CN114057608B

CN114057608B - Method for purifying triisocyanate

Info

Publication number: CN114057608B
Application number: CN202111355947.0A
Authority: CN
Inventors: 黄木华; 彭山青; 张志豪; 杨天宇; 刘艳
Original assignee: Beijing Institute of Technology BIT
Current assignee: Beijing Institute of Technology BIT
Priority date: 2021-11-16
Filing date: 2021-11-16
Publication date: 2022-10-21
Anticipated expiration: 2041-11-16
Also published as: CN114057608A

Abstract

The invention discloses a method for purifying triisocyanate, which uses polynorbornene imide porous material as a solid adsorbent to purify triisocyanate so as to ensure that triisocyanate is transparent. Specifically, the polynorbornene imide porous material provided by the invention combines imide functional group with polynorbornene skeleton structure, has the characteristic of micropore-mesopore hierarchical pore structure mainly comprising micropores, has rich functional groups, high specific surface area, larger total pore volume and smaller average pore diameter, and plays an important role in the fields related to environment and energy, such as organic pollutant adsorption, heterogeneous catalysis, gas storage and the like. In addition, the porous material provided by the invention has excellent performance of good thermal stability, and has potential application prospect.

Description

Method for purifying triisocyanate

Technical Field

The present invention relates to the field of new organic porous polymeric materials and polyisocyanates, which mainly relates to a method for purifying triisocyanates.

Background

Polyisocyanates are a class of chemicals that contain reactive groups and are closely related to human life, however, there are still significant challenges for the purification of polyisocyanate products (angew. Chem. Int.ed.,2013,52,9422-9441 chem.rev.,2013,113,80-118 rscadvances,2016,6, 114453-114482. At present, reduced pressure distillation is mainly adopted for purifying isocyanate, so that the energy consumption is high, the efficiency is low, and the method is not suitable for purifying triisocyanate with high boiling point (such as lexan glue and the like). It is therefore important to find a process which is suitable for purifying polyisocyanates at room temperature. Among them, it is an effective solution to develop a porous adsorbent material having selective adsorption of impurities in polyisocyanate products.

With the intensive research on porous materials, researchers find that the introduction of N and O atoms into porous polymer materials can not only regulate the network structure of the polymer, but also promote the adsorption and separation of the polymer on gases, organic molecules and metal particles. For example, azo groups are introduced to construct a porous azo crosslinked polymer, so that the dipole-quadrupole effect between the porous azo crosslinked polymer and carbon dioxide gas molecules is enhanced, and the constructed porous azo crosslinked polymer shows excellent carbon dioxide adsorption performance (Nat Commun 2013,4, 1357.). The nitrogen-containing porous polymer of polycarboxylate imidazole salt shows selective adsorption effect on organic alcohol compounds (Chem Commun.2014,50 (20), 2595-2597.). As another example, "organic cages" containing imine structures can selectively separate their isomers according to the size of the organic molecule (nat. Chem.,2013,5 (4), 276-281). Organic porous polymers (POPs) are novel high-molecular porous materials which are formed by connecting light elements such as C, H, O, N and the like through covalent bonds and have microporous, mesoporous or hierarchical pore structures, have the advantages of large specific surface area, low density, adjustable pore diameter and the like, have great potential on adsorption performance, and are widely applied to the fields of gas storage, separation, organic environmental pollutant treatment and the like. Among the numerous types of organic porous polymer materials, materials having a selective adsorption separation function are rare. Organic porous polymers have long been studied for adsorption of harmful substances such as ions, dyes and the like in water (J.colloid Interface Sci.2017,507, 42-50.). The functional group design of the functionalized porous polymer at present is mainly to select a specific functional group to be introduced into a polymer framework or a pore channel through a pre-functionalization or post-functionalization strategy. Synthetic methods have been developed that include: aldehyde-amine condensation, boric acid esterification reaction, scholl coupling, yamamoto coupling, sonogashira coupling, cyclotrimerization coupling, oxidation coupling, reduction coupling, ring-opening metathesis polymerization reaction and the like.

Therefore, the current synthesis method of functionalized porous polymer materials mainly has the following defects: (1) The introduction of reactive groups into porous polymers cannot be reasonably achieved; (2) The synthesis process mainly adopts noble metal (such as Pd and Au) for catalysis, and long-time high-temperature synthesis is required. The synthesis process has the problems of high cost, low efficiency, harsh reaction conditions and the like.

Considering the limited introduction of active groups, low synthesis efficiency and high cost in the synthesis process of the functionalized porous polymer, the technical problems which need to be urgently solved by the technical personnel in the field are as follows: the method adopts a reasonable method for introducing active groups into the porous polymer and uses a method with low price of initial raw materials, high efficiency and mild reaction conditions to synthesize the porous polymer.

Considering that the conventional isocyanate purification methods do not satisfy our need for triisocyanate purification, the technical problems which are urgently solved by those skilled in the art are: the triisocyanate is purified by a method which has a good thermal stability, effectively reduces the energy consumption for production and reduces the environmental pollution, and particularly, the high-boiling-point, impurity-containing, dark-colored triisocyanate can be purified to be transparent.

Disclosure of Invention

In order to solve the problems, the invention provides a method for purifying triisocyanate, which uses a polynorbornene imide porous material to purify triisocyanate. The polynorbornene imide porous material has the characteristic of a micropore-mesopore hierarchical pore structure with micropores as main components, and also has good thermal stability.

In a first aspect, the present invention provides a method for purifying triisocyanates using polynorbornene imide porous materials.

Optionally, the polynorbornene imide porous material has a structure of a micropore-mesopore hierarchical pore structure with micropores as main components, and the structural formula of the polynorbornene imide porous material is shown as the following formula I:

optionally, the preparation step of the polynorbornene imide porous material comprises:

step 1, using exo or endo configuration norbornene acid anhydride shown in a structural formula III to perform dehydration reaction with trifunctional aromatic amine or tetrafunctional aromatic amine shown in a structural formula IV to obtain trifunctional/tetrafunctional norbornene imide shown in a structural formula II;

step 2, taking tri-functionality/tetra-functionality norbornene imide shown in the structural formula II as a reactant, and carrying out an olefin ring-opening metathesis polymerization reaction under the action of a ruthenium metal catalyst to obtain polynorbornene imide shown in the structural formula I;

the invention discloses a method for purifying triisocyanate. The method purifies isocyanate by taking a polynorbornene imide porous material as a solid adsorbent so as to ensure that the isocyanate is transparent. Specifically, the polynorbornene imide porous material provided by the invention combines imide functional group with polynorbornene skeleton structure, has the characteristic of micropore-mesopore hierarchical pore structure mainly comprising micropores, has rich functional groups, high specific surface area, larger total pore volume and smaller average pore diameter, and plays an important role in the fields related to environment and energy, such as organic pollutant adsorption, heterogeneous catalysis, gas storage and the like. In addition, the porous material provided by the invention has excellent performance of good thermal stability, and has potential application prospect.

Compared with the prior art, the embodiment of the invention has the following advantages:

the embodiment of the application provides a polynorbornene imide porous material for purifying triisocyanate. The polynorbornene skeleton and the imide structure are introduced into the material, so that the adsorption capacity of the pore channel of the polymer to certain impurities in isocyanate is enhanced; and has good thermal stability. Based on these characteristics, it can be used as a solid adsorbent for purifying isocyanate, especially for purifying triisocyanate with high boiling point, impurities and dark color such as Likelan gum.

Drawings

FIG. 1 is a process for preparing a polynorbornene imide porous material for purifying triisocyanate and a process for preparing the same in the embodiment of the present invention;

FIG. 2 shows the preparation of the monomer Exo-II-a according to an example of the invention ¹ H-NMR(CDCl ₃ 400MHz, 298K) spectrum;

FIG. 3 shows the preparation of monomers Exo-II-b according to an example of the invention ¹ H-NMR(CDCl ₃ 400MHz, 298K) spectrum;

FIG. 4 shows the preparation of monomers Exo-II-c according to an example of the invention ¹ H-NMR(CDCl ₃ 400MHz, 298K) spectrum;

FIG. 5 shows the preparation of monomers Exo-II-d according to an example of the invention ¹ H-NMR(CDCl ₃ 400MHz, 298K) spectrum;

FIG. 6 shows the preparation of monomers Exo-II-e according to an example of the invention ¹ H-NMR(CDCl ₃ 400MHz, 298K) spectrum;

FIG. 7 shows the preparation of monomers Exo-II-f according to an example of the invention ¹ H-NMR(CDCl ₃ 400MHz, 298K) spectrum;

FIG. 8 shows the preparation of monomers Exo-II-f according to an example of the invention ¹ H-NMR(DMSO-d ₆ 400MHz, 298K) spectrum;

FIG. 9 shows the preparation of monomer Endo-II-a in an example of the present invention ¹ H-NMR(CDCl ₃ 400MHz, 298K) spectrum;

FIG. 10 shows the preparation of monomer Endo-II-b in an example of the present invention ¹ H-NMR(CDCl ₃ 400MHz, 298K) spectrum;

FIG. 11 shows the preparation of monomer Endo-II-f in an example of the present invention ¹ H-NMR(CDCl ₃ 400MHz, 298K) spectrum;

FIG. 12 shows APT of Exo-II-a monomer in an example of the present invention ¹³ C-NMR(CDCl ₃ 100mhz, 298k) spectrum;

FIG. 13 shows APT of monomer Exo-II-b in an example of the present invention ¹³ C-NMR(CDCl ₃ 100MHz, 298K);

FIG. 14 shows APT of monomer Exo-II-c in an example of the present invention ¹³ C-NMR(CDCl ₃ 100mhz, 298k) spectrum;

FIG. 15 shows APT of monomers Exo-II-d according to an example of the present invention ¹³ C-NMR(CDCl ₃ 100mhz, 298k) spectrum;

FIG. 16 shows APT of Exo-II-e monomers in examples of the present invention ¹³ C-NMR(CDCl ₃ 100mhz, 298k) spectrum;

FIG. 17 shows APT of Exo-II-f monomers in an example of the present invention ¹³ C-NMR(CDCl ₃ 100mhz, 298k) spectrum;

FIG. 18 shows the preparation of monomers Exo-II-f according to an example of the invention ¹³ C-NMR(DMSO-d ₆ 100MHz, 298K);

FIG. 19 shows APT of monomer Endo-II-a in an example of the present invention ¹³ C-NMR(CDCl ₃ 100MHz, 298K);

FIG. 20 is an APT of monomer Endo-II-b in an example of the present invention ¹³ C-NMR(CDCl ₃ 100mhz, 298k) spectrum;

FIG. 21 shows APT of monomer Endo-II-f in an example of the present invention ¹³ C-NMR(CDCl ₃ 100MHz, 298K);

FIG. 22 shows CP-MS- ¹³ C-NMR(A),CPNQS ¹³ C-NMR(B),CPPI- ¹³ C-NMR(C)andCP-MS- ¹³ C-NMR-P15=0.05ms (D) spectrum;

FIG. 23 shows CP-MS- ¹³ C-NMR(A),CPNQS ¹³ C-NMR(B),CPPI- ¹³ C-NMR(C)andCP-MS- ¹³ C-NMR-P15=0.05ms (D) spectrum;

FIG. 24 shows CP-MS- ¹³ C-NMR(A),CPNQS ¹³ C-NMR(B),CPPI- ¹³ C-NMR(C)andCP-MS- ¹³ C-NMR-P15=0.05ms (D) spectrum;

FIG. 25 shows CP-MS- ¹³ C-NMR(A),CPNQS ¹³ C-NMR(B),and CPPI- ¹³ A C-NMR (C) spectrum;

FIG. 26 shows CP-MS- ¹³ C-NMR(A),CPNQS ¹³ C-NMR(B),CPPI- ¹³ C-NMR(C)and CP-MS- ¹³ C-NMR-P15=0.05ms (D) spectrum;

FIG. 27 shows CP-MS- ¹³ C-NMR(A),CPNQS ¹³ C-NMR(B),CPPI- ¹³ C-NMR(C)nd CP-MS- ¹³ C-NMR-P15=0.05ms (D) spectrum;

FIG. 28CP-MS of porous material Endo-I-a in the example of the invention ¹³ C-NMR spectrum;

FIG. 29 shows CP-MS- ¹³ A C-NMR spectrum;

FIG. 30 shows porous materials Exo-I-d (5 mg,10mg and 20 mg) before and after purification of Sokena gum (DesmodurRE, 10 mg/mL) in examples of the present invention ¹ H nuclear magnetic resonance spectrogram (CDCl) ₃ ,400MHz)；

FIG. 31 shows porous materials Exo-I-d (10 mg), exo-I-e (10 mg) and Exo-I-f (10 mg) before and after purification of Sockner gel (Desmodur RE,10 mg/mL) according to an example of the present invention ¹ H nuclear magnetic resonance spectrogram (CDCl) ₃ ,400MHz)；

FIG. 32 shows porous material Exo-I-d (10 mg) before and after purification with respect to lexan (Desmodur RE,15 mg/mL) in an example of the present invention ¹ H nuclear magnetic resonance spectrogram (CDCl) ₃ ,400MHz)；

FIG. 33 shows porous material Exo-I-d (10 mg) before and after purification with respect to lexan (Desmodur RE,20 mg/mL) in an example of the present invention ¹ H nuclear magnetic resonance spectrogram (CDCl) ₃ ,400MHz)；

FIG. 34 shows the porous material Exo-I-d (10 mg) used before and after 5 cycles of purification of lexan gum (Desmodur RE,10 mg/mL) in accordance with an embodiment of the present invention ¹ H nuclear magnetic resonance spectrogram (CDCl) ₃ ,400MHz)；

FIG. 35 shows the nuclear magnetic resonance hydrogen (CDCl) spectra of the lexan gum after Exo-I-d purification in accordance with the present invention ₃ ，400MHz,298K)；

FIG. 36 shows the nuclear magnetic resonance carbon spectrum (CDCl) of Exo-I-d purified lexan gum according to example of the present invention ₃ ，100MHz,298K)；

FIG. 37 is a comparison of NMR spectra (CDCl) of lexan gel before (a and b) and after (c) purification from Exo-I-d in an example of the invention ₃ ，400MHz,298K)；

FIG. 38 is an infrared spectrum of a monomer Exo-II-a in an example of the present invention;

FIG. 39 is an infrared spectrum of a monomer Exo-II-b in an example of the present invention;

FIG. 40 is an infrared spectrum of a monomer Exo-II-c in an example of the present invention;

FIG. 41 is an infrared spectrum of a monomer Exo-II-d in an example of the present invention;

FIG. 42 is an infrared spectrum of a monomer Exo-II-e in an example of the present invention;

FIG. 43 is an infrared spectrum of a monomer Exo-II-f in an example of the present invention;

FIG. 44 is an infrared spectrum of a monomer Exo-I-a in an example of the present invention;

FIG. 45 is an infrared spectrum of a porous material Exo-I-b in an example of the present invention;

FIG. 46 is an infrared spectrum of a porous material Exo-I-c in an example of the present invention;

FIG. 47 is an infrared spectrum of a porous material Exo-I-d in an example of the present invention;

FIG. 48 is an infrared spectrum of a porous material Exo-I-e in an example of the present invention;

FIG. 49 is an infrared spectrum of a porous material Exo-I-f in an example of the present invention;

FIG. 50 is an infrared spectrum of an ethyl acetate solution of Likena gum according to an embodiment of the present invention before purification;

FIG. 51 is a chart of the infrared spectra of the Likelton gel after Exo-I-d purification in accordance with the present invention;

FIG. 52 is a chart of Exo-I-d infrared spectra of porous materials Exo-I-d, exo-I-d/dye, dye and activated Exo-I-d in an example of the present invention;

FIG. 53 is a chart of the Exo-I-d, exo-I-e and Exo-I-f IR spectra after cyclic activation of purified lexan gel according to example of the present invention;

FIG. 54 is a nitrogen isothermal adsorption-desorption diagram (SA) of the porous material Exo-I-a in the example of the present invention _BET ＝807m ² .g ^-1 ，T＝77K)；

FIG. 55 is a graph showing a distribution of pore diameters of a porous material Exo-I-a in an example of the present invention;

FIG. 56 is a nitrogen isothermal adsorption-desorption graph (SA) of the porous material Exo-I-c in the example of the present invention _BET ＝854m ² .g ^-1 ，T＝77K)；

FIG. 57 is a pore size distribution diagram of the porous material Exo-I-b in the example of the present invention;

FIG. 58 is a graph showing the isothermal adsorption-desorption of nitrogen (SA) of the porous material Exo-I-c in the example of the present invention _BET ＝810m ² .g ^-1 ，T＝77K)；

FIG. 59 is a graph showing a pore size distribution of a porous material Exo-I-c in an example of the present invention;

FIG. 60 is a graph showing the isothermal adsorption-desorption of nitrogen gas (SA) for porous materials Exo-I-d in examples of the present invention _BET ＝1138m ² .g ^-1 ，T＝77K)；

FIG. 61 is a graph showing a distribution of pore diameters of a porous material Exo-I-d in an example of the present invention;

FIG. 62 is a nitrogen isothermal adsorption-desorption diagram (SA) of the porous material Exo-I-e in the example of the present invention _BET ＝1202m ² .g ^-1 ，T＝77K)；

FIG. 63 is a pore size distribution diagram of a porous material Exo-I-e in an example of the present invention;

FIG. 64 is a nitrogen isothermal adsorption-desorption diagram (SA) of the porous material Exo-I-f in the example of the present invention _BET ＝1094m ² .g ^-1 ，T＝77K)；

FIG. 65 is a graph showing a pore size distribution of a porous material Exo-I-f according to an example of the present invention;

FIG. 66 is a thermogravimetric analysis (TGA) of the porous materials Exo-I-a to Exo-I-f under a nitrogen atmosphere in an example of the present invention;

FIG. 67 is a scanning electron micrograph of porous materials Exo-I-a through Exo-I-f according to an embodiment of the present invention;

FIG. 68 is a transmission electron microscope photograph of porous materials Exo-I-a to Exo-I-f according to an embodiment of the present invention;

FIG. 69 is a UV-Vis spectrum (dye absorption peak: 570 nm) (A) and a standard working curve (B) of an ethyl triisocyanate acetate solution in an example of the present invention;

FIG. 70 is a comparison of UV-Vis spectra of different masses of Exo-I-d (5 mg) (A), (10 mg) (B) and (20 mg) (C) purified ethyl acetate triisocyanate in accordance with an example of the present invention;

FIG. 71 is a comparison of UV-Vis spectra of Exo-I-d (10 mg) purified ethyl acetate triisocyanate solutions (10 mg/mL) (A), (15 mg/mL) (B) and (20 mg/mL) (C) at various concentrations in an example of the present invention;

FIG. 72 is a UV-Vis comparison chart of ethyl acetate solution (10 mg/mL) of purified triisocyanate in Exo-I-d (10 mg) (A), exo-I-e (10 mg) (B) and Exo-I-f (10 mg) (C) according to example of the present invention;

FIG. 73 is a graph comparing the decolorization efficiency of Exo-I-d, exo-I-e, and Exo-I-f with a purified ethyl acetate triisocyanate solution in examples of the present invention;

FIG. 74 is a glass sheet bonded with unpurified lexan gum (DRE) and purified lexan gum (D-DRE) of different masses (2mg, 4mg, 6mg) in an example of the present invention;

FIG. 75 is a comparison of light transmittance tests for glass sheets in accordance with examples of the present invention.

Detailed Description

The present invention will be described in detail below with reference to examples.

In a first aspect, embodiments of the present invention provide a method for purifying triisocyanate, which uses a polynorbornene imide porous material to purify triisocyanate.

In a second aspect, embodiments of the present invention provide a polynorbornene imide porous material. Specifically, the polynorbornene imide porous material is the polynorbornene imide porous material provided by the first aspect, and the structure of the polynorbornene imide porous material is a micropore-mesopore hierarchical pore structure with micropores as main components, so that the adsorption capacity of pore channels of the polymer on certain impurities in isocyanate is enhanced;

in a third aspect, the embodiment of the invention provides a preparation method of a polynorbornene imide porous material. Specifically, the steps include:

101, performing dehydration reaction on exo or endo configuration norbornene anhydride shown in a structural formula III and trifunctional aromatic amine or tetrafunctional aromatic amine shown in a structural formula IV to obtain trifunctional/tetrafunctional norbornene imide shown in a structural formula II;

102, taking tri-functionality/tetra-functionality norbornene imide shown in the structural formula II as a reactant, and carrying out a ring-opening metathesis polymerization reaction of olefin under the action of a ruthenium metal catalyst to obtain polynorbornene imide shown in the structural formula I;

preferably, the specific steps of step 1 above include:

adding a first organic solvent into norbornene anhydride shown in a structural formula III for dissolving, slowly adding an alkaline reagent after dissolving, continuously adding trifunctional aromatic amine or tetrafunctional aromatic amine shown in a structural formula IV for dehydration reaction to obtain trifunctional or tetrafunctional norbornene imide shown in a structural formula II, wherein the reaction time is 2-12h, and the reaction temperature is 25-140 ℃.

Preferably, the specific steps of step 2 include:

adding a second organic solvent into the tri-functionality/tetra-functionality norbornene imide shown in the structural formula II for dissolving, adding a Ru metal catalyst for catalytic reaction after dissolving, adding vinyl ether into a reaction system for quenching after raw material conversion, and drying to obtain the polynorbornene imide polymer shown in the structural formula I, wherein the reaction time is 0.5-12h, and the reaction temperature is 0-60 ℃.

Preferably, the trifunctional aromatic amine and the tetrafunctional aromatic amine represented by the structural formula IV are any one of 1,3, 5-triaminobenzene, tris (4-aminophenyl) methane, tris (4-aminophenyl) triazine, tris (4-aminophenyl) benzene, 2', 7' -tetraamino-9, 9' -spirobifluorene and tetrakis (4-aminophenyl) methane.

Preferably, the first organic solvent is one of toluene, xylene, chlorobenzene, N-dimethylformamide and N-methylpyrrolidone;

the alkaline reagent is any one of triethylamine, tripropylamine and pyridine.

Preferably, the molar ratio of the above-mentioned basic agent to the norbornene anhydride represented by the structural formula III is 1;

using a norbornene anhydride represented by structural formula III and a tri-functional aromatic amine and a tetra-functional aromatic amine represented by structural formula IV at a molar ratio of 1.0 to 2.0.

Preferably, the second organic solvent used above includes any one of dichloromethane, chloroform, acetone, 1, 4-dioxane, tetrahydrofuran, ethyl acetate and N, N-dimethylformamide;

the Ru metal catalyst used is any one of first-generation, second-generation and third-generation Grubbs catalysts and first-generation and second-generation Hoveyda-Grubbs catalysts.

Preferably, the molar ratio of trifunctional/tetrafunctional norbornene imide represented by the structural formula II to Ru catalyst used is from 1.001 to 1.

In order to make the technical personnel in the field understand the invention better, the preparation, characterization and purification effects of the polynorbornene imide porous material provided by the invention are illustrated by a plurality of specific examples.

EXAMPLE 1 Exo-configuration preparation of Polynorbornadimide porous Material I-a

Step 1: preparation of norbornene imide monomer II-a of Exo-configuration

1,3, 5-triaminobenzene hydrochloride (1.23g, 10.0mmol,1.0 equiv.) and exo-norbornene anhydride (5.4 g,33.0mmol,1.1 equiv.) were weighed into a 250mL single-necked flask, and toluene (100 mL) and triethylamine (3 mL) were added, respectively, and heated to 135 ℃; the reaction solution became clear from turbidity at the beginning, and precipitates gradually precipitated as the reaction proceeded. After 5h of reaction, cooling to room temperature, and carrying out reduced pressure suction filtration; the filter cake was washed 2-3 times with water and ethanol and dried by heating to give an off-white solid (5.41g, 96% yield).

¹ H NMR(400MHz,CDCl ₃ )δ(ppm):7.48(s,3H),6.35(s,6H),3.40(s,6H),2.85(s,6H),1.62(d,J＝10.0Hz,3H),1.47(d,J＝10.0Hz,3H)； ¹³ C NMR(100MHz,CDCl ₃ )δ(ppm):176.14,138.02,132.53,122.73,47.83,45.85,43.29.HRMS(ESI):m/z calcd for C ₃₃ H ₂₈ N ₃ O ₆ ⁺ [M+H] ⁺ 562.1973,found 562.1967.FIT-IR(cm ^-1 ):2971,2938,2871,1786,1707,1612,1466,1359,1278,1178,1017,890,783,723,669.

Step 2: preparation of Exo-configuration polynorbornene imide porous material I-a

Weighing trifunctional norbornene imide monomer II-a (0.56g, 1.0mmol,1.0 equiv.) and Grubbs-II (43mg, 0.05mmol, 0.05equiv.) into a 250mL single-neck flask, adding dichloromethane (50 mL) and 1, 4-dioxane (50 mL) respectively, and heating to 45 ℃; stirring the reaction solution for 10min, changing the reaction solution from clear to gel, reacting for 30min, cooling to room temperature, and carrying out reduced pressure suction filtration; the gel was washed with dichloromethane, 1, 4-dioxane, DMSO, etOH and water and lyophilized to give a pale solid I-a (0.55g, 98% yield).

¹³ C CP/MS NMR,δ(ppm):175.22,135.83,131.92,121.07,50.72,44.70,41.61.FT-IR(cm ^-1 ):2971,2867,1788,1720,1603,1465,1347,1167,1064,967,877,774,677,621.Elemental Analysis:C(69.43％),N(7.32％),H(5.19％).

EXAMPLE 2 Exo-configuration preparation of Polynorbornadimide porous Material I-b

Step 1: preparation of norbornene imide monomers II-b of Exo configuration

Tris (4-aminophenyl) methane (2.9g, 10.0mmol,1.0 equiv.) and exo-norbornene anhydride (5.4g, 33mmol, 1.10 equiv.) were weighed into a 250mL single-necked flask, toluene (100 mL) and triethylamine (3 mL) were added, respectively, and the mixture was heated to 130 ℃ and heated; the reaction solution became clear from turbid at the beginning, and precipitates gradually precipitated as the reaction proceeded. After reacting for 6 hours, cooling to room temperature, and carrying out reduced pressure suction filtration; the filter cake was washed 2-3 times with water and ethanol, and then dried by heating to give a pale solid (7.02g, 91% yield).

¹ H NMR(400MHz,CDCl ₃ )δ(ppm):7.22(s,12H),6.35(t,J＝1.9Hz,6H),5.62(s,1H),3.43–3.39(m,6H),2.86(d,J＝1.2Hz,6H),1.62(d,J＝9.9Hz,3H),1.47(d,J＝9.9Hz,3H)； ¹³ C NMR(100MHz,CDCl ₃ )δ(ppm):177.02,143.21,138.01,130.40,130.17,126.30,55.78,47.85,45.86,43.00.HRMS(ESI):m/z calcd for C ₄₆ H ₃₈ N ₃ O ₆ ⁺ [M+H] ⁺ 728.2755,found 728.2755.FIT-IR(cm ^-1 ):2992,2938,2877,1774,1707,1513,1371,1298,1177,1057,1017,950,872,743,642.

Step 2: preparation of Exo-configured polynorbornene imide porous material I-b

Weighing trifunctional norbornene imide monomer II-b (0.73g, 1.0mmol,1.0 equiv.) and Grubbs-II (43mg, 0.05mmol, 0.05equiv.) into a 250mL single-necked flask, adding dichloromethane (50 mL) and 1, 4-dioxane (50 mL), respectively, and heating to 45 ℃; stirring the reaction solution for 10min to obtain gel from clear state, reacting for 30min, cooling to room temperature, and vacuum filtering; the gel was washed with dichloromethane, 1, 4-dioxane, DMSO, etOH and water and lyophilized to give a pale white solid I-b (0.72g, 99% yield).

¹³ C CP/MS NMR,δ(ppm):176.69,142.98,136.75,130.27,125.89,67.33,52.32,45.87,43.26.FT-IR(cm ^-1 ):2944,2911,2871,1780,1713,1513,1371,1178,1064,1024,964,877,783,756,716,629.

EXAMPLE 3 Exo-configuration preparation of Polynorbornadimide porous Material I-c

Step 1: preparation of norbornene imide monomers II-c of Exo configuration

Tris (4-aminophenyl) triazine (3.54g, 10.0mmol, 1.0equiv.) and exo-norbornene anhydride (5.4g, 33mmol, 1.1equiv.) were weighed in a 250mL single-necked flask, and toluene (100 mL) and triethylamine (3 mL) were added, respectively, and heated to 130 ℃; the reaction solution became clear from turbid at the beginning, and precipitates gradually precipitated as the reaction proceeded. After reacting for 6h, cooling to room temperature, and carrying out reduced pressure suction filtration; the filter cake was washed 2-3 times with water and ethanol and then dried by heating to give a pale white solid (7.4 g,93% yield).

¹ H NMR(400MHz,CDCl ₃ )δ(ppm):8.84(d,J＝8.2Hz,6H),7.54(d,J＝8.3Hz,6H),6.40(s,6H),3.47(s,6H),2.93(s,6H),1.68(d,J＝10.0Hz,3H),1.56(d,J＝10.0Hz,3H)； ¹³ C NMR(100MHz,CDCl ₃ )δ(ppm):176.72,170.97,138.08,135.92,135.62,129.77,126.35,48.01,45.97,43.13.HRMS(ESI):m/z calcd for C ₄₈ H ₃₇ N ₆ O ₆ ⁺ [M+H] ⁺ 793.2769,found 793.2771.FIT-IR(cm ^-1 ):3459,3319,3212,2984,2871,1780,1713,1606,1513,1419,1365,1292,1185,1017,816,790,716.

And 2, step: preparation of Exo-configured polynorbornene imide porous Material I-c

Weighing trifunctional norbornene imide monomer II-c (0.79g, 1.0mmol, 1.0equiv.) and Grubbs-II (43mg, 0.05mmol, 0.05equiv.) into a 250mL single-neck flask, adding dichloromethane (50 mL) and 1, 4-dioxane (50 mL) respectively, and heating to 45 ℃; stirring the reaction solution for 10min to obtain gel from clear state, reacting for 30min, cooling to room temperature, and vacuum filtering; the gel was washed with dichloromethane, 1, 4-dioxane, DMSO, etOH and water and lyophilized to give a pale solid I-c (0.77g, 97% yield).

¹³ C CP/MS NMR,δ(ppm):174.60,169.22,148.91,134.13,127.35,112.39,50.00,44.45,41.35.FT-IR(cm ^-1 ):2991,2956,2853,1782,1720,1609,1513,1416,1367,1174,1057,1023,967,822,753,629.

ElementalAnalysis:C(74.95％),N(7.15％),H(5.04％).

EXAMPLE 4 Exo-configured Polynorborneneimide porous materials I-d preparation

Step 1: preparation of norbornene imide monomers II-d of Exo configuration

Tris (4-aminophenyl) benzene (3.51g, 10.0mmol,1.0 equiv.) and exo-norbornene anhydride (5.4 g,33mmol,1.1 equiv.) were weighed into a 250mL single-necked flask, toluene (100 mL) and triethylamine (3 mL) were added, respectively, and the mixture was heated to 130 ℃ for heating; the reaction solution became clear from turbidity at the beginning, and precipitates gradually precipitated as the reaction proceeded. After reacting for 6h, cooling to room temperature, and carrying out reduced pressure suction filtration; washing the filter cake with water and ethanol for 2-3 times, and heating to dry to obtain a pale white solid (7.1g, 91% yield).

¹ H NMR(400MHz,CDCl ₃ )δ(ppm):7.77(d,J＝8.4Hz,9H),7.43(d,J＝8.4Hz,6H),6.38(t,J＝1.9Hz,6H),3.46(t,J＝1.9Hz,6H),2.92(d,J＝1.3Hz,6H),1.72–1.63(m,3H),1.55(d,J＝9.9Hz,3H)； ¹³ C NMR(100MHz,CDCl ₃ )δ(ppm):177.07,141.65,141.20,138.05,131.38,128.13,126.84,125.65,47.97,45.90,43.06.HRMS(ESI):m/z calcd for C ₅₁ H ₄₀ N ₃ O ₆ ⁺ [M+H] ⁺ 790.2912,found 790.2917.FIT-IR(cm ^-1 ):3071,2984,2871,1774,1699,1600,1519,1452,1371,1291,1171,1017,950,877,830,790,716,622.

Step 2: preparation of Exo-configured polynorbornene imide porous Material I-d

Weighing trifunctional norbornene imide monomer II-d (0.79g, 1.0mmol, 1.0equiv.) and Grubbs-II (43mg, 0.05mmol, 0.05equiv.) into a 250mL single-neck flask, adding dichloromethane (50 mL) and 1, 4-dioxane (50 mL) respectively, and heating to 45 ℃; stirring the reaction solution for 10min to obtain gel from clear state, reacting for 30min, cooling to room temperature, and vacuum filtering; the gel was washed with dichloromethane, 1, 4-dioxane, DMSO, etOH and water and lyophilized to give a pale white solid I-d (0.78g, 98% yield).

¹³ C CP/MS NMR,δ(ppm):175.18,139.69,136.33,130.99,125.96,50.71,44.84,41.26.FT-IR(cm ^-1 ):2991,2950,2860,1789,1713,1603,1513,1367,1444,1161,1057,967,891,836,753,621.

ElementalAnalysis:C(70.33％),N(11.51％),H(4.74％).

EXAMPLE 5 Exo-configuration polynorbornene imide porous Material I-e preparation

Step 1: preparation of norbornene imide monomers II-e in Exo configuration

2,2', 7' -tetraamino-9, 9' -spirobifluorene (3.72g, 10.0mmol, 1.0equiv.) and exo-norbornene anhydride (7.4g, 44mmol, 1.1equiv.) were weighed in a 250mL single-necked flask, and toluene (60 mL) and triethylamine (2 mL) were added, respectively, and heated to 135 ℃; the reaction solution became clear from turbidity at the beginning, and precipitates gradually precipitated as the reaction proceeded. After reacting for 6h, cooling to room temperature, and carrying out reduced pressure suction filtration; the filter cake was washed 2-3 times with water and ethanol and dried by heating to give a yellow solid (9.02g, 94% yield).

¹ H NMR(400MHz,CDCl ₃ )δ(ppm):7.90(d,J＝8.1Hz,4H),7.33(dd,J＝8.2,1.9Hz,4H),6.73(d,J＝1.9Hz,4H),6.29(t,J＝1.9Hz,8H),3.34(s,8H),2.75(s,8H),1.55(d,J＝9.8Hz,4H),1.42(d,J＝9.9Hz,4H)； ¹³ C NMR(100MHz,CDCl ₃ )δ(ppm):176.57,148.36,140.84,137.97,131.89,126.65,122.63,120.77,65.94,47.79,45.62,43.24.

HRMS(ESI):m/z calcd for C ₆₁ H ₄₈ N ₅ O ₈ ⁺ [M+NH ₄ ] ⁺ 978.3497,found 978.3498.FIT-IR(cm ^-1 ):2911,2877,1774,1707,1606,1472,1371,1284,1171,1147,1017,870,716,616.

Step 2: preparation of Exo-configured polynorbornene imide porous Material I-e

Weighing tetrafunctional norbornene imide monomer II-e (0.962g, 1.0mmol, 1.0equiv.) and Grubbs-II (43mg, 0.05mmol, 0.05equiv.) into a 250mL single-neck flask, adding dichloromethane (50 mL) and 1, 4-dioxane (50 mL) respectively, and heating to 45 ℃; stirring the reaction solution for 5min to obtain gel from clear state, reacting for 30min, cooling to room temperature, and vacuum filtering; the gel was washed with dichloromethane, 1, 4-dioxane, DMSO, etOH and water and lyophilized to give a pale solid I-e (0.95g, 99% yield).

¹³ C CP/MS NMR,δ(ppm):174.73,147.79,135.52,131.50,126.16,119.60,65.72,50.47,44.62,42.14.FT-IR(cm ^-1 ):2944,2871,1786,1713,1620,1472,1359,1171,1057,970,883,830,790,723,616.

ElementalAnalysis:C(73.45％),N(5.78％),H(4.71％).

Example 6 Exo-configuration preparation of Polynorborneneimide porous materials I-f

Step 1: preparation of norbornene imide monomers II-f of Exo-configuration

Tetrakis (4-aminophenyl) methane (3.8g, 10.0mmol, 1.0equiv.) and exo-norbornene anhydride (7.4g, 44mmol, 1.1equiv.) were weighed in a 250mL single-necked flask, and toluene (100 mL) and triethylamine (3 mL) were added, respectively, and the temperature was raised to 135 ℃ for heating; the reaction solution became clear from turbidity at the beginning, and precipitates gradually precipitated as the reaction proceeded. After reacting for 6h, cooling to room temperature, and carrying out reduced pressure suction filtration; the filter cake was washed 2-3 times with water and ethanol and dried under heating to give an off-white solid (8.9 g,93% yield).

¹ H NMR(400MHz,CDCl ₃ )δ(ppm):7.33(d,J＝7.5Hz,8H),7.24(d,J＝1.5Hz,8H),6.36(t,J＝1.8Hz,8H),3.41(q,J＝1.7Hz,8H),2.86(s,8H),1.62(d,J＝9.9Hz,4H),1.47(d,J＝9.9Hz,4H)； ¹³ C NMR(100MHz,CDCl ₃ )δ(ppm):176.92,145.74,138.02,131.55,130.14,125.44,63.39,47.83,45.91,43.01. ¹ H NMR(400MHz,DMSO-d ₆ )δ(ppm):7.36(d,J＝8.7Hz,8H),7.24(d,J＝8.8Hz,8H),6.32(t,J＝1.8Hz,8H),3.19–3.13(m,8H),2.81(s,1H),1.39(q,J＝9.7Hz,8H)； ¹³ C NMR(100MHz,DMSO-d ₆ )δ(ppm):177.17,146.22,138.26,130.94,130.51,126.91,64.57,47.91,45.47,43.11.

HRMS(ESI):m/z calcd for C ₆₁ H ₅₂ N ₅ O ₈ ⁺ [M+NH ₄ ] ⁺ 982.3810,found 982.3795.

FIT-IR(cm ^-1 ):3078,2971,2877,1774,1713,1599,1499,1452,1365,1318,1291,1024,937,877,837,750,723,629.

Step 2: preparation of Exo-configured polynorbornene imide porous material I-f

Weighing tetrafunctional norbornene imide monomer II-f (0.965g, 1.0mmol, 1.0equiv.) and Grubbs-II (43mg, 0.05mmol, 0.05equiv.) into a 250mL single-neck flask, adding dichloromethane (50 mL) and 1, 4-dioxane (50 mL) respectively, and heating to 45 ℃; stirring the reaction solution for 5min to obtain gel from clear state, reacting for 30min, cooling to room temperature, and vacuum filtering; the gel was washed with dichloromethane, 1, 4-dioxane, DMSO, etOH and water and lyophilized to give a pale white solid I-f (0.95g, 98% yield).

¹³ C CP/MS NMR,δ(ppm):177.58,146.67,132.57,128.77,65.81,53.13,47.17,43.92.FT-IR(cm ^-1 ):2964,2857,1786,1707,1633,1512,1371,1178,1051,977,756,629.

ElementalAnalysis:C(70.99％),N(5.33％),H(5.34％).

EXAMPLE 7 preparation of Endo-configured polynorbornene imide porous Material I-a

Step 1: preparation of Endo-configured norbornene imide monomer II-a

1,3, 5-triaminobenzene hydrochloride (1.23g, 10.0mmol,1.0 equiv.) and endo-norbornene anhydride (5.4 g,33.0mmol,1.1 equiv.) were weighed into a 250mL single-necked flask, and DMF (100 mL) and triethylamine (3 mL) were added, respectively, and heated to 135 ℃; the reaction solution became clear from turbidity at the beginning, and precipitates gradually precipitated as the reaction proceeded. After 5h of reaction, cooling to room temperature, and carrying out reduced pressure suction filtration; washing the filter cake with water and ethanol for 2-3 times, and drying under heating to obtain an off-white solid (5.31g, 94% yield).

¹ H NMR(400MHz,CDCl ₃ )δ(ppm):7.19(s,3H),6.23(s,6H),3.48(dd,J＝3.1,1.6Hz,6H),3.40(dd,J＝2.9,1.6Hz,6H),1.77(d,J＝8.8Hz,3H),1.59(d,J＝8.8Hz,3H)； ¹³ C NMR(100MHz,CDCl ₃ )δ(ppm):175.91,134.68,132.24,123.02,52.25,45.76,45.55.

Step 2: preparing Endo-configuration polynorbornene imide porous material I-a

Weighing trifunctional norbornene imide monomer II-a (0.56g, 1.0mmol,1.0 equiv.) and Hoveyda-Grubbs-II (35mg, 0.05mmol, 0.05equiv.) into a 250mL single-neck flask, adding DMF (100 mL) respectively, and heating to 60 ℃; stirring the reaction solution for 10min to obtain gel from clear state, reacting for 30min, cooling to room temperature, and vacuum filtering; the gel was washed with dichloromethane, 1, 4-dioxane, DMSO, etOH and water and lyophilized to give a pale solid I-a (0.54g, 96% yield).

EXAMPLE 8 preparation of Endo-configured polynorbornene imide porous Material I-b

Step 1: preparation of Endo-configured norbornene-imide monomers II-b

Tris (4-aminophenyl) methane (2.9g, 10.0mmol, 1.0equiv.) and endo-norbornene anhydride (5.4g, 33mmol, 1.1equiv.) were weighed into a 250mL single-necked flask, xylene (100 mL) and tripropylamine (1 mL) were added, respectively, and the mixture was heated to 130 ℃; the reaction solution became clear from turbidity at the beginning, and precipitates gradually precipitated as the reaction proceeded. After reacting for 6 hours, cooling to room temperature, and carrying out reduced pressure suction filtration; the filter cake was washed 2-3 times with water and ethanol and dried under heating to give a pale white solid (6.9 g,90% yield).

¹ H NMR(400MHz,CDCl ₃ )δ(ppm):7.23–7.12(m,6H),7.12–6.92(m,6H),6.25(s,6H),5.55(s,1H),3.50(s,6H),3.42(s,6H),1.78(d,J＝8.6Hz,3H),1.61(d,J＝9.0Hz,3H)； ¹³ C NMR(100MHz,CDCl ₃ )δ(ppm):176.79,143.13,134.69,130.33,130.08,126.52,55.80,52.31,45.77,45.53.

And 2, step: preparing Endo-configuration polynorbornene imide porous material I-b

Weighing trifunctional norbornene imide monomers II-b (0.73g, 1.0mmol,1.0 equiv.) and Grubbs-III (45mg, 0.05mmol, 0.05equiv.) into a 250mL single-neck flask, adding tetrahydrofuran (100 mL), and heating to 45 ℃; stirring the reaction solution for 10min to obtain gel from clear state, reacting for 30min, cooling to room temperature, and vacuum filtering; the gel was washed with dichloromethane, 1, 4-dioxane, DMSO, etOH and water and lyophilized to give a pale white solid I-b (0.71g, 98% yield).

¹³ C CP/MS NMR,δ(ppm):173.62,141.23,128.79,46.94,43.92,39.56.

EXAMPLE 9 preparation of Endo-configured polynorbornene imide porous materials I-f

Step 1: preparation of Endo-configured norbornene imide monomers II-f

Tetrakis (4-aminophenyl) methane (3.8g, 10.0mmol, 1.0equiv.) and endo-norbornene anhydride (7.4g, 44mmol, 1.1equiv.) were weighed into a 250mL single-necked flask, and N-methylpyrrolidone (100 mL) and pyridine (3 mL) were added, respectively, and the mixture was heated to 135 ℃; the reaction solution became clear from turbidity at the beginning, and precipitates gradually precipitated as the reaction proceeded. After reacting for 6 hours, cooling to room temperature, and carrying out reduced pressure suction filtration; the cake was washed with water and ethanol 2 to 3 times, and then dried by heating to give a yellowish white solid (8.6 g,91% yield).

¹ H NMR(400MHz,CDCl ₃ )δ(ppm):7.22(d,J＝8.6Hz,8H),7.06(d,J＝8.4Hz,8H),6.24(s,8H),3.49(s,8H),3.45–3.38(m,8H),1.76(d,J＝8.8Hz,4H),1.59(d,J＝8.8Hz,4H)； ¹³ C NMR(100MHz,CDCl ₃ )δ176.73,145.62,134.63,131.50,130.01,125.63,52.23,45.74.

Step 2: preparation of Endo-configured polynorbornene imide porous Material I-f

Weighing tetrafunctional norbornene imide monomer II-f (0.965g, 1.0mmol, 1.0equiv.) and Grubbs-II (43mg, 0.05mmol, 0.05equiv.) into a 250mL single-neck flask, adding acetone (100 mL) respectively, and stirring at room temperature; stirring the reaction solution for 5min, changing the reaction solution from clear to gel, reacting for 6h, cooling to room temperature, and carrying out reduced pressure suction filtration; the gel was washed with dichloromethane, 1, 4-dioxane, DMSO, etOH and water and lyophilized to give a pale solid I-f (0.95g, 98% yield).

¹³ C CP/MS NMR,δ(ppm):175.93,146.55,131.26,127.53,64.75,48.95,45.94,41.66.

The embodiment of the invention provides a preparation method of a polynorbornene imide porous material for purifying triisocyanate, which can be used for preparing a large amount of organic porous polymeric materials with imide and polynorbornene structures under the mild condition by carrying out efficient ring-opening metathesis polymerization reaction on a polyfunctional imide monomer under the action of a ruthenium catalyst. According to the organic porous polymer material with the imide functionalized polynorbornene structure, which is prepared by the invention, the imide group which is not reacted with the isocyanate group can realize the efficient purification of triisocyanate (lexan) under mild conditions through the effects of hydrogen bond interaction, electrostatic induction and the like.

Example 10 pore size analysis of imide-functionalized polynorbornene porous Material (porous Material I)

In the embodiment of the invention, based on the efficient ring-opening metathesis polymerization reaction of the norbornene imide monomer containing multiple functionality under the action of the ruthenium catalyst, the prepared imide functionalized polynorbornene structure organic porous polymer has excellent performances of high specific surface area, abundant pore structures, good stability and the like, and has a potential application prospect. The porous property of the organic porous polymer with an imide functionalized polynorbornene structure is characterized and the application direction of the organic porous polymer with the imide functionalized polynorbornene structure is described. The specific surface area of the porous material is usually measured by a gas adsorption-desorption isotherm method, i.e., a gas molecule (such as nitrogen) is used as a probe, and adsorption isotherms are obtained by recording adsorption amounts corresponding to different pressures of the porous material under a constant temperature condition. The specific BET surface area is then calculated by derivation from the BET model. BET is an acronym of three scientists (Brunauer, emmett and Teller), and the basic formula of multi-molecular-layer adsorption derived by three scientists from classical statistical theory, namely the famous BET equation, becomes the theoretical basis of particle surface adsorption science and is widely applied to particle surface adsorption performance research and data processing of related detection instruments.

Referring to fig. 54 to 65, there are shown graphs of pore size distribution calculated by NLDFT of the porous materials I prepared in examples 1 to 6 of the present invention.

The values of specific surface area and pore volume of the porous materials I prepared in examples 1 to 6 of the present invention are shown in table 1:

[a].BET value of Exo-I-a～Exo-I-f calculated from N ₂ adsorbted at P/P ₀ ＝0.05-0.3；[b].Pore size distribution ofExo-I-a～Exo-I-f calculated by NLDFT；[c].Pore volumes was calculated from the N ₂ adsorbted at P/P ₀ ＝0.99.

in this example, pore size calculation was performed on the prepared porous material I by using the NLDFT method, and the pore size distribution diagrams shown in fig. 54 to 65 were plotted. The data in fig. 54-65 show that the prepared porous material I has a microporous-mesoporous hierarchical pore structure characteristic with micropores as the main.

The imide functional group of the imide functional organic porous polymer material with the polynorbornene structure and the organic porous polymer with the polynorbornene skeleton structure have rich functional groups, high specific surface area, larger total pore volume and smaller average pore diameter, and play an important role in the fields related to environment and energy, such as organic pollutant adsorption, heterogeneous catalysis, gas storage and the like.

Example 11 thermogravimetric Property testing of Polynorbornenylimide porous Material (porous Material I)

In this example, a thermogravimetric test is performed on the prepared porous material I, and the test result is shown in fig. 66, and the porous material I hardly decomposes at a temperature below 260 ℃, which indicates that the prepared porous material I has good thermal stability. The porous material I starts to degrade after a temperature higher than 260 c and shows a multi-stage degradation phenomenon. Firstly, the degradation at 260-300 ℃ in the first stage is obvious, the mass loss is about 5 percent, cyclopentadiene is released by the reverse D-A reaction of incompletely reacted norbornene units in the structure at high temperature, the degradation rate at 400-500 ℃ in the second stage is slow, and the mass loss is about 50 percent, which is caused by the loss of imide units in the structure. The degradation after 500 ℃ in the third stage is caused by loss of C atoms, and the degradation rate is slow.

The porous material I has higher degradation temperature and good thermal stability, and is favorable for popularization and application of the material in harsh environments such as high temperature and the like.

EXAMPLE 12 scanning Electron microscope Performance testing of porous Material I

In this example, a scanning electron microscope test was performed on the prepared azobenzene-linked polynorbornene porous material, specifically taking porous material I as an example, and a scanning electron microscope test was performed on the porous material. This example performed a scanning electron microscope test on the prepared porous material I. As shown in fig. 67, the experimental results of the scanning electron microscope thereof showed that: the porous material I has a fluffy distribution of particles, and a plurality of small pore structures are distributed in the porous material I, as shown in fig. 68, and the experimental result of the transmission electron microscope shows that: the particles of the porous material I are distributed in a lamellar stacking manner. This is in combination with N ₂ The isothermal adsorption test proves that the porous material I has larger specific surface area and the micropore-mesopore property is consistent.

Example 13 porous materials Exo-I-d purification of triisocyanate at different concentrations

28mL of a commercially available triisocyanate ethyl acetate solution with the concentration of 27wt% is diluted by 12mL and prepared into a triisocyanate ethyl acetate solution with the concentration of 100mg/mL for later use. The concentration solution was further diluted to prepare different concentrations of 10.0mg/mL, 15.0mg/mL and 20.0mg/mL. The purification of triisocyanate by porous material Exo-I-d is researched by an ultraviolet-visible spectrum and nuclear magnetic resonance hydrogen spectrum quantitative method, and the purification method comprises the following steps: adding the ethyl acetate solution of the triisocyanate into a porous material Exo-I-d to perform an adsorption experiment, and monitoring the change of ultraviolet-visible absorption peaks of the solution after different adsorption time and balance to obtain the decoloring efficiency and the separation efficiency. The decoloring efficiency and the separation efficiency are obtained by calculating formulas (1) and (2), respectively:

A ₀ initial absorbance of the solution before adsorption, A _e The absorbance of the solution after adsorption equilibrium.

C ₀ Initial absorbance of the solution before adsorption, C _e The absorbance of the solution after adsorption equilibrium.

The specific purification steps of triisocyanate are:

the porous material Exo-I-d (10 mg), the stirring magnetons and 5mL of ethyl triisocyanate acetate solutions with initial concentrations of 10mg/mL, 15mg/mL and 20 mg/mL) were weighed out separately and added to a 10mL sample bottle. Stirring at room temperature, and performing UV-visible test on the solution after 1min, 5min, 10min, 20min, 30min, 60min, 1h and 2h to obtain absorbance for calculating decolorizing efficiency. The mixture after the adsorption equilibrium was separated by filtration (0.22 um organic membrane), the filtrate (50 uL) was pipetted using a 50uL pipette gun, and 450uLCDCl was added ₃ And after the materials are uniformly mixed, performing a nuclear magnetic resonance hydrogen spectrum test to obtain the concentration change for calculating the separation efficiency of the lexan gum. In addition, the filtrate obtained by separation can be subjected to decompression and concentration to obtain a light white solid, and the porous material Exo-I-d obtained by separation and the impurity mixture can be recycled after being washed and activated by DMF, ethanol and water. The decoloring efficiency and the separation efficiency are shown in Table 2.

EXAMPLE 14 purification of triisocyanates from porous materials Exo-I-d of different masses

Respectively weighing porous materials Exo-I-d (10 mg, 15mg and 20 mg), stirring magnetons and 5mL of triisocyanogen with the initial concentration of 10mg/mLThe ethyl acetate ester solution was added to a 10mL sample bottle. Stirring at room temperature, and performing UV-visible test on the solution after 1min, 5min, 10min, 20min, 30min, 60min, 1h and 2h to obtain absorbance for calculating decolorizing efficiency. Filtering the mixture after adsorption equilibrium (0.22 um organic filter membrane), removing the filtrate (50 uL) with a 50uL pipette gun, adding 450uLCDCl ₃ And after being uniformly mixed, performing a nuclear magnetic resonance hydrogen spectrum test to obtain the concentration change for calculating the separation efficiency of the triisocyanate. In addition, the filtrate obtained by separation can be subjected to decompression and concentration to obtain a light white solid, and the porous material Exo-I-d obtained by separation and the impurity mixture can be recycled after being washed and activated by DMF, ethanol and water. The decoloring efficiency and the separation efficiency are shown in Table 2.

EXAMPLE 15 porous Material Exo-I-e/Exo-I-f purification of triisocyanate

The porous materials Exo-I-e/Exo-I-f (each 10 mg), the stirring magnetons and 5mL of triisocyanate ethyl acetate solution with the initial concentration of 10mg/mL are respectively weighed and added into a 10mL sample bottle. Stirring at room temperature, and performing UV-visible test on the solution after 1min, 5min, 10min, 20min, 30min, 60min, 1h and 2h to obtain absorbance for calculating decolorizing efficiency. The mixture after the adsorption equilibrium was separated by filtration (0.22 um organic membrane), the filtrate (50 uL) was pipetted using a 50uL pipette gun, and 450uLCDCl was added ₃ And after being uniformly mixed, performing a nuclear magnetic resonance hydrogen spectrum test to obtain the concentration change for calculating the separation efficiency of the lexan gum. In addition, the filtrate obtained by separation can be subjected to decompression concentration to obtain a light white solid, and the porous material Exo-I-e/Exo-I-f obtained by separation and the impurity mixture can be recycled after being washed and activated by DMF, ethanol and water. The decoloring efficiency and the separation efficiency are shown in Table 2.

Exo-I-d, exo-I-e, and Exo-I-f for triisocyanate purification

^a The decolorization efficiency and the separation efficiency are respectively measuredAnd testing and calculating the solution after adsorption balance by using an ultraviolet-visible spectrum and a nuclear magnetic hydrogen spectrum. According to experimental results, the porous material is used for purifying triisocyanate, and the decoloring efficiency and the separation efficiency are high.

EXAMPLE 16 purification recycle of triisocyanates from porous materials I-d

10mL of the Likenagel/ethyl acetate solution (10.0 mg/mL) was pipetted into a 20mL sample vial using a 5mL pipette, and Exo-I-d (20 mg) was weighed into the sample vial solution and stirred at room temperature. And (3) carrying out ultraviolet-visible test on the solution after stirring for 30min to determine the decolorization efficiency. The mixture after adsorption was separated by filtration (0.22 um organic membrane), and the filtrate (50 uL) was pipetted using a 50uL pipette gun and added with 450uLCDCl ₃ And after the materials are uniformly mixed, performing a nuclear magnetic resonance hydrogen spectrum test to obtain the concentration change for calculating the separation efficiency of the lexan gum. In addition, the filtrate obtained by separation can be subjected to decompression and concentration to obtain a light white solid, and the porous material I-d obtained by separation and the impurity mixture can be recycled after being washed and activated by DMF, ethanol and water. According to the above operation, the porous material Exo-I-d was recycled for 6 times, and the decoloring efficiency and the separation efficiency were as shown in Table 3.

Exo-I-d Effect on triisocyanate purification recycle

^a The decolorizing efficiency and the separating efficiency are respectively obtained by testing and calculating the ultraviolet-visible spectrum and the nuclear magnetic hydrogen spectrum of the solution after the adsorption balance is measured. According to experimental results, the porous material Exo-I-d still has higher decolorization efficiency and separation efficiency after 6 times of cyclic purification.

Comparison of transparency of triisocyanate bonded glass flakes before and after purification of example 17

Weighing unpurified lexana gum (DRE, 2mg,4mg and 6mg) and purified lexana gum (D-DRE, 2mg,4mg and 6mg) and respectively dissolving the unpurified lexana gum and the purified lexana gum in a small amount of ethyl acetate (100 uL). Thereafter, ethyl acetate solutions of lexan gum were respectively dropped on cover glass sheets (size: 24mm × 24mm, blank transmittance 99.7%) to be uniformly coated and bonded, and when the solvent was evaporated and dried, the sheets were respectively subjected to a transmittance test according to ISO standard (D65 illuminant). The test results are shown in table 4, and fig. 74 and 75:

TABLE 4 comparison of transparency of triisocyanate bonded glass flakes before and after purification

The experimental results show that the transparency of the purified lexan gum is obviously higher than that of the unpurified lexan gum. For simplicity of explanation, the method embodiments are shown 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, in accordance with the present invention, occur in other orders and/or concurrently. 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 present invention provides a polynorbornene imide porous material for purifying triisocyanate and a preparation method thereof, which are described in detail above, wherein specific examples are applied to illustrate the principle and the embodiment of the present invention, and the description of the above examples is only used to help understanding the method of the present invention and the core concept thereof; meanwhile, for a person skilled in the art, according to the idea of the present invention, the specific embodiments and the application range may be changed, and in summary, the content of the present specification should not be construed as a limitation to the present invention.

Claims

1. A process for purifying triisocyanates, characterized by: purifying triisocyanate using a polynorbornene imide porous material having an imide-functionalized polynorbornene structure; the structure of the polynorbornene imide porous material is a micropore-mesopore hierarchical pore structure with micropores as main parts, the structural formula and a connecting group are shown as the following I, wherein n is the number of repeating units:

。

2. the method of claim 1, wherein the step of preparing the polynorbornene imide porous material comprises:

step 1, performing dehydration reaction on exo or endo configuration norbornene anhydride shown in a structural formula III and trifunctional aromatic amine or tetrafunctional aromatic amine shown in a structural formula IV to obtain trifunctional/tetrafunctional norbornene imide shown in a structural formula II;

。

3. the method according to claim 2, wherein the specific steps of step 1 include:

adding a first organic solvent into the norbornene anhydride shown in the structural formula III for dissolving, slowly adding an alkaline reagent after dissolving, continuously adding the trifunctional aromatic amine or the tetrafunctional aromatic amine shown in the structural formula IV for dehydration reaction to obtain the trifunctional or tetrafunctional norbornene imide shown in the structural formula II, wherein the reaction time is 2-12h, and the reaction temperature is 25-140 ℃.

4. The method according to claim 2, wherein the specific step of step 2 comprises:

5. The method according to claim 2, wherein the trifunctional aromatic amine and the tetrafunctional aromatic amine of formula iv are any one of 1,3, 5-triaminobenzene, tris (4-aminophenyl) methane, tris (4-aminophenyl) triazine, tris (4-aminophenyl) benzene, 2',7,7' -tetraamino-9, 9' -spirobifluorene and tetrakis (4-aminophenyl) methane.

6. The method of claim 3, wherein the first organic solvent is one of toluene, xylene, chlorobenzene, N-dimethylformamide, and N-methylpyrrolidone;

the alkaline reagent is any one of triethylamine, tripropylamine and pyridine.

7. The method according to claim 3, wherein the molar ratio of the basic agent to the norbornene anhydride represented by the formula III is 1:2 to 1:10;

the molar ratio of the norbornene anhydride shown in the structural formula III to the trifunctional aromatic amine/tetrafunctional aromatic amine shown in the structural formula IV is 1.0:1.0-2.0:1.0.

8. The method according to claim 4, wherein the second organic solvent used comprises any one of dichloromethane, chloroform, acetone, 1, 4-dioxane, tetrahydrofuran, ethyl acetate and N, N-dimethylformamide;

9. The method of claim 4 wherein the molar ratio of trifunctional/tetrafunctional norbornene imide of formula II to Ru catalyst is from 1:0.001 to 1:0.1.