent as a solvent, and long carbon chain diamine and long carbon chain diacid undergo a neutralization reaction to generate nylon salt.
The first aspect of the invention provides a method for preparing long carbon chain nylon salt, which comprises the following steps:
(1) Dissolving diamine in a first organic solvent to obtain a diamine solution;
(2) Dissolving dibasic acid in a second organic solvent to obtain a dibasic acid solution;
(3) Mixing the diamine solution and the diacid solution to react to obtain a nylon salt solution, and separating to obtain the long carbon chain nylon salt;
wherein the diamine is at least one of aliphatic diamine with the carbon number of more than or equal to 8 between two carbon atoms with amino groups connected on a main carbon chain, and/or the dibasic acid is at least one of aliphatic dibasic acid with the carbon number of more than or equal to 8 between two carbon atoms with carboxyl groups connected on the main carbon chain;
the first organic solvent and the second organic solvent are the same or different and are independently selected from ester organic solvents.
According to some embodiments of the invention, the diamine is at least one aliphatic diamine having 10-20 carbon atoms between two carbon atoms with an amino group attached to the main carbon chain.
According to some embodiments of the invention, the diamine is at least one aliphatic diamine with 10-16 carbon atoms between two carbon atoms with amino groups attached to the main carbon chain.
According to some embodiments of the invention, the diamine is dodecadiamine.
According to some embodiments of the invention, the dibasic acid is at least one of aliphatic dibasic acids having 8-18 carbon atoms between two carbon atoms with a carboxyl group attached to the main carbon chain.
According to some embodiments of the invention, the dibasic acid is at least one of aliphatic dibasic acids having 8-14 carbon atoms between two carbon atoms with a carboxyl group attached to the main carbon chain.
According to some embodiments of the invention, the diacid is dodecadiacid.
According to some embodiments of the invention, the diamine is selected from C 10 -C 22 At least one of the aliphatic diamines, preferably selected from C 12 -C 18 At least one of aliphatic diamines.
According to some embodiments of the invention, the diacid is selected from C 12 -C 22 At least one of the aliphatic dibasic acids, preferably selected from C 12 -C 18 At least one of aliphatic dibasic acids.
According to some embodiments of the invention, the first organic solvent and the second organic solvent are the same or different and are each independently selected from at least one of an aliphatic ester organic solvent or an aromatic ester organic solvent.
According to some embodiments of the invention, the ester solvent comprises a general formula
At least one of the compounds shown is a compound,
wherein R is 1 And R is 2 Identical or different, each independently selected from C 1 -C 10 Preferably C 1 -C 10 Alkyl, C of (2) 6 -C 15 Aryl, C of (2) 7 -C 15 Aralkyl or C of (C) 7 -C 15 More preferably C 1 -C 6 Alkyl, C of (2) 6 -C 10 Aryl, C of (2) 7 -C 10 Aralkyl or C of (C) 7 -C 10 Alkylaryl groups of (a). According to some embodiments of the invention, R 1 Selected from C 1 -C 3 Alkyl and C of (C) 6 -C 10 Aryl radicals R of (2) 2 Selected from C 1 -C 6 Is a hydrocarbon group.
According to some embodiments of the invention, R 1 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, phenyl, and the like.
According to some embodiments of the invention, R 2 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl and the like.
According to some embodiments of the invention, the ester solvent is selected from at least one of ethyl acetate, butyl acetate, methyl acetate, isobutyl acetate, ethyl formate and hexyl benzoate, preferably ethyl acetate.
According to some embodiments of the invention, the diamine in step (1) and the diacid in step (2) are used in a molar ratio of (1.01:1) - (1.10:1). In some embodiments, the diamine in step (1) and the diacid in step (2) are used in a molar ratio of (1.01:1) - (1.05:1)
According to some embodiments of the invention, in step (1), the diamine is used in an amount of (1:2) - (1:5) by mass ratio to the first organic solvent.
According to some embodiments of the invention, in step (2), the amount of the dibasic acid and the second organic solvent is in a mass ratio of (1:5) - (1:8).
According to some embodiments of the invention, the temperature of the dissolution in step (1) is 60-90 ℃, preferably 65-80 ℃, such as 65 ℃, 70 ℃, 75 ℃,80 ℃ and any value in between.
According to some embodiments of the invention, the temperature of the dissolution in step (2) is 60-90 ℃, preferably 65-80 ℃, such as 65 ℃, 70 ℃, 75 ℃,80 ℃ and any value in between.
According to some embodiments of the invention, the temperature of the mixing reaction in step (3) is 60-90 ℃, preferably 65-80 ℃, such as 65 ℃, 70 ℃, 75 ℃,80 ℃ and any value in between.
According to some embodiments of the invention, the time of the mixing reaction in step (3) is 2-6h, preferably 3-5h, e.g. 3h, 3.5h, 4h, 4.5h, 5h and any value in between.
According to some embodiments of the present invention, the separating in the step (3) includes cooling the nylon salt solution, adding water to separate the nylon salt solution into an upper layer and a lower layer, filtering the separated lower layer liquid, and drying to obtain the long carbon chain nylon salt.
According to some embodiments of the invention, the cooling cools the nylon salt solution to 15-30 ℃.
According to some embodiments of the invention, the volume of added water is 0.8-2 times, e.g., 0.8 times, 1 times, 1.5 times, 2 times, and any value in between, the volume of the nylon salt solution.
According to the invention, water is added into the cooled nylon salt solution, and the ester solvent and the water are not mutually soluble, so that the nylon salt solution is divided into an upper layer and a lower layer, wherein the lower layer is nylon salt and water, and the upper layer is the ester solvent. The ester solvent of the upper layer can be recycled. The invention utilizes the immiscibility of the two solvents to prepare the long carbon chain nylon salt, and better solves the problems of solvent recovery, high energy consumption and the like in the prior art.
In a second aspect the invention provides the use of a method according to the first aspect of the invention for the preparation of nylon 1212.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention uses the ester organic solvent as the solvent, the long carbon chain diamine and the long carbon chain diacid are subjected to neutralization reaction to generate the nylon salt, thereby avoiding the adverse effect on the nylon polymerization reaction caused by using ethanol as the solvent in the prior art, and the conditions are mild, and the yield and bulk density of the obtained nylon salt are obviously improved.
(2) The ester solvent and water used in the invention are not mutually soluble, which is beneficial to recovery, and can shorten the process flow and reduce the production cost.
Drawings
FIG. 1 is a schematic diagram of a process for preparing a long carbon chain nylon salt of the present invention.
Detailed Description
In order that the invention may be more readily understood, a detailed description of the invention will be presented below in conjunction with examples, it being emphasized that the following description is exemplary only and should not be taken as limiting the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used are conventional products which are commercially available or which are obtainable using conventional or published methods, without the manufacturer's knowledge.
FIG. 1 is a schematic diagram of a method for preparing a long carbon chain nylon salt according to an embodiment of the present invention, wherein diamine is first dissolved in a first organic solvent to obtain a diamine solution; dissolving dibasic acid in a second organic solvent to obtain a dibasic acid solution; and mixing the diamine solution and the diacid solution to react to obtain the nylon salt solution. And then cooling the obtained nylon salt solution, adding water to divide the nylon salt solution into an upper layer and a lower layer, wherein the lower layer is nylon salt and water, the upper layer is an ester solvent, removing the upper layer of the ester solvent (recyclable), and filtering and drying the separated lower layer of liquid to obtain the long carbon chain nylon salt.
Example 1
(1) 101.1g of dodecyl diamine (1, 12-diamino dodecane) and 200g of ethyl acetate are added into a three-neck flask together, heated to 70 ℃, and stirred for full dissolution;
(2) 115.1g of dodecadiacid (1, 10-sebacic acid) and 600g of ethyl acetate are added into a three-neck flask together, heated to 70 ℃, and stirred for full dissolution;
(3) The obtained hot solution of the twelve-carbon diamine in ethyl acetate is dripped into the hot solution of the twelve-carbon diacid in ethyl acetate, the reaction is carried out while stirring, the reaction temperature is kept at 70 ℃, the reaction is continued for 3.0 hours after the material is added, the cooling is carried out, when the temperature is reduced to 25 ℃, deionized water with the same volume ratio as the solvent is added, the upper clarified ethyl acetate is recycled after layering, the lower mixed solution is filtered by suction to obtain white nylon salt, and after the drying is carried out in a vacuum oven at 80 ℃, the bulk density and the yield are tested, and the result is shown in a table 1.
Example 2
(1) 105.2g of dodecyl diamine (1, 12-diamino dodecane) and 200g of ethyl acetate are added into a three-neck flask together, heated to 70 ℃, and stirred for full dissolution to obtain an ethyl acetate hot solution of the dodecyl diamine;
(2) 115.1g of dodecanedioic acid (1, 10-sebacic acid) and 600g of ethyl acetate are added into a three-neck flask together, heated to 70 ℃, and stirred for full dissolution to obtain an ethyl acetate hot solution of the dodecanedioic acid;
(3) Dripping the obtained hot solution of the twelve-carbon diamine in the hot solution of the twelve-carbon diacid in ethyl acetate, reacting while stirring, keeping the reaction temperature at 70 ℃, continuing to react for 3.0 hours after finishing adding materials, cooling, adding deionized water with the same volume ratio as the solvent when the temperature is reduced to 25 ℃, recycling the upper clarified ethyl acetate after layering, filtering the lower mixed solution to obtain white nylon salt, drying in a vacuum oven at 80 ℃, and testing the bulk density and the yield after completely drying, wherein the result is shown in a table 1.
Example 3
(1) 111.2g of dodecyl diamine (1, 12-diamino dodecane) and 200g of ethyl acetate are added into a three-neck flask together, heated to 70 ℃, and stirred for full dissolution to obtain an ethyl acetate hot solution of the dodecyl diamine;
(2) 115.1g of dodecanedioic acid (1, 10-sebacic acid) and 600g of ethyl acetate are added into a three-neck flask together, heated to 70 ℃, and stirred for full dissolution to obtain an ethyl acetate hot solution of the dodecanedioic acid;
(3) Dripping the obtained hot solution of the twelve-carbon diamine in the hot solution of the twelve-carbon diacid in ethyl acetate, reacting while stirring, keeping the reaction temperature at 70 ℃, continuing to react for 3.0 hours after finishing adding materials, cooling, adding deionized water with the same volume ratio as the solvent when the temperature is reduced to 25 ℃, recycling the upper clarified ethyl acetate after layering, filtering the lower mixed solution to obtain white nylon salt, drying in a vacuum oven at 80 ℃, and testing the bulk density and the yield after completely drying, wherein the result is shown in a table 1.
Example 4
(1) 105.2g of dodecyl diamine (1, 12-diamino dodecane) and 200g of ethyl acetate are added into a three-neck flask together, heated to 65 ℃, and stirred for full dissolution to obtain an ethyl acetate hot solution of the dodecyl diamine;
(2) 115.1g of dodecanedioic acid (1, 10-sebacic acid) and 600g of ethyl acetate are added into a three-neck flask together, heated to 65 ℃, and stirred for full dissolution to obtain an ethyl acetate hot solution of the dodecanedioic acid;
(3) Dropwise adding the hot solution of the dodecadiamine into the hot solution of the dodecadiacid, reacting while stirring, keeping the reaction temperature at 65 ℃, continuing to react for 3.0 hours after finishing adding materials, cooling, adding deionized water with the same volume ratio as the solvent when the temperature is reduced to 25 ℃, layering, recycling the upper clarified ethyl acetate, filtering the lower mixed solution to obtain white nylon salt, drying in a vacuum oven at 80 ℃, and testing the bulk density and the yield after completely drying, wherein the result is shown in a table 1.
Example 5
(1) 105.2g of dodecyl diamine (1, 12-diamino dodecane) and 200g of ethyl acetate are added into a three-neck flask together, heated to 80 ℃, and stirred for full dissolution to obtain an ethyl acetate hot solution of the dodecyl diamine;
(2) 115.1g of dodecanedioic acid (1, 10-sebacic acid) and 600g of ethyl acetate are added into a three-neck flask together, heated to 80 ℃, and stirred for full dissolution to obtain an ethyl acetate hot solution of the dodecanedioic acid;
(3) Dropwise adding the hot solution of the dodecadiamine into the hot solution of the dodecadiacid, reacting while stirring, keeping the reaction temperature at 80 ℃, continuing to react for 3.0 hours after finishing adding materials, cooling, adding deionized water with the same volume ratio as the solvent when the temperature is reduced to 25 ℃, layering, recycling the upper clarified ethyl acetate, filtering the lower mixed solution to obtain white nylon salt, drying in a vacuum oven at 80 ℃, and testing the bulk density and the yield after completely drying, wherein the result is shown in a table 1.
Example 6
(1) 105.2g of dodecyl diamine (1, 12-diamino dodecane) and 200g of ethyl acetate are added into a three-neck flask together, heated to 70 ℃, and stirred for full dissolution to obtain an ethyl acetate hot solution of the dodecyl diamine;
(2) 115.1g of dodecanedioic acid (1, 10-sebacic acid) and 600g of ethyl acetate are added into a three-neck flask together, heated to 70 ℃, and stirred for full dissolution to obtain an ethyl acetate hot solution of the dodecanedioic acid;
(3) Dropwise adding the hot solution of the dodecadiamine into the hot solution of the dodecadiacid, reacting while stirring, keeping the reaction temperature at 70 ℃, continuing to react for 5.0 hours after finishing adding materials, cooling, adding deionized water with the same volume ratio as the solvent when the temperature is reduced to 25 ℃, layering, recycling the upper clarified ethyl acetate, filtering the lower mixed solution to obtain white nylon salt, drying in a vacuum oven at 80 ℃, and testing the bulk density and the yield after completely drying, wherein the result is shown in a table 1.
Example 7
(1) 105.2g of dodecyl diamine (1, 12-diamino dodecane) and 200g of ethyl acetate are added into a three-neck flask together, heated to 70 ℃, and stirred for full dissolution to obtain an ethyl acetate hot solution of the dodecyl diamine;
(2) 115.1g of dodecanedioic acid (1, 10-sebacic acid) and 600g of ethyl acetate are added into a three-neck flask together, heated to 70 ℃, and stirred for full dissolution to obtain an ethyl acetate hot solution of the dodecanedioic acid;
(3) Dropwise adding the hot solution of dodecanediamine in the hot solution of dodecanedioic acid in ethyl acetate, stirring and reacting, keeping the reaction temperature at 70 ℃, continuing to react for 3.0 hours after the materials are added, cooling, adding deionized water twice as much as the solvent when the temperature is reduced to 25 ℃, layering, recycling the upper clarified ethyl acetate, filtering the lower mixed solution to obtain white nylon salt, drying in a vacuum oven at 80 ℃, and testing the bulk density and yield after the complete drying, wherein the result is shown in table 1.
Example 8
(1) 105.2g of dodecyl diamine (1, 12-diamino dodecane) and 200g of ethyl acetate are added into a three-neck flask together, heated to 70 ℃, and stirred for full dissolution to obtain an ethyl acetate hot solution of the dodecyl diamine;
(2) 115.1g of dodecanedioic acid (1, 10-sebacic acid) and 800g of ethyl acetate are added into a three-neck flask together, heated to 70 ℃, and stirred for full dissolution to obtain an ethyl acetate hot solution of the dodecanedioic acid;
(3) Dropwise adding the hot solution of the dodecadiamine into the hot solution of the dodecadiacid, reacting while stirring, keeping the reaction temperature at 70 ℃, continuing to react for 3.0 hours after finishing adding materials, cooling, adding deionized water with the same volume as a solvent when the temperature is reduced to 25 ℃, layering, recycling the upper clarified ethyl acetate, filtering the lower mixed solution to obtain white nylon salt, drying in a vacuum oven at 80 ℃, and testing the bulk density and yield after completely drying, wherein the result is shown in a table 1.
Example 9
(1) 105.2g of dodecyl diamine (1, 12-diamino dodecane) and 200g of butyl acetate are added into a three-neck flask together, heated to 70 ℃, and stirred for full dissolution to obtain butyl acetate hot solution of the dodecyl diamine;
(2) 115.1g of dodecanedioic acid (1, 10-sebacic acid) and 600g of butyl acetate are added into a three-neck flask together, heated to 70 ℃, and stirred for full dissolution to obtain a butyl acetate hot solution of the dodecanedioic acid;
(3) The obtained hot butyl acetate solution of the dodecadiamine is dropwise added into the hot butyl acetate solution of the dodecadiacid, the reaction is carried out while stirring, the reaction temperature is kept at 70 ℃, the reaction is continued for 3.0 hours after the addition of materials is completed, the cooling is carried out, when the temperature is reduced to 25 ℃, deionized water with the same volume as the solvent is added, the upper clarified butyl acetate is recycled after layering, the lower mixed solution is subjected to suction filtration to obtain white nylon salt, and after the drying in a vacuum oven at 80 ℃, the bulk density and the yield are tested, and the result is shown in a table 1.
Example 10
(1) 105.2g of dodecyl diamine (1, 12-diaminododecane) and 500g of hexyl benzoate are added into a three-neck flask together, heated to 80 ℃, and stirred for full dissolution to obtain a hexyl benzoate hot solution of the dodecyl diamine;
(2) 115.1g of dodecanedioic acid (1, 10-sebacic acid) and 800g of hexyl benzoate are added into a three-neck flask together, heated to 80 ℃, and stirred for full dissolution to obtain a hot solution of hexyl benzoate of the dodecanedioic acid;
(3) The obtained hot solution of dodecyl diamine in hexyl benzoate is dripped into the hot solution of dodecyl diacid in hexyl benzoate, the reaction is carried out while stirring, the reaction temperature is kept at 80 ℃, the reaction is continued for 3.0 hours after the material addition is finished, the cooling is carried out, when the temperature is reduced to 25 ℃, deionized water twice as much as the solvent is added, the upper clear ethyl acetate is recycled after layering, the lower mixed solution is subjected to suction filtration to obtain white nylon salt, the mixture is dried in a vacuum oven at 100 ℃, and the bulk density and the yield are tested after the mixture is completely dried, and the result is shown in a table 1.
Comparative example 1
(1) 105.2g of dodecyl diamine (1, 12-diamino dodecane) and 200g of ethanol are added into a three-neck flask, heated to 70 ℃, and stirred for full dissolution to obtain ethanol hot solution of the dodecyl diamine;
(2) 115.1g of dodecanedioic acid (1, 10-sebacic acid) and 600g of ethanol are added into a three-neck flask together, heated to 70 ℃, and stirred for full dissolution to obtain an ethanol hot solution of the dodecanedioic acid;
(3) The hot ethanol solution of the dodecadiamine is dropwise added into the hot ethanol solution of the dodecadiacid, the reaction is carried out while stirring, the reaction temperature is kept at 70 ℃, the reaction is continued for 3.0 hours after the material is added, the temperature is cooled down to 25 ℃, white nylon salt is obtained after suction filtration, the nylon salt is dried in a vacuum oven at 80 ℃, and the bulk density and the yield are tested after the nylon salt is completely dried, so that the results are shown in the following table 1.
TABLE 1
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (10)
1. A method for preparing long carbon chain nylon salt, which comprises the following steps:
(1) Dissolving diamine in a first organic solvent to obtain a diamine solution;
(2) Dissolving dibasic acid in a second organic solvent to obtain a dibasic acid solution;
(3) Mixing the diamine solution and the diacid solution to react to obtain a nylon salt solution, and separating to obtain the long carbon chain nylon salt;
wherein the diamine is at least one of aliphatic diamine with the carbon number of more than or equal to 8 between two carbon atoms with amino groups connected on a main carbon chain, and/or the dibasic acid is at least one of aliphatic dibasic acid with the carbon number of more than or equal to 8 between two carbon atoms with carboxyl groups connected on the main carbon chain;
the first organic solvent and the second organic solvent are the same or different and are each independently selected from ester organic solvents.
2. The preparation method according to claim 1, wherein the diamine is at least one of aliphatic diamines having 10 to 20 carbon atoms between two carbon atoms having an amino group attached to a main carbon chain, preferably at least one of aliphatic diamines having 10 to 16 carbon atoms between two carbon atoms having an amino group attached to a main carbon chain;
and/or the dibasic acid is at least one of aliphatic dibasic acid with 8-18 carbon atoms between two carbon atoms with carboxyl groups on the main carbon chain, preferably at least one of aliphatic dibasic acid with 8-14 carbon atoms between two carbon atoms with carboxyl groups on the main carbon chain.
3. The method according to claim 1 or 2, wherein the ester-based organic solvent comprises at least one of an aliphatic ester-based organic solvent and an aromatic ester-based organic solvent,
preferably, the ester organic solvent comprises the general formula
At least one of the compounds shown is a compound,
wherein R is 1 And R is 2 Identical or different, each independently selected from C 1 -C 10 Preferably C 1 -C 10 Alkyl, C of (2) 6 -C 15 Aryl, C of (2) 7 -C 15 Aralkyl or C of (C) 7 -C 15 More preferably C 1 -C 6 Alkyl, C of (2) 6 -C 10 Aryl, C of (2) 7 -C 10 Aralkyl or C of (C) 7 -C 10 Alkylaryl groups of (a);
more preferably, the ester-based organic solvent is at least one selected from the group consisting of ethyl acetate, butyl acetate, methyl acetate, isobutyl acetate, ethyl formate and hexyl benzoate.
4. A process according to any one of claims 1 to 3, wherein the diamine in step (1) and the diacid in step (2) are used in a molar ratio of (1.01:1) - (1.10:1).
5. The method according to any one of claims 1 to 4, wherein in the step (1), the diamine and the first organic solvent are used in an amount of (1:2) - (1:5) by mass ratio;
and/or the temperature of said dissolution in step (1) is 60-90 ℃, preferably 65-80 ℃.
6. The production method according to any one of claims 1 to 5, wherein in the step (2), the amount of the dibasic acid and the second organic solvent is used in terms of mass ratio (1:5) - (1:8);
and/or the temperature of said dissolution in step (2) is 60-90 ℃, preferably 65-80 ℃.
7. The preparation process according to any one of claims 1 to 6, wherein the temperature of the mixing reaction in step (3) is 60-90 ℃, preferably 65-80 ℃, and/or the time of the mixing reaction is 2-6h, preferably 3-5h.
8. The method according to any one of claims 1 to 7, wherein the separation in the step (3) comprises cooling the nylon salt solution, adding water to separate the nylon salt solution into an upper layer and a lower layer, separating the lower layer, filtering the lower layer liquid, and drying to obtain the long carbon chain nylon salt.
9. The method of claim 8, wherein the cooling cools the nylon salt solution to 15-30 ℃; and/or the volume of the added water is 0.8-2 times of the volume of the nylon salt solution;
preferably, the preparation method further comprises recycling the upper liquid obtained by separation, wherein the upper liquid comprises the ester solvent.
10. Use of the preparation method of any one of claims 1-9 in the preparation of nylon 1212.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586265A (en) * | 2018-04-13 | 2018-09-28 | 南京工业大学 | Pentanediamine sebacate and its crystal |
| CN109265353A (en) * | 2018-10-16 | 2019-01-25 | 南京工业大学 | Pentanediamine dodecanedioic acid salt and its crystal |
| CN109265355A (en) * | 2018-10-16 | 2019-01-25 | 南京工业大学 | Pentanediamine suberate and its crystal |
| CN112745222A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Synthetic method of nylon salt |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586265A (en) * | 2018-04-13 | 2018-09-28 | 南京工业大学 | Pentanediamine sebacate and its crystal |
| CN109265353A (en) * | 2018-10-16 | 2019-01-25 | 南京工业大学 | Pentanediamine dodecanedioic acid salt and its crystal |
| CN109265355A (en) * | 2018-10-16 | 2019-01-25 | 南京工业大学 | Pentanediamine suberate and its crystal |
| CN112745222A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Synthetic method of nylon salt |
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