CN110862336A - Alcohol amine chain extender, preparation method and application - Google Patents

Alcohol amine chain extender, preparation method and application Download PDF

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Publication number
CN110862336A
CN110862336A CN201911036401.1A CN201911036401A CN110862336A CN 110862336 A CN110862336 A CN 110862336A CN 201911036401 A CN201911036401 A CN 201911036401A CN 110862336 A CN110862336 A CN 110862336A
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chain extender
parts
diamine
alkanolamine
mass
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王军威
李晓云
亢茂青
赵雨花
冯月兰
李其峰
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Shanxi Institute of Coal Chemistry of CAS
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Shanxi Institute of Coal Chemistry of CAS
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    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C271/20—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by nitrogen atoms not being part of nitro or nitroso groups
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    • C07C271/28—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring to a carbon atom of a non-condensed six-membered aromatic ring
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Abstract

The invention relates to an alcohol amine chain extender and a preparation method and application thereof, belonging to the technical field of preparation methods and application of alcohol amine chain extenders. The invention mainly solves the technical problems of poor water resistance, solvent resistance, mechanical property and thermal property of the existing polyurethane material. The invention provides a chemical formula of an alcohol amine chain extender, and also provides a preparation method of the alcohol amine chain extender, which comprises the following steps: 1) synthesizing cyclic carbonate compounds; 2) synthesizing alcohol amine chain extender; the application of the alcohol amine chain extender comprises the following steps: 1) preparing a polyurethane prepolymer; 2) and preparing the polyurethane material. The invention has the advantages of low cost, good water resistance, high elongation at break, high tensile strength, high thermal stability and the like.

Description

Alcohol amine chain extender, preparation method and application
Technical Field
The invention belongs to the technical field of preparation methods and applications of alcohol amine chain extenders, and particularly relates to an alcohol amine chain extender and a preparation method and application thereof.
Background
The polyurethane is a high molecular polymer containing urethane groups in a molecular structure, and is mainly prepared by reacting a binary/polyol compound with a binary/poly-isocyanate compound to generate a prepolymer and then crosslinking and curing the prepolymer by a chain extender. The polyurethane raw material has high adjustability, excellent performance and adjustability, has high elasticity of rubber, high strength of plastic and better solvent resistance, low temperature resistance and weather resistance, can be prepared into hard bubbles, soft bubbles, coatings, adhesives, elastomers, sealants and the like, and is widely applied to the industries of machinery, buildings, electrical appliances, transportation, sports equipment, medicine, furniture, clothes and the like. However, the conventional polyurethane has a molecular structure with easily hydrolysable chemical groups, such as ester bonds, urea bonds and the like, so that the water resistance is poor, and the application range is limited to a certain extent.
In order to improve the water resistance of polyurethane materials, researchers have taken various approaches to improve, for example, patent CN103709359A discloses a method for improving the water resistance of polyurethane, which improves the water resistance of polyurethane by adding polytetrafluoroethylene micropowder filler with high hydrophobicity into polyurethane materials, and improves the hydrolysis resistance of materials on the basis of retaining the mechanical properties of polyurethane materials. Patent CN104164176B discloses a method for preparing silver ear-shaped zinc oxide by an alkali etching method, wherein the obtained zinc oxide has uniform appearance and size, large specific surface and certain roughness, and is introduced into aqueous polyurethane emulsion for modification, so that the water resistance and antibacterial property of the aqueous polyurethane coating are effectively improved. According to the molecular designability in the chemical synthesis process, in the process of synthesizing the waterborne polyurethane, after the polyether polyol reacts with the toluene diisocyanate for a period of time and the dimethylolpropionic acid is added, the epoxy resin with excellent water resistance and chemical stability is added, so that the water resistance of the synthesized waterborne polyurethane is obviously improved.
The polyurethane foaming material is obtained by adding silane coupling agent gamma-aminopropyl triethoxysilane with different proportions into raw material polyether polyol by Shimei and the like (Shimei and the like, Wuhan university of science and technology, 36(2),2013 and 135-139), and the influence of the coupling agent on the water resistance of the material is researched, so that the water absorption of the rigid polyurethane foam added with the coupling agent is obviously reduced; the coupling agent can reduce the surface tension of the polyurethane foam material during foam nucleus forming and promote foaming, and when the addition amount of the coupling agent is 5%, the appearance of foam pores is good, and the surface hydrophobic capacity of the material is strong; and the coupling agent participates in chemical reaction inside the foam, so that the water resistance of the substrate is improved from the bonding angle.
From the raw materials for synthesizing polyurethane, Huda Pont et al, (03)1993,37) synthesizes a polyurethane sealing element with excellent performance by adopting poly epsilon-caprolactone diol as raw materials, and the obtained polyurethane has better sealing effect and higher mechanical property, and is particularly doubled in water resistance compared with polyether materials. Compared with the common polyurethane sealing element working in oil medium under the same working condition, the poly epsilon-caprolactone type polyurethane sealing element working in acid and alkaline water medium reaches and exceeds the common polyurethane sealing element working in oil medium in service life.
The method for improving the water resistance of the polyurethane material mainly comprises additive modification, namely adding water-resistant filler, blending with a water-resistant polymer, chemically modifying by grafting and introducing a substance with strong water resistance, or starting from polymer polyol for synthesizing the polyurethane material to improve the hydrophobicity and the crosslinking degree of the polyurethane material, and reducing the permeability of water to the polyurethane material, thereby improving the water resistance of the polyurethane. In contrast, the research on improving the water resistance of polyurethane materials by changing the chain extender with a small amount in polyurethane synthesis has not found through search.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides an alcohol amine chain extender, a preparation method and application thereof, and solves the technical problems of poor water resistance, solvent resistance, mechanical property and thermal property of the existing polyurethane material.
The invention is realized by the following technical scheme:
an alcohol amine chain extender, the structural formula of the alcohol amine chain extender is as follows:
Figure RE-GDA0002366615600000021
wherein
Figure RE-GDA0002366615600000022
Figure RE-GDA0002366615600000031
A preparation method of an alcohol amine chain extender comprises the following steps:
1) synthesis of cyclic carbonate compounds
Adding diglycidyl ether and a catalyst into a high-pressure reaction kettle, heating to 90-150 ℃, and continuously introducing CO2Reacting for 25-45 h under the pressure of 0.5-4 MPa, and filtering the catalyst to obtain a cyclic carbonate compound; wherein the adding amount of the catalyst is 1-20% of the weight of the diglycidyl ether;
2) synthesis of alcohol amine chain extender
Adding a cyclic carbonate compound into a reactor, adding a diamine compound into the reactor, heating to 30-120 ℃ under stirring, carrying out heat preservation reaction for 3-15 h, vacuumizing and distilling excess diamine compound for 3-20 h under reduced pressure at 40-150 ℃ and under the vacuum degree of-0.08-0.09 MPa after the reaction is finished, and obtaining an alcohol amine chain extender; wherein the molar ratio of the cyclic carbonate to the diamine compound is 1: 2-10;
further, the diglycidyl ether in the step 1) is one of ethylene glycol diglycidyl ether, butanediol diglycidyl ether, bisphenol a diglycidyl ether, hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, or polypropylene glycol diglycidyl ether.
Further, the catalyst in the step 1) is metal salt, quaternary ammonium salt, amino alcohol, macroporous alkaline anion exchange resin or ZnBr2And one or more of ionic liquid composite catalyst, magnesium-aluminum composite oxide and halide of Lewis acidic metallic zinc.
Further, the metal salt is lithium bromide, lithium chloride, potassium bromide, potassium iodide or sodium bromide.
Further, the quaternary ammonium salt is tetrabutylammonium bromide, tetrabutylammonium iodide or tetrabutylammonium chloride.
Further, the macroporous basic anion exchange resin is strongly basic styrene ion exchange resin or acrylic acid series ion exchange resin.
Further, the styrene ion exchange resin is D296, D201, 201 × 7 or D301; the acrylic ion exchange resin is D314, D311 or D318.
Further, the diamine compound in the step 2) includes one of hexamethylene diamine, p-phenylene diamine, propane diamine, butane diamine, ethylene diamine, pentane diamine, octane diamine, m-phenylene diamine, or cyclohexane diamine.
The application of the alcohol amine chain extender comprises the following steps:
1) preparing a polyurethane prepolymer: adding 20-500 parts by mass of polymer polyol into a reactor, heating to 80-140 ℃, continuously stirring, keeping the vacuum degree at-0.08-0.09 MPa, vacuumizing and dehydrating for 1.5-4 h, placing to reduce the temperature to 30-70 ℃, adding 2.5-905.6 parts by mass of diisocyanate compound, heating to 70-95 ℃, and reacting for 2-5 h to prepare a polyurethane prepolymer with 4-12% of free isocyanate groups-NCO by mass;
2) preparing a polyurethane material: weighing 10 parts by mass of polyurethane prepolymer, adding 5-25 parts by mass of solvent to dissolve the polyurethane prepolymer, dissolving 2-5 parts by mass of chain extender in 5-25 parts by mass of solvent, mixing the chain extender and the solvent, uniformly stirring to obtain a polyurethane solution, and removing the solvent to obtain the polyurethane material.
Further, the polymer polyol in the step 1) is one or more of polyether glycol, polyester glycol and biomass material polyol.
Further, the polyether glycol is one or more of polytetramethylene ether glycol, polypropylene oxide glycol, polyethylene oxide glycol and polybutadiene polyol.
Further, the polyester diol is one or more of poly adipate, poly epsilon-caprolactone diol and polycarbonate diol.
Further, the polyadipate is one or more of polyethylene glycol adipate, polybutylene glycol adipate, polyethylene glycol-propylene glycol adipate, polyethylene glycol-butylene glycol adipate, polyethylene glycol adipate and polyethylene glycol-neopentyl glycol adipate.
Further, the biomass material is castor oil or vegetable oil.
Further, the polymer polyol has a molecular weight in the range of 1000-2000.
Further, the diisocyanate compound in step 1) is an aromatic diisocyanate compound, an aliphatic diisocyanate compound, or a modified diisocyanate compound.
Further, the aromatic diisocyanate compound is toluene diisocyanate, 4' -diphenylmethane diisocyanate, p-phenylene diisocyanate or 1, 5-naphthalene diisocyanate.
Further, the aliphatic diisocyanate compound is 1, 6-hexamethylene diisocyanate, isophorone diisocyanate, or 4, 4' -dicyclohexylmethane diisocyanate.
Further, the modified diisocyanate compound is one or more of liquefied 4, 4' -diphenylmethane diisocyanate, CDMI50-80 series, urethane modified isocyanate, dimeric, trimeric, biuret modified isocyanate, carbodiimide modified isocyanate or blocked modified isocyanate.
Further, in the step 2), the solvent is one or more of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, acetonitrile or nitromethane.
The invention converts CO into2The cyclic carbonate compound generated by the cycloaddition reaction is subjected to aminolysis reaction to prepare an alcohol amine chain extender, the special structure of the chain extender leads that intramolecular hydrogen bonds can be formed between oxygen atoms of carbamate groups and hydroxyl hydrogen atoms on β carbon atoms in the finally generated polyurethane material, so that an intramolecular seven-membered ring structure is formed, the structure can generate tautomerism, and the tautomerism resonance structure generates charge redistribution to generate a stabilizing effect, so that the water resistance and solvent resistance of the polyurethane material are improved.
The resulting polyurethane materials were tested according to the following criteria.
Performance test standard:
(1) water and solvent resistance test
Soaking the prepared polyurethane material in deionized water and a corresponding solvent toluene at 25 ℃, standing and weighing the mass change condition of the sample, and calculating the swelling degree of the sample according to the following formula when the weight is constant:
Figure RE-GDA0002366615600000051
s represents the degree of swelling, m0Denotes the initial mass, m1Is the weight that reaches a constant weight after swelling.
(2) Mechanical Properties
Dumbbell-shaped specimens were prepared and tested as specified in the standard GB1039-92, tensile strength being in accordance with the GB/T528-1998 standard and elongation at break being in accordance with the GB528-82 standard, under conditions of room temperature 25 ℃ and humidity 55%.
(3) Heat resistance
Heat resistance was determined by Thermogravimetry (TGA): 5-7mg of the sample is measured by a thermogravimetric analyzer in nitrogen, the temperature rise speed is 10 ℃/min, and the temperature rise range is 30-600 ℃.
Compared with the prior art, the invention has the advantages that:
1. the raw materials are easy to obtain, the cost is lower, the production process is simple, the method belongs to addition polymerization reaction, and no waste is generated;
2. the water resistance of the polyurethane material is improved by starting with a raw material chain extender for synthesizing polyurethane, and the modification effect is good;
3. the polyurethane material prepared by the novel chain extender has obvious microphase separation, very high elongation at break and high tensile strength, and good thermal stability.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
1. Preparation of alcohol amine chain extender
2) Synthesis of cyclic carbonate compounds
Adding 150 parts by mass of butanediol diglycidyl ether and 20 parts by mass of styrene ion exchange resin D296 into a 500mL high-pressure reaction kettle, heating to 90 ℃, and continuously introducing CO2Reacting for 40h under the pressure of 3MPa, and filtering the catalyst to obtain a cyclic carbonate compound;
3) synthesis of alcohol amine chain extender
Adding 100 parts of cyclic carbonate compound into a reactor, adding 82.8 parts of ethylenediamine (the molar ratio of m (cyclic carbonate): m (diamine): 1:4) into the reactor, heating to 130 ℃ under stirring, then keeping the temperature for reaction for 4 hours, vacuumizing and distilling excess diamine compound for 5 hours under reduced pressure at 90 ℃ and the vacuum degree of-0.08 MPa after the reaction is finished, and removing residual ethylenediamine to obtain an alcohol amine chain extender;
2. preparation of polyurethane prepolymer
Adding 100 parts by mass of polytetramethylene ether glycol into a reactor, heating to 80 ℃, continuously stirring, keeping the vacuum degree at-0.08 MPa, vacuumizing and dehydrating for 4h, standing to reduce the temperature to 30 ℃, adding 46.9 parts of 4, 4' -diphenylmethane diisocyanate, and heating to 95 ℃ for reaction for 2h to obtain a polyurethane prepolymer with 5.0% of free isocyanate groups-NCO by mass;
3. preparing a polyurethane material: weighing 10 parts by mass of PTMG-MDI type polyurethane prepolymer containing 5.0 wt% -NCO, adding 10 parts of N-methyl pyrrolidone to dissolve the PTMG-MDI type polyurethane prepolymer, dissolving 2.2 parts of chain extender (the chain extension coefficient is 0.9) in 10 parts of N-methyl pyrrolidone, mixing and uniformly stirring the PTMG-MDI type polyurethane prepolymer and the N-methyl pyrrolidone, pouring the mixture into a polytetrafluoroethylene die, and baking under an infrared lamp to remove the solvent to prepare the polyurethane elastic film.
Example 2
1. Preparation of alcohol amine chain extender
1) Synthesis of cyclic carbonate compounds
Adding 150 parts by mass of ethylene glycol diglycidyl ether and 1.5 parts by mass of tetrabutylammonium bromide into a 500mL high-pressure reaction kettle, heating to 150 ℃, and continuously introducing CO2Reacting for 40h under the pressure of 0.7MPa, and filtering the catalyst to obtain a cyclic carbonate compound;
2) synthesis of alcohol amine chain extender
Adding 100 parts of cyclic carbonate compound into a reactor, adding 45.8 parts of ethylenediamine (the molar ratio of m (cyclic carbonate): m (diamine): 1:2) into the reactor, heating to 70 ℃ under stirring, then carrying out heat preservation reaction for 10 hours, vacuumizing and decompressing to distill excessive diamine compound for 20 hours under the conditions of 100 ℃ and the vacuum degree of-0.085 MPa after the reaction is finished, and removing residual ethylenediamine to obtain an alcohol amine chain extender;
2. preparation of polyurethane prepolymer
Adding 100 parts by mass of polycarbonate diol (PCDL-1000) into a reactor, heating to 100 ℃, continuously stirring, keeping the vacuum degree at-0.09 MPa, vacuumizing to dehydrate for 3.5h, standing to reduce the temperature to 70 ℃, adding 46.9 parts of 4, 4' -diphenylmethane diisocyanate, heating to 70 ℃, reacting for 5h, and obtaining a polyurethane prepolymer with 5.0% of free isocyanate groups-NCO by mass;
3. preparing a polyurethane material: weighing 10 parts by mass of PTMG-MDI type polyurethane prepolymer containing 5.0 wt% -NCO, adding 8 parts of N, N-dimethylformamide to dissolve the prepolymer, dissolving 2.1 parts of chain extender (the chain extension coefficient is 0.9) in 10 parts of N, N-dimethylformamide, mixing and stirring the two uniformly, pouring the mixture into a polytetrafluoroethylene die, and baking under an infrared lamp to remove the solvent to prepare the polyurethane elastic membrane.
Example 3
1. Preparation of alcohol amine chain extender
1) Synthesis of cyclic carbonate compounds
Adding 150 parts by mass of diethylene glycol diglycidyl ether, 3.5 parts by mass of potassium bromide and 1 part of tetrabutylammonium bromide composite catalyst into a 500mL high-pressure reaction kettle, heating to 130 ℃, and continuously introducing CO2Reacting for 20h under the pressure of 2MPa, and filtering the catalyst to obtain a cyclic carbonate compound;
2) synthesis of alcohol amine chain extender
Adding 100 parts of cyclic carbonate compound into a reactor, adding 303.2 parts of hexamethylenediamine (the molar ratio is m (cyclic carbonate): m (diamine): 1:8) into the reactor, heating to 30 ℃ under stirring, then keeping the temperature for reaction for 15 hours, vacuumizing and distilling excess diamine compound for 3 hours under reduced pressure at the temperature of 150 ℃ and the vacuum degree of-0.09 MPa after the reaction is finished, and removing residual hexamethylenediamine to obtain an alcohol amine chain extender;
2. preparation of polyurethane prepolymer
Adding 100 parts by weight of poly adipic acid-1, 4-butanediol ester diol (PBA-2000) into a reactor, heating to 140 ℃, continuously stirring, keeping the vacuum degree at-0.085 MPa, vacuumizing and dehydrating for 1.5h, placing to reduce the temperature to 70 ℃, adding 30.3 parts of toluene diisocyanate, heating to 95 ℃, and reacting for 2.5h to prepare a polyurethane prepolymer with 8.0% by weight of free isocyanate groups-NCO;
3. preparing a polyurethane material: weighing 10 parts by mass of PBA-TDI type polyurethane prepolymer containing 8.0 wt% -NCO, adding 12 parts of N, N-dimethylacetamide to dissolve the prepolymer, dissolving 4.9 parts of chain extender (the chain extension coefficient is 0.95) in 10 parts of N, N-dimethylacetamide, mixing and stirring the two uniformly, pouring the mixture into a polytetrafluoroethylene die, and baking under an infrared lamp to remove the solvent to prepare the polyurethane elastic film.
Example 4
1. Preparation of alcohol amine chain extender
1) Synthesis of cyclic carbonate compounds
Adding 150 parts by mass of hexanediol diglycidyl ether and 7.5 parts by mass of magnesium-aluminum composite oxide into a 500mL high-pressure reaction kettle, heating to 100 ℃, and continuously introducing CO2Reacting for 25h under the pressure of 4MPa, and filtering the catalyst to obtain a cyclic carbonate compound;
2) synthesis of alcohol amine chain extender
Adding 100 parts of cyclic carbonate compound into a reactor, adding 339.5 parts of p-phenylenediamine (the molar ratio of m (cyclic carbonate): m (diamine): 1:10) into the reactor, heating to 30 ℃ under stirring, then keeping the temperature for reaction for 6h, vacuumizing and decompressing to distill excessive diamine compound for 20h under the conditions of 60 ℃ and vacuum degree of-0.08 MPa after the reaction is finished, and removing residual p-phenylenediamine to obtain an alcohol amine chain extender;
2. preparation of polyurethane prepolymer
Adding 50 parts by mass of polyoxypropylene glycol (PPG-1000) and 50 parts by mass of polytetramethylene ether glycol into a reactor, heating to 130 ℃, continuously stirring, keeping the vacuum degree at-0.09 MPa, vacuumizing and dehydrating for 4h, standing to reduce the temperature to 70 ℃, adding 52.4 parts of isophorone diisocyanate compound, heating to 95 ℃ and reacting for 2h to obtain a polyurethane prepolymer with 7.5% by mass of free isocyanate groups-NCO;
3. preparing a polyurethane material: weighing 10 parts by mass of PPG-PTMG-IPDI type polyurethane prepolymer containing 7.5 wt% -NCO, adding 5 parts of dimethyl sulfoxide to dissolve the prepolymer, dissolving 2.1 parts of chain extender (chain extension coefficient is 0.9) in 12 parts of dimethyl sulfoxide, mixing and stirring the two uniformly, pouring the mixture into a polytetrafluoroethylene die, and baking under an infrared lamp to remove the solvent to prepare the polyurethane elastic membrane.
Example 5
1. Preparation of alcohol amine chain extender
1) Synthesis of cyclic carbonate compounds
Adding 150 parts by mass of neopentyl glycol diglycidyl ether and 10 parts by mass of D201 into a 500mL high-pressure reaction kettle, heating to 110 ℃, and continuously introducing CO2Reacting for 40h under the pressure of 0.9MPa, and filtering the catalyst to obtain a cyclic carbonate compound;
2) synthesis of alcohol amine chain extender
Adding 100 parts of cyclic carbonate compound into a reactor, adding 77.1 parts of propane diamine (the molar ratio of m (cyclic carbonate): m (diamine): 1:3.5) into the reactor, heating to 110 ℃ under stirring, then carrying out heat preservation reaction for 4h, vacuumizing and decompressing to distill excessive diamine compound for 15h under the conditions of 60 ℃ and vacuum degree of-0.09 MPa after the reaction is finished, and removing residual propane diamine to obtain an alcohol amine chain extender;
2. preparation of polyurethane prepolymer
Adding 100 parts by mass of poly-epsilon-caprolactone diol into a reactor, heating to 100 ℃, continuously stirring, keeping the vacuum degree at-0.085 MPa, vacuumizing and dehydrating for 2h, standing to reduce the temperature to 65 ℃, adding 32.7 parts of 1, 6-hexamethylene diisocyanate compound, heating to 80 ℃ and reacting for 3.5h to obtain a polyurethane prepolymer with 6.0% of free isocyanate groups-NCO;
3. preparing a polyurethane material: weighing 10 parts by mass of PCL-HDI type polyurethane prepolymer containing 6.0 wt% -NCO, adding 5 parts of acetonitrile to dissolve the prepolymer, dissolving 3.5 parts of chain extender (chain extension coefficient is 1.0) in 25 parts of acetonitrile, mixing and stirring the two uniformly, pouring the mixture into a polytetrafluoroethylene die, and baking under an infrared lamp to remove the solvent to prepare the polyurethane elastic film.
Example 6
1. Preparation of alcohol amine chain extender
1) Synthesis of cyclic carbonate compounds
Adding 150 parts by mass of butanediol diglycidyl ether and 4.5 parts by mass of lithium bromide into a 500mL high-pressure reaction kettle, heating to 120 ℃, and continuously introducing CO2Reacting for 25h under the pressure of 2.5MPa, and filtering the catalyst to obtain a cyclic carbonate compound;
2) synthesis of alcohol amine chain extender
Adding 100 parts of cyclic carbonate compound into a reactor, adding 127.6 parts of propylene diamine (the molar ratio of m (cyclic carbonate): m (diamine): 1:5) into the reactor, heating to 80 ℃ under stirring, then keeping the temperature for reaction for 4 hours, vacuumizing and distilling excess diamine compound for 120 hours under the conditions of 80 ℃ and vacuum degree of-0.085 MPa after the reaction is finished, and removing residual propylene diamine to obtain an alcohol amine chain extender;
2. preparation of polyurethane prepolymer
Adding 100 parts by mass of poly (1, 6-hexanediol adipate) (PHA-1000) into a reactor, heating to 90 ℃, continuously stirring, keeping the vacuum degree at-0.09 MPa, vacuumizing and dehydrating for 3.5h, standing to reduce the temperature to 60 ℃, adding 33.8 parts of p-phenylene diisocyanate, heating to 90 ℃ and reacting for 2h to obtain a polyurethane prepolymer with 7.0% by mass of free isocyanate groups-NCO;
3. preparing a polyurethane material: weighing 10 parts by mass of PHA-PPDI type polyurethane prepolymer containing 7.0 wt% -NCO, adding 10 parts by mass of nitromethane for dissolving, dissolving 3.8 parts by mass of chain extender (chain extension coefficient is 1.05) in 8 parts by mass of nitromethane, mixing and stirring the two uniformly, pouring the mixture into a polytetrafluoroethylene die, and baking under an infrared lamp to remove the solvent to prepare the polyurethane elastic film.
Example 7
1. Preparation of alcohol amine chain extender
1) Synthesis of cyclic carbonate compounds
Adding 150 parts by mass of hexanediol diglycidyl ether and 30 parts by mass of acrylic acid basic anion exchange resin D314 into a 500mL high-pressure reaction kettle, heating to 100 ℃, and continuously introducing CO2Reacting for 25h under the pressure of 4MPa, and filtering the catalyst to obtain a cyclic carbonate compound;
2) synthesis of alcohol amine chain extender
Adding 100 parts of cyclic carbonate compound into a reactor, adding 339.5 parts of p-phenylenediamine (the molar ratio is m (cyclic carbonate): m (diamine): 1:10) into the reactor, heating to 30 ℃ under stirring, then keeping the temperature for reaction for 6h, vacuumizing and decompressing to distill excessive diamine compound for 20h under the conditions of 60 ℃ and vacuum degree of-0.085 MPa after the reaction is finished, and removing residual p-phenylenediamine to obtain an alcohol amine chain extender;
2. preparation of polyurethane prepolymer
Adding 80 parts by mass of polypropylene oxide glycol (PPG-1000) and 20 parts by mass of poly epsilon-caprolactone glycol into a reactor, heating to 130 ℃, continuously stirring, keeping the vacuum degree at-0.09 MPa, vacuumizing and dehydrating for 4h, standing to reduce the temperature to 70 ℃, adding 42.4 parts by mass of isophorone diisocyanate, heating to 95 ℃ and reacting for 2h to obtain a polyurethane prepolymer with 9.0% by mass of free isocyanate groups-NCO;
3. preparing a polyurethane material: weighing 10 parts by mass of PPG-PCL-HDI polyurethane prepolymer containing 9.0 wt% -NCO, adding 10 parts of dimethyl sulfoxide to dissolve the prepolymer, dissolving 4.7 parts of chain extender (chain extension coefficient is 0.9) in 12 parts of dimethyl sulfoxide, mixing and stirring the two uniformly, pouring the mixture into a polytetrafluoroethylene die, and baking under an infrared lamp to remove the solvent to prepare the polyurethane elastic film.
Example 8
1. Preparation of alcohol amine chain extender
1) Synthesis of cyclic carbonate compounds
Adding 150 parts by mass of neopentyl glycol diglycidyl ether and 10 parts by mass of tetrabutylammonium chloride into a 500mL high-pressure reaction kettle, heating to 110 ℃, and continuously introducing CO2Reacting for 40h under the pressure of 0.9MPa, and filtering the catalyst to obtain a cyclic carbonate compound;
2) synthesis of alcohol amine chain extender
Adding 100 parts of cyclic carbonate compound into a reactor, adding 77.1 parts of propane diamine (the molar ratio of m (cyclic carbonate): m (diamine): 1:3.5) into the reactor, heating to 110 ℃ under stirring, then carrying out heat preservation reaction for 4h, vacuumizing and decompressing to distill excessive diamine compound for 15h under the conditions of 60 ℃ and vacuum degree of-0.09 MPa after the reaction is finished, and removing residual propane diamine to obtain an alcohol amine chain extender;
2. preparation of polyurethane prepolymer
Adding 60 parts by mass of polycarbonate diol (PCDL-2000) and 40 parts by mass of polybutylene adipate (PCL-1000) into a reactor, heating to 130 ℃, continuously stirring, keeping the vacuum degree at-0.09 MPa, vacuumizing and dehydrating for 4 hours, placing to reduce the temperature to 70 ℃, adding 37.3 parts of isophorone diisocyanate compound, heating to 95 ℃, and reacting for 2 hours to obtain a polyurethane prepolymer with 6.0 mass parts of free isocyanate groups-NCO;
3. preparing a polyurethane material: weighing 10 parts by mass of PCDL-PCL-IPDI type polyurethane prepolymer containing 6.0 wt% -NCO, adding 10 parts of N, N-dimethylformamide to dissolve the prepolymer, dissolving 3.6 parts of chain extender (chain extension coefficient is 0.9) in 12 parts of N, N-dimethylformamide, mixing and stirring the two uniformly, pouring the mixture into a polytetrafluoroethylene die, and baking under an infrared lamp to remove the solvent to prepare the polyurethane elastic film.
The relevant properties of the polyurethane elastic film prepared by the above process are listed in the following table.
Figure RE-GDA0002366615600000111
As the present invention may be embodied in several forms without departing from the spirit or essential characteristics thereof, it should also be understood that the above-described embodiments are not limited by any of the details of the foregoing description, but rather should be construed broadly within its scope as defined in the appended claims, and therefore all changes and modifications that fall within the meets and bounds of the claims, or equivalences of such meets and bounds are therefore intended to be embraced by the appended claims.

Claims (21)

1. An alcohol amine chain extender, which is characterized in that: the alcohol amine chain extender has the following structural formula:
Figure FDA0002251622900000011
wherein
Figure FDA0002251622900000012
Figure FDA0002251622900000013
Figure FDA0002251622900000014
2. The method for preparing an alkanolamine chain extender as claimed in claim 1, wherein: the method comprises the following steps:
1) synthesis of cyclic carbonate compounds
Adding diglycidyl ether and a catalyst into a high-pressure reaction kettle, heating to 90-150 ℃, and continuously introducing CO2Reacting for 25-45 h under the pressure of 0.5-4 MPa, and filtering the catalyst to obtain a cyclic carbonate compound; wherein, the adding amount of the catalyst is 1 to 20 percent of the weight of the diglycidyl ether;
2) synthesis of alcohol amine chain extender
Adding a cyclic carbonate compound into a reactor, adding a diamine compound into the reactor, heating to 30-120 ℃ under stirring, carrying out heat preservation reaction for 3-15 h, vacuumizing and distilling excess diamine compound for 3-20 h under reduced pressure at 40-150 ℃ and under the vacuum degree of-0.08-0.09 MPa after the reaction is finished, and obtaining an alcohol amine chain extender; wherein the molar ratio of the cyclic carbonate to the diamine compound is 1: 2-10;
3. the method for preparing an alkanolamine chain extender as claimed in claim 2, wherein: the diglycidyl ether in the step 1) is one of ethylene glycol diglycidyl ether, butanediol diglycidyl ether, bisphenol a diglycidyl ether, hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, or polypropylene glycol diglycidyl ether.
4. The method for preparing an alkanolamine chain extender as claimed in claim 2, wherein: the catalyst in the step 1) is metal salt, quaternary ammonium salt, amino alcohol, macroporous alkaline anion exchange resin and ZnBr2And one or more of ionic liquid composite catalyst, magnesium-aluminum composite oxide and halide of Lewis acidic metallic zinc.
5. The method for preparing an alkanolamine chain extender as claimed in claim 4, wherein: the metal salt is lithium bromide, lithium chloride, potassium bromide, potassium iodide or sodium bromide.
6. The method for preparing an alkanolamine chain extender as claimed in claim 4, wherein: the quaternary ammonium salt is tetrabutylammonium bromide, tetrabutylammonium iodide or tetrabutylammonium chloride.
7. The method for preparing an alkanolamine chain extender as claimed in claim 4, wherein: the macroporous basic anion exchange resin is strong-base styrene ion exchange resin or acrylic acid series ion exchange resin.
8. The method for preparing an alkanolamine chain extender as claimed in claim 4, wherein: the styrene ion exchange resin is D296, D201, 201 multiplied by 7 or D301; the acrylic ion exchange resin is D314, D311 or D318.
9. The method for preparing an alkanolamine chain extender as claimed in claim 2, wherein: the diamine compound in the step 2) comprises one of hexamethylene diamine, p-phenylene diamine, propane diamine, butane diamine, ethylene diamine, pentamethylene diamine, octamethylene diamine, m-phenylene diamine or cyclohexane diamine.
10. Use of an alkanolamine chain extender according to claims 1-9, characterized in that: the method comprises the following steps:
1) preparing a polyurethane prepolymer: adding 20-500 parts by mass of polymer polyol into a reactor, heating to 80-140 ℃, continuously stirring, keeping the vacuum degree at-0.08-0.09 MPa, vacuumizing and dehydrating for 1.5-4 h, placing to reduce the temperature to 30-70 ℃, adding 2.5-905.6 parts by mass of diisocyanate compound, heating to 70-95 ℃, and reacting for 2-5 h to prepare a polyurethane prepolymer with 4-12% of free isocyanate groups-NCO by mass;
2) preparing a polyurethane material: weighing 10 parts by mass of polyurethane prepolymer, adding 5-25 parts by mass of solvent to dissolve the polyurethane prepolymer, dissolving 2-5 parts by mass of chain extender in 5-25 parts by mass of solvent, mixing the chain extender and the solvent, uniformly stirring to obtain a polyurethane solution, and removing the solvent to obtain the polyurethane material.
11. Use of an alkanolamine chain extender as claimed in claim 10, characterized in that: the polymer polyol in the step 1) is one or more of polyether glycol, polyester glycol and biomass material polyol.
12. Use of an alkanolamine chain extender as claimed in claim 11, characterized in that: the polyether glycol is one or more of polytetramethylene ether glycol, polypropylene oxide glycol, polyethylene oxide glycol and polybutadiene polyalcohol.
13. Use of an alkanolamine chain extender as claimed in claim 11, characterized in that: the polyester diol is one or more of poly adipate, poly epsilon-caprolactone diol and polycarbonate diol.
14. Use of an alkanolamine chain extender as claimed in claim 13, characterized in that: the polyadipate is one or more of polyethylene glycol adipate, polybutylene glycol adipate, polyethylene glycol-propylene glycol adipate, polyethylene glycol-butylene glycol adipate, polyethylene glycol adipate and polyethylene glycol-neopentyl glycol adipate.
15. Use of an alkanolamine chain extender as claimed in claim 11, characterized in that: the biomass material is castor oil or vegetable oil.
16. Use of an alkanolamine chain extender as claimed in claim 10, characterized in that: the polymer polyol has a molecular weight in the range of 1000-2000.
17. Use of an alkanolamine chain extender as claimed in claim 10, characterized in that: the diisocyanate compound in step 1) is an aromatic diisocyanate compound, an aliphatic diisocyanate compound or a modified diisocyanate compound.
18. Use of an alkanolamine chain extender as claimed in claim 17, characterized in that: the aromatic diisocyanate compound is toluene diisocyanate, 4' -diphenylmethane diisocyanate, p-phenylene diisocyanate or 1, 5-naphthalene diisocyanate.
19. Use of an alkanolamine chain extender as claimed in claim 17, characterized in that: the aliphatic diisocyanate compound is 1, 6-hexamethylene diisocyanate, isophorone diisocyanate or 4, 4' -dicyclohexylmethane diisocyanate.
20. Use of an alkanolamine chain extender as claimed in claim 17, characterized in that: the modified diisocyanate compound is one or more of liquefied 4, 4' -diphenylmethane diisocyanate, CDMI50-80 series, carbamate modified isocyanate, dimeric, trimeric and biuret modified isocyanate, carbodiimide modified isocyanate or blocked modified isocyanate.
21. Use of an alkanolamine chain extender as claimed in claim 10, characterized in that: in the step 2), the solvent is one or more of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, acetonitrile or nitromethane.
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