CN112851955B - Organic metal hybrid nucleating agent and preparation method and application thereof - Google Patents

Organic metal hybrid nucleating agent and preparation method and application thereof Download PDF

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CN112851955B
CN112851955B CN202011562657.9A CN202011562657A CN112851955B CN 112851955 B CN112851955 B CN 112851955B CN 202011562657 A CN202011562657 A CN 202011562657A CN 112851955 B CN112851955 B CN 112851955B
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nucleating agent
hybrid nucleating
solvent
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CN112851955A (en
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荀子敬
余若冰
刘修才
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East China University of Science and Technology
Cathay R&D Center Co Ltd
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Cathay R&D Center Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/24—Crystallisation aids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention relates to an organic metal hybrid nucleating agent and a preparation method and application thereof, and the preparation method comprises the following steps: respectively drying the metal salt and the organic ligand, and grinding into powder; adding metal salt into a solvent for ultrasonic dissolution to obtain a solution A, adding an organic ligand into the solvent for ultrasonic dissolution to obtain a solution B, and uniformly mixing the A, B solution; magnetically stirring and reacting for 12-42 h at the temperature of 20-160 ℃, wherein the magnetic stirring speed is 600-4000 r/min; and (3) carrying out ultrasonic-assisted dispersion, vacuum filtration and centrifugal washing on the product, drying at 50-95 ℃ for 6-24 h, and carrying out reduced pressure activation at 150-190 ℃ for 12-24 h. Compared with the prior art, the invention introduces metal ions to form coordination bonding with amide groups aiming at the molecular structure that nylon 56 can only form partial hydrogen bonds, and the organic frame part provides surface dents to accommodate the molecular chains of polyamide 56, thereby promoting nucleation, having high nucleation efficiency and improving the physical properties of the material PA 56.

Description

Organic metal hybrid nucleating agent and preparation method and application thereof
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to an organic metal hybrid nucleating agent, and a preparation method and application thereof.
Background
Polyamide, namely nylon, is an engineering plastic with excellent performance, has high mechanical strength, high softening point, wear resistance, heat resistance and good electrical insulation, can keep stronger strength and rigidity at higher temperature, and is widely applied to the fields of automobiles, electronics and electrics, packaging, aerospace and the like.
At present, nylon mainly comprises two varieties of nylon 6 and nylon 66, which are mainly synthesized by petroleum base, but the gradual exhaustion of petroleum resources and the gradual rise of environmental protection problems limit the development of nylon materials, and bio-based materials become new choices. Since the bio-based nylon 56 is obtained by polymerizing pentamethylenediamine and adipic acid, and the pentamethylenediamine is obtained from L-lysine produced by biological fermentation, the bio-based forty-one percent bio-based nylon 56 produced from pentamethylenediamine as a raw material attracts attention as a new nylon variety.
As can be seen from the molecular chain diagram of nylon 56 (fig. 2): because 100% of hydrogen bonds cannot be formed between amide groups of macromolecules of PA56, the crystallinity of PA56 is lower than that of conventional nylon 6 and nylon 66, and the use of bio-based PA56 in the field of engineering plastics is limited. In order to improve the physical properties of the PA56 material, increasing the crystallization rate and degree, the most effective way is to add nucleating agents.
Currently used polyamide nucleating agents can be classified into two types: inorganic nucleating agents and organic nucleating agents.
The inorganic type nucleating agent is the most used nucleating agent. The clay is mainly divided into two types, wherein the clay comprises montmorillonite, kaolin, talcum powder and the like; the oxides include SiO 2 、MgO、ZnO、Al 2 O 3 、ZrO 2 The nucleating agent has wide sources and low price, but can affect the light transmission and the glossiness of the product, has poor compatibility and affects the crystallization effect;
the organic nucleating agent mainly comprises high molecular substances such as polycarbonate, polyarylethersulfone and the like, does not affect the transparency and the glossiness, but has higher price and general nucleating efficiency.
Therefore, how to provide a nucleating agent with high nucleating efficiency, which can improve the processing performance of PA56 and improve the mechanical performance of PA56 becomes a problem to be solved by the industry.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an organic metal hybrid nucleating agent, a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme: a preparation method of an organic metal hybrid nucleating agent comprises the following steps:
s100, respectively drying the metal salt and the organic ligand at 20 ℃ for 2h, and grinding into powder particles;
s200, adding metal salt into a solvent for ultrasonic dissolution to obtain a solution A, adding an organic ligand into the solvent for ultrasonic dissolution to obtain a solution B, and uniformly mixing A, B solutions;
s300, performing magnetic stirring for 2 hours at the temperature of 20 ℃, then heating to 25-160 ℃ for reaction for 12-40 hours, wherein the magnetic stirring speed is 600-4000 r/min;
s400, drying the product for 6-24 hours at 50-95 ℃ after ultrasonic-assisted dispersion, vacuum filtration and centrifugal washing, and activating the product for 12-24 hours at 150-190 ℃ under reduced pressure.
Further, the metal salt is one or more of cobalt nitrate hexahydrate, nickel acetate tetrahydrate, zinc nitrate hexahydrate, magnesium chloride hexahydrate, magnesium nitrate hexahydrate, aluminum chloride hexahydrate, ferric chloride hexahydrate and copper chloride.
Further, the organic ligand is at least one of terephthalic acid, dihydroxy terephthalic acid, trimesic acid, 2-methylimidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 3-amino-1, 2, 3-triazole, glycine, lactic acid, ethylene diamine tetraacetic acid and adipic acid.
Further, in step S200, the solvent is at least one of deionized water, methanol, ethanol, isopropanol, tetrahydrofuran, acetone, N-dimethylformamide, and N, N-dimethylacetamide.
Preferably, the metal salt is zinc nitrate hexahydrate, the organic ligand is 2-methylimidazole, and the organic solvent is a methanol solvent.
Further, in the step S200, the mass-to-volume ratio of the metal salt to the solvent in the solution a is 1 g: 20ml to 80ml, wherein the mass volume ratio of the organic ligand to the solvent in the solution B is 1 g: 10 ml-70 ml, wherein the mass ratio of the metal salt to the organic ligand is 1: 0.5 to 5.
The reaction temperature in the step S300 is 25-100 ℃; the magnetic stirring speed is 1200 r/min-3200 r/min, and the reaction time is 12 h-30 h. Preferably, the reaction temperature is 20-35 ℃; the magnetic stirring speed is 1200 r/min-2400 r/min, and the reaction time is 12 h-28 h; further preferably, the reaction temperature is 20-35 ℃; the magnetic stirring speed is 1200 r/min-2400 r/min, and the reaction time is 12 h-28 h.
Preferably, the ultrasonic-assisted dispersion time in step S400 is 40min, the number of centrifugal washing times is 2-6 (preferably 5), the drying temperature is 60 ℃, and the drying time is 12 h.
The organic metal hybrid nucleating agent is prepared by adopting the method.
The application of the organic metal hybrid nucleating agent is to act on the preparation of nylon 56, wherein the content of the organic metal hybrid nucleating agent in the nylon 56 is 0.001% -5%.
The application method specifically comprises the following steps: and drying the organic metal hybrid nucleating agent and the PA56, then blending, adding other auxiliaries, and carrying out extrusion granulation in an extruder to obtain the PA56 material with high crystallization rate.
The other auxiliary agents comprise one or more of an antioxidant, a weather resisting agent, a flame retardant, a filler, a toner and a reinforcing fiber;
the extrusion temperature of the extruder is 265 ℃, and the extrusion rotating speed is 100 r/min.
Compared with the prior art, the invention has the following advantages and effects:
(1) the invention is applied to the processing field of polyamide materials, has simple preparation process and low production cost, and is suitable for industrial mass production;
(2) according to the invention, only a partial hydrogen bond molecular structure can be formed on nylon 56, metal ions are introduced to form coordinate bonding with amide groups, the organic frame part provides surface dents to contain polyamide 56 molecular chains, thus nucleation is promoted, the nucleation efficiency is high, the physical properties of the PA56 material can be improved, and the prepared PA56 organic metal hybrid nucleating agent has the characteristics of small addition amount and obvious nucleation effect;
(3) the PA56 organometallic hybrid nucleating agent prepared by the invention can improve the crystallinity of the PA56 material and the crystallization rate of the PA56 material;
(4) the nucleating effect of the prepared PA56 organometallic hybrid nucleating agent on a bio-based PA56 material is superior to that of a traditional inorganic nano silicon dioxide nucleating agent;
(5) the PA56 organometallic hybrid nucleating agent prepared by the invention has better nucleating effect on the bio-based PA56 material than the commercial organic nucleating agent.
Drawings
FIG. 1 is a flow chart of the preparation of PA56 organic metal hybrid material nucleating agent;
FIG. 2 is a molecular chain diagram of bio-based nylon 56;
FIG. 3 is an SEM image of an organometallic hybrid nucleating agent of example 3;
FIG. 4 is a DSC of 210 ℃ isothermal crystallization of application example 3 and application comparative example;
FIG. 5 is a DSC of 214 ℃ isothermal crystallization of application example 3 and application comparative example;
FIG. 6 is a DSC of isothermal crystallization at 218 ℃ of application example 3 and application comparative example;
FIG. 7 is a DSC of 210 ℃ isothermal crystallization of application example 4 and application comparative example;
FIG. 8 is a DSC of 214 ℃ isothermal crystallization of application example 4 and application comparative example;
FIG. 9 is a DSC of isothermal crystallization at 218 ℃ of application example 4 and application comparative example;
FIG. 10 is a graph of temperature-crystallinity of 5 ℃/min non-isothermal crystallization process for application example 4 and application comparative example;
FIG. 11 is a graph of 10 ℃/min non-isothermal crystallization process temperature versus crystallinity for application example 4 and application comparative example.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
As shown in FIG. 1, the preparation method of the PA56 organometallic hybrid material nucleating agent comprises the following steps:
s100, respectively drying the metal salt and the organic ligand for 2 hours at the temperature of 20 ℃, and grinding the metal salt and the organic ligand into fine particles with the particle size of 0.1 mm;
s200, ultrasonically dissolving metal salt in a solvent to obtain a solution A, adding an organic ligand into the solvent to ultrasonically dissolve the metal salt to obtain a solution B, and uniformly mixing A, B solutions;
s300, performing magnetic stirring for 2 hours at the temperature of 20 ℃, then heating to 25-160 ℃ for reaction for 12-40 hours, wherein the magnetic stirring speed is 600-4000 r/min;
s400, drying the product for 6-24 h at 50-95 ℃ after ultrasonic-assisted dispersion, vacuum filtration and centrifugal washing for 2-6 times, and activating for 12-24h at 150-190 ℃ under reduced pressure.
The resulting nucleating agent was used in the production of PA56, comprising the following steps:
1) weighing an organic metal hybrid nucleating agent and PA56 with a certain mass fraction, and drying in a vacuum oven at 80 ℃ for 12 hours for subsequent use;
2) blending the pre-treated material obtained in the step 1) with an organic metal hybrid nucleating agent and PA56, and then extruding and granulating in an extruder; the extrusion temperature is 265 ℃, the extrusion rotating speed is 100r/min, and the PA56 material with high crystallization rate can be obtained.
The specific embodiment is as follows:
example 1
Preparation of organic metal hybrid nucleating agent by liquid phase stirring method
A preparation method of the PA56 organometallic hybrid nucleating agent comprises the following steps:
s100, respectively drying zinc nitrate hexahydrate and 2-methylimidazole at 20 ℃ for 2 hours, and grinding into fine particles with the particle size of 0.1 mm;
s200, weighing 1.5g of zinc nitrate hexahydrate, and dissolving the zinc nitrate hexahydrate in 70ml of N, N-dimethylformamide solvent to obtain a solution A. 3.5g of 2-methylimidazole was weighed out and dissolved in 85ml of methanol solvent to obtain a B solution.
S300, uniformly mixing the A, B solution, and carrying out magnetic stirring at the temperature of 20 ℃, wherein the magnetic stirring speed is 2200r/min, and the reaction time is 20 h;
s300, performing magnetic stirring for 2 hours at the temperature of 20 ℃, then heating to 25 ℃ for reaction for 20 hours, wherein the magnetic stirring speed is 2200 r/min;
s400, dispersing the product for 40min with the aid of ultrasound, centrifuging and washing for 5 times, drying at 60 ℃ for 12h, and activating at 150 ℃ under reduced pressure for 8h to obtain the organic metal hybrid nucleating agent which is marked as Zn 1.5/3.5 -T 25 n 2200 t 20 。
Example 2
Preparation of organic metal hybrid nucleating agent by liquid phase stirring method
A preparation method of the PA56 organometallic hybrid nucleating agent comprises the following steps:
the difference from example 1 is that magnetic stirring is carried out at 30 ℃ and the nucleating agent is noted as Zn 1.5/3.5 -T 30 n 2200 t 20 。
Example 3
Preparation of organic metal hybrid nucleating agent by liquid phase stirring method
A preparation method of the PA56 organometallic hybrid nucleating agent comprises the following steps:
the difference from example 1 is that magnetic stirring is carried out at 35 ℃ and the nucleating agent is noted as Zn 1.5/3.5 -T 35 n 2200 t 20 . As shown in FIG. 3, which is an SEM image of the organometallic hybrid nucleating agent, it can be seen that the particle size is uniform and the minimum particle size is around 70 nm.
The nucleating agents prepared in examples 1 to 3 were used in the production of PA56, and the specific application examples are as follows:
comparative application
1) 1000g of bio-based nylon 56 was placed in a vacuum oven at 80 ℃ for 12 hours for subsequent use;
2) extruding 1000g of bio-based nylon 56 of the pretreatment material obtained in the step 1) in an extruder for granulation; the extrusion temperature is 265 ℃, the extrusion rotating speed is 100r/min, and the PA56 material with high crystallization rate can be obtained.
Application example 1
The organometallic hybrid nucleating agent prepared in the embodiment 1 is applied to the processing process of PA56, and the specific processing process is as follows:
1) 1000g of bio-based nylon 56 and 3g of PA56 organometallic hybrid material nucleating agent are placed in a vacuum oven for drying for 12 hours at 80 ℃ for subsequent use;
2) blending 1000g of bio-based nylon 56 obtained in the step 1) and 3g of organic metal hybrid nucleating agent, and then extruding and granulating in an extruder; the extrusion temperature is 265 ℃, the extrusion rotating speed is 100r/min, and the PA56 material with high crystallization rate can be obtained.
Application example 2
The organometallic hybrid nucleating agent prepared in the embodiment 1 is applied to the processing process of PA56, and the specific processing process is as follows:
1) 1000g of bio-based nylon 56 and 5g of PA56 organometallic hybrid material nucleating agent are placed in a vacuum oven for drying for 12 hours at 80 ℃ for subsequent use;
2) blending 1000g of bio-based nylon 56 obtained in the step 1) and 5g of organic metal hybrid nucleating agent, and then extruding and granulating in an extruder; the extrusion temperature is 265 ℃, the extrusion rotating speed is 100r/min, and the PA56 material with high crystallization rate can be obtained.
Application example 3
The organometallic hybrid nucleating agent prepared in the example 2 is applied to the process of PA56, and the specific process is the same as that of the application example 1.
Application example 4
The organometallic hybrid nucleating agent prepared in the embodiment 2 is applied to the processing of PA56, and the specific processing is the same as that of the application example 2.
Application example 5
The organometallic hybrid nucleating agent prepared in the embodiment 3 is applied to the processing of PA56, and the specific processing is the same as that of the application example 1.
Application example 6
The organometallic hybrid nucleating agent prepared in the embodiment 3 is applied to the processing of PA56, and the specific processing is the same as that of the application example 2.
FIG. 4 is a DSC of 210 ℃ isothermal crystallization of application example 3 and application comparative example, and it can be seen that example 3 as a nucleating agent increases the crystallization rate of PA56 at 210 ℃;
FIG. 5 is a DSC of 214 ℃ isothermal crystallization of application example 3 and application comparative example, and it can be seen that example 3 as a nucleating agent increases the crystallization rate of PA56 at 214 ℃;
FIG. 6 is a DSC of 218 ℃ isothermal crystallization of application example 3 and application comparative example, and it can be seen that example 3 as a nucleating agent increases the crystallization rate of PA56 at 218 ℃.
TABLE 1 influence of different reaction temperatures on the semi-crystallization time and the degree of crystallization
Figure BDA0002859756530000071
The semi-crystallization time is the time until the crystallization process of the polymer material is performed to half, and the semi-crystallization time is usually used to express the speed of the crystallization rate. The shorter the semi-crystallization time, the faster the crystallization rate.
The crystallinity is an important index for measuring the crystallization performance of semi-crystalline polymers and is measured by a differential scanning calorimeter. The crystallinity is expressed by the following formula:
Figure BDA0002859756530000072
in the formula: Δ H 0 -PA 56 standard enthalpy of crystallization, 188.68J/g;
ΔH mc -enthalpy of melt crystallization per gram of PA56 system.
In summary, it can be seen from the results of the comparative examples and the application examples 1-6 in Table 1 that the organometallic hybrid nucleating agents obtained in the reaction temperature ranges of 25 ℃ to 35 ℃ in the examples 1, 2 and 3 can accelerate the crystallization rate of PA56 and improve the crystallinity. The relatively high and low temperatures alter the crystallization rate and crystallinity of the metal organic framework material, further affecting surface area and particle size.
Example 4
Liquid phase stirring method for preparing nucleating agent
A preparation method of the PA56 organometallic hybrid nucleating agent comprises the following steps:
s100, respectively drying cobalt nitrate hexahydrate and 2-methylimidazole at 20 ℃ for 2 hours, and grinding into fine particles with the particle size of 0.1 mm;
s200, weighing 1g of cobalt nitrate hexahydrate, and dissolving the cobalt nitrate hexahydrate in 70ml of N, N-dimethylacetamide solvent to obtain a solution A. 3g of 2-methylimidazole was weighed and dissolved in 85ml of methanol solvent to obtain a B solution.
S300, performing magnetic stirring for 2 hours at the temperature of 20 ℃, then heating to 25 ℃ for reaction for 30 hours, wherein the magnetic stirring speed is 2000 r/min;
s400, assisting the product by ultrasoundDispersing for 40min, centrifuging and washing for 5 times, drying at 60 deg.C for 12h, and activating at 150 deg.C under reduced pressure for 8h to obtain the organic metal hybrid nucleating agent marked as Co 1/3 -T 25 n 2000 t 30 。
Example 5
The magnetic stirring speed is 2400r/min, other preparation conditions and adsorption experiments are the same as those of the example 4, and the obtained nucleating agent is recorded as Co 1/3 -T 25 n 2400 t 30 。
Application example 7
The organometallic hybrid nucleating agent prepared in the embodiment 4 is applied to the process of PA56, and the specific process is the same as that of the application example 1.
Application example 8
The organometallic hybrid nucleating agent prepared in the embodiment 4 is applied to the processing of PA56, and the specific processing is the same as that of the application example 2.
Application example 9
The organometallic hybrid nucleating agent prepared in the example 5 is applied to the process of PA56, and the specific process is the same as that of the application example 1.
Application example 10
The organometallic hybrid nucleating agent prepared in the example 5 is applied to the processing of PA56, and the specific processing is the same as that of the application example 2.
FIG. 7 is a DSC of 210 ℃ isothermal crystallization of application example 4 and application comparative example, and it can be seen that example 4 as a nucleating agent increases the crystallization rate of PA56 at 210 ℃;
FIG. 8 is a DSC of 214 ℃ isothermal crystallization of application example 4 and application comparative example, and it can be seen that example 4 as a nucleating agent increases the crystallization rate of PA56 at 214 ℃;
FIG. 9 is a DSC of 218 ℃ isothermal crystallization of application example 4 and application comparative example, and it can be seen that example 4 as a nucleating agent increases the crystallization rate of PA56 at 218 ℃;
FIG. 10 is a temperature-crystallinity graph of 5 ℃/min non-isothermal crystallization process for application example 4 and application comparative example, and it can be seen that example 4 as a nucleating agent increases the crystallization rate of PA56 at a cooling rate of 5 ℃/min;
FIG. 11 is a graph of 10 ℃/min non-isothermal crystallization process temperature versus crystallinity for application example 4 and application comparative example, and it can be seen that example 4 acts as a nucleating agent increasing the crystallization rate of PA56 at a cooling rate of 10 ℃/min.
TABLE 2 influence of different stirring rates on the semi-crystallization time and the degree of crystallization
Group of Reaction temperature (. degree.C.) Stirring speed (r/min) Mixing time (h)
Example 4 25 2000 30
Example 5 25 2400 30
TABLE 3 influence of different stirring rates on the semi-crystallization time and the degree of crystallization
Figure BDA0002859756530000091
As can be seen from the data in Table 3, the change in the magnetic stirring rate during the reaction process affects the influence of the organometallic hybrid nucleating agent on the crystallization half-time and crystallinity of PA 56. The magnetic stirring speed influences the contact probability of the metal center and the organic ligand, and further influences the coordination of the metal-organic framework material, so that the bonding effect of the surface functional group of the metal-organic framework material and the PA56 amide group is finally influenced.
Example 6
Liquid phase stirring method for preparing nucleating agent
A preparation method of the PA56 organometallic hybrid nucleating agent comprises the following steps:
s100, respectively drying nickel acetate tetrahydrate and dihydroxy terephthalic acid at 20 ℃ for 2 hours, and grinding into fine particles with the particle size of 0.1 mm;
s200, weighing 2.5g of nickel acetate tetrahydrate, and dissolving the nickel acetate tetrahydrate in 70ml of deionized water to obtain a solution A. 2g of dihydroxyterephthalic acid was weighed and dissolved in 85ml of tetrahydrofuran solvent to obtain a B solution.
S300, performing magnetic stirring for 2 hours at the temperature of 20 ℃, then heating to 100 ℃ for reaction for 24 hours, wherein the magnetic stirring speed is 2500 r/min;
s400, dispersing the product for 40min with the aid of ultrasonic waves, centrifugally washing for 5 times, drying at 60 ℃ for 12h, and activating at 150 ℃ under reduced pressure for 8h to obtain the organic metal hybrid nucleating agent which is marked as Ni 2.5/2 -T 100 n 2500 t 24 。
Example 7
Liquid phase stirring method for preparing nucleating agent
The preparation method of the organic metal hybrid nucleating agent comprises the following steps:
the reaction time was 30h, the other preparation conditions were the same as in example 6, and the resulting adsorbent was denoted Ni 2.5/2 -T 100 n 2500 t 30 。
Application example 11
The organometallic hybrid nucleating agent prepared in the embodiment 6 is applied to the processing of PA56, and the specific processing is the same as that of the application example 1.
Application example 12
The organometallic hybrid nucleating agent prepared in the embodiment 6 is applied to the processing of PA56, and the specific processing is the same as that of the application example 2.
Application example 13
The organometallic hybrid nucleating agent prepared in the embodiment 7 is applied to the process of PA56, and the specific process is the same as that of the application example 1.
Application example 14
The organometallic hybrid nucleating agent prepared in the example 7 is applied to the process of PA56, and the specific process is the same as that of the application example 2.
TABLE 4 influence of different stirring times on the semi-crystallization time and the degree of crystallization
Group of Reaction temperature (. degree.C.) Stirring speed (r/min) Mixing time (h)
Example 6 100 2500 24
Example 7 100 2500 30
TABLE 5 influence of different stirring times on the semi-crystallization time and the degree of crystallization
Figure BDA0002859756530000101
As can be seen from the data in Table 5, the influence of the organometallic hybrid nucleating agent on the crystallization half time and the crystallinity of PA56 can be influenced by the change of the magnetic stirring time during the reaction process.
Example 8
A preparation method of a PA56 organic metal hybrid material nucleating agent comprises the following steps:
s100, respectively drying metal salt copper chloride and organic ligand lactic acid for 2 hours at 20 ℃, and grinding into fine particles with the particle size of 0.1 mm;
s200, ultrasonically dissolving metal salt in solvent deionized water to obtain a mixture with the mass-volume ratio of 1 g: adding an organic ligand into solvent deionized water, and performing ultrasonic dissolution to obtain a solution with the mass-volume ratio of 1 g: 10mlB solution, and mixing the A, B solution uniformly, wherein the mass ratio of the metal salt to the organic ligand is 1: 0.5;
s300, performing magnetic stirring for 2 hours at the temperature of 20 ℃, then heating to 25 ℃ for reaction for 40 hours, wherein the magnetic stirring speed is 600 r/min;
s400, carrying out ultrasonic-assisted dispersion, vacuum filtration and centrifugal washing on the product for 2 times, drying at 50 ℃ for 6 hours, and carrying out reduced pressure activation at 150 ℃ for 24 hours.
The resulting nucleating agent was used in the production of PA56, comprising the following steps:
1) putting the organic metal hybrid nucleating agent and PA56 into a vacuum oven at 80 ℃ for drying for 12 hours for later use;
2) blending the pre-treated material obtained in the step 1) with an organometallic hybrid nucleating agent PA56, wherein the content of the organometallic hybrid nucleating agent in PA56 is 0.001%, and extruding and granulating in an extruder; the extrusion temperature is 265 ℃, the extrusion rotating speed is 100r/min, and the PA56 material with high crystallization rate can be obtained. The half-crystallization time was 0.56 minutes and the crystallinity was 35.8%.
Example 9
A preparation method of a PA56 organic metal hybrid material nucleating agent comprises the following steps:
s100, respectively drying metal salt ferric chloride hexahydrate and organic ligand ethylenediamine tetraacetic acid at 20 ℃ for 2 hours, and grinding into fine particles with the particle size of 0.1 mm;
s200, ultrasonically dissolving metal salt in tetrahydrofuran serving as a solvent to obtain a mixture with the mass-volume ratio of 1 g: adding an organic ligand into tetrahydrofuran solvent for ultrasonic dissolution to obtain a solution with the mass-volume ratio of 1 g: 70mlB, and uniformly mixing A, B solution, wherein the mass ratio of the metal salt to the organic ligand is 1: 5;
s300, performing magnetic stirring for 2 hours at the temperature of 20 ℃, then heating to 160 ℃ for reaction for 12 hours, wherein the magnetic stirring speed is 4000 r/min;
s400, carrying out ultrasonic-assisted dispersion, vacuum filtration and centrifugal washing on the product for 6 times, drying at 95 ℃ for 24 hours, and carrying out reduced pressure activation at 190 ℃ for 12 hours.
The resulting nucleating agent was used in the production of PA56, comprising the following steps:
1) putting the organic metal hybrid nucleating agent and PA56 into a vacuum oven at 80 ℃ for drying for 12 hours for later use;
2) blending the pre-treated material obtained in the step 1) with an organometallic hybrid nucleating agent PA56, wherein the content of the organometallic hybrid nucleating agent in PA56 is 5%, and performing extrusion granulation in an extruder; the extrusion temperature is 265 ℃, the extrusion rotating speed is 100r/min, and the PA56 material with high crystallization rate can be obtained. The half-crystallization time was 0.55 minutes and the crystallinity was 39.5%.
It can be seen that the nucleation efficiency is improved both in the amounts and under the reaction conditions described in the present invention.
Finally, it should be noted that: the above description is only a few of the preferred embodiments of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (7)

1. The application of the organic metal hybrid nucleating agent is characterized in that the organic metal hybrid nucleating agent is acted on the nylon 56, wherein the content of the organic metal hybrid nucleating agent in the nylon 56 is 0.001% -5%;
the organic metal hybrid nucleating agent is prepared by the following method:
s100, respectively drying the metal salt and the organic ligand, and grinding into powder;
s200, adding metal salt into a solvent for ultrasonic dissolution to obtain a solution A, adding an organic ligand into the solvent for ultrasonic dissolution to obtain a solution B, and uniformly mixing A, B solutions;
s300, carrying out magnetic stirring reaction at 20-160 ℃ for 12-42 h, wherein the magnetic stirring speed is 600-4000 r/min;
s400, drying the product for 6-24 hours at 50-95 ℃ after ultrasonic-assisted dispersion, vacuum filtration and centrifugal washing, and activating the product for 12-24 hours at 150-190 ℃ under reduced pressure;
the metal salt and the organic ligand are as follows: cobalt nitrate hexahydrate and 2-methylimidazole, nickel acetate tetrahydrate and dihydroxyterephthalic acid, ferric chloride hexahydrate and ethylenediaminetetraacetic acid, or zinc nitrate hexahydrate and 2-methylimidazole.
2. The use of the organometallic hybrid nucleating agent according to claim 1, wherein the solvent in step S200 is at least one of deionized water, methanol, ethanol, isopropanol, tetrahydrofuran, acetone, N-dimethylformamide and N, N-dimethylacetamide.
3. The use of organometallic hybrid nucleating agent according to claim 1, wherein the solvent is N, N-dimethylformamide solvent.
4. The use of the organometallic hybrid nucleating agent according to claim 1, wherein the mass-to-volume ratio of the metal salt to the solvent in the solution A in the step S200 is 1 g: 20 ml-80 ml, wherein the mass volume ratio of the organic ligand to the solvent in the solution B is 1 g: 10 ml-70 ml, wherein the mass ratio of the metal salt to the organic ligand is 1: 0.5 to 5.
5. The application of the organometallic hybrid nucleating agent according to claim 1, wherein the reaction temperature in the step S300 is 25-100 ℃; the magnetic stirring speed is 1200 r/min-3200 r/min, and the reaction time is 12 h-30 h.
6. The application of the organometallic hybrid nucleating agent as defined in claim 1 is characterized in that the application method specifically comprises the following steps: and drying the organic metal hybrid nucleating agent and PA56, blending, adding other auxiliaries, and performing extrusion granulation in an extruder to obtain the PA56 material with high crystallization rate.
7. The use of the organometallic hybrid nucleating agent according to claim 6, wherein the other auxiliary agents comprise one or more of an antioxidant, a weather-resistant agent, a flame retardant, a filler, a toner and a reinforcing fiber;
the extrusion temperature of the extruder is 265 ℃, and the extrusion rotating speed is 100 r/min.
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