CN113150381B - 1, 4-naphthalene dicarboxylic acid di-smoke hydrazide nucleating agent and preparation method thereof - Google Patents
1, 4-naphthalene dicarboxylic acid di-smoke hydrazide nucleating agent and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to an organic polymer auxiliary compoundThe technical field of preparation or chemical processing discloses a1, 4-naphthalene dicarboxylic acid isonicotinyl hydrazide nucleating agent, which has the structure as follows:the preparation method comprises the following steps of (1), mixing 1, 4-naphthalene dicarboxylic acid, thionyl chloride and N, N' -dimethylformamide catalyst, slowly heating, and stirring and refluxing; and evaporating again to obtain 1, 4-naphthalene dicarboxylic acid dichloride. Step (2), mixing 1, 4-naphthaloyl chloride with nicotinamide, N' -dimethylformamide and triethylamine for reaction to form a secondary mixed solution, and cleaning the secondary mixed solution; and after the cleaning is finished, drying to obtain the 1, 4-naphthalic acid isonicotinyl hydrazide nucleating agent. The nucleating agent provided by the invention is applied to semi-crystalline plastics, can realize high crystallinity of the semi-crystalline plastics, improves the heat resistance of the semi-crystalline plastics, and expands the application range of the semi-crystalline plastics.
Description
Technical Field
The invention belongs to the field of organic polymer auxiliary compounds and preparation or chemical processing thereof, and in particular relates to a1, 4-naphthalene dicarboxylic acid dihydrazide nucleating agent and a preparation method thereof.
Background
The nucleating agent is a novel auxiliary agent suitable for synthesizing semi-crystalline plastics, and can shorten the molding cycle, improve the rigidity, the heat distortion temperature, the impact resistance and other physical and mechanical properties of products by changing the crystallization behavior of resin, accelerating the crystallization rate, increasing the nucleation crystallization density and promoting the grain size refinement.
The nucleating agent mainly comprises an inorganic nucleating agent and an organic nucleating agent, wherein the inorganic nucleating agent mainly comprises talcum, montmorillonite, mica, halloysite, calcium carbonate, zinc citrate, silicon dioxide and the like; the organic nucleating agent mainly comprises fatty carboxylic acid metal compounds, sorbitol derivatives, aromatic carboxylic acid derivatives, organic phosphates, wood acids and derivatives thereof, sodium benzoate, bis (p-tert-butylbenzoic acid) aluminum carboxyl and the like. The organic nucleating agent can overcome the defect of poor compatibility of the inorganic nucleating agent and the semi-crystalline plastic matrix, so the organic nucleating agent is generally used for molding semi-crystalline plastic.
The heat resistance of semi-crystalline plastics is poor, for example, the heat distortion temperature of polylactic acid is only about 60 ℃, so that the semi-crystalline plastics can only be used in a low-temperature environment, and the application range of the semi-crystalline plastics is greatly limited.
Disclosure of Invention
The invention aims to provide a1, 4-naphthalic acid di-smoke hydrazide nucleating agent and a preparation method thereof, which are used for solving the problem of poor heat resistance of semi-crystalline plastics.
In order to achieve the aim, the invention provides the following technical proposal, the 1, 4-naphthalene dicarboxylic acid dihydrazide nucleating agent has the structure that,
the invention also provides another technical scheme, a preparation method of the 1, 4-naphthalic acid isonicotinyl hydrazide nucleating agent, which comprises the following steps:
step (1): acylation reaction
13-18g of 1, 4-naphthalene dicarboxylic acid, 100-200ml of thionyl chloride and 1-6ml of N, N' -dimethylformamide catalyst are mixed, the mixture is heated at the heating rate of 2-6 ℃/min until the heating temperature reaches 80 ℃, and the mixture is stirred and refluxed for 30-45 hours in the heating process to form a mixed solution; evaporating the mixed solution to obtain 1, 4-naphthalene dicarboxylic acid dichloride; the reaction process is as follows:
step (2): amination reaction
Mixing 0.005-0.01mol of 1, 4-naphthaloyl chloride with 0.002-0.006mol of nicotinamide, 100-150ml of N, N' -dimethylformamide and 1-5ml of triethylamine, reacting to form a secondary mixed solution, and cleaning the secondary mixed solution by using deionized water; drying after cleaning is finished to obtain the 1, 4-naphthalic acid dihydrazide nucleating agent; the reaction process is as follows:
the beneficial effects of this technical scheme:
1. the nucleating agent provided by the technical scheme is prepared through an acylation reaction and an amination reaction and is used for processing semi-crystalline plastics. In the process of processing semi-crystalline plastics, the semi-crystalline plastics can begin to crystallize at 150 ℃ or above, and the temperature is closer to the melting temperature of the raw materials, in other words, the semi-crystalline plastics can begin to crystallize without cooling to a low crystallization temperature, so that the crystallization time is greatly shortened, and the crystallinity is improved.
2. At present, partial semi-crystalline plastics (such as polylactic acid) can not be crystallized basically at the cooling rate of 1 ℃/min, so that the whole crystallization process is very slow, and therefore, the industrial production is limited; when the nucleating agent provided by the technical scheme is used for processing semi-crystalline plastics, the semi-crystalline plastics can also have crystallization peak values under extremely fast cooling rate (such as 40-50 ℃/min), crystallization is realized in the cooling process, the crystallization time can be greatly shortened, and the actual industrial production (in order to improve the efficiency, the cooling rate can be accelerated in the actual industrial production) is satisfied.
3. Experiments prove that when the nucleating agent provided by the technical scheme is used for processing semi-crystalline plastics, the crystallinity of the semi-crystalline plastics is very high and can reach about 64%, compared with the existing low crystallinity of the semi-crystalline plastics, the crystallinity is greatly improved, and the crystallinity is directly reflected on the heat resistance of the semi-crystalline plastics; therefore, the heat resistance of the semi-crystalline plastic processed by the nucleating agent provided by the technical scheme is greatly improved, the heat resistance temperature can reach about 150 ℃, and the application range of the semi-crystalline plastic is widened.
4. The detection proves that the flow property of the semi-crystalline plastic prepared by the nucleating agent provided by the technical scheme reaches 10.9g/10min, and the nucleating agent has great promotion effect on industrial application of the semi-crystalline plastic.
Further, in the step (1), the mixture is cooled to room temperature before evaporation.
The beneficial effects are that: through cooling the mixed liquor to room temperature, can play the effect of decompression, and then avoid the mixed liquor to appear the condition of bumping when evaporating, reduce the loss of product, and then improve output.
Further, in the step (1), the mixed solution is evaporated in a vacuum environment.
The beneficial effects are that: impurity doping in the external environment is avoided, and the purity of the prepared 1, 4-naphthalene dicarboxylic acid dichloride is ensured to be high; meanwhile, the evaporation effect is good in a vacuum environment.
Further, in the step (2), 1, 4-naphthalene dicarboxylic acid dichloride, nicotinamide, N' -dimethylformamide and triethylamine are mixed by using an ultrasonic technique.
The beneficial effects are that: by using the ultrasonic technology for mixing, the uniformity of mixing can be improved.
In the step (2), before the secondary mixed solution is cleaned, ice bath is carried out and stirred for 2 hours, wherein the stirring speed is 1800-2600r/min.
The beneficial effects are that: by reducing the temperature of the secondary mixed solution, the temperature of the 1, 4-naphthalene dicarboxylic acid chloride in the mixed solution can be reduced, the activity of the 1, 4-naphthalene dicarboxylic acid chloride is reduced, the situation that the 1, 4-naphthalene dicarboxylic acid chloride diffuses at high temperature to cause insufficient reaction or the occurrence of byproducts is avoided, and the quality and purity of the prepared nucleating agent are improved.
Further, in the step (2), after the ice bath, the secondary mixed solution is heated to 70 ℃ and is kept for 6 hours.
The beneficial effects are that: the overflow of the acid chloride can be reduced by the low temperature, but the activity of the acid chloride is reduced and insufficient reaction occurs at the low temperature, so that the activity of the acid chloride which does not participate in the reaction can be improved by raising the temperature again, and the acid chloride can be fully reacted.
And (3) in the step (2), when the secondary mixed solution is cleaned, pouring the secondary mixed solution into deionized water, and carrying out suction filtration to obtain a filter cake.
The beneficial effects are that: impurities in the suspension can be removed, and the subsequent cleaning effect is improved.
Further, in the step (2), the filter cake is washed three times by deionized water.
The beneficial effects are that: and the method can remove more impurities after repeated cleaning, so that the purity of the prepared nucleating agent is improved.
Further, in the step (2), the filter cake is dried under vacuum with a temperature of 35 ℃.
The beneficial effects are that: the evaporation is carried out under the vacuum condition, so that the influence of the external environment on the purity of the prepared nucleating agent can be reduced, and meanwhile, the drying effect is better under the vacuum condition.
Drawings
FIG. 1 is a reaction process of a nucleating agent provided by the present invention;
FIG. 2 is a graph of nuclear magnetic resonance of a nucleating agent provided by the present invention;
FIG. 3 is a DSC curve of sample 1-sample 5 when cooled at a rate of 1 ℃/min at a melting temperature of 170 ℃;
FIG. 4 is a DSC curve of sample 1-sample 5 when cooled at a rate of 1 ℃/min at a melting temperature of 180 ℃;
FIG. 5 is a DSC curve of sample 1-sample 5 when cooled at a rate of 1 ℃/min at a melting temperature of 190 ℃;
FIG. 6 is a DSC curve of sample 1-sample 5 when cooled at a rate of 1℃per minute at a melting temperature of 200 ℃
FIG. 7 is a DSC curve of comparative sample 1-comparative sample 4 when cooled at a rate of 1 ℃/min at a melting temperature of 180 ℃;
FIG. 8 is a DSC curve of comparative sample 1-comparative sample 4 when cooled at a rate of 1 ℃/min at a melting temperature of 190 ℃;
FIG. 9 is a DSC curve of comparative sample 1-comparative sample 4 when cooled at a rate of 1 ℃/min at a melting temperature of 200 ℃;
FIG. 10 is a DSC curve of comparative sample 5-comparative sample 8 when cooled at a rate of 1 ℃/min at a melting temperature of 180 ℃;
FIG. 11 is a DSC curve of comparative sample 5-comparative sample 8 when cooled at a rate of 1 ℃/min at a melting temperature of 190 ℃;
FIG. 12 is a DSC curve of comparative sample 5-comparative sample 8 when cooled at a rate of 1 ℃/min at a melting temperature of 200 ℃;
FIG. 13 is a DSC curve of sample 2-sample 5 when cooled at a rate of 40 ℃/min at a melting temperature of 190 ℃;
FIG. 14 is a DSC curve of sample 2-sample 5 when cooled at a rate of 50 ℃/min at a melting temperature of 190 ℃;
FIG. 15 DSC curves of samples 2-5 isothermal for 180min at 140 ℃;
FIG. 16 DSC curves of samples 2-5 isothermal for 180min at 142 ℃;
FIG. 17 DSC curves of samples 2-5 isothermal for 180min at 144 ℃;
FIG. 18 DSC curve of sample 2-sample 5 isothermal for 180min at 146 ℃;
FIG. 19 DSC curve of sample 2-sample 5 isothermal for 180min at 148 ℃;
FIG. 20 DSC curve of sample 2-sample 5 isothermal for 180min at 150 ℃;
FIG. 21 is a graph showing the change in crystallinity with crystallization time at 140℃for samples 2-5;
FIG. 22 is a graph of PAID and PLLA geometry and leading edge track energy;
FIG. 23 is an isothermal crystallization graph of samples 2-5;
FIG. 24 is a graph of thermal weight loss for samples 1-5;
FIG. 25 is a flow chart of samples 1-5;
FIG. 26 is a graph of tensile strength for samples 1-5;
FIG. 27 is a graph showing the elastic modulus of samples 1 to 5.
Detailed Description
The following is a further detailed description of the embodiments:
the parameters for examples 1-6 of 1, 4-naphthalenedicarboxylic acid isonicotinyl hydrazide nucleating agents are shown in Table 1:
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | |
| 1, 4-naphthalenedicarboxylic acid (g) | 15 | 13 | 14 | 16 | 17 | 18 |
| Thionyl chloride (ml) | 150 | 100 | 120 | 160 | 175 | 200 |
| Dimethylformamide catalyst (ml) | 3 | 1 | 2 | 4 | 5 | 6 |
| Tobacco hydrazide (mol) | 0.004 | 0.002 | 0.003 | 0.0035 | 0.0045 | 0.006 |
| N, N-dimethylformamide (ml) | 120 | 100 | 110 | 130 | 140 | 150 |
| Triethylamine (ml) | 3 | 1 | 2 | 3.5 | 4.5 | 5 |
A1, 4-naphthalene dicarboxylic acid isonicotinyl hydrazide nucleating agent has the structure:
carrying out molecular structure characterization on the 1, 4-naphthalic acid isonicotinyl hydrazide nucleating agent by using a Fourier transform infrared spectrometer and a nuclear magnetic resonance tester, wherein the nuclear magnetic resonance result is shown in figure 2; the infrared test data are: (FT-IR) v: 3439.6 3234.2, 3007.0, 1683.1, 1659.4, 1630.2, 1596.0, 1580.9, 1524.8, 1477.4, 1422.8, 1380.7, 1348.3, 1308.7, 1264.1, 1198.9, 1169.5, 1149.2, 1087.2, 1030.1, 901.8, 825.9, 767.7, 711.1, 630.8cm -1 . The nuclear magnetic resonance spectrum is: ( 1 H NMR)δ：ppm；10.91(s，1H，NH)，10.71(s，1H，NH)，9.15(s，1H，Py)，8.32～8.82(m，3H，Py)，7.61～7.78(m，3H，Naphth)。
The preparation method of the 1, 4-naphthalic acid isonicotinyl hydrazide nucleating agent is described by taking example 1 as an example, and the reaction process is shown in fig. 1.
The preparation method of the 1, 4-naphthalic acid isonicotinyl hydrazide nucleating agent comprises the following steps:
step (1): acylation reaction
15g of 1, 4-naphthalenedicarboxylic acid are mixed with 150ml of thionyl chloride and 3ml of N, N' -dimethylformamide as a catalyst to form a mixture. The mixture was then heated at a heating rate of 5 c/min and when the heating temperature increased to 80 c, the heating was stopped. And stirring and refluxing the mixture in the heating process to enable the mixture to fully react, and stirring and refluxing for 36 hours to form a mixed solution.
Cooling the mixed solution to room temperature, and evaporating the mixed solution in a vacuum environment to obtain 1, 4-naphthalene dicarboxylic acid dichloride; the reaction process is as follows:
step (2): amination reaction
Extracting 0.008mol of 1,4 naphthalene dicarboxylic acid dichloride prepared in the step (1), adding 0.004mol of nicotinamide, 120ml of N, N' -dimethylformamide and 3ml of triethylamine, and carrying out a mixing reaction by utilizing an ultrasonic technology to form a secondary mixed solution;
the secondary mixed solution is subjected to ice bath for 2 hours, and is continuously stirred in the ice bath process, wherein the stirring speed is 1800-2600r/min, and 2300r/min is used in the embodiment. After ice bath, the secondary mixture was warmed to 70 ℃ and incubated for 6h.
And pouring the secondary mixed solution into deionized water, cleaning, and performing suction filtration to obtain a filter cake. Washing the filter cake for three times by using deionized water, placing the washed filter cake under a vacuum condition, and drying the washed filter cake by using the temperature of 35 ℃ to obtain the 1, 4-naphthalic acid di-smoke hydrazide nucleating agent; the reaction process is as follows:
examples 2-6 differ from example 1 only in the parameters shown in table 1.
Experiment:
the structure of the diphenylpropionic acid sebacoyl hydrazide nucleating agent selected as comparative example 1 is:
the infrared spectrum test data of the diphenylpropionic acid sebacoyl hydrazide nucleating agent are as follows: IR (KBr) v: 3448.0 3315.8, 3216.3, 3029.2, 2924.0, 2850.4, 1633.4, 1600.7, 1530.3, 1483.5, 1450.9, 1414.5, 1377.3, 1219.4, 1188.7, 1159.4, 1071.1, 1029.9, 933.0, 750.3, 720.9, 698.2cm "1. The nuclear magnetic resonance spectrum is: 1H NMR (DMSO, 400 MHz) delta: ppm;9.72 (s, 1H, NH), 9.67 (s 1H, NH), 7.09-7.33 (m, 5H, ar), 2.81-2.84 (t, 4H, CH 2), 2.40-2.44 (t, 2H, CH 2), 1.18-1.25 (m, 6H, CH 2).
The adipic acid dibenzoyl hydrazine nucleating agent is selected as the comparative example 2, and the adipic acid dibenzoyl hydrazine nucleating agent has the structure that:
the infrared spectrum test data of the adipic acid dibenzoyl hydrazine nucleating agent are as follows: infraredspectrum (IR) v: 3362.3 3236.2, 3032.8, 2940.3, 2863.8, 1693.6, 1647.9, 1603.9, 1575.9, 1523.2, 1491.2, 1467.1, 1420.5, 1385.8, 1343.6, 1308.8, 1270.5, 1222.2, 1187.1, 1168.2, 1128.8, 1027.8, 968.8, 929.1, 900.6, 804.0, 692.2cm "1; the nuclear magnetic resonance spectrum is: 1H nuclearmagnetic resonance (1H NMR,400 MHz) δ: ppm;0.33 (s, 1H, NH), 9.89 (s, 1H, NH), 7.48-7.88 (m, 5H, ar), 2.22 (s, 2H, CH 2), 1.62 (s, 2H, CH 2).
Preparing an experimental sample:
the left-handed polylactic acid (PLLA) and the nucleating agent (NAHA) provided in example 1 were dried under vacuum at 35 ℃ for 48 hours to remove residual moisture, and the left-handed polylactic acid (PLLA) and the nucleating agent (NAHA) were melt-blended in a rotary mixer to form a mixture. The rotary mixer used in the embodiment comprises a mixing barrel, a rotary rod coaxially fixed in the mixing barrel, a motor coaxially fixed with the rotary rod barrel, a feeding port and a discharging port, wherein the rotary rod is wound with spiral blades; the periphery of the mixing barrel is provided with a heating coil which is communicated with a power supply, and a switch is arranged between a passage formed by the heating coil and the power supply.
During blending, the temperature of mixing is set to 190 ℃, the rotating rod rotating speed is set to 32rpm/min or 64rpm/min, the rotating rod rotating speed is preferably 64rpm/min in the present application, and the mixing time is 7min. The mixture was hot-pressed at 20MPa and 180℃and cold-pressed at room temperature for 5min to give a sample having a thickness of 0.4 mm. When preparing the sample, the nucleating agent accounts for 0wt%, 0.5wt%, 1wt%, 2wt% and 3wt% respectively in the materials, and the sample is named as sample 1: PLLA (i.e., PLLA0wt% NAHA), sample 2: plla0.5wt% NAHA, sample 3: PLLA1wt% NAHA, sample 4: PLLA2wt% NAHA, sample 5: PLLA3wt% NAHA.
The dibenzoyl propionic acid sebacoyl Hydrazide (HAD) and the l-polylactic acid (PLLA) provided in comparative example 1 were blended in the same manner as described above to prepare comparative example samples, and the proportions of the nucleating agents in the materials during blending were 0.5wt%, 1wt%, 2wt% and 3wt%, respectively, and the prepared comparative example samples were marked as: comparative example sample 1: PLLA0.5wt% HAD, comparative sample 2: PLLA1wt% HAD, comparative sample 3: PLLA2wt% HAD, comparative sample 4: PLLA3wt% HAD.
The adipic acid dibenzoyl hydrazine (BAAD) and the l-polylactic acid (PLLA) provided in comparative example 2 were blended to prepare comparative example samples, and the concentration of the nucleating agent at the time of blending was 0.5wt%, 1wt%, 2wt% and 3wt%, and the prepared comparative example samples were marked as follows: comparative example sample 5: PLLA0.5wt% BAAD, comparative example sample 6: PLLA1wt% BAAD, comparative sample 7: PLLA2wt% BAAD, comparative sample 8: PLLA3wt% BAAD.
The following experiments were performed on the above samples 1 to 5 and comparative samples 1 to 8:
non-isothermal crystallization behavior of polylactic acid (PLLA)
1.1 DSC curve analysis at a cooling rate of 1 ℃/min
The melting and crystallizing DSC curves of the samples 1 to 5 were analyzed by Differential Scanning Calorimetry (DSC), and the samples 1 to 5 were melted at temperatures of 170 ℃, 180 ℃, 190 ℃ and 200 ℃ and then cooled at a cooling rate of 1 ℃/min, wherein the DSC curves are shown in FIG. 3, FIG. 4, FIG. 5 and FIG. 6, and the specific parameters of the samples 2 to 5 are shown in Table 2.
TABLE 2
The DSC curves of the above-mentioned melting crystals of comparative example 1-8 were analyzed by Differential Scanning Calorimetry (DSC), and after melting at 180 ℃, 190 ℃ and 200 ℃, the comparative example 1-8 were cooled at a cooling rate of 1 ℃/min, and the DSC curves are shown in FIG. 7, FIG. 8, FIG. 9, FIG. 10, FIG. 11, and FIG. 12, respectively.
As can be seen from a combination of fig. 3-12 and table 2, the crystallization process includes two stages of nucleation and crystal growth, and no melting crystallization peak occurs because there is no doping of NAHA in sample 1, while PLLA itself has very poor nucleation capability. Comparative examples 1-8, when cooled at a cooling rate of 1 deg.c/min at a melting temperature of 180 deg.c, 190 deg.c and 200 deg.c, exhibited melting crystallization peaks, wherein the melting crystallization peaks of samples 1-4 occurred between 123 deg.c and 133 deg.c, and the melting crystallization peaks of comparative examples 5-8 occurred between 136 deg.c and 144 deg.c.
Whereas sample 2-sample 5 cooled at a cooling rate of 1 c/min at a melting temperature of 170 c, 180 c, 190 c and 200 c, a melting crystallization peak (up to 160 c) occurred above 145 c, indicating that PLLA started to crystallize at this time, and its initial crystallization temperature was much higher than that of sample 1 and comparative sample 1-comparative sample 8, since the crystallization rate was lower than the cooling rate. It is explained that sample 2-sample 5 starts to crystallize when the crystallization is close to the melting temperature of PLLA, in other words, PLLA starts to crystallize without cooling to a low crystallization temperature, so that the complete crystallization time of PLLA is shortened and the crystallization rate is accelerated. Meanwhile, as the concentration of NAHA in PLLA increases, the melting crystallization peak moves towards the high temperature direction, which indicates that the initial temperature of crystallization increases, the crystallization of PLLA is further accelerated, the crystallization time is shortened, and the crystallization rate is improved.
Generally, the melting point of pure PLLA is 160 to 170 ℃, and the theoretical crystallization temperature is not less than the glass transition temperature and not more than 0.85 times the melting point, so that the theoretical upper limit of the PLLA crystallization temperature is 144.5 ℃. Whereas sample 2-sample 5 had an onset of crystallization at a melting temperature of 170℃of more than 160℃which means that the theoretical upper limit of crystallization was exceeded after the addition of NAHA to PLLA.
In summary, by doping 1, 4-naphthalenedicarboxylic acid isonicotinyl hydrazide Nucleating Agent (NANH) during polymerization of l-polylactic acid (PLLA), crystallization can occur at high temperature, and the time for the crystallization behavior to begin breaks through the theoretical crystallization temperature upper limit of PLLA, which is a breakthrough in the art. And according to the crystallinity calculation formula: melting temperature reduction crystallization enthalpy/(93X (1-X)), wherein the melting temperature reduction crystallization enthalpy is Δhc,93 is the crystallization enthalpy corresponding to 100% crystallization, and X is the percentage content of NANH, and it is calculated that when the melting temperature is 200 ℃, the temperature is reduced at a rate of 1 ℃/min, so that the crystallinity of sample 5 can reach 63.96% (the crystallinity of usually pure PLLA and PLLA doped with the existing nucleating agent is very low), and the crystallinity is greatly improved.
Moreover, since the crystallinity of PLLA is increased, the internal structure of PLLA is regular at high temperature, and the structural difficulty of destroying the rule at high temperature is high, so that the heat resistance of PLLA can be improved; and the crystallinity is increased, so that the prepared PLLA is more heat-resistant, and the temperature range of PLLA use is enlarged. Through detection, the PLLA has the heat-resistant temperature reaching more than 150 ℃ through doping NAHA into the PLLA, and the PLLA service temperature in industry is completely met.
1.2 DSC curve analysis of sample 2-sample 5 at cooling rates of 40 ℃/min, 50 ℃/min
FIGS. 13 and 14 are DSC graphs showing cooling rates of 40 ℃/min and 50 ℃/min after melting sample 2 to sample 5 at 190 ℃. In practical applications, in view of time cost, rapid cooling is generally required, and thus a DSC curve at a multi-stage cooling rate is analyzed. It was found from the test that even at such high cooling rates as 40℃per minute and 50℃per minute, the crystallization peaks of the samples 2 to 5 were still able to appear, and particularly the crystallization peaks of the samples 4 and 5 were particularly remarkable. Therefore, the nucleating agent provided by the invention has very good promotion and acceleration effects on nucleation and crystallization of PLLA.
1.3 DSC curve analysis of samples 2 to 5 isothermal 180min at 140℃142℃144℃146℃148℃150℃respectively
The DSC curves of the melt crystallization of the above comparative example sample 2 to comparative example sample 5 were analyzed by Differential Scanning Calorimetry (DSC), and the DSC curves of the samples 2 to 5 were isothermal for 180 minutes in the high temperature range of 140℃to 150℃as shown in FIGS. 15 to 20, respectively.
Theoretically, in the high temperature region of 140 ℃ to 150 ℃, the molecular chain movement capability of the polylactic acid is strong, and self homogeneous nucleation is almost impossible, but the melting process shows that a melting peak exists, crystallization is proved to occur in the isothermal process, and the crystallization is carried out on the premise that the nucleation is carried out, which shows that the crystallization and the nucleation of the polylactic acid can be promoted by doping NAHA, and the effect of NANH in a polylactic acid matrix is proved. In addition, as the crystallization temperature increases, the melting peak moves to the high temperature direction, and the grown crystal is more perfect due to the fact that the crystal grows more fully at the higher temperature, so that the crystal moves to the high temperature direction, the method can be suitable for actual production of enterprises, and the existing process is improved.
1.4 analysis of the crystallization degree of sample 2-sample 5 at 140℃as a function of crystallization time
Sample 2-sample 5 showed a change in crystallinity with crystallization time at a high temperature of 140℃as shown in FIG. 21. From FIG. 21, it can be seen that sample 2-sample 5 rapidly crystallized at a high temperature of 140℃and, particularly, the first 2 minutes, the crystallization rate rapidly increased, and after 2 minutes, the crystallization rate became smooth. Wherein, the crystallization can be completed in about 2.3min for sample 4 and sample 5, and in about 3.2min for sample 3. This means that sample 2-sample 5 can rapidly complete crystallization, and thus can be applied to industrial production, resulting in improved productivity.
Leading edge track energy of 2PAID and PLLA
Preliminary theoretical analysis was performed using the DMol3 system of MS software, resulting in the geometry and leading edge orbital energy map of PAID and PLLA as shown in fig. 22. HOMO (highest occupied molecular orbital) and LUMO (lowest energy orbital) of PAID are-0.2011 eV and-0.099 eV, respectively, HOMO (highest occupied molecular orbital) and LUMO (lowest energy orbital) of PLLA are-11.082 eV and PLLA is 0.251eV, respectively. According to the leading-edge orbital theory, the energy difference between the LUMO of PAID and the HOMO of PLLA is 10.983eV, and the LUMO-HOMO energy difference smaller than PLLA itself is 11.333eV; according to the leading-edge orbital theory, the energy difference between the LUMO of PAID and the HOMO of PLLA is 10.983eV, and the LUMO-HOMO energy difference smaller than PLLA itself is 11.333eV; through further analysis of PLLA and PAID molecular structures, it is thought that its interactions may occur at c=o of PLLA and N-H of PAID; thus, the interaction between PIAD and PLLA can increase the nucleation effect of PLLA.
Isothermal crystallization behavior of polylactic acid (PLLA)
Isothermal crystallization profile of sample 5 was analyzed by Differential Scanning Calorimetry (DSC) and the results are shown in figure 23. As can be seen from FIG. 23, sample 5 had a crystallization time of 0.3min at a crystallization temperature of 135℃and was able to complete crystallization in a short period of time, thereby shortening the crystallization time.
4 thermal weightlessness experimental analysis
For the thermal weight loss stability analysis of samples 1 to 5, a Q500 apparatus from TA company was used, the samples were placed in the apparatus, and the temperature was raised from room temperature to 650 degrees per minute under flowing air at 5 degrees per minute, and the experimental results are shown in FIG. 24. As can be seen from fig. 24, doping NAHA in PLLA resulted in a small decrease in the initial thermal decomposition temperature of PLLA, but the magnitude of the decrease was very small, and the initial thermal decomposition temperature of sample 5 was also decreased by only 7.6 ℃ (at temperatures above 330 ℃, the effect of the decrease in initial thermal decomposition temperature of 7.6 ℃ was very small), with little impact on the specific use. In general, the polymer is doped with an auxiliary agent, and the initial decomposition temperature of the original polymer is greatly reduced due to the compatibility of the auxiliary agent or the low decomposition temperature of the auxiliary agent, while the initial thermal decomposition temperature of the PLLA is affected by NAHA, so that the PLLA has small influence on the thermal decomposition resistance effect of the PLLA and can not be used greatly, and the PLLA still has a wider application range.
5 flow test analysis
The results of the fluidity test analysis of samples 1 to 5 at 180℃under a standard load of 21.6kg are shown in FIG. 25. As can be seen from fig. 25, by doping NAHA into PLLA, the fluidity of PLLA can be greatly improved, especially, sample 5 has fluidity up to 10.9g/10min, which is very advantageous for subsequent product processing, and can enable rapid flow and molding of product, and save very large processing time cost.
6 tensile Strength test analysis
Samples 1-5 were tested for tensile strength, with specific parameters shown in FIG. 26. As can be seen from fig. 26, the tensile strength of sample 2-sample 5 is significantly higher than that of sample 1, wherein the tensile strength of sample 4 reaches 52.5MPa, which is 1.25 times that of sample 1.
7 elastic modulus experiment analysis
The elastic modulus test was performed on samples 1 to 5, and specific parameters are shown in fig. 27. As can be seen from fig. 27, the elastic modulus of sample 2-sample 5 is significantly higher than that of sample 1, wherein the elastic modulus of sample 2 reaches 2040MPa, which is 1.3 times that of sample 1.
It will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit of the invention, and these should also be considered as the scope of the invention, which does not affect the effect of the invention and the utility of the patent.
Claims (9)
1, 4-naphthalene dicarboxylic acid isonicotinyl hydrazide nucleating agent which is characterized in that: the structure of the utility model is that,
the method comprises the steps of carrying out a first treatment on the surface of the The preparation method of the 1, 4-naphthalic acid isonicotinyl hydrazide nucleating agent comprises the following steps:
step (1): acylation reaction
13-18g of 1, 4-naphthalene dicarboxylic acid, 100-200ml of thionyl chloride and 1-6ml of thionyl chloride are mixedN，N′Mixing the dimethylformamide catalyst, heating the mixture at a heating rate of 2-6 ℃/min until the heating temperature reaches 80 ℃, and stirring and refluxing the mixture for 30-45h in the heating process to form a mixed solution; evaporating the mixed solution to obtain 1, 4-naphthalene dicarboxylic acid dichloride; the reaction process is as follows:
；
step (2): amination reaction
Mixing 0.005-0.01mol of 1, 4-naphthalene dicarboxylic acid dichloride with 0.002-0.006mol of nicotinamide hydrazide, and 100-150mlN，N′-dimethylformamide and 1-5ml of triethylamine are mixed and reacted to form secondary mixed solution, and deionized water is used for cleaning the secondary mixed solution; drying after cleaning is finished to obtain the 1, 4-naphthalic acid dihydrazide nucleating agent; the reaction process is as follows:
。
2. the method for preparing the 1, 4-naphthalic acid isonicotinyl hydrazide nucleating agent according to claim 1, which is characterized in that: in the step (1), the mixture is cooled to room temperature before evaporation.
3. The method for preparing the 1, 4-naphthalic acid isonicotinyl hydrazide nucleating agent according to claim 2, which is characterized in that: in the step (1), the mixed solution is evaporated in a vacuum environment.
4. A process for preparing a1, 4-naphthalenedicarboxylic acid isonicotinyl hydrazide nucleating agent according to claim 3, wherein: in the step (2), ultrasonic technology is used for preparing the 1, 4-naphthalene dicarboxylic acid dichloride, nicotinamide, and the like,N，N′-dimethylformamide and triethylamine.
5. The method for preparing the 1, 4-naphthalic acid isonicotinyl hydrazide nucleating agent according to claim 4, wherein the method comprises the following steps: in the step (2), before the secondary mixed solution is cleaned, ice bath is carried out and stirred for 2 hours, wherein the stirring speed is 1800-2600r/min.
6. The method for preparing the 1, 4-naphthalic acid isonicotinyl hydrazide nucleating agent according to claim 5, wherein the method comprises the following steps: in the step (2), after ice bath, the secondary mixed solution is heated to 70 ℃ and is kept for 6 hours.
7. The method for preparing the 1, 4-naphthalic acid isonicotinyl hydrazide nucleating agent according to claim 6, wherein the method comprises the following steps: in the step (2), when the secondary mixed solution is cleaned, pouring the secondary mixed solution into deionized water, and carrying out suction filtration to obtain a filter cake.
8. The method for preparing the 1, 4-naphthalic acid isonicotinyl hydrazide nucleating agent according to claim 7, wherein: in the step (2), the filter cake is washed three times by deionized water.
9. The method for preparing the 1, 4-naphthalic acid isonicotinyl hydrazide nucleating agent according to claim 8, wherein: in the step (2), the filter cake is dried under vacuum at 35 ℃.
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