CN117776977A - 1, 6-pyrene diisocyanate, preparation method thereof and application thereof in modified polyurethane elastomer - Google Patents
1, 6-pyrene diisocyanate, preparation method thereof and application thereof in modified polyurethane elastomer Download PDFInfo
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- 229920003225 polyurethane elastomer Polymers 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920002635 polyurethane Polymers 0.000 claims abstract description 55
- 239000004814 polyurethane Substances 0.000 claims abstract description 55
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims abstract description 41
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006396 nitration reaction Methods 0.000 claims abstract description 15
- 238000013016 damping Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000000806 elastomer Substances 0.000 claims abstract description 8
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- 238000005810 carbonylation reaction Methods 0.000 claims abstract description 3
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- 229920006306 polyurethane fiber Polymers 0.000 claims abstract description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 3
- 239000011541 reaction mixture Substances 0.000 claims description 79
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 62
- 238000006243 chemical reaction Methods 0.000 claims description 48
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- 239000000047 product Substances 0.000 claims description 30
- 229960000583 acetic acid Drugs 0.000 claims description 29
- 239000012362 glacial acetic acid Substances 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- OWJJRQSAIMYXQJ-UHFFFAOYSA-N pyrene-1,6-diamine Chemical compound C1=C2C(N)=CC=C(C=C3)C2=C2C3=C(N)C=CC2=C1 OWJJRQSAIMYXQJ-UHFFFAOYSA-N 0.000 claims description 23
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
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- 239000002244 precipitate Substances 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 17
- 239000000376 reactant Substances 0.000 claims description 17
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 238000006722 reduction reaction Methods 0.000 claims description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims description 14
- 230000009467 reduction Effects 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000003480 eluent Substances 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 239000012948 isocyanate Substances 0.000 claims description 8
- 150000002513 isocyanates Chemical class 0.000 claims description 8
- 238000002386 leaching Methods 0.000 claims description 8
- 239000012265 solid product Substances 0.000 claims description 8
- 150000001263 acyl chlorides Chemical class 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 5
- 238000010828 elution Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 239000006260 foam Substances 0.000 claims description 3
- 238000005984 hydrogenation reaction Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 230000001546 nitrifying effect Effects 0.000 claims description 2
- 238000005266 casting Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 29
- 239000000203 mixture Substances 0.000 abstract description 29
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- 230000008569 process Effects 0.000 abstract description 4
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 34
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 24
- 239000007864 aqueous solution Substances 0.000 description 16
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 5
- -1 amine hydrochloride Chemical class 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000004088 foaming agent Substances 0.000 description 4
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- WZLFPVPRZGTCKP-UHFFFAOYSA-N 1,1,1,3,3-pentafluorobutane Chemical compound CC(F)(F)CC(F)(F)F WZLFPVPRZGTCKP-UHFFFAOYSA-N 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- 229920005830 Polyurethane Foam Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical group OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 150000002527 isonitriles Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000011496 polyurethane foam Substances 0.000 description 2
- 238000011417 postcuring Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical group C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- KTNUVDBUEAQUON-UHFFFAOYSA-N 1,3-Dinitropyrene Chemical compound C1=C2C([N+](=O)[O-])=CC([N+]([O-])=O)=C(C=C3)C2=C2C3=CC=CC2=C1 KTNUVDBUEAQUON-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- GUXACCKTQWVTLG-UHFFFAOYSA-N 1,6-Dinitropyrene Chemical compound C1=C2C([N+](=O)[O-])=CC=C(C=C3)C2=C2C3=C([N+]([O-])=O)C=CC2=C1 GUXACCKTQWVTLG-UHFFFAOYSA-N 0.000 description 1
- BLYXNIHKOMELAP-UHFFFAOYSA-N 1,8-Dinitropyrene Chemical compound C1=C2C([N+](=O)[O-])=CC=C(C=C3)C2=C2C3=CC=C([N+]([O-])=O)C2=C1 BLYXNIHKOMELAP-UHFFFAOYSA-N 0.000 description 1
- ALRLPDGCPYIVHP-UHFFFAOYSA-N 1-nitropyrene Chemical compound C1=C2C([N+](=O)[O-])=CC=C(C=C3)C2=C2C3=CC=CC2=C1 ALRLPDGCPYIVHP-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses 1, 6-pyrene diisocyanate, wherein pyrene is subjected to nitration reaction to obtain a nitration product, and the nitration product is reduced to amino and then subjected to a carbonylation reaction to prepare the 1, 6-pyrene diisocyanate. Based on the same inventive concept, the invention also provides a preparation method of the 1, 6-pyrene diisocyanate, which has simple technical process and yield of more than 30 percent. Based on the same inventive concept, the invention also provides a polyurethane foaming composition. In addition, the invention also provides application of the 1, 6-pyrene diisocyanate serving as a polyurethane block in polyurethane rubber and elastomer, high-strength foam materials, polyurethane fibers, pouring polyurethane rubber, polyurethane emulsion and paint, adhesive and damping foam materials. The polyurethane material prepared from the 1, 6-pyrene diisocyanate has the advantages of high temperature resistance, solvent resistance, friction resistance and high impact resistance; the modulus property and the high-temperature fatigue resistance of the microporous polyurethane elastomer foaming material under the high-temperature condition are improved.
Description
Technical Field
The invention belongs to the field of modified polyurethane elastomers, and particularly relates to 1, 6-pyrene diisocyanate, a preparation method thereof and application thereof in the modified polyurethane elastomer.
Background
Polyurethane is usually produced by the reaction of isonitrile acid ester and polyol, and isocyanate is used as an important organic intermediate and widely applied to the fields of polyurethane elastomer, high-grade fiber, high-performance adhesive, paint coating, waterproof material, dedusting material, shock absorption damping and the like. The isonitrile acid ester plays an important role in the application field of polyurethane as a partial block structure in polyurethane, and the rigidity, structural order, molecular weight and molecular regularity determine the application range of polyurethane. However, polyurethane has the defects of large internal heat, general high temperature resistance, weak polar solvent resistance, weak strong acid and alkali medium resistance and the like under high-frequency oscillation conditions or high-temperature conditions.
Thus, improvements are needed in the art.
Disclosure of Invention
The invention aims to provide 1, 6-pyrene diisocyanate, a preparation method thereof and application thereof in modified polyurethane elastomer aiming at the existing polyurethane production technology. The invention is suitable for preparing polyurethane materials, and the prepared polyurethane materials have the advantages of high temperature resistance, solvent resistance, friction resistance and high impact resistance; the modified polyurethane material can also be used for modifying polyurethane materials to improve the modulus performance, high-temperature fatigue resistance and wear resistance of polyurethane elastomer, pouring polyurethane rubber and microporous foaming materials under the high-temperature condition; the high-temperature damping material is applied to the microporous foaming material, so that the high-temperature damping application limit of the material is improved, the material density is reduced, and the service life of the material is prolonged.
The technical scheme of the invention is realized as follows:
the first aim of the invention is to provide 1, 6-pyrene diisocyanate, wherein a nitration product is obtained through a nitration reaction of pyrene, and the nitration product is reduced to an amino group and then subjected to a carboylation reaction.
The 1, 6-pyrene diisocyanate provided by the invention is prepared by carrying out nitration reaction on pyrene, not separating, reducing to amino, and then carrying out a carbonylation reaction, wherein the prepared 1, 6-pyrene diisocyanate is used as a hard segment structure of a synthetic polyurethane material.
1, 6-pyrene diisocyanate as described above, the pyrene density being 1.27.+ -. 0.1g/cm 3 The melting point is 145-148 ℃, and the molecular weight is 202.251.
The 1, 6-pyrene diisocyanate has the nitration reaction solvent of glacial acetic acid and density of 1.049g/cm 3 Nitrate of sodiumThe chemical reaction reagent is any one of the following (1) - (3): (1) nitric acid and glacial acetic acid; (2) a mixed solution of nitric acid and sulfuric acid; (3) a mixed solution of nitrate and acetic acid.
The reduction to sulfide reduction, hydrogenation reduction or iron powder reduction is the 1, 6-pyrene diisocyanate as described above. Preferably, the reduction is sulfide reduction.
The 1, 6-pyrene diisocyanate is characterized in that the carboylation reagent in the carboylation reaction is phosgene or triphosgene.
The invention also provides a preparation method of the 1, 6-pyrene diisocyanate, which comprises the following steps:
step one, adding glacial acetic acid into pyrene, and uniformly stirring at 80-100 ℃ to obtain a reaction mixture 1; preferably, in the first step, the mass-to-volume ratio (g: mL) of pyrene to glacial acetic acid is (1:1) - (1:20), and when the mass-to-volume ratio (g: mL) is greater than 1:1, the pyrene is insufficiently dissolved due to too small consumption of glacial acetic acid, so that the reaction yield is low; when the mass-to-volume ratio (g: mL) is larger than 1:20, the production efficiency is too low due to excessive acetic acid consumption; more preferably, the mass to volume ratio of pyrene and acetic acid in the first step is (1 g:2 mL).
Step two, slowly adding the nitrifying reaction reagent into the reaction mixture 1 in the step one, and stirring the obtained yellow suspension at 80-100 ℃ for 0.5-2 h to obtain a reaction mixture 2; preferably, the yellow suspension obtained is stirred at 90℃for 1h, giving reaction mixture 2; preferably, the nitration reaction reagent in the second step is a mixture of nitric acid and glacial acetic acid; more preferably, in the second step, the volume ratio of the nitric acid to the glacial acetic acid is (1:2) - (1:5); most preferably, in the second step, the volume ratio of nitric acid to glacial acetic acid is (1:2). The reaction temperature of this step helps to increase the reaction rate and product selectivity.
Step three, cooling the reaction mixture 2 in the step two to room temperature, filtering the obtained precipitate, leaching with methanol, and drying under vacuum to obtain a reaction mixture 3, namely a nitrified product; preferably, the nitrified product crude product is a mixture containing 1, 6-dinitropyrene, 1, 8-dinitropyrene, 1, 3-dinitropyrene and 1-nitropyrene; the step is a simple separation method easy to operate, and can rapidly realize purification and purification of the product.
Step four, carrying out reduction reaction on the reaction mixture 3 obtained in the step three to obtain a reaction mixture 4;
for example, in some embodiments of the present invention, the reaction mixture 3 obtained in step three is reduced with sulfide, the reaction mixture 3 obtained in step three is suspended in a mixture of ethanol and NaSH aqueous solution, the solution is heated to reflux for 2 to 5 hours, and then the entire reaction mixture is cooled to obtain a reaction mixture 4; preferably, the reaction mixture 3 obtained in the third step is suspended in a mixture of ethanol and NaSH aqueous solution, the solution is heated and refluxed for 3 hours, and then the whole reaction mixture is cooled to obtain a reaction mixture 4; wherein the mass concentration of the NaSH aqueous solution is 40%, and the volume-to-mass ratio of the ethanol to the NaSH in the ethanol and NaSH aqueous solution is 200mL:17.3g; step four is preferably sulfide reduction, the reaction condition is mild, the operation is simple, and the method can be used for large-scale production.
Or in some embodiments of the invention, the reaction mixture 3 obtained in the third step is reduced by hydrogenation, the nitrified product obtained in the third step is added into distilled water, sulfuric acid is added, after nitrogen purging, palladium-carbon catalyst is added, hydrogen is introduced at the flow rate of 50-70 mL/min, and the temperature is raised to 70-90 ℃ to obtain precipitate; preferably, adding distilled water into the nitrified product obtained in the step three, adding sulfuric acid with the mass percent of 15%, purging with nitrogen, adding a palladium-carbon catalyst with the mass percent of 10%, introducing hydrogen at the flow rate of 60mL/min, and heating to 80 ℃ to obtain a precipitate.
Or in some embodiments of the invention, the reaction mixture 3 obtained in the third step is reduced by adopting iron powder, the iron powder is added into the reaction mixture 3 obtained in the third step, the pH is regulated by ammonium chloride and water, the mixture is heated to 30-50 ℃ and stirred uniformly, and then the mixture is heated to 90-100 ℃ and reacted for 1-2 hours to obtain a reaction mixture 4; preferably, iron powder is added into the reaction mixture 3 obtained in the step three, the pH is regulated to 5 by using 12 percent of ammonium chloride and water, the mixture is heated to 40 ℃ and uniformly stirred, and then the mixture is heated to 95 ℃ for reaction for 1.5 hours, so as to obtain a reaction mixture 4;
step five, drying the precipitate obtained from the reaction mixture 4 after filtering and cooling in the step four under vacuum, and performing column separation and purification by taking n-hexane and ethyl acetate in a volume ratio of (1:1) - (1:3) as eluent in a gradient manner to obtain a reactant 5, namely a yellow solid product of 1, 6-diaminopyrene; preferably, the volume ratio of the n-hexane to the ethyl acetate is 1:2; under this condition, the yield of 1, 6-diaminopyrene is 30% -35%. The organic solvents can be recycled by using the mixture of n-hexane and ethyl acetate as the eluent, and the step has the advantages of high efficiency, simplicity, environmental protection, resource saving and high yield.
Step six, the product 1, 6-diaminopyrene obtained in the step five is subjected to phosgenation reaction for 2-6 hours at 30-60 ℃ by taking chlorobenzene as a catalyst and continuously introducing phosgene to obtain a reactant 6; preferably, the product 1, 6-diaminopyrene obtained in the step five is subjected to phosgenation reaction for 3 hours at 40 ℃ by taking chlorobenzene as a catalyst and continuously introducing phosgene to obtain a reactant 6; the method is simple and convenient to operate and high in conversion rate.
And step seven, slowly heating the reactant 6 obtained in the step six to 100-150 ℃, continuously introducing phosgene to perform a two-stage phosgenation reaction, and further reacting and converting the hydrochloride of amine and an acyl chloride intermediate into organic isocyanate to obtain the 1, 6-pyrene diisocyanate. Preferably, the temperature is slowly raised to 130 ℃ and phosgene is continuously introduced to carry out the two-stage phosgenation reaction. Therefore, the initial reaction speed is relatively high, and the temperature needs to be increased along with the progress of the reaction, so that the reaction conversion rate is improved. Preferably, the NCO content of the 1, 6-pyrene diisocyanate is 28.4%.
The reaction of the present invention is shown below:
the third object of the present invention is to provide a method for preparing polyurethane by a one-step foaming method, comprising the steps of: and (3) adding the polyurethane foaming composition into a mould, rapidly stirring and uniformly mixing, foaming, curing and curing to obtain the polyurethane foam.
The fifth object of the present invention is to provide a method for preparing polyurethane by a prepolymer method, comprising the steps of:
(1) Reacting excessive 1, 6-pyrene diisocyanate with polypropylene glycol at 95 ℃ to form a prepolymer with the terminal-NCO group content less than or equal to 12.0%;
(2) Pouring: mixing the prepolymer and the chain extender component according to the mass ratio of 100:10.5, injecting the reaction feed liquid into a die, curing the prepolymer and demoulding the die; wherein: the chain extender comprises the following components in parts by weight: 45 parts of chain extender 1, 6-hexanediol, 36 parts of catalyst tetramethyl ethylenediamine, 14 parts of foaming agent and 5 parts of surfactant;
(3) Post-curing: and (5) putting the demoulded product into an oven, curing, and standing for 5d at room temperature to obtain the polyurethane.
The sixth object of the invention is to provide an application of 1, 6-pyrene diisocyanate as polyurethane block in polyurethane rubber and elastomer, polyurethane fiber, pouring polyurethane rubber, polyurethane emulsion and paint, polyurethane adhesive, damping foam and other materials in building, home, clothing, medical treatment, automobile manufacturing, sports equipment, electronic communication and aerospace. Experiments prove that the polyurethane prepared by the one-step foaming method of the 1, 6-pyrene diisocyanate has smaller constant compression set, better elastic recovery performance and larger loss factor, and the polyurethane microporous elastomer prepared by the polyurethane microporous elastomer has better damping performance and fast energy loss under the same condition. In addition, the polyurethane prepared by the prepolymerization method of the 1, 6-pyrene diisocyanate has higher tensile strength and tearing strength, the change ratio of the 70 ℃/1 week soaking tensile property is close to 1, the maintenance is better, the change is smaller, and the polyurethane prepared by the prepolymerization method of the 1, 6-pyrene diisocyanate has higher medium resistance.
The beneficial effects of the invention are as follows:
1. the 1, 6-pyrene diisocyanate provided by the invention comprises the unique four benzene rings which are connected together through conjugated bonds to form a large conjugated system, has strong molecular structure stability and higher molecular weight and modulus, so that the polyurethane prepared by the polyurethane has higher elastic modulus, higher thermal stability and higher friction resistance.
2. The 1, 6-pyrene diisocyanate provided by the invention has the advantages that the 1, 6-pyrene diisocyanate has a symmetrical and compact molecular structure, and a compact block is formed in polyurethane and excellent phase separation is realized. The molecular structure and the microphase separation structure enable the prepared polyurethane to have excellent wear resistance, fatigue resistance and high temperature resistance; in addition, the 1, 6-pyrene diisocyanate contains benzene rings, the chain segment rigidity is relatively large, the intermolecular acting force is strong, the molecular space arrangement is compact, the invasion of a medium is prevented, and the medium resistance is relatively high.
3. The molecular structure of pyrene is generally limited to a planar structure, and the reaction of NCO (isocyanate groups) on 1,6 positions of the 1, 6-pyrene diisocyanate, a chain extender and polyalcohol provided by the invention enables the layered structure to have a more diversified three-dimensional crosslinking structure, so that the polyurethane prepared by the invention has better mechanical properties.
4. The 1, 6-pyrene diisocyanate is an important organic intermediate and plays an important role in the future, and the invention provides key support for the research and development and application of high-performance materials. With the increase of the demand of the market for high-end diisocyanate, the 1, 6-pyrene diisocyanate has wider development prospect.
Detailed Description
The following description of the embodiments of the present invention will clearly and fully describe the technical solutions of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used in this specification includes any and all combinations of one or more of the associated listed items.
The experimental methods used in the following examples are conventional methods unless otherwise specified.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
In the following examples, the pyrene was purchased from Hubei Xindi chemical Co., ltd., CAS No.:129-00-0, density of 1.28g/cm 3 The molecular weight is 202.25.
The nitric acid is purchased from MaoMing, male and MaoMing chemical Co., ltd, the purity is 63%, the chloride (Cl)% -is less than or equal to 0.0001, and the Sulfate (SO) 4 )≤0.001。
The ethanol is purchased from Shandong Chen Yu chemical industry Co Ltd, and the acidity is less than or equal to 0.03mmol/100g.
The glacial acetic acid was purchased from sigma aldrich (Shanghai) trade limited and had a density of 1.049g/cm 3 。
The NaHS is purchased from Jinan Toyoda chemical industry Co., ltd, CAS number is 16721-80-5, and density is 1.79g/cm 3 。
Example 1:
the embodiment provides 1, 6-pyrene diisocyanate, and the preparation method comprises the following specific steps:
step one, adding 50mL of glacial acetic acid into 25g of pyrene (123.6 mmol), and uniformly stirring at 90 ℃ to dissolve the mixture to obtain a reaction mixture 1;
step two, slowly adding a mixture of 19mL of nitric acid and 50mL of glacial acetic acid into the reaction mixture 1, and stirring the obtained yellow suspension at 90 ℃ for reaction for 1h to obtain a reaction mixture 2;
step three, cooling the reaction mixture 2 in the step two to room temperature, filtering the obtained precipitate, leaching with methanol, and drying for 1.5h under vacuum to obtain a reaction mixture 3, namely a nitrified product;
suspending the reaction mixture 3 obtained in the step three in a mixture of ethanol and NaSH aqueous solution, heating and refluxing the solution for 3 hours, and then cooling the whole reaction mixture to obtain a reaction mixture 4; in this embodiment, the mass concentration of the NaSH aqueous solution is 40%, and the volume to mass ratio of the ethanol to the NaSH in the ethanol and NaSH aqueous solution is 200mL:17.3g;
step five, drying the precipitate obtained by filtering the cooled reaction mixture 4 in the step four under vacuum, and performing column separation and purification by taking n-hexane and ethyl acetate with a volume ratio of 1:2 as eluent gradient elution to obtain a yellow solid product, namely 1, 6-diaminopyrene, wherein the yield is 9.19 g and 32%;
the structure of 1, 6-diaminopyrene provided in this example was identified as follows:
GC-MS：232.1(m/z)；
nuclear magnetic measurement: 1H NMR (400 MHz, DMSO-d 6) delta 7.80 (d, 2H, ar-H), 7.74 (d, 2H, ar-H), 7.68 (d, 2H, ar-H), 7.26 (d, 2H, ar-H), 5.93 (d, 4H, ar-NH 2);
13C NMR(100MHz,DMSO-d6)δ142.78,127.09,125.48,124.34,123.06,117.27,116.61,113.39；
step six, the product 1, 6-diaminopyrene obtained in the step five is subjected to phosgenation reaction for 3 hours at 40 ℃ by taking 100mL chlorobenzene as a solvent and continuously introducing phosgene at 1.5g/min, and the pressure of a reaction kettle is kept at 0.05Mpa, so as to obtain a reactant 6;
step seven, slowly heating the reactant 6 obtained in the step six to 130 ℃, continuously introducing phosgene at a speed of 1.5g/min, continuously introducing phosgene at a pressure of 0.05Mpa in a reaction kettle to perform a two-stage phosgenation reaction, and further reacting and converting intermediates such as amine hydrochloride, acyl chloride and the like into organic isocyanate to finally prepare 1, 6-pyrene diisocyanate, wherein the yield is 10.6 g, and the yield is 95%;
the structure of 1, 6-pyrene diisocyanate provided in this example was identified as follows:
nuclear magnetic measurement: 1H NMR (400 MHz, DMSO-d 6) delta 8.48 (d, 2H, ar-H), 8.06 (d, 2H, ar-H), 7.89 (d, 2H, ar-H), 7.43 (d, 2H, ar-H);
13C NMR(100MHz,DMSO-d6)δ135.8,131.6,129.1,127.8,126.9,125.7,125.2,124.0，122.9。
example 2:
the embodiment provides 1, 6-pyrene diisocyanate, and the preparation method comprises the following specific steps:
step one, adding 50mL of glacial acetic acid into 25g of pyrene (123.6 mmol), and uniformly stirring at 90 ℃ to dissolve the mixture to obtain a reaction mixture 1;
step two, slowly adding a mixture of 19mL of nitric acid and 45mL of sulfuric acid with the purity of 80% into the reaction mixture 1, and stirring the obtained yellow suspension at 90 ℃ for reaction for 1h to obtain a reaction mixture 2;
step three, cooling the reaction mixture 2 in the step two to room temperature, filtering the obtained precipitate, leaching with methanol, and drying for 1h under vacuum to obtain a reaction mixture 3, namely a nitrified product;
step four, suspending the reaction mixture 3 obtained in the step three in a mixture of ethanol and NaSH aqueous solution, heating and refluxing the solution for 3h, and then cooling the whole reaction mixture to obtain a reaction mixture 4, wherein in the embodiment, the mass concentration of the NaSH aqueous solution is 40%, and the volume-to-mass ratio of the ethanol to the NaSH in the ethanol and NaSH aqueous solution is 200mL:17.3g;
step five, drying the precipitate obtained by filtering the cooled reaction mixture 4 in the step four under vacuum, and separating and purifying by using a column with the volume ratio of n-hexane/ethyl acetate as an eluent of 1:2 to obtain a yellow solid product, namely 1, 6-diaminopyrene, wherein the yield is 9.76 g and 34%;
the structure of 1, 6-diaminopyrene provided in this example was identified as follows:
GC-MS：232.1(m/z)；
nuclear magnetic measurement: 1H NMR (400 MHz, DMSO-d 6) delta 7.80 (d, 2H, ar-H), 7.74 (d, 2H, ar-H), 7.68 (d, 2H, ar-H), 7.26 (d, 2H, ar-H), 5.93 (d, 4H, ar-NH 2);
13C NMR(100MHz,DMSO-d6)δ142.78,127.09,125.48,124.34,123.06,117.27,116.61,113.39；
step six, the product 1, 6-diaminopyrene obtained in the step five is subjected to phosgenation reaction for 3 hours at 40 ℃ by taking 100mL chlorobenzene as a solvent and continuously introducing phosgene at 1.5g/min, and the pressure of a reaction kettle is kept at 0.05Mpa, so as to obtain a reactant 6;
step seven, slowly heating the reactant 6 obtained in the step six to 130 ℃, continuously introducing phosgene at a speed of 1.5g/min, keeping the pressure of the reaction kettle at 0.05Mpa, continuously introducing phosgene to perform a two-stage phosgenation reaction, further reacting and converting intermediates such as amine hydrochloride, acyl chloride and the like into organic isocyanate, and finally preparing 10.87 g of 1, 6-pyrene diisocyanate with a yield of 91%;
the structure of 1, 6-pyrene diisocyanate provided in this example was identified as follows:
nuclear magnetic measurement: 1H NMR (400 MHz, DMSO-d 6) delta 8.48 (d, 2H, ar-H), 8.06 (d, 2H, ar-H), 7.89 (d, 2H, ar-H), 7.43 (d, 2H, ar-H);
13C NMR(100MHz,DMSO-d6)δ135.8,131.6,129.1,127.8,126.9,125.7,125.2,124.0，122.9。
example 3:
the embodiment provides 1, 6-pyrene diisocyanate, and the preparation method comprises the following specific steps:
step one, adding 50mL of glacial acetic acid into 25g of pyrene (123.6 mmol), and uniformly stirring at 90 ℃ to dissolve the mixture to obtain a reaction mixture 1;
step two, slowly adding a mixture of 18.3g of magnesium nitrate and 50mL of glacial acetic acid into the reaction mixture 1, and stirring the obtained yellow suspension at 90 ℃ for reaction for 1h to obtain a reaction mixture 2;
step three, cooling the reaction mixture 2 in the step two to room temperature, filtering the obtained precipitate, leaching with methanol, and drying for 2 hours under vacuum to obtain a reaction mixture 3, namely a nitrified product;
suspending the reaction mixture 3 obtained in the step three in a mixture of ethanol and NaSH aqueous solution, heating and refluxing the solution for 3 hours, and then cooling the whole reaction mixture to obtain a reaction mixture 4; in this embodiment, the mass concentration of the NaSH aqueous solution is 40%, and the volume to mass ratio of the ethanol to the NaSH in the ethanol and NaSH aqueous solution is 200mL:17.3g;
step five, drying the reaction mixture 4 after filtration and cooling in the step four under vacuum, and performing column separation and purification by taking n-hexane and ethyl acetate with a volume ratio of 1:2 as eluent gradient elution to obtain a yellow solid product, namely 1, 6-diaminopyrene, wherein the yield is 9.47 g and the yield is 33%;
the structure of 1, 6-diaminopyrene provided in this example was identified as follows:
GC-MS：232.1(m/z)；
nuclear magnetic measurement: 1H NMR (400 MHz, DMSO-d 6) delta 7.80 (d, 2H, ar-H), 7.74 (d, 2H, ar-H), 7.68 (d, 2H, ar-H), 7.26 (d, 2H, ar-H), 5.93 (d, 4H, ar-NH 2);
13C NMR(100MHz,DMSO-d6)δ142.78,127.09,125.48,124.34,123.06,117.27,116.61,113.39；
step six, the product 1, 6-diaminopyrene obtained in the step five is subjected to phosgenation reaction for 3 hours at 40 ℃ by taking 100mL of chlorobenzene as a solvent and continuously introducing phosgene at 1.5g/min, wherein the pressure of a reaction kettle is kept at 0.05Mpa, so as to obtain a reactant 6;
step seven, slowly heating the reactant 6 obtained in the step six to 130 ℃, continuously introducing phosgene at the speed of 1.5g/min, keeping the pressure of a reaction kettle at 0.05Mpa, further reacting and converting intermediates such as amine hydrochloride, acyl chloride and the like into organic isocyanate, and finally preparing 1, 6-pyrene diisocyanate, wherein the yield is 11.0 g and 97%;
the structure of 1, 6-pyrene diisocyanate provided in this example was identified as follows:
nuclear magnetic measurement: 1H NMR (400 MHz, DMSO-d 6) delta 8.48 (d, 2H, ar-H), 8.06 (d, 2H, ar-H), 7.89 (d, 2H, ar-H), 7.43 (d, 2H, ar-H);
13C NMR(100MHz,DMSO-d6)δ135.8,131.6,129.1,127.8,126.9,125.7,125.2,124.0，122.9。
example 4:
the embodiment provides 1, 6-pyrene diisocyanate, and the preparation method comprises the following specific steps:
step one, adding 50mL of glacial acetic acid into 25g of pyrene (123.6 mmol), and uniformly stirring at 90 ℃ to dissolve the mixture to obtain a reaction mixture 1;
step two, slowly adding a mixture of 19mL of nitric acid and 50mL of glacial acetic acid into the reaction mixture 1, and stirring the obtained yellow suspension at 90 ℃ for reaction for 1h to obtain a reaction mixture 2;
step three, cooling the reaction mixture 2 in the step two to room temperature, filtering the obtained precipitate, leaching with methanol, and drying for 2 hours under vacuum to obtain a reaction mixture 3, namely a nitrified product;
adding 40mL of distilled water into the nitrified product obtained in the step three, adding 50mL of sulfuric acid with the mass percent of 15%, purging with nitrogen, adding 10% of palladium-carbon catalyst, introducing hydrogen at the flow rate of 60mL/min, and heating to 80 ℃ to obtain a precipitate;
step five, filtering the obtained precipitate, drying the precipitate under vacuum, and separating and purifying the precipitate by using a column with the volume ratio of n-hexane to ethyl acetate being 1:2 as an eluent to obtain a yellow solid product, namely 1, 6-diaminopyrene, wherein the yield is 10.0 g and 35%;
the structure of 1, 6-diaminopyrene provided in this example was identified as follows:
GC-MS：232.1(m/z)；
nuclear magnetic measurement: 1H NMR (400 MHz, DMSO-d 6) delta 7.80 (d, 2H, ar-H), 7.74 (d, 2H, ar-H), 7.68 (d, 2H, ar-H), 7.26 (d, 2H, ar-H), 5.93 (d, 4H, ar-NH 2);
13C NMR(100MHz,DMSO-d6)δ142.78,127.09,125.48,124.34,123.06,117.27,116.61,113.39；
step six, the product 1, 6-diaminopyrene obtained in the step five is subjected to phosgenation reaction for 3 hours at 40 ℃ by taking 100mL of chlorobenzene as a solvent and continuously introducing phosgene at 1.5g/min, wherein the pressure of a reaction kettle is kept at 0.05Mpa, so as to obtain a reactant 6;
step seven, slowly heating the reactant 6 obtained in the step six to 130 ℃, continuously introducing phosgene at a speed of 1.5g/min, continuously introducing phosgene at a pressure of 0.05Mpa in a reaction kettle to perform a two-stage phosgenation reaction, and further reacting and converting intermediates such as amine hydrochloride, acyl chloride and the like into organic isocyanate to finally prepare 1, 6-pyrene diisocyanate, wherein the yield is 10.94 g and 89%;
the structure of 1, 6-pyrene diisocyanate provided in this example was identified as follows:
nuclear magnetic measurement: 1H NMR (400 MHz, DMSO-d 6) delta 8.48 (d, 2H, ar-H), 8.06 (d, 2H, ar-H), 7.89 (d, 2H, ar-H), 7.43 (d, 2H, ar-H);
13C NMR(100MHz,DMSO-d6)δ135.8,131.6,129.1,127.8,126.9,125.7,125.2,124.0，122.9。
example 5:
the embodiment provides 1, 6-pyrene diisocyanate, and the preparation method comprises the following specific steps:
step one, adding 50mL of glacial acetic acid into 25g of pyrene (123.6 mmol), and uniformly stirring at 90 ℃ to dissolve the mixture to obtain a reaction mixture 1;
step two, slowly adding a mixture of 19mL of nitric acid and 50mL of glacial acetic acid into the reaction mixture 1, and stirring the obtained yellow suspension at 90 ℃ for reaction for 1h to obtain a reaction mixture 2;
step three, cooling the reaction mixture 2 in the step two to room temperature, filtering the obtained precipitate, leaching with methanol, and drying for 1h under vacuum to obtain a reaction mixture 3, namely a nitrified product;
adding 7g of iron powder into the reaction mixture 3 obtained in the step three, regulating the pH to 5 by using 12% ammonium chloride and water in percentage by mass, heating to 40 ℃ and uniformly stirring, and then heating to 95 ℃ for reacting for 1.5h to obtain a reaction mixture 4;
step five, the precipitate obtained by filtering the reaction mixture 4 obtained in the step four is dried under vacuum, and is subjected to column separation and purification by taking n-hexane and ethyl acetate with a volume ratio of 1:2 as eluent gradient elution, so that a yellow solid product, namely 1, 6-diaminopyrene, is obtained, the yield is 9.8 g, and the yield is 34%;
the structure of 1, 6-diaminopyrene provided in this example was identified as follows:
GC-MS：232.1(m/z)；
nuclear magnetic measurement: 1H NMR (400 MHz, DMSO-d 6) delta 7.80 (d, 2H, ar-H), 7.74 (d, 2H, ar-H), 7.68 (d, 2H, ar-H), 7.26 (d, 2H, ar-H), 5.93 (d, 4H, ar-NH 2);
13C NMR(100MHz,DMSO-d6)δ142.78,127.09,125.48,124.34,123.06,117.27,116.61,113.39；
step six, the product 1, 6-diaminopyrene obtained in the step five is subjected to phosgenation reaction for 2 hours at 40 ℃ by taking 100mL chlorobenzene as a solvent and continuously introducing phosgene at 1.5g/min, and the pressure of a reaction kettle is kept at 0.05Mpa, so that a reactant 6 is obtained.
Step seven, slowly heating the reactant 6 obtained in the step six to 130 ℃, continuously introducing phosgene at the speed of 1.5g/min, continuously introducing phosgene at the pressure of 0.05Mpa in a reaction kettle to perform a two-stage phosgenation reaction, and further reacting and converting intermediates such as amine hydrochloride, acyl chloride and the like into organic isocyanate to finally prepare 1, 6-pyrene diisocyanate, wherein the yield is 11.1 g, and the yield is 93%;
the structure of 1, 6-pyrene diisocyanate provided in this example was identified as follows:
nuclear magnetic measurement: 1H NMR (400 MHz, DMSO-d 6) delta 8.48 (d, 2H, ar-H), 8.06 (d, 2H, ar-H), 7.89 (d, 2H, ar-H), 7.43 (d, 2H, ar-H);
13C NMR(100MHz,DMSO-d6)δ135.8,131.6,129.1,127.8,126.9,125.7,125.2,124.0，122.9。
example 6:
the embodiment provides 1, 6-pyrene diisocyanate, and the preparation method comprises the following specific steps:
step one, adding 50mL of glacial acetic acid into 25g of pyrene (123.6 mmol), and uniformly stirring at 90 ℃ to dissolve the mixture to obtain a reaction mixture 1;
step two, slowly adding a mixture of 19mL of nitric acid and 50mL of glacial acetic acid into the reaction mixture 1, and stirring the obtained yellow suspension at 90 ℃ for reaction for 1h to obtain a reaction mixture 2;
step three, cooling the reaction mixture 2 in the step two to room temperature, filtering the obtained precipitate, leaching with methanol, and drying for 2 hours under vacuum to obtain a reaction mixture 3, namely a nitrified product;
suspending the reaction mixture 3 obtained in the step three in a mixture of ethanol and NaSH aqueous solution, heating and refluxing the solution for 3 hours, and then cooling the whole reaction mixture to obtain a reaction mixture 4; in this embodiment, the mass concentration of the NaSH aqueous solution is 40%, and the volume to mass ratio of the ethanol to the NaSH in the ethanol and NaSH aqueous solution is 200mL:17.3g;
step five, filtering the reaction mixture 4 obtained after filtering and cooling in the step four, drying the precipitate under vacuum, and separating and purifying the precipitate by using n-hexane and ethyl acetate with a volume ratio of 1:2 as eluent to obtain a yellow solid product, namely 1, 6-diaminopyrene, wherein the yield is 8.6 g and 30%;
the structure of 1, 6-diaminopyrene provided in this example was identified as follows:
GC-MS:232.1 (m/z) by nuclear magnetic measurement: 1H NMR (400 MHz, DMSO-d 6) delta 7.80 (d, 2H, ar-H), 7.74 (d, 2H, ar-H), 7.68 (d, 2H, ar-H), 7.26 (d, 2H, ar-H), 5.93 (d, 4H, ar-NH 2);
13C NMR(100MHz,DMSO-d6)δ142.78,127.09,125.48,124.34,123.06,117.27,116.61,113.39；
step six, dissolving the product 1,6 diaminopyrene obtained in the step five in 45mL of 1, 2-dichloroethane, dropwise adding the solution into 55g of triphosgene tetrahydrofuran solution, wherein the mass concentration of the triphosgene tetrahydrofuran solution is 20%, and carrying out heating reflux reaction to finally obtain 1, 6-pyrene diisocyanate, the yield of which is 9.7 g and the yield of which is 92%;
the structure of 1, 6-pyrene diisocyanate provided in this example was identified as follows:
nuclear magnetic measurement: 1H NMR (400 MHz, DMSO-d 6) delta 8.48 (d, 2H, ar-H), 8.06 (d, 2H, ar-H), 7.89 (d, 2H, ar-H), 7.43 (d, 2H, ar-H);
13C NMR(100MHz,DMSO-d6)δ135.8,131.6,129.1,127.8,126.9,125.7,125.2,124.0，122.9。
the present invention provides a method for preparing polyurethane by using 1, 6-pyrene diisocyanate and 1, 5-naphthalene diisocyanate (hereinafter referred to as "NDI") described in examples 1 to 6, respectively, through a one-step foaming process, and simultaneously provides a method for preparing polyurethane by using 1, 6-pyrene diisocyanate and diphenylmethane diisocyanate (hereinafter referred to as "MDI") described in examples 1 to 6, respectively, through a prepolymerization process.
The method comprises the following steps: polyurethane prepared by one-step foaming method
Application example 1:
a method for preparing polyurethane by a one-step foaming method, comprising the following steps:
and (3) adding the polyurethane foaming composition into a mold, rapidly stirring and uniformly mixing, wherein the stirring speed is 3000r/min, the stirring time is 20s, foaming, curing and curing are carried out, the curing temperature is 90 ℃, and the curing time is 24 hours, so that the polyurethane foam is prepared.
Here, the polyurethane foaming composition comprises 100 parts of 1, 6-hexanediol, the molar ratio of 1, 6-pyrene diisocyanate to 1, 6-hexanediol prepared in the embodiment 1 is 1.2:1, the foaming agent is deionized water 3.5 parts, the chain extender is 1, 4-butanediol 0.9 parts, and the catalyst is triethylenediamine 1.1 parts; the isocyanate group (hereinafter abbreviated as "NCO") content in the 1, 6-pyrene diisocyanate was 28.4%.
Application example 2:
the difference from application 1 is that the present application example replaces "preparation of 1, 6-pyrene diisocyanate of this example 1" with "NDI", and the other steps and conditions are the same. The NCO content of NDI used in this application example was 40.0%.
The second method is as follows: preparation of polyurethane by prepolymer method
Application example 3:
a method for preparing polyurethane by a prepolymer method, comprising the following steps:
(1) Reacting excessive diisocyanate with polypropylene glycol at 95 ℃ to generate prepolymer with terminal NCO groups, wherein the NCO content is 12%; in the application example, the diisocyanate used was 1, 6-pyrene diisocyanate prepared in the example 1, and the NCO content of the 1, 6-pyrene diisocyanate was 28.4%;
(2) Pouring: mixing the prepolymer and the chain extender component according to the mass ratio of 100:10.5, wherein the mixing speed is 1500r/min, stirring for 30s, injecting the reaction feed liquid into a mold with the temperature of 95 ℃, and demolding after pre-curing; wherein: the chain extender comprises the following components in parts by weight: 45 parts of chain extender 1, 6-hexanediol, 36 parts of catalyst tetramethyl ethylenediamine, 14 parts of foaming agent HFC-365mfc and excellent surfactantFLOW 499u 5 parts; wherein the foaming agent HFC-365mfc is purchased from Shandong Orthosiphon Li Long chemical industry Co., ltd, and the surfactant Ukara->FLOW is purchased from eukawa chemistry (Shanghai) limited.
(3) Post-curing: and curing the demolded product in a baking oven at 105 ℃ for 16 hours, and standing for 5 days at room temperature to obtain polyurethane.
Application example 4:
the difference from application example 3 is that the application example replaces "preparation of 1, 6-pyrene diisocyanate in this example 1" with "MDI", and the other steps and conditions are the same. The NCO content of the MDI used in this application example was 32.0%.
The polyurethane prepared by the one-step foaming process of application example 1 by using 1, 6-pyrene diisocyanate and application example 2 by using NDI has the performance shown in Table 1.
TABLE 1 results of Performance test of polyurethane prepared by one-step foaming
The performance of the polyurethane prepared by the prepolymerization method of the 1, 6-pyrene diisocyanate and MDI is shown in Table 2.
TABLE 2 Performance test results of polyurethane prepared by the prepolymer method
According to the results shown in Table 1, the polyurethane prepared by the one-step foaming method using the 1, 6-pyrene diisocyanate has the characteristics that the polyurethane microporous elastomer has smaller constant compression set, which shows that the polyurethane microporous elastomer has better elastic recovery performance and larger loss factor, and shows that the polyurethane microporous elastomer has quick energy loss and better damping performance under the same condition. According to Table 2, it is shown that the polyurethane prepared by the prepolymerization method using 1, 6-pyrene diisocyanate has higher tensile strength and tear strength, the change ratio of the 70 ℃ per 1 week soaking tensile property is close to 1, the retention is better, the change is smaller, and the polyurethane prepared by the prepolymerization method using 1, 6-pyrene diisocyanate has higher medium resistance.
The data show that the polyurethane product prepared by the method has better application prospect in the aspects of being used as a high-strength damping element and a corrosion-resistant element for bearing dynamic fatigue.
The above embodiments are described only for the convenience of understanding the use by those skilled in the art, and those skilled in the art can select an appropriate production process according to the product needs. It should be understood that the foregoing description is only of some embodiments of the present invention and is not intended to limit the invention, but is intended to cover all modifications, equivalents, alternatives, and modifications falling within the spirit and principles of the invention.
Claims (10)
1. The 1, 6-pyrene diisocyanate is characterized in that pyrene is subjected to nitration reaction to obtain a nitration product, and the nitration product is reduced to amino and then subjected to a carbonylation reaction to prepare the 1, 6-pyrene diisocyanate.
2. The 1, 6-pyrene diisocyanate of claim 1, wherein the pyrene density is 1.27 ± 0.1g/cm 3 The melting point is 145-148 ℃.
3. The 1, 6-pyrene diisocyanate according to claim 1, wherein the nitration solvent in the nitration reaction is glacial acetic acid, and the nitration reaction reagent is any one of the following (1) to (3): (1) nitric acid and glacial acetic acid; (2) a mixed solution of nitric acid and sulfuric acid; (3) a mixed solution of nitrate and acetic acid.
4. The 1, 6-pyrene diisocyanate of claim 1, wherein the reduction is sulfide reduction, hydrogenation reduction or iron powder reduction.
5. The 1, 6-pyrene diisocyanate of claim 4, wherein the reduction is sulfide reduction.
6. The 1, 6-pyrene diisocyanate of claim 1, wherein the carbosylating reagent in the carbosylating reaction is phosgene, triphosgene.
7. The method for producing 1, 6-pyrene diisocyanate according to any one of claims 1 to 6, comprising the steps of:
step one, adding glacial acetic acid into pyrene, and uniformly stirring at 80-100 ℃ to obtain a reaction mixture 1;
slowly adding the nitrifying reagent into the reaction mixture 1 in the first step, and stirring the obtained yellow suspension at 80-100 ℃ for 0.5-2 h to obtain a reaction mixture 2;
step three, cooling the reaction mixture 2 in the step two to room temperature, filtering the obtained precipitate, leaching with methanol, and drying under vacuum to obtain a reaction mixture 3, namely a nitrified product;
step four, carrying out reduction reaction on the reaction mixture 3 obtained in the step three to obtain a reaction mixture 4;
step five, drying the reaction mixture 4 obtained after filtering and cooling in the step four under vacuum, and performing column separation and purification by taking n-hexane and ethyl acetate in a volume ratio of (1:1) - (1:3) as eluent gradient elution to obtain a reactant 5, namely a yellow solid product of 1, 6-diaminopyrene;
step six, taking chlorobenzene as a solvent for continuously introducing phosgene to carry out phosgenation reaction for 2-6 hours at the temperature of 30-60 ℃ to obtain a reactant 6;
and step seven, slowly heating the reactant 6 obtained in the step six to 100-150 ℃, continuously introducing phosgene to perform a two-stage phosgenation reaction, and further reacting and converting the hydrochloride of amine and an acyl chloride intermediate into organic isocyanate to obtain the 1, 6-pyrene diisocyanate.
8. The method for producing 1, 6-pyrene diisocyanate according to claim 6, wherein the mass to volume ratio (g: mL) of pyrene to glacial acetic acid in the first step is (1:1) to (1:20).
9. The method for producing 1, 6-pyrene diisocyanate according to claim 6, wherein the volume ratio of nitric acid to glacial acetic acid in the second step is (1:2) to (1:5).
10. Use of the 1, 6-pyrene diisocyanate according to any one of claims 1 to 6 or the 1, 6-pyrene diisocyanate prepared according to the preparation method of any one of claims 7 to 9 as polyurethane block in polyurethane rubber and elastomer, high strength foam, polyurethane fiber, casting polyurethane rubber, polyurethane emulsion and paint, polyurethane adhesive and vibration damping foam fields.
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