CN114874129A - Preparation method of blocked isocyanate capable of being deblocked efficiently at low temperature - Google Patents
Preparation method of blocked isocyanate capable of being deblocked efficiently at low temperature Download PDFInfo
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- CN114874129A CN114874129A CN202210670653.5A CN202210670653A CN114874129A CN 114874129 A CN114874129 A CN 114874129A CN 202210670653 A CN202210670653 A CN 202210670653A CN 114874129 A CN114874129 A CN 114874129A
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- Prior art keywords
- isocyanate
- diisocyanate
- blocked
- hydroxyphthalimide
- blocked isocyanate
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- 239000012948 isocyanate Substances 0.000 title claims abstract description 87
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 5
- -1 N-hydroxyphthalimide compound Chemical class 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- DYQFCTCUULUMTQ-UHFFFAOYSA-N 1-isocyanatooctane Chemical compound CCCCCCCCN=C=O DYQFCTCUULUMTQ-UHFFFAOYSA-N 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000001294 propane Substances 0.000 claims description 4
- HACRKYQRZABURO-UHFFFAOYSA-N 2-phenylethyl isocyanate Chemical compound O=C=NCCC1=CC=CC=C1 HACRKYQRZABURO-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000005056 polyisocyanate Substances 0.000 claims description 3
- 229920001228 polyisocyanate Polymers 0.000 claims description 3
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 claims description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 2
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- OQURWGJAWSLGQG-UHFFFAOYSA-N 1-isocyanatopropane Chemical compound CCCN=C=O OQURWGJAWSLGQG-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- ABWDWYZSKJSXRD-UHFFFAOYSA-N N=C=O.N=C=O.C1CC=CC1 Chemical compound N=C=O.N=C=O.C1CC=CC1 ABWDWYZSKJSXRD-UHFFFAOYSA-N 0.000 claims description 2
- OMRDSWJXRLDPBB-UHFFFAOYSA-N N=C=O.N=C=O.C1CCCCC1 Chemical compound N=C=O.N=C=O.C1CCCCC1 OMRDSWJXRLDPBB-UHFFFAOYSA-N 0.000 claims description 2
- HDONYZHVZVCMLR-UHFFFAOYSA-N N=C=O.N=C=O.CC1CCCCC1 Chemical compound N=C=O.N=C=O.CC1CCCCC1 HDONYZHVZVCMLR-UHFFFAOYSA-N 0.000 claims description 2
- JGCWKVKYRNXTMD-UHFFFAOYSA-N bicyclo[2.2.1]heptane;isocyanic acid Chemical compound N=C=O.N=C=O.C1CC2CCC1C2 JGCWKVKYRNXTMD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 125000005442 diisocyanate group Chemical group 0.000 claims description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- HNHVTXYLRVGMHD-UHFFFAOYSA-N n-butyl isocyanate Chemical compound CCCCN=C=O HNHVTXYLRVGMHD-UHFFFAOYSA-N 0.000 claims description 2
- 125000005415 substituted alkoxy group Chemical group 0.000 claims description 2
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- 125000003107 substituted aryl group Chemical group 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- CFMZSMGAMPBRBE-UHFFFAOYSA-N 2-hydroxyisoindole-1,3-dione Chemical class C1=CC=C2C(=O)N(O)C(=O)C2=C1 CFMZSMGAMPBRBE-UHFFFAOYSA-N 0.000 abstract description 17
- 239000002981 blocking agent Substances 0.000 abstract description 14
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 150000002923 oximes Chemical class 0.000 abstract description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000004814 polyurethane Substances 0.000 description 8
- 229920002635 polyurethane Polymers 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 230000000903 blocking effect Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 230000000638 stimulation Effects 0.000 description 4
- HFZILYOGBNDBNK-UHFFFAOYSA-N 2-hydroxy-5-methylisoindole-1,3-dione Chemical compound CC1=CC=C2C(=O)N(O)C(=O)C2=C1 HFZILYOGBNDBNK-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- MKACMVMZUIQKNY-UHFFFAOYSA-N 2-hydroxy-5-nitroisoindole-1,3-dione Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)N(O)C(=O)C2=C1 MKACMVMZUIQKNY-UHFFFAOYSA-N 0.000 description 1
- RDSGFRPPTCEREC-UHFFFAOYSA-N 2-hydroxy-5-phenylisoindole-1,3-dione Chemical compound C1(=CC=CC=C1)C=1C=C2C(C(=O)N(C2=O)O)=CC=1 RDSGFRPPTCEREC-UHFFFAOYSA-N 0.000 description 1
- OUZLROHALHKYIY-UHFFFAOYSA-N 5-chloro-2-hydroxyisoindole-1,3-dione Chemical compound C1=C(Cl)C=C2C(=O)N(O)C(=O)C2=C1 OUZLROHALHKYIY-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 208000018459 dissociative disease Diseases 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003544 oxime group Chemical group 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a preparation method of blocked isocyanate capable of being deblocked at low temperature with high efficiency, which comprises the following preparation steps: reacting N-hydroxyphthalimide compounds with isocyanate at room temperature under the condition of no catalyst to obtain the enclosed isocyanate. The blocked isocyanate prepared by the invention has dynamic thermal reversibility and is stable at room temperature, can be spontaneously dissociated into isocyanate and N-hydroxyphthalimide (compounds) when placed at a temperature of more than or equal to 80 ℃, and when the temperature is increased to 120 ℃ to achieve dynamic balance, about 50 percent of the blocked isocyanate is dissociated into the isocyanate and the N-hydroxyphthalimide (compounds). The blocked isocyanate prepared by the invention can realize high-efficiency deblocking only at a low temperature, has deblocking rate far higher than that of the existing oxime blocking agent, and simultaneously has good light stability. The preparation method has mild conditions, does not need harsh conditions, has simple process and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of blocked isocyanate, and particularly relates to a preparation method of blocked isocyanate capable of being deblocked at low temperature with high efficiency.
Background
Isocyanate is a main material for synthesizing polyurethane, and the synthesized polyurethane product has flexible diversity and excellent performance, is made into products such as foam plastics, elastomers, fibers, coatings, adhesives, synthetic leather and the like, is widely used in the fields of production and life, medical health, national defense and the like, and is known as 'fifth plastic'.
Isocyanate (-NCO) has higher reaction activity due to the unique structure, can not only react with a compound containing active hydrogen, but also react to form a dimer or a trimer, so that the isocyanate compound has the problems of shorter storage period, higher requirement on use conditions, incapability of continuous production and the like. Aiming at the problem, the stable blocked isocyanate can be formed by blocking the isocyanate (-NCO) through a blocking agent, so that the isocyanate loses the capability of reacting with other groups under the storage condition, and the isocyanate is prevented from reacting with active hydrogen. When the isocyanate is used, the blocked isocyanate is subjected to reverse reaction under a proper condition to release blocking and release-NCO, so that the isocyanate can react with a target active hydrogen compound to form a polyurethane material. In recent years, blocked isocyanates have been widely used in the fields of paints, aqueous polyurethanes, and the like.
Currently, the common blocking agents in practical application are roughly classified into the following five types: 1) alcohol type sealing agents which have relatively high stability but need to be added with catalysts in the sealing process and need high temperature in deblocking; 2) phenolic blocking agents which have a relatively low deblocking temperature, but which mostly react with isocyanates at a relatively slow rate; 3) amines and amides, the deblocking temperature of such blocking agents being very high; 4) the oxime blocking agent has higher reaction activity of oxime groups and isocyanate groups than alcohols and phenols, so the deblocking temperature of the blocking agent is much lower than that of phenols and alcohols, the application range is wider, but the blocking agent has poor light stability and unsatisfactory deblocking efficiency (only 11% of oxime urethane returns to isocyanate and oxime when equilibrium is reached at 120 ℃ through temperature-variable nuclear magnetic monitoring); 5) caprolactam type blocking agents, which have an unsatisfactory deblocking efficiency, dissociate back to the starting material only about 10% at 120 ℃ at equilibrium. It follows that, although the isocyanate blocking agents mentioned above have been developed in great length, there are still a number of problems, for example: (a) in the sealing process, a catalyst is required to be added, organic metal or organic amine and the like are generally adopted as the catalyst, such as dibutyltin dilaurate, stannous octoate, triethylamine, triethylene imine and the like, and the catalyst has high toxicity and can bring certain limit to the application of the prepared polyurethane product; the deblocking temperature is high, i.e., high energy consumption is required, and the stability of the polyurethane material is also affected; (b) the deblocking efficiency is low, so that the resource is wasted; (c) the poor light stability may lead to discoloration of polyurethane materials prepared from blocked isocyanates over prolonged use. The above problems limit the application and popularization of polyurethane materials using isocyanate as a raw material to some extent.
Disclosure of Invention
Aiming at the problems of catalyst requirement during blocking, low deblocking efficiency, poor light stability and the like of the existing blocking agent, the invention provides a method for blocking isocyanate by using an N-hydroxyphthalimide compound as a blocking agent to prepare blocked isocyanate capable of being deblocked at low temperature and high efficiency, and particularly realizes blocking of isocyanate groups by utilizing the reaction of nitrogen hydroxyl in the N-hydroxyphthalimide compound and isocyanate groups (NCO).
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of blocked isocyanate capable of being deblocked efficiently at low temperature comprises the following steps: reacting an N-hydroxyphthalimide compound shown by the following general formula (II) with isocyanate under the condition of no catalyst to obtain closed isocyanate, wherein the structural general formula of the closed isocyanate is shown by the formula (I):
wherein R1 is independently selected from the group consisting of H, unsubstituted or substituted alkyl, unsubstituted or substituted aryl, unsubstituted or substituted alkoxy, unsubstituted or substituted heteroatom substituent; r2 is a residue obtained by removing an isocyanate group from a polyisocyanate comprising 1 or 2 or more selected from the group consisting of an aliphatic isocyanate, an alicyclic isocyanate, an araliphatic isocyanate, an aromatic isocyanate and a heterocyclic isocyanate; x is independently selected from an integer of 1-10.
Preferably, the molar weight ratio of the N-hydroxyphthalimide compound to the isocyanate is 1-3: 1.
preferably, the reaction is carried out at room temperature.
Preferably, the alkyl is a hydrocarbon group with 1-20 carbon atoms, and more preferably an alkyl with 1-12 carbon atoms and an aryl with 6-12 carbon atoms; particularly preferably a chain alkyl group having 1 to 12 carbon atoms and a cyclic alkyl group having 3 to 12 carbon atoms; examples of the linear alkyl group having 1 to 12 carbon atoms include linear or branched linear alkyl groups having 1 to 12 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, isononyl, decyl, undecyl and dodecyl.
Preferably, the aliphatic isocyanate is straight-chain aliphatic monoisocyanate or polyisocyanate with 3-10 carbon atoms; examples thereof include n-octyl isocyanate, n-butyl isocyanate, propyl isocyanate, hexamethylene diisocyanate, 1, 3-propane diisocyanate, 1, 2-propane diisocyanate, 1, 4-butane diisocyanate, 2, 3-butane diisocyanate, 1, 3-butane diisocyanate and 1, 6-hexane diisocyanate.
Preferably, the aromatic isocyanate is any one of 2-phenylethyl isocyanate, toluene diisocyanate, 4 ' -diphenyl diisocyanate, 1, 5-naphthalene diisocyanate, diphenylmethane diisocyanate, 4 ' -toluidine diisocyanate, and 4, 4 ' -diphenyl ether diisocyanate.
Preferably, the alicyclic isocyanate is any one of isophorone diisocyanate, 1, 3-cyclopentane diisocyanate, 1, 3-cyclopentene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, and norbornane diisocyanate.
Preferably, the araliphatic isocyanate is any one of xylylene diisocyanate and tetramethylxylylene diisocyanate.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention utilizes N-hydroxyphthalimide compounds as a blocking agent to react with isocyanate at room temperature without a catalyst to prepare the blocked isocyanate which can be efficiently deblocked at low temperature, namely N-hydroxyphthalimide amino ester compounds, the N-hydroxyphthalimide amino ester compounds have dynamic thermal reversibility and are stable at room temperature, can be spontaneously dissociated into isocyanate and N-hydroxyphthalimide (compounds) when being placed at the temperature of more than or equal to 80 ℃, and when the temperature is increased to 120 ℃ to reach balance, about 50 percent of the blocked isocyanate is dissociated into the isocyanate and the N-hydroxyphthalimide (compounds). The blocked isocyanate prepared by the invention can realize efficient deblocking at a lower temperature, the deblocking rate is far higher than that of the existing oxime blocking agent (the deblocking efficiency is 11%), and the blocked isocyanate also has good light stability.
(2) The preparation method has mild conditions, does not need harsh reaction conditions (such as high temperature, organic alkali, metal catalyst and the like), has simple process and has wide application prospect.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic diagram of a general structural formula of a blocked isocyanate prepared by the present invention;
FIG. 2 is a temperature-changing nuclear magnetic hydrogen spectrum of the blocked isocyanate prepared by the present invention under the condition of thermal stimulation in a thermal dissociation experiment;
FIG. 3 is a nuclear magnetic spectrum of each substance in a dynamic exchange experiment;
FIG. 4 is a nuclear magnetic hydrogen spectrum of the blocked isocyanate prepared by the present invention under the condition of thermal stimulation in a dynamic exchange experiment.
Detailed Description
In the following description, for purposes of explanation and not limitation, specific details are set forth, such as particular system structures, techniques, etc. in order to provide a thorough understanding of the embodiments of the invention. It will be apparent, however, to one skilled in the art that the present invention may be practiced in other embodiments that depart from these specific details.
Example 1
N-hydroxyphthalimide (163.0mg, 1.0mmol) was dissolved in 20mmL of anhydrous tetrahydrofuran, and 2-phenylethyl isocyanate (147.0mg, 1.0mmol) was added in an equivalent amount, and after stirring at room temperature for reaction for 3 hours, the solvent was distilled off under reduced pressure to obtain BI-1 as a white solid (308.0 g), in 99% yield.
And (3) characterization results: 1 H NMR(400MHz，CDCl 3 ，ppm)δ8.30(br，1H)，8.22-8.16(m，5H)，8.04-7.95(m，4H)，3.22-3.06(m，2H)，1.83-1.77(m，2H)；ESI-HRMS Calcd for C 17 H 14 N 2 O 4 Na[M+H] + ：333.0851，Found：333.0856，Error：0.5ppm.
example 2
N-hydroxyphthalimide (163.0mg, 1.0mmol) was dissolved in 20mmL of anhydrous tetrahydrofuran, equivalent N-octyl isocyanate (155.2mg, 1.0mmol) was added, the reaction was stirred at room temperature for 3 hours, and then the solvent was distilled off under reduced pressure to obtain BI-2 as a white solid (311.0 g), with a yield of 98%.
And (3) characterization results: 1 H NMR(500MHz，DMSO-d 6 ，ppm)δ8.29(br，1H)，7.96-7.92(m，4H)，3.11-3.08(m，2H)，1.49-1.47(m，2H)，1.29-1.27(m，10H)，0.88(t，J＝6.5Hz，3H)；ESI-HRMS Calcd for C 17 H 22 N 2 O 4 Na[M+H] + ：341.1477，Found：341.1479，Error：0.2ppm.
example 3
4-methyl-N-hydroxyphthalimide (179.0mg, 1.0mmol) was dissolved in 20mmL of anhydrous tetrahydrofuran, and after adding equivalent amount of N-octyl isocyanate (155.2mg, 1.0mmol), the reaction was stirred at room temperature for 3 hours, and then the solvent was distilled off under reduced pressure to obtain BI-3 as a white solid (325.0 g, 98% yield).
And (3) characterization results: 1 H NMR(500MHz，DMSO-d 6 ，ppm)δ8.32(br，1H)，7.83(d，J＝12 1H)，7.78(s，1H)，3.29(s，3H)，3.13-3.09(m，2H)，1.48-1.47(m，2H)，1.29-1.27(m，10H)，0.88(t，J＝6.5Hz，3H)；ESI-HRMS Calcd for C 17 H 24 N 2 O 4 Na[M+H] + 355.3898，Found：355.3894，Error：0.4ppm.
example 4
4-chloro-N-hydroxyphthalimide (199.5mg, 1.0mmol) was dissolved in 30mmL of anhydrous tetrahydrofuran, and after adding equivalent amount of N-octyl isocyanate (155.2mg, 1.0mmol), the reaction was stirred at room temperature for 3.5 hours, and the solvent was distilled off under reduced pressure to obtain BI-4 as a white solid, 321.5g, 97% yield.
And (3) characterization results: 1 H NMR(500MHz，DMSO-d 6 ，ppm)δ8.29(br，1H)，7.85(d，J＝12.0 1H)，7.79(s，1H)，3.14-3.10(m，2H)，1.52-1.49(m，2H)，1.33-1.29(m，10H)，0.89(t，J＝6.5Hz，3H)；ESI-HRMS Calcd for C 17 H 21 ClN 2 O 4 Na[M+H] + 375.1088，Found：375.1086，Error：0.2ppm.
example 5
4-phenyl-N-hydroxyphthalimide (241.1mg, 1.0mmol) was dissolved in 30mmL of anhydrous tetrahydrofuran, and after adding equivalent amount of N-octyl isocyanate (155.2mg, 1.0mmol), stirring at room temperature for reaction for 3.5 hours, the solvent was distilled off under reduced pressure to obtain BI-5 as a white solid (318.3 g), yield was 96%.
And (3) characterization results: 1 H NMR(500MHz，DMSO-d 6 ，ppm)δ8.29(br，1H)，7.85(d，J＝12.0 1H)，7.79(s，1H)，7.33-7.52(m,5H),3.14-3.10(m，2H)，1.52-1.49(m，2H)，1.33-1.29(m，10H)，0.89(t，J＝6.5Hz，3H)；ESI-HRMS Calcd for C 17 H 21 ClN 2 O 4 Na[M+H] + 417.1790，Found：417.1793，Error：0.3ppm.
example 6
4-Nitro-N-hydroxyphthalimide (210.0mg, 1.0mmol) was dissolved in 30mmL of anhydrous tetrahydrofuran, and after adding equivalent amount of N-octyl isocyanate (155.2mg, 1.0mmol), the reaction was stirred at room temperature for 3.5 hours, and the solvent was distilled off under reduced pressure to obtain BI-6 as a white solid, 315.1g, in 95% yield.
And (3) characterization results: 1 H NMR(500MHz，DMSO-d 6 ，ppm)δ8.29(br，1H)，8.12(d，J＝12.0 1H)，7.92(s，1H)，3.14-3.10(m，2H)，1.55-1.52(m，2H)，1.34-1.30(m，10H)，0.93(t，J＝6.5Hz，3H)；ESI-HRMS Calcd for C 17 H 21 ClN 2 O 4 Na[M+H] + 417.1790，Found：417.1793，Error：0.3ppm.
performance testing
(1) Thermal dissociation properties
The response behavior of the prepared closed isocyanate, namely the N-hydroxyphthalimido ester compound under the condition of thermal stimulation is monitored by an in-situ temperature-changing nuclear magnetic detection means.
Specifically, 0.1mmol of the blocked isocyanate BI-2 prepared in example 2(31.8mg) was added to 0.6mL of anhydrous deuterated dimethyl sulfoxide (DMSO-d) in a glove box 6 ) After sealing, the material is put into an in-situ temperature-changing nuclear magnetic monitoring instrument, the material is heated to 120 ℃ from room temperature through temperature programming, the material is balanced about 20min after each temperature rise, a nuclear magnetic hydrogen spectrum (1H NMR) is measured once before and after the temperature rise, the temperature rise is carried out at the next stage, and the experimental result is shown in figure 2.
From the results in FIG. 2, it is shown that when the temperature is increased to 80 ℃, the characteristic peak of isocyanate appears in the nuclear magnetic hydrogen spectrum, when the temperature is increased to 100 ℃, about 30% of the blocked isocyanate BI-2 is dissociated back to the raw material, and when the temperature is increased to 120 ℃ and stabilized, about 54% of the blocked isocyanate BI-2 is dissociated back to the raw material, i.e., N-hydroxyphthalimide and N-octyl isocyanate. Thus, the reaction between N-hydroxyphthalimide and isocyanate is a dynamic thermoreversible reaction, and the blocked isocyanate BI-2 can be dissociated into N-octyl isocyanate and N-hydroxyphthalimide (NHPI) under heating, wherein the dissociation reaction formula is shown as the following formula (i):
(2) dynamic exchange reaction experiment
The response behavior of the prepared blocked isocyanate under the condition of thermal stimulation is verified through a dynamic exchange experiment.
Specifically, with reference to FIGS. 3-4, 4-methyl-N-hydroxyphthalimide (0.5mmol,88.5mg) was combined with an equivalent of the blocked isocyanate BI-2(4ab, 0.5mmol, 159.0mg) prepared in example 2 in a glove box with 5mL of anhydrous DMSO-d 6 Heating to 100 deg.C under nitrogen protection, reacting for 1 hr, reacting at 50 deg.C for 24 hr, taking reaction solution, performing nuclear magnetic hydrogen spectrum test, and analyzing by 1H NMRThe composition of the reaction solution and the results of nuclear magnetic hydrogen spectroscopy are shown in FIG. 4, and from the results in FIG. 4, it is found that a part of N-hydroxyphthalimide (NHPI) is produced in the system, and the molar ratio of the N-hydroxyphthalimide to the 4-methyl-N-hydroxyphthalimide is close to 1: 1, and a new N-hydroxyphthalimido ester compound, BI-3, is produced, the specific reaction formula being shown in formula (ii) below, and the molar ratio of the new N-hydroxyphthalimido ester compound to the blocked isocyanate BI-2 is also close to 1: 1, the blocked isocyanate, namely the N-hydroxyphthalimido ester compound prepared by the invention can be confirmed to have dynamic exchange reaction under the heating condition.
The results of the variable temperature nuclear magnetic hydrogen spectrum are combined, the reaction of the N-hydroxyphthalimide (compound) and the isocyanate is fully proved to be a dynamic thermal reversible reaction, and the N-hydroxyphthalimide (compound) is further fully proved to be a high-efficiency isocyanate sealing agent.
(3) Light stability Properties
When the blocked isocyanate BI-1 prepared in example 1 was exposed to daylight for one month, the sample did not show any yellowing or any signs, indicating that the blocked isocyanate prepared according to the invention has good light stability.
The present invention is not limited to the above-described embodiments, and those skilled in the art will be able to make various modifications without creative efforts from the above-described conception, and fall within the scope of the present invention.
Claims (5)
1. A preparation method of blocked isocyanate capable of being deblocked efficiently at low temperature is characterized by comprising the following steps: reacting an N-hydroxyphthalimide compound shown in the following general formula (II) with isocyanate under the condition of no catalyst to obtain a closed isocyanate, wherein the structural formula of the closed isocyanate is shown in a formula I:
wherein R1 is independently selected from the group consisting of H, unsubstituted or substituted alkyl, unsubstituted or substituted aryl, unsubstituted or substituted alkoxy, unsubstituted or substituted heteroatom substituent; r2 is a residue obtained by removing an isocyanate group from a polyisocyanate comprising 1 or 2 or more selected from the group consisting of an aliphatic isocyanate, an alicyclic isocyanate, an araliphatic isocyanate, an aromatic isocyanate and a heterocyclic isocyanate; x is independently selected from an integer of 1-10.
2. The method for producing a blocked isocyanate according to claim 1, wherein the molar ratio of the N-hydroxyphthalimide compound to the isocyanate is 1 to 3: 1.
3. the method for preparing a blocked isocyanate according to claim 1, wherein the alkyl group is a hydrocarbon group having 1 to 20 carbon atoms; the heteroatom substituent is any one of halogen, amino, hydroxyl or sulfydryl.
4. The method for producing a blocked isocyanate according to claim 1, wherein the aliphatic isocyanate is any one of n-octyl isocyanate, n-butyl isocyanate, propyl isocyanate, hexamethylene diisocyanate, 1, 3-propane diisocyanate, 1, 2-propane diisocyanate, 1, 4-butane diisocyanate, 2, 3-butane diisocyanate, 1, 3-butane diisocyanate, and 1, 6-hexane diisocyanate; the aromatic isocyanate is any one of 2-phenylethyl isocyanate, toluene diisocyanate, 4 ' -diphenyl diisocyanate, 1, 5-naphthalene diisocyanate, diphenylmethane diisocyanate, 4 ' -toluidine diisocyanate and 4, 4 ' -diphenyl ether diisocyanate; the alicyclic isocyanate is any one of isophorone diisocyanate, 1, 3-cyclopentane diisocyanate, 1, 3-cyclopentene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate and norbornane diisocyanate; the aromatic aliphatic isocyanate is any one of xylylene diisocyanate and tetramethyl xylylene diisocyanate.
5. Process for the preparation of blocked isocyanates according to claim 1, characterized in that the reaction is carried out at room temperature.
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