CN109851824B - Method for continuously producing polyamide functional master batch and polyamide functional master batch - Google Patents
Method for continuously producing polyamide functional master batch and polyamide functional master batch Download PDFInfo
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Abstract
The invention discloses a method for continuously producing polyamide functional master batches and the polyamide functional master batches. The method comprises the following steps: continuously conveying the functional powder slurry pre-dispersed material prepared by mixing water, caprolactam and functional powder to a functional powder slurry multistage grinding device for grinding and dispersing; uniformly mixing the obtained functional powder slurry, caprolactam melt and a catalyst by a dynamic mixer, adjusting the temperature by a heat exchanger, and then entering a high-pressure hydrolysis reactor for ring-opening reaction; removing excessive water from the functional master batch oligomer fusant through an oligomer fusant dehydrator, and then entering an atmospheric polymerization reactor for polymerization reaction; and removing caprolactam monomer from the obtained polyamide functional master batch melt through a film evaporation devolatilization system, and then directly granulating and molding to obtain the polyamide functional master batch. The functional powder in the polyamide functional master batch continuously produced by the method is highly and uniformly dispersed, and is suitable for producing products such as high-quality fibers, films and the like.
Description
Technical Field
The invention relates to the technical field of high polymer material synthesis, in particular to a method for continuously producing polyamide functional master batches and the polyamide functional master batches.
Background
At present, the preparation method of the polyamide functional master batch is mainly a functional master batch pre-spinning coloring method. The functional mother particles are aggregates prepared by uniformly loading an excessive amount of pigment or dye into resin. The functional master batch is prepared by a melt blending method, and the carrier resin and the functional powder are uniformly mixed above the viscous flow temperature of the carrier resin by virtue of strong shearing force provided by mixing equipment, so that the functional powder is stably and uniformly dispersed in the carrier resin with a certain particle size. In the melt blending method, the dispersion of the functional powder in the high-viscosity carrier resin melt mainly depends on the mechanical shearing force provided by the mixing equipment, so that the functional powder is difficult to be highly and uniformly dispersed in the carrier resin melt in a small scale, and the functional master batch prepared by the melt blending method is difficult to be suitable for preparing fine denier or superfine denier functional fibers.
Disclosure of Invention
In view of this, the invention provides a method for continuously producing polyamide functional masterbatch and the polyamide functional masterbatch, so as to realize continuous and stable preparation of polyamide functional masterbatch with highly uniform dispersion of functional powder.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for continuously producing a polyamide functional master batch, the method comprising the steps of:
(1) continuously conveying the functional powder slurry pre-dispersed material prepared by mixing water, caprolactam and functional powder to a functional powder slurry multistage grinding device for grinding and dispersing to obtain functional powder slurry;
(2) uniformly mixing the functional powder slurry prepared in the step (1), a caprolactam melt and a catalyst by a dynamic mixer, adjusting the temperature by a heat exchanger, and then entering a high-pressure hydrolysis reactor for ring-opening reaction to obtain a polyamide functional master batch oligomer melt;
(3) removing excessive water from the polyamide functional master batch oligomer melt prepared in the step (2) through an oligomer melt dehydrator, and then allowing the polyamide functional master batch oligomer melt to enter an atmospheric polymerization reactor for polymerization reaction to obtain a polyamide functional master batch melt;
(4) and (4) directly granulating and forming the polyamide functional master batch melt prepared in the step (3) after removing caprolactam monomers by a film evaporation devolatilization system to obtain the polyamide functional master batch.
Furthermore, the multi-stage grinding device for functional powder slurry is formed by connecting 1-5 grinding machines in series.
Further, in the step (2), the high-pressure hydrolysis reactor is a tower reactor with a built-in mixing unit, and the materials flow in a plug flow manner from bottom to top.
Further, in the step (5), the film evaporation and dehumidification system consists of a multi-stage film evaporation device and a steam condensation system.
Furthermore, the multistage film evaporation device is formed by connecting 1-3 film evaporators in series.
Further, the vapor condensing system includes a vapor condenser and a spray trap.
Further, in the step (2), the catalyst is protonic acid.
Further, in the step (1), the average particle diameter of the functional powder in the functional powder slurry is not more than 0.5 μm.
Furthermore, in the step (1), the mass ratio of the water, the caprolactam and the functional powder is 1 (0.5-1) to 0.22-3.
Further, in the step (2), the addition amount of the catalyst is 30-1500 ppm of the mass of the caprolactam melt; the addition amount of the functional powder slurry is 15-250 wt% of the mass of the caprolactam melt.
Further, in the step (2), the temperature of the heat exchanger is 130-200 ℃.
Further, in the step (2), the reaction temperature of the ring-opening reaction is 200-300 ℃, the reaction pressure is 1.6-8.6 MPa, and the reaction time is 10-90 min.
Further, in the step (3), the temperature of the oligomer melt dehydrator is 220-300 ℃, the retention time of the materials in the oligomer melt dehydrator is 15-60 min, and the pressure is reduced to 100kPa from 1.6-8.6 MPa.
Further, in the step (3), the reaction temperature of the polymerization reaction is 225-300 ℃, the reaction pressure is 100kPa, and the reaction time is 10-20 h.
Further, in the step (4), the temperature of the multistage thin film evaporation device in the thin film evaporation devolatilization system is 225-300 ℃, and the pressure is 0.6-6 kPa; the temperature of cooling water of a steam condenser of a steam condensing system in the film evaporation devolatilization system is 68-98 ℃; the temperature of the spray chilled water of the spray catcher of the steam condensing system in the film evaporation devolatilization system is 0-35 ℃.
According to another aspect of the present invention, a polyamide functional masterbatch is provided, which is prepared by the above-mentioned production method.
Further, the relative viscosity of the polyamide functional master batch is 1.5-3.5, the content of hot water extractables is not higher than 5%, and the filter pressing value DF is not higher than 30kPa2/g。
The invention has the following beneficial effects:
the invention provides a method for continuously producing polyamide functional master batches aiming at the problems in the existing preparation method of polyamide functional master batches, and can realize continuous production of polyamide functional master batches with highly uniformly dispersed functional powder. The method is easy to implement industrially, and can realize large-scale industrial continuous production of the polyamide functional master batch, so that the production efficiency of the polyamide functional master batch is greatly improved, and the production cost is greatly reduced.
According to the invention, the functional powder slurry multistage grinding device is introduced into the polyamide functional master batch continuous polymerization production system, and the functional powder slurry continuous preparation process is integrated into the polyamide functional master batch continuous polymerization production process flow, so that on one hand, the quality stability of the continuously produced polyamide functional master batch can be further improved; on the other hand, the production cost of the polyamide functional master batch can be further reduced. In addition, the invention adopts caprolactam water solution as the solvent of the functional powder slurry, can reduce the water content in the functional powder slurry, so as to effectively reduce the water content introduced into a reaction system by adding the functional powder slurry, thereby improving the stability of production operation and reducing the energy consumption of production.
The present invention adopts tower reactor as high pressure hydrolysis reactor and introduces the hydrolysis and ring-opening process of caprolactam into the continuous polymerization production process of polyamide functional agglomerate. By adjusting the addition amount of the catalyst and the reaction temperature, reaction pressure and reaction time of the hydrolysis ring-opening reaction, the caprolactam can be efficiently hydrolyzed and ring-opened into the aminocaproic acid with strong polarity, which has strong interaction force with the functional powder, so that the functional powder is highly uniformly dispersed in the polyamide functional master batch oligomer generated by the hydrolysis ring-opening reaction.
According to the invention, a film evaporation devolatilization process is introduced into the continuous polymerization production process flow of the polyamide functional master batch, so that caprolactam monomers existing in a melt of the polyamide functional master batch produced by continuous polymerization can be efficiently removed, and the polyamide functional master batch produced by continuous polymerization can meet the requirements of subsequent spinning, film drawing and injection molding; therefore, the extraction and drying procedures of the traditional polyamide chip continuous polymerization production are omitted, the energy consumption and the water consumption of the production of the polyamide functional master batch can be greatly reduced, and the green and environment-friendly characteristics of the production process of the polyamide functional master batch are remarkably improved.
The invention also provides a polyamide functional master batch which has higher functional powder dispersion uniformity compared with like products in the prior art.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings.
In the drawings:
FIG. 1 is a schematic view of a production process for continuously producing polyamide functional master batch.
Detailed Description
The invention provides a method for continuously producing polyamide functional master batches and the polyamide functional master batches, aiming at solving the problems in the prior art, so as to realize the continuous and stable preparation of the polyamide functional master batches with highly uniformly dispersed functional powder.
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description will be made on the method for continuously producing the polyamide functional masterbatch and the polyamide functional masterbatch according to the present invention, and the specific implementation manner, structure, characteristics and effects thereof, with reference to the accompanying drawings and preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the features, structures, or characteristics of one or more embodiments may be combined in any suitable manner.
The term "and/or" herein is merely an association describing an associated object, meaning that three relationships may exist, e.g., a and/or B, with the specific understanding that: both a and B may be included, a may be present alone, or B may be present alone, and any of the three cases can be provided.
As mentioned in the background art, in the prior art, the technical problem that the prepared polyamide functional master batch has poor spinning performance due to the fact that functional powder is difficult to uniformly disperse in a polyamide melt exists. In order to improve the above-mentioned drawbacks of the prior art, the present invention provides a method for continuously producing polyamide functional masterbatch, as shown in fig. 1. The embodiment of the invention carries out the continuous production of the polyamide functional master batch according to the flow shown in figure 1: continuously conveying the functional powder slurry pre-dispersed material prepared by mixing water, caprolactam and functional powder to a functional powder slurry multistage grinding device for grinding and dispersing to obtain functional powder slurry; uniformly mixing the obtained functional powder slurry, caprolactam melt and a catalyst by a dynamic mixer, adjusting the temperature by a heat exchanger, and then entering a high-pressure hydrolysis reactor for ring-opening reaction to obtain polyamide functional master batch oligomer melt; removing excessive water from the oligomer melt dehydrator of the obtained functional master batch oligomer melt, and then, allowing the oligomer melt to enter an atmospheric polymerization reactor for polymerization reaction to obtain a polyamide functional master batch melt; and removing caprolactam monomer from the obtained polyamide functional master batch melt through a film evaporation devolatilization system, and then directly granulating and molding to obtain the polyamide functional master batch.
According to the method for continuously producing the polyamide functional master batches, the functional powder slurry multistage grinding device is introduced into the polyamide functional master batch continuous polymerization production system, and the functional powder slurry continuous preparation process is integrated into the polyamide functional master batch continuous polymerization production process flow, so that on one hand, the quality stability of the continuously produced polyamide functional master batches can be further improved; on the other hand, the production cost of the polyamide functional master batch can be further reduced. A novel tower reactor is used as a high-pressure hydrolysis reactor, and a hydrolytic ring-opening process of caprolactam is introduced into a continuous polymerization production process flow of polyamide functional master batches. By adjusting the addition amount of the catalyst and the reaction temperature, reaction pressure and reaction time of the hydrolysis ring-opening reaction, the caprolactam can be efficiently hydrolyzed and ring-opened into the aminocaproic acid with strong polarity, which has strong interaction force with the functional powder, so that the functional powder is highly uniformly dispersed in the polyamide functional master batch oligomer generated by the hydrolysis ring-opening reaction. The film evaporation devolatilization process of the polyamide functional master batch melt is introduced into the continuous polymerization production process flow of the polyamide functional master batch, and caprolactam monomers in the polyamide functional master batch melt produced by continuous polymerization can be efficiently removed, so that the content of hot water extractable oligomers in the polyamide functional master batch produced by continuous polymerization can meet the requirements of subsequent spinning, film drawing and injection molding. The integration of the continuous preparation process of the functional powder slurry, the hydrolysis ring-opening process, the normal-pressure polymerization process, the film evaporation devolatilization process and the granulation molding process can realize the high-efficiency and low-cost continuous production of the polyamide functional master batch, and the functional powder in the produced polyamide functional master batch is highly uniformly dispersed.
In the method for continuously producing the polyamide functional master batch, the functional powder slurry multistage grinding device is formed by connecting 1-5 grinding machines in series. The average particle size of the functional powder in the functional powder slurry obtained by continuous preparation can be regulated and controlled by regulating the number of the grinding machines connected in series in the multi-stage grinding device for the functional powder slurry and the particle size of the grinding medium in the grinding machine. The functional powder slurry pre-dispersing material continuously conveyed to the functional powder slurry multistage grinding device can continuously prepare the functional powder slurry with highly uniformly dispersed functional powder through the functional powder slurry multistage grinding device. The average grain diameter of the functional powder in the continuously prepared functional powder slurry is not higher than 0.5 mu m. The average particle size of the functional powder in the functional powder slurry for continuous polymerization of the polyamide functional master batch is controlled within the range, so that the average particle size of the functional powder in the polyamide functional master batch in subsequent production can be effectively controlled, and the functional powder has high dispersion uniformity in the polyamide functional master batch.
In the method for continuously producing the polyamide functional master batch, the functional powder is uniformly mixed and dispersed in caprolactam in a dynamic mixing mode, so that almost homogeneous physical blending is achieved. Suitable dynamic mixers include shear pumps, planetary gear dynamic mixers, dynamic and static ring gear dynamic mixers, ball and socket dynamic mixers.
In the method for continuously producing the polyamide functional master batch, the high-pressure hydrolysis reactor is a tower reactor with a built-in mixing unit, and materials flow in a plug flow manner from bottom to top. The mixing unit internals arranged in the tower reactor can ensure the sufficient mixing of the materials in the radial direction, thereby ensuring the structural uniformity of the prepared polyamide functional master batch oligomer.
In the method for continuously producing the polyamide functional master batch, the film evaporation and demonomerization system consists of a multi-stage film evaporation device and a steam condensation system, wherein the multi-stage film evaporation device is formed by connecting 1-3 film evaporators in series; the vapor condensing system includes a vapor condenser and a spray trap. The film evaporator is a new type high-efficiency evaporator which can continuously and uniformly force the material to form film on the heating surface by rotating the film-scraping device in the cylinder body, can carry out falling film evaporation under the vacuum condition, has large heat transfer coefficient, high evaporation intensity, short overflowing time and large operation elasticity, and is especially suitable for degassing and desolventizing heat-sensitive materials and high-viscosity materials. Caprolactam monomer in the polyamide functional master batch melt can be efficiently removed by a multistage film evaporation device formed by connecting 1-3 film evaporators in series, so that the content of hot-water extractable oligomer in the polyamide functional master batch produced by continuous polymerization can meet the requirements of subsequent spinning, film drawing and injection molding. The steam condensing system of film evaporation list-removing system contains steam condenser and sprays the trap, and steam condenser mainly carries out high-efficient condensation to the caprolactam steam of taking out from multistage film evaporation plant and collects, sprays the trap and mainly carries out the high-efficient trapping that sprays in order to prevent that caprolactam from getting into the vacuum pump, blockking up the vacuum pump from the noncondensable gas of taking out in the steam condenser.
In the method for continuously producing the polyamide functional master batch, the catalyst for the hydrolysis ring-opening reaction is protonic acid, and the addition of protons can promote the cation ring-opening of caprolactam, so the reaction rate of the hydrolysis ring-opening reaction of caprolactam can be effectively improved by adding the protonic acid as the catalyst. The protonic acid as the catalyst includes, but is not limited to, phosphoric acid, pyrophosphoric acid, metaphosphoric acid, hypophosphorous acid, phosphorous acid, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, hydrochloric acid, hypochlorous acid. The addition amount of the catalyst is 30-1500 ppm of the mass of the caprolactam melt. The addition amount of the catalyst is controlled within the range, and the catalyst has higher catalytic reaction activity on the hydrolysis ring-opening reaction of caprolactam.
In the method for continuously producing the polyamide functional master batch, water, caprolactam and functional powder are used as raw materials to prepare the functional powder slurry pre-dispersing material. The functional powder has functions of coloring, antibiosis, radiation protection, antibiosis, electric conduction, heat conduction, far infrared, flame retardance, negative ion, fluorescence or magnetism and the like, and comprises but is not limited to carbon black, pigment white 6, pigment brown 3, pigment blue 5, pigment blue 15:1, pigment blue 15:3, pigment blue 15:4, pigment blue 15:6, pigment blue 16, pigment blue 28, pigment blue 29, pigment blue 60, pigment violet 19, pigment violet 23, pigment violet 29, pigment red 101, pigment red 102, pigment red 108, pigment red 112, pigment red 122, pigment red 146, pigment red 149, pigment red 170, pigment red light emitting device, pigment blue light emitting device, pigment red light emitting device, and the like, etc,Pigment red 171, pigment red 172, pigment red 175, pigment red 176, pigment red 177, pigment red 178, pigment red 179, pigment red 185, pigment red 202, pigment red 207, pigment red 208, pigment red 214, pigment red 241, pigment red 242, pigment red 254, pigment red 255, pigment red 263, pigment red 264, pigment red 272, pigment yellow 6, pigment yellow 13, pigment yellow 14, pigment yellow 17, pigment yellow 21, pigment yellow 37, pigment yellow 77, pigment yellow 74, pigment yellow 81, pigment yellow 97, pigment yellow 107, pigment yellow 110, pigment yellow 120, pigment yellow 129, pigment yellow 138, pigment yellow 139, pigment yellow 147, pigment yellow 148, pigment yellow 150, pigment yellow 151, pigment yellow 155, pigment yellow 168, pigment yellow 174, pigment yellow 180, pigment yellow 187, pigment yellow 192, pigment yellow 195, pigment yellow 196, pigment yellow 197, pigment orange 34, pigment orange 36, pigment orange 43, pigment 61, pigment orange 36, pigment orange 43, pigment yellow 195, pigment yellow 197, pigment yellow, Pigment orange 64, pigment orange 68, pigment orange 70, pigment orange 73, pigment green 5, pigment green 7, pigment green 36, pigment green 50, yellow-green luminous powder (ZnS: Cu), long-afterglow fluorescent powder (SrMgAl)4O8:Eu2+Dy3+) Sky blue luminous powder (Sr)2MgSi2O7) Orange luminous powder (Y)2O2Eu, Mg, Ti) and yellow-green luminous powder (SrAl)2O4Eu, Dy), blue-green luminous powder (Sr)4A14O25Eu, Dy), orange-red luminous powder (Y)2O2S: eu.mg: Ti), silver, germanium, silver oxide, cuprous oxide, zinc oxide, aluminum oxide, titanium dioxide, silicon dioxide, graphene, carbon nanotubes, aluminum nitride, boron nitride, silicon carbide, graphite, bamboo charcoal, coffee carbon, zirconium carbide, zirconium oxide, titanium carbide, hafnium carbide, tourmaline, mirabilite, opal, bizarre stone, layered double hydroxide, mica, jade, magnesium hydroxide, zinc borate, ferroferric oxide or tin antimony oxide, indium tin oxide. In a preferred embodiment of the invention, the mass ratio of the water, the caprolactam and the functional powder in the functional powder slurry pre-dispersing material is 1 (0.5-1) to (0.22-3). The caprolactam water solution is adopted as the solvent of the functional powder slurry, so that the water content in the functional powder slurry can be reduced, the water content introduced into a reaction system by adding the functional powder slurry can be effectively reduced, and the production can be improvedThe operation stability and the production energy consumption are reduced. The addition amount of the functional powder slurry is 15-250 wt% of the mass of the caprolactam melt. The addition amount of the functional powder slurry is controlled within the range, so that the concentration of the functional powder in the prepared polyamide functional master batch can meet the requirements of subsequent spinning, film drawing and injection molding.
In the method for continuously producing the polyamide functional master batch, the functional powder slurry, the caprolactam melt and the catalyst are uniformly mixed by the dynamic mixer, the temperature of the mixture is adjusted by the heat exchanger, and the mixture enters the high-pressure hydrolysis reactor, wherein the temperature of the heat exchanger is 130-200 ℃. Before entering the high-pressure hydrolysis reactor, the blend formed by the functional powder slurry, the caprolactam melt and the catalyst is preheated by the heat exchanger, so that the influence on the hue of the product caused by thermal decomposition of caprolactam in the blend due to rapid heating can be effectively avoided.
In the method for continuously producing the polyamide functional master batch, the polyamide functional master batch oligomer melt is dehydrated by the oligomer melt dehydrator and then enters the high-pressure polymerization reactor for polymerization reaction. In the polymerization reaction stage of the polyamide functional master batch, the more water in the reaction system, the more unfavorable the molecular chain is for further growth. Therefore, in the polymerization reaction stage, the regulation and control of the water content in the reaction system is an important measure for improving and stabilizing the molecular weight. The oligomer melt dehydrator is a flash evaporator, and the water in the melt is removed by utilizing the principle of flash evaporation. The temperature of the oligomer melt dehydrator is 220-300 ℃, the retention time of the materials in the oligomer melt dehydrator is 15-60 min, and the pressure is reduced to 100kPa from 1.6-8.6 MPa.
In the method for continuously producing the polyamide functional master batch, the reaction temperature of the ring-opening reaction is 200-300 ℃, the reaction pressure is 1.6-8.6 MPa, and the reaction time is 10-90 min. The ring-opening reaction condition is controlled within the range, so that the hydrolytic ring-opening conversion rate of caprolactam can meet the requirement of subsequent polymerization reaction. The reaction temperature of the polymerization reaction is 225-300 ℃, the reaction pressure is 100kPa, and the reaction time is 10-20 h. The polymerization reaction conditions are controlled within the range, so that the polyamide functional master batch with the relative viscosity of 1.5-3.5 can be prepared, and the viscosity requirements of subsequent spinning, film drawing and injection molding can be met.
In the method for continuously producing the polyamide functional master batch, the polyamide functional master batch melt is directly granulated after the caprolactam monomer is removed by the film evaporation devolatilization system, so that the polyamide functional master batch is obtained. The temperature of the multistage film evaporation device in the film evaporation devolatilization system is 225-300 ℃, and the pressure is 0.6-6 kPa. The evaporation and devolatilization conditions of the film are controlled in the range, so that the monomeric caprolactam with high content and normal pressure boiling point of 268 ℃ in the polyamide functional master batch melt can be efficiently removed. The temperature of cooling water of a steam condenser of a steam condensing system in the film evaporation devolatilization system is 68-98 ℃. The temperature of the cooling water conveyed into the jacket of the steam condenser is controlled within the range, and the caprolactam steam extracted from the multistage film evaporation device can be efficiently condensed and collected. The temperature of the spray chilled water of the spray catcher of the steam condensing system in the film evaporation devolatilization system is 0-35 ℃. The temperature of the spray catcher is controlled within the range, so that the non-condensable gas from the steam condenser can be efficiently caught, and the phenomenon that the vacuum pump has overlarge pumping load due to the pumping away of the chilled water can be prevented.
In another exemplary embodiment of the present invention, a polyamide functional masterbatch is further provided, which is prepared by any one of the above methods for continuously producing polyamide functional masterbatch. The polyamide functional master batch provided by the invention has the relative viscosity of 1.5-3.5, the hot water extractable matter content of not higher than 5% and the filter pressing value DF of not higher than 30kPa.cm2(ii)/g; compared with the polyamide functional master batch produced by the existing melt blending method, the polyamide functional master batch has lower filter pressing value, which shows that the polyamide functional master batch provided by the invention has higher dispersion uniformity of functional powder. The filter pressing value is an effective characteristic value for representing the dispersion degree of the functional powder in the polymeric matrix. Filter pressing value DF (kPa.cm) of functional master batch2,/g), test method: the test mixture is composed of the functional master batches with the weight of m1 and polyamide 6 with the weight of m2, the total weight of the test mixture is 4000g, and the content of the functional powder in the test mixture is 100 g; the melt metering pump with the length-diameter ratio of phi 25mm multiplied by 25D and the volume of 1.2cc is adoptedThe area S of the melt pressure sensor and the filter screen is 3.8cm2The four layers of combined filter screens of 60-100-; the filter pressing performance test process conditions are as follows: the melt temperature is 270 ℃, the pressure set value before the melt metering pump is 6.5MPa, and the metering flow of the melt metering pump is 38 g/min; firstly, 500g of polyamide 6 is extruded from a filter pressing performance tester, the recorded equilibrium pressure is the initial pressure Ps, then 4000g of test mixture is extruded from the filter pressing performance tester, then 500g of polyamide 6 is extruded from the filter pressing performance tester, the recorded equilibrium pressure is the termination pressure PT, and finally, according to the formula:
calculating to obtain a filter pressing value DF;
example 1
(1) Continuously conveying a functional powder slurry pre-dispersed material prepared by mixing water, caprolactam and pigment blue 15:3 to a functional powder slurry multistage grinding device for grinding and dispersing, wherein the mass ratio of the water to the caprolactam to the pigment blue 15:3 is 1:0.8:1.8, and the functional powder slurry multistage grinding device is formed by connecting 3 grinding machines in series to obtain the functional powder slurry with the pigment blue 15:3 content of 50 wt% and the average particle size of 0.28 mu m;
(2) uniformly mixing the functional powder slurry prepared in the step (1), a caprolactam melt and a catalyst by a dynamic mixer, adjusting the temperature by a heat exchanger, and then entering a high-pressure hydrolysis reactor for ring-opening reaction, wherein the catalyst is phosphoric acid, the addition amount of the catalyst is 90ppm of the mass of the caprolactam melt, the addition amount of the functional powder slurry is 78% of the mass of the caprolactam melt, the temperature of the heat exchanger is 160 ℃, the reaction temperature of the ring-opening reaction is 260 ℃, the reaction pressure is 4.7MPa, and the reaction time is 30min, so as to obtain a polyamide functional master batch oligomer melt;
(3) removing excessive water from the polyamide functional master batch oligomer melt prepared in the step (2) through an oligomer melt dehydrator, and then, allowing the polyamide functional master batch oligomer melt to enter a normal pressure polymerization reactor for polymerization reaction, wherein the temperature of the oligomer melt dryer is 260 ℃, the retention time of materials in the oligomer melt dehydrator is 30min, the pressure is reduced from 4.7MPa to 100kPa, the reaction temperature of the polymerization reaction is 260 ℃, the reaction pressure is 100kPa, and the reaction time is 10h, so that the polyamide functional master batch melt is obtained;
(4) and (4) directly carrying out granulation molding on the polyamide functional master batch melt prepared in the step (3) after removing caprolactam monomer by a film evaporation devolatilization system to obtain the polyamide functional master batch. Wherein the multistage film evaporation device in the film evaporation devolatilization system is formed by connecting 2 film evaporators in series, the temperature of the multistage film evaporation device is 280 ℃, and the pressure is 2.0 kPa; the temperature of cooling water of a steam condenser of a steam condensing system in the film evaporation devolatilization system is 98 ℃, and the temperature of spray chilled water of a spray catcher of the steam condensing system is 15 ℃.
The polyamide functional master batch has the relative viscosity of 2.0, the hot water extractables content of 0.9wt percent and the filter pressing value DF of 7.6kPa.cm2/g。
Example 2
(1) Continuously conveying the functional powder slurry pre-dispersed material prepared by mixing water, caprolactam and carbon black to a functional powder slurry multistage grinding device for grinding and dispersing, wherein the mass ratio of the water to the caprolactam to the carbon black is 1:0.8:1.2, and the functional powder slurry multistage grinding device is formed by connecting 3 grinding machines in series to obtain the functional powder slurry with the carbon black content of 40 wt% and the average particle size of 0.15 mu m.
(2) Uniformly mixing the functional powder slurry prepared in the step (1), a caprolactam melt and a catalyst by a dynamic mixer, adjusting the temperature by a heat exchanger, and then entering a high-pressure hydrolysis reactor for ring-opening reaction, wherein the catalyst is phosphoric acid, the addition amount of the catalyst is 500ppm of the mass of the caprolactam melt, the addition amount of the functional powder slurry is 75% of the mass of the caprolactam melt, the temperature of the heat exchanger is 130 ℃, the reaction temperature of the ring-opening reaction is 220 ℃, the reaction pressure is 2.3MPa, and the reaction time is 60min, so as to obtain a polyamide functional master batch oligomer;
(3) removing excessive water from the polyamide functional master batch oligomer melt prepared in the step (2) through an oligomer melt dehydrator, and then, allowing the polyamide functional master batch oligomer melt to enter a normal pressure polymerization reactor for polymerization reaction, wherein the temperature of the oligomer melt dryer is 260 ℃, the retention time of materials in the oligomer melt dehydrator is 30min, the pressure is reduced from 2.3MPa to 100kPa, the reaction temperature of the polymerization reaction is 260 ℃, the reaction pressure is 100kPa, and the reaction time is 15h, so that the polyamide functional master batch melt is obtained;
(4) and (4) directly carrying out granulation molding on the polyamide functional master batch melt prepared in the step (3) after removing caprolactam monomer by a film evaporation devolatilization system to obtain the polyamide functional master batch. Wherein the multistage film evaporation device in the film evaporation devolatilization system is formed by connecting 3 film evaporators in series, the temperature of the multistage film evaporation device is 240 ℃, and the pressure is 1 kPa; the temperature of cooling water of a steam condenser of a steam condensing system in the film evaporation devolatilization system is 70 ℃, and the temperature of spray chilled water of a spray catcher of the steam condensing system is 5 ℃.
The polyamide functional master batch has the relative viscosity of 2.4, the hot water extractables content of 0.08wt percent and the filter pressing value DF of 2.1kPa.cm2/g。
Example 3
(1) Continuously conveying a functional powder slurry pre-dispersed material prepared by mixing water, caprolactam and pigment red 179 to a functional powder slurry multistage grinding device for grinding and dispersing, wherein the mass ratio of the water to the caprolactam to the pigment red 179 is 1:1:3, and the functional powder slurry multistage grinding device is formed by connecting 5 grinding machines in series to obtain the functional powder slurry with the pigment red 179 content of 60 wt% and the average particle size of 0.24 mu m;
(2) uniformly mixing the functional powder slurry prepared in the step (1), a caprolactam melt and a catalyst by a dynamic mixer, adjusting the temperature by a heat exchanger, and then feeding the mixture into a high-pressure hydrolysis reactor to perform a ring-opening reaction, wherein the catalyst is metaphosphoric acid, the addition amount of the catalyst is 1500ppm of the mass of the caprolactam melt, the addition amount of the functional powder slurry is 250% of the mass of the caprolactam melt, the temperature of the heat exchanger is 180 ℃, the reaction temperature of the ring-opening reaction is 250 ℃, the reaction pressure is 4.0MPa, and the reaction time is 30min, so as to obtain a polyamide functional master batch oligomer melt;
(3) removing excessive water from the polyamide functional master batch oligomer melt prepared in the step (2) through an oligomer melt dehydrator, and then, allowing the polyamide functional master batch oligomer melt to enter a normal pressure polymerization reactor for polymerization reaction, wherein the temperature of the oligomer melt dryer is 220 ℃, the retention time of materials in the oligomer melt dehydrator is 60min, the pressure is reduced from 4.0MPa to 100kPa, the reaction temperature of the polymerization reaction is 225 ℃, the reaction pressure is 100kPa, and the reaction time is 20h, so that the polyamide functional master batch melt is obtained;
(4) and (4) directly carrying out granulation molding on the polyamide functional master batch melt prepared in the step (3) after removing caprolactam monomer by a film evaporation devolatilization system to obtain the polyamide functional master batch. Wherein the multistage film evaporation device in the film evaporation devolatilization system is formed by connecting 1 film evaporator in series, the temperature of the multistage film evaporation device is 225 ℃, and the pressure is 0.6 kPa; the temperature of cooling water of a steam condenser of a steam condensing system in the film evaporation devolatilization system is 68 ℃, and the temperature of spray chilled water of a spray catcher of the steam condensing system is 0 ℃.
The polyamide functional master batch has the relative viscosity of 1.5, the hot water extractables content of 5wt percent and the filter pressing value DF of 10.3kPa.cm2/g。
Example 4
(1) Continuously conveying a functional powder slurry pre-dispersing material prepared by mixing water, caprolactam and pigment orange 68 to a functional powder slurry multistage grinding device for grinding and dispersing, wherein the mass ratio of the water to the caprolactam to the pigment orange 68 is 1:1:0.22, and the functional powder slurry multistage grinding device is formed by connecting 2 grinding machines in series to obtain the functional powder slurry with the pigment orange 68 content of 10 wt% and the average particle size of 0.4 mu m;
(2) uniformly mixing the functional powder slurry prepared in the step (1), a caprolactam melt and a catalyst by a dynamic mixer, adjusting the temperature by a heat exchanger, and then entering a high-pressure hydrolysis reactor for ring-opening reaction, wherein the catalyst is phosphoric acid, the addition amount of the catalyst is 30ppm of the mass of the caprolactam melt, the addition amount of the functional powder slurry is 70% of the mass of the caprolactam melt, the temperature of the heat exchanger is 130 ℃, the reaction temperature of the ring-opening reaction is 200 ℃, the reaction pressure is 1.6MPa, and the reaction time is 90min, so as to obtain a polyamide functional master batch oligomer melt;
(3) removing excessive water from the polyamide functional master batch oligomer melt prepared in the step (2) through an oligomer melt dehydrator, and then, allowing the polyamide functional master batch oligomer melt to enter a normal pressure polymerization reactor for polymerization reaction, wherein the temperature of the oligomer melt dryer is 220 ℃, the retention time of materials in the oligomer melt dehydrator is 60min, the pressure is reduced from 1.6MPa to 100kPa, the reaction temperature of the polymerization reaction is 240 ℃, the reaction pressure is 100kPa, and the reaction time is 16h, so that a polyamide functional master batch melt is obtained;
(4) and (4) directly carrying out granulation molding on the polyamide functional master batch melt prepared in the step (3) after removing caprolactam monomer by a film evaporation devolatilization system to obtain the polyamide functional master batch. Wherein the multistage film evaporation device in the film evaporation devolatilization system is formed by connecting 2 film evaporators in series, the temperature of the multistage film evaporation device is 260 ℃, and the pressure is 3.0 kPa; the temperature of cooling water of a steam condenser of a steam condensing system in the film evaporation devolatilization system is 98 ℃, and the temperature of spray chilled water of a spray catcher of the steam condensing system is 20 ℃.
The polyamide functional master batch has the relative viscosity of 2.0, the content of hot water extractables of 1.5wt percent and the filter pressing value DF of 17.4kPa.cm2/g。
Example 5
(1) Continuously conveying a functional powder slurry pre-dispersing material prepared by mixing water, caprolactam and pigment yellow 192 to a functional powder slurry multistage grinding device for grinding and dispersing, wherein the mass ratio of the water to the caprolactam to the pigment yellow 192 is 1:0.5:1.5, and the functional powder slurry multistage grinding device is formed by connecting 3 grinding machines in series to obtain the functional powder slurry with the pigment yellow 192 content of 50 wt% and the average particle size of 0.36 mu m;
(2) uniformly mixing the functional powder slurry prepared in the step (1), a caprolactam melt and a catalyst by a dynamic mixer, adjusting the temperature by a heat exchanger, and then feeding the mixture into a high-pressure hydrolysis reactor to perform a ring-opening reaction, wherein the catalyst is phosphoric acid, the addition amount of the catalyst is 90ppm of the mass of the caprolactam melt, the addition amount of the functional powder slurry is 15% of the mass of the caprolactam melt, the temperature of the heat exchanger is 200 ℃, the reaction temperature of the ring-opening reaction is 300 ℃, the reaction pressure is 8.6MPa, and the reaction time is 10min, so as to obtain a polyamide functional master batch oligomer melt;
(3) removing excessive water from the polyamide functional master batch oligomer melt prepared in the step (2) through an oligomer melt dehydrator, and then, allowing the polyamide functional master batch oligomer melt to enter a normal pressure polymerization reactor for polymerization reaction, wherein the temperature of the oligomer melt dryer is 300 ℃, the retention time of materials in the oligomer melt dehydrator is 15min, the pressure is reduced from 8.6MPa to 100kPa, the reaction temperature of the polymerization reaction is 300 ℃, the reaction pressure is 100kPa, and the reaction time is 20h, so that the polyamide functional master batch melt is obtained;
(4) and (4) directly carrying out granulation molding on the polyamide functional master batch melt prepared in the step (3) after removing caprolactam monomer by a film evaporation devolatilization system to obtain the polyamide functional master batch. Wherein the multistage film evaporation device in the film evaporation devolatilization system is formed by connecting 3 film evaporators in series, the temperature of the multistage film evaporation device is 300 ℃, and the pressure is 6.0 kPa; the temperature of cooling water of a steam condenser of a steam condensing system in the film evaporation devolatilization system is 98 ℃, and the temperature of spray chilled water of a spray catcher of the steam condensing system is 35 ℃.
The polyamide functional master batch has the relative viscosity of 3.5, the hot water extractables content of 0.6wt percent and the filter pressing value DF of 8.6kPa.cm2/g。
Example 6
(1) And continuously conveying the functional powder slurry pre-dispersed material prepared by mixing water, caprolactam and antibacterial agent cuprous oxide to a functional powder slurry multistage grinding device for grinding and dispersing, wherein the mass ratio of the water to the caprolactam to the antibacterial agent cuprous oxide is 1:0.8:1.2, and the functional powder slurry multistage grinding device is formed by connecting 3 grinding machines in series, so that the functional powder slurry with the antibacterial agent cuprous oxide content of 40 wt% and the average particle size of 0.11 mu m is obtained.
(2) Uniformly mixing the functional powder slurry prepared in the step (1), a caprolactam melt and a catalyst by a dynamic mixer, adjusting the temperature by a heat exchanger, and then entering a high-pressure hydrolysis reactor for ring-opening reaction, wherein the catalyst is phosphoric acid, the addition amount of the catalyst is 500ppm of the mass of the caprolactam melt, the addition amount of the functional powder slurry is 75% of the mass of the caprolactam melt, the temperature of the heat exchanger is 130 ℃, the reaction temperature of the ring-opening reaction is 220 ℃, the reaction pressure is 2.3MPa, and the reaction time is 60min, so as to obtain a polyamide functional master batch oligomer;
(3) removing excessive water from the polyamide functional master batch oligomer melt prepared in the step (2) through an oligomer melt dehydrator, and then, allowing the polyamide functional master batch oligomer melt to enter a normal pressure polymerization reactor for polymerization reaction, wherein the temperature of the oligomer melt dryer is 260 ℃, the retention time of materials in the oligomer melt dehydrator is 30min, the pressure is reduced from 2.3MPa to 100kPa, the reaction temperature of the polymerization reaction is 260 ℃, the reaction pressure is 100kPa, and the reaction time is 15h, so that the polyamide functional master batch melt is obtained;
(4) and (4) directly carrying out granulation molding on the polyamide functional master batch melt prepared in the step (3) after removing caprolactam monomer by a film evaporation devolatilization system to obtain the polyamide functional master batch. Wherein the multistage film evaporation device in the film evaporation devolatilization system is formed by connecting 3 film evaporators in series, the temperature of the multistage film evaporation device is 260 ℃, and the pressure is 1 kPa; the temperature of cooling water of a steam condenser of a steam condensing system in the film evaporation devolatilization system is 70 ℃, and the temperature of spray chilled water of a spray catcher of the steam condensing system is 5 ℃.
The polyamide functional master batch has the relative viscosity of 2.4, the hot water extractables content of 0.5wt percent and the filter pressing value DF of 4.8kPa.cm2/g。
Example 7
(1) Continuously conveying a functional powder slurry pre-dispersed material prepared by mixing water, caprolactam and a far infrared agent zirconium carbide to a functional powder slurry multistage grinding device for grinding and dispersing, wherein the mass ratio of the water to the caprolactam to the far infrared agent zirconium carbide is 1:0.5:1.5, and the functional powder slurry multistage grinding device is formed by connecting 2 grinding machines in series to obtain the functional powder slurry with the far infrared agent zirconium carbide content of 50 wt% and the average particle size of 0.31 mu m;
(2) uniformly mixing the functional powder slurry prepared in the step (1), a caprolactam melt and a catalyst by a dynamic mixer, adjusting the temperature by a heat exchanger, and then feeding the mixture into a high-pressure hydrolysis reactor to perform a ring-opening reaction, wherein the catalyst is phosphoric acid, the addition amount of the catalyst is 90ppm of the mass of the caprolactam melt, the addition amount of the functional powder slurry is 15% of the mass of the caprolactam melt, the temperature of the heat exchanger is 200 ℃, the reaction temperature of the ring-opening reaction is 300 ℃, the reaction pressure is 8.6MPa, and the reaction time is 10min, so as to obtain a polyamide functional master batch oligomer melt;
(3) removing excessive water from the polyamide functional master batch oligomer melt prepared in the step (2) through an oligomer melt dehydrator, and then, allowing the polyamide functional master batch oligomer melt to enter a normal pressure polymerization reactor for polymerization reaction, wherein the temperature of the oligomer melt dryer is 300 ℃, the retention time of materials in the oligomer melt dehydrator is 15min, the pressure is reduced from 8.6MPa to 100kPa, the reaction temperature of the polymerization reaction is 300 ℃, the reaction pressure is 100kPa, and the reaction time is 20h, so that the polyamide functional master batch melt is obtained;
(4) and (4) directly carrying out granulation molding on the polyamide functional master batch melt prepared in the step (3) after removing caprolactam monomer by a film evaporation devolatilization system to obtain the polyamide functional master batch. Wherein the multistage film evaporation device in the film evaporation devolatilization system is formed by connecting 3 film evaporators in series, the temperature of the multistage film evaporation device is 300 ℃, and the pressure is 6.0 kPa; the temperature of cooling water of a steam condenser of a steam condensing system in the film evaporation devolatilization system is 98 ℃, and the temperature of spray chilled water of a spray catcher of the steam condensing system is 35 ℃.
The polyamide functional master batch has the relative viscosity of 3.5, the hot water extractables content of 0.6wt percent and the filter pressing value DF of 7.7kPa.cm2/g。
Example 8
(1) Continuously conveying a functional powder slurry pre-dispersing material prepared by blending water, caprolactam and an anti-ultraviolet agent zinc oxide to a functional powder slurry multistage grinding device for grinding and dispersing, wherein the mass ratio of the water to the caprolactam to the anti-ultraviolet agent zinc oxide is 1:1:0.22, and the functional powder slurry multistage grinding device is formed by connecting 1 grinding machine in series to obtain the functional powder slurry with the anti-ultraviolet agent zinc oxide content of 10 wt% and the average particle size of 0.5 mu m;
(2) uniformly mixing the functional powder slurry prepared in the step (1), a caprolactam melt and a catalyst by a dynamic mixer, adjusting the temperature by a heat exchanger, and then entering a high-pressure hydrolysis reactor for ring-opening reaction, wherein the catalyst is phosphoric acid, the addition amount of the catalyst is 30ppm of the mass of the caprolactam melt, the addition amount of the functional powder slurry is 70% of the mass of the caprolactam melt, the temperature of the heat exchanger is 130 ℃, the reaction temperature of the ring-opening reaction is 200 ℃, the reaction pressure is 1.6MPa, and the reaction time is 90min, so as to obtain a polyamide functional master batch oligomer melt;
(3) removing excessive water from the polyamide functional master batch oligomer melt prepared in the step (2) through an oligomer melt dehydrator, and then, allowing the polyamide functional master batch oligomer melt to enter a normal pressure polymerization reactor for polymerization reaction, wherein the temperature of the oligomer melt dryer is 220 ℃, the retention time of materials in the oligomer melt dehydrator is 60min, the pressure is reduced from 1.6MPa to 100kPa, the reaction temperature of the polymerization reaction is 240 ℃, the reaction pressure is 100kPa, and the reaction time is 16h, so that a polyamide functional master batch melt is obtained;
(4) and (4) directly carrying out granulation molding on the polyamide functional master batch melt prepared in the step (3) after removing caprolactam monomer by a film evaporation devolatilization system to obtain the polyamide functional master batch. Wherein the multistage film evaporation device in the film evaporation devolatilization system is formed by connecting 2 film evaporators in series, the temperature of the multistage film evaporation device is 260 ℃, and the pressure is 3.0 kPa; the temperature of cooling water of a steam condenser of a steam condensing system in the film evaporation devolatilization system is 98 ℃, and the temperature of spray chilled water of a spray catcher of the steam condensing system is 20 ℃.
The polyamide functional master batch has the relative viscosity of 2.0, the content of hot water extractables of 1.5wt percent and the filter pressing value DF of 21.6kPa.cm2/g。
Example 9
(1) Continuously conveying a functional powder slurry pre-dispersed material prepared by mixing water, caprolactam and mica serving as a heat conducting agent to a functional powder slurry multistage grinding device for grinding and dispersing, wherein the mass ratio of the water to the caprolactam to the mica serving as the heat conducting agent is 1:0.8:1.8, and the functional powder slurry multistage grinding device is formed by connecting 2 grinding machines in series to obtain the functional powder slurry with the heat conducting agent mica content of 50 wt% and the average particle size of 0.43 mu m;
(2) uniformly mixing the functional powder slurry prepared in the step (1), a caprolactam melt and a catalyst by a dynamic mixer, adjusting the temperature by a heat exchanger, and then entering a high-pressure hydrolysis reactor for ring-opening reaction, wherein the catalyst is phosphoric acid, the addition amount of the catalyst is 90ppm of the mass of the caprolactam melt, the addition amount of the functional powder slurry is 78% of the mass of the caprolactam melt, the temperature of the heat exchanger is 160 ℃, the reaction temperature of the ring-opening reaction is 260 ℃, the reaction pressure is 4.7MPa, and the reaction time is 30min, so as to obtain a polyamide functional master batch oligomer melt;
(3) removing excessive water from the polyamide functional master batch oligomer melt prepared in the step (2) through an oligomer melt dehydrator, and then, allowing the polyamide functional master batch oligomer melt to enter a normal pressure polymerization reactor for polymerization reaction, wherein the temperature of the oligomer melt dryer is 260 ℃, the retention time of materials in the oligomer melt dehydrator is 30min, the pressure is reduced from 4.7MPa to 100kPa, the reaction temperature of the polymerization reaction is 280 ℃, the reaction pressure is 100kPa, and the reaction time is 20h, so that a polyamide functional master batch melt is obtained;
(4) and (4) directly carrying out granulation molding on the polyamide functional master batch melt prepared in the step (3) after removing caprolactam monomer by a film evaporation devolatilization system to obtain the polyamide functional master batch. Wherein the multistage film evaporation device in the film evaporation devolatilization system is formed by connecting 2 film evaporators in series, the temperature of the multistage film evaporation device is 280 ℃, and the pressure is 2.0 kPa; the temperature of cooling water of a steam condenser of a steam condensing system in the film evaporation devolatilization system is 98 ℃, and the temperature of spray chilled water of a spray catcher of the steam condensing system is 15 ℃.
The polyamide functional master batch has the relative viscosity of 2.8, the hot water extractables content of 0.9wt percent and the filter pressing value DF of 30kPa.cm2/g。
Example 10
(1) Continuously conveying a functional powder slurry pre-dispersed material prepared by mixing water, caprolactam and a heat conducting agent aluminum nitride to a functional powder slurry multistage grinding device for grinding and dispersing, wherein the mass ratio of the water to the caprolactam to the heat conducting agent aluminum nitride is 1:1:3, and the functional powder slurry multistage grinding device is formed by connecting 5 grinding machines in series to obtain the functional powder slurry with the heat conducting agent aluminum nitride content of 60 wt% and the average particle size of 0.15 mu m;
(2) uniformly mixing the functional powder slurry prepared in the step (1), a caprolactam melt and a catalyst by a dynamic mixer, adjusting the temperature by a heat exchanger, and then feeding the mixture into a high-pressure hydrolysis reactor to perform a ring-opening reaction, wherein the catalyst is metaphosphoric acid, the addition amount of the catalyst is 1500ppm of the mass of the caprolactam melt, the addition amount of the functional powder slurry is 250% of the mass of the caprolactam melt, the temperature of the heat exchanger is 180 ℃, the reaction temperature of the ring-opening reaction is 250 ℃, the reaction pressure is 4.0MPa, and the reaction time is 30min, so as to obtain a polyamide functional master batch oligomer melt;
(3) removing excessive water from the polyamide functional master batch oligomer melt prepared in the step (2) through an oligomer melt dehydrator, and then, allowing the polyamide functional master batch oligomer melt to enter a normal pressure polymerization reactor for polymerization reaction, wherein the temperature of the oligomer melt dryer is 220 ℃, the retention time of materials in the oligomer melt dehydrator is 60min, the pressure is reduced from 4.0MPa to 100kPa, the reaction temperature of the polymerization reaction is 225 ℃, the reaction pressure is 100kPa, and the reaction time is 20h, so that the polyamide functional master batch melt is obtained;
(4) and (4) directly carrying out granulation molding on the polyamide functional master batch melt prepared in the step (3) after removing caprolactam monomer by a film evaporation devolatilization system to obtain the polyamide functional master batch. Wherein the multistage film evaporation device in the film evaporation devolatilization system is formed by connecting 1 film evaporator in series, the temperature of the multistage film evaporation device is 225 ℃, and the pressure is 0.6 kPa; the temperature of cooling water of a steam condenser of a steam condensing system in the film evaporation devolatilization system is 68 ℃, and the temperature of spray chilled water of a spray catcher of the steam condensing system is 0 ℃.
The polyamide functional master batch has the relative viscosity of 1.5, the hot water extractables content of 5wt percent and the filter pressing value DF of 8.9kPa.cm2/g。
Comparative example 1
The polyamide chips and pigment blue 15:3 are uniformly mixed by a high-speed mixer according to the mass ratio of 7.5:2.5, then are subjected to melt mixing by a double-screw extruder at the temperature of 260 ℃, and are extruded and granulated to obtain the polyamide functional master batch. The polyamide functional master batch has the relative viscosity of 2.0, the hot water extractables content of 0.9wt percent and the filter pressing value DF of38.6kPa.cm2/g。
The polyamide functional masterbatch prepared in the above examples 1 to 10 and comparative example 1 were subjected to performance tests, the test items are as follows: average particle size (μm) of functional powder in the functional powder slurry, test method: testing by using a dynamic light scattering particle size analyzer; the relative viscosity of the polyamide functional master batch is tested by the following method: refer to FZ/T51004-2011; the testing method comprises the following steps: refer to FZ/T51004-2011; pressure filtration value DF (kPa.cm) of polyamide functional master batch2,/g), test method: the test mixture is composed of the functional master batches with the weight of m1 and polyamide 6 with the weight of m2, the total weight of the test mixture is 4000g, and the content of the functional powder in the test mixture is 100 g; comprises a single screw extruder with the length-diameter ratio of phi 25mm multiplied by 25D, a melt metering pump with the volume of 1.2cc, a melt pressure sensor and a filter screen with the area S of 3.8cm2The four layers of combined filter screens of 60-100-; the filter pressing performance test process conditions are as follows: the melt temperature is 270 ℃, the pressure set value before the melt metering pump is 6.5MPa, and the metering flow of the melt metering pump is 38 g/min; firstly, 500g of polyamide 6 is extruded from a filter pressing performance tester, the recorded equilibrium pressure is the initial pressure Ps, then 4000g of test mixture is extruded from the filter pressing performance tester, then 500g of polyamide 6 is extruded from the filter pressing performance tester, the recorded equilibrium pressure is the termination pressure PT, and finally, according to the formula:
and calculating to obtain a filter pressing value DF. The test results are shown in Table 1.
As can be seen from the data in Table 1, the pressure filtration values DF of the polyamide functional master batches prepared by the method for continuously producing the polyamide functional master batches of the invention are not allHigher than 30kPa.cm2And the pressure filtration value is lower than that of the polyamide functional master batch prepared by adopting a melt blending method, which shows that the polyamide functional master batch prepared by the method for continuously producing the polyamide functional master batch has higher functional powder dispersion uniformity.
The polyamide functional master batches prepared in the embodiment 1 and the comparative example 1 of the invention adopt the same additive amount of pigment blue 15:3, but the pigment blue 15:3 in the embodiment 1 is added into caprolactam melt in the form of continuously prepared functional powder slurry, and the polyamide functional master batches are prepared by ring opening reaction, polymerization reaction, film evaporation devolatilization treatment and grain cutting and forming; in the comparative example 1, the pigment blue 15:3 is directly and uniformly mixed with the polyamide slices, and then the mixture is subjected to melt blending and extrusion granulation by a double-screw extruder to prepare the polyamide functional master batch. In the process of preparing the polyamide functional master batch by the melt blending method, the dispersion of the functional powder in the high-viscosity polyamide melt is mainly realized by the mechanical shearing force provided by the mixing equipment, so that the high uniform dispersion of the functional powder particles in the polyamide melt is difficult to realize, and the dispersion uniformity of the functional powder particles in the prepared polyamide functional master batch is poor. The functional powder slurry is prepared by adopting a grinder, and under the high-speed operation of a disperser of the grinder, the grinding medium of the grinder generates strong collision, friction and shearing actions with solid functional powder particles, so that the functional powder is efficiently and uniformly dispersed in a caprolactam water solution in a small scale. The polyamide functional master batch with highly uniformly dispersed functional powder particles is prepared by efficiently mixing the functional powder slurry and caprolactam melt through a dynamic mixer, and then performing ring opening reaction, polymerization reaction, film evaporation devolatilization treatment and granulation molding, so that the agglomeration of pigment blue 15:3 particles in the preparation process of the polyamide functional master batch is effectively reduced. The pressure filtration value DF of the polyamide functional master batch in the example 1 is 7.6kPa.cm2Compared with the pressure filtration value DF of the polyamide functional master batch in the comparative example 1, the pressure filtration value is 38.6kPa.cm2/g。
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (11)
1. A method for continuously producing polyamide functional master batches is characterized by comprising the following steps:
(1) continuously conveying a functional powder slurry pre-dispersing material prepared by mixing water, caprolactam and functional powder to a functional powder slurry multistage grinding device for grinding and dispersing to obtain functional powder slurry, wherein the mass ratio of the water to the caprolactam to the functional powder is (0.5-1) to (0.22-3);
(2) uniformly mixing the functional powder slurry prepared in the step (1), a caprolactam melt and a catalyst by a dynamic mixer, adjusting the temperature by a heat exchanger, and then allowing the mixture to enter a high-pressure hydrolysis reactor for ring opening reaction to obtain a polyamide functional master batch oligomer melt, wherein the addition amount of the catalyst is 30-1500 ppm of the mass of the caprolactam melt, and the catalyst is protonic acid; the addition amount of the functional powder slurry is 15-250 wt% of the mass of the caprolactam melt; the reaction temperature of the ring-opening reaction is 200-300 ℃, the reaction pressure is 1.6-8.6 MPa, and the reaction time is 10-90 min;
(3) removing excessive water from the polyamide functional master batch oligomer melt prepared in the step (2) through an oligomer melt dehydrator, and then allowing the polyamide functional master batch oligomer melt to enter an atmospheric polymerization reactor for polymerization reaction to obtain a polyamide functional master batch melt;
(4) and (4) directly granulating and forming the polyamide functional master batch melt prepared in the step (3) after removing caprolactam monomers by a film evaporation devolatilization system to obtain the polyamide functional master batch.
2. The method for continuously producing polyamide functional masterbatch according to claim 1, wherein in the step (1), the functional powder slurry multi-stage grinding device is formed by connecting 1-5 grinding machines in series.
3. The method for continuously producing polyamide functional masterbatch according to claim 1, wherein in the step (2), the high-pressure hydrolysis reactor is a tower reactor with a built-in mixing unit, and the materials flow in a plug flow manner from bottom to top.
4. The method for continuously producing polyamide functional masterbatch according to claim 1, wherein in the step (5), the thin film evaporation devolatilization system is composed of a multi-stage thin film evaporation device and a steam condensation system.
5. The method for continuously producing the polyamide functional masterbatch according to claim 4, wherein the multistage thin film evaporation device is formed by connecting 1-3 thin film evaporators in series; the vapor condensing system includes a vapor condenser and a spray trap.
6. The method for continuously producing a polyamide functional masterbatch according to claim 1, wherein in the step (1), the average particle diameter of the functional powder in the functional powder slurry is not higher than 0.5 μm.
7. The method for continuously producing the polyamide functional masterbatch according to claim 1, wherein in the step (2), the temperature of the heat exchanger is 130-200 ℃.
8. The method for continuously producing the polyamide functional masterbatch according to claim 1, wherein in the step (3), the temperature of the oligomer melt dehydrator is 220 to 300 ℃, the retention time of the materials in the oligomer melt dehydrator is 15 to 60min, and the pressure is reduced from 1.6 to 8.6MPa to 100 kPa.
9. The method for continuously producing the polyamide functional masterbatch according to claim 1, wherein in the step (3), the reaction temperature of the polymerization reaction is 225 to 300 ℃, the reaction pressure is 100kPa, and the reaction time is 10 to 20 hours.
10. The method for continuously producing the polyamide functional masterbatch according to claim 1, wherein in the step (4), the temperature of the multi-stage thin film evaporation device in the thin film evaporation devolatilization system is 225 to 300 ℃, and the pressure is 0.6 to 6 kPa; the temperature of cooling water of a steam condenser of a steam condensing system in the film evaporation devolatilization system is 68-98 ℃; the temperature of the spray chilled water of the spray catcher of the steam condensing system in the film evaporation devolatilization system is 0-35 ℃.
11. The polyamide functional masterbatch is characterized by being prepared by the method for continuously producing the polyamide functional masterbatch according to any one of claims 1 to 10, wherein the polyamide functional masterbatch has a relative viscosity of 1.5-3.5, a hot water extractables content of not higher than 5%, and a filter pressing value DF of not higher than 30kPa.cm2/g。
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| CN101905492A (en) * | 2010-07-19 | 2010-12-08 | 广东新会美达锦纶股份有限公司 | Method for producing functional nylon-6 slice |
| CN102464799A (en) * | 2010-11-15 | 2012-05-23 | 中国水产科学研究院东海水产研究所 | Coloring method of nylon-6 by using liquid coloring technology |
| JP2014501309A (en) * | 2010-12-28 | 2014-01-20 | シャンハイ ジーニアス アドバンスド マテリアル（グループ） カンパニー リミテッド | Nanoparticle / polyamide composite material, preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101905492A (en) * | 2010-07-19 | 2010-12-08 | 广东新会美达锦纶股份有限公司 | Method for producing functional nylon-6 slice |
| CN102464799A (en) * | 2010-11-15 | 2012-05-23 | 中国水产科学研究院东海水产研究所 | Coloring method of nylon-6 by using liquid coloring technology |
| JP2014501309A (en) * | 2010-12-28 | 2014-01-20 | シャンハイ ジーニアス アドバンスド マテリアル（グループ） カンパニー リミテッド | Nanoparticle / polyamide composite material, preparation method and application thereof |
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