CN115707728A - Preparation method of long carbon chain nylon and long carbon chain nylon - Google Patents
Preparation method of long carbon chain nylon and long carbon chain nylon Download PDFInfo
- Publication number
- CN115707728A CN115707728A CN202110957945.2A CN202110957945A CN115707728A CN 115707728 A CN115707728 A CN 115707728A CN 202110957945 A CN202110957945 A CN 202110957945A CN 115707728 A CN115707728 A CN 115707728A
- Authority
- CN
- China
- Prior art keywords
- nylon
- gas
- pressure
- antioxidant
- carbon chain
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Polyamides (AREA)
Abstract
The invention discloses a preparation method of long carbon chain nylon and the obtained long carbon chain nylon. The preparation method comprises the steps of mixing components including a nylon salt raw material, water, a catalyst, a molecular weight regulator and an antioxidant, and polymerizing to obtain the long-carbon-chain nylon; wherein the bulk density of the nylon salt raw material is 0.5-1.0 g/cm 3 . The polymerization process is stable and controllable, and the obtained long carbon chain nylon has good relative viscosity, strength and chroma.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a preparation method of long carbon chain nylon and the long carbon chain nylon.
Background
Long carbon chain nylons generally refer to nylons having a methylene length of 10 carbons or more in the chain segment and include nylon 11, nylon 12, nylon 1212, nylon 1012, nylon 1313, and the like. From the chain structure of the long carbon chain nylon resin, the methylene in a macromolecular chain is longer, and the density of an amido group is low, so the long carbon chain nylon has the characteristics that the conventional nylon 6 and the nylon 66 have high toughness and flexibility, low water absorption, high dimensional stability and the like, besides the common performances of common nylon such as lubricity, wear resistance, compression resistance and easy processability.
For example, nylon 1212 is a long carbon chain nylon having characteristics of low density, low water absorption, good dimensional stability, excellent drug resistance, corrosion resistance, wear resistance, fatigue resistance, and good low temperature impact resistance. The composite material is mainly used in the industries of automobiles, electrical appliances, machinery and the like, such as coil frameworks, insulating layers of wires and cables, fuel oil pipelines, oil pressure system pipelines, guide pipes and the like. The process for preparing the dodecanedioic acid generally comprises a butadiene process, a petroleum light wax fermentation process and a preparation process taking cyclohexanone as a raw material. China's petroleum is mostly paraffin-base petroleum, and some oil fields have wax content as high as 40%, and the wax must be removed during petroleum refining. Therefore, the raw materials are very abundant and relatively cheap.
Usually, the nylon 1212 is prepared by firstly neutralizing dodecanedioic acid and dodecanediamine into nylon 1212 salt and then polymerizing, and the problems of long time consumption, low yield, high energy consumption, unstable polymerization, easy oxidation of the nylon 1212 and the like exist in the whole polymerization process by adopting the existing patents.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides a preparation method of long carbon chain nylon, which adopts the bulk density of 0.5-1.0 g/cm 3 The nylon salt raw material can solve the problem that materials are easy to oxidize in the polymerization process, and the obtained product has better mechanical properties.
One of the purposes of the invention is to provide a preparation method of long carbon chain nylon, which comprises the steps of mixing components including a nylon salt raw material, water, a catalyst, a molecular weight regulator and an antioxidant, and polymerizing to obtain the long carbon chain nylon; wherein the bulk density of the nylon salt raw material is 0.5-1.0 g/cm 3 Preferably 0.6 to 0.9g/cm 3 。
The weight ratio of the nylon salt tablet to water is preferably 1 (0.05-0.5), more preferably 1 (0.15-0.35), and may be, for example, 1:0.05, 1:0.1, 1:0.15, 1:0.2, 1:0.25, 1:0.3, 1:0.35, 1:0.4, 1:0.45, 1:0.5, etc.
The catalyst is selected from at least one of phosphoric acid, phosphorous acid, hypophosphorous acid, sodium phosphite and sodium hypophosphite, and is more preferably selected from at least one of phosphorous acid and sodium hypophosphite; preferably, the weight ratio of the catalyst to the nylon salt is (0.05-0.5%): 1, more preferably (0.05-0.2%): 1.
The molecular weight regulator is selected from at least one of monoacid, diacid, monoamine and diamine, and is more preferably selected from at least one of lauric acid and dodecanedioic acid; preferably, the weight ratio of the molecular weight regulator to the nylon salt is (0.05-0.5%): 1, more preferably (0.05-0.2%): 1;
the antioxidant is at least one selected from bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, antioxidant 1790, antioxidant 3114, antioxidant 1098, hindered phenols, hindered aromatic amines, hydroquinones, antioxidant 1010, antioxidant 1222, antioxidant 168 and antioxidant 330; more preferably, the weight ratio of the antioxidant to the nylon salt is (0.05% -0.5%) to 1, and more preferably (0.05% -0.2%) to 1.
The polymerization can be carried out by a batch polymerization process or a solid phase polycondensation process, preferably under a protective atmosphere, such as from nitrogen and/or inert gas. More preferably, a batch polymerization method is employed.
Wherein, when the polymerization is carried out by the batch polymerization method, the polymerization is carried out as follows:
1) Mixing the components, and heating and boosting the pressure to react in a protective atmosphere;
2) Slowly deflating, namely maintaining the pressure in the system constant, and then decompressing to normal pressure;
3) Carrying out reaction under normal pressure;
4) And discharging after the reaction is finished, optionally cooling, and then pelletizing to obtain the long carbon chain nylon.
In step 1), the reaction proceeds as follows: reacting for 0.2-5.0 h at 180-240 ℃ under 1.2-2.2 MPa; preferably, the reaction is carried out for 0.5 to 4.0 hours at the temperature of between 200 and 220 ℃ and under the pressure of between 1.5 and 2.0 MPa;
in the step 2), slowly releasing gas, so that the pressure in the system is maintained at 1.2-2.5 MPa within 0.2-3.0 hours at the beginning, and then is reduced to normal pressure within 0.2-4.0 hours; preferably, the air is slowly released, so that the pressure in the system is maintained at 1.5-2.0 MPa within 0.5-2.0 hours at the beginning and is reduced to the normal pressure within 0.5-3.0 hours later;
in step 3), the reaction proceeds as follows: performing the reaction at 180-300 ℃ for 0.2-8.0 h; preferably, the reaction is carried out at 200-260 ℃ for 0.5-6.0 h.
Wherein, when the polymerization adopts a solid phase polycondensation method, the polymerization is carried out as follows:
1') mixing the components, and raising the temperature and the pressure in a protective atmosphere;
2') reacting while keeping the temperature and the pressure unchanged to obtain a prepolymer;
3') cooling to room temperature after the reaction is finished, taking out the prepolymer, and filtering and drying the prepolymer to obtain long-carbon-chain nylon oligomer powder;
4') granulating the long carbon chain nylon oligomer powder to obtain long carbon chain nylon oligomer particles;
5') carrying out solid-phase polymerization on the long carbon chain nylon oligomer particles to obtain the long carbon chain nylon.
In the step 1'), the temperature is raised to 150 to 250 ℃ within 0.5 to 1.5h, and the pressure is raised to 0.8 to 2MPa; preferably, the temperature is raised to 180-200 ℃ within 0.8-1.2 h, and the pressure is raised to 1.0-1.5 MPa;
in the step 2'), the temperature and the pressure are kept unchanged for reaction for 0.2 to 8.0 hours; preferably, the temperature and the pressure are kept unchanged for reaction for 0.5 to 6.0 hours;
wherein, in step 1 ') and step 2'), hydrothermal polymerization is carried out;
in step 5'), the solid-phase polymerization is carried out as follows: solid-phase tackifying the long carbon chain nylon oligomer particles for 2-20 h at 120-200 ℃ under the vacuum or inert gas purging condition of 0-10 Pa; preferably, the long carbon chain nylon oligomer particles are subjected to solid phase tackifying for 5 to 15 hours at the temperature of between 150 and 175 ℃ under the vacuum condition of between 0 and 5Pa or under the inert gas purging condition.
In the preparation method of the invention, the nylon salt raw material is preferably prepared by the following steps:
a) Preparing nylon salt powder by adopting dibasic acid and diamine;
b) And granulating the nylon salt powder, and pressing into tablets to obtain the nylon salt raw material.
In the step a) of the present invention,
the diamine is preferably selected from C 10 The above diamines are more preferably selected from C 10 ～C 20 Diamines such as laurylamine;
the dibasic acid is preferably selected from C 10 The above dibasic acids are more preferably selected from C 10 ～C 20 Dibasic acids such as dodecanedioic acid;
the molar ratio of the dibasic acid to the diamine is preferably 1 (1-1.05), and more preferably 1 (1-1.01).
Preferably, the step a) may comprise the sub-steps of:
a-1) mixing dibasic acid with a solvent A, and heating to obtain a solution A;
a-2) mixing diamine and a solvent B, and heating to obtain a solution B;
a-3) adding the solution B into the solution A for reaction;
a-4) cooling after the reaction is finished, filtering and drying to obtain nylon salt powder.
Wherein, the first and the second end of the pipe are connected with each other,
in the step a-1), the solvent A is selected from at least one of ethanol, methanol and propanol; the weight ratio of the dibasic acid to the solvent A is 1 (2-10), preferably 1 (3-7); heating to 50-95 deg.c for 10-50 min, preferably 60-75 deg.c for 20-40 min.
In the step a-2), the solvent B is selected from at least one of ethanol, methanol and propanol; the weight ratio of the diamine to the solvent B is 1 (1-6), preferably 1 (1-3); heating to 40-90 deg.c for 10-50 min, preferably 50-70 deg.c for 20-40 min.
In the step a-3), the reaction is carried out at 50-100 ℃ for 0.2-4 h, preferably at 70-80 ℃ for 0.5-2 h.
In the step a-4), the temperature is cooled to below 40 ℃, preferably below 30 ℃.
Preferably, the step b) may comprise the sub-steps of:
b-1) granulating the nylon salt powder to prepare particles with the particle size of 0.5-2.0 mm, preferably 0.8-1.5 mm;
b-2) tabletting the granules into tablets with the diameter of 5.0-20.0 mm and the thickness of 1.0-5.0 mm, preferably into tablets with the diameter of 5.0-10.0 mm and the thickness of 1.0-3.0 mm.
In the step b-1), the granulation comprises wet granulation or dry granulation; wherein the content of the first and second substances,
the wet granulation preferably comprises: uniformly mixing 100 parts of nylon salt powder and 10-30 parts of water, granulating to obtain wet granules, and drying to obtain dry granules;
the dry granulation preferably comprises: mixing 100 parts of nylon salt powder with 50-200 parts of pure water, drying to obtain a monolithic solid, or pressing the nylon salt powder into a sheet, and then granulating the monolithic solid or the sheet to obtain dry particles.
The density of the nylon salt raw material obtained by the steps is 0.8-1.2 g/cm 3 (ii) a The bulk density of the nylon salt raw material can reach 0.5 to 1.0g/cm 3 。
The second purpose of the invention is to provide the long carbon chain nylon obtained by the preparation method.
The preparation method can obtain long carbon chain nylon such as nylon 11, nylon 12, nylon 1212, nylon 1012, nylon 1313 and the like.
Compared with nylon salt powder raw materials, the bulk density of the nylon salt raw materials is improved by 4-5 times, and the problems of unstable polymerization process, easy material oxidation and the like in the prior art are well solved. Meanwhile, the filling amount of the nylon salt can be increased, the filling amount of water is reduced, the yield is increased by 2-4 times, the energy consumption in the reaction process is reduced to 1/10-1/5 of the original energy consumption, and the obtained product has better mechanical properties.
Compared with the prior art, the invention has the following beneficial effects:
(1) By adopting the method, the yield can be improved, the energy consumption can be reduced, and the problems of low yield, high energy consumption and the like in the prior art are well solved;
(2) By adopting the scheme of the invention, the polymerization process is stable and controllable, and the obtained long carbon chain nylon has good relative viscosity, strength and chroma, and obtains better technical effect.
The invention is further illustrated by the following examples.
Detailed Description
While the present invention will be described in conjunction with specific embodiments thereof, it is to be understood that the following embodiments are presented by way of illustration only and not by way of limitation, and that numerous insubstantial modifications and adaptations of the invention may be made by those skilled in the art in light of the teachings herein.
The starting materials used in the examples and comparative examples are, if not particularly limited, those disclosed in the prior art, and may be, for example, obtained as they are or prepared according to the production methods disclosed in the prior art.
According to a preferred embodiment of the present invention, for preparing nylon 1212 by using dodecanediamine and dodecanedioic acid, the preparation method may comprise the following steps:
(i) Neutralizing the dodecanediamine and the dodecanedioic acid to prepare nylon 1212 salt;
(ii) Nylon 1212 salt powder is made into granules with good fluidity and particle diameter of 0.5-2.0 mm by a granulator;
(iii) Pressing the granules into tablets with the diameter of 5.0-20.0 mm and the thickness of 1.0-5.0 mm by a tablet press;
(iv) Adding the raw material tablets, water, a catalyst, a molecular weight regulator and an antioxidant into a polymerization kettle, heating, carrying out high-pressure prepolymerization reaction, reducing the pressure to normal pressure, and carrying out final polycondensation reaction to obtain the long-carbon-chain nylon.
In the above embodiment, the specific process for neutralizing and salifying in step (i) is as follows: (1) Adding dodecanedioic acid and 2-10 times of ethanol into a neutralization kettle, heating to 50-95 ℃ for dissolving, and keeping for 10-50 minutes; (2) Adding 1-6 times of ethanol and dodecadiamine (the molar ratio of the dibasic acid to the diamine is 1 (1-1.05)) into a dissolving kettle, heating to 40-90 ℃ for dissolving, and keeping for 10-50 minutes; (3) Pumping all the dodecanediamine ethanol solution into a neutralization kettle by a pump, reacting while stirring, controlling the reaction temperature at 50-100 ℃, continuing to react for 0.2-4 hours after the materials are added, cooling the neutralization kettle to reduce the temperature to below 40 ℃, filtering the neutralized solution by a filter, and drying by a drying oven to obtain the nylon 1212 salt.
In the above embodiment, the specific process of granulating in step (ii) is wet granulation: (1) Uniformly mixing 100 parts of nylon 1212 salt powder and 10-30 parts of pure water; (2) preparing wet granules with the grain diameter of 0.5-2.0 mm by a granulator; (3) Dried by a vacuum oven to obtain dry particles with particle size of 0.5-2.0 mm and better fluidity.
In the above embodiment, the specific process of granulating in the step (ii) may be dry granulation: (1) Uniformly mixing 100 parts of nylon 1212 salt powder and 50-200 parts of pure water, and drying by a vacuum oven to obtain a whole dry solid; (2) The nylon 1212 salt powder can also be pressed flat into thin slices by a press or a roller; (3) And (3) making the monolithic solid or the flake into dry granules with the particle size of 0.5-2.0 mm and better fluidity by a granulator.
In the above embodiment, the tablet compressed in the step (iii) has a diameter of 5.0 to 20.0mm, a thickness of 1.0 to 5.0mm, and a density of 0.8 to 1.2g/cm 3 The bulk density is 0.5-1.0 g/cm 3 。
In the above embodiment, the weight ratio of the nylon salt raw material to the water in the step (iv) is 1 (0.05 to 0.5).
In the above embodiment, in the step (iv), the catalyst is selected from at least one of phosphoric acid, phosphorous acid, hypophosphorous acid, sodium phosphite, and sodium hypophosphite; preferably, the weight ratio of the catalyst to the nylon salt is (0.05-0.5%) 1.
In the above embodiment, in step (iv), the feedstock further comprises an antioxidant; preferably, the antioxidant is at least one selected from bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, antioxidant 1790, antioxidant 3114, antioxidant 1098, hindered phenols, hindered aromatic amines, hydroquinones, antioxidant 1010, antioxidant 1222, antioxidant 168 and antioxidant 330; more preferably, the weight ratio of the antioxidant to the nylon salt is (0.05-0.5%) 1.
In the above embodiment, the molecular weight modifier is at least one selected from the group consisting of a monobasic acid, a dibasic acid, a diamine, and a monoamine; preferably, the weight ratio of the molecular weight regulator to the nylon salt is (0.05-0.5%) 1.
In the above embodiment, the specific process for polymerizing the nylon 1212 in step (iv) is: (1) Mixing nylon 1212 salt, water, catalyst, molecular weight regulator and antioxidant according to the proportion of 1 (0.05-0.5) to (0.05-0.5) and adding the mixture into a polymerization kettle, vacuumizing and replacing air in the kettle with nitrogen; (2) Heating to raise the temperature, raising the temperature in the kettle to 180-240 ℃, raising the pressure in the kettle to 1.2-2.2 MPa, and keeping the temperature and the pressure to react for 0.2-5.0 hours; (3) Slowly deflating to maintain the pressure in the kettle at 1.2-2.5 MPa within 0.2-3.0 hours, and then reducing the pressure in the kettle to normal pressure within 0.2-4.0 hours; (4) Keeping the reaction temperature of 180-300 ℃ under normal pressure, reacting for 0.2-8.0 hours, stopping stirring, opening a discharge valve, filling nitrogen, discharging the material through a tape injection head, cooling and granulating to obtain the nylon 1212 product.
The method for testing the bulk density of the nylon salt raw material comprises the following steps:
a measuring cylinder with the volume of 1L is selected in a laboratory, one part of a nylon salt sample (nylon salt powder or nylon salt tablets) is weighed, the nylon salt sample is poured slowly from a position 50mm above the center of the measuring cylinder by a funnel or a material spoon, the sample falls in a free-falling body, and when the sample on the upper part of the measuring cylinder is in a cone shape and the periphery of the measuring cylinder is full, the feeding is stopped. And then, strickling off the two sides along the central line of the opening of the cylinder by using a ruler (the volumetric cylinder is not touched in the test process), weighing the total mass of the test sample and the volumetric cylinder, and calculating the bulk density.
[ example 1 ]
Nylon salifying: (1) Adding 900.5g of dodecanedioic acid and 4500g of ethanol into a neutralization kettle, heating to 75 ℃ for dissolving, and keeping for 30 minutes; (2) Adding 783.5g of dodecadiamine and 1000 g of ethanol into a dissolving kettle, heating to 60 ℃ for dissolving, and keeping for 30 minutes; (3) Pumping all the dodecanediamine ethanol solution into a neutralization kettle by a pump, reacting while stirring, controlling the reaction temperature at 78 ℃, continuing to react for 1.0 hour after the materials are added, cooling the neutralization kettle to reduce the temperature to below 30 ℃, filtering the neutralization solution by a filter, and drying in a drying oven to obtain nylon 1212 salt;
granulating nylon salt: (1) Uniformly mixing 100 parts of nylon 1212 salt powder and 100 parts of pure water, and drying by a vacuum oven to obtain a whole dry solid; (2) Dry granules with good fluidity and the particle size of about 1.0mm are prepared by a granulator; and (3) carrying out nylon salt tabletting: pressing the granules into tablets with diameter of 10.0mm and thickness of 2.0mm by tablet press, and density of 1.0g/cm 3 Bulk density of 0.64g/cm 3 ；
Polymerization of nylon 1212: (1) 1200g of nylon 1212 salt, 300g of water, a catalyst, a molecular weight regulator, an antioxidant and the like are uniformly mixed and then added into a 2.0L high-temperature high-pressure polymerization kettle, wherein the catalyst is selected from sodium hypophosphite, the molecular weight regulator is selected from lauric acid, and the antioxidant is selected from antioxidant 1010, and the adding amount of the catalyst is 0.1wt%; (2) Heating for 1.0h, raising the temperature to 210 ℃, raising the pressure in the kettle to 1.8MPa, and keeping the temperature and the pressure for reaction for 2.0 h; (3) Slowly releasing the gas, so that the pressure in the kettle is maintained at 1.8MPa within 1.0 hour at the beginning, and the pressure in the kettle is reduced to the normal pressure within 1.0 hour thereafter; (4) And (3) keeping the reaction temperature of 240 ℃ under normal pressure, reacting for 2.0 hours, stopping stirring, opening a discharge valve, introducing nitrogen, discharging the material through a tape injection head, cooling, and granulating to obtain the nylon 1212 product.
[ example 2 ]
The nylon salt formation procedure was as in example 1.
Granulating nylon salt: (1) Uniformly mixing 100 parts of nylon 1212 salt powder and 20 parts of pure water; (2) preparing wet granules with the grain diameter of 1.0mm by a granulator; (3) Drying by a vacuum oven to obtain dry particles with particle size of 1.0mm and good fluidity; the procedure for tabletting nylon salt was the same as in example 1, whereinThe density of the Longyan tablet is 1.0g/cm 3 Bulk density of 0.66g/cm 3 。
The procedure for polymerizing nylon 1212 was the same as in example 1.
[ example 3 ]
The nylon salt formation procedure was the same as in example 1.
Granulating nylon salt: (1) Uniformly mixing 100 parts of nylon 1212 salt powder and 100 parts of pure water, and drying by a vacuum oven to obtain a whole dry solid; (2) Preparing dry granules with good fluidity and with the grain diameter of about 0.5mm by a granulator; the procedure for tableting the nylon salt was the same as in example 1, wherein the density of the nylon salt tablet was 1.01g/cm 3 Bulk density of 0.65g/cm 3 。
The nylon 1212 polymerization procedure was the same as in example 1.
[ example 4 ] A method for producing a polycarbonate
The nylon salt formation procedure was as in example 1.
Granulating nylon salt: (1) Uniformly mixing 100 parts of nylon 1212 salt powder with 100 parts of pure water, and drying by using a vacuum oven to obtain a whole block of dry solid; (2) Dry granules with good fluidity and the particle size of about 2.0mm are prepared by a granulator;
the procedure for tableting the nylon salt was the same as in example 1, wherein the density of the nylon salt tablet was 0.98g/cm 3 Bulk density of 0.62g/cm 3 。
The procedure for polymerizing nylon 1212 was the same as in example 1.
[ example 5 ] A method for producing a polycarbonate
The nylon salt formation procedure was the same as in example 1.
The procedure for granulating nylon salt was the same as in example 1.
And (3) carrying out nylon salt tabletting: pressing the granules into tablets with diameter of 5mm and thickness of 1.0mm by tablet press, wherein the density of nylon salt tablet is 1.03g/cm 3 Bulk density of 0.72g/cm 3 。
The procedure for polymerizing nylon 1212 was the same as in example 1.
[ example 6 ]
The nylon salt formation procedure was the same as in example 1.
The procedure for granulating nylon salt was the same as in example 1.
NylonSalt tabletting: pressing the granules into tablets with diameter of 20mm and thickness of 2.0mm by tablet press, wherein the density of nylon salt tablet is 0.96g/cm 3 Bulk density of 0.60g/cm 3 。
The nylon 1212 polymerization procedure was the same as in example 1.
[ example 7 ]
The nylon salt formation procedure was the same as in example 1.
The procedure for granulating nylon salt was the same as in example 1.
The procedure for tabletting nylon salt was the same as in example 1.
Polymerization of nylon 1212: (1) 1200g of nylon 1212 salt, 60g of water, a catalyst, a molecular weight regulator, an antioxidant and the like are uniformly mixed and then added into a 2.0L high-temperature high-pressure polymerization kettle, wherein the catalyst is selected from sodium hypophosphite, the molecular weight regulator is selected from lauric acid, and the antioxidant is selected from antioxidant 1098, and the addition amount of the catalyst is 0.1wt%; (2) Heating for 1.0h, raising the temperature to 210 ℃, raising the pressure in the kettle to 1.8MPa, and keeping the temperature and the pressure for reaction for 2.0 h; (3) Slowly releasing the gas, so that the pressure in the kettle is maintained at 1.8MPa within 1.0 hour at the beginning, and the pressure in the kettle is reduced to the normal pressure within 1.0 hour thereafter; (4) And (3) keeping the reaction temperature at 240 ℃ under normal pressure, reacting for 2.0 hours, stopping stirring, opening a discharge valve, introducing nitrogen, discharging the material through a tape injection head, cooling, and granulating to obtain the nylon 1212 product.
[ example 8 ]
The nylon salt formation procedure was as in example 1.
The procedure for granulating nylon salt was the same as in example 1.
The procedure for tabletting nylon salt was the same as in example 1.
Polymerization of nylon 1212: (1) 1200g of nylon 1212 salt, 600g of water, a catalyst, a molecular weight regulator, an antioxidant and the like are uniformly mixed and then added into a 2.0L high-temperature high-pressure polymerization kettle, wherein the catalyst is selected from sodium hypophosphite, the molecular weight regulator is selected from lauric acid, and the antioxidant is selected from antioxidant 1098, and the addition amount of the catalyst is 0.1wt%; (2) Heating for 1.0h, raising the temperature to 210 ℃, raising the pressure in the kettle to 1.8MPa, and keeping the temperature and the pressure for reaction for 2.0 h; (3) Slowly deflating to ensure that the pressure in the kettle is maintained at 1.8MPa within 1.0 hour at the beginning and is reduced to the normal pressure within 1.0 hour thereafter; (4) And (3) keeping the reaction temperature at 240 ℃ under normal pressure, reacting for 2.0 hours, stopping stirring, opening a discharge valve, introducing nitrogen, discharging the material through a tape injection head, cooling, and granulating to obtain the nylon 1212 product.
[ example 9 ] A method for producing a polycarbonate
Nylon salifying: (1) Adding 900.5g of dodecanedioic acid and 2700g of methanol into a neutralization kettle, heating to 60 ℃ for dissolving, and keeping for 40 minutes; (2) Adding 791.3g of dodecadiamine and 791.3g of ethanol into a dissolving kettle, heating to 50 ℃ for dissolving, and keeping for 40 minutes; (3) Pumping all the dodecacarbon diamine ethanol solution into a neutralization kettle by a pump, reacting while stirring, controlling the reaction temperature at 70 ℃, continuing to react for 2.0 hours after the materials are added, cooling the neutralization kettle to reduce the temperature to below 35 ℃, filtering the neutralization solution by a filter, and drying in a drying oven to obtain nylon 1212 salt;
the procedure for granulating nylon salt was the same as in example 1.
The procedure for tableting the nylon salt was the same as in example 1, wherein the density of the nylon salt tablet was 1.0g/cm 3 Bulk density of 0.64g/cm 3 。
Polymerization of nylon 1212: (1) Uniformly mixing 1200g of nylon 1212 salt with 300g of water, a catalyst, a molecular weight regulator, an antioxidant and the like, and adding the mixture into a 2.0L high-temperature high-pressure polymerization kettle, wherein the catalyst is selected from phosphorous acid, the molecular weight regulator is selected from lauric acid, and the antioxidant is selected from antioxidant 1010, and the addition amount of the catalyst is 0.05wt%; (2) Heating for 1.0h to 180 ℃, increasing the pressure in the kettle to 1.2MPa, and keeping the temperature and the pressure to react for 5.0h; (3) Slowly releasing the gas, so that the pressure in the kettle is maintained at 1.2MPa within the first 2.0 hours, and the pressure in the kettle is reduced to the normal pressure within the next 0.5 hour; (4) And (3) keeping the reaction temperature of 200 ℃ under normal pressure, reacting for 8.0 hours, stopping stirring, opening a discharge valve, introducing nitrogen, discharging the material through a tape injection head, cooling, and granulating to obtain the nylon 1212 product.
[ example 10 ]
Nylon salifying: (1) Adding 900.5g of dodecanedioic acid and 6300g of propanol into a neutralization kettle, heating to 70 ℃ for dissolving, and keeping for 20 minutes; (2) 822.7g of dodecanediamine and 2374 g of ethanol are added into a dissolving kettle, heated to 70 ℃ for dissolving, and kept for 20 minutes; (3) Pumping all the dodecacarbon diamine ethanol solution into a neutralization kettle by a pump, reacting while stirring, controlling the reaction temperature at 80 ℃, continuing to react for 0.5 hour after adding materials, cooling the neutralization kettle to reduce the temperature to below 40 ℃, filtering the neutralization solution by a filter, and drying in a drying oven to obtain nylon 1212 salt;
the procedure for granulating nylon salt was the same as in example 1.
The procedure for tableting the nylon salt was the same as in example 1, wherein the density of the nylon salt tablet was 1.0g/cm 3 Bulk density of 0.64g/cm 3 。
Polymerization of nylon 1212: (1) 1200g of nylon 1212 salt, 300g of water, a catalyst, a molecular weight regulator, an antioxidant and the like are uniformly mixed and then added into a 2.0L high-temperature high-pressure polymerization kettle, wherein the catalyst is selected from sodium phosphite, the molecular weight regulator is selected from dodecanedioic acid, and the antioxidant is selected from the antioxidant 1098, and the addition amounts of the components are 0.2wt%; (2) Heating for 1.0h to 240 ℃, increasing the pressure in the kettle to 2.2MPa, and keeping the temperature and the pressure to react for 1.0 h; (3) Slowly deflating to ensure that the pressure in the kettle is maintained at 2.2MPa within 0.5 hour at the beginning and is reduced to the normal pressure within 3.0 hours thereafter; (4) And (3) keeping the reaction temperature of 300 ℃ under normal pressure, reacting for 1.0 hour, stopping stirring, opening a discharge valve, introducing nitrogen, discharging the material through a tape injection head, cooling and granulating to obtain the nylon 1212 product.
[ COMPARATIVE EXAMPLE 1 ]
The nylon salt formation procedure was as in example 1, with the bulk density of the nylon salt powder being 0.22g/cm 3 。
Polymerization of nylon 1212: (1) Directly mixing 400g of nylon 1212 salt powder with 400g of water, a catalyst, a molecular weight regulator, an antioxidant and the like uniformly, and then adding the mixture into a 2.0L high-temperature high-pressure polymerization kettle, wherein the catalyst is selected from sodium hypophosphite, the molecular weight regulator is selected from lauric acid, and the antioxidant is selected from antioxidant 1098, and the adding amount of the catalyst is 0.1wt%; (2) Heating for 1.0h, raising the temperature to 210 ℃, raising the pressure in the kettle to 1.8MPa, and keeping the temperature and the pressure for reaction for 2.0 h; (3) Slowly deflating to ensure that the pressure in the kettle is maintained at 1.8MPa within 1.0 hour at the beginning and is reduced to the normal pressure within 1.0 hour thereafter; (4) And (3) keeping the reaction temperature of 240 ℃ under normal pressure, reacting for 2.0 hours, stopping stirring, opening a discharge valve, introducing nitrogen, discharging the material through a tape injection head, cooling, and granulating to obtain the nylon 1212 product.
[ COMPARATIVE EXAMPLE 2 ]
The nylon salt formation procedure was as in example 1, with the bulk density of the nylon salt powder being 0.22g/cm 3 。
Granulating nylon salt: (1) Uniformly mixing 100 parts of nylon 1212 salt powder and 100 parts of pure water, and drying by a vacuum oven to obtain a whole dry solid; (2) The obtained dry granules with good fluidity and particle diameter of about 1.0mm are obtained by a granulator, and the bulk density is 0.28g/cm 3 ；
Polymerization of nylon 1212: (1) Directly mixing 400g of nylon 1212 salt particles with 400g of water, a catalyst, a molecular weight regulator, an antioxidant and the like uniformly, and adding the mixture into a 2.0L high-temperature high-pressure polymerization kettle, wherein the catalyst is selected from sodium hypophosphite, the molecular weight regulator is selected from lauric acid, and the antioxidant is selected from antioxidant 1098, and the addition amount of the catalyst is 0.1wt%; (2) Heating for 1.0h to 210 ℃, increasing the pressure in the kettle to 1.8MPa, and keeping the temperature and the pressure to react for 2.0 h; (3) Slowly releasing the gas, so that the pressure in the kettle is maintained at 1.8MPa within 1.0 hour at the beginning, and the pressure in the kettle is reduced to the normal pressure within 1.0 hour thereafter; (4) And (3) keeping the reaction temperature at 240 ℃ under normal pressure, reacting for 2.0 hours, stopping stirring, opening a discharge valve, introducing nitrogen, discharging the material through a tape injection head, cooling, and granulating to obtain the nylon 1212 product.
The nylon products obtained in the examples and the comparative examples are subjected to mechanical property and yellowness index detection, wherein the tensile strength is tested by adopting a standard GB/T1040.1-2006, the impact strength is tested by adopting a standard GB/T1043.1-2008, the yellowness index is tested by adopting a standard GB/T2409-1980, and the results are shown in Table 1:
table 1:
| item | Tensile strength (Mpa) | Notched impact strength (kJ/m) 2 ) | Yellowness index |
| Example 1 | 42.1 | 14.2 | 10.3 |
| Example 2 | 41.9 | 14.2 | 10.2 |
| Example 3 | 42.2 | 14.5 | 10.6 |
| Example 4 | 41.8 | 13.7 | 10.5 |
| Example 5 | 42.3 | 14.6 | 10.4 |
| Example 6 | 41.7 | 13.8 | 10.3 |
| Example 7 | 41.5 | 13.3 | 14.5 |
| Example 8 | 42.2 | 14.3 | 9.8 |
| Example 9 | 38.1 | 8.7 | 9.5 |
| Example 10 | 40.8 | 12.1 | 15.4 |
| Comparative example 1 | 40.5 | 11.8 | 13.2 |
| Comparative example 2 | 40.7 | 11.6 | 13.4 |
As can be seen from table 1, it is,
(1) As seen from the comparison of example 1 with comparative examples 1 and 2, the bulk density of the raw material was raised from 0.2 to 0.5 to 1.0g/cm by granulating and tabletting prior to feeding and polymerizing 3 More reactants can be charged than with direct feed, the batch throughput is increased from 400g to 1200g for the same reactor, the energy consumption is lower, and the product tensile strength and impact strength are lowerBetter, lower oxidation degree;
(2) The different forms of granulation have less influence on the final result; the nylon salt particles have smaller particle size, and the tablets are smaller, so that the mixing is more sufficient, the final reaction degree is higher, and the product performance is better;
(3) In the polymerization process, too little water is added to make the prepolymerization process more susceptible to oxidation, but if more water is added, the removal of water at a later stage requires more time and heat, so that the amount of water added needs to be in a moderate range.
(4) Nylon 1212 with similar performance can be obtained by adopting different salifying solvents, different catalysts and the like.
Claims (16)
1. A preparation method of long carbon chain nylon comprises the steps of mixing components including a nylon salt raw material, water, a catalyst, a molecular weight regulator and an antioxidant, and polymerizing to obtain the long carbon chain nylon; wherein the bulk density of the nylon salt raw material is 0.5-1.0 g/cm 3 Preferably 0.6 to 0.9g/cm 3 。
2. The method of claim 1, wherein:
the weight ratio of the nylon salt raw material to water is 1 (0.05-0.5), preferably 1 (0.15-0.35); and/or the presence of a gas in the gas,
the catalyst is selected from at least one of phosphoric acid, phosphorous acid, hypophosphorous acid, sodium phosphite and sodium hypophosphite; preferably, the weight ratio of the catalyst to the nylon salt raw material is (0.05-0.5%): 1; and/or the presence of a gas in the gas,
the molecular weight regulator is selected from at least one of monoacid, diacid, monoamine and diamine; preferably, the weight ratio of the molecular weight regulator to the nylon salt raw material is (0.05-0.5%): 1; and/or the presence of a gas in the gas,
the antioxidant is at least one selected from bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, antioxidant 1790, antioxidant 3114, antioxidant 1098, hindered phenols, hindered aromatic amines, hydroquinones, antioxidant 1010, antioxidant 1222, antioxidant 168 and antioxidant 330; more preferably, the weight ratio of the antioxidant to the nylon salt raw material (0.05-0.5%) is 1.
3. The method of claim 1, wherein:
the polymerization is carried out by a batch polymerization method or a solid phase polycondensation method, and preferably, the polymerization is carried out under a protective atmosphere.
4. The production method according to claim 3, characterized by, when the batch polymerization method is employed, performing:
1) Mixing the components, and heating and boosting the pressure to react in a protective atmosphere;
2) Slowly deflating, namely maintaining the pressure in the system constant, and then decompressing to normal pressure;
3) Carrying out reaction under normal pressure;
4) Discharging after the reaction is finished, optionally cooling and then pelletizing to obtain the long carbon chain nylon.
5. The method of claim 4, wherein:
in step 1), the reaction proceeds as follows: reacting for 0.2-5.0 h at 180-240 ℃ under 1.2-2.2 MPa; preferably, the reaction is carried out for 0.5 to 4.0 hours at the temperature of between 200 and 220 ℃ and under the pressure of between 1.5 and 2.0 MPa; and/or the presence of a gas in the gas,
in the step 2), slowly releasing gas to ensure that the pressure in the system is maintained at 1.2-2.5 MPa within 0.2-3.0 hours at the beginning and is reduced to normal pressure within 0.2-4.0 hours later; preferably, the air is slowly released, so that the pressure in the system is maintained at 1.5-2.0 MPa within 0.5-2.0 hours at the beginning and is reduced to the normal pressure within 0.5-3.0 hours later; and/or the presence of a gas in the gas,
in step 3), the reaction proceeds as follows: performing the reaction at 180-300 ℃ for 0.2-8.0 h; preferably, the reaction is carried out at 200-260 ℃ for 0.5-6.0 h.
6. The production method according to claim 3, wherein when the solid phase polycondensation method is used, the following is performed:
1') mixing the components, and raising the temperature and the pressure under a protective atmosphere;
2') reacting while keeping the temperature and the pressure unchanged to obtain a prepolymer;
3') cooling to room temperature after the reaction is finished, taking out the prepolymer, and filtering and drying the prepolymer to obtain long-carbon-chain nylon oligomer powder;
4') granulating the long carbon chain nylon oligomer powder to obtain long carbon chain nylon oligomer particles;
5') carrying out solid-phase polymerization on the long carbon chain nylon oligomer particles to obtain the long carbon chain nylon.
7. The method of claim 6, wherein:
in the step 1'), the temperature is raised to 150 to 250 ℃ within 0.5 to 1.5h, and the pressure is raised to 0.8 to 2MPa; preferably, the temperature is raised to 180-200 ℃ within 0.8-1.2 h, and the pressure is raised to 1.0-1.5 MPa; and/or the presence of a gas in the atmosphere,
in the step 2'), the temperature and the pressure are kept unchanged for reaction for 0.2 to 8.0 hours; preferably, the temperature and the pressure are kept unchanged for reaction for 0.5 to 6.0 hours; and/or the presence of a gas in the gas,
in step 5'), the solid-phase polymerization is carried out as follows: solid-phase tackifying the long carbon chain nylon oligomer particles for 2-20 h at 120-200 ℃ under the vacuum or inert gas purging condition of 0-10 Pa; preferably, the long carbon chain nylon oligomer particles are subjected to solid phase tackifying for 5 to 15 hours at the temperature of between 150 and 175 ℃ under the vacuum condition of between 0 and 5Pa or under the inert gas purging condition.
8. The method according to claim 1, wherein the nylon salt raw material is prepared by the steps of:
a) Preparing nylon salt powder by adopting dibasic acid and diamine;
b) And granulating the nylon salt powder, and pressing into tablets to obtain the nylon salt raw material.
9. The method of claim 8, wherein in step a):
the diamine is selected from C 10 The above diamines, preferably from C 10 ～C 20 The diamine of (a); and/or the presence of a gas in the atmosphere,
the dibasic acid is selected from C 10 The dibasic acids above, preferably from C 10 ～C 20 The dibasic acid of (1); and/or the presence of a gas in the gas,
the molar use ratio of the dibasic acid to the diamine is 1 (1-1.05), and preferably 1 (1-1.01).
10. The method for preparing according to claim 8, characterized in that step a) comprises the following sub-steps:
a-1) mixing dibasic acid with a solvent A, and heating to obtain a solution A;
a-2) mixing diamine and a solvent B, and heating to obtain a solution B;
a-3) adding the solution B into the solution A for reaction;
a-4) cooling after the reaction is finished, filtering and drying to obtain nylon salt powder.
11. The method for preparing according to claim 10, characterized in that in said step a-1):
the solvent A is selected from at least one of ethanol, methanol and propanol; and/or the presence of a gas in the atmosphere,
the weight ratio of the dibasic acid to the solvent A is 1 (2-10), preferably 1 (3-7); and/or the presence of a gas in the gas,
heating to 50-95 deg.c for 10-50 min.
12. The method for preparing according to claim 10, characterized in that in the step a-2):
the solvent B is selected from at least one of ethanol, methanol and propanol; and/or the presence of a gas in the atmosphere,
the weight ratio of the diamine to the solvent B is 1 (1-6), preferably 1 (1-3); and/or the presence of a gas in the gas,
heating to 40-90 deg.c for 10-50 min.
13. The method of manufacturing according to claim 10, wherein:
in the step a-3), the reaction is carried out for 0.2 to 4 hours at the temperature of between 50 and 100 ℃, and preferably for 0.5 to 2 hours at the temperature of between 70 and 80 ℃; and/or the presence of a gas in the gas,
in step a-4), cooling to below 40 ℃, preferably to below 30 ℃.
14. The method for preparing according to claim 8, characterized in that step b) comprises the following sub-steps:
b-1) granulating the nylon salt powder into particles with the particle size of 0.5-2.0 mm;
b-2) tabletting the granules into tablets with the diameter of 5.0-20.0 mm and the thickness of 1.0-5.0 mm.
15. The method of claim 14, wherein:
in the step b-1), the granulation comprises wet granulation or dry granulation; wherein the content of the first and second substances,
the wet granulation preferably comprises: uniformly mixing 100 parts of nylon salt powder and 10-30 parts of water, granulating to obtain wet granules, and drying to obtain dry granules;
the dry granulation preferably comprises: mixing 100 parts of nylon salt powder with 50-200 parts of water, drying to obtain a whole solid, or pressing the nylon salt powder into a sheet, and then granulating the whole solid or the sheet to obtain dry particles.
16. A long carbon chain nylon obtained by the production method according to any one of claims 1 to 15.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110957945.2A CN115707728A (en) | 2021-08-20 | 2021-08-20 | Preparation method of long carbon chain nylon and long carbon chain nylon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110957945.2A CN115707728A (en) | 2021-08-20 | 2021-08-20 | Preparation method of long carbon chain nylon and long carbon chain nylon |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115707728A true CN115707728A (en) | 2023-02-21 |
Family
ID=85212324
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110957945.2A Pending CN115707728A (en) | 2021-08-20 | 2021-08-20 | Preparation method of long carbon chain nylon and long carbon chain nylon |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115707728A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2951228A1 (en) * | 2013-01-30 | 2015-12-09 | DSM IP Assets B.V. | Process for the preparation of a polyamide |
| CN107286338A (en) * | 2017-07-28 | 2017-10-24 | 湖南华曙高科技有限责任公司 | A kind of selective laser sintering polyamide material and preparation method thereof |
| US20170349705A1 (en) * | 2014-12-17 | 2017-12-07 | Cathay R&D Center Co., Ltd. | Nylon salt and preparation method therefor |
| CN109824887A (en) * | 2019-01-31 | 2019-05-31 | 珠海派锐尔新材料有限公司 | A kind of preparation method of nylon-type microsphere powder |
| CN112280032A (en) * | 2020-11-03 | 2021-01-29 | 北京化工大学 | Preparation method of long carbon chain nylon material |
-
2021
- 2021-08-20 CN CN202110957945.2A patent/CN115707728A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2951228A1 (en) * | 2013-01-30 | 2015-12-09 | DSM IP Assets B.V. | Process for the preparation of a polyamide |
| US20170349705A1 (en) * | 2014-12-17 | 2017-12-07 | Cathay R&D Center Co., Ltd. | Nylon salt and preparation method therefor |
| CN107001625B (en) * | 2014-12-17 | 2020-06-19 | 上海凯赛生物技术股份有限公司 | Nylon salt and preparation method thereof |
| CN107286338A (en) * | 2017-07-28 | 2017-10-24 | 湖南华曙高科技有限责任公司 | A kind of selective laser sintering polyamide material and preparation method thereof |
| CN109824887A (en) * | 2019-01-31 | 2019-05-31 | 珠海派锐尔新材料有限公司 | A kind of preparation method of nylon-type microsphere powder |
| CN112280032A (en) * | 2020-11-03 | 2021-01-29 | 北京化工大学 | Preparation method of long carbon chain nylon material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100541421B1 (en) | Hydrogenated product of copolymer and process for producing the same | |
| CN113292719B (en) | Polyamide resin containing imide structure and preparation method thereof | |
| CN105601814A (en) | Industrialized production method of trans-butadiene-isoprene copolymer rubber | |
| CN109054166A (en) | A kind of preparation method of heat-proof impact-resistant polypropylene material | |
| CN113881036B (en) | Preparation method of long carbon chain nylon and nylon obtained by preparation method | |
| CN114181390B (en) | Bio-based high-temperature-resistant polyamide and preparation method thereof | |
| CN112831041A (en) | Terephthalic acid type unsaturated polyester and preparation method thereof | |
| CN116217867A (en) | High-temperature-resistant hot-pressing polyurethane sheet insole combination material and preparation method thereof | |
| CN104774454B (en) | A kind of high temperature resistant nylon PA66T materials and preparation method thereof | |
| CN113265046A (en) | High-strength heat-insulation nylon material | |
| CN111057233B (en) | Copolymerized semi-aromatic polyamide and preparation method thereof | |
| CN115707728A (en) | Preparation method of long carbon chain nylon and long carbon chain nylon | |
| CN103910878B (en) | A kind of lysine synthesis semi-aromatic nylon and preparation method thereof | |
| CN109575274B (en) | Preparation method of nylon 512 | |
| CN115197416B (en) | Continuous solid phase polycondensation method for producing PA46 and PA MXD6 | |
| CN114805791B (en) | Preparation method of long carbon chain polyamide based on pentanediamine | |
| CN114075326B (en) | Plasticizer and manufacturing method thereof | |
| CN1255442C (en) | Synthesis of medium and low relative molecular mass trans-1,4-polyisoprene wax and trans-1,4-poly butadiene wax | |
| CN113999389A (en) | Film of copolymer of long-chain nylon and biuret and preparation method thereof | |
| CN100537617C (en) | Improved intermittent bulk propylene polymerizing production process and sectional propylene polymerizing production process | |
| CN114426589B (en) | Production method of butadiene rubber | |
| CN113045749A (en) | Synthesis method of long carbon chain polyamide material | |
| CN110669215A (en) | Method for preparing glass fiber reinforced nylon by in-situ polymerization and glass fiber reinforced nylon prepared by using method | |
| JPS63105473A (en) | Manufacture of carbon plate for fuel cell | |
| CN110551284A (en) | Preparation method of poly (p-phenylene-benzobisoxazole) fibers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |