CN115677976A - Preparation method of polyurethane modified epoxy resin and polyurethane modified epoxy resin - Google Patents
Preparation method of polyurethane modified epoxy resin and polyurethane modified epoxy resin Download PDFInfo
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- CN115677976A CN115677976A CN202211351400.8A CN202211351400A CN115677976A CN 115677976 A CN115677976 A CN 115677976A CN 202211351400 A CN202211351400 A CN 202211351400A CN 115677976 A CN115677976 A CN 115677976A
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 82
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 82
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 70
- 239000004814 polyurethane Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 35
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 33
- -1 ester polyol Chemical class 0.000 claims abstract description 33
- 229920000570 polyether Polymers 0.000 claims abstract description 33
- 229920005862 polyol Polymers 0.000 claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- 239000004593 Epoxy Substances 0.000 claims abstract description 27
- 239000012948 isocyanate Substances 0.000 claims abstract description 23
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 23
- 150000003384 small molecules Chemical class 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 19
- 150000002009 diols Chemical class 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 16
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 claims description 15
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 15
- GJOWSEBTWQNKPC-UHFFFAOYSA-N 3-methyloxiran-2-ol Chemical compound CC1OC1O GJOWSEBTWQNKPC-UHFFFAOYSA-N 0.000 claims description 13
- 229920001610 polycaprolactone Polymers 0.000 claims description 12
- 229920001451 polypropylene glycol Polymers 0.000 claims description 12
- 239000004305 biphenyl Substances 0.000 claims description 11
- 208000005156 Dehydration Diseases 0.000 claims description 10
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 10
- 230000018044 dehydration Effects 0.000 claims description 10
- 238000006297 dehydration reaction Methods 0.000 claims description 10
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 9
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000004632 polycaprolactone Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000005442 diisocyanate group Chemical group 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a preparation method of polyurethane modified epoxy resin, which comprises the steps of adding dehydrated polyether/ester polyol into isocyanate, and reacting to obtain an isocyanate-terminated polyurethane prepolymer; reacting isocyanate-terminated polyurethane prepolymer, epoxy compound and anhydrous dichloromethane to obtain polyurethane modified epoxy resin; the epoxy compound is a small molecule epoxy compound. The invention also discloses the polyurethane modified epoxy resin obtained by the preparation method. The invention realizes the precise synthesis of the polyurethane modified epoxy resin.
Description
Technical Field
The invention relates to a preparation method of polyurethane modified epoxy resin and the polyurethane modified epoxy resin, belonging to the technical field of polymer synthesis.
Background
The unmodified cured epoxy resin has poor molecular toughness, so that the use of the material is limited. The polyurethane modified epoxy resin generally introduces a flexible polyurethane chain segment into an epoxy resin chain or introduces other flexible chain segments by taking polyurethane as a transition structure, so that the overall flexibility of the molecular chain is increased, and the toughness of the material is further improved.
With respect to the preparation method of the urethane-modified epoxy resin, there are some disadvantages and needs to be improved in the controllability of the product structure and the method, such as: (1) Generally, the obtained polyurethane modified epoxy resin has a complex structure, and has byproducts of other chemical structures, so that the resin performance is influenced; (2) The preparation method has low controllable adjustment degree on different chain segments of the modified epoxy resin, and is difficult to realize precise design and synthesis.
Disclosure of Invention
The invention aims to overcome the defects and provides a preparation method of polyurethane modified epoxy resin and the polyurethane modified epoxy resin, which solve the technical problems that the existing polyurethane modified epoxy resin has high content of by-products and is difficult to realize accurate structure regulation and control, and realize accurate synthesis of the polyurethane modified epoxy resin.
In order to achieve the above purpose, the invention provides the following technical scheme:
a preparation method of polyurethane modified epoxy resin comprises the following steps:
adding dehydrated polyether/ester polyol into isocyanate, and reacting to obtain an isocyanate-terminated polyurethane prepolymer;
reacting isocyanate-terminated polyurethane prepolymer, epoxy compound and anhydrous dichloromethane to obtain polyurethane modified epoxy resin; the epoxy compound is a small molecule epoxy compound.
Further, the isocyanate is more than one of 4,4' -diphenyl diisocyanate MDI, hexamethylene diisocyanate HDI or toluene diisocyanate TDI;
the polyether/ester polyol is more than one of polypropylene glycol PPG, polytetrahydrofuran glycol PTMG or polycaprolactone diol PCL.
Further, the epoxy compound is epoxypropanol.
Further, the molar ratio of isocyanate to polyether/ester polyol is 2 to 2.5;
the mol ratio of the isocyanate-terminated polyurethane prepolymer to the epoxy compound is 1.5-2.
Further, the molecular weight of the polyether/ester polyol after dehydration treatment is 250-2000.
Further, the method for dehydrating the polyether/ester polyol comprises the following steps:
keeping the temperature of 105-115 ℃ for 2-3 h under the vacuum condition.
Further, the method for adding dehydrated polyether/ester polyol into isocyanate to obtain the isocyanate-terminated polyurethane prepolymer after reaction comprises the following steps:
setting the total mass of polyether/ester polyol added into isocyanate as W;
adding 45-W-55% of polyether/ester polyol into isocyanate, heating the obtained mixture to 75-85 ℃, reacting for 0.5-1.5 h, cooling to 40-60 ℃, adding the rest polyether/ester polyol into the isocyanate, heating the obtained mixture to 75-85 ℃, and reacting for 1.5-3.5 h to obtain the isocyanate-terminated polyurethane prepolymer.
Further, the reaction conditions of the isocyanate-terminated polyurethane prepolymer, the epoxy compound and the anhydrous dichloromethane to obtain the polyurethane modified epoxy resin are that the reaction is carried out for 4 to 6 hours at the temperature of between 40 and 60 ℃ in the atmosphere of inert gas.
Further, the molecular weight of the polyether/ester polyol increases, and the flexibility of the resulting polyurethane-modified epoxy resin increases.
A polyurethane modified epoxy resin is obtained by adopting the preparation method.
Compared with the prior art, the invention has at least one of the following beneficial effects:
(1) The invention creatively provides a preparation method of polyurethane modified epoxy resin, which takes a small molecular epoxy compound as a raw material to react with a polyurethane prepolymer, thereby realizing the precise synthesis of the polyurethane modified epoxy resin;
(2) The polyurethane soft segment in the molecular structure of the polyurethane modified epoxy resin can effectively increase the flexibility of the whole molecule;
(3) In the preparation process, the polyurethane modified epoxy resin with an accurate structure can be obtained by changing the molecular weights of different polyether/ester polyols, and the structural performance relationship of the polyurethane modified epoxy resin is favorably determined.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of a polyurethane modified epoxy resin obtained in example 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance spectrum of a polyurethane modified epoxy resin obtained in example 2 of the present invention;
FIG. 3 is a nuclear magnetic resonance spectrum of a polyurethane modified epoxy resin obtained in example 3 of the present invention;
FIG. 4 is a nuclear magnetic resonance spectrum of the urethane-modified epoxy resin obtained in comparative example 1.
Detailed Description
The features and advantages of the present invention will become more apparent and apparent from the following detailed description of the invention.
The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments. While the various aspects of the embodiments are presented in drawings, the drawings are not necessarily drawn to scale unless specifically indicated.
Common polyurethane modified epoxy resin generally utilizes hydroxyl on epoxy resin to react with isocyanate groups on a prepolymer, most of synthetic raw materials are polymers containing hydroxyl, such as bisphenol A type epoxy resin, and the polymers contain a plurality of hydroxyl groups and can react with the prepolymers terminated by a plurality of isocyanate groups, so that the structure of the final polyurethane modified epoxy resin is difficult to regulate and control in the reaction process. The invention provides a preparation method of polyurethane modified epoxy resin with controllable structure, which takes a micromolecule epoxy compound as a raw material, and the structure of the micromolecule epoxy compound contains active hydroxyl and epoxy groups, so that on one hand, the reactivity with isocyanate groups is ensured, on the other hand, the micromolecule epoxy compound is taken as the raw material to react with polyurethane prepolymer to generate the polyurethane modified epoxy resin with accurate structure, the accurate synthesis of the polyurethane modified epoxy resin is realized, the epoxy resin is toughened by a chemical modification method, and the application range of the epoxy resin is expanded.
In a preferred embodiment, the invention relates to a method for preparing a polyurethane modified epoxy resin, which comprises the following specific steps:
and adding the dehydrated polyether/ester polyol into isocyanate twice to react to generate an isocyanate-terminated polyurethane prepolymer, and reacting the isocyanate-terminated polyurethane prepolymer with a small molecular epoxy compound and anhydrous dichloromethane to obtain the polyurethane modified epoxy resin with an accurate structure.
In the above preparation method, the isocyanate is one of 4,4' -diphenyl diisocyanate (MDI), hexamethylene Diisocyanate (HDI) and Toluene Diisocyanate (TDI).
In the above preparation method, the polyether/ester polyol is one of polypropylene glycol (PPG), polytetrahydrofuran glycol (PTMG), and polycaprolactone diol (PCL).
In the above production method, the isocyanate: the molar ratio of polyether/ester polyol is 2-2.5, and isocyanate is slightly excessive, so that the method is favorable for synthesizing a prepolymer with an end-capping structure as a raw material of subsequent polyurethane modified epoxy resin.
In the above preparation method, the molecular weight of the dehydrated polyether/ester polyol is 250 to 2000.
In the preparation method, the polyether/ester polyol dehydration method is to keep the reaction temperature of the polyether/ester polyol for 2 to 3 hours at 105 to 115 ℃ under the condition of vacuum pumping, so that the dehydration is facilitated, the side reaction of isocyanate and water is reduced, and the purity of the prepolymer is improved.
In the preparation method, the polyether/ester polyol is added into the isocyanate twice, namely about 50 percent of polyether/ester polyol is added firstly, the temperature is raised to 75-85 ℃ for reaction for 0.5-1.5 h, then the temperature is lowered to 40-60 ℃, the rest polyether/ester polyol is added, the temperature is raised to 75-85 ℃ for reaction for 1.5-3.5 h, the polyether/ester polyol is added in times, so that the excessive isocyanate in the reaction process is kept, the prepolymer with a capped end structure is obtained, the purity of the prepolymer of the system is improved, the temperature control is favorable for controlling the reaction rate, and the process implosion is prevented.
In the preparation method, the small molecular epoxy compound is epoxy propanol, one end of the molecular structure is hydroxyl, the other end of the molecular structure is epoxy group, and the active hydrogen on the hydroxyl and isocyanate are subjected to polyaddition reaction, so that the epoxy propanol is connected at two ends of the isocyanate-terminated polyurethane prepolymer to obtain the epoxy group-terminated polymer.
In the preparation method, the isocyanate-terminated polyurethane prepolymer: the mol ratio of the small molecular epoxy compound is 1.5-2, which is beneficial to completely generate the modified resin with the end sealed by the epoxy group.
In the preparation method, the isocyanate-terminated polyurethane prepolymer and the micromolecular epoxy compound react for 4-6 h at 40-60 ℃ in nitrogen atmosphere, so that the reaction rate is controlled, and the process implosion is prevented.
The invention provides a novel polyurethane modified epoxy resin, wherein a micromolecular epoxy compound is adopted as a raw material in a synthetic route to react with an isocyanate-terminated polyurethane prepolymer, so that the polyurethane modified epoxy resin with an accurate structure can be obtained, and the polyurethane modified epoxy resin with an accurate structure can be obtained by changing the molecular weights of different polyether/ester polyols, so that the structural performance relation of the polyurethane modified epoxy resin can be favorably determined.
The second step in the synthesis of polyurethane modified epoxy resin is the reaction of the prepolymer with terminal isocyanate group and epoxy compound, the reaction principle is the polyaddition reaction of isocyanate group and active hydrogen on hydroxyl group, taking bisphenol a type epoxy resin as an example, the material is a small molecular polymer, and the structure contains a plurality of hydroxyl groups, so the reaction site of the prepolymer and the bisphenol a type epoxy resin is difficult to control in the reaction process, there are the following possibilities that (1) both ends of the prepolymer are connected with different compounds, and the epoxy compound is connected with only one prepolymer; (2) connecting two ends of the prepolymer on the same compound to form a ring; and (3) connecting a plurality of prepolymers to the bisphenol A epoxy resin. In the above case, only (1) is an ideal synthetic route, and in the rest cases, it is a byproduct. In the invention, the epoxypropanol is preferably selected to react with the isocyanate-terminated polyurethane prepolymer, so that the polyurethane modified epoxy resin with an accurate structure can be obtained, and no by-product exists.
Example 1
A preparation method of polyurethane modified epoxy resin comprises the following specific steps:
adding 60.5g of polytetrahydrofuran diol (PTMG 250) subjected to dehydration treatment (keeping the temperature at 105 ℃ for 2h under vacuum condition) into 500g of 4,4 '-diphenyl diisocyanate (MDI), heating to 75 ℃ for reaction for 1h, cooling to 60 ℃, adding the rest 60.0g of polytetrahydrofuran diol (PTMG 250) subjected to dehydration treatment (keeping the temperature at 105 ℃ for 2h under vacuum condition), heating to 75 ℃ for reaction for 1.5h, and generating an isocyanate-terminated polyurethane prepolymer, wherein the 4,4' -diphenyl diisocyanate (MDI): total molar ratio of polytetrahydrofuran diol (PTMG 250) was 2.
The mol ratio of the isocyanate-terminated polyurethane prepolymer to the epoxypropanol is 1:2, mixing the components in an anhydrous dichloromethane solvent, reacting for 4 hours at 40 ℃ in a nitrogen atmosphere to obtain the polyurethane modified epoxy resin with an accurate structure, wherein the nuclear magnetic resonance spectrogram of the product is shown in figure 1, the positions of structural peaks in the spectrogram correspond to chemical structures one by one, and the intensities are consistent, which indicates that the synthesized polyurethane modified epoxy resin has a definite structure.
Example 2
A preparation method of polyurethane modified epoxy resin comprises the following specific steps:
adding 129.1g of polytetrahydrofuran diol (PTMG 650) subjected to dehydration treatment (keeping the temperature at 115 ℃ for 2h under vacuum condition) into 500g of 4,4 '-diphenyl diisocyanate (MDI), heating to 75 ℃ for reaction for 0.5h, cooling to 40 ℃, adding the rest 129.0g of polytetrahydrofuran diol (PTMG 650) subjected to dehydration treatment (keeping the temperature at 115 ℃ for 2h under vacuum condition), heating to 75 ℃ for reaction for 3.5h, and generating an isocyanate-terminated polyurethane prepolymer, wherein the content of 4,4' -diphenyl diisocyanate (MDI): total molar ratio of polytetrahydrofuran diol (PTMG 650) is 2.5.
The mol ratio of the isocyanate-terminated polyurethane prepolymer to the epoxypropanol is 1:1.5 mixing in an anhydrous dichloromethane solvent, reacting for 6h at 40 ℃ in a nitrogen atmosphere to obtain the polyurethane modified epoxy resin with an accurate structure, wherein the nuclear magnetic resonance spectrogram of the product is shown in figure 2, the positions of structural peaks in the spectrogram correspond to chemical structures one by one, and the intensities are consistent, which indicates that the synthesized polyurethane modified epoxy resin has a definite structure.
Example 3
A preparation method of polyurethane modified epoxy resin comprises the following specific steps:
adding 263.3g of polytetrahydrofuran diol (PTMG 1000) subjected to dehydration treatment (keeping at 110 ℃ for 3h under the vacuum condition) into 500g of 4,4 '-diphenyl diisocyanate (MDI), heating to 85 ℃ for reaction for 1.5h, cooling to 60 ℃, adding the residual 263.0g of polytetrahydrofuran diol (PTMG 1000) subjected to dehydration treatment, heating to 85 ℃ for reaction for 2.0h, and generating an isocyanate-terminated polyurethane prepolymer, wherein the content of 4,4' -diphenyl diisocyanate (MDI): total molar ratio of polytetrahydrofuran diol (PTMG 1000) was 2.
The mol ratio of the isocyanate-terminated polyurethane prepolymer to the epoxy propanol is 1:2, mixing the components in an anhydrous dichloromethane solvent, reacting for 6 hours at 50 ℃ in a nitrogen atmosphere to obtain the polyurethane modified epoxy resin with an accurate structure, wherein the nuclear magnetic resonance spectrogram of the product is shown in figure 3, the positions of structural peaks in the spectrogram correspond to chemical structures one by one, and the intensities are consistent, which indicates that the synthesized polyurethane modified epoxy resin has a definite structure.
In examples 1 to 3, the polyester polyols had different molecular weights, and the resulting products had different soft segment lengths and different peak intensities in nuclear magnetic spectra.
Example 4
A preparation method of polyurethane modified epoxy resin comprises the following specific steps:
adding 369.4g of dehydrated polypropylene glycol (PPG 1000) into 500g of Hexamethylene Diisocyanate (HDI) (maintaining for 2h at 110 ℃ under the condition of vacuumizing), heating to 80 ℃ for reaction for 0.5h, cooling to 50 ℃, adding the remaining 369g of dehydrated polypropylene glycol (PPG 1000), heating to 80 ℃ for reaction for 3.5h, and generating an isocyanate-terminated polyurethane prepolymer, wherein the weight ratio of Hexamethylene Diisocyanate (HDI): the total molar ratio of polypropylene glycol (PPG 1000) was 2.
The mol ratio of the isocyanate-terminated polyurethane prepolymer to the epoxy propanol is 1:2, mixing the components in an anhydrous dichloromethane solvent, and reacting for 5 hours at 40 ℃ in a nitrogen atmosphere to obtain the polyurethane modified epoxy resin with an accurate structure, wherein the structural formula is as follows:
example 5
A preparation method of polyurethane modified epoxy resin comprises the following specific steps:
adding 400.1g of dehydrated polytetrahydrofuran diol (PTMG 2000) into 500g of 4,4 '-diphenyl diisocyanate (MDI), heating to 80 ℃, reacting for 1.0h, cooling to 60 ℃, adding the rest 400.0g of dehydrated polytetrahydrofuran diol (PTMG 2000), heating to 80 ℃, reacting for 2.5h, and generating isocyanate-terminated polyurethane prepolymer, wherein the content of 4,4' -diphenyl diisocyanate (MDI): the total molar ratio of polytetrahydrofuran diol (PTMG 2000) was 2.5.
The mol ratio of the isocyanate-terminated polyurethane prepolymer to the epoxy propanol is 1:1.5 mixing in an anhydrous dichloromethane solvent, and reacting at 60 ℃ for 6h in a nitrogen atmosphere to obtain the polyurethane modified epoxy resin with an accurate structure, wherein the structural formula is as follows:
example 6
A preparation method of polyurethane modified epoxy resin comprises the following specific steps:
adding 287.9g of dehydrated polycaprolactone diol (PCL 1000) (keeping the temperature at 110 ℃ for 3h under the condition of vacuumizing) into 500g of Toluene Diisocyanate (TDI), heating to 80 ℃ for reaction for 1.0h, cooling to 60 ℃, adding the remaining 287.9g of dehydrated polycaprolactone diol (PCL), heating to 80 ℃ for reaction for 2.5h, and generating an isocyanate-terminated polyurethane prepolymer, wherein the Toluene Diisocyanate (TDI): the total molar ratio of polycaprolactone diol (PCL 1000) was 2.5.
The mol ratio of the isocyanate-terminated polyurethane prepolymer to the epoxypropanol is 1:1.5 mixing in an anhydrous dichloromethane solvent, and reacting at 60 ℃ for 6h in a nitrogen atmosphere to obtain the polyurethane modified epoxy resin with an accurate structure, wherein the structural formula is as follows:
comparative example 1:
in the comparison example, bisphenol A epoxy resin is used for replacing epoxy propanol to obtain a nuclear magnetic resonance spectrogram of polyurethane modified epoxy resin as shown in figure 4, wherein a signal peak of hydrogen on methylene on an epoxy group appears at 2.69-2.77ppm, a signal peak of last hydrogen on methyl on the epoxy group appears at 2.85-2.93ppm, and a signal peak of amido bond hydrogen appears at 6.75-7.19ppm, which shows that the polyurethane grafted epoxy resin is successfully prepared, but a large number of miscellaneous peaks exist in the nuclear magnetic spectrogram and are difficult to correspond to structures one by one, and byproducts exist in the synthesis process, so that the accuracy of the product structure is effectively improved by using the epoxy propanol.
The invention has low by-product and controllable molecular structure, can realize the accurate adjustment of the flexible chain segment in the molecular structure according to the actual requirement, can improve the design and processing efficiency, and obtains the high-quality polyurethane modified epoxy resin, which is difficult to realize by the traditional modification method.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the embodiments and implementations of the invention without departing from the spirit and scope of the invention, and are within the scope of the invention. The scope of the invention is defined by the appended claims.
Those skilled in the art will appreciate that those matters not described in detail in the present specification are not particularly limited to the specific examples described herein.
Claims (10)
1. A preparation method of polyurethane modified epoxy resin is characterized by comprising the following steps:
adding dehydrated polyether/ester polyol into isocyanate, and reacting to obtain an isocyanate-terminated polyurethane prepolymer;
reacting isocyanate-terminated polyurethane prepolymer, epoxy compound and anhydrous dichloromethane to obtain polyurethane modified epoxy resin; the epoxy compound is a small molecule epoxy compound.
2. The method for preparing the polyurethane modified epoxy resin according to claim 1, wherein the isocyanate is one or more of 4,4' -diphenyl diisocyanate MDI, hexamethylene diisocyanate HDI or toluene diisocyanate TDI;
the polyether/ester polyol is more than one of polypropylene glycol PPG, polytetrahydrofuran glycol PTMG or polycaprolactone diol PCL.
3. The method of claim 1, wherein the epoxy compound is epoxypropanol.
4. The method of claim 1, wherein the molar ratio of isocyanate to polyether/ester polyol is 2-2.5;
the molar ratio of the isocyanate-terminated polyurethane prepolymer to the epoxy compound is 1.5-2.
5. The method of claim 1, wherein the molecular weight of the dehydrated polyether/ester polyol is 250 to 2000.
6. The method for preparing polyurethane modified epoxy resin according to claim 1, wherein the polyether/ester polyol dehydration treatment comprises:
keeping the temperature of 105-115 ℃ for 2-3 h under the vacuum condition.
7. The method for preparing polyurethane modified epoxy resin according to claim 1, wherein the method for adding dehydrated polyether/ester polyol into isocyanate to obtain isocyanate-terminated polyurethane prepolymer after reaction comprises:
setting the total mass of polyether/ester polyol added into isocyanate as W;
adding 45-W-55-W-percent polyether/ester polyol into isocyanate, heating the obtained mixture to 75-85 ℃, reacting for 0.5-1.5 h, cooling to 40-60 ℃, adding the rest polyether/ester polyol into the isocyanate, heating the obtained mixture to 75-85 ℃, and reacting for 1.5-3.5 h to obtain the isocyanate-terminated polyurethane prepolymer.
8. The method for preparing polyurethane modified epoxy resin according to claim 1, wherein the reaction conditions for obtaining polyurethane modified epoxy resin by reacting isocyanate-terminated polyurethane prepolymer, epoxy compound and anhydrous dichloromethane are under an inert gas atmosphere and at 40-60 ℃ for 4-6 h.
9. The method of claim 1, wherein the polyether/ester polyol has an increased molecular weight and the resulting urethane-modified epoxy resin has an increased flexibility.
10. A urethane-modified epoxy resin obtained by the method for producing a urethane-modified epoxy resin according to any one of claims 1 to 9.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4384102A (en) * | 1981-01-08 | 1983-05-17 | Bayer Aktiengesellschaft | Process for the preparation of compounds having s-triazine units and epoxide groups |
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| CN114181372A (en) * | 2021-12-14 | 2022-03-15 | 中威北化科技有限公司 | High-toughness epoxy resin suitable for RTM (resin transfer molding) rapid curing requirement and synthesis method thereof |
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| CN114181372A (en) * | 2021-12-14 | 2022-03-15 | 中威北化科技有限公司 | High-toughness epoxy resin suitable for RTM (resin transfer molding) rapid curing requirement and synthesis method thereof |
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