Pyrazolyl ureido-based polyurea urethane, and preparation method and application thereof

A technology of pyrazole urea group and urea urethane, applied in the field of polyurea urethane material, can solve the problems of restricting the application of dynamic sterically hindered urea bonds and the like

Active Publication Date: 2020-04-07
INST OF CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the isocyanate intermediate produced by dissociation is relatively active and sensitive to moisture, which limits the application of dynamic sterically hindered urea bonds to a certain extent.

Method used

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  • Pyrazolyl ureido-based polyurea urethane, and preparation method and application thereof
  • Pyrazolyl ureido-based polyurea urethane, and preparation method and application thereof
  • Pyrazolyl ureido-based polyurea urethane, and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0087] The preparation of embodiment 1 containing pyrazole carbamide group compound

[0088]

[0089] 4-Methylpyrazole 1c was dissolved in 5 mL of anhydrous DCM, n-octyl isocyanate was added, reacted at room temperature for 1 h, concentrated, and column chromatography (n-hexane / EtOAc=80:1 to 30:1) gave white solid 11bc (3.37 g, 99% yield).

[0090] The structural confirmation data are as follows: 1 H NMR (300MHz, CDCl 3 ,ppm)δ7.95(s,1H),7.38(s,1H),7.10(br,s,1H),3.37(q,J=6.7Hz,2H),2.07(s,3H),1.63-1.54 (m,2H),1.31-1.25(m,10H),0.86(t,J=6.5Hz,3H); 13 C NMR (75MHz, CDCl 3 ,ppm)δ149.8,142.9,126.6,118.6,40.2,31.7,29.6,29.1,29.1,26.7,22.5,14.0,8.7; IR(neat,cm -1 )3352,3121,2951,2921,2852,1707,1525,1468,1389,1271,1010,836,754; ESI-HRMS calculated value C 13 h 23 N 3 NaO[M+Na] + :260.1733, experimental value: 260.1735, error ((calculated value-experimental value) / calculated value): -0.8ppm.

[0091]

[0092] The synthesis operation was similar to 11bc to obtain 11bd (99%...

Embodiment 2

[0115]

[0116] 4-Pyrazolecarboxylic acid 12 (29.97g, 262mmol) and 2-allyloxyethanol (35.53g, 341mmol) were dissolved in 180mL of anhydrous DMF, and EDCI (55.25g, 288mmol) and DMAP (12.8g, 105mmol) were added successively ), stirred at room temperature for 3d. Concentrate the solution at 70°C to remove DMF, then add 200 mL of water, Et 2 O (3×300mL) was extracted, the organic phases were combined, and successively washed with 10wt% citric acid (4×100mL), saturated NaHCO 3 Wash with saturated brine, Na 2 SO 4 Dry and concentrate. Distilled under reduced pressure at 110°C for 20 min to remove 2-allyloxyethanol to obtain light yellow liquid compound 13 (31.05 g, 60% yield).

[0117] The structural confirmation data are as follows: 1 H NMR (300MHz, CDCl 3 ,ppm)δ11.52(br,s,1H),8.07(s,2H),5.97-5.84(m,1H),5.29(dq,J=17.2Hz,J=1.6Hz,1H),5.20(dq , J=10.4Hz, J=1.3Hz, 1H), 4.42(t, J=4.8Hz, 2H), 4.06(dt, J=5.6Hz, J=1.3Hz, 2H), 3.75(t, J=4.8 Hz,2H); 13 CNMR (75MHz, CDCl 3 , ppm)...

Embodiment 3

[0124] Embodiment 3 Preparation of polyureaurethane based on pyrazole urea group structure

[0125]

[0126] Dissolve the dipyrazole compound 14 (2.501 g, 1 equivalent) prepared in Example 2 above in 6 mL of anhydrous CHCl 3 , HDI (0.725g, 1 equivalent) was added and reacted at room temperature for 10h. The reaction solution was evaporated at room temperature for 16 hours, and then vacuumed at 70° C. for 48 hours. The obtained white solid 16 was hot-pressed for 30 minutes (130° C., 10 MPa) to obtain a complete film sample, which was stored in a desiccator.

[0127] The structural confirmation data are as follows: 1 H NMR (300MHz, CDCl 3 ,ppm)δ8.70(s,2H),7.98(s,2H),7.25(t,J=5.9Hz,2H),4.41(t,J=4.5Hz,4H),3.72(t,J=4.7 Hz,4H),3.65-3.56(m,12H),3.44(q,J=6.7Hz,4H),2.70(t,J=6.9Hz,4H),2.63(t,J=7.2Hz,4H), 1.91-1.82(m,4H),1.70-1.62(4H),1.48-1.42(4H).

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Abstract

The invention belongs to the field of polyurea urethane materials, and provides pyrazolyl ureido-based polyurea urethane which is obtained by reaction of a pyrazolyl compound, a sulfydryl compound andan isocyanate compound; the reaction can be realized at room temperature, the method is simple, the preparation cost is low, and the method is suitable for large-scale industrial production. The pyrazolyl ureido-containing polyurea urethane has thermal reversibility, is relatively stable at room temperature, can be spontaneously dissociated into a compound containing isocyanate and pyrazole whenthe temperature rises to 80 DEG C or above, and can be subjected to hot press molding and reaction again to obtain the pyrazolyl ureido-based polyurea urethane. Compared with a dynamic sterically hindered urea bond dissociated at room temperature, the pyrazolyl ureido-based polyurea urethane has higher hydrolysis resistance, the practicability of the pyrazolyl ureido-based polyurea urethane product is greatly improved, and recycling of the thermosetting polyurea urethane can be realized.

Description

technical field [0001] The invention belongs to the field of polyureaurethane materials, in particular to a pyrazole urea-based polyureaurethane and its preparation method and application. Background technique [0002] Urea linkages can be prepared by addition reactions of isocyanates and organic amines. Due to the resonance stabilization effect of carbonyl and nitrogen atom, the general urea bond is a kind of very stable and irreversible covalent bond, and the compounds containing urea bond are also a kind of very stable compound. The cleavage of urea bonds usually requires very harsh conditions, such as acid or alkali systems, high temperature, metal catalysts and enzymes, etc. Polyurea has a hydrolytic half-life of about 10,000 years under neutral conditions. [0003] Polyurea resins are polymers based on urea linkages. Polyurea resin is a kind of polymer prepared by polyaddition reaction of polyamine and polyisocyanate, and is often used in coatings, adhesives, fibers...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08G18/38C08G18/73C07D231/12C07D231/14
CPCC07D231/12C07D231/14C08G18/3857C08G18/73
Inventor 徐坚刘文星乔志阳珠生赵宁
Owner INST OF CHEM CHINESE ACAD OF SCI
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