CN110964162B - Pyrazole ureido-based polyureaurethane and preparation method and application thereof - Google Patents
Pyrazole ureido-based polyureaurethane and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3857—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur having nitrogen in addition to sulfur
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
Abstract
The invention belongs to the field of polyureaurethane materials, and provides a pyrazole urea-based polyureaurethane which is obtained by reacting a pyrazole compound, a mercapto compound and an isocyanate compound, wherein the reaction can be realized at room temperature, and the method is simple, low in preparation cost and suitable for large-scale industrial production. The polyurea urethane containing the pyrazole ureido has thermal reversibility, is stable at room temperature, can be spontaneously dissociated into a compound containing isocyanate and pyrazole when the temperature is raised to be more than 80 ℃, and can be subjected to hot press molding again to react to obtain the polyurea urethane based on the pyrazole ureido; compared with a dynamic steric hindrance urea bond which can be dissociated at room temperature, the hydrolysis resistance is higher, the practicability of the polyurea urethane product based on the pyrazole urea group is greatly improved, and the thermosetting polyurea urethane can be recycled.
Description
Technical Field
The invention belongs to the field of polyureaurethane materials, and particularly relates to a pyrazole ureido-based polyureaurethane and a preparation method and application thereof.
Background
The urea linkage can be prepared by the addition reaction of an isocyanate and an organic amine. Due to the resonance stabilization of carbonyl and nitrogen atoms, general urea bonds are a very stable and irreversible covalent bond, and compounds containing urea bonds are also a very stable compound. Cleavage of urea bonds typically requires very harsh conditions such as acid or base systems, high temperatures, metal catalysts and enzymes, etc. The hydrolysis half-life of the polyurea under neutral conditions is up to about 1 ten thousand years.
The polymer constructed based on urea bonds is a polyurea resin. Polyurea resins are a class of polymers prepared from polyamines and polyisocyanates by polyaddition reactions and are commonly used in the fields of coatings, adhesives, fibers and elastomers. The polyamine is mainly commercially available as amino terminated polyether of Jeffamine series from Huntsman corporation. The reaction of it with isocyanate has very high activity, and provides raw material for the development of spray polyurea elastomer.
Urea linkages are also frequently used in the construction of polyureaurethane resins. For thermosetting polyureaurethane resins, the chemical crosslinking process is generally fixed, and has no recycling and reprocessing capability, which is not favorable for environmental protection and energy conservation. Polyureaurethane constructed based on dynamic reversible covalent bonds can solve this problem. The existing dynamic reversible urea bond technology is a steric hindrance urea bond, namely, a substituent with large steric hindrance (such as tertiary butyl) is introduced into one nitrogen atom, so that the coplanar action of a p track and a pi track of a carbonyl group of the nitrogen atom can be hindered, the resonance stabilization action is obviously reduced, and the steric hindrance urea bond can generate dissociation reaction at room temperature. However, the isocyanate intermediate produced by dissociation is relatively active and sensitive to moisture, which limits the application of the dynamic hindered urea bond to some extent.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a pyrazole ureido-based polyureaurethane obtained by reacting a pyrazole compound shown in the formula I, a mercapto compound shown in the formula II and an isocyanate compound shown in the formula III;
R2-(SH)x
II
wherein R is1Selected from unsubstituted or optionally substituted by one, two or more RaSubstituted with the following groups: c1-12Alkylene radical, C3-20Cycloalkylene radical, C6-20Arylene, 5-20 membered heteroarylene, 3-20 membered heterocyclylene, and C1-12Alkylene radical, C3-20Cycloalkylene radical, C6-20A group consisting of at least any two of arylene, 5-20 membered heteroarylene and 3-20 membered heterocyclylene joined together, and C in which at least one carbon atom in the carbon chain is replaced by O or S2-12An alkylene group;
R2selected from unsubstituted or optionally substituted by one, two or more RbThe following groups are substituted: c1-12Alkylene radical, C3-20Cycloalkylene radical, C6-20Arylene, 5-20 membered heteroarylene, 3-20 membered heterocyclylene, C in which at least one carbon atom in the carbon chain is replaced by O or S2-12An alkylene group;
a is selected from unsubstituted or optionally substituted by one, two or more RcSubstituted with the following groups: c1-12Alkylene radical, C3-20Cycloalkylene, 3-20 membered heterocyclylene, C6-20Arylene, 5-20 membered heteroarylene, and C1-12Alkylene radical, C3-20Cycloalkylene, 3-20 membered heterocyclylene, C6-20A group consisting of at least any two of arylene and 5-20 membered heteroarylene connected together;
x and y are the same or different and are independently selected from integers of 2 to 10;
Ra、Rb、Rcidentical or different, independently of one another, from the group consisting of ═ O, halogen and C1-12Alkyl or C1-12An alkoxy group;
the recurring unit of the pyrazole urea-based polyureaurethane comprises a pyrazole urea-based structure represented by formula IV:
in the formula IV, the reaction mixture is shown in the specification,
representing a chemical bond to another group.
According to an embodiment of the invention, R in formula I1Selected from the following groups unsubstituted or optionally substituted by one, two or more ═ O: c with 1 to 3 carbon atoms in the carbon chain replaced by O or S4-8An alkylene group;
according to an embodiment of the invention, R in formula II2Selected from C in which 1 to 3 carbon atoms in the carbon chain are replaced by O or S4-8An alkylene group;
according to an embodiment of the invention, a in formula III is selected from unsubstituted or optionally substituted by one, two or more ═ O or C1-6Alkyl-substituted groups as follows: c2-8Alkylene radical, C3-8Cycloalkylene, 3-8 membered heterocyclylene, C6-12Arylene group, and C2-8Alkylene radical, C3-8Cycloalkylene, 3-8 membered heterocyclylene, C6-12At least any two of the arylene groups are linked to form a group.
As an example, the pyrazole compounds of the formula I are selected from
As an example, the mercapto compound of formula II is selected from
As an example, the isocyanate compound represented by formula III is selected from at least one of the following compounds: toluene Diisocyanate (TDI), diphenylmethane diisocyanate, naphthalene diisocyanate, p-phenylene diisocyanate, dimethylbiphenyl diisocyanate, polymethylene polyphenyl isocyanate, 1, 6-Hexamethylene Diisocyanate (HDI), trimethyl-1, 6-hexamethylene diisocyanate, xylylene isocyanate, tetramethylm-xylylene diisocyanate, isophorone diisocyanate, 1, 4-cyclohexane diisocyanate, hydrogenated methylene diphenyl isocyanate, hydrogenated toluene diisocyanate, cyclohexane dimethylene diisocyanate, norbornane diisocyanate, hexamethylene diisocyanate trimer, toluene diisocyanate dimer, TDI-trimethylolpropane adduct, toluene diisocyanate trimer, diphenylmethane diisocyanate trimer, tolylene diisocyanate trimer, tolyl, Isophorone diisocyanate trimer.
Preferably, the pyrazole urea-based polyureaurethane can be a random copolymer or a block copolymer.
Preferably, the pyrazole urea-based polyureaurethane is a thermoplastic or thermoset polyureaurethane.
According to an embodiment of the present invention, the pyrazole urea-based polyureaurethane has the following structure:
according to an embodiment of the present invention, the thermosetting pyrazole urea-based polyureaurethane has the following structure:
further, the present invention also provides a method for preparing the above-mentioned pyrazole urea-based polyureaurethane, comprising: reacting the pyrazole compound shown in the formula I, the sulfhydryl compound shown in the formula II and the isocyanate compound shown in the formula III.
The reaction is carried out in a free radical initiated reaction system, for example, under conditions of thermal initiation, photoinitiation (e.g., blue light initiation), redox initiation;
according to an embodiment of the present invention, the reaction is performed in the presence of a photoinitiator, which may be at least one selected from the group consisting of benzil dimethyl ether (DMPA), benzoin ethyl ether, benzoin isopropyl ether, benzophenone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexyl phenyl methanone.
According to an embodiment of the present invention, the above reaction may be performed in an organic solvent selected from an alcohol solvent, a haloalkane solvent, a ketone solvent, an ester solvent, an ether solvent, an amide solvent, a sulfone solvent, an aromatic hydrocarbon solvent, or a sulfur-containing solvent; for example, the organic solvent is selected from one, two or more of methanol, ethanol, propanol, isopropanol, N-butanol, isobutanol, N-pentanol, N-octanol, acetone, butanone, chloroform, dichloromethane, diethyl ether, dibutyl ether, carbon disulfide, 1-methyl-2-pyrrolidone, N '-dimethylformamide, N' -dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, ethyl acetate, dioxane, acetonitrile, benzene, toluene, or xylene.
According to the embodiment of the invention, the temperature of the reaction is 10-30 ℃.
According to an embodiment of the present invention, when the polyureaurethane is thermosetting, the preparation method thereof comprises:
s2) carrying out ultraviolet illumination reaction on the pyrazole compound shown in the formula I and the mercapto compound shown in the formula II in the presence of a photoinitiator to obtain a monomer B;
s3) reacting the monomer A obtained in the step S1) and the monomer B obtained in the step S2) with an isocyanate compound shown in a formula III to obtain thermosetting polyureaurethane;
wherein the mercapto compounds represented by formula II used in steps S1) and S2) are the same or different, provided that at least one is substituted by more than three mercapto groups;
alternatively, the first and second electrodes may be,
According to an embodiment of the present invention, in scheme 2, the molar ratio of the isocyanate compound represented by formula III to the pyrazole compound represented by formula I is 100: (50-75).
According to the embodiment of the invention, the curing temperature is 25-40 ℃, and the curing time is 1-3 days.
According to an embodiment of the present invention, the preparation method further comprises a step of removing the solvent after completion of curing, comprising: and (3) drying the cured product in vacuum for 1-3 days at the temperature of 30-90 ℃.
The invention also provides the use of the pyrazole urea-based polyureaurethane for producing water-repellent, corrosion-resistant, medical, abrasion-resistant and surface finishing materials.
For example, the coating is used for preparing pipeline anticorrosive coatings, steel structure anticorrosive coatings, elastic anti-collision materials, automobile connecting pieces (such as universal connectors), gastroscope hoses or medical rubber tubes and the like.
The invention also provides an intermediate for preparing the pyrazole ureido-based polyureaurethane, which is obtained by reacting a pyrazole compound shown in the formula I and a mercapto compound shown in the formula II,
R2-(SH)x
II
wherein R is1、R2X has the definition as described above.
The present application also provides the use of an intermediate as described above for the preparation of a pyrazole urea-based polyureaurethane.
The application also provides a preparation method of the intermediate, which comprises the step of reacting the pyrazole compound shown in the formula I with the mercapto compound shown in the formula II.
Further, the invention also provides a method for realizing recycling of the polyurea polyurethane based on the pyrazole urea group, which comprises the following steps: and (3) crushing the thermosetting polyureaurethane, heating for decomposition, and carrying out hot press molding again to prepare the polyureaurethane.
According to an embodiment of the present invention, the method of breaking may be chopping the polyureaurethane.
According to an embodiment of the invention, the heating temperature is above 80 ℃, for example between 80 ℃ and 120 ℃, such as 100 ℃.
According to an embodiment of the invention, the pressurization may be carried out while heating, and the pressurization pressure is 1 to 20MPa, for example 1 to 10MPa, such as 5 MPa.
The present invention also provides a compound represented by the following formula 11bc, or 11ac, or S7, or S9,
the present invention also provides the use of a compound of formula 11bc, or 11ac, or S7, or S9, for verifying the stability and/or hydrolysis resistance of a pyrazolureyl-based polyureaurethane as described above.
The present invention also provides a process for preparing a compound of formula 11bc, or 11ac, or S7, or S9 as described above, comprising:
reacting 4-methylpyrazole with n-octyl isocyanate to obtain a compound shown as a formula 11 bc; alternatively, the first and second electrodes may be,
reacting phenethyl isocyanate with 4-methylpyrazole to obtain a compound shown in a formula 11 ac; alternatively, the first and second electrodes may be,
reacting 1-isocyanate-3-trifluoromethylbenzene with 4-methylpyrazole to obtain a compound shown as a formula S7; alternatively, the first and second electrodes may be,
the ethyl 4-pyrazoloate is reacted with n-octyl isocyanate to give the compound of formula S9.
The invention has the beneficial effects that:
the invention provides a polyurea urethane based on pyrazole ureido, which is obtained by reacting a pyrazole compound, a mercapto compound and an isocyanate compound. The pyrazole compound and the high-activity polyfunctional pyrazole prepared from the mercapto compound can be polymerized with the isocyanate compound at room temperature without a catalyst to obtain a polyurea urethane product based on pyrazole ureido, and the preparation method is simple, low in preparation cost and suitable for large-scale industrial production.
The pyrazole ureido group-containing polymer has thermal reversibility, is stable at room temperature, and can be spontaneously dissociated into a compound containing isocyanate and pyrazole when the temperature is increased to be more than 80 ℃; the room temperature stability of the polymer can be verified by a small molecule compound containing a pyrazole ureido group. Compared with the polymer containing dynamic steric hindrance urea bonds which can be dissociated at room temperature, the obtained polymer has stronger hydrolysis resistance, and the practicability of the pyrazole urea-based polyureaurethane product is greatly improved. Compared with the conventional polymer containing urea bonds, the high-temperature-resistant polymer can be decomposed by utilizing high temperature without very harsh conditions such as acid or alkali systems, high temperature, metal catalysts, enzymes and the like, so that the application range is higher than that of the conventional polymer containing urea bonds and dynamic steric hindrance urea bonds, and the development and utilization performance are higher.
The structure of the prepared polyureaurethane is based on the dynamic pyrazole carbamido group with thermal reversibility, and the recycling of the thermosetting polyureaurethane can be realized under the heating condition. The main reason is that the introduction of dynamic chemical bonds plays a decisive role in the polymerization processability, so that the polymer responds to external stimuli and the self-repairing and reprocessing performances of the thermosetting material are endowed.
The stability and hydrolysis resistance of the polymer prepared by the method can be verified by a small molecule compound containing pyrazole ureido. The use of small molecules for validation may save costs.
Drawings
In FIG. 1, (A) is the normal urea linkage, (B) is the hindered urea linkage and (C) is the chemical structure of the pyrazolecarboxylurea group.
FIG. 2 is a scheme for the preparation of a pyrazole urea-based polyureaurethane (PPzU).
FIG. 3 is (A) an exchange reaction diagram of 11bc and ethylpyrazole-4-carboxylate, showing that the pyrazolureyl group is irreversible at room temperature; (B) hydrolysis test of 11ac shows that the hydrolysis resistance is excellent.
FIG. 4 (A) an IR spectrum of PPzU 18; (B) GPC profile of dynamic depolymerization and repolymerization of PPzU 18.
FIG. 5 is a graph of the raw and recycled stress-strain curves of (A)17a, (B)17B and (C)17C (the inset shows the thermoforming process of 17C).
FIG. 6 is (A) the solubility of linear PPzU16 in common solvents; (B) is the GPC curve of each sample in the linear PPzU16 water degradation experiment.
Definition and description of terms
Unless otherwise indicated, the numerical ranges set forth in the specification and claims are equivalent to at least each and every specific integer numerical value set forth therein. For example, a numerical range of "2 to 10" is equivalent to reciting each integer value in the numerical range of "2 to 10," i.e., 2,3, 4,5, 6,7, 8,9, 10. It is to be understood that "more" in one, two, or more of the substituents used herein when describing substituents shall mean an integer ≧ 3, such as 3,4, 5,6, 7,8, 9, or 10.
The term "halogen" denotes fluorine, chlorine, bromine and iodine.
The term "C1-12Alkylene is understood to mean preferably a straight-chain or branched saturated alkylene radical having from 1 to 12 carbon atoms, preferably C1-10An alkylene group. "C1-10Alkylene "is understood to preferably mean a straight-chain or branched saturated alkylene radical having 1,2, 3,4, 5,6, 7,8, 9 or 10 carbon atoms. The alkylene group is, for example, methylene, ethylene, propylene, butylene, pentylene, hexylene, isopropylene, isobutylene, sec-butylene, tert-butylene, isopentylene. In particular, the radicals have 1,2, 3,4, 5,6 carbon atoms ("C)1-6Alkylene) such as methylene, ethylene, propylene, butylene.
The term "C3-20Cycloalkylene is understood to mean a saturated monocyclic, bicyclic hydrocarbon ring or bridged ring having 3 to 20 carbon atoms, preferably "C3-10Cycloalkylene ". The term "sub-C3-10Cycloalkyl "is understood to mean a saturated monocyclic or bicyclic hydrocarbon ring having 3,4, 5,6, 7,8, 9 or 10 carbon atoms. The sub C3-10The cycloalkyl group may be a monocyclic hydrocarbon group, such as cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctyleneA cyclic or acyclic nonyl or decyl group, or a bicyclic hydrocarbon group such as a decaline ring.
The term "3-20 membered heterocyclylene" means a saturated monocyclic or bicyclic hydrocarbon ring containing 1-5 heteroatoms independently selected from N, O and S, preferably "3-10 membered heterocyclylene". The term "3-10 membered heterocyclyl" means a saturated monocyclic or bicyclic hydrocarbon ring comprising 1-5, preferably 1-3 heteroatoms selected from N, O and S. The heterocyclylene group may be attached to the rest of the molecule through any two of the carbon atoms or nitrogen atoms (if present). In particular, the heterocyclic group may include, but is not limited to: 4-membered rings such as azetidinylene, oxetanylene; 5-membered rings such as tetrahydrofurylene, dioxolene, pyrrolidinylene, imidazolidinylene, pyrazolylene, pyrrolinylene; or a 6-membered ring such as tetrahydropyranyl, piperidyl, morpholinyl, dithianyl, thiomorpholinyl, piperazinyl, or trithianyl; or a 7-membered ring, such as diazepanyl. Optionally, the heterocyclylene group may be benzo-fused. The heterocyclylene group may be bicyclic, for example but not limited to a 5,5 membered ring, such as a hexahydrocyclopenta [ c ] pyrrol-2 (1H) -ylidene ring, or a 5,6 membered bicyclic, such as a hexahydropyrrolo [1,2-a ] pyrazin-2 (1H) -ylidene ring. The nitrogen atom containing ring may be partially unsaturated, i.e. it may contain one or more double bonds, such as but not limited to 2, 5-dihydro-1H-pyrrolylene, 4H- [1,3,4] thiadiazinylene, 4, 5-dihydrooxazolylene or 4H- [1,4] thiazilene, or it may be benzo-fused, such as but not limited to dihydroisoquinolylene. According to the invention, the heterocyclylene group is non-aromatic.
The term "C6-20Arylene is understood to mean preferably an aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring having 6 to 20 carbon atoms, preferably "C-ylene6-14Aryl ". The term "sub-C6-14Aryl "is to be understood as preferably representing an aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring having 6,7, 8,9, 10, 11, 12, 13 or 14 carbon atoms (" C)6-14Aryl group "), in particular a ring having 6 carbon atoms (" C6Arylene radicals ") For example phenylene; or biphenylene, or a ring having 9 carbon atoms ("C9Arylene group), such as indanylene or indenylene, or a ring having 10 carbon atoms ("C10Arylene radicals), such as tetralinylene, dihydronaphthylene or naphthylene radicals, or rings having 13 carbon atoms ("C-ylene radical13Aryl radicals), such as the fluorenylidene radical, or a ring having 14 carbon atoms ("C14Arylene "), such as anthracenylene.
The term "5-20 membered heteroarylene" is understood to include monocyclic, bicyclic or tricyclic aromatic ring systems: having 5 to 20 ring atoms and comprising 1 to 5 heteroatoms independently selected from N, O and S, such as "5-14 membered heteroarylene". The term "5-14 membered heteroarylene" is understood to include monocyclic, bicyclic or tricyclic aromatic ring systems: which has 5,6, 7,8, 9,10, 11, 12, 13 or 14 ring atoms, in particular 5 or 6 or 9 or 10 carbon atoms, and which comprises 1 to 5, preferably 1 to 3, heteroatoms each independently selected from N, O and S. And, in addition, may be benzo-fused in each case. Specifically, the heteroaryl group is selected from the group consisting of a thienyl group, a furanylene group, a pyrrolylene group, an oxazolylene group, a thiazolyl group, an imidazolyl group, a pyrazolyl group, an isoxazolylene group, an isothiazolylene group, an oxadiazoylene group, a triazolylene group, a thiadiazolylene group, a thia-4H-pyrazolyl group and the like, and a benzo derivative thereof and the like.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
EXAMPLE 1 preparation of pyrazole-urea-containing Compounds
4-methylpyrazole 1c was dissolved in 5mL of anhydrous DCM, n-octyl isocyanate was added, the reaction was carried out at room temperature for 1h, concentration was carried out, and column chromatography (n-hexane/EtOAc ═ 80:1 to 30:1) gave 11bc as a white solid (3.37g, 99% yield).
The structure validation data is as follows:1H NMR(300MHz,CDCl3,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)；13C NMR(75MHz,CDCl3,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, respectively; calculation of ESI-HRMS C13H23N3NaO[M+Na]+260.1733, experimental value 260.1735, error ((calculated-experimental value)/calculated) 0.8ppm.
The synthetic procedure was analogous to 11bc to give 11bd as a white solid (99% yield).
The structure validation data is as follows:1H NMR(300MHz,CDCl3,ppm)δ8.20(d,J＝2.7Hz,1H),7.55(d,J＝1.2Hz,1H),7.20(br,s,1H),6.34(dd,J＝2.6Hz,J＝1.7Hz,1H),3.38(q,J＝6.8Hz,2H),1.64-1.54(m,2H),1.30-1.24(m,10H),0.85(t,J＝6.8Hz,3H)；13C NMR(75MHz,CDCl3,ppm)δ149.6,141.8,128.5,108.0,40.3,31.7,29.5,29.1,29.1,26.7,22.5,14.0；IR(neat,cm-1)3345,2928,2857,1725,1527,1386,1334,1257,1209,1037,761, respectively; calculation of ESI-HRMS C12H21N3NaO[M+Na]+246.1577, experimental value 246.1580, error 1.2ppm.
The synthetic procedure was analogous to that for 11bc, giving 11ac as a white solid (98% yield).
The structure validation data is as follows:1H NMR(300MHz,CDCl3,ppm)δ7.96(s,1H),7.34(s,1H),7.32-7.19(m,6H),3.66-3.59(m,2H),2.89(t,J＝7.2Hz,2H),2.06(s,3H)；13C NMR(75MHz,CDCl3,ppm)δ149.7,143.0,138.4,128.6,128.5,126.5,126.4,118.7,41.4,35.8,8.7；IR(neat,cm-1)3367,3112,3030,2938,1712,1534,1454,1390,1357,1236,1193,967,747,697, respectively; calculation of ESI-HRMS C13H15N3NaO[M+Na]+252.1107, experimental value 252.1108, error of-0.4 ppm.
The synthetic procedure was analogous to 11bc to give 11ad as a white solid (97% yield).
The structure validation data is as follows:1H NMR(300MHz,CDCl3,ppm)δ8.21(d,J＝2.7Hz,1H),7.53(d,J＝0.9Hz,1H),7.34-7.20(m,6H),6.34(dd,J＝2.6Hz,J＝1.5Hz,1H),3.69-3.62(m,2H),2.91(t,J＝7.2Hz,2H)；13C NMR(75MHz,CDCl3,ppm)δ149.6,142.0,138.3,128.6,128.6,128.4,126.5,108.1,41.5,35.8；IR(neat,cm-1)3342,2937,1724,1524,1387,1334,1256,1207,1036,946,755,699, respectively; calculation of ESI-HRMS C13H13N3NaO[M+Na]+238.0951, experimental value 238.0953, error of-0.9 ppm.
Dissolving aryl isocyanate (3.50mmol) in anhydrous DCM, adding 4-methylpyrazole (3.50mmol) at 0 ℃, removing the ice water bath, and reacting at room temperature for 10 min. Concentration and column chromatography gave solid S3-S7 in quantitative yield. The characterization data of S3-S7 are as follows:
1H NMR(300MHz,CDCl3,ppm)δ8.91(br,s,1H),8.05(s,1H),7.51-7.48(m,3H),6.92-6.89(m,2H),3.81(s,3H),2.13(s,3H)；13C NMR(75MHz,CDCl3,ppm)δ156.6,147.1,143.3,129.7,126.7,121.4,119.5,114.3,55.5,8.9；IR(neat,cm-1)3338,3118,2933,1709,1597,1520,1424,1390,1266,1210,974,823,755, respectively; calculation of ESI-HRMS C12H14N3O2[M+H]+232.1081, experimental value 232.1083, error of-0.9 ppm.
1H NMR(300MHz,CDCl3,ppm)δ8.97(br,s,1H),8.05(s,1H),7.49-7.47(m,3H),7.17(d,J＝8.1Hz,2H),2.34(s,3H),2.13(s,3H)；13C NMR(75MHz,CDCl3,ppm)δ146.9,143.3,134.1,134.1,129.6,126.6,119.6,119.5,20.8,8.9；IR(neat,cm-1)3329,3096,2923,1721,1595,1539,1416,1391,1211,969,811,773, respectively; calculation of ESI-HRMS C12H14N3O2[M+H]+216.1131, experimental value 216.1133, error of-0.8 ppm.
1H NMR(300MHz,d6-DMSO,ppm)δ10.44(s,1H),8.18(s,1H),7.78-7.72(m,3H),7.23-7.17(m,2H),2.09(s,3H)；13C NMR(75MHz,d6-DMSO,ppm)δ158.1(d,J＝239.3Hz),147.5,143.7,134.0(d,J＝2.5Hz),127.2,122.6(d,J＝8.0Hz),119.1,115.3(d,J＝22.1Hz),8.6；IR(neat,cm-1)3341,3119,1711,1614,1557,1386,1214,974,825,773, respectively; calculation of ESI-HRMS C11H11FN3O[M+H]+220.0881, experimental value 220.0882 and error 0.8ppm.
1H NMR(300MHz,CDCl3,ppm)δ9.04(br,s,1H),8.03(s,1H),7.57-7.52(m,2H),7.47(s,1H),7.35-7.30(m,2H),2.13(s,3H)；13C NMR(75MHz,CDCl3,ppm)δ146.8,143.6,135.3,129.5,129.2,126.6,120.7,119.8,8.9；IR(neat,cm-1)3341,3121,1713,1603,1552,1387,1102,977,819,739, respectively; calculation of ESI-HRMS C11H11ClN3O[M+H]+236.0585, experimental value 236.0587, error of-0.9 ppm.
1H NMR(300MHz,d6-DMSO,ppm)δ10.72(s,1H),8.19(s,1H),8.00(d,J＝8.5Hz,2H),7.74(s,1H),7.70(d,J＝8.6Hz,2H),2.08(s,3H)；13C NMR(75MHz,d6-DMSO,ppm)δ147.4,144.0,141.5,127.3,125.9(q,J＝3.5Hz),124.3(q,J＝269.7Hz),124.1(q,J＝31.8Hz),120.5,119.5,8.5；IR(neat,cm-1)3331,3123,1711,1600,1551,1418,1331,1158,1112,1008,973,827,736, respectively; calculation of ESI-HRMS C12H11F3N3O[M+H]+270.0849, experimental value 270.0851 and error 0.8ppm.
Ethyl 4-pyrazolecarboxylate (0.663g,4.64mmol) was dissolved in 4mL anhydrous CHCl3N-octyl isocyanate (0.720g,4.64mmol) was added and reacted at room temperature overnight. Concentration and column chromatography (n-hexane: EtOAc: 30:1) gave S9(1.34g, 98% yield) as a white solid.1H NMR(300MHz,CDCl3,ppm)δ8.67(s,1H),7.96(s,1H),7.19(br,s,1H),4.32(q,J＝7.1Hz,2H),3.42(q,J＝6.8Hz,2H),1.68-1.58(m,2H),1.38-1.27(m,13H),0.87(t,J＝6.7Hz,3H)；13C NMR(75MHz,CDCl3,ppm)δ162.2,148.8,142.5,131.6,117.5,60.6,40.6,31.7,29.5,29.1,29.1,26.7,22.6,14.3,14.0；IR(neat,cm-1)3352,3117,2921,2851,1719,1528,1279,1194,1113,1030,971,840,775, respectively; calculation of ESI-HRMS C15H26N3O3[M+H]+296.1969, experimental value 296.1971 and error 0.8ppm.
Example 2
4-Pyrazolecarboxylic acid 12(29.97g,262mmol) and 2-allyloxyethanol (35.53g,341mmol) were dissolved in 180mL of anhydrous DMF, EDCI (55.25g,288mmol) and DMAP (12.8g,105mmol) were added in this order, and the reaction was stirred at room temperature for 3 d. The solution was concentrated at 70 ℃ to remove DMF and 200mL of water, Et2O (3X 300mL), and the combined organic phases were successively extracted with 10 wt% citric acid (4X 100mL), saturated NaHCO3Washed with saturated brine, Na2SO4Drying and concentrating. Distillation was carried out at 110 ℃ under reduced pressure for 20min to remove 2-allyloxyethanol, yielding compound 13 as a pale yellow liquid (31.05g, 60% yield).
The structure validation data is as follows:1H NMR(300MHz,CDCl3,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＝4.8Hz,2H)；13C NMR(75MHz,CDCl3,ppm)δ163.1,136.5,134.2,117.5,114.4,72.1,68.0,63.4；IR(neat,cm-1)3253,2955,2868,1717,1563,1403,1326,1225,1157,992,768, respectively; calculation of ESI-HRMS C9H12N2NaO3[M+Na]+219.0740, experimental value 219.0742, error of-0.8 ppm.
Compound 13(14.13g,72mmol) and 2,2' - (ethanediylbiooxo) bisethanethiol (6.84g,36mmol) were dissolved in 30mL DCM, and 0.5 mol% (for the double bond) DMPA (0.091g,0.36mmol) was added. Irradiating the reaction system under 365nm ultraviolet lamp, and stirring at room temperatureStirring and reacting for 60 min. The solvent was removed by concentration, and then 21mL of acetone was added to dissolve the resulting solution. The solution was added dropwise to n-hexane/Et2O (80mL/120mL), and the mixture was allowed to stand for layer separation, and the lower organic layer was removed and concentrated to give a pale yellow liquid 14(19.50g, 95% yield).
The structure validation data is as follows:1H NMR(300MHz,CDCl3,ppm)δ9.40(br,s,2H),8.03(s,4H),4.22(t,J＝6.2Hz,4H),3.62-3.58(m,8H),2.67(t,J＝6.9Hz,4H),2.56(t,J＝7.1Hz,4H),1.81-1.73(m,4H),1.71-1.63(m,4H)；13C NMR(75MHz,CDCl3ppm) delta 163.2,136.3,114.5,70.7,70.1,63.7,31.9,31.2,27.6, 26.1; calculation of ESI-HRMS C24H38N4NaO8S2[M+Na]+597.2023, experimental value 597.2029, error of-0.8 ppm.
Compound 13(20.29g,71mmol) and trimethylolpropane tris (3-mercaptopropionate) (TTMP) (14.31g,23.5mmol) were dissolved in 50mL DCM, and 0.5 mol% (for the double bond) DMPA (0.132g,0.35mmol) was added. The reaction system is irradiated under an ultraviolet lamp of 365nm and stirred and reacted for 60min at room temperature. The solvent was removed by concentration, and 35mL of acetone was added to dissolve the residue. The solution was added dropwise to n-hexane/Et2O (70mL/280mL), and the mixture was allowed to stand for layer separation, and the lower organic layer was removed and concentrated to give a pale yellow liquid 15(32.82g, 97% yield).
The structure validation data is as follows:1H NMR(300MHz,CDCl3,ppm)δ10.82(br,s,3H),8.06(s,6H),4.37(t,J＝4.6Hz,6H),4.01(s,6H),3.70(t,J＝4.6Hz,6H),3.56(t,J＝6.0Hz,6H),2.69(t,J＝6.8Hz,6H),2.59-2.54(m,12H),1.86-1.77(m,6H),1.44(q,J＝7.4Hz,2H),0.83(t,J＝7.5Hz,3H)；13C NMR(75MHz,CDCl3ppm) delta 171.7,163.0,136.5,114.4,69.3,68.7,63.8,63.3,40.6,34.5,29.3,28.5,26.8,22.8, 7.2; calculation of ESI-HRMS C42H63N6O15S3[M+H]+987.3508, experimental value 987.3498, error of-1.0 ppm.
Example 3 preparation of a polyureaurethane based on a pyrazole-ureido Structure
The dipyrazole compound 14(2.501g,1 equivalent) prepared in example 2 above was dissolved in 6mL of anhydrous CHCl3HDI (0.725g,1 eq) was added and the reaction was carried out at room temperature for 10 h. The reaction solution was evaporated at room temperature for 16 hours and then vacuumed at 70 ℃ for 48 hours. The obtained white solid 16 was hot-pressed for 30min (130 ℃ C., 10MPa), and a complete film sample was obtained and stored in a desiccator.
The structure validation data is as follows:1H NMR(300MHz,CDCl3,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＝4.7Hz,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).
EXAMPLE 4 preparation of thermosetting polyureaurethane
Taking PPzU 17c as an example, the preparation operation is as follows: dissolving the trispyrazole compound 15(2.507g,1 equivalent) in anhydrous CHCl3(2.5mL), to which was added HDI (0.634g,1.5 eq), and mixed with stirring at room temperature for 2 min. The reaction solution was cast into an aluminum mold (50mm L. times.50 mm W), placed in a desiccator for 24 hours, demolded, and further placed in a vacuum oven at 70 ℃ for 48 hours to completely remove the solvent. The resulting sample 17c was stored in a desiccator. Samples 17a and 17b were also prepared by adjusting the proportions of the trispyrazole compound 15, HDI and the bispyrazole compound 14 in the same manner.
The characterization data of the properties of the PPzUs prepared are shown in Table 1.
TABLE 1 characterization of the properties of the PPzUs prepared
Dissolving dipyrazole compound 14(0.83mmol) in anhydrous CHCl3(4mL), 1, 3-bis (isocyanatomethyl) cyclohexane (0.83mmol) was added thereto, and the reaction was stirred at room temperature for 10 h. The solvent was removed and used directly for characterization testing.1H NMR(300MHz,CDCl3,ppm)δ8.70(2H),7.99(2H),7.33(2H),4.42-4.39(4H),3.74-3.71(4H),3.66-3.56(12H),3.50-3.28(4H),2.70(t,J＝7.0Hz,4H),2.63(t,J＝7.2Hz,4H),1.91-1.82(7H),1.68-1.24(5H),1.02-0.71(2H).
Example 5 thermosetting pyrazole urea-based polyurethane reprocessing experiments
Recovery experiments of thermoset polyureaurethane: the thermosetting polyureaurethane prepared in example 4 was cut into small pieces, placed in a square mold (length 50 mm. times.width 50mm), hot-pressed at 100 ℃ under 5MPa for 60 minutes, and then cooled to room temperature within about 10 minutes using condensed water, and demolded to obtain a recovered sample. The sample can be hot-pressed and molded repeatedly. The recovered samples were subjected to mechanical property tests, and the results are shown in Table 2.
TABLE 2
Example 6 Room temperature stability and hydrolysis resistance testing of pyrazole urea-based compounds
6.1 test of Room temperature stability of Compound 11bc
The pyrazole ureido group in the polymer prepared by the invention has room temperature stability. The stability can be verified by exchange reaction and hydrolysis reaction of the pyrazole ureido group-containing small molecule compound. After mixing pyrazole ureido-containing compound 11bc prepared in example 1 and ethyl 4-pyrazolecarboxylate in a molar ratio of 1:2 and reacting at room temperature for 3d, no formation of an exchange product was observed. Further heating to 37 ℃ was carried out for 20d, and only 1% of the exchanged product was detected (see FIG. 3A). This indicates that the pyrazole ureido group is irreversible at room temperature, i.e., the pyrazole ureido group-containing compound (polymer) is excellent in stability at room temperature.
6.2 test of hydrolytic stability of Compound 11ac
The pyrazole ureido group-containing compound (polymer) prepared by the invention has hydrolysis resistance. The verification method comprises the following steps: 0.1M Pyrazolecarbamido-containing Compound 11ac prepared in example 1 at d6-DMSO/D2After the mixed solution of O (v: v ═ 5:1) was reacted at 37 ℃ for 1d, formation of diphenylethylurea as a hydrolysis product was observed, and the conversion was about 2%; after 168h, the hydrolysis conversion rate can reach 6% (see fig. 3B). Since the pyrazole ureido group is irreversible at room temperature, we speculate that the hydrolysis reaction proceeds through a water molecule catalyzed addition-elimination mechanism rather than a hydrolysis process in which the urea bond dissociates to form an isocyanate. Thus, the pyrazole ureido group-containing compound (polymer) herein is to be compared with the hindered urea bond-containing compound (polymer) ((R))>55% hydrolysis conversion) with excellent hydrolytic stability.
Example 7 stability experiment of Linear PPzU16
The linear PPzU16 prepared in example 3 was tested for solubility in common solvents at room temperature (see fig. 6A) with the following solubility results: in CHCl3The solubility of the intermediate is optimal, and the intermediate is partially soluble in dioxane, dichloroethane, N-methylpyrrolidone, carbon tetrachloride, formamide, ethanol and methanol and is hardly soluble in dimethyl sulfoxide, acetonitrile, ethyl acetate, acetone, tetrahydrofuran and N, N-dimethylformamide.
The water degradation experiment was performed on linear PPzU16 as follows: at 37 ℃ 0.1M PPzU16 was taken at d6-DMSO and D2O (v/v 19: 1) in a mixture of 0h, 28h, 48h and 7GPC measurements were carried out on samples of 8h, 100h, 144h (see FIG. 6B), and the experiments showed that the molecular weight of PPzU16 did not change after 6 days, again indicating good stability of the pyrazole urea-based polyureaurethane.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The polyurea urethane based on pyrazole ureido is characterized by being obtained by reacting a pyrazole compound shown in a formula I, a mercapto compound shown in a formula II and an isocyanate compound shown in a formula III;
R2-(SH)x
II
wherein R is1Selected from unsubstituted or optionally substituted by one, two or more RaSubstituted with the following groups: c1-12Alkylene radical, C3-20Cycloalkylene radical, C6-20Arylene, 5-20 membered heteroarylene, 3-20 membered saturated heterocyclylene, 3-20 membered unsaturated non-aromatic heterocyclylene, and C1-12Alkylene radical, C3-20Cycloalkylene radical, C6-20A group consisting of at least any two of arylene, 5-20 membered heteroarylene, 3-20 membered saturated heterocyclylene and 3-20 membered unsaturated non-aromatic heterocyclylene, C in which at least one carbon atom in the carbon chain is replaced by O or S2-12An alkylene group;
R2selected from unsubstituted or optionally substituted by one, two or more RbThe following groups are substituted:C1-12alkylene radical, C3-20Cycloalkylene radical, C6-20Arylene, 5-20 membered heteroarylene, 3-20 membered saturated heterocyclylene, 3-20 membered unsaturated non-aromatic heterocyclylene, C wherein at least one carbon atom in the carbon chain is replaced by O or S2-12An alkylene group;
a is selected from unsubstituted or optionally substituted by one, two or more RcSubstituted with the following groups: c1-12Alkylene radical, C3-20Cycloalkylene, 3-20 membered saturated heterocycloalkylene, C6-20Arylene, 5-20 membered heteroarylene, 3-20 membered unsaturated non-aromatic heterocyclic group and C1-12Alkylene radical, C3-20Cycloalkylene, 3-20 membered saturated heterocycloalkylene, C6-20A group comprising at least any two of an arylene group, a 5-20 membered heteroarylene group and a 3-20 membered unsaturated heterocyclic group having no aromatic character;
x and y are the same or different and are independently selected from integers of 2 to 10;
Ra、Rb、Rcidentical or different, independently of one another, from the group consisting of ═ O, halogen and C1-12Alkyl or C1-12An alkoxy group;
the recurring unit of the pyrazole urea-based polyureaurethane comprises a pyrazole urea-based structure represented by formula IV:
in the formula IV, the reaction mixture is shown in the specification,
representing a chemical bond to another group.
2. The pyrazole ureido based polyureaurethane of claim 1 wherein R in formula I1Selected from the following groups unsubstituted or optionally substituted by one, two or more ═ O: c with 1 to 3 carbon atoms in the carbon chain replaced by O or S4-8An alkylene group;
in the formula II R2Selected from C in which 1 to 3 carbon atoms in the carbon chain are replaced by O or S4-8An alkylene group;
in formula III A is selected from unsubstituted or optionally substituted by one, two or more ═ O or C1-6Alkyl-substituted groups as follows: c2-8Alkylene radical, C3-8Cycloalkylene, 3-8 membered saturated heterocycloalkylene, C6-12Arylene group, and C2-8Alkylene radical, C3-8Cycloalkylene, 3-to 8-membered saturated heterocycloalkylene, 3-to 8-membered unsaturated non-aromatic heterocyclylene, C6-12At least any two of the arylene groups are linked to form a group.
3. The pyrazole urea-based polyureaurethane of claim 1 wherein,
the pyrazole compound shown as the formula I is selected from
The mercapto compound shown in formula II is selected from
The isocyanate compound shown in the formula III is selected from at least one of the following compounds: toluene Diisocyanate (TDI), diphenylmethane diisocyanate, naphthalene diisocyanate, p-phenylene diisocyanate, dimethylbiphenyl diisocyanate, polymethylene polyphenyl isocyanate, 1, 6-hexamethylene diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate, xylylene isocyanate, tetramethylm-xylylene diisocyanate, isophorone diisocyanate, 1, 4-cyclohexane diisocyanate, hydrogenated methylene diphenyl isocyanate, hydrogenated toluene diisocyanate, cyclohexane dimethylene diisocyanate, norbornane diisocyanate, hexamethylene diisocyanate trimer, toluene diisocyanate dimer, TDI-trimethylolpropane adduct, toluene diisocyanate trimer, diphenylmethane diisocyanate trimer, isophorone diisocyanate trimer.
4. The pyrazole urea-based polyureaurethane of any of claims 1-3 wherein the pyrazole urea-based polyureaurethane is a random copolymer or a block copolymer.
5. The pyrazole urea-based polyureaurethane of claim 4 wherein the pyrazole urea-based polyureaurethane is thermoplastic or thermoset.
6. The pyrazole urea-based polyureaurethane of claim 5 wherein the pyrazole urea-based polyureaurethane has the structure:
7. process for the preparation of a pyrazole urea based polyureaurethane according to any of claims 1 to 6 comprising: reacting a pyrazole compound shown in a formula I, a sulfhydryl compound shown in a formula II and an isocyanate compound shown in a formula III;
R2-(SH)x
II
wherein R is1、R2X, y have the definitions as set forth in any one of claims 1-6.
8. The method of claim 7, wherein the polyureaurethane is thermoset and the method comprises:
scheme 1, S1) carrying out ultraviolet illumination reaction on a pyrazole compound shown in a formula I and a mercapto compound shown in a formula II in the presence of a photoinitiator to obtain a monomer A;
s2) carrying out ultraviolet illumination reaction on the pyrazole compound shown in the formula I and the mercapto compound shown in the formula II in the presence of a photoinitiator to obtain a monomer B;
s3) reacting the monomer A obtained in the step S1) and the monomer B obtained in the step S2) with an isocyanate compound shown in a formula III to obtain thermosetting polyureaurethane;
wherein the mercapto compounds represented by formula II used in steps S1) and S2) are the same or different, provided that at least one is substituted by more than three mercapto groups;
alternatively, the first and second electrodes may be,
scheme 2, reacting and curing the pyrazole compound shown in the formula I, the mercapto compound shown in the formula II and the isocyanate compound shown in the formula III; provided that the isocyanate-based compound of formula III contains at least three isocyanate groups.
9. The method for recycling a pyrazole urea-based polyureaurethane of any of claims 1 to 6 wherein the polyureaurethane is thermoset, comprising: and (3) crushing the thermosetting polyureaurethane, heating for decomposition, and carrying out hot press molding again to prepare the polyureaurethane.
10. Use of the pyrazole urea-based polyureaurethane according to any of claims 1 to 6 for the preparation of water-proofing, corrosion-proofing, medical appliances, abrasion-proofing and surface finishing materials.
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