CN118271899A - Bio-based non-isocyanate polyurethane binder with cluster luminescence property and preparation method thereof - Google Patents
Bio-based non-isocyanate polyurethane binder with cluster luminescence property and preparation method thereof Download PDFInfo
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 38
- 239000004814 polyurethane Substances 0.000 title claims abstract description 38
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- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 27
- 239000011230 binding agent Substances 0.000 title claims abstract description 26
- 238000004020 luminiscence type Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 37
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
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- 239000003054 catalyst Substances 0.000 claims abstract description 27
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- 238000001723 curing Methods 0.000 claims description 49
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- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 12
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- 238000000576 coating method Methods 0.000 claims description 3
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims description 3
- VSTXCZGEEVFJES-UHFFFAOYSA-N 1-cycloundecyl-1,5-diazacycloundec-5-ene Chemical compound C1CCCCCC(CCCC1)N1CCCCCC=NCCC1 VSTXCZGEEVFJES-UHFFFAOYSA-N 0.000 claims description 2
- FVKFHMNJTHKMRX-UHFFFAOYSA-N 3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidine Chemical compound C1CCN2CCCNC2=N1 FVKFHMNJTHKMRX-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
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- 239000000976 ink Substances 0.000 description 17
- 125000003700 epoxy group Chemical group 0.000 description 11
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- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 3
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Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention belongs to the technical field of high polymer materials, and discloses a bio-based non-isocyanate polyurethane binder with cluster luminescence property and a preparation method thereof. The preparation method comprises the following steps: s1, inserting CO 2 into epoxy linseed oil, and adding a catalyst for reaction to obtain cyclic carbonate linseed oil; s2, mixing and dissolving the cyclocarbonate linseed oil and a curing agent in a solvent, adding a catalyst for reaction, and heating and curing to obtain the cyclocarbonate linseed oil; the curing agent is one of hyperbranched polyethyleneimine, polyamide-amine, polypropyleneimine and polylysine and Priamine-1074 are mixed for use. The hyperbranched polyamine in the curing agent can construct the bio-based NIPU with a supermolecular crosslinking structure, so that the obtained bio-based NIPU polymer material has excellent mechanical property, thermal stability, chemical resistance and various luminous properties, the preparation process is simple, the problems of toxicity and environmental pollution commonly existing in isocyanate polyurethane are solved, the obtained bio-based NIPU has excellent performance, and the application fields of paint, printing ink and the like are widened.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a bio-based non-isocyanate polyurethane binder with cluster luminescence property and a preparation method thereof.
Background
The ink is a viscous colloidal fluid which is prepared by uniformly mixing a binder (resin), pigment, filler, an auxiliary agent and a solvent and repeatedly rolling. As an important material for printing, it is used in various fields such as books and periodicals, package decoration, architectural decoration and electronic circuit boards. The material can be used for displaying patterns and characters on a printing stock through printing or spray painting. As social demands increase, ink varieties and yields expand and grow accordingly. Fluorescent inks are one of the important types of ink. Fluorescent inks are typically prepared by milling a fluorescent pigment with a polymeric resin binder, solvent and auxiliary agent. The fluorescent pigment can absorb energy under the irradiation of ultraviolet light to excite photons, and release the energy in a low visible light form, so that fluorescent phenomena of different colors are generated. However, these fluorescent pigments are mainly inorganic materials and have coarse particles and poor compatibility with binders. The preparation of fluorescent pigments from inorganic pigments is very demanding in terms of printing, it is necessary to ensure that the fluorescent ink has sufficient concentration when used, and thick coating is performed on the printed matter, so that a satisfactory fluorescent effect is ensured. This clearly increases the cost and range of use of the ink.
In order to cope with the dilemma of using inks with fluorescent pigments, many researchers have developed new ways to reduce the ink's Emotion towards fluorescent pigments, starting from ink vehicle designs. Polyurethane has excellent stability, chemical resistance, adhesion and rebound resilience, and is widely used for ink adhesives. However, the traditional polyurethane material is increasingly serious in resource crisis caused by petrochemical resource resistance, and has the problems of low mechanical strength, low fluorescence strength and single fluorescence luminescence color, so that the actual requirements in the application of the ink are difficult to meet.
Disclosure of Invention
In view of the above-mentioned problems in the prior art, the inventors propose the development of bio-based non-isocyanate polyurethane ink vehicles with cluster-emitting properties using renewable resource vegetable oils. The bio-based non-isocyanate polyurethane is synthesized by converting epoxy vegetable oil into cyclic carbonate vegetable oil and using bio-based diamine Priamine and hyperbranched structure polyamine in combination as a curing agent through a simple preparation process. The hyperbranched structure polyamine is beneficial to the polyurethane to form a compact supermolecular network, so that photons are excited by absorbing energy under the light stimulation and fluorescence is generated by releasing the energy, and the proportion of the hyperbranched structure polyamine to Priamine and 1074 can regulate and control the supermolecular network structure of the polyurethane so as to regulate and control the color of the fluorescence. In addition, the polyhydroxy structure and the flexibility Priamine and 1074 in the polyurethane can provide cohesive energy for the polyurethane so as to endow the polyurethane binder with excellent mechanical property and thermal stability, so that the requirements of the ink on the mechanical property, the thermal stability and the fluorescence diversity required by the binder in actual use are met.
The primary aim of the invention is to provide a preparation method of a bio-based non-isocyanate polyurethane binder with cluster luminescence property, which takes epoxy linseed oil (ELSO) as a raw material, carries out coupling reaction with CO 2 to prepare cyclic carbonate linseed oil (CLSO) with high conversion rate, and then carries out polyaddition reaction with a curing agent monomer to obtain NIPU, wherein the prepared NIPU polymer material has excellent chemical resistance, thermal stability and mechanical property, and has diversified luminescence property, so that the NIPU polymer material is expected to be applied to the fields of paint, printing ink and the like.
In order to achieve the above purpose, the present invention provides the following technical solutions:
A preparation method of a bio-based non-isocyanate polyurethane binder with cluster luminescence property comprises the following steps:
S1, inserting CO 2 into epoxy linseed oil (ELSO), and reacting under the condition of adding a catalyst to obtain cyclic carbonate linseed oil;
S2, mixing and dissolving the cyclic carbonate linseed oil prepared in the step S1 and a curing agent in a solvent, adding a catalyst, stirring, and heating and curing to obtain the modified linseed oil;
The curing agent is one of hyperbranched Polyethyleneimine (PEI) (formula 1), polyamide-amine (PAMAM) (formula 2), polypropylene imine (PPI) (formula 3) and Polylysine (PLL) (formula 4) and Priamine1074 is mixed for use.
Preferably, the catalyst in the step S1 is tetrabutylammonium bromide (TBAB) or tetrabutylammonium iodide, and the dosage is 2wt.% to 8wt.% of epoxy linseed oil.
Preferably, the CO 2 introduced in the step S1 enables the pressure of the reaction system to reach 2MPa to 7MPa.
Preferably, the reaction temperature in the step S1 is 100-150 ℃ and the reaction time is 6-24 h.
Preferably, the catalyst in the step S2 is one of 1,5, 7-triazabicyclo [4.4.0] dec-5-ene (TBD), 1, 8-diazabicyclo undec-7-ene (DBU) and 4-Dimethylaminopyridine (DMAP), and the dosage is 1wt.% to 6wt.% of cyclocarbonate linseed oil.
Preferably, the molar ratio of the cyclocarbonate linseed oil to the curing agent in the step S2 is 1:1, and the molar ratio of one of hyperbranched Polyethyleneimine (PEI), polyamide-amine (PAMAM), polypropyleneimine (PPI) and Polylysine (PLL) to Priamine 1074:1074 in the curing agent is 0.25:0.75-0.75:0.25.
The bio-based non-isocyanate polyurethane binder with excellent mechanical property, thermal stability, chemical resistance and various luminous properties can be obtained by controlling the molar ratio of the two amines in the curing agent.
Preferably, the dissolving solvent in the step S2 is butanone or tetrahydrofuran, the reaction temperature is 60-100 ℃, and the reaction time is 1-10 h.
Preferably, the heating curing condition in the step S2 is that the temperature is 100-140 ℃ and the curing is carried out for 6-24 hours.
The invention also aims to provide the bio-based non-isocyanate polyurethane binder with cluster luminescence property, which is prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention is to replace high-toxicity isocyanate to synthesize polyurethane by generating non-isocyanate polyurethane through the addition reaction of cyclic carbonate and curing agent.
(2) According to the invention, vegetable oil is used as a raw material, epoxy groups on branched chains are subjected to cyclic carbonic acid esterification to replace petroleum-based cyclic carbonic ester, and then one of hyperbranched Polyethyleneimine (PEI), polyamide-amine (PAMAM), polypropylene imine (PPI) and Polylysine (PLL) is selected to be mixed with Priamine1074 to use a curing agent, so that bio-based non-isocyanate polyurethane is synthesized through a simple preparation process, and the pollution of petroleum-based materials to the environment is improved; the material has excellent mechanical property, chemical resistance and thermal stability, and can meet the application requirements of coating and printing ink.
(3) The invention prepares the bio-based non-isocyanate polyurethane with cluster luminescence property by controlling the mole ratio of two amines in the curing agent, and can obtain the non-isocyanate polyurethane which emits blue light, green light, yellow light and red light according to the different contents of the two amines in the curing agent, thereby expanding the application in the fields of paint, printing ink and the like.
Drawings
FIG. 1 is a schematic diagram of the synthetic route of the present invention (example 1).
FIG. 2 shows 1 HNMR spectra (a), GPC (b), FTIR spectra (c) of CLSOs prepared in examples and comparative examples according to the present invention.
Fig. 3 is FTIR spectra prepared for inventive and comparative examples.
FIG. 4 is a TGA of bio-based NIPU films prepared in the examples and comparative examples of the present invention.
Fig. 5 is a statistical graph of solvent resistance and specific data for biobased NIPU polymer networks prepared in examples and comparative examples of the present invention.
FIG. 6 is a visual image of cluster luminescence, fluorescence excitation emission spectra of bio-based NIPU films of examples and comparative examples of the invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The test methods used in the following examples are conventional methods unless otherwise specified; the materials, reagents and the like used, unless otherwise specified, are those commercially available.
Example 1
A bio-based non-isocyanate polyurethane binder with cluster luminescence property is prepared by the following method:
S1.ELSO (50 g) and catalyst TBAB (2.5 g,5wt.% ELSO) were charged into an autoclave equipped with a mechanical stirrer and carbon dioxide was introduced to bring the pressure to 5MPa. The reaction is carried out at 120 ℃ and the reaction time is controlled at 12 hours to obtain the functional linseed oil with cyclic carbonate functionality;
S2, under the condition that DBU catalyst (with the dosage of 3wt.% CLSO) is added, the cyclic carbonate linseed oil (CLSO) prepared in the step S1 and a curing agent are mixed and dissolved in butanone according to the mol ratio of 1:1, the mol ratio of hyperbranched Polyethyleneimine (PEI) to Priamine 1074:0.75 in the curing agent is 0.25:1074, then the mixture is stirred at 78 ℃ for 2 hours and then poured into a glass dish, and then the glass dish is put into an oven for curing at 105 ℃ for 20 hours, and the sample is recorded as NIPU-PEI 0.25.
Example 2
A bio-based non-isocyanate polyurethane binder with cluster luminescence property is prepared by the following method:
S1.ELSO (50 g) and catalyst TBAB (2.5 g,5wt.% ELSO) were charged into an autoclave equipped with a mechanical stirrer and carbon dioxide was introduced to bring the pressure to 5MPa. The reaction is carried out at 120 ℃ and the reaction time is controlled at 12 hours to obtain the functional linseed oil with cyclic carbonate functionality;
S2, under the condition that DBU catalyst (with the dosage of 3wt.% CLSO) is added, the cyclic carbonate linseed oil (CLSO) prepared in the step S1 and a curing agent are mixed and dissolved in butanone according to the mol ratio of 1:1, the mol ratio of hyperbranched Polyethyleneimine (PEI) to Priamine 1074:0.5 in the curing agent is 0.5, then the mixture is stirred at 78 ℃ for 2 hours and then poured into a glass dish, and then the glass dish is put into an oven for curing at 105 ℃ for 20 hours, and a sample is recorded as NIPU-PEI 0.5.
Example 3
A bio-based non-isocyanate polyurethane binder with cluster luminescence property is prepared by the following method:
S1.ELSO (50 g) and catalyst TBAB (2.5 g,5wt.% ELSO) were charged into an autoclave equipped with a mechanical stirrer and carbon dioxide was introduced to bring the pressure to 5MPa. The reaction is carried out at 120 ℃ and the reaction time is controlled at 12 hours to obtain the functional linseed oil with cyclic carbonate functionality;
S2, under the condition that DBU catalyst (with the dosage of 3wt.% CLSO) is added, the cyclic carbonate linseed oil (CLSO) prepared in the step S1 and a curing agent are mixed and dissolved in butanone according to the mol ratio of 1:1, the mol ratio of hyperbranched Polyethyleneimine (PEI) to Priamine 1074:0.25 in the curing agent is 0.75:1074, then the mixture is stirred at 78 ℃ for 2 hours and then poured into a glass dish, and then the glass dish is put into an oven for curing at 105 ℃ for 20 hours, and the sample is recorded as NIPU-PEI 0.75.
Example 4
A bio-based non-isocyanate polyurethane binder with cluster luminescence property is prepared by the following method:
S1.ELSO (50 g) and catalyst TBAB (2.5 g,5wt.% ELSO) were charged into an autoclave equipped with a mechanical stirrer and carbon dioxide was introduced to bring the pressure to 5MPa. The reaction is carried out at 120 ℃ and the reaction time is controlled at 12 hours to obtain the functional linseed oil with cyclic carbonate functionality;
S2, under the condition that DBU catalyst (the dosage is 3wt.% CLSO) is added, the cyclic carbonate linseed oil (CLSO) prepared in the step S1 and a curing agent are mixed and dissolved in butanone according to the mol ratio of 1:1, the mol ratio of polyamide-amine (PAMAM) to Priamine 1074:1074 in the curing agent is 0.25:0.75, then the mixture is stirred at 78 ℃ for 2 hours and then poured into a glass dish, then the glass dish is put into an oven for curing at 105 ℃ for 20 hours, and a sample is recorded as NIPU-PAMAM 0.25.
Example 5
A bio-based non-isocyanate polyurethane binder with cluster luminescence property is prepared by the following method:
S1.ELSO (50 g) and catalyst TBAB (2.5 g,5wt.% ELSO) were charged into an autoclave equipped with a mechanical stirrer and carbon dioxide was introduced to bring the pressure to 5MPa. The reaction is carried out at 120 ℃ and the reaction time is controlled at 12 hours to obtain the functional linseed oil with cyclic carbonate functionality;
S2, under the condition that DBU catalyst (with the dosage of 3wt.% CLSO) is added, the cyclic carbonate linseed oil (CLSO) prepared in the step S1 and a curing agent are mixed and dissolved in butanone according to the mol ratio of 1:1, the mol ratio of polypropylene imine (PPI) to Priamine 1074:0.75 in the curing agent is 0.25:1074, then the mixture is stirred at 78 ℃ for 2 hours and then poured into a glass dish, and then the glass dish is put into an oven for curing at 105 ℃ for 20 hours, and the sample is recorded as NIPU-PPI 0.25.
Example 6
A bio-based non-isocyanate polyurethane binder with cluster luminescence property is prepared by the following method:
S1.ELSO (50 g) and catalyst TBAB (2.5 g,5wt.% ELSO) were charged into an autoclave equipped with a mechanical stirrer and carbon dioxide was introduced to bring the pressure to 5MPa. The reaction is carried out at 120 ℃ and the reaction time is controlled at 12 hours to obtain the functional linseed oil with cyclic carbonate functionality;
S2, under the condition that DBU catalyst (with the dosage of 3wt.% CLSO) is added, the cyclic carbonate linseed oil (CLSO) prepared in the step S1 and a curing agent are mixed and dissolved in butanone according to the mol ratio of 1:1, the mol ratio of Polylysine (PLL) to Priamine 1074:1074 in the curing agent is 0.25:0.75, then the mixture is stirred at 78 ℃ for 2 hours and then poured into a glass dish, and then the glass dish is put into an oven for curing at 105 ℃ for 20 hours, and a sample is recorded as NIPU-PLL 0.25.
Comparative example 1
A bio-based non-isocyanate polyurethane binder with cluster luminescence property is prepared by the following method:
S1.ELSO (50 g) and catalyst TBAB (2.5 g,5wt.% ELSO) were charged into an autoclave equipped with a mechanical stirrer and carbon dioxide was introduced to bring the pressure to 5MPa. The reaction is carried out at 120 ℃ and the reaction time is controlled at 12 hours to obtain the functional linseed oil with cyclic carbonate functionality;
S2, under the condition that DBU catalyst (the dosage is 3wt.% CLSO) is added, the cyclic carbonate linseed oil (CLSO) prepared in the step S1 and a curing agent are mixed and dissolved in butanone according to the mol ratio of 1:1, the curing agent only contains Priamine1074, then the mixture is stirred at 78 ℃ for 2 hours and then poured into a glass dish, and then the glass dish is put into an oven for curing at 105 ℃ for 20 hours, and the sample is NIPU-Priamine1074 1.
Comparative example 2
A bio-based non-isocyanate polyurethane binder with cluster luminescence property is prepared by the following method:
S1.ELSO (50 g) and catalyst TBAB (2.5 g,5wt.% ELSO) were charged into an autoclave equipped with a mechanical stirrer and carbon dioxide was introduced to bring the pressure to 5MPa. The reaction is carried out at 120 ℃ and the reaction time is controlled at 12 hours to obtain the functional linseed oil with cyclic carbonate functionality;
S2, under the condition that DBU catalyst (with the dosage of 3wt.% CLSO) is added, the cyclic carbonate linseed oil (CLSO) prepared in the step S1 and a curing agent are mixed and dissolved in butanone according to the mol ratio of 1:1, the curing agent only contains medium hyperbranched Polyethyleneimine (PEI), then the mixture is stirred at 78 ℃ for 2 hours and then poured into a glass dish, and then the glass dish is put into an oven for curing at 105 ℃ for 20 hours, and the sample is recorded as NIPU-PEI 1.
To further illustrate the successful synthesis and excellent effect of the preparation scheme of the present application, the resulting materials were characterized and tested.
The test method is as follows:
(1) Chemical structure test:
1 H nuclear magnetic resonance (1 H NMR) analysis was performed on a brookfield AV 600M spectrometer (germany) with deuterated chloroform as solvent and tetramethylsilane as internal standard. 1 HNMR is used to determine structural features of ELSO and CLSO, and to calculate the functionality of the synthesized CLSO.
The chemical structure of the NIPU film was characterized using a Nicolet IS10 FTIR spectrometer (Thermo Fisher, USA). Attenuated total reflectance analysis was performed by Thermo Nicolet Nexus 670,670 to record the chemical structure of the NIPU film, scanning range 4000 to 400cm -1, scanning times 32.
(2) Mechanical property test:
The test was carried out at room temperature using an MTS universal tester, the rate of stretching being 100mm/min. The experimental and comparative samples were tested 3 times in parallel. Experimental example after curing to a dry film at room temperature, the film was cut into strips of 3cm in length and 1cm in width.
(3) Test method of TGA curve:
thermogravimetric analysis (TGA) was performed using a NETZSCH-STA 449C thermal analyzer. The sample weighing 5mg was placed in an aluminum crucible and tested under nitrogen atmosphere at a rate of 10℃min -1, from 30℃to 700 ℃.
(4) Chemical resistance test
The dried sample (about 50mg, M 1) was filled into a 100ml amber glass bottle, immersed in acid, base and ethanol solvents at room temperature for 6 days, dried in a vacuum oven at 60℃for 48h and then weighed (M 2):
(5) Analysis of fluorescence Properties
Fluorescence tests were performed on an F-7000 spectrometer (Hitachi, japan) with a 150W xenon lamp built in. The scanning speed is 1200nm-min -1. Fluorescence testing was used to characterize the cluster luminescence properties of the NIPU films.
Analysis of results
1. Analysis of chemical Structure
The results of CLSO characterization prepared in the comparative examples and examples of the present invention are shown in fig. 2. Under the catalysis of TBAB, the product is orange-brown viscous liquid through cycloaddition reaction of CO 2 and ELSO. The chemical structures of ELSO and CLSO were characterized by FTIR, GPC, 1H NMR. The 1H NMR results shown in FIG. 2a confirm the conversion of ELSO to CLSO. Specifically, after conversion, peaks at 2.85-3.28ppm corresponding to ELSO epoxide groups disappeared, while signals at 4.45-5.10ppm corresponding to CLSO cyclocarbonate groups appear, indicating complete consumption of the ELSO epoxide groups, forming CLSO. GPC in FIG. 2b determines molecular weight distribution of ELSO and CLSO. The CLSO peak time was 18.22min first and all were unimodal, with a corresponding peak value below that of ELSO at 18.70min, indicating an increase in molecular weight after conversion. As shown by the FTIR spectrum in FIG. 2C, the infrared peak (824 cm -1) representing the epoxy group was attenuated and disappeared, while the new carbonyl peak (1795 cm -1) and the new C-O peak (1047 cm -1) representing the cyclic carbonate group were gradually enhanced. The above results confirm successful conversion of ELSO to CLSO.
To further investigate the conversion efficiency of epoxy groups in ELSO to cyclic carbonate groups in CLSO, the normalized integrated area of epoxy groups in ELSO and cyclic carbonate groups in CLSO was calculated with reference to the 5.2-5.3ppm signal corresponding to-CH-in the triglyceride (fig. 2 (a)). According to formula (1), the amount of epoxy groups (Em) is calculated from the b signal of the epoxy ring (2.85-3.28 ppm). Also, the number of cyclic carbonate groups (Cm) was calculated from the relevant c signal (4.45-5.10 ppm) according to formula (2). Emi represents the initial number of epoxy groups (i.e., the number of epoxy groups not involved in the reaction), emf represents the final number of epoxy groups (i.e., the number of epoxy groups remaining at the end of the reaction). Finally, the conversion (%C), carbonization or yield (%Y) and selectivity (%S) are calculated according to formulas (3) - (5) 25.
Conversion of ELSO to CLSO: conversion%c=97.25%, selectivity%s= 77.38%, yield%y=75.25%.
As shown in FIG. 3, the absorption peak of CLSO cyclic carbonic acid ester carbonyl group at 1795cm -1 in the infrared spectrum of the comparative example and example NIPU of the present invention disappeared, the N-H stretching vibration of polyurethane bond and the broad absorption peak of O-H stretching vibration of derivative hydroxyl group at 3200-3500cm -1 in the polymer system appeared, and the typical absorption peak of C=O stretching vibration of generated polyurethane bond at 1700-1730cm -1 appeared. These indicate that biobased NIPU films have been prepared successfully.
2. Mechanical properties
The mechanical properties of the biobased NIPU prepared in the comparative examples and examples of the present invention are shown in Table 1. As the comparative example 1 only uses Priamine-1074 as the curing agent, the prepared comparative example 1 NIPU-Priamine-1074- 1 has low structural density, weaker mechanical property, 1.2MPa of tensile strength and 153.49% of elongation at break. Whereas the use of polyethyleneimine as a single curative for comparative example 2 resulted in comparative example 2NIPU-PEI 1 having too much rigid structure to exhibit brittleness (elongation at break of only 8.31%). Examples 1-6, which have NIPU properties regulated, have not only excellent tensile strength but also excellent toughness compared to comparative examples 1 and 2, which utilize a hyperbranched structure of Polyethyleneimine (PEI), polyamide-amine (PAMAM), polypropyleneimine (PPI), and Polylysine (PLL) mixed with Priamine and 1074. This is due to the hyperbranched rigid structure provided by the hyperbranched polyamine to achieve high strength of the polyurethane binder and the flexibility Priamine1074 imparting flexibility to the material to achieve toughness of the polyurethane binder, wherein example 3NIPU-PEI 0.75 has a highest tensile strength of 47.8MPa and maintains an elongation at break of 49.55%.
TABLE 1 biological based NIPU film mechanical test results
3. Thermal stability
The thermal stability of the all biobased NIPU films prepared in the comparative examples and examples was evaluated by TGA under nitrogen. All samples exhibited similar degradation behavior with increasing temperature. As shown in fig. 4. Comparative example 1NIPU-Priamine1074 1 prepared from Priamine1074 had an initial decomposition temperature (corresponding to a temperature of 5% weight loss, T 5%) of 200 ℃, due to the tendency of the low density structural NIPU constructed with the flexible chains of Priamine1074 to decompose into small molecule fragments during heating. Whereas comparative example 2NIPU-PEI1, which uses polyethylene imine (PEI) alone as the curing agent, has an initial decomposition temperature of 220℃because of the stress concentration defects in the material caused by the ultra-highly branched rigid structure, which defects are thermally decomposed prior to the molecular chains. Examples 1 to 6 modified by mixing hyperbranched Polyethyleneimine (PEI), polyamide-amine (PAMAM), polypropyleneimine (PPI) and Polylysine (PLL) with Priamine and 1074 all have an initial decomposition temperature which is significantly increased by > 250 ℃. This is because the hyperbranched Polyethyleneimine (PEI), polyamide-amine (PAMAM), polypropyleneimine (PPI) and Polylysine (PLL) mixed with Priamine and 1074 embodiments ensure compactness of the material and reduce defects inside the material due to the synergistic effect of the supramolecular structure polyamine and flexible Priamine and 1074 during heating, thereby improving thermal stability.
4. Chemical resistance
The comparative example of the present invention and the evaluation of chemical resistance carried out in aqueous hydrochloric acid, aqueous sodium hydroxide and ethanol solvent are shown in fig. 5. Compared with comparative example 1 with loose structure and comparative example 2 with internal defects, the bio-based NIPU of the examples 1-6 has good acid resistance, alkali resistance and solvent resistance, the mass percentage of the samples of the examples 1-6 can still reach about 90% after the test, the mass percentage of the samples of the comparative example 1 and comparative example 2 is only 70%, and the chemical resistance is enhanced along with the increase of the content and branching degree of the hyperbranched curing agent and the reduction of the internal defects of the materials (the mass percentage of the samples of the examples 2-6 can reach more than 95%). This is due to the non-defective hyperbranched compact structure of hyperbranched structures of Polyethylenimine (PEI), polyamide-amine (PAMAM), polypropylenimine (PPI) and Polylysine (PLL) and Priamine1074 co-constructed NIPU making the material difficult to attack by chemicals.
5. Photoluminescence performance
As shown in fig. 6, the bio-based NIPU film prepared by the embodiment of the invention shows remarkable luminescence behavior at different excitation wavelengths. In addition, examples 1-3 can emit green light, yellow light and red light at the excitation wavelength due to different hyperbranched PEI contents, because the NIPU structure prepared by higher PEI content is more compact, so that the aggregation degree of the luminous clusters is improved, the rotation among molecules is limited, the energy consumed by the excited state molecules due to the rotation of the molecules is reduced, and the excited state molecules can release energy in a luminescence mode and emit light with different wavelengths (the luminescence wavelength is shown in a fluorescence emission spectrum of fig. 6). Examples 4-6, however, can emit light from deep blue to light blue due to the addition of polyamide-amine (PAMAM), poly (propyleneimine) (PPI) and poly (lysine) (PLL) with different degrees of branching, which is caused by different degrees of spatial interactions in the material and spatial delocalized overlapping of electron clouds, and further, n→pi transition occurs under uv excitation to exhibit blue fluorescence. In comparative example 1, fluorescence was not observed under the ultraviolet light condition, because the nisu structure constructed by Priamine and 1074 has low density, spatial interaction in the material and spatial delocalization overlapping of electron clouds are difficult to realize, and therefore, luminescence behavior caused by exciting electron transition cannot be realized. Comparative example 2 also did not show fluorescence under uv light conditions, because fluorescence quenching was not observed due to the strong spatial interactions within the defective hyperbranched polymer material and the high degree of spatial delocalization overlap of the electron cloud.
The above-described embodiments of the present invention are merely examples for clearly illustrating the technical solution of the present invention, and not all embodiments of the present invention. Any modification, equivalent replacement, improvement, etc. that comes within the spirit and principle of the claims of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A method for preparing a bio-based non-isocyanate polyurethane binder with cluster luminescence properties, comprising the steps of:
S1, inserting CO 2 into epoxy linseed oil, and adding a catalyst to react to obtain cyclic carbonate linseed oil;
s2, mixing and dissolving the cyclic carbonate linseed oil prepared in the step S1 and a curing agent in a solvent, adding a catalyst, stirring for reaction, and heating and curing to obtain the modified linseed oil;
The curing agent is one of polyethylene imine, polyamide-amine, polypropylene imine and polylysine with hyperbranched structures, and is used by mixing with Priamine and 1074.
2. The preparation method according to claim 1, wherein the catalyst in the step S1 is tetrabutylammonium bromide or tetrabutylammonium iodide, and the amount of the tetrabutylammonium iodide is 2-8 wt.% of the epoxy linseed oil.
3. The method according to claim 1, wherein the CO 2 is introduced in an amount to achieve a reaction system pressure of 2MPa to 7MPa in step S1.
4. The preparation method according to claim 1, wherein the reaction temperature in the step S1 is 100-150 ℃ and the reaction time is 6-24 h.
5. The preparation method according to claim 1, wherein the catalyst in the step S2 is one of 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, 1, 8-diazabicyclo undec-7-ene and 4-dimethylaminopyridine, and the amount of the catalyst is 1wt.% to 6wt.% of cyclocarbonate linseed oil.
6. The method according to claim 1, wherein the molar ratio of the cyclic carbonate linseed oil to the curing agent in step S2 is 1:1, and the molar ratio of one of the hyperbranched polyethyleneimine, the polyamide-amine, the polypropyleneimine and the polylysine in the curing agent to Priamine1074 is 0.25:0.75-0.75:0.25.
7. The preparation method according to claim 1, wherein the dissolution solvent in the step S2 is butanone or tetrahydrofuran, the reaction temperature is 60-100 ℃, and the reaction time is 1-10 h.
8. The preparation method according to claim 1, wherein the heating and curing conditions in the step S2 are 100-140 ℃ and curing is performed for 6-24 hours.
9. The biobased non-isocyanate polyurethane binder with cluster light emitting properties prepared by the method of any one of claims 1-8.
10. The use of the biobased non-isocyanate polyurethane binder with cluster light emitting properties of claim 9 in the preparation of coatings, ink materials.
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