CN113881039A - Preparation method of aromatic bicyclic carbonate and hybrid non-isocyanate polyurethane - Google Patents
Preparation method of aromatic bicyclic carbonate and hybrid non-isocyanate polyurethane Download PDFInfo
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Abstract
A preparation method of aromatic bicyclic carbonate and hybrid non-isocyanate polyurethane belongs to the technical field of polyurethane. Firstly, diphenol reacts with 3-chloro-1, 2-propanediol to remove HCl in alkaline solution to obtain aromatic tetraol, then the aromatic tetraol reacts with carbonic diester in the presence of a catalyst to synthesize aromatic bicyclic carbonate, the aromatic bicyclic carbonate reacts with excessive diamine in the absence of a catalyst and a solvent to synthesize amino-terminated polyhydroxyurethane, and the amino-terminated polyhydroxyurethane and aliphatic (or aromatic) diepoxide react and are cured to prepare aromatic hybrid non-isocyanate polyurethane. The method is based on cheap diphenol, epoxy and diamine, the raw materials are easy to obtain, the operation is simple and convenient, and the aromatic hybrid non-isocyanate polyurethane prepared by the method has excellent mechanical properties, and shows excellent solvent resistance and thermal stability.
Description
Technical Field
The invention relates to a method for synthesizing aromatic bicyclic carbonate by a new method, and synthesizing cross-linked non-isocyanate polyurethane by reacting with diamine and epoxy hybridization. The concrete contents are as follows: reacting diphenol with 3-chloro-1, 2-propanediol in an alkaline solution to remove HCl to obtain aromatic tetraol, and reacting with carbonic diester in the presence of a catalyst to synthesize aromatic bicyclic carbonate; aromatic dicyclic carbonate and excessive diamine react to synthesize amino terminated Polyhydroxyurethane (PHUs) in the absence of catalyst and solvent, and the amino terminated polyhydroxyurethane and aliphatic (or aromatic) diepoxide react to cure to prepare aromatic hybrid non-isocyanate polyurethane, and the method belongs to the technical field of polyurethane.
Technical Field
Conventional Polyurethanes (PUs) require the use of diisocyanate monomers in their synthesis, which are toxic and can be harmful to the environment and human body in terms of their production, use and residues in the final product. To address this problem, non-isocyanate polyurethanes (NIPUs) have been of widespread interest and research by scientists in the last several decades. The synthesis of NIPUs has mainly three routes: 1) AB type azide condensation, 2) exchange reaction of urethane with diol, etc., and 3) aminolysis reaction of cyclic carbonate. Among them, the preparation of Polyhydroxyurethanes (PHUs) by ammonolysis of cyclic carbonates with polyamines has received the most attention. Compared with traditional polyurethane, PHUs contain a plurality of side hydroxyl groups in molecules, and the side hydroxyl groups and urethane groups are easy to form intermolecular and intramolecular hydrogen bonds, so that the PHUs are endowed with higher organic solvent and chemical corrosion resistance.
At present, linear and crosslinking PHUs can be prepared by using the reaction of dicarbonate and aliphatic or alicyclic polyamine, but the method is easy to generate side reaction to generate a urea bond, oxazolidone and alcohol structure without reactivity, so that the molecular weight of the linear PHUs is lower, the performance of the crosslinking PHUs is not ideal, and the actual requirements are difficult to meet.
The prior binary or multi-cyclic carbonate monomers used for PHUs are mostly synthesized by reacting pre-synthesized epoxy resin with carbon dioxide at high temperature and high pressure (J.Appl.Polym.Sci.2019, 136,47266; Green chem.,2012,14,1447), have high requirements on equipment and processes, often need high-boiling-point solvents to dissolve reactants and products, and have complicated product separation, so that the preparation cost of the cyclic carbonate monomers is high, and the popularization and application of the method are limited.
The invention provides a novel method for preparing hybridized non-isocyanate polyurethane based on aromatic bicyclic carbonate, which is simple and efficient.A diphenol reacts with 3-chloro-1, 2-propanediol in an alkaline solution to remove HCl to obtain aromatic tetraol, and then the aromatic tetraol reacts with carbonic diester in the presence of a catalyst to synthesize the aromatic bicyclic carbonate; the amino-terminated Polyurethane (PHUs) is synthesized by reacting the amino-terminated polyurethane with excessive diamine under the conditions of no catalyst and no solvent, and the aromatic hybrid non-isocyanate polyurethane is prepared by reacting and curing the amino-terminated polyurethane with aliphatic (or aromatic) diepoxide.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a method for synthesizing an aromatic bicyclic carbonate monomer by using cyclic carbonate esterification of aromatic tetraol, and preparing aromatic hybrid non-isocyanate polyurethane by reacting with diamine and performing epoxy hybridization. The reaction method has the advantages of easily obtained raw materials, simple and convenient operation and excellent performance of the prepared hybrid non-isocyanate polyurethane.
The invention firstly uses diphenol and 3-chlorine-1, 2-propylene glycol to react for removing HCl to obtain aromatic tetraol, and then the aromatic tetraol reacts with carbonic diester in the presence of a catalyst to synthesize aromatic bicyclic carbonate; reacting the amino terminated poly (hydroxyl urethane) (PHUs) with excessive diamine under the conditions of no catalyst and no solvent to synthesize amino terminated poly (hydroxyl urethane) (PHUs); and finally, PHUs and aliphatic (or aromatic) diepoxides are reacted and cured to prepare the aromatic hybrid non-isocyanate polyurethane. The method comprises the following specific steps:
1) preparation of aromatic tetrol: dissolving diphenol in 12 wt% sodium hydroxide aqueous solution (molar ratio of diphenol to NaOH is 0.5) in nitrogen atmosphere, feeding according to the molar ratio of 3-chloro-1, 2-propanediol to diphenol being 2:1, stirring and reacting for 4h at 80-100 ℃, extracting by using n-butyl alcohol to obtain an organic phase, distilling under reduced pressure to remove solvent, and recrystallizing to obtain the aromatic tetraol.
2) Preparation of aromatic bicyclic carbonate: feeding aromatic tetrol and carbonic acid diester according to a molar ratio of 1 (6-10), adding a small amount of carbonate catalyst, carrying out ester exchange reaction at 70-120 ℃ for 12-24 h, standing the reaction solution to room temperature, carrying out suction filtration, and recrystallizing to obtain aromatic bicyclic carbonate monomer powder.
3) Preparation of amino-terminated polyhydroxyurethanes: mixing the aromatic bicyclic carbonate obtained in the step 2) and diamine according to a molar ratio of f (f +1) (wherein f is 1-3), and stirring at 60-120 ℃ to react to obtain a transparent liquid state, thereby obtaining the amino-terminated polyurethane material.
4) Preparation of aromatic hybrid non-isocyanate polyurethane: mixing the amino-terminated polyurethane obtained in the step 3) and aliphatic (or aromatic) diepoxide according to a molar ratio of 1:2, uniformly stirring at 60-150 ℃, pouring into a mold, putting into an oven, and curing at 70-150 ℃ for 2 hours to obtain the aromatic hybrid non-isocyanate polyurethane material.
Wherein, the structure of the aromatic tetrol obtained in the step 1) is shown as (I):
wherein R is1Is composed of
And the like.
The alkali used in the step 1) is one of sodium hydroxide and potassium hydroxide.
The structure of the aromatic bicyclic carbonate synthesized in the step 2) is shown as (II):
wherein R is1Is composed of
And the like.
The carbonate catalyst used in the step 2) is one or more of lithium carbonate, sodium carbonate and potassium carbonate; the carbonic acid diester is one or more of dimethyl carbonate, diethyl carbonate, diphenyl carbonate and ethylene carbonate.
The diamine used in step 3) has the following structure (III):
wherein R is2Is (CH)2)m(m is 2 to 12). Such as one or more of ethylenediamine, butanediamine, hexanediamine, decanediamine, undecanediamine and dodecadiamine.
The aliphatic (or aromatic) diepoxy structure used in the step 4) is shown as (IV):
wherein R is3Is (CH)2)n(n is 2 to 12), or
The aliphatic and aromatic diepoxides used in the step 4) are one or more of ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and bisphenol a diglycidyl ether.
The general formula of the amino-terminated polyurethane obtained in the step 3) is shown as (V):
wherein R is1Is composed of
Etc.; r2Is (CH)2)m(m＝2～12)。
The general formula of the aromatic hybrid non-isocyanate polyurethane obtained in the step 4) is shown as (VI):
wherein R is3Is (CH)2)n(n is 2 to 12), or
The invention has the following effects:
the invention utilizes a new method to synthesize aromatic bicyclic carbonate, which reacts with diamine to synthesize amino-terminated Polyhydroxyurethane (PHUs), and then reacts with aliphatic (or aromatic) diepoxide to cure, so as to prepare aromatic hybrid non-isocyanate polyurethane.
The method is simple and efficient to operate, the prepared hybrid non-isocyanate polyurethane has excellent mechanical property, the tensile strength of 59.52MPa, excellent solvent resistance and thermal stability, and the initial degradation temperature of the polyurethane is higher than 250 ℃.
Detailed Description
According to the GB/T1040-2006 standard, the product is made into a standard dumbbell type sample, the stretching speed is 20mm/min, and the tensile strength and the elongation at break are measured by an INSTRON-1185 universal tensile machine.
The present invention will be described in detail below with reference to preferred examples according to the above-described embodiments, but the present invention is not limited to the following examples.
Example 1:
1) preparation of hydroquinone bis (2, 3-dihydroxypropyl) ether: weighing 24 parts by weight of sodium hydroxide, dissolving the sodium hydroxide in 176 parts by weight of deionized water to prepare a sodium hydroxide solution, adding 33 parts by weight of hydroquinone, and then heating to 50 ℃ to stir and react for 1 hour; then, 66.3 parts of 3-chloro-1, 2-propanediol is added dropwise, and the time is 1 hour; the reaction was then stopped after the mixture was allowed to react at 100 ℃ for 4 h. Extracting the reaction solution by using 120 parts of n-butanol for three times, washing an organic phase by using 30 parts of deionized water, carrying out rotary evaporation concentration on the organic phase, crystallizing at room temperature, filtering and drying to obtain 55.96 parts of brownish red crude product powder; the crude product is then recrystallized to yield 46.19 parts of white hydroquinone bis (2, 3-dihydroxypropyl) ether powder in 59.6% yield and having a melting point of 126 ℃.
2) Preparation of hydroquinone biscyclocarbonate: 38.37 parts of hydroquinone bis (2, 3-dihydroxypropyl) ether obtained in step 1) of example 1, 141.76 parts of diethyl carbonate and 0.36 part of anhydrous potassium carbonate were mixed, and then refluxed at 120 ℃ for 12 hours to complete the reaction. Standing at room temperature to fully separate out a reaction product, filtering, drying and recrystallizing to finally obtain 27.62 parts of hydroquinone biscyclocarbonate with the yield of 59.4 percent and the melting point of 178 ℃.
3) 3.1 parts of hydroquinone bicyclic carbonate obtained in the step 2) of the embodiment 1 is weighed according to the weight parts and mixed with 2.32 parts of hexamethylene diamine, the mixture is stirred and reacted for 3 hours at the temperature of 120 ℃, and the reaction is stopped, so that amino-terminated linear non-isocyanate polyurethane PHU-H1 based on hydroquinone is obtained, and the molecular weight of the amino-terminated linear non-isocyanate polyurethane PHU-H1 is 755 g/mol.
4) The product PHU-H12 and the butanediol diglycidyl ether 1.0715 in the step 3) of the embodiment 1 are respectively weighed according to the parts by weight, stirred and uniformly mixed at 120 ℃, poured into a tetrafluoro mold, and cured for 2 hours at 60 ℃ to obtain the aliphatic epoxy cured p-phenylene bisphenol hybrid non-isocyanate polyurethane (HNIPU-H1), wherein the tensile strength is 15.38MPa, and the elongation at break is 57.98%. The product is insoluble in common organic solvents such as ethanol, acetone, chloroform, toluene, dimethylformamide, dimethyl sulfoxide, etc.; its initial thermal decomposition temperature was 260 ℃.
Example 2:
1) 3.1 parts of hydroquinone bicyclic carbonate obtained in the step 2) of the embodiment 1 is weighed according to the parts by weight and mixed with 1.5455 parts of hexamethylene diamine, the mixture is stirred and reacted for 3 hours at the temperature of 120 ℃, the reaction is stopped, and the amino-terminated linear non-isocyanate polyurethane PHU-H2 based on hydroquinone is obtained, and the molecular weight of the amino-terminated linear non-isocyanate polyurethane PHU-H2 is 1561 g/mol.
2) The product PHU-H22 and the butanediol diglycidyl ether 0.5182 in the step 1) of the embodiment 2 are respectively weighed according to the parts by weight, stirred and uniformly mixed at 120 ℃, poured into a tetrafluoro mold, and cured for 2 hours at 60 ℃ to obtain the aliphatic epoxy cured p-phenylene bisphenol hybrid non-isocyanate polyurethane (HNIPU-H2), wherein the tensile strength is 36.85MPa, and the elongation at break is 16.81%. The product is insoluble in common organic solvents such as ethanol, acetone, chloroform, toluene, dimethylformamide, dimethyl sulfoxide, etc.; its initial thermal decomposition temperature was 251 ℃.
Example 3:
1) preparation of bisphenol a bis (2, 3-dihydroxypropyl) ether: weighing 24 parts by weight of sodium hydroxide, dissolving the sodium hydroxide in 176 parts by weight of deionized water to prepare a sodium hydroxide solution, adding 68.46 parts of bisphenol A, heating to 50 ℃, and stirring for reaction for 1 hour; then 66.3 parts of 3-chloro-1, 2-propanediol is dripped, and the time is consumed for 1 hour; the reaction was then stopped after the mixture was allowed to react at 80 ℃ for 4 h. Extracting the reaction solution by using 120 parts of n-butanol for three times, washing an organic phase by using 30 parts of deionized water, carrying out rotary evaporation and concentration on the organic phase, crystallizing at room temperature, filtering and drying to obtain 88.35 parts of white powder; the crude product is then recrystallized to give 70 parts of white bisphenol A bis (2, 3-dihydroxypropyl) ether powder in 62% yield and having a melting point of 90 ℃.
2) Preparation of bisphenol a bicyclic carbonate: 37.64 parts of bisphenol A bis (2, 3-dihydroxypropyl) ether obtained in step 1) of example 3, 94.5 parts of diethyl carbonate and 0.26 part of anhydrous potassium carbonate were mixed, and the mixture was refluxed at 90 ℃ for 24 hours to complete the reaction. Standing at room temperature to fully separate out a reaction product, filtering, drying and recrystallizing to finally obtain 31.28 parts of p-phenylene diphenol bicyclocararbonate, wherein the yield is 73 percent and the melting point is 160 ℃.
3) 4.28 parts of bisphenol A biscyclocarbonate product obtained in step 2) of example 3 and 2.32 parts of hexamethylenediamine are weighed in parts by weight and stirred at 60 ℃ for 3 hours to react, and the reaction is stopped to obtain amino-terminated linear non-isocyanate polyurethane PHU-A1 based on bisphenol A, which is 836 g/mol.
4) The product PHU-A12 of the step 3) of the embodiment 3 and 1.22 parts of butanediol diglycidyl ether are respectively weighed according to the parts by weight, stirred and mixed uniformly at 60 ℃, poured into a tetrafluoro mold, and cured for 2 hours at 120 ℃ to obtain the aliphatic epoxy cured bisphenol A hybrid non-isocyanate polyurethane (HNIPU-A1), wherein the tensile strength is 38.15MPa, and the elongation at break is 28.61%. The product is insoluble in common organic solvents such as ethanol, acetone, chloroform, toluene, dimethylformamide, dimethyl sulfoxide, etc.; its initial thermal decomposition temperature was 289 ℃.
Example 4:
1) 4.28 parts of bisphenol A biscyclocarbonate product obtained in step 2) of example 3 are weighed in parts by weight and reacted with 1.74 parts of hexamethylenediamine at 80 ℃ for 3 hours with stirring, and the reaction is stopped to obtain the amino-terminated linear non-isocyanate polyurethane PHU-A2 based on bisphenol A, which is 1532 g/mol.
2) The product PHU-A22 of the step 1) of the embodiment 4 and 0.67 part of butanediol diglycidyl ether are respectively weighed according to the parts by weight, stirred and mixed uniformly at 90 ℃, poured into a tetrafluoro mold, and cured for 2 hours at 120 ℃ to obtain the aliphatic epoxy cured bisphenol A hybrid non-isocyanate polyurethane (HNIPU-A2), wherein the tensile strength is 46.10MPa, the elongation at break is 20.32%, the gel content is 83.10%, and the initial degradation temperature is higher than 281 ℃.
Example 5:
the product PHU-A12 of the step 3) of the embodiment 3 and 2.06 parts of bisphenol A diglycidyl ether are respectively weighed according to the parts by weight, stirred and uniformly mixed at 60 ℃, poured into a tetrafluoro mold, and cured for 2 hours at 120 ℃ to obtain the aromatic epoxy cured bisphenol A hybrid non-isocyanate polyurethane (HNIPU-A3), which has the highest tensile strength of 59.56MPa, the elongation at break of 23.74 percent, the gel content of 81.48 percent and the initial degradation temperature of higher than 299 ℃.
Example 6:
1) preparation of bisphenol S bis (2, 3-dihydroxypropyl) ether: weighing 24 parts by weight of sodium hydroxide, dissolving the sodium hydroxide in 176 parts by weight of deionized water to prepare a sodium hydroxide solution, adding 75.08 parts of bisphenol S, heating to 50 ℃, stirring for reaction for 1 hour, and dropwise adding 66.3 parts of 3-chloro-1, 2-propanediol, wherein the time is 1 hour; after the mixture was reacted at 100 ℃ for 4 hours, the reaction was stopped. Extracting the reaction solution by using 120 parts of n-butanol for three times, washing an organic phase by using 30 parts of deionized water, carrying out rotary evaporation and concentration on the organic phase, crystallizing at room temperature, filtering and drying to obtain 116.25 parts of white powder; the crude product is then recrystallized to give 104 parts of white bisphenol S bis (2, 3-dihydroxypropyl) ether powder in 88% yield and having a melting point of 125 ℃.
2) Preparation of bisphenol S bicyclic carbonate: 59.75 parts of bisphenol S bis (2, 3-dihydroxypropyl) ether obtained in step 1) of example 6, 141.76 parts of diethyl carbonate and 0.40 part of anhydrous potassium carbonate were mixed, and the mixture was refluxed at 120 ℃ for 12 hours to complete the reaction. Standing at room temperature to fully separate out a reaction product, filtering, drying and recrystallizing to finally obtain 43.02 parts of p-phenylene diphenol type bicyclocarbonate, wherein the yield is 63.68 percent and the melting point is 225 ℃.
3) 4.50 parts of bisphenol S bicyclic carbonate which is a product obtained in the step 2) of the embodiment 6 is weighed according to the parts by weight, 2.32 parts of hexamethylene diamine is added, and the mixture is stirred and reacted for 3 hours at the temperature of 120 ℃, so that the amino-terminated linear non-isocyanate polyurethane PHU-S1 based on bisphenol S is obtained, and the molecular weight of the amino-terminated linear non-isocyanate polyurethane PHU-S1 is 1031 g/mol.
4) The product PHU-S12 of the step 3) of the embodiment 6 and 0.78 part of butanediol diglycidyl ether are respectively weighed according to the parts by weight, stirred and uniformly mixed at 150 ℃, poured into a tetrafluoro mold, and cured for 2 hours at 150 ℃ to obtain the aliphatic epoxy cured bisphenol S type hybrid non-isocyanate polyurethane HNIPU-S1, wherein the tensile strength is 45.07MPa, the elongation at break is 22.17%, the gel content is 78.96%, and the initial degradation temperature is higher than 281 ℃.
Claims (6)
1. The preparation method of aromatic bicyclic carbonate and hybridized non-isocyanate polyurethane is characterized in that the preparation method is a method for synthesizing hybridized non-isocyanate polyurethane based on the reaction of aromatic bicyclic carbonate, aliphatic or aromatic epoxy and diamine, a new synthesis method of aromatic bicyclic carbonate, and a method for synthesizing amino-terminated Polyhydroxyurethane (PHUs) by the reaction of aromatic bicyclic carbonate, aliphatic or aromatic epoxy and diamine, and the amino-terminated Polyhydroxyurethane (PHUs) is reacted and cured with the aliphatic or aromatic epoxy under the conditions of no catalyst and no solvent to prepare aromatic hybridized non-isocyanate polyurethane (HNIPUs); the method specifically comprises the following steps:
1) preparation of aromatic tetrol: dissolving diphenol in an alkaline aqueous solution in nitrogen atmosphere, feeding the diphenol and 3-chloro-1, 2-propanediol in a molar ratio of 1:2, stirring and reacting at 80-100 ℃ for 4 hours, extracting by using n-butyl alcohol to obtain an organic phase, distilling under reduced pressure to remove the solvent, and recrystallizing to obtain aromatic tetrol;
2) preparation of aromatic bicyclic carbonate: feeding aromatic tetrol and carbonic acid diester according to a molar ratio of 1 (6-10), adding a small amount of carbonate catalyst, carrying out ester exchange reaction at 70-120 ℃ for 12-24 h, standing the reaction solution to room temperature, carrying out suction filtration, and recrystallizing to obtain aromatic bicyclic carbonate monomer powder;
3) preparation of amino-terminated polyhydroxyurethanes: mixing the aromatic bicyclic carbonate obtained in the step 2) with diamine according to a molar ratio of f (f +1) (f is 1-3), and stirring at 60-120 ℃ to react to obtain a transparent liquid state so as to obtain an amino-terminated polyurethane material;
4) preparation of aromatic hybrid non-isocyanate polyurethane: compounding the amino-terminated polyurethane obtained in the step 3) with aliphatic or aromatic diepoxide according to a molar ratio of 1:2, uniformly stirring at 60-150 ℃, pouring into a mold, and curing in an oven at 70-150 ℃ for 2h to obtain the aromatic hybrid non-isocyanate polyurethane material.
2. The process according to claim 1, characterized in that in step 1) an aromatic tetrol is synthesized, having the structure (i):
wherein R is1Is composed of
Isoaromatic structures;
the structure of the aromatic bicyclic carbonate synthesized in the step 2) is shown as (II):
the structure of the diamine used in the step 3) is shown as (III):
wherein R is2Is (CH)2)m，m＝2～12；
The aliphatic or aromatic diepoxy structure used in step 4) is shown as (IV):
wherein R is3Is (CH)2)nN is 2 to 12, or
3. The method according to claim 1, wherein the base used in step 1) is one of sodium hydroxide and potassium hydroxide.
4. The method according to claim 1, characterized in that the carbonate catalyst used in step 2) is one or more of lithium carbonate, sodium carbonate and potassium carbonate; the carbonic acid diester is one or more of dimethyl carbonate, diethyl carbonate, diphenyl carbonate and ethylene carbonate.
5. The method according to claim 1, wherein the diamine used in step 3) is one or more selected from the group consisting of ethylenediamine, butanediamine, hexanediamine, decanediamine, undecanediamine and dodecanediamine.
6. The process according to claim 1, wherein the aliphatic and aromatic diepoxides used in step 4) are one or more selected from ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and bisphenol a diglycidyl ether.
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| HE, X等: "Synthesis and Characterization of Dimmer-Acid-Based Nonisocyanate Polyurethane and Epoxy Resin Composite", 《POLYMERS》 * |
| SIMANTA DOLEY等: "In situ development of bio‐based polyurethane‐ blend ‐epoxy hybrid materials and their nanocomposites with modified graphene oxide via non‐isocyanate route", 《POLYMER INTERNATIONAL》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115403765A (en) * | 2022-10-05 | 2022-11-29 | 大连理工大学 | Chemically recyclable high-strength non-isocyanate polyurethane and preparation method thereof |
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| CN113881039B (en) | 2022-11-15 |
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