CN111763316B - Polythiocarbamate and preparation method thereof - Google Patents
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
- C08G71/04—Polyurethanes
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
本发明属于高分子材料技术领域，具体的涉及一种聚硫代氨基甲酸酯及其制备方法。本发明提供的方法以氧硫化碳和2‑甲基氮丙啶为原料，无需使用催化剂，可以在本体或溶剂条件下共聚合得到聚硫代氨基甲酸酯，所述的反应优选在0～120℃的温度下进行。本发明开发的方法具有如下优点：无需催化剂，自身即可反应；原料廉价易得，合成简便，不使用传统体系中有毒的巯基化合物与异氰酸酯化合物；制备得到的聚硫代氨基甲酸酯主链结构明确，且具有全交替结构；分子间有强烈的氢键作用，热性能优异，无金属残留且无色；合成过程操作简便，反应条件温和，反应速率快，反应过程环保。该材料对重金属汞离子有较强的吸附作用，可用于吸附水体系中的汞离子。
The invention belongs to the technical field of polymer materials, in particular to a polythiocarbamate and a preparation method thereof. The method provided by the invention uses carbon oxysulfide and 2-methylaziridine as raw materials, without using a catalyst, and can obtain polythiocarbamate by copolymerization under bulk or solvent conditions, and the reaction is preferably in the range of 0- carried out at a temperature of 120°C. The method developed by the invention has the following advantages: it can react by itself without a catalyst; the raw materials are cheap and easy to obtain, the synthesis is simple, and the toxic mercapto compounds and isocyanate compounds in the traditional system are not used; the prepared polythiocarbamate main chain The structure is clear and has a fully alternating structure; there are strong hydrogen bonds between molecules, excellent thermal properties, no metal residue and colorless; the synthesis process is simple and easy to operate, the reaction conditions are mild, the reaction rate is fast, and the reaction process is environmentally friendly. The material has a strong adsorption effect on heavy metal mercury ions, and can be used to adsorb mercury ions in water systems.
Description
Technical Field
The invention belongs to the field of synthesis of high polymer materials, and particularly relates to polythiocarbamate and a preparation method thereof.
Background
The polythiourethane has sulfur-containing and nitrogen-containing polymers with excellent optical properties, chemical stability and thermal stability, and has wide potential application value in the aspects of optical materials, high-performance fibers, adhesives and engineering plastics. Usually, polythiourethane is prepared by reacting dihydric or polyhydric mercaptan with dihydric or polyhydric isocyanate, and the synthetic method of the raw materials of the dihydric or polyhydric mercaptan is complicated and fussy, and in addition, the toxicity of the isocyanate is high, so that the synthetic route has great limitation.
Carbon Oxysulfide (COS) is an atmospheric pollutant released from the combustion of fossil fuels, coal gases, many chemical processes, volcanic eruptions, and plant or protein spoilage processes. Carbon oxysulfide in the troposphere causes acid rain and ozone layer destruction through a series of photochemical reactions. However, carbon oxysulfide contains a sulfur atom in its molecule and thus can be considered as a natural sulfur-containing synthetic monomer. The preparation of sulfur-containing polymers by using carbon oxysulfide as a sulfur-containing polymeric monomer as a raw material is undoubtedly an effective chemical synthesis strategy which changes waste into valuable and accords with the sustainable development concept.
The patent (CN1171924C) discloses a process for preparing polythiourethanes by polymerizing a self-made mixture of polythiols and polyisocyanates in situ in a mold. Firstly, prepolymerization is carried out for 10-60 minutes at 50-80 ℃, bubbles are removed in vacuum, the mixture is injected into a mold, the temperature is increased to 80-100 ℃, the reaction is carried out for 2-5 hours, and cooling is carried out to obtain the polythiourethane. It is completely different from this patent in terms of synthetic raw materials and polymerization method.
The patent (CN1405198A) discloses a method for preparing polythiourethane optical plastics, which is obtained by first synthesizing thiol containing multiple mercapto groups, and then mixing with polyisocyanate for condensation polymerization. It is completely different from this patent in terms of synthetic raw materials and polymerization method.
The patent (CN105229046A) discloses a polythiourethane casting resin for producing optical lenses, which uses a method of copolymerizing mercaptan and isocyanate, and is completely different from the synthetic raw materials and polymerization method used in the patent.
So far, no report of direct copolymerization of carbonyl sulfide and 2-methyl aziridine as a ring nitrogen monomer to generate polythiourethane with an asymmetric chain structure is found, and no report of regioselective synthesis of polythiourethane is found.
Disclosure of Invention
The invention aims to provide polythiourethane prepared by copolymerizing carbonyl sulfide and a ring nitrogen monomer 2-methyl aziridine and a preparation method thereof.
The scheme for solving the technical problems is as follows:
a polythio carbamate is prepared from carbonyl sulfide and 2-methyl aziridine through polymerizing at certain reaction temp and autogenous pressure in the presence of catalyst,
wherein the chemical structural formula of the polythiourethane is shown as formula 1:
in formula 1: n is an integer of 10 to 500;
the polydispersity index of the molecular weight of the polythiourethane is 1.1 to 1.9;
the chemical structural formula of the polythiourethane can be determined by nuclear magnetic resonance hydrogen spectrum and carbon spectrum, and matrix-assisted time-of-flight mass spectrometry.
The polythiourethane is obtained by polymerizing carbonyl sulfide and 2-methylaziridine (CAS number: 75-55-8) serving as raw materials under the condition of a raw material body or a solvent at a certain reaction temperature; the reaction system does not use a catalyst, and is simple.
Wherein n is the number of repeating units on the main chain of the polymer, the molecular weight of the repeating units is 117g/mol, when n is 10-500, the molecular weight of the corresponding polymer is 1170-58500 g/mol, namely about 1.2-58.5 kg/mol, and the polythiourethane with the molecular weight in the range can better show certain mechanical strength and higher glass transition temperature. The molecular weight polydispersity index (abbreviated as PDI) is 1.1-1.9, and when PDI is less than 2, the molecular weight distribution of a polymer is relatively uniform, and the closer the PDI value is to 1, the more uniform the molecular weight distribution is. Polymers with a uniform molecular weight distribution will perform better in terms of both mechanical and thermal properties.
The bulk conditions refer to the reaction in a system of carbon oxysulfide and 2-methylaziridine itself only, without the addition of an additional solvent; the solvent condition means that a good solvent capable of dissolving the product of the polythiourethane is added to dilute the whole system, so that the reaction can be prevented from being ended in advance when the monomer is not completely converted due to overhigh viscosity of the system in the polymerization process. The polymerization reaction in the diluted reaction system obtained by adding the solvent can be more uniform and thorough, and the molecular weight of the polymer can be improved.
The fact that no catalyst is used in the reaction process means that the reaction system has high activity and can normally carry out reaction without adding a catalyst. It should be noted that the absence of catalyst does not mean that it is not possible to add catalyst, and the addition of catalyst to accelerate the reaction should not be considered as an innovation on the basis of the present invention.
The reaction temperature is 0-120 ℃, and the reaction time is 0.1-24 hours; the reaction temperature is preferably 20-100 ℃, and the reaction time is preferably 0.5-12 hours; more preferably 20-80 ℃ for 1-6 hours.
The molar ratio of the carbonyl sulfide to the 2-methylaziridine in the reaction raw materials is 1: 1-10: 1, and preferably 2: 1-5: 1.
The pressure of the carbonyl sulfide in the reaction raw materials is 0.1-10 MPa, preferably 0.5-5 MPa, and more preferably 1-2 MPa. The reaction can be carried out by selecting a proper reaction vessel according to the autogenous pressure of the system, and generally, a pressure-resistant stainless steel reaction kettle is selected for the gas-liquid reaction.
The reaction may be carried out in a solvent selected from at least one of N, N-dimethylformamide, N-dimethylacetamide, nitrogen methyl pyrrolidone, dimethyl sulfoxide, hexamethylphosphoramide, toluene, pyridine, acetone, dichloromethane, chloroform, tetrahydrofuran, dioxane, and ethyl acetate.
As a preferred technical scheme of the invention, when the reaction conditions are as follows: the reaction temperature is 20 ℃, the reaction time is 1 hour, and the molar ratio of the carbonyl sulfide to the 2-methyl aziridine in the reaction raw materials is 5: 1; the pressure of the carbonyl sulfide in the reaction raw material is 1.5MPa, the solvent is tetrahydrofuran, the conversion rate of the prepared polythiourethane raw material 2-methyl aziridine can reach 96%, and the selectivity of the polymer product is more than 99%.
Compared with the prior art, the invention has the following advantages:
1. the method developed by the invention can react without a catalyst.
2. The method has the advantages of cheap and easily obtained raw materials, simple and convenient synthesis and is superior to the traditional synthesis method of reacting very complex and toxic sulfhydryl compounds with isocyanate.
3. The polythiourethane prepared by the invention has a definite main chain structure, a fully-alternating structure, strong hydrogen bonding action among molecules, excellent thermal property, no metal residue and no color, and the polymer has good adsorption capacity on metal mercury ions in a water system and can be used in the fields of mercury ion adsorption removal and recovery.
4. The synthesis process is simple and convenient to operate, the reaction condition is mild, the reaction rate is high, and the reaction process is environment-friendly.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of polythiourethane obtained in example 3;
FIG. 2 is a nuclear magnetic carbon spectrum of the polythiourethane obtained in example 3;
FIG. 3 is a matrix-assisted time-of-flight mass spectrum of the polythiourethane obtained in example 3;
FIG. 4 is a Differential Scanning Calorimetry (DSC) curve of the polythiourethane obtained in example 3;
FIG. 5 is a thermogravimetric analysis (TGA) curve of the polythiourethane obtained in example 3;
FIG. 6 is a nuclear magnetic hydrogen spectrum of extracted small molecules of cyclic by-products;
FIG. 7 is a nuclear magnetic hydrogen spectrum of the crude product obtained in example 5;
FIG. 8 is a general reaction scheme for the synthesis of polythiourethanes according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the description is intended to be exemplary only, and is not intended to limit the scope of the present invention.
In this reaction, there is a concept of product selectivity, and when carbon oxysulfide reacts with 2-methyl aziridine, a polymer product, i.e., polythiourethane, can be generated, and a cyclic small molecule compound can also be generated, as shown in formula 2. Product selectivity of the reaction is defined as the percentage of polymer product in the total product and is calculated as follows:
the selectivity of the polymer product is equal to the number of moles of the polymer repeating chain segments/(the number of moles of the polymer repeating chain segments + the number of moles of the cyclic product). times.100%, and the parameter can be calculated by the integral area ratio of the same type of protons in the nuclear magnetic hydrogen spectrum.
The calculation process is illustrated as follows:
firstly, we can obtain pure substances of small molecule byproducts by an extraction separation method, and perform nuclear magnetic hydrogen spectrum characterization on the pure substances, as shown in fig. 6: protons on the methine carbon of the small molecule appear at the b 'peak position, the 2 protons linked to the methylene carbon appear at the c' peak positions at both 3.46ppm and 2.98ppm, and the integrated areas of the three peaks are equal, consistent with the number of protons in their chemical structure. From this nuclear magnetic result we first determined the nuclear magnetic peak position and integration of the small molecule.
Taking the nuclear magnetism of the crude product of example 5 as an example, as shown in FIG. 7: the b peak at 3.8ppm is attributed to the proton on the methine carbon of the polymer, which coincides with the b' peak of the small molecule and cannot be directly integrated to obtain the area of the b peak. Indirectly by integrating the c ' peak at 3.46ppm (setting the value to 1), the b ' peak area is also 1 because the integrated areas of the b ' peak and the c ' peak are equal, and the integrated sum of the b ' peak and the b peak is 3.45, so the b peak area is 3.45-1-2.45, so the selectivity of the polymer is 2.45/3.45 × 100% — 71%. Other spectra were also calculated in the same way.
It was evaluated that a reaction condition was excellent and the reaction result was required to have: high monomer conversion (2-methylaziridine conversion in the present system)>90%) and high selectivity of polymer product (polymer%>90%) polymer product having a high molecular weight (M)w>10kg/mol) and narrow molecular weight distribution (PDI)<2) The polymer has a fully alternating structure, etc.
Examples 1 to 16
The parameters are shown in Table 1
Before polymerization, drying a 10mL high-pressure reaction kettle at the temperature of more than 100 ℃ for about 2 hours to remove water, and cooling the reaction kettle to room temperature in a dryer; 1mL of 2-methylaziridine was added to the autoclave, a quantity of solvent (about 2mL) was added for the solvent set example, the autoclave was then closed, and carbon oxysulfide was added to the pressure (the molar ratio of carbon oxysulfide to 2-methylaziridine is shown in Table 1). And (3) placing the reaction kettle at the specified reaction temperature, and uniformly stirring for the specified reaction time. And (3) after the reaction is finished, reducing the temperature of the reaction kettle to normal temperature, discharging carbonyl sulfide gas, opening the kettle, taking a small amount of crude product, and sending the crude product to Nuclear Magnetic Resonance (NMR) to determine the proportion of the polymer and the cyclic by-product in the crude product and the conversion rate of 2-methylaziridine. After the reaction is finished, diluting the crude product solution to 5mL by using the solvent initially added in the reaction, precipitating the diluted solution in poor solvent methanol (100mL) to obtain solid precipitate, separating solid from liquid, dissolving the solid product obtained by separation with the reaction solvent again to 5mL, precipitating in poor solvent methanol (100mL), and carrying out solid-liquid separation. The dissolution, dilution and precipitation are repeated for 3 times or more. And (3) drying the finally separated solid product in an oven at 100-150 ℃ for 12 hours to obtain a white or light yellow solid, characterizing the finally obtained polymer, further determining the main chain structure by nuclear magnetic resonance, and determining the molecular weight and the molecular weight distribution of the polymer by gel chromatography, wherein the test results are shown in Table 1.
One group in which the best performances were obtained in terms of conversion, molecular weight of the polymer and selectivity of the polymer is example 3 of table 1, from which the chemical structure of the product obtained was demonstrated by means of nuclear magnetic resonance (hydrogen spectrum in fig. 1, carbon spectrum in fig. 2) and matrix-assisted time-of-flight mass spectrometry (fig. 3) to be polythiourethane structures having a fully alternating structure, i.e. carbon oxysulfide alternated with 2-methylaziridine to form polymer repeating units.
The glass transition temperature and the initial thermal decomposition temperature of the product are respectively characterized by differential scanning calorimetry (figure 4) and thermogravimetric analysis (figure 5), and the polythiourethane is proved to have good thermal stability.
TABLE 1 copolymerization of carbonyl sulfide (abbreviated as COS) and 2-methylaziridine (abbreviated as MeAz) under different reaction conditionsa
a1mL of 2-methylaziridine was added to the reaction.bMwPDI is the polydispersity, as weight average molecular weight, as determined by Gel Permeation Chromatography (GPC) in the DMF mobile phase.
The synthesized polythiourethane has better adsorption effect on divalent metal mercury ions in an aqueous solution, and the polymer product in the example 3 is used for carrying out an adsorption experiment on the mercury ions in the aqueous solution, and the steps are as follows: 10mL of 20mg/L mercuric chloride (II) aqueous solution was put into a beaker, a certain mass of polymer was put into the beaker, insoluble matter was filtered off after stirring for 12 hours to obtain a clear solution, and the clear solution was subjected to inductively coupled plasma atomic emission spectroscopy (ICP) to measure the concentration of mercury (II) ions, the results of which are shown in Table 2 below. The adsorption efficiency is equal to the concentration of adsorbed mercury ions/original mercury ion concentration multiplied by 100 percent (original mercury ion concentration-mercury ion concentration after adsorption)/original mercury ion concentration multiplied by 100 percent.
TABLE 2 adsorption of polythiocarbamates on divalent metallic mercury ions in aqueous solutions
As can be seen from the data in Table 2, after the polymer with proper mass is added into the mercury ion-containing aqueous solution and stirred for a period of time, the polymer can adsorb more than 99.9 percent of free mercury ions in the aqueous solution, which proves that the polymer has stronger adsorption effect on the mercury ions and is a potential mercury ion adsorption and recovery agent.
Although the embodiments of the present invention have been described in detail, it should be understood that various changes, substitutions, and alterations can be made hereto without departing from the spirit and scope of the invention.
Claims (2)
1. A method for preparing polythiourethane, which is characterized in that: the method comprises the following steps: carbon oxysulfide and 2-methyl aziridine are used as raw materials, and polythiocarbamate is obtained by polymerization under the condition of a solvent and under a certain reaction temperature and autogenous pressure;
the chemical structural formula of the polythiourethane is shown as formula 1:
In formula 1: n is an integer of 10 to 500; the polydispersity index of the molecular weight of the polythiourethane is 1.1 to 1.9;
the reaction temperature is 20 ℃, the reaction time is 1 hour, and the molar ratio of the carbonyl sulfide to the 2-methyl aziridine in the reaction raw materials is 5: 1; the pressure of the carbonyl sulfide in the reaction raw materials is 1.5MPa, and the solvent is tetrahydrofuran.
2. Use of polythiocarbamates prepared by the process according to claim 1, wherein: used for adsorbing mercury ions in a water system.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB679671A (en) * | 1949-03-12 | 1952-09-24 | Tno | Linear polyurea derivatives |
| GB956460A (en) * | 1959-07-13 | 1964-04-29 | Monsanto Chemicals | Production of thiocarbamates and thiocarbazates |
| US3213108A (en) * | 1962-08-09 | 1965-10-19 | Thiokol Chemical Corp | Process for making ethylene sulfide and intermediate product for use therein |
| CN101869825A (en) * | 2010-05-06 | 2010-10-27 | 同济大学 | Preparation method of mercury ion adsorbent made from activated sludge |
| TW201321494A (en) * | 2011-08-17 | 2013-06-01 | Nalco Co | Removal of mercury and mercuric compounds from crude oil streams |
| CN103275314A (en) * | 2013-05-27 | 2013-09-04 | 浙江大学 | Preparation method of polymonosulfo-carbonate with regular chain structure |
| WO2014086974A1 (en) * | 2012-12-07 | 2014-06-12 | Espci Innov | Processable semi-crystalline polymer networks |
| CN106243336A (en) * | 2016-08-15 | 2016-12-21 | 浙江大学 | A kind of crystalliferous Polythiocarbonate and preparation method thereof |
| CN110483772A (en) * | 2019-09-10 | 2019-11-22 | 常熟理工学院 | A kind of polythiourea and preparation method thereof with self-healing capability |
-
2019
- 2019-11-28 CN CN201911190194.5A patent/CN111763316B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB679671A (en) * | 1949-03-12 | 1952-09-24 | Tno | Linear polyurea derivatives |
| GB956460A (en) * | 1959-07-13 | 1964-04-29 | Monsanto Chemicals | Production of thiocarbamates and thiocarbazates |
| US3213108A (en) * | 1962-08-09 | 1965-10-19 | Thiokol Chemical Corp | Process for making ethylene sulfide and intermediate product for use therein |
| CN101869825A (en) * | 2010-05-06 | 2010-10-27 | 同济大学 | Preparation method of mercury ion adsorbent made from activated sludge |
| TW201321494A (en) * | 2011-08-17 | 2013-06-01 | Nalco Co | Removal of mercury and mercuric compounds from crude oil streams |
| WO2014086974A1 (en) * | 2012-12-07 | 2014-06-12 | Espci Innov | Processable semi-crystalline polymer networks |
| CN103275314A (en) * | 2013-05-27 | 2013-09-04 | 浙江大学 | Preparation method of polymonosulfo-carbonate with regular chain structure |
| CN106243336A (en) * | 2016-08-15 | 2016-12-21 | 浙江大学 | A kind of crystalliferous Polythiocarbonate and preparation method thereof |
| CN110483772A (en) * | 2019-09-10 | 2019-11-22 | 常熟理工学院 | A kind of polythiourea and preparation method thereof with self-healing capability |
Non-Patent Citations (5)
| Title |
|---|
| Alternating copolymerization of carbonyl sulfide with aziridines;Hisao Yokota, Masatsune Kondo;《Journal of Polymer Science Part A-1: Polymer Chemistry》;19710101;第9卷(第1期);第13页第1段第1-3行、第14段第5-8行、第14页第1段、第19页、第21页,参见第16页倒数第3段 * |
| Non-Isocyanate and Catalyst-Free Synthesis of a Recyclable Polythiourethane with Cyclic Structure;Wu, Shuang;《ACS SUSTAINABLE CHEMISTRY & ENGINEERING》;20200413;第8卷(第14期);5693-5703 * |
| Salen催化剂催化2-甲基氮丙啶与氧硫化碳反应;吴双，左晓兵，罗铭;《广州化工》;20210831;第49卷(第15期);27-29 * |
| Zwitterionic Alternating Polymerization to Generate Semicrystalline and Recyclable Cyclic Polythiourethanes;Tan, Dawei;《ACS MACRO LETTERS》;20200616;第9卷(第6期);866-871 * |
| 氧硫化碳的化学;余中心;《农药》;19810325(第03期);17-19 * |
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