CN114835598A - Steric hindrance type di-secondary amine compound, preparation method and polyurea resin - Google Patents
Steric hindrance type di-secondary amine compound, preparation method and polyurea resin Download PDFInfo
- Publication number
- CN114835598A CN114835598A CN202110689262.3A CN202110689262A CN114835598A CN 114835598 A CN114835598 A CN 114835598A CN 202110689262 A CN202110689262 A CN 202110689262A CN 114835598 A CN114835598 A CN 114835598A
- Authority
- CN
- China
- Prior art keywords
- secondary amine
- compound
- amine compound
- sterically hindered
- alkyl group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920002396 Polyurea Polymers 0.000 title claims abstract description 23
- 229920005989 resin Polymers 0.000 title claims abstract description 23
- 239000011347 resin Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims abstract description 43
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 16
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 8
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 22
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 9
- 125000004185 ester group Chemical group 0.000 claims description 7
- 125000001033 ether group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000007858 starting material Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 12
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 abstract description 7
- 239000000853 adhesive Substances 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 3
- 230000001737 promoting effect Effects 0.000 abstract description 3
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 48
- 238000006243 chemical reaction Methods 0.000 description 42
- -1 maleic acid ester Chemical class 0.000 description 19
- 239000003054 catalyst Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 150000002081 enamines Chemical class 0.000 description 14
- ZFYDXGYZOCZQLB-UHFFFAOYSA-L C(S(=O)(=O)[O-])(Cl)(Cl)Cl.C(S(=O)(=O)[O-])(Cl)(Cl)Cl.[Zn+2] Chemical compound C(S(=O)(=O)[O-])(Cl)(Cl)Cl.C(S(=O)(=O)[O-])(Cl)(Cl)Cl.[Zn+2] ZFYDXGYZOCZQLB-UHFFFAOYSA-L 0.000 description 10
- 229940126062 Compound A Drugs 0.000 description 9
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000004440 column chromatography Methods 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- VYGSFTVYZHNGBU-UHFFFAOYSA-N trichloromethanesulfonic acid Chemical compound OS(=O)(=O)C(Cl)(Cl)Cl VYGSFTVYZHNGBU-UHFFFAOYSA-N 0.000 description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 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 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229910020366 ClO 4 Inorganic materials 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- 229920000805 Polyaspartic acid Polymers 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- KLRHPHDUDFIRKB-UHFFFAOYSA-M indium(i) bromide Chemical compound [Br-].[In+] KLRHPHDUDFIRKB-UHFFFAOYSA-M 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 108010064470 polyaspartate Proteins 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000000447 dimerizing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002952 polymeric resin Substances 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
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C229/30—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and unsaturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
- C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/16—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions not involving the amino or carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
- C07C229/10—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
- C07C229/14—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of carbon skeletons containing rings
-
- 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3234—Polyamines cycloaliphatic
-
- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/675—Low-molecular-weight compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/02—Polyureas
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- 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
- C08G2150/00—Compositions for coatings
Abstract
The invention relates to synthesis of compounds, in particular to a steric type di-secondary amine compound, a preparation method and a polyurea resin. The preparation raw materials of the compound comprise a dimeric beta-dicarbonyl compound and a primary amine. The invention provides a steric hindrance type di-secondary amine compound, wherein R' directly connected with secondary amine is controlled to be branched alkane or cyclic alkaneHydrocarbon, and the like, and controlling R on adjacent carbon atoms 1 The carbon atom number of the compound can promote the synthesis of the compound, improve the yield, effectively improve the curing time of polyisocyanate, bring good comprehensive properties such as smooth surface gloss and adhesive force and the like, and meet various application requirements. The inventors have found that the structure in which a β -ester group is linked to a secondary amine group in a compound is more advantageous in promoting the extension of the curing time when it is reacted with a polyisocyanate to adjust workability.
Description
Technical Field
The invention relates to synthesis of compounds, in particular to a steric type di-secondary amine compound, a preparation method and a polyurea resin.
Background
The polyurea resin is a polymer resin obtained by addition condensation of a substance containing isocyanate-NCO and a substance containing amino, has the characteristics of excellent corrosion resistance, water resistance, wear resistance and the like, can be rapidly cured at room temperature or low temperature without a catalyst, does not contain VOC and the like, and has wide application.
The rapid curing of the polyurea resin also brings problems of poor yellowing resistance, small adhesive force of a base material and the like, at present, the curing time of the polyurea resin is slowed down mainly by third-generation polyurea such as polyaspartic acid ester, wherein the polyaspartic acid ester is mainly prepared from diamine and maleic acid ester, the change of the structure and the change of the curing time are limited, the construction time can be prolonged by only ten minutes at most, and the requirements of construction and application are difficult to meet.
Therefore, it is necessary to provide a new compound and a preparation method thereof, which are used as raw materials of polyurea resin, and can adjust the curing speed while controlling the comprehensive performance so as to meet the construction requirements.
Disclosure of Invention
In order to solve the above problems, the present invention provides, in a first aspect, a sterically hindered type di-secondary amine compound having a structural formula represented by formula (1) or formula (2):
r is a cyclic alkyl group, a chain alkyl group or a chain ether group; r 1 Is a cyclic alkyl or a chain alkyl; r' is a branched alkyl or cyclic alkyl.
In a preferred embodiment of the present invention, the carbon atom of R is less than 20.
As a preferable technical scheme of the invention, R is 1 Is less than 20.
In a preferred embodiment of the present invention, the number of carbon atoms of R' is less than 20.
In a preferred embodiment of the present invention, the number of carbon atoms of R' is less than 12.
In a preferred embodiment of the present invention, when R' is a cyclic alkyl group, a hydrogen atom on the cyclic alkyl group is substituted with an alkyl group, an alkoxy group or an ester group.
In a preferred embodiment of the present invention, when R 'is a branched alkyl group, R' includes a tertiary carbon.
As a preferable technical scheme of the invention, the preparation raw materials of the compound comprise a dimeric beta-dicarbonyl compound and a primary amine, and the molar ratio is 1: (2-2.5);
the structural formula of the dimeric beta-dicarbonyl compound is shown as a formula (3):
r is a cyclic alkyl group, a chain alkyl group or a chain ether group; r 1 Is a cyclic alkyl or a chain alkyl;
the structural formula of the primary amine is shown as the formula (4):
r' is a branched alkyl or cyclic alkyl.
In a second aspect, the present invention provides a process for the preparation of a sterically hindered di-secondary amine compound as described above, comprising:
the dimeric beta-dicarbonyl compound reacts with primary amine, and then is extracted or hydrogenated and reduced to prepare the dimeric beta-dicarbonyl compound.
In a second aspect, the invention provides a polyurea resin comprising the sterically hindered di-secondary amine compound and a polyisocyanate.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention provides a steric hindrance type di-secondary amine compound, wherein R' directly connected with secondary amine is controlled to adopt substituent with larger steric hindrance such as branched alkane or cyclic alkane, and R on adjacent carbon atoms is controlled 1 The carbon atom number of the compound can promote the synthesis of the compound, improve the yield, effectively improve the curing time of polyisocyanate, bring good comprehensive properties such as smooth surface gloss and adhesive force and the like, and meet various application requirements.
(3) And the inventors found that the structure in which a beta-ester group is linked to a secondary amine group in a compound, that is, the beta-position of a carbonyl group is linked to an ester group in the preparation raw material, is more advantageous in promoting the extension of the curing time when it reacts with a polyisocyanate due to the effect of intramolecular/intermolecular hydrogen bonding than when it does not link an ester group or the ester group and the carbonyl group are located far apart, thereby adjusting workability.
(4) Furthermore, because of the greater steric hindrance of R' at both ends of the secondary amine group, and R on the ortho-carbon 1 The function of the substituent groups is that molecular chains are mutually hindered and are difficult to extend and cross in the spraying process of the polyurea resin, the problems of glossiness, adhesive force and the like after curing are also influenced, and the length of R between two ester groups of the compound is controlled, and R' and R are controlled 1 The chain length of the coating is favorable for forming a uniform coating in the spraying and curing processes, and the comprehensive performance of the coating is improved.
(5) The inventor finds that the carbonyl compound and the amino are generally synthesized under the catalysis of the catalyst under the conditions of heating and solvent, the use of a large amount of solvent can cause cost increase and environmental pollution, the yield is difficult to reach more than 90 percent, and in order to improve the yield, excessive primary amine is generally required to be added, which can cause that the subsequent primary amine and the catalyst are difficult to completely remove, the subsequent curing performance is influenced, even partial gel is generated, or the adhesion, luster and smoothness of a coating film are influenced, but the invention not only is beneficial to promoting the reaction activity and the reaction rate at normal temperature by controlling the molar quantity of the primary amine and using a proper catalyst, such as a metal complex catalyst, in particular a metal halogenated carboxylic acid or halogenated sulfonic acid catalyst, but also is beneficial to acting with the unreacted primary amine and being jointly extracted into a water phase in the subsequent treatment process, the residue of primary amine and catalyst in the compound is reduced, and the influence on the subsequent curing performance is avoided.
(6) In addition, the enamine compound represented by the formula (1) obtained from a ketone and an amine according to the present invention may be directly used in a polyurea resin, and may also be reduced by hydrogenation to obtain a secondary amine compound represented by the formula (2) as a raw material of the polyurea resin, and may provide a coating film having a suitable curing time and overall properties, such as adhesion, gloss, tensile strength, etc.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. 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. In case of conflict, the present specification, including definitions, will control.
The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "either" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.
The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.
In a first aspect, the present invention provides a sterically hindered di-secondary amine compound having a structural formula represented by formula (1) or formula (2):
r is a cyclic alkyl group, a chain alkyl group or a chain ether group; r 1 Is a cyclic alkyl or a chain alkyl; r' is a branched alkyl or cyclic alkyl.
In one embodiment, R of the present invention has less than 20 carbon atoms, more preferably, R has at least 2 carbon atoms, and can be, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, such as 2-19, 2-15, 2-12, and the like, and examples of R include chain alkyl, such as- (CH) alkyl 2 ) n N is 2-19; chain ether radicals, e.g., - (XO) m X, X is C1-C4 straight-chain alkyl, such as methyl, ethyl, propyl, n-butyl, m is 1-18, cyclic alkyl, such as
(R 4 Is H or methyl),
In one embodiment, R is as defined herein 1 Less than 20 carbon atoms, and there may be mentioned 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, such as R 1 Has less than 10 carbon atoms, e.g. R 1 Has less than 6 carbon atoms as R 1 Examples of (2) include cyclic alkyl groups such as cyclopropane, cyclobutane and cyclopentane, and chain alkyl groups such as isopropyl iPr, n-butyl nBu, methyl Me, tert-butyl tBu, isopentyl, neopentyl and sec-butyl.
In one embodiment, R ' of the present invention has less than 20 carbon atoms, more preferably, R ' has less than 12 carbon atoms, and more preferably, R ' has 3 or more carbon atoms.
In one embodiment, when R 'is a cyclic alkyl group according to the present invention, a hydrogen atom on the cyclic alkyl group is substituted by an alkyl group, an alkoxy group or an ester group, preferably, when R' is a cyclic alkyl group, a hydrogen atom on the cyclic alkyl group is substituted by a C1 to C3 alkyl group or a C1 to C3 alkoxy group, and the number of the hydrogen atoms to be substituted is not particularly limited, and may be substituted by 1, 2, 3, 4, or the like, and is not particularly limited, and may be substituted by various substituents.
In one embodiment, when R 'is a branched alkyl group, R' includes a tertiary carbon.
As examples of R', there may be mentioned branched alkyl radicals, such as the isopropyl iPr, tert-butyl tBu, isopentyl, neopentyl, sec-butyl, cyclic alkyl radicals, such as
In one embodiment, the starting materials for the preparation of the compounds of the present invention comprise a dimeric β -dicarbonyl compound and a primary amine in a molar ratio of 1: (2 to 2.5) examples of the solvent include, 1: 2. 1: 2.05, 1: 2.1, 1: 2.15, 1: 2.2, 1: 2.25, 1: 2.3, 1: 2.35, 1: 2.4, 1: 2.45, 1: 2.5; preferably 1: (2.05-2.2).
In one embodiment, the dimeric β -dicarbonyl compound of the present invention has a structural formula as shown in formula (3):
r is a cyclic alkyl group, a chain alkyl group or a chain ether group; r 1 Is a cyclic alkyl group or a chain alkyl group.
In one embodiment, the primary amines of the present invention have the formula (4):
r' is a branched alkyl or cyclic alkyl.
More preferably, the starting materials for the preparation of the compounds of the present invention also include catalysts, examples of which include, but are not limited to, metal complex catalysts, the metal being Fe, Mg, Zn, Bi, Sc, Yb, In, Na, Ce, Cu, etc., and there may be mentioned halogenated carboxylic or halogenated sulfonic acid catalysts of the metal, such as trifluoromethanesulfonic, perchloric, trichloromethanesulfonic acid catalysts of the metal, such as Fe (OTf) 3 、Mg(ClO 4 ) 2 、Bi(OTf) 3 、Sc(OTf) 3 、Yb(OTf) 3 、Zn(ClO 4 ) 2 ·6H 2 O; or metal acetic acid, nitric acid, halogenated catalysts, e.g. NaHSO 4 、InBr 3 、CoCl 2 ·6H 2 O、CeCl 3 ·7H 2 O、Cu(NO 3 ) 2 ·3H 2 O、Zn(OAc) 2 ·2H 2 O; or boron trifluoride catalysts, e.g. BF 3 ·OEt 2 。
Further preferably, the molar ratio of the catalyst to the dimeric beta-dicarbonyl compound is (0.005-0.02): 1, there may be mentioned, for example, 0.005: 1. 0.007: 1. 0.01: 1. 0.012: 1. 0.015: 1. 0.017 by weight: 1. 0.02: 1.
in a second aspect, the present invention provides a process for the preparation of a sterically hindered di-secondary amine compound as described above, comprising:
the dimeric beta-dicarbonyl compound reacts with primary amine, and then is extracted or hydrogenated and reduced to prepare the dimeric beta-dicarbonyl compound.
The di-secondary amine compound of the structural formula (1) is directly prepared by dimerizing a beta-dicarbonyl compound and primary amine. In one embodiment, the method of making the sterically hindered di-secondary amine compound of the present invention comprises: the dimeric beta-dicarbonyl compound reacts with primary amine, and then is extracted and dried to prepare the dimeric beta-dicarbonyl compound. The reaction can be obtained at normal temperature (20-25 ℃), the end point of the reaction can be monitored and determined by TLC, and the reaction is terminated when the peak of TLC is not changed.
The solvent to be extracted in the present invention is an organic solvent and water, and examples of the organic solvent include, but are not limited to, esters, ethers, halogenated alkanes, preferably esters, and there may be exemplified ethyl acetate, methyl acetate, butyl acetate, methyl propionate and the like. In order to promote the reaction of the dimeric beta-dicarbonyl compound, excess primary amine is generally adopted, and the primary amine has good solubility in both organic solvent and water, so that the removal of the primary amine is influenced.
The di-secondary amine compound of the structural formula (2) can be obtained by hydrogenation reduction of the di-secondary amine compound of the structural formula (1). The present invention is not particularly limited to hydrogenation reduction, and is a process well known in the art, and in one embodiment, the hydrogenation reduction according to the present invention comprises: dissolving the di-sec-amine compound of the structural formula (1) in a solvent, cooling to 0 ℃ or below, adding a reducing agent for reaction, extracting, washing and drying to obtain the di-sec-amine compound of the structural formula (2).
The reducing agent is not specifically defined in the present invention, and NaBH may be mentioned 3 CN，NaBH 4 ，NaBH(Ac) 3 In one embodiment, the molar ratio of the reducing agent of the present invention to the di-secondary amine compound of formula (1) is (8-15): 1, there may be mentioned, 8: 1. 9: 1. 10: 1. 11: 1. 12: 1. 13: 1. 14: 1. 15: 1. the solvent for the hydrogenation reduction of the present invention is a solvent well known in the art, and is not particularly limited, and methanol, ethanol, dichloromethane, tetrahydrofuran may be mentioned.
In order to further improve the purity of the di-secondary amine compounds of structural formulas (1) and (2), column chromatography purification can be performed, and column chromatography and the like are performed by using silica gel (200-300 meshes) and a petroleum ether/ethyl acetate mobile phase, and the like, and the purification is not particularly limited.
The third aspect of the present invention provides a polyurea resin comprising the sterically hindered di-secondary amine compound and a polyisocyanate. As examples of the polyisocyanate, there may be mentioned isophorone diisocyanate, lysine diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, HDI trimer, MDI trimer and the like.
Examples
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
Examples 1 to 7 provide enamine-type secondary diamines
Example 1
This example provides a sterically hindered di-secondary amine compound A 1 The structural formula of the compound is shown as follows:
R 1 ＝iPr，R＝-CH 2 CH 2 -，
the preparation raw materials of the steric hindrance type secondary amine compound comprise a binary beta-dicarbonyl compound, primary amine and ferric trifluoromethanesulfonate, wherein the molar ratio of the binary beta-dicarbonyl compound to the primary amine to the ferric trifluoromethanesulfonate is 1: 2.1: 0.01; the structural formula of the binary beta-dicarbonyl compound is as follows:
the primary amine has the structural formula:
this example also provides a method for preparing a sterically hindered di-secondary amine compound, comprising: 0.01 equivalent of ferric trifluoromethanesulfonate is added into a mixed reaction system of primary amine (2.1 equivalents) and a binary beta-dicarbonyl compound (1 equivalent) to react at room temperature. TLC monitors the reaction progress, when the reaction is complete, ethyl acetate and water are used for washing out the catalyst, drying and removing water are carried out, and ethyl acetate is removed under reduced pressure, so that the corresponding product is obtained. The obtained enamine type secondary diamine compound can be directly used as polyurea resin, and the yield is 96.2%.
Example 2
This example provides a sterically hindered di-secondary amine compound A 2 The structural formula of the compound is shown as follows:
R 1 ＝nBu，R＝-CH 2 CH 2 O CH 2 CH 2 -，
the preparation raw materials of the steric hindrance type secondary amine compound comprise a binary beta-dicarbonyl compound, primary amine and zinc trichloromethane sulfonate with the molar ratio of 1: 2.1: 0.01; the structural formula of the binary beta-dicarbonyl compound is as follows:
the primary amine has the structural formula:
this example also provides a method for preparing a sterically hindered di-secondary amine compound, comprising: 0.01 equivalent of zinc trichloromethane sulfonate is added into a mixed reaction system of primary amine (2.1 equivalents) and binary beta-dicarbonyl compound (1 equivalent) for reaction at room temperature. TLC monitors the reaction progress, when the reaction is complete, ethyl acetate and water are used for phase washing to remove the catalyst, and then the ethyl acetate is removed by drying and removing water and reducing pressure to obtain the corresponding product. The obtained enamine type secondary diamine compound can be directly used as polyurea resin, and the yield is 95.3%.
Example 3
This example provides a sterically hindered di-secondary amine compound A 3 The structural formula of the compound is shown as follows:
R 1 ＝Me，R＝-CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 -，
the preparation raw materials of the steric hindrance type secondary amine compound comprise a binary beta-dicarbonyl compound, primary amine and zinc trichloromethane sulfonate with the molar ratio of 1: 2.1: 0.01; the structural formula of the binary beta-dicarbonyl compound is as follows:
the primary amine has the structural formula:
this example also provides a method for preparing a sterically hindered di-secondary amine compound, comprising: 0.01 equivalent of zinc trichloromethane sulfonate is added into a mixed reaction system of primary amine (2.1 equivalents) and binary beta-dicarbonyl compound (1 equivalent) for reaction at room temperature. TLC monitors the reaction progress, when the reaction is complete, ethyl acetate and water are used for phase washing to remove the catalyst, and then the ethyl acetate is removed by drying and removing water and reducing pressure to obtain the corresponding product. The obtained enamine type secondary diamine compound can be directly used as polyurea resin, and the yield is 95.7%.
Example 4
This example provides a sterically hindered di-secondary amine compound A 4 The structural formula of the compound is shown as follows:
R 1 ＝iPr，
the preparation raw materials of the steric hindrance type secondary amine compound comprise a binary beta-dicarbonyl compound, primary amine and zinc trichloromethane sulfonate with the molar ratio of 1: 2.1: 0.01; the structural formula of the binary beta-dicarbonyl compound is as follows:
the primary amine has the structural formula:
this example also provides a method for preparing a sterically hindered di-secondary amine compound, comprising: 0.01 equivalent of zinc trichloromethane sulfonate is added into a mixed reaction system of primary amine (2.1 equivalents) and binary beta-dicarbonyl compound (1 equivalent) for reaction at room temperature. TLC monitors the reaction progress, when the reaction is complete, ethyl acetate and water are used for phase washing to remove the catalyst, and then the ethyl acetate is removed by drying and removing water and reducing pressure to obtain the corresponding product. The obtained enamine type secondary diamine compound can be directly used as polyurea resin, and the yield is 92.8%.
Example 5
This example provides a sterically hindered di-secondary amine compound A 5 The structural formula of the compound is shown as follows:
R 1 ＝iPr，
R’＝tBu。
the preparation raw materials of the steric hindrance type secondary amine compound comprise a binary beta-dicarbonyl compound, primary amine and zinc trichloromethane sulfonate with the molar ratio of 1: 2.1: 0.01; the structural formula of the binary beta-dicarbonyl compound is as follows:
the primary amine has the structural formula:
this example also provides a method for preparing a sterically hindered di-secondary amine compound, comprising: 0.01 equivalent of zinc trichloromethane sulfonate is added into a mixed reaction system of primary amine (2.1 equivalents) and binary beta-dicarbonyl compound (1 equivalent) for reaction at room temperature. TLC monitors the reaction progress, when the reaction is complete, ethyl acetate and water are used for phase washing to remove the catalyst, and then the ethyl acetate is removed by drying and removing water and reducing pressure to obtain the corresponding product. The obtained enamine type secondary diamine compound can be directly used as polyurea resin, and the yield is 91.6%.
Example 6
This example provides a sterically hindered di-secondary amine compound A 6 The structural formula of the compound is shown as follows:
R 1 ＝iPr，R＝-(CH 2 ) 6 -，
the preparation raw materials of the steric hindrance type secondary amine compound comprise a binary beta-dicarbonyl compound, primary amine and zinc trichloromethane sulfonate with the molar ratio of 1: 2.1: 0.01; the structural formula of the binary beta-dicarbonyl compound is as follows:
the primary amine has the structural formula:
this example also provides a method for preparing a sterically hindered di-secondary amine compound, comprising: 0.01 equivalent of zinc trichloromethane sulfonate is added into a mixed reaction system of primary amine (2.1 equivalents) and binary beta-dicarbonyl compound (1 equivalent) for reaction at room temperature. TLC monitors the reaction progress, when the reaction is complete, ethyl acetate and water are used for phase washing to remove the catalyst, and then the ethyl acetate is removed by drying and removing water and reducing pressure to obtain the corresponding product. The obtained enamine type secondary diamine compound can be directly used as polyurea resin, and the yield is 90.6%.
Example 7
This example provides a sterically hindered di-secondary amine compound A 7 The structural formula of the compound is shown as follows:
R 1 ＝tBu，R＝-(CH 2 ) 10 -，
the preparation raw materials of the steric hindrance type secondary amine compound comprise a binary beta-dicarbonyl compound, primary amine and ferric trichloromethane sulfonate with the molar ratio of 1: 2.1: 0.01; the structural formula of the binary beta-dicarbonyl compound is as follows:
the primary amine has the structural formula:
this example also provides a method for preparing a sterically hindered di-secondary amine compound, comprising: 0.01 equivalent of ferric trichloromethane sulfonate is added into a mixed reaction system of primary diamine B7(1 equivalent) and beta-dicarbonyl compound A7(2.1 equivalents) for reaction at room temperature. TLC monitors the reaction progress, when the reaction is complete, ethyl acetate and water are used for phase washing to remove the catalyst, and then the ethyl acetate is removed by drying and removing water and reducing pressure to obtain the corresponding product. The obtained enamine type secondary diamine compound can be directly used as polyurea resin, and the yield is 95.6%.
Examples 8 to 9 provide enamine-reduced secondary amines
Example 8
This example provides a hindered di-secondary amine compound B of enamine reduction type 7 The structural formula of the compound is shown as follows:
R 1 ＝tBu，R＝-(CH 2 ) 10 -，
this example also provides a method for preparing a sterically hindered di-secondary amine compound, comprising: mixing enamine type secondary diamine compound A 7 (1 eq.) in dry CH 2 Cl 2 Adding NaBH into the solution (20mL), cooling to 0 ℃, and slowly adding NaBH in batches 4 (10 equiv.) to NaBH 4 The addition was complete and the reaction was continued at this temperature for one hour. After warming to room temperature, TLC monitored the end of the reaction, and when the reaction was complete, the excess NaBH was quenched with saturated ammonium chloride solution 4 . Reaction(s) ofLiquid CH 2 Cl 2 Extraction (3X 20mL) was carried out three times, and the organic phases were combined, washed with saturated brine and dried over anhydrous sodium sulfate. And distilling under reduced pressure to remove the solvent to obtain a crude product of enamine reduction type secondary diamine compound. Further purification was achieved by column chromatography in 85% yield.
Example 9
This example provides a hindered di-secondary amine compound B of enamine reduction type 5 The structural formula of the compound is shown as follows:
R 1 ＝iPr，
R’＝tBu。
this example also provides a method for preparing a sterically hindered di-secondary amine compound, comprising: mixing enamine type secondary diamine compound A 5 (1 eq.) in dry CH 2 Cl 2 Adding NaBH into the solution (20mL), cooling to 0 ℃, and slowly adding NaBH in batches 4 (10 equiv.) to NaBH 4 The addition was complete and the reaction was continued at this temperature for one hour. After warming to room temperature, TLC monitored the end of the reaction, and when the reaction was complete, the excess NaBH was quenched with saturated ammonium chloride solution 4 . CH for reaction solution 2 Cl 2 Extraction (3X 20mL) was carried out three times, and the organic phases were combined, washed with saturated brine and dried over anhydrous sodium sulfate. And distilling under reduced pressure to remove the solvent to obtain a crude product of enamine reduction type secondary diamine compound. Further purification was achieved by column chromatography in 89% yield.
Evaluation of Performance
The molar ratio of the secondary amine groups to the isocyanate groups of the aspartic resin and HDI provided in the examples was 1: 1.1 mixing, coating on PC-ABS, curing, gloss according to GB/T9754-1988, adhesion (test by the pull-open method) according to GB/T5210-2006, pencil hardness according to GB/T6739-1986 and gel time according to GB/T23446-2009, the results of which are given in Table 1.
Table 1 performance characterization test
From the test results, the steric hindrance type di-secondary amine compound provided by the invention has high yield, can be used for preparing polyurea resin, and the obtained coating film has good curing performance, smooth surface, no holes or bubbles and good comprehensive performance.
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (10)
1. A steric hindrance type di-secondary amine compound, which is characterized in that the structural formula of the compound is shown as a formula (1) or a formula (2):
r is a cyclic alkyl group, a chain alkyl group or a chain ether group; r 1 Is a cyclic alkyl or a chain alkyl; r' is a branched alkyl or cyclic alkyl.
2. Sterically hindered di-secondary amine compound according to claim 1, characterized in that R has less than 20 carbon atoms.
3. Sterically hindered di-secondary amine compound according to claim 1, characterized in that R 1 Is less than 20.
4. Sterically hindered di-secondary amine compound according to claim 1, characterized in that the number of carbon atoms of R' is less than 20.
5. Sterically hindered di-secondary amine compound according to claim 4, characterized in that the number of carbon atoms of R' is less than 12.
6. A sterically hindered di-secondary amine compound according to claim 1, characterized in that when R' is a cyclic alkyl group, the hydrogen atom of the cyclic alkyl group is substituted by an alkyl group, an alkoxy group or an ester group.
7. A sterically hindered di-secondary amine compound according to claim 1, characterized in that when R 'is a branched alkyl group, a tertiary carbon is included in R'.
8. A sterically hindered di-secondary amine compound according to any of claims 1 to 7, characterized in that the starting materials for the preparation of said compound comprise a dimeric β -dicarbonyl compound and a primary amine in a molar ratio of 1: (2-2.5);
the structural formula of the dimeric beta-dicarbonyl compound is shown as a formula (3):
r is a cyclic alkyl group, a chain alkyl group or a chain ether group; r 1 Is a cyclic alkyl or a chain alkyl;
the structural formula of the primary amine is shown as a formula (4):
r' is a branched alkyl or cyclic alkyl.
9. A process for the preparation of a sterically hindered di-secondary amine compound according to claim 8, characterized in that it comprises:
the dimeric beta-dicarbonyl compound reacts with primary amine, and then is extracted or hydrogenated and reduced to prepare the dimeric beta-dicarbonyl compound.
10. A polyurea resin comprising the sterically hindered di-secondary amine compound according to any one of claims 1 to 8 and a polyisocyanate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110689262.3A CN114835598A (en) | 2021-06-22 | 2021-06-22 | Steric hindrance type di-secondary amine compound, preparation method and polyurea resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110689262.3A CN114835598A (en) | 2021-06-22 | 2021-06-22 | Steric hindrance type di-secondary amine compound, preparation method and polyurea resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114835598A true CN114835598A (en) | 2022-08-02 |
Family
ID=82561470
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110689262.3A Pending CN114835598A (en) | 2021-06-22 | 2021-06-22 | Steric hindrance type di-secondary amine compound, preparation method and polyurea resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114835598A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0457128A2 (en) * | 1990-05-15 | 1991-11-21 | Miles Inc. | Novel amine-terminated compounds |
| US20040220369A1 (en) * | 2003-05-02 | 2004-11-04 | Chen Harry (Zhong-Xiao) | Methods for preparing and applying polyurea elastomers and coatings |
| WO2006066031A1 (en) * | 2004-12-15 | 2006-06-22 | E. I. Du Pont De Nemours And Company | Durable coating compositions containing novel aspartic amine compounds |
| CN108586272A (en) * | 2018-06-28 | 2018-09-28 | 浙江昌明药业有限公司 | A kind of preparation method of 3- aminopropanols or 3- alanine derivatives |
| CN108779237A (en) * | 2016-04-29 | 2018-11-09 | 汉高股份有限及两合公司 | Amine functional polymer and the method for preparing this polymer |
| CN110396053A (en) * | 2019-07-30 | 2019-11-01 | 深圳市前海博扬研究院有限公司 | Asparagus fern polyureas performed polymer and preparation method and a kind of coating |
| CN111620789A (en) * | 2020-06-12 | 2020-09-04 | 深圳市前海博扬研究院有限公司 | Preparation method of aspartate resin |
| CN112334553A (en) * | 2018-07-30 | 2021-02-05 | Sika技术股份公司 | Polyurethane composition with long processing time and high strength |
| CN112920068A (en) * | 2021-01-26 | 2021-06-08 | 深圳飞扬兴业科技有限公司 | Synthetic method and application of polyaspartic acid ester |
-
2021
- 2021-06-22 CN CN202110689262.3A patent/CN114835598A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0457128A2 (en) * | 1990-05-15 | 1991-11-21 | Miles Inc. | Novel amine-terminated compounds |
| US20040220369A1 (en) * | 2003-05-02 | 2004-11-04 | Chen Harry (Zhong-Xiao) | Methods for preparing and applying polyurea elastomers and coatings |
| WO2006066031A1 (en) * | 2004-12-15 | 2006-06-22 | E. I. Du Pont De Nemours And Company | Durable coating compositions containing novel aspartic amine compounds |
| CN108779237A (en) * | 2016-04-29 | 2018-11-09 | 汉高股份有限及两合公司 | Amine functional polymer and the method for preparing this polymer |
| CN108586272A (en) * | 2018-06-28 | 2018-09-28 | 浙江昌明药业有限公司 | A kind of preparation method of 3- aminopropanols or 3- alanine derivatives |
| CN112334553A (en) * | 2018-07-30 | 2021-02-05 | Sika技术股份公司 | Polyurethane composition with long processing time and high strength |
| CN110396053A (en) * | 2019-07-30 | 2019-11-01 | 深圳市前海博扬研究院有限公司 | Asparagus fern polyureas performed polymer and preparation method and a kind of coating |
| CN111620789A (en) * | 2020-06-12 | 2020-09-04 | 深圳市前海博扬研究院有限公司 | Preparation method of aspartate resin |
| CN112920068A (en) * | 2021-01-26 | 2021-06-08 | 深圳飞扬兴业科技有限公司 | Synthetic method and application of polyaspartic acid ester |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6266782B2 (en) | Process for preparing isocyanate homopolymers containing uretdione groups | |
| CN110981741A (en) | Method for preparing polyaspartic acid ester | |
| CN110790691A (en) | Hyperbranched secondary thiol compound, preparation method thereof and epoxy resin composition containing hyperbranched secondary thiol compound | |
| CN114835598A (en) | Steric hindrance type di-secondary amine compound, preparation method and polyurea resin | |
| CN114634458A (en) | Oxazolidine latent curing agent, preparation method thereof and method for preparing polyurethane material | |
| CN114671821A (en) | Polyfunctional oxazolidine latent curing agent and synthesis method thereof | |
| CN114790162B (en) | Low-atomization environment-friendly plasticizer | |
| CN108395512B (en) | Bio-based polyurethane containing carbonate structure as well as preparation method and application thereof | |
| JPH02174750A (en) | Secondary polyetheramine,preparation thereof and preparationof polyurehtnane therefrom in the absence of catalyst | |
| CN109651437B (en) | Chiral nitrogen-phosphorus ligand, preparation method thereof and method for resolving racemic menthol | |
| JP5223305B2 (en) | Method for producing fluorine-containing keto alcohol and derivatives thereof | |
| CN117242057A (en) | Process for preparing intermediates useful in the synthesis of sphingosine-1-phosphate receptor agonists | |
| CN110204569B (en) | Silane coupling agent with dual stimulus responses and preparation method and application thereof | |
| CN108997117B (en) | Novel method for preparing 4-acetoxyl-2-methyl-2-butenal | |
| CN113501828B (en) | 2,8-dioxaspiro [4.5] decane-1-ketone, and preparation method and application thereof | |
| CN114874436B (en) | Preparation method of mercapto-modified unsaturated fatty acid based non-isocyanate polyurethane | |
| CN113399000B (en) | Catalyst and preparation method thereof, catalyst composition and method for preparing straight-chain alcohol from epoxy compound | |
| KR101600557B1 (en) | New polyurethane reaction catalyst and synthesizing method thereof | |
| CN101343213B (en) | Allyl ether series compound and preparation thereof | |
| CN110759878B (en) | Synthetic method of phenyl tetrahydrofuran ether compound | |
| CN111087623B (en) | Polysiloxane side chain liquid crystal polymer with smectic phase and application thereof | |
| CN115974808B (en) | Preparation method of 2-benzyl-7-chloro [1,2-e ] indeno [1,3,4] oxadiazine dimethyl ester | |
| CN111848926B (en) | Fluorine modified curing agent and preparation method thereof | |
| CN113717207B (en) | Method for synthesizing indene compounds | |
| CN112851470B (en) | Method for synthesizing chiral secondary alcohol compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |