CN113861058A - Triamido methylbenzene nucleating agent, preparation method and use method - Google Patents

Triamido methylbenzene nucleating agent, preparation method and use method Download PDF

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CN113861058A
CN113861058A CN202111100910.3A CN202111100910A CN113861058A CN 113861058 A CN113861058 A CN 113861058A CN 202111100910 A CN202111100910 A CN 202111100910A CN 113861058 A CN113861058 A CN 113861058A
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nucleating agent
triaminotoluene
polypropylene
structural formula
reaction
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CN113861058B (en
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黄木华
刘博瀚
彭山青
贾琼
邓汉林
张志豪
罗贤升
杨天宇
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Beijing Institute of Technology BIT
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Abstract

The invention provides a triamido toluene nucleating agent, a preparation method and a use method thereof. Wherein, the triamido toluene nucleating agent is an N, N, N-triacyl-2, 4, 6-triaminotoluene compound, can be used as the nucleating agent and is used for nucleating polymers at high temperature. Moreover, when the triaminomethylbenzene nucleating agent acts on a polymer as a nucleating agent, the haze of a polymer film can be effectively reduced, and the crystallization temperature and the product quality of a combination can be effectively improved, for example, when the triaminomethylbenzene nucleating agent acts on a T30S plate, the haze value is reduced by 12.98, and the crystallization temperature is improved by 10.3 ℃ compared with a T30S plate without the nucleating agent. Meanwhile, the nucleating agent provided by the invention has the advantages of stable intermediate property, mild reaction conditions in each step, low cost, short synthesis time, effective reduction of danger in the synthesis process and the like during synthesis, and is beneficial to industrial production. Therefore, the nucleating agent provided by the invention has wide application prospect.

Description

Triamido methylbenzene nucleating agent, preparation method and use method
Technical Field
The invention relates to the field of chemical industry and materials, and mainly relates to a triamido toluene nucleating agent, a preparation method and a use method thereof.
Background
Polypropylene is a semi-crystalline polymer, has a certain transparency, and has excellent processability, electrical insulation and rigidity, and has become a general-purpose polymer material with low price in recent years, and is widely used in the fields of transparent packaging, medical instruments, household goods, microwave appliances and the like. However, in some fields of use, polypropylene materials are required to have lower haze and higher crystallization temperature to improve product quality and shorten molding cycle. In order to reduce the haze and raise the crystallization temperature of polypropylene materials, the main method used in industry is to add a nucleating agent.
In the prior art, the nucleating agents can be divided into inorganic nucleating agents, organic nucleating agents and high-molecular nucleating agents according to the components of the nucleating agents. Most of the high-transparency polypropylene with high gloss, excellent rigidity and excellent toughness in the market is produced by adopting a sorbitol nucleating agent and adding the nucleating agent outside a kettle. However, sorbitol nucleating agents have the disadvantages of being used in large amounts and being prone to odor generation during processing.
In recent years, amide nucleating agents have also been favored, for example, one known commercially available nucleating agent is known under the name XT 386. The substance is a centrosymmetric structure, can be cooled to form crystals before a polypropylene matrix during polypropylene melt processing, induces polypropylene crystallization, increases the polypropylene crystallization temperature, and reduces the grain size to achieve the effect of reducing haze. However, the nucleating agent has the disadvantages of more synthesis steps and high synthesis difficulty, which causes the high price of the nucleating agent, thereby limiting the large-scale industrial application of the nucleating agent.
Therefore, a new nucleating agent with obvious nucleating effect and low synthesis cost is needed in the field.
Disclosure of Invention
In order to solve the problems, the invention provides a triamido toluene nucleating agent, a preparation method and a use method, and provides a polymer nucleating agent which has an obvious nucleating effect and has the advantages of low synthesis cost, simple synthesis route, easiness in operation and the like for the technical field. The specific contents are as follows:
in a first aspect, the invention provides a triamido methylbenzene nucleating agent, wherein an N, N, N-triacyl-2, 4, 6-triaminotoluene compound with a structural general formula shown in a structural formula I is used as the nucleating agent for nucleating a polymer at high temperature;
Figure BDA0003270686560000021
wherein R is a straight-chain or branched-chain alkyl group having 1 to 6 carbon atoms, an unsubstituted 5 to 6 cycloalkyl group, a straight-chain or branched-chain 5 to 6 cycloalkyl group substituted with an alkyl group having 1 to 4 carbon atoms, a 5 to 6 cycloalkyl group derived from a halogen atom, an aryl group, or a straight-chain or branched-chain aryl group substituted with an alkyl group having 1 to 4 carbon atoms.
Optionally, in the structural general formula of the N, N-triacyl-2, 4, 6-triaminotoluene compound shown in the structural formula I, R is one of methyl, ethyl, N-propyl, isopropyl, butyl, isobutyl, tert-butyl, cyclohexyl, cyclopentyl, phenyl and naphthyl.
Optionally, the polymer is any one of polypropylene, resin and polylactic acid.
In a second aspect, the present invention provides a method for preparing the triaminomethylbenzene nucleating agent described in the first aspect, which comprises:
step 1: taking 2,4, 6-trinitrotoluene shown in a structural formula III as a raw material, and carrying out catalytic hydrogenation reaction to obtain 2,4, 6-trinitrotoluene shown in a structural formula II;
step 2: carrying out transacylation reaction on 2,4, 6-triaminotoluene shown in a structural formula II and ester shown in a structural formula IV or V under an alkaline condition to generate a target product shown in a structural formula I;
Figure BDA0003270686560000031
optionally, in the catalytic hydrogenation reaction in the step 1, the pressure of the hydrogen used is in the range of 0.1-0.8 MPa, and the catalyst used is a palladium/carbon catalyst or a raney nickel catalyst; when the catalyst is a palladium/carbon catalyst, the mass ratio of the palladium/carbon catalyst to the 2,4, 6-trinitrotoluene is 0.01: 1-0.2: 1, and when the catalyst is a Raney nickel catalyst, the mass ratio of the Raney nickel catalyst to the 2,4, 6-trinitrotoluene is 0.05: 1-0.5: 1;
the reaction temperature of the catalytic hydrogenation reaction is 15-75 ℃, the reaction time is 0.5-12 h, and the reaction solvent at least comprises one of methanol, ethanol, isopropanol, acetonitrile, chloroform, ethyl acetate, methyl propionate, methyl pivalate, ethyl pivalate and tetrahydrofuran.
Optionally, in the basic condition of the step 2, the molar ratio of the used base to the 2,4, 6-triaminotoluene shown in the structural formula II is 3-4.5: 1, and the molar ratio of the ester shown in the structural formula IV or V to the base is 1-5: 1;
the alkali is one of sodium tert-butoxide, potassium tert-butoxide, lithium tert-butoxide, sodium bis (trimethylsilyl) amide, lithium bis (trimethylsilyl) amide, potassium bis (trimethylsilyl) amide, n-butyllithium or lithium diisopropylamide;
the reaction temperature under the alkaline condition is 0-30 ℃, the reaction time is 0.5-10 h, and the reaction solvent at least comprises one of tetrahydrofuran, dioxane, toluene and ethylene glycol dimethyl ether.
In a third aspect, the present invention provides a method for using the triaminomethylbenzene nucleating agent of the first aspect, the method comprising:
mixing the triamido toluene nucleating agent, the polymer to be nucleated and an anti-aging agent to prepare a polypropylene sample containing the triamido toluene nucleating agent;
melt mixing the polypropylene sample;
preparing the melt-mixed polypropylene sample into a preset model;
and quenching or quenching the preset model to obtain a model sample.
Optionally, the mass fraction of the triamido toluene nucleating agent is 0.005-0.2% and the mass fraction of the anti-aging agent is 0.05-0.1% based on the mass of the polymer to be nucleated being equal to 100;
optionally, the anti-aging agent consists of anti-aging agent 1010 and anti-aging agent 168.
Optionally, the mass ratio of the anti-aging agent 1010 to the anti-aging agent 168 is 1: 1-2.
The invention provides a triamido toluene nucleating agent, a preparation method and a use method thereof. Wherein, the triamido toluene nucleating agent is an N, N, N-triacyl-2, 4, 6-triaminotoluene compound, and can be used for polymer nucleation at high temperature. And when the triamido toluene nucleating agent is used as a nucleating agent to act on a polymer, the haze of a polymer film can be reduced, and the crystallization temperature and the product quality of a combination can be improved. Compared with the prior art, the invention at least comprises the following advantages:
1. the main raw material of the triamido toluene nucleating agent provided by the invention is retired 2,4, 6-triamino toluene (TNT). On one hand, the decommissioned TNT has extremely high annual output, low price and cost far lower than other raw materials, so the production cost of the nucleating agent can be effectively reduced; on the other hand, when TNT is used as a raw material, the target product triamido toluene nucleating agent can be prepared by directly adopting two steps of nitro reduction and N-acylation, so that the nucleating agent has the characteristics of simple synthetic route and contribution to realizing industrial production.
2. The triamido toluene nucleating agent provided by the invention uses reactants or catalysts which are common products in chemical industry during preparation, has wide sources, and can further reduce the preparation cost to a great extent.
3. The triamido toluene nucleating agent provided by the invention has the advantages of simple operation steps, high reaction rate, high reaction conversion rate and easy separation and collection of intermediate and final products during preparation.
4. The triamido toluene nucleating agent provided by the invention has the advantages of high reaction yield in each step, environmental friendliness and less byproducts during preparation, so that the preparation process can reduce the discharge of wastes in the synthesis process, effectively ensure the quality and purity of the triamido toluene nucleating agent, and is more favorable for realizing the production of high-quality triamido toluene nucleating agent.
In conclusion, the triamido methylbenzene nucleating agent provided by the invention can effectively reduce the haze of a polymer film, improve the crystallization temperature of a conjugate and the product quality of the conjugate, takes retired TNT as a raw material, and adopts a two-step simple organic reaction synthesis method, so that the triamido methylbenzene nucleating agent has the advantages of stable intermediate property, mild reaction conditions of each step, low cost, short synthesis time, effective reduction of danger in the synthesis process and the like, and is beneficial to industrial production.
Drawings
FIG. 1 shows a flow diagram of a method for synthesizing a triaminotoluene-based nucleating agent in an embodiment of the present invention;
FIG. 2 shows a NMR spectrum of N, N, N-triacetyl-2, 4, 6-triaminotoluene (Ia) prepared in example 1 of the present invention;
FIG. 3 shows a NMR carbon spectrum of N, N, N-triacetyl-2, 4, 6-triaminotoluene (Ia) prepared in example 1 of the present invention;
FIG. 4 shows an infrared spectrum of N, N, N-triacetyl-2, 4, 6-triaminotoluene (Ia) prepared in example 1 of the present invention;
FIG. 5 shows a high resolution mass spectrum of N, N, N-triacetyl-2, 4, 6-triaminotoluene (Ia) prepared in example 1 of the present invention;
FIG. 6 shows a NMR spectrum of N, N, N-tri-tert-butyryl-2, 4, 6-triaminotoluene (Id) prepared in example 2 of the present invention;
FIG. 7 shows a NMR carbon spectrum of N, N, N-tri-tert-butyryl-2, 4, 6-triaminotoluene (Id) prepared in example 2 of the present invention;
FIG. 8 shows an infrared spectrum of N, N, N-tri-tert-butyryl-2, 4, 6-triaminotoluene (Id) prepared in example 2 of the present invention;
FIG. 9 shows a high resolution mass spectrum of N, N, N-tri-tert-butyryl-2, 4, 6-triaminotoluene (Id) prepared in example 2 of the present invention;
FIG. 10 shows the NMR spectrum of N, N, N-tritentanoyl-2, 4, 6-triaminotoluene (Ig) prepared in example 3 of this invention;
FIG. 11 shows the NMR carbon spectrum of N, N, N-tritentanoyl-2, 4, 6-triaminotoluene (Ig) prepared in example 3 of this invention;
FIG. 12 shows an infrared spectrum of N, N, N-tritentanoyl-2, 4, 6-triaminotoluene (Ig) prepared in example 3 of the present invention;
FIG. 13 shows a high resolution mass spectrum of N, N, N-tritentanoyl-2, 4, 6-triaminotoluene (Ig) prepared in example 3 of the present invention;
FIG. 14 is a DSC curve of polypropylene T30S with 1 ‰ N, N, N-triacetyl-2, 4, 6-triaminotoluene (Ia) added in application example 1, and a DSC curve of polypropylene without nucleating agent added;
FIG. 15 is a histogram of haze values of polypropylene T30S with 1 ‰ N, N, N-triacetyl-2, 4, 6-triaminotoluene (Ia) added in application example 1, and a histogram of haze values of polypropylene without nucleating agent added;
FIG. 16 is a bar graph of haze values for polypropylene K4912 with 1% o N, N, N-triacetyl-2, 4, 6-triaminotoluene (Ia) added and for polypropylene with 1% o commercial amide nucleator XT386 added in comparative example 1 of the present invention;
FIG. 17 is a DSC curve of polypropylene K4912 with 1% o of N, N, N-triacetyl-2, 4, 6-triaminotoluene (Ia) added thereto and a DSC curve of polypropylene with 1% o of commercially available amide nucleating agent XT386 added thereto in comparative example 1 of the present invention;
FIG. 18 is a bar graph of haze values for polypropylene T30S with 1% o N, N, N-triacetyl-2, 4, 6-triaminotoluene (Ia) added and for polypropylene with 1% o commercial amide nucleator XT386 in comparative example 2 of the present invention;
FIG. 19 is a DSC of polypropylene T30S with 1% o N, N, N-triacetyl-2, 4, 6-triaminotoluene (Ia) added, and a DSC of polypropylene with 1% o commercial amide nucleator XT386 added in comparative example 2 of the present invention.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The specific experimental procedures or conditions not specified in the examples can be performed according to the procedures or conditions of the conventional experimental procedures described in the prior art in this field. The reagents and other instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
In a first aspect, the embodiment of the invention provides a triamido methylbenzene nucleating agent, wherein an N, N, N-triacyl-2, 4, 6-triaminotoluene compound with a structural general formula shown in a structural formula I is used as the nucleating agent for nucleating a polymer at high temperature;
Figure BDA0003270686560000071
wherein R is a straight-chain or branched-chain alkyl group having 1 to 6 carbon atoms, an unsubstituted 5 to 6 cycloalkyl group, a straight-chain or branched-chain 5 to 6 cycloalkyl group substituted with an alkyl group having 1 to 4 carbon atoms, a 5 to 6 cycloalkyl group derived from a halogen atom, an aryl group, or a straight-chain or branched-chain aryl group substituted with an alkyl group having 1 to 4 carbon atoms.
The triamido toluene nucleating agent provided by the embodiment can effectively reduce the haze of a polymer film, improve the crystallization temperature of a conjugate and improve the product quality of the conjugate, takes retired TNT as a raw material, and has the advantages of stable intermediate property, mild reaction conditions of each step, low cost, short synthesis time, effective reduction of danger in the synthesis process and the like through a two-step simple organic reaction synthesis method, and is beneficial to industrial production.
In the specific implementation of this embodiment, in the general structural formula of the N, N-triacyl-2, 4, 6-triaminotoluene compound shown in the structural formula I, preferably R is one of methyl, ethyl, N-propyl, isopropyl, butyl, isobutyl, tert-butyl, cyclohexyl, cyclopentyl, phenyl and naphthyl. The corresponding compounds are respectively: n, N, N-triacetyl-2, 4, 6-triaminotoluene (Ia), N, N, N-tripropionyl-2, 4, 6-triaminotoluene (Ib), N, N, N-tri-N-butyryl-2, 4, 6-triaminotoluene (Ic), N, N, N-triisobutyryl-2, 4, 6-triaminotoluene (Id), N, N, N-tri-N-valeryl-2, 4, 6-triaminotoluene (Ie), N, N, N-triisovaleryl-2, 4, 6-triaminotoluene (If), N, N, N-trinitrovaleryl-2, 4, 6-triaminotoluene (Ig), N, N, N-tricyclohexylformyl-2, 4, 6-triaminotoluene (Ih), N, N, N-tricyclopentylformyl-2, 4, 6-triaminotoluene (Ii), N, N, N-tribenzoyl-2, 4, 6-triaminotoluene (Ij), N, N, N-trinaphthoyl-2, 4, 6-triaminotoluene (Ik). The corresponding structural formulae for these compounds are as follows:
Figure BDA0003270686560000081
in the specific implementation of this embodiment, when the triaminotoluene nucleating agent is used, the preferable polymer may be any one of polypropylene, resin, and polylactic acid.
In a second aspect, the embodiments of the present invention provide a method for preparing the triaminomethylbenzene nucleating agent described in the first aspect. In specific implementation, the method comprises the following steps:
step 1: taking 2,4, 6-trinitrotoluene shown in a structural formula III as a raw material, and carrying out catalytic hydrogenation reaction to obtain 2,4, 6-trinitrotoluene shown in a structural formula II;
step 2: carrying out transacylation reaction on 2,4, 6-triaminotoluene shown in a structural formula II and ester shown in a structural formula IV or V under an alkaline condition to generate a target product shown in a structural formula I;
Figure BDA0003270686560000082
in the present embodiment, the preferred reaction conditions in the catalytic hydrogenation reaction of step 1 are as follows:
the pressure range of the used hydrogen is 0.1-0.8 MPa, and the used catalyst is a palladium/carbon catalyst or a Raney nickel catalyst; wherein, when the catalyst is a palladium/carbon catalyst, the mass ratio of the palladium/carbon catalyst to the 2,4, 6-trinitrotoluene is 0.01: 1-0.2: 1, and when the catalyst is a Raney nickel catalyst, the mass ratio of the Raney nickel catalyst to the 2,4, 6-trinitrotoluene is 0.05: 1-0.5: 1;
the reaction temperature of the catalytic hydrogenation reaction is 15-75 ℃, the reaction time is 0.5-12 h, and the reaction solvent at least comprises one of methanol, ethanol, isopropanol, acetonitrile, chloroform, ethyl acetate, methyl propionate, methyl pivalate, ethyl pivalate and tetrahydrofuran.
In the embodiment, in the alkaline condition of step 2, the preferable reaction conditions are as follows:
the molar ratio of the used alkali to the 2,4, 6-triaminotoluene shown in the structural formula II is 3-4.5: 1, and the molar ratio of the ester shown in the structural formula IV or V to the alkali is 1-5: 1;
the used alkali is one of sodium tert-butoxide, potassium tert-butoxide, lithium tert-butoxide, sodium bis (trimethylsilyl) amide, lithium bis (trimethylsilyl) amide, potassium bis (trimethylsilyl) amide, n-butyllithium or lithium diisopropylamide;
the reaction temperature under the alkaline condition is 0-30 ℃, and the reaction time is 0.5-10 h;
the reaction solvent can be one of tetrahydrofuran, dioxane, toluene and glycol dimethyl ether.
In a third aspect, the embodiment of the present invention provides a method for using the triaminomethylbenzene nucleating agent described in the first aspect. The using method comprises the following steps:
mixing the triamido toluene nucleating agent, the polymer to be nucleated and the anti-aging agent to prepare a polypropylene sample containing the triamido toluene nucleating agent;
melt mixing a polypropylene sample;
preparing the melted and mixed polypropylene sample into a preset model through a hot press or an injection molding machine;
and quenching or quenching the preset model to obtain a model sample.
In the concrete implementation of the embodiment, on the basis that the mass of the polymer to be nucleated is equal to 100, when a polypropylene sample is prepared, the preferable mass fraction of the triamido toluene nucleating agent is 0.005-0.2%, and the preferable mass fraction of the anti-aging agent is 0.05-0.1%;
in this embodiment, the anti-aging agent is composed of the anti-aging agent 1010 and the anti-aging agent 168. In specific implementation, the preferred mass ratio of the anti-aging agent 1010 to the anti-aging agent 168 is 1: 1-2.
It should be noted that the value ranges of the above substances and the value ranges of the above parameters are only preferred embodiments of the present invention, and the present invention is not limited to the values, and all the value ranges applicable to the present invention are feasible.
In order to make the present invention more comprehensible to those skilled in the art, the triaminomethylbenzene nucleating agent provided by the present invention and the preparation method thereof are illustrated below by way of specific examples. However, it should be noted that: the scope of the invention is not limited to the following examples.
The structural formulas of the reactants and products of the following examples 1-11 are as follows:
Figure BDA0003270686560000101
EXAMPLE 1 nucleating agent N, N, N-triacetyl-2, 4, 6-triaminotoluene (Ia)
TNT (3.4g,15.0mmol) was dissolved in ethyl acetate (30ml) to obtain a TNT solution, which was subjected to hydrogenation at room temperature under high pressure (0.6MPa) in the presence of a Pd/C catalyst (0.3 g). When the reaction starts, the pressure of the reaction kettle is rapidly reduced to be below 0.2MPa from 0.6MPa, hydrogen is supplemented to enable the pressure to reach 0.6MPa again, and the pressure of the reaction kettle is still obviously reduced. Checking the air tightness to confirm that no air leakage occurs, repeating the aeration operation for 3 times until the pressure in the high-pressure reaction kettle does not drop, confirming that the reaction reaches the end point, and stopping stirring. After the reaction, the solution was first filtered to obtain a solid containing the catalyst and a dark red solution, after the Pd/C catalyst was filtered off, anhydrous ethanol preheated at 70 ℃ was poured into the solution, after the solution was cooled, a white precipitate precipitated at the bottom, and after filtration, a white solid II (1.7g, 83%) was collected.
The white solid II (1.7g, 12.4mmol) collected in the above step, IVa (4.4ml, 55.8mmol) and NaOtBu (5.4g, 55.8mmol) were dissolved in tetrahydrofuran (30ml) to obtain a solution, which was subjected to transacylation at room temperature. After 1 hour of the reaction, ice water was added dropwise to the system to stop the reaction, and a part of white solid was observed to be precipitated during the dropwise addition. Stirring was stopped, and after completion of the reaction, the product was filtered and washed repeatedly with anhydrous ethanol, and after filtration, Ia (3.0g, 93%) was collected as a white solid.
The white solid Ia obtained was then subjected to a series of characterizations including nuclear magnetic hydrogen spectroscopy, nuclear magnetic carbon spectroscopy, infrared and high resolution mass spectroscopy. FIG. 2 shows a NMR spectrum of N, N, N-triacetyl-2, 4, 6-triaminotoluene (Ia) prepared in example 1 of the present invention; FIG. 3 shows a NMR carbon spectrum of N, N, N-triacetyl-2, 4, 6-triaminotoluene (Ia) prepared in example 1 of the present invention; FIG. 4 shows an infrared spectrum of N, N, N-triacetyl-2, 4, 6-triaminotoluene (Ia) prepared in example 1 of the present invention; FIG. 5 shows a high resolution mass spectrum of N, N, N-triacetyl-2, 4, 6-triaminotoluene (Ia) prepared in example 1 of the present invention; the specific characterization data are as follows:
1H-NMR(400MHz,DMSO-D6)δ(ppm):9.88(s,1H,NH),9.35(s,2H,NH),7.46(s,2H,Ar-H),2.03(s,6H),2.00(s,3H),1.95(s,3H).
13C-NMR(100MHz,DMSO-D6)δ(ppm):168.01,136.67,136.35,121.89,113.60,23.84,23.08,12.53.
FT-IR(ATR,cm-1):3273(m),1650(s),1611(s),1525(s),1468(m),1417(s),1369(s),1269(s),1038(w),1018(w),971(w),872(m),863(m),788(w),719(m),601(m),573(w),508(s).
HR-MS(ESI):264.13457(M+H+),281.16102(M+NH4 +),286.11650(M+Na+).
EXAMPLE 2 nucleating agent N, N, N-tri-tert-butyryl-2, 4, 6-triaminotoluene (Id)
TNT (3.4g,15mmol) was dissolved in ethyl acetate (30ml) to obtain a TNT solution, which was subjected to hydrogenation at room temperature under high pressure (0.6MPa) in the presence of a Pd/C catalyst (0.3 g). When the reaction starts, the pressure of the reaction kettle is rapidly reduced to be below 0.2MPa from 0.6MPa, hydrogen is supplemented to enable the pressure to reach 0.6MPa again, and the pressure of the reaction kettle is still obviously reduced. Checking the air tightness to confirm that no air leakage occurs, repeating the aeration operation for 3 times until the pressure in the high-pressure reaction kettle does not drop, confirming that the reaction reaches the end point, and stopping stirring. After the reaction, the solution was first filtered to obtain a solid containing the catalyst and a dark red solution, after the Pd/C catalyst was filtered off, anhydrous ethanol preheated at 70 ℃ was poured into the solution, after the solution was cooled, a white precipitate precipitated at the bottom, and after filtration, a white solid II (1.7g, 83%) was collected.
White solid II (1.7g, 12.4mmol) collected in the above step, IVd (6.4ml, 55.8mmol) and LiOtBu (4.5g, 55.8mmol) were dissolved in dioxane (30ml) to obtain a solution, and transacylation was performed at room temperature. After 1 hour of the reaction, ice water was added dropwise to the system to stop the reaction, and a part of white solid was observed to be precipitated during the dropwise addition. Stirring was stopped and after the reaction was complete the product was filtered and washed repeatedly with anhydrous ethanol and after filtration a white solid Id (1.0g, 24%) was collected.
The resulting white solid Id was then subjected to a series of characterizations including nuclear magnetic hydrogen, carbon, infrared and high resolution mass spectra. FIG. 6 shows a NMR spectrum of N, N, N-tri-tert-butyryl-2, 4, 6-triaminotoluene (Id) prepared in example 2 of the present invention; FIG. 7 shows a NMR carbon spectrum of N, N, N-tri-tert-butyryl-2, 4, 6-triaminotoluene (Id) prepared in example 2 of the present invention; FIG. 8 shows an infrared spectrum of N, N, N-tri-tert-butyryl-2, 4, 6-triaminotoluene (Id) prepared in example 2 of the present invention; FIG. 9 shows a high resolution mass spectrum of N, N, N-tri-tert-butyryl-2, 4, 6-triaminotoluene (Id) prepared in example 2 of the present invention; the specific characterization data are as follows:
1H-NMR(400MHz,DMSO-D6)δ(ppm):9.75(m,1H,NH),9.26(m,2H,NH),7.44(s,2H,Ar-H),3.33(s,1H),2.62(w,2H),1.92(s,3H),1.10(s,12H),1.05(s,6H).
13C NMR(101MHz,DMSO)δ175.54,137.10,137.00,123.34,114.88,40.62,40.41,40.20,39.99,39.78,39.58,39.37,35.30,34.72,20.07,19.95,12.80.
FT-IR(ATR,cm-1):3244(w),3053(w),2967(w),2932(w),2874(w),1658(s),1602(m),1544(s),1457(m),1415(m),1387(m),1292(w),1232(s),1211(m),1177(m),1096(m),1011(w),964(w),945(w),931(w),882(w),860(m),771(w),741(m),720(m),638(w),598(w),550(w),536(w).
HR-MS(ESI):348.227536(M+H+),365.253646(M+NH4 +),370.210531(M+Na+),386.184542(M+K+).
EXAMPLE 3 nucleating agent N, N, N-Tripivaloyl-2, 4, 6-Triaminotoluene (Ig)
TNT (3.4g,15mmol) was dissolved in ethyl acetate (30ml) to obtain a TNT solution, which was subjected to hydrogenation at room temperature under high pressure (0.6MPa) in the presence of a Pd/C catalyst (0.3 g). When the reaction starts, the pressure of the reaction kettle is rapidly reduced to be below 0.2MPa from 0.6MPa, hydrogen is supplemented to enable the pressure to reach 0.6MPa again, and the pressure of the reaction kettle is still obviously reduced. Checking the air tightness to confirm that no air leakage occurs, repeating the aeration operation for 3 times until the pressure in the high-pressure reaction kettle does not drop, confirming that the reaction reaches the end point, and stopping stirring. After the reaction, the solution was first filtered to obtain a solid containing the catalyst and a dark red solution, after the Pd/C catalyst was filtered off, anhydrous ethanol preheated at 70 ℃ was poured into the solution, after the solution was cooled, a white precipitate precipitated at the bottom, and after filtration, a white solid II (1.7g, 83%) was collected.
White solid II (1.7g, 12.4mmol), Vg (8.3ml, 55.8mmol) and KOtBu (6.3g, 55.8mmol) collected in the above step were dissolved in ethylene glycol dimethyl ether (30ml) to obtain a solution, and transacylation reaction was performed at room temperature. After 1 hour of the reaction, ice water was added dropwise to the system to stop the reaction, and a part of white solid was observed to be precipitated during the dropwise addition. Stirring was stopped, the product was filtered after the reaction was over and repeatedly washed with anhydrous ethanol, and white solid Ig (2.9g, 60%) was collected after filtration.
The white solid Ig obtained was then subjected to a series of characterizations including nuclear magnetic hydrogen spectroscopy, nuclear magnetic carbon spectroscopy, infrared and high resolution mass spectroscopy. FIG. 10 shows the NMR spectrum of N, N, N-tritentanoyl-2, 4, 6-triaminotoluene (Ig) prepared in example 3 of this invention; FIG. 11 shows the NMR carbon spectrum of N, N, N-tritentanoyl-2, 4, 6-triaminotoluene (Ig) prepared in example 3 of this invention; FIG. 12 shows an infrared spectrum of N, N, N-tritentanoyl-2, 4, 6-triaminotoluene (Ig) prepared in example 3 of the present invention; FIG. 13 shows a high resolution mass spectrum of N, N, N-tritentanoyl-2, 4, 6-triaminotoluene (Ig) prepared in example 3 of the present invention; the specific characterization data are as follows:
1H-NMR(400MHz,DMSO-D6)δ(ppm):9.17(s,1H,NH),8.98(s,2H,NH),7.41(s,2H,Ar-H),1.88(s,3H),1.23(s,18H),1.20(s,9H).
13C-NMR(100MHz,DMSO-D6)δ(ppm):176.21,176.18,136.66,136.36,125.76,116.90,38.99,38.52,27.31,27.07,12.07.
FT-IR(ATR,cm-1):3316(w),2964(m),2906(w),2872(w),1704(w),1654(s),1601(m),1511(s),1479(m),1420(s),1367(m),1304(w),1190(m),1030(w),930(m),864(m),816(w),768(w),684(m),533(m).
HR-MS(ESI):390.27449(M+H+),407.30088(M+NH4 +),412.25263(M+Na+).
the applicant should note that the triaminomethylbenzene nucleating agent provided in this example can be synthesized by any of the procedures described in any of examples 1 to 3, and the difference is mainly determined by the structural characteristics of the R substituent. Therefore, they are not listed in this embodiment.
In order to make the person skilled in the art better understand the nucleation effect of the nucleating agent provided by the present invention, the following uses a plurality of specific application examples to illustrate the use method and nucleation performance of the triamido toluene nucleating agent provided by the present invention.
Application example 1
1 thousandth of the age resistor 1010 and 1 thousandth of the age resistor 168 were added to polypropylene T30S, and 1 thousandth of N, N, N-triacetyl-2, 4, 6-triaminotoluene (Ia) was added at the same time, and thoroughly mixed to prepare a premix, and then the whole premix was fed into a twin-screw extruder. And (3) extruding and granulating at 190 ℃ by using a double-screw extruder to obtain a T30S polypropylene master batch containing the N, N, N-triacetyl-2, 4, 6-triaminotoluene (Ia). And (3) putting the master batch into an injection molding machine, using a plate-shaped mold, performing injection molding at the temperature of 190 ℃ or lower for 15 seconds under the pressure maintaining time, and demolding to obtain the polypropylene T30S board with lower haze.
The master batch obtained above was subjected to DSC measurement to obtain crystallization temperature data. DSC test condition is N2Heating to 200 deg.C at 10 deg.C/min under 50ml/min, maintaining for 5 min to eliminate heat history, and cooling to 80 deg.C at-10 deg.C/min from 200 deg.C. The obvious endothermic peak appeared in the cooling process is the crystallization peak, and the peak position is the measured crystallizationAnd (3) temperature.
The plate obtained above was placed under a haze meter to test the optical properties. The test uses light source D65, ISO standard. 5 points were selected for each sample and the mean calculated for the data.
Through tests, the crystallization temperature of the T30S board added with 1 per mill of N, N, N-triacetyl-2, 4, 6-triaminotoluene (Ia) is increased by 10.3 ℃ (shown in figure 14) compared with the crystallization temperature of the T30S board without the nucleating agent, and the haze value is reduced by 12.98 (shown in figure 15).
The haze value and crystallization temperature obtained by the test were changed based on the same operation by changing only the amount of N, N, N-triacetyl-2, 4, 6-triaminotoluene (Ia) added, see Table 1.
Application example 2
1 thousandth of an anti-aging agent 1010 and 1 thousandth of an anti-aging agent 168 were added to polypropylene T30S, and 1 thousandth of N, N, N-tripropionyl-2, 4, 6-triaminotoluene (Ib) was added at the same time, and thoroughly mixed to prepare a premix, and then the whole premix was fed into a twin-screw extruder. The mixture was extruded and pelletized at 190 ℃ using a twin-screw extruder to obtain a T30S polypropylene master batch containing N, N, N-tripropionyl-2, 4, 6-triaminotoluene (Ib). And (3) putting the master batch into an injection molding machine, using a plate-shaped mold, performing injection molding at the temperature of 190 ℃ or lower for 15 seconds under the pressure maintaining time, and demolding to obtain the polypropylene T30S board with lower haze.
Also, based on the same operation, only the amount of N, N, N-triacetyl-2, 4, 6-triaminotoluene (Ib) added was changed, and the haze value and the crystallization temperature were measured by the same measuring method as in example 1. The haze and crystallization temperature obtained by the test are shown in Table 1.
Application example 3
1% o of an anti-aging agent 1010 and 1% o of an anti-aging agent 168 were added to polypropylene T30S, and 1% o of N, N, N-tri-N-butyryl-2, 4, 6-triaminotoluene (Ic) was added at the same time, and thoroughly mixed to prepare a premix, and then the whole premix was fed into a twin-screw extruder. The mixture was extruded and pelletized at 190 ℃ using a twin-screw extruder to obtain a T30S polypropylene master batch containing N, N, N-tri-N-butyryl-2, 4, 6-triaminotoluene (Ic). And (3) putting the master batch into an injection molding machine, using a plate-shaped mold, performing injection molding at the temperature of 190 ℃ or lower for 15 seconds under the pressure maintaining time, and demolding to obtain the polypropylene T30S board with lower haze.
Also, based on the same operation, only the amount of N, N, N-tri-N-butyryl-2, 4, 6-triaminotoluene (Ic) added was changed, and the haze value and the crystallization temperature were measured by the same test method as in example 1. The haze and crystallization temperature obtained by the test are shown in Table 1.
Application example 4
1% o of the age resistor 1010 and 1% o of the age resistor 168 were added to the polypropylene T30S, and 1% o of N, N, N-triisobutanoyl-2, 4, 6-triaminotoluene (Id) was added at the same time, and thoroughly mixed to prepare a premix, and then the whole premix was fed into a twin-screw extruder. The mixture was extruded and pelletized at 190 ℃ using a twin-screw extruder to obtain a T30S polypropylene master batch containing N, N, N-triisobutanoyl-2, 4, 6-triaminotoluene (Id). And (3) putting the master batch into an injection molding machine, using a plate-shaped mold, performing injection molding at the temperature of 190 ℃ or lower for 15 seconds under the pressure maintaining time, and demolding to obtain the polypropylene T30S board with lower haze.
Also, based on the same operation, only the amount of N, N, N-triisobutanoyl-2, 4, 6-triaminotoluene (Id) added was changed, and the haze value and the crystallization temperature were measured by the same test method as in example 1. The haze and crystallization temperature obtained by the test are shown in Table 1.
Application example 5
1 thousandth of the age resister 1010 and 1 thousandth of the age resister 168 were added to the polypropylene T30S, and 1 thousandth of N, N, N-tri-N-pentanoyl-2, 4, 6-triaminotoluene (Ie) was added at the same time, and thoroughly mixed to prepare a premix, and then the whole premix was put into a twin-screw extruder. And (3) extruding and granulating at 190 ℃ by using a double-screw extruder to obtain a T30S polypropylene master batch containing N, N, N-tri-N-pentanoyl-2, 4, 6-triaminotoluene (Ie). And (3) putting the master batch into an injection molding machine, using a plate-shaped mold, performing injection molding at the temperature of 190 ℃ or lower for 15 seconds under the pressure maintaining time, and demolding to obtain the polypropylene T30S board with lower haze.
Also, based on the same operation, only the amount of N, N, N-tri-N-pentanoyl-2, 4, 6-triaminotoluene (Ie) added was changed, and the haze value and the crystallization temperature were measured by the same test method as in example 1. The haze and crystallization temperature obtained by the test are shown in Table 1.
Application example 6
1% o of an age resistor 1010 and 1% o of an age resistor 168 were added to polypropylene T30S, and 1% o of N, N, N-triisopentanoyl-2, 4, 6-triaminotoluene (If) was added at the same time, and thoroughly mixed to prepare a premix, and then the whole premix was fed into a twin-screw extruder. The mixture was extruded and pelletized at 190 ℃ using a twin-screw extruder to obtain a T30S polypropylene master batch containing N, N, N-triisovaleryl-2, 4, 6-triaminotoluene (If). And (3) putting the master batch into an injection molding machine, injecting and molding at 190 ℃ by using a plate-shaped mold, wherein the mold temperature is room temperature or lower, the pressure maintaining time is 15 seconds, and demolding to obtain the polypropylene T30S board with lower haze.
And, based on the same operation, only the amount of N, N, N-triisopentanoyl-2, 4, 6-triaminotoluene (If) added was changed, and the haze value and the crystallization temperature were measured by the same test method as in example 1. The haze and crystallization temperature obtained by the test are shown in Table 1.
Application example 7
1 thousandth of the age resister 1010 and 1 thousandth of the age resister 168 were added to polypropylene T30S, and 1 thousandth of N, N, N-tritertvaleryl-2, 4, 6-triaminotoluene (Ig) was added at the same time, and thoroughly mixed to prepare a premix, and then the whole premix was put into a twin-screw extruder. And extruding and granulating at 190 ℃ by using a double-screw extruder to obtain a T30S polypropylene master batch containing N, N, N-trinitroamyl-2, 4, 6-triaminotoluene (Ig). And (3) putting the master batch into an injection molding machine, using a plate-shaped mold, performing injection molding at the temperature of 190 ℃ or lower for 15 seconds under the pressure maintaining time, and demolding to obtain the polypropylene T30S board with lower haze.
Also, based on the same operation, only the amount of N, N, N-trineopentanoyl-2, 4, 6-triaminotoluene (Ig) added was changed, and the haze value and the crystallization temperature were measured by the same test method as in example 1. The haze and crystallization temperature obtained by the test are shown in Table 1.
Application example 8
1 thousandth of the age resistor 1010 and 1 thousandth of the age resistor 168 were added to polypropylene T30S, and 1 thousandth of N, N, N-tricyclohexylformyl-2, 4, 6-triaminotoluene (Ih) was added at the same time, and thoroughly mixed to prepare a premix, and then the whole premix was fed into a twin-screw extruder. The mixture was extruded and pelletized at 190 ℃ using a twin-screw extruder to obtain a T30S polypropylene master batch containing N, N, N-tricyclohexylformyl-2, 4, 6-triaminotoluene (Ih). And (3) putting the master batch into an injection molding machine, using a plate-shaped mold, performing injection molding at the temperature of 190 ℃ or lower for 15 seconds under the pressure maintaining time, and demolding to obtain the polypropylene T30S board with lower haze.
Also, based on the same operation, only the amount of N, N, N-tricyclohexylformyl-2, 4, 6-triaminotoluene (Ih) added was changed, and the haze value and the crystallization temperature were measured by the same test method as in example 1. The haze and crystallization temperature obtained by the test are shown in Table 1.
Application example 9
1% o of an anti-aging agent 1010 and 1% o of an anti-aging agent 168 were added to polypropylene T30S, and simultaneously 1% o of N, N, N-tricyclopentylformyl-2, 4, 6-triaminotoluene (Ii) was added, and they were thoroughly mixed to prepare a premix, and then the whole premix was fed into a twin-screw extruder. The mixture was extruded and pelletized at 190 ℃ using a twin-screw extruder to obtain a T30S polypropylene master batch containing N, N, N-tricyclopentylformyl-2, 4, 6-triaminotoluene (Ii). And putting the master batch into a flat vulcanizing machine, pressing at 190 ℃ by using a plate-shaped die, preheating for 3 minutes, exhausting for 1 time, pressurizing to 7MPa, maintaining the pressure for 5 minutes, then decompressing, carrying out underwater quenching together with the die, and then demoulding to obtain the polypropylene T30S plate with lower haze.
Also, based on the same operation, only the amount of N, N, N-tricyclopentylformyl-2, 4, 6-triaminotoluene (Ii) added was changed, and the haze value and the crystallization temperature were measured by the same test method as in example 1. The haze and crystallization temperature obtained by the test are shown in Table 1.
Application example 10
1 thousandth of the age resistor 1010 and 1 thousandth of the age resistor 168 were added to polypropylene T30S, and 1 thousandth of N, N, N-tribenzoyl-2, 4, 6-triaminotoluene (Ij) was added at the same time, and thoroughly mixed to prepare a premix, and then the whole premix was fed into a twin-screw extruder. The mixture was extruded and pelletized at 190 ℃ using a twin-screw extruder to obtain a T30S polypropylene master batch containing N, N, N-tribenzoyl-2, 4, 6-triaminotoluene (Ij). And putting the master batch into a flat vulcanizing machine, pressing at 190 ℃ by using a plate-shaped mold, preheating for 3 minutes, exhausting for 1 time, pressurizing to 7MPa, maintaining the pressure for 5 minutes, cooling by adopting flowing water, quenching the mold, and then releasing pressure and demolding to obtain the polypropylene T30S board with low haze.
Also, based on the same operation, only the amount of N, N, N-tribenzoyl-2, 4, 6-triaminotoluene (Ij) added was changed, and the haze value and the crystallization temperature were measured by the same test method as in example 1. The haze and crystallization temperature obtained by the test are shown in Table 1.
Application example 11
1 thousandth of the age resistor 1010 and 1 thousandth of the age resistor 168 were added to polypropylene T30S, and 1 thousandth of N, N, N-trinaphthoyl-2, 4, 6-triaminotoluene (Ik) was added at the same time, and thoroughly mixed to prepare a premix, and then the whole premix was fed into a twin-screw extruder. And (3) extruding and granulating at 190 ℃ by using a double-screw extruder to obtain a T30S polypropylene master batch containing N, N, N-trinaphthoyl-2, 4, 6-triaminotoluene (Ik). And (3) putting the master batch into an injection molding machine, using a plate-shaped mold, performing injection molding at the temperature of 190 ℃ or lower for 15 seconds under the pressure maintaining time, and demolding to obtain the polypropylene T30S board with lower haze.
Also, based on the same operation, only the amount of N, N, N-trinaphthoyl-2, 4, 6-triaminotoluene (Ik) added was changed, and the haze value and the crystallization temperature were measured by the same test method as in example 1. The haze and crystallization temperature obtained by the test are shown in Table 1.
Comparative example 1
The nucleating agent used in this comparative example was commercial XT386, having the chemical name N, N, N-trittanoylated-1, 3, 5-triaminobenzene.
1 ‰ of the anti-aging agent 1010 and 1 ‰ of the anti-aging agent 168 were added to polypropylene T30S, and 1 ‰ of commercial XT386 was added at the same time, and mixed thoroughly to make a premix, and then the whole premix was fed into a twin screw extruder. Extrusion granulation was carried out at 190 ℃ using a twin-screw extruder to obtain a T30S polypropylene masterbatch containing commercially available XT 386. And (3) putting the master batch into an injection molding machine, using a plate-shaped mold, performing injection molding at the temperature of 190 ℃ or lower for 15 seconds under the pressure maintaining time, and demolding to obtain the polypropylene T30S board with lower haze.
Also, based on the same operation, only the amount of commercial XT386 added was changed and the haze value and crystallization temperature were tested using the same test method as in example 1. The haze and crystallization temperature obtained by the test are shown in Table 1.
Comparative example 2
The nucleating agent used in this comparative example was commercially available NX8000, which is a sorbitol-based nucleating agent.
1 ‰ of the anti-aging agent 1010 and 1 ‰ of the anti-aging agent 168 were added to polypropylene T30S, and 1 ‰ of the commercially available NX8000 was added at the same time, and mixed thoroughly to make a premix, and then the whole premix was fed into a twin-screw extruder. The pellets were extruded at 190 ℃ using a twin-screw extruder to obtain a T30S polypropylene masterbatch containing commercially available NX 8000. And (3) putting the master batch into an injection molding machine, using a plate-shaped mold, performing injection molding at the temperature of 190 ℃ or lower for 15 seconds under the pressure maintaining time, and demolding to obtain the polypropylene T30S board with lower haze.
Also, based on the same operation, only the amount of NX8000 added was changed and the haze value and the crystallization temperature were measured by the same test method as in example 1. The haze and crystallization temperature obtained by the test are shown in Table 1.
As can be seen from the data in table 1, the present embodiment provides a nucleating agent that also has a lower haze value (the optimum haze value can be as low as 65.27%) and a higher crystallization temperature (the optimum crystallization temperature can be as high as 129.5 ℃) compared to the two nucleating agents XT386 and NX8000 which are relatively common on the market and are also widely used at present.
TABLE 1 haze value and crystallization temperature of each nucleating agent in application examples 1 to 11
Figure BDA0003270686560000201
Figure BDA0003270686560000211
The structure of each nucleating agent in table 1 above is as follows:
Figure BDA0003270686560000212
Figure BDA0003270686560000221
in addition, in order to better illustrate the nucleating agent provided by the present embodiment, the nucleating agent has a better nucleating effect compared with the existing nucleating agent. In this example, a conventional commercially available nucleating agent XT386 was used as a comparative example, and the concrete description thereof was made. The method comprises the following specific steps:
COMPARATIVE EXAMPLE 1 (grade of polypropylene: K4912)
The prepared K4912 plate (1mm thick) containing 1% o of N, N, N-triacetyl-2, 4, 6-triaminotoluene (Ia) is placed under a haze meter to test the optical performance. The test uses light source D65, ISO standard. 5 points were selected for each sample and the mean calculated for the data. The haze of a sample of K4912 polypropylene containing 1% o commercial XT386 was measured using the same conditions. The test data is shown in fig. 16, and as can be seen from the data in fig. 16, the K4912 haze with 1% o N, N-triacetyl-2, 4, 6-triaminotoluene (Ia) is 22.72% which is about 4.05% lower than the T30S haze with 1% o commercial XT 386.
The prepared K4912 polypropylene master batch containing 1 ‰ N, N-triacetyl-2, 4, 6-triaminotoluene (Ia) was subjected to DSC test to obtain crystallization temperature data. DSC test condition is N2Heating to 200 deg.C at 10 deg.C/min under 50ml/min, and maintaining for 5 minThe temperature is reduced from 200 ℃ to 80 ℃ at a speed of-10 ℃/min. The obvious endothermic peak appeared in the cooling process is the crystallization peak, and the peak position is the measured crystallization temperature. The crystallization temperature of a sample of K4912 polypropylene containing 1 ‰ commercial XT386 was determined under the same conditions. The test data is shown in FIG. 17, and as can be seen from the data shown in FIG. 17, the crystallization temperature of K4912 containing 1% o N, N, N-triacetyl-2, 4, 6-triaminotoluene (Ia) is 119.0 ℃ which is about 0.8 ℃ higher than the crystallization temperature of T30S containing 1% o commercial XT 386.
COMPARATIVE EXAMPLE 2 (grade of polypropylene: T30S)
The prepared T30S plate (1mm thick) containing 1 per mill of N, N, N-triacetyl-2, 4, 6-triaminotoluene (Ia) was placed under a haze meter to test the optical performance. The test uses light source D65, ISO standard. 5 points were selected for each sample and the mean calculated for the data. The haze was measured for a sample of T30S polypropylene containing 1% o commercial XT386 and a sample of T30S polypropylene without nucleating agent using the same conditions. The test data is shown in FIG. 18, and as can be seen from the data shown in FIG. 18, the haze of T30S containing 1% o N, N, N-triacetyl-2, 4, 6-triaminotoluene (Ia) is 65.27%, which is about 12.98% lower than the nucleating agent-free T30S sample, and about 2.53% lower than the haze of T30S containing 1% o commercial XT 386.
The prepared T30S polypropylene master batch containing 1% o N, N-triacetyl-2, 4, 6-triaminotoluene (Ia) was subjected to DSC test to obtain crystallization temperature data. DSC test condition is N2Heating to 200 deg.C at 10 deg.C/min under 50ml/min, maintaining for 5 min to eliminate heat history, and cooling to 80 deg.C at-10 deg.C/min from 200 deg.C. The obvious endothermic peak appeared in the cooling process is the crystallization peak, and the peak position is the measured crystallization temperature. The crystallization temperatures of the T30S polypropylene sample containing 1 ‰ commercial XT386, and the crystallization temperature of the T30S polypropylene sample without nucleating agent were determined using the same conditions. The test data is shown in FIG. 19, and as can be seen from the data shown in FIG. 19, the crystallization temperature of T30S containing 1% o N, N, N-triacetyl-2, 4, 6-triaminotoluene (Ia) is 129.5 deg.C, about 10.3 deg.C higher than the T30S sample without nucleating agent, and about 4.5 deg.C higher than the crystallization temperature of T30S containing 1% o commercial XT 386.
It should be noted that the steps and methods in the embodiments of the present application are not limited to the corresponding embodiments, and the details of the operations and the cautions of the embodiments are all corresponding to each other.
For simplicity of explanation, the method embodiments are described as a series of acts or combinations, but those skilled in the art will appreciate that the present invention is not limited by the order of acts, as some steps may occur in other orders or concurrently in accordance with the invention. Further, those skilled in the art will appreciate that the embodiments described in the specification are preferred embodiments and that the acts and elements referred to are not necessarily required to practice the invention.
The triamido toluene nucleating agent, the preparation method and the use method provided by the invention are described in detail above, the use method in the invention describes the principle and the implementation mode of the invention by specific examples, and the description of the above examples is only used for helping to understand the method and the core idea of the invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, there may be variations in the specific embodiments and the scope of the methods of use, and in summary, the content of the present specification should not be construed as a limitation to the present invention.

Claims (10)

1. A triamido toluene nucleating agent is characterized in that an N, N, N-triacyl-2, 4, 6-triaminotoluene compound with a structural general formula shown in a structural formula I is used as the nucleating agent for polymer nucleation at high temperature;
Figure FDA0003270686550000011
wherein R is a straight-chain or branched-chain alkyl group having 1 to 6 carbon atoms, an unsubstituted 5 to 6 cycloalkyl group, a straight-chain or branched-chain 5 to 6 cycloalkyl group substituted with an alkyl group having 1 to 4 carbon atoms, a 5 to 6 cycloalkyl group derived from a halogen atom, an aryl group, or a straight-chain or branched-chain aryl group substituted with an alkyl group having 1 to 4 carbon atoms.
2. The triaminomethylbenzene nucleating agent according to claim 1, wherein in the general structural formula of the N, N-triacyl-2, 4, 6-triaminotoluene compound represented by the structural formula I, R is one of methyl, ethyl, N-propyl, isopropyl, butyl, isobutyl, tert-butyl, cyclohexyl, cyclopentyl, phenyl and naphthyl.
3. The triaminomethylbenzene-based nucleating agent according to claim 1, wherein the polymer is any one of polypropylene, a resin, and polylactic acid.
4. A process for producing the triaminomethylbenzene-based nucleating agent according to any one of claims 1 to 3, which comprises:
step 1: taking 2,4, 6-trinitrotoluene shown in a structural formula III as a raw material, and carrying out catalytic hydrogenation reaction to obtain 2,4, 6-trinitrotoluene shown in a structural formula II;
step 2: carrying out transacylation reaction on 2,4, 6-triaminotoluene shown in a structural formula II and ester shown in a structural formula IV or V under an alkaline condition to generate a target product shown in a structural formula I;
Figure FDA0003270686550000021
5. the method of claim 4, wherein in the catalytic hydrogenation reaction of step 1, the pressure of hydrogen used is in the range of 0.1 to 0.8MPa, and the catalyst used is a palladium/carbon catalyst or a Raney nickel catalyst; when the catalyst is a palladium/carbon catalyst, the mass ratio of the palladium/carbon catalyst to the 2,4, 6-trinitrotoluene is 0.01: 1-0.2: 1, and when the catalyst is a Raney nickel catalyst, the mass ratio of the Raney nickel catalyst to the 2,4, 6-trinitrotoluene is 0.05: 1-0.5: 1;
the reaction temperature of the catalytic hydrogenation reaction is 15-75 ℃, the reaction time is 0.5-12 h, and the reaction solvent at least comprises one of methanol, ethanol, isopropanol, acetonitrile, chloroform, ethyl acetate, methyl propionate, methyl pivalate, ethyl pivalate and tetrahydrofuran.
6. The method as claimed in claim 4, wherein in the basic condition of the step 2, the molar ratio of the base to the 2,4, 6-triaminotoluene shown in the structural formula II is 3-4.5: 1, and the molar ratio of the ester shown in the structural formula IV or V to the base is 1-5: 1;
the alkali is one of sodium tert-butoxide, potassium tert-butoxide, lithium tert-butoxide, sodium bis (trimethylsilyl) amide, lithium bis (trimethylsilyl) amide, potassium bis (trimethylsilyl) amide, n-butyllithium or lithium diisopropylamide;
the reaction temperature under the alkaline condition is 0-30 ℃, the reaction time is 0.5-10 h, and the reaction solvent at least comprises one of tetrahydrofuran, dioxane, toluene and ethylene glycol dimethyl ether.
7. The method of using the triaminomethylbenzene nucleating agent as defined in any one of claims 1 to 3, which comprises:
mixing the triamido toluene nucleating agent, the polymer to be nucleated and an anti-aging agent to prepare a polypropylene sample containing the triamido toluene nucleating agent;
melt mixing the polypropylene sample;
preparing the melt-mixed polypropylene sample into a preset model;
and quenching or quenching the preset model to obtain a model sample.
8. The use according to claim 7, wherein the mass fraction of the triaminomethylbenzene-based nucleating agent is 0.005-0.2% and the mass fraction of the anti-aging agent is 0.05-0.1%, based on the mass of the polymer to be nucleated being equal to 100.
9. The use according to claim 7 or 8, characterized in that said anti-ageing agent consists of anti-ageing agent 1010 and anti-ageing agent 168.
10. The use method of the anti-aging agent for the automobile, as claimed in claim 9, wherein the mass ratio of the anti-aging agent 1010 to the anti-aging agent 168 is 1: 1-2.
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