CN102617827A - Curing agent modified 1,6-hexamethylene diisocyanate biuret (HDI biuret) and preparation method thereof - Google Patents
Curing agent modified 1,6-hexamethylene diisocyanate biuret (HDI biuret) and preparation method thereof Download PDFInfo
- Publication number
- CN102617827A CN102617827A CN2011100284048A CN201110028404A CN102617827A CN 102617827 A CN102617827 A CN 102617827A CN 2011100284048 A CN2011100284048 A CN 2011100284048A CN 201110028404 A CN201110028404 A CN 201110028404A CN 102617827 A CN102617827 A CN 102617827A
- Authority
- CN
- China
- Prior art keywords
- hdi
- biuret
- divalent alcohol
- curing agent
- water
- 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.)
- Granted
Links
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical class O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 title claims description 109
- 239000005057 Hexamethylene diisocyanate Substances 0.000 title claims description 101
- 238000006243 chemical reaction Methods 0.000 claims abstract description 92
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000000376 reactant Substances 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims description 27
- 230000004048 modification Effects 0.000 claims description 20
- 238000012986 modification Methods 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Substances OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 19
- 238000005070 sampling Methods 0.000 claims description 17
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- -1 1,2-propylene glycol ester Chemical class 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 230000009466 transformation Effects 0.000 claims description 13
- 238000004821 distillation Methods 0.000 claims description 10
- 230000018044 dehydration Effects 0.000 claims description 9
- 238000006297 dehydration reaction Methods 0.000 claims description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- 239000003607 modifier Substances 0.000 claims description 9
- 150000002009 diols Chemical class 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- 150000003384 small molecules Chemical class 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 150000002334 glycols Chemical class 0.000 claims description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 3
- SSYDTHANSGMJTP-ZXZARUISSA-N (3s,4r)-oxolane-3,4-diol Chemical compound O[C@H]1COC[C@H]1O SSYDTHANSGMJTP-ZXZARUISSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- JFGVTUJBHHZRAB-UHFFFAOYSA-N 2,6-Di-tert-butyl-1,4-benzenediol Chemical compound CC(C)(C)C1=CC(O)=CC(C(C)(C)C)=C1O JFGVTUJBHHZRAB-UHFFFAOYSA-N 0.000 claims description 2
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 claims description 2
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 claims description 2
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 2
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 2
- NRPMYFMXYNVNCX-UHFFFAOYSA-N 3-(3-ethoxyphenoxy)propane-1,1-diol Chemical compound C(C)OC=1C=C(OCCC(O)O)C=CC=1 NRPMYFMXYNVNCX-UHFFFAOYSA-N 0.000 claims description 2
- RUQNFHWKALNWAE-UHFFFAOYSA-N 3-(3-hydroxyphenoxy)propane-1,1-diol Chemical compound OC(CCOC1=CC(O)=CC=C1)O RUQNFHWKALNWAE-UHFFFAOYSA-N 0.000 claims description 2
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical compound CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- TUQOCWCQMKECRI-UHFFFAOYSA-N CCCCC(O)O.CCNCC Chemical compound CCCCC(O)O.CCNCC TUQOCWCQMKECRI-UHFFFAOYSA-N 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- AYDQIZKZTQHYIY-UHFFFAOYSA-N OC(=O)C1(C)CC(C(O)=O)=CC=C1 Chemical compound OC(=O)C1(C)CC(C(O)=O)=CC=C1 AYDQIZKZTQHYIY-UHFFFAOYSA-N 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 claims description 2
- WZWSOGGTVQXXSN-UHFFFAOYSA-N cyclohexanone;toluene Chemical compound CC1=CC=CC=C1.O=C1CCCCC1 WZWSOGGTVQXXSN-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 claims description 2
- 229940100573 methylpropanediol Drugs 0.000 claims description 2
- 238000012544 monitoring process Methods 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 2
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Substances CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims 2
- 229940058015 1,3-butylene glycol Drugs 0.000 claims 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims 1
- 235000019437 butane-1,3-diol Nutrition 0.000 claims 1
- VSSAZBXXNIABDN-UHFFFAOYSA-N cyclohexylmethanol Chemical compound OCC1CCCCC1 VSSAZBXXNIABDN-UHFFFAOYSA-N 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract description 5
- 230000001070 adhesive effect Effects 0.000 abstract description 5
- 239000011527 polyurethane coating Substances 0.000 abstract description 4
- 239000012939 laminating adhesive Substances 0.000 abstract 1
- 239000003973 paint Substances 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- 239000002699 waste material Substances 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 9
- 238000013461 design Methods 0.000 description 8
- 239000010408 film Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000000576 coating method Methods 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920002396 Polyurea Polymers 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 239000006101 laboratory sample Substances 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 238000003541 multi-stage reaction Methods 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 description 1
- FWVCSXWHVOOTFJ-UHFFFAOYSA-N 1-(2-chloroethylsulfanyl)-2-[2-(2-chloroethylsulfanyl)ethoxy]ethane Chemical compound ClCCSCCOCCSCCCl FWVCSXWHVOOTFJ-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C275/46—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups containing any of the groups, X being a hetero atom, Y being any atom, e.g. acylureas
- C07C275/58—Y being a hetero atom
- C07C275/62—Y being a nitrogen atom, e.g. biuret
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/302—Water
- C08G18/305—Water creating amino end groups
-
- 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
- C08G18/3203—Polyhydroxy compounds
- C08G18/3212—Polyhydroxy compounds containing cycloaliphatic groups
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7806—Nitrogen containing -N-C=0 groups
- C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
- C08G18/7831—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing biuret groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
- C08G18/8012—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with diols
-
- 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
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
Abstract
The invention relates to a polyurethane coating and an adhesive curing agent and preparation methods thereof, and concretely relates to curing agent modified HDI biuret and a preparation method thereof. The preparation method mainly solves problems low HDI conversion rate, and energy waste caused by multitime monomer recovery of known methods for preparing HDI biuret through reacting HDI with water. The curing agent of the invention is generated by reacting a dihydric alcohol, water and the HDI in an organic solvent, wherein the molar ratio of the dihydric alcohol to the HDI is 0.05-0.2:1, the molar ratio of water to the residual HDI is 1:3-4, and the weight ratio of the solvent to (reactants of the dihydric alcohol, water and the HDI) is 0-60:40-100. The curing agent modified HDI biuret which has a low viscosity and makes the one-time feeding conversion rate of HDI monomers reach 80-98% is mainly used as a curing agent for automobile and high grade car paints, and boil-resistant laminating adhesives, and has a nonyellowing characteristic at a high temperature under ultraviolet ray.
Description
Technical field
The present invention relates to a kind of polyurethane coating, adhesive solidification agent and preparation method thereof, is a kind of modification hexamethylene diisocyanate solidifying agent and preparation method thereof specifically.
Background technology
1; Hexamethylene-diisocyanate (HDI) belongs to not flavescence aliphatic diisocyanate; Be the main raw material of high performance polyurethane coating and tackiness agent, be characterized in polyurethane products light, the Heat stability is good processed the yellowing phenomenon can taking place under the uviolizing out of doors; Under the high temperature steaming condition, the chemical reaction that aromatic isocyanate becomes carcinogenic aromatic amine can not take place, be a kind of raw material very important in the vulcabond raw material.But the HDI monomer is bigger because of its volatility, and toxicity is also big during construction, and method in common all is with HDI and H in the world
2O reaction is processed and is applied to other purposes again after HDI biuret or HDI autohemagglutination become the HDI tripolymer.
HDI and H
2It is following that O reacts the reaction formula of processing biuret:
From the structure of HDI biuret (biuret triisocyanate), should be by the reaction of 3 moles of HDI and 1 mole of water and generate.Introduce the method for manufacture of HDI biuret according to relevant urethane books, if, will can not get product by 3: the 1 moles of a large amount of oyster white dopes of meeting generation that feed intake; Increase along with the HDI molar ratio; White depositions (polyureas) reduces gradually, evidence, mol ratio be 6: 1 more suitable.Prior art just lets HDI excessive more than one times when raw material feeds intake, and the monomeric transformation efficiency of HDI is the highest in the reaction does not reach 50% yet, and excessive HDI monomer reclaims with thin-film evaporator, supplies to recycle once more.The production technique of prior art not only efficient is low, and repeatedly reclaims monomer and cause energy dissipation.
Patent documentation Chinese invention patent ublic specification of application CN101475680A is in the method for disclosed spray method synthesizing hexamethylene diisocyanate on July 8 (HDI) biuret in 2009; Its patent No. is 200910003621.4; Having introduced spray method can be evenly dispersed in the material water to reduce the generation of polyureas; The mol ratio of HDI and water is 2～15, does not still solve the low problem of HDI biuret transformation efficiency.
Summary of the invention
The objective of the invention is the monomeric transformation efficiency of HDI to be brought up to 80～98% in order to remedy the deficiency of prior art, and product do not have that white depositions generates curing agent modified 1, the own isocyanic ester biuret of 6-.
Technical solution of the present invention is: at first with divalent alcohol section H DI is carried out modification; To remain HDI and water again by 3～4: 1 mol ratio feeds intake; The circulating reaction technology of taking substep to add water, stepwise reaction is processed modification HDI biuret solidifying agent; Wherein HDI is 1, the abbreviation of the own isocyanic ester biuret of 6-.
The present invention is the activity that changes section H DI with divalent alcohol to the purpose that section H DI carries out modification, and the activity difference in the formation system between the differing mol so that the reaction of follow-up generation biuret can be carried out in order, is avoided polymeric generation.
The circulating reaction technology that substep of the present invention adds water, stepwise reaction has formed the excessive local environment of HDI relative in the system, and the direction that helps reacting towards generating biuret carries out.
The present invention is to be solvent with the organic solvent, generates described two by divalent alcohol, water and HDI reaction
Unit's alcohol is 0.05～0.2: 1 with the mol ratio of HDI; Described water is 1: 3～4 with the mol ratio of residue HDI; The mol ratio of the OH base of the water that promptly feeds intake and the NCO base of HDI is near the structure proportion of biuret triisocyanate, and the weight ratio of the consumption that described solvent load and reactant divalent alcohol, water and HDI add up to is 0～60: 40～100.
The HDI of the present invention transformation efficiency that feeds intake is 80～98%, and no white depositions generates, and product viscosity is low,
Have only 2000～4000 mpa.s (25 ℃).
Preparing method of the present invention, its step is following:
A, in reaction kettle, add HDI and organic solvent, the back that stirs adds the divalent alcohol through dehydration, is warming up to 60 ℃, 60～90 ℃ of reactions 1～6 hour, makes the HDI modifier;
B, be cooled to below 70 ℃, add first part's water, react and be warmed up to 75～100 ℃ of reactions 1～3 hour after 0.5～1.5 hour, be warmed up to 120～140 ℃ again and reacted 1～3 hour; Be cooled to below 70 ℃, add second section water, repeat above-mentioned technological process; Until the water that adds whole meterings; React be warmed up to after 0.5～1.5 hour 75～100 ℃ the reaction 1～3 hour, be warmed up to again 120～140 ℃ the reaction 1～5 hour, at this moment between; The degree of carrying out through the content monitoring reaction that detects NCO to reactant sampling is when the content of NCO tends towards stability, is during near theoretical value reaction end;
C, sampling detect solid content, viscosity, NCO percentage composition and the transformation efficiency of product;
D, the distillation under vacuum with conventional, film evaporation method or solvent extration are extracted solvent and small amount of residual HDI in the product out, are cooled to below 70 ℃ to add organic solvent by the requirement of product solid content, stir, and discharging gets modification HDI biuret solidifying agent.
Divalent alcohol described in the technical solution of the present invention is polyester diol, polyether Glycols, other divalent alcohol or small molecules divalent alcohol, wherein any one or two or more mixtures.
Polyester diol described in the technical solution of the present invention for gather hexanodioic acid-ethylene glycol and 1,2-propylene glycol ester divalent alcohol, gather hexanodioic acid-butanediol ester divalent alcohol, gather sebacic acid-hexanodioic acid-terepthaloyl moietie-the DOPCP divalent alcohol, gather m-phthalic acid-hexanodioic acid-NSC 6366-glycol ether ester divalent alcohol, polycarbonate diol or polycaprolactone divalent alcohol.
Polyether Glycols described in the technical solution of the present invention is polyoxytrimethylene divalent alcohol, polyoxyethylene-propylene divalent alcohol or THF homopolymer divalent alcohol.
Other divalent alcohol described in the technical solution of the present invention is terminal hydroxy group vinyl resin or terminal hydroxy group Synolac.
Small molecules divalent alcohol described in the technical solution of the present invention is the 3-methyl isophthalic acid; 5-pentanediol, NSC 6366, terepthaloyl moietie, glycol ether, cyclohexanediol, methyl propanediol, TCD three ring glycol, 1; Ammediol, 1,4-hydroxymethyl-cyclohexane, 1,4-butyleneglycol, 1; 3-butyleneglycol, 1; 5-pentanediol, diethylammonium pentanediol, 1,2-Ucar 35, glycol ether, erythritan, 1,6-pinakon, neopentyl glycol, butyl ethyl Ucar 35,2; 2-two (4-hydroxy phenyl) propane, hydroxypivalyl hydroxypivalate neopentyl alcohol ester, Resorcinol double hydroxyethyl ether, two (2-hydroxyethyl) ethers of quinhydrones, Resorcinol bis-hydroxypropyl ether, Resorcinol bis-hydroxypropyl ethyl ether, 2,5-ditert-butylhydro quinone, DPG, tripropylene glycol or Rutgers 612.
Water described in the technical solution of the present invention is deionized water or zero(ppm) water.
Organic solvent described in the technical solution of the present invention is the ester class of vinyl acetic monomer, N-BUTYL ACETATE, ethylene glycol ether acetate, propylene glycol monomethyl ether acetate, methylcarbonate, diethyl carbonate, diphenyl carbonate; The ketone of acetone, butanone, cyclohexanone; Toluene, YLENE aromatic hydrocarbons; Dioxane, THF, N, dinethylformamide reaches wherein two or more mixture.
Among preparing method's step a of the present invention; From the symplex structure of HDI, two NCO groups active identical be that the gordian technique of making biuret is started with; At first with divalent alcohol and section H DI reaction earlier; Generate a kind of HDI modifier, this makes in the system between the molecule, the activity between the NCO group has formed difference.The principle of the invention is that follow-up generation biuret reaction has been created condition.
In
formula: R is the part-structure beyond the divalent alcohol hydroxyl-removal.
Among preparing method's step b of the present invention, with the water break into portions of metering, adding several times, is for the excessive relatively local environment of HDI in the formation system again, helps reaction and progressively generates biuret.Behind the adding first part water, earlier 75～100 ℃ of reactions of low temperature 1～3 hour, this stage is that HDI and water react, the very fast and HDI reaction generation urea groups vulcabond of elder generation's generation primary amine and carbonic acid gas, primary amine; Be warmed up to 120～140 ℃ of reactions 1～3 hour again, this stage is that urea groups vulcabond and HDI reaction generate biuret.Be cooled to below 70 ℃, add the second part water again, the above-mentioned technological process that circulates until the water that adds whole meterings, is finished above-mentioned technological process.In each stage of above-mentioned reaction; Because each molecular activity exists difference; Gradation adds the technology of water, gradation low temperature and pyroreaction, helps between the differing mol, the reaction between the different activities group can carry out by speed in order, helps the generation of unit molecule biuret; Avoid and reduced the generation of " polyureas ", also promptly do not have white depositions.
Reaction end of the present invention is after adding last water, and NCO content confirms to react whether this end in the sampling detecting reactant, when the content of NCO no longer descends, tends towards stability, is during near the Design Theory value reaction end.Monomeric processing can be quoted relevant patent and the introduction of urethane books to small amount of residual HDI distillation under vacuum, film evaporation method or solvent extration carry out.
The HDI one feeding monomer conversion of product of the present invention is 80～98%, and the height of its transformation efficiency is relevant with the divalent alcohol kind and the consumption of selection, and generalized case can both reach more than 90%.The present invention is comparing below 50% with the one feeding monomer conversion of the HDI biuret of domestic and international prior art manufacturing, has improved nearly one times.
The molecular characterization of product of the present invention is to contain divalent alcohol modification HDI structure and biuret structure simultaneously; Divalent alcohol modification HDI structure is represented in above-mentioned reaction formula (A); Biuret structure characterizes 2245cm-with the biuret structure charateristic avsorption band of the infrared spectrogram of laboratory sample of the present invention
1The place is-the NCO absorption peak 2935cm-
1The place is the absorption peak of methyl and methylene radical, 3305cm-
1The place is-NH-absorption peak 1735cm-
1For-CO-absorption peak, therefore think that product of the present invention has biuret structure.
The present invention also aims to provide a kind of divalent alcohol modification HDI biuret series curing agent product; The introducing of divalent alcohol has changed HDI biuret curing agents; Can design some property by customer requirements; For example increase that solidifying agent is given the snappiness of goods, rigidity, wear resistance, flexibility and with the consistency of resin etc., select different diols can produce a series of modification HDI biuret solidifying agent, satisfy the needs of polyurethane coating, tackiness agent various uses.
Modification HDI biuret solidifying agent of the present invention and supporting Synolac, vinyl resin etc. have good intermiscibility.
The present invention will have manufacturing HDI biuret solidifying agent technology now and reach a new high, and improve production efficiency of products, reduce the monomeric distillation recovered frequency of HDI, increase plant factor, reduced energy consumption and made the HDI product diversification.
Product of the present invention has not flavescence characteristic under ultraviolet ray and the high temperature mainly as the solidifying agent of automobile, high-grade car coating and the compound film adhesive of anti-the boiling.
The present invention compared with prior art has following advantage: one, structure diversification.The present invention has introduced the divalent alcohol structure in HDI biuret molecular structure, make the diversification of modification HDI biuret solidifying agent structure, helps the expansion of end-use.Two, production efficiency is high.The present invention can be enhanced about more than once the production efficiency of prior art, and product does not have the white depositions generation.Three, technology is advanced.Gradation of the present invention adds water, gradation and has changed the process method of traditional manufacturing HDI biuret at the circulating reaction technology of low temperature and pyroreaction, and technology is simple, and plant factor is high.Four, energy consumption is low.Technology of the present invention has reduced the energy consumption that a large amount of residual monomers repeatedly reclaim, recycle.Five, product viscosity is low.Viscosity of the present invention is low, and solid content has reduced consumption of organic solvent up to more than 90%.Six, product index of the present invention (following content is weight percentage) as follows:
(1) outward appearance: colourless to light yellow transparent liquid;
(2) solid content: 40～90%;
(3) NCO content: 16～23.5%, in total solids;
(4) storage period: 1 year.
Description of drawings
Fig. 1 is the infrared spectrogram that laboratory sample of the present invention detects with IR.
Embodiment
A, in reaction kettle, add 168 gram HDI and 22 gram N-BUTYL ACETATEs, the back that stirs adds the three ring glycol through 19.6 gram TCD of dehydration, is warming up to 60 ℃, 60～70 ℃ of reactions 1 hour, is raised to 70～80 ℃ of reactions 1 hour again, makes the HDI modifier; B, be cooled to below 70 ℃, add 2.4 gram water for the first time, react and be warmed up to 80～90 ℃ of reactions 1.5 hours after 1 hour, be warmed up to 120～130 ℃ again and reacted 1 hour; Be cooled to below 70 ℃, add for the second time 1.2 gram water, react and be warmed up to 80～90 ℃ of reactions 1.5 hours after 0.5 hour, be warmed up to 120～130 ℃ again and reacted 1 hour; Be cooled to below 70 ℃, add 1.2 gram water for the third time, react and be warmed up to 80～90 ℃ of reactions 1.5 hours after 0.5 hour, be warmed up to 120～130 ℃ and reacted 1 hour; Be warmed up to 125～135 ℃ of reactions once more,, whenever detect the NCO percentage composition at a distance from sampling in 0.5 hour in this section period, when being worth 19.6% near Design Theory, the termination reaction of lowering the temperature immediately; C, sampling detect, and the solid content of product is 90%, and viscosity is 2800mpa.s (25 ℃), and NCO content is 19.3%, and transformation efficiency is 96% (in total solids); D, extract N-BUTYL ACETATE and small amount of residual HDI in the product out, be cooled to and add 22 gram N-BUTYL ACETATEs below 70 ℃, stir with distillation under vacuum, discharging, 214 gram solid contents are 90% modification HDI biuret solidifying agent.Residual HDI content through detecting this solidifying agent is 0.42%.
Embodiment 2
A, in reaction kettle, add 168 gram HDI and 81 gram N-BUTYL ACETATEs; The back adding that stirs gathers sebacic acid-hexanodioic acid-terepthaloyl moietie-DOPCP divalent alcohol (molecular weight is 1000) through 70 grams of dehydration; Be warming up to 60 ℃; 60～70 ℃ of reactions 1.5 hours, be raised to 70～80 ℃ of reactions 2 hours again, make the HDI modifier; B, be cooled to below 70 ℃, add 2.5 gram water for the first time, react and be warmed up to 75～85 ℃ of reactions 1.5 hours after 1.5 hours, be warmed up to 120～130 ℃ again and reacted 1.5 hours; Be cooled to below 70 ℃, add for the second time 1.3 gram water, react and be warmed up to 75～85 ℃ of reactions 1 hour after 1 hour, be warmed up to 120～130 ℃ again and reacted 1 hour; Be cooled to below 70 ℃, add 0.8 gram water for the third time, react and be warmed up to 75～85 ℃ of reactions 1 hour after 0.5 hour, be warmed up to 120～130 ℃ again and reacted 1 hour; Be cooled to below 70 ℃, the 4th adding 0.56 restrains water, reacts to be warmed up to 75～85 ℃ of reactions 1 hour after 0.5 hour, is warmed up to 120～130 ℃ of reactions 1 hour again; Be warmed up to 125～135 ℃ of reactions once more,, whenever detect the NCO percentage composition at a distance from sampling in 0.5 hour in this section period, when being worth 13% near Design Theory, the termination reaction of lowering the temperature immediately; C, sampling detect, and the solid content of product is 75%, and viscosity is 3100mpa.s (25 ℃), and NCO content is 12.7%, and transformation efficiency is 91% (in total solids); D, extract N-BUTYL ACETATE and small amount of residual HDI in the product out, be cooled to and add 50 gram N-BUTYL ACETATEs and 31 gram vinyl acetic monomers below 70 ℃, stir with distillation under vacuum, discharging, 324 gram solid contents are 75% modification HDI biuret solidifying agent.Residual HDI content through detecting this solidifying agent is 0.35%.
A, in reaction kettle, add 168 gram HDI and 73 gram N-BUTYL ACETATEs, the back that stirs adds 9.4 grams 1 through dehydration, and the 5-pentanediol is warming up to 60 ℃, 60～70 ℃ of reactions 1 hour, is raised to 70～80 ℃ of reactions 1 hour again; Adding is through 35 gram terminal hydroxy group vinyl resins (molecular weight is 1000) of dehydration again, and 70～80 ℃ of reactions 1 hour, 80～90 ℃ were reacted 1 hour, and made the HDI modifier; B, be cooled to below 70 ℃, add 2.3 gram water for the first time, react and be warmed up to 75～85 ℃ of reactions 1.5 hours after 1 hour, be warmed up to 120～130 ℃ again and reacted 1.5 hours; Be cooled to below 70 ℃, add for the second time 1.1 gram water, react and be warmed up to 75～85 ℃ of reactions 1.5 hours after 0.5 hour, be warmed up to 120～130 ℃ again and reacted 1.5 hours; Be cooled to below 70 ℃, add 1.1 gram water for the third time, react and be warmed up to 75～85 ℃ of reactions 1 hour after 0.5 hour, be warmed up to 120～130 ℃ and reacted 1 hour; Be warmed up to 125～135 ℃ of reactions once more,, whenever detect the NCO percentage composition at a distance from sampling in 0.5 hour in this section period, when being worth 14.5% near Design Theory, the termination reaction of lowering the temperature immediately; C, sampling detect, and the solid content of product is 75%, and viscosity is 2100mpa.s (25 ℃), and NCO content is 14.2%, and transformation efficiency is 90% (in total solids); D, extract N-BUTYL ACETATE and small amount of residual HDI in the product out, be cooled to and add 50 gram N-BUTYL ACETATEs and 23 gram propylene glycol monomethyl ether acetate below 70 ℃, stir with distillation under vacuum, discharging, 290 gram solid contents are 75% modification HDI biuret solidifying agent.
Embodiment 4
A, in reaction kettle, add 168 gram HDI and 69 gram N-BUTYL ACETATEs; The back adding that stirs restrains two (hydroxyethyl) ethers of Resorcinols through 34.7 of dehydration, is warming up to 60 ℃, reacts 1 hour at 60～70 ℃; Be raised to 70～80 ℃ of reactions 1 hour again, make the HDI modifier; B, be cooled to below 70 ℃, add 2.0 gram water for the first time, react and be warmed up to 80～90 ℃ of reactions 1 hour after 0.5 hour, be warmed up to 120～130 ℃ again and reacted 1 hour; Be cooled to below 70 ℃, add for the second time 1.0 gram water, react and be warmed up to 80～90 ℃ of reactions 1.5 hours after 0.5 hour, be warmed up to 120～130 ℃ again and reacted 1 hour; Be cooled to below 70 ℃, add 0.9 gram water for the third time, react and be warmed up to 80～90 ℃ of reactions 1 hour after 0.5 hour, be warmed up to 120～130 ℃ and reacted 1 hour; Be warmed up to 125～135 ℃ of reactions once more,, whenever detect the NCO percentage composition at a distance from sampling in 0.5 hour in this section period, when being worth 15.2% near Design Theory, the termination reaction of lowering the temperature immediately; C, sampling detect, and the solid content of product is 75%, and viscosity is 1600mpa.s (25 ℃), and NCO content is 15.0%, and transformation efficiency is 94% (in total solids); D, extract N-BUTYL ACETATE and small amount of residual HDI in the product out, be cooled to and add 69 gram N-BUTYL ACETATEs below 70 ℃, stir with distillation under vacuum, discharging, 275.5 gram solid contents are 75% modification HDI biuret solidifying agent.
Embodiment 5
A, in reaction kettle, add 168 gram HDI and 84 gram N-BUTYL ACETATEs; The back adding that stirs restrained polytetrahydrofuran diols (molecular weight is 1000) through 80 of dehydration, is warming up to 60 ℃, 60～70 ℃ of reactions 3 hours; Be raised to 70～80 ℃ of reactions 2.5 hours again, make the HDI modifier; B, be cooled to below 70 ℃, add 2.5 gram water for the first time, react and be warmed up to 75～85 ℃ of reactions 2.5 hours after 1.5 hours, be warmed up to 120～130 ℃ again and reacted 2.5 hours; Be cooled to below 70 ℃, add for the second time 1.3 gram water, react and be warmed up to 75～85 ℃ of reactions 1.5 hours after 0.5 hour, be warmed up to 120～130 ℃ again and reacted 1.5 hours; Be cooled to below 70 ℃, add 1.2 gram water for the third time, react and be warmed up to 75～85 ℃ of reactions 1 hour after 0.5 hour, be warmed up to 120～130 ℃ and reacted 1 hour; Be warmed up to 125～135 ℃ of reactions once more,, whenever detect the NCO percentage composition at a distance from sampling in 0.5 hour in this section period, when being worth 12.5% near Design Theory, the termination reaction of lowering the temperature immediately; C, sampling detect, and the solid content of product is 75%, and viscosity is 2100mpa.s (25 ℃), and NCO content is 12.2%, and transformation efficiency is 92% (in total solids); D, extract N-BUTYL ACETATE and small amount of residual HDI in the product out, be cooled to and add 50 gram N-BUTYL ACETATEs and 34 gram ethylene glycol ether acetates below 70 ℃, stir with distillation under vacuum, discharging, 337 gram solid contents are 75% modification HDI biuret solidifying agent.
Embodiment 6
A, in reaction kettle, add 168 gram HDI and 61 gram N-BUTYL ACETATEs, the back that stirs adds 10.4 gram NSC 6366s through dehydration, is warming up to 60 ℃, 60～70 ℃ of reactions 1 hour, is raised to 70～80 ℃ of reactions 1 hour again, makes the HDI modifier; B, be cooled to below 70 ℃, add 1.8 gram water for the first time, react and be warmed up to 80～90 ℃ of reactions 1 hour after 0.5 hour, be warmed up to 120～130 ℃ again and reacted 1 hour; Be cooled to below 70 ℃, add for the second time 0.9 gram water, react and be warmed up to 80～90 ℃ of reactions 1.5 hours after 0.5 hour, be warmed up to 120～130 ℃ again and reacted 1 hour; Be cooled to below 70 ℃, add 0.9 gram water for the third time, react and be warmed up to 80～90 ℃ of reactions 1 hour after 0.5 hour, be warmed up to 120～130 ℃ and reacted 1 hour; Be warmed up to 125～135 ℃ of reactions once more,, whenever detect the NCO percentage composition at a distance from sampling in 0.5 hour in this section period, when being worth 20.7% near Design Theory, the termination reaction of lowering the temperature immediately; C, sampling detect, and the solid content of product is 75%, and viscosity is 3100mpa.s (25 ℃), and NCO content is 20.4%, and transformation efficiency is 80% (in total solids); D, extract N-BUTYL ACETATE and small amount of residual HDI in the product out, be cooled to and add 61 gram N-BUTYL ACETATEs below 70 ℃, stir with distillation under vacuum, discharging, 242 gram solid contents are 75% modification HDI biuret solidifying agent.
Application implementation example 1
Product 30 grams of embodiment 1 and the hydroxyl component of 100 gram phthalic resin coatings mix, and the coating lacquer film properties that makes is following: dryness: 25 ℃, surface drying time 50 minutes is done solid work 12 hours time; Test performance after 3 days: gloss (60 °): >=95%; Hardness: Shao Shi D50; Shock strength: 428N.cm; Sticking power: 1 grade; Snappiness: 1mm.
The method of inspection: gloss is pressed GB9754-88, hardness and is pressed GB1730-79, shock strength and press that GB1732-93, sticking power press GB1720-89, snappiness is pressed the GB1731-79 standard.
Application implementation example 2
Product 40 gram of embodiment 3 and 100 gram Hydroxylated acrylic resin solution mixing, the coating lacquer film properties that makes is following: dryness: 25 ℃, surface drying time 50 minutes, when doing solid work 12 hours; Test performance after 3 days: gloss (60 °): >=95%; Hardness >=Shao Shi D60; Shock strength: 480N.cm; Sticking power: 1 grade; Snappiness: 1mm.
Application implementation example 3
Product 35 grams of embodiment 2 and package compound are mixed with hydroxyl component 100 grams of polyurethane adhesive; Be used for the compound of pure aluminum foil and CPP film; In 50 ℃ solidify 72 hours after; Carry out T type peeling strength test by GB/T 2791-1995 " tackiness agent T peeling strength test method flexible material is to flexible material ", stripping strength is 1030g/15mm, and the laminated film behind cooking test does not find that film has separation phenomenon.
Reference:
1, the Li Shaoxiong of Chemical Industry Press's " polyurethane adhesive ", Liu Yijun write, the 3rd printing in January, 2000 Beijing.
2, coatings industry the 38th volume in October, 2008 the 10th phase " HDI biuret polyurethane curing agent synthetic with the separating of remaining HDI ".
3, Chinese invention patent application number: 200910003621.4, title: the method for spray method synthesizing hexamethylene diisocyanate (HDI) biuret.
Claims (10)
1. a curing agent modified hexamethylene diisocyanate biuret is characterized in that containing divalent alcohol modification HDI structure and biuret structure in this solidifying agent, is to be solvent with the organic solvent, is generated by divalent alcohol, water and HDI reaction;
The mol ratio of described divalent alcohol and HDI is 0.05～0.2: 1, and described water is 1: 3～4 with the mol ratio of residue HDI, and the weight ratio of the consumption that described solvent load and reactant divalent alcohol, water and HDI add up to is 0～60: 40～100; Wherein HDI is the abbreviation of hexamethylene diisocyanate.
2. the preparation method of a kind of curing agent modified hexamethylene diisocyanate according to claim 1 (HDI) biuret, it is characterized in that: preparation process is following:
A, in reaction kettle, add HDI and organic solvent, the back that stirs adds the divalent alcohol through dehydration, is warming up to 60 ℃, 60～90 ℃ of reactions 1～6 hour, makes the HDI modifier;
B, be cooled to below 70 ℃, add first part's water, react and be warmed up to 75～100 ℃ of reactions 1～3 hour after 0.5～1.5 hour, be warmed up to 120～140 ℃ again and reacted 1～3 hour; Be cooled to below 70 ℃, add second section water, repeat above-mentioned technological process; Until the water that adds whole meterings; React be warmed up to after 0.5～1.5 hour 75～100 ℃ the reaction 1～3 hour, be warmed up to again 120～140 ℃ the reaction 1～5 hour, at this moment between; The degree of carrying out through the content monitoring reaction that detects NCO to reactant sampling is when the content of NCO tends towards stability, is during near theoretical value reaction end;
C, sampling detect solid content, viscosity, NCO percentage composition and the transformation efficiency of product;
D, the distillation under vacuum with conventional, film evaporation method or solvent extration are extracted solvent and small amount of residual HDI in the product out, are cooled to below 70 ℃ to add organic solvent by the requirement of product solid content, stir, and discharging gets modification HDI biuret solidifying agent.
3. a kind of curing agent modified hexamethylene diisocyanate biuret according to claim 1 is characterized in that: add divalent alcohol in the described HDI monomer, with divalent alcohol section H DI is carried out modification, generate biuret with the water reaction again.
4. according to claim 1 a kind of curing agent modified 1; The hexamethylene-diisocyanate biuret; It is characterized in that described divalent alcohol is polyester diol, polyether Glycols, other divalent alcohol or small molecules divalent alcohol, wherein any one or two or more mixtures.
5. according to claim 4 a kind of curing agent modified 1; The hexamethylene-diisocyanate biuret, it is characterized in that described polyester diol for gather hexanodioic acid-ethylene glycol and 1,2-propylene glycol ester divalent alcohol, gather hexanodioic acid-butanediol ester divalent alcohol, gather sebacic acid-hexanodioic acid-terepthaloyl moietie-the DOPCP divalent alcohol, gather m-phthalic acid-hexanodioic acid-NSC 6366-glycol ether ester divalent alcohol, polycarbonate diol or polycaprolactone divalent alcohol.
6. a kind of curing agent modified hexamethylene diisocyanate biuret according to claim 4 is characterized in that described polyether glycol is polyoxytrimethylene divalent alcohol, polyoxyethylene-propylene divalent alcohol or THF homopolymer divalent alcohol.
7. a kind of curing agent modified hexamethylene diisocyanate biuret according to claim 4 is characterized in that described other divalent alcohol is terminal hydroxy group vinyl resin or terminal hydroxy group Synolac.
8. according to claim 4 a kind of curing agent modified 1; The hexamethylene-diisocyanate biuret; It is characterized in that described small molecules divalent alcohol is the 3-methyl isophthalic acid, 5-pentanediol, NSC 6366, terepthaloyl moietie, glycol ether, cyclohexanediol, methyl propanediol, TCD three ring glycol, 1, ammediol, 1; 4-hydroxymethyl-cyclohexane, 1; 4-butyleneglycol, 1,3 butylene glycol, 1,5-pentanediol, diethylammonium pentanediol, 1; 2-Ucar 35, glycol ether, erythritan, 1; 6-pinakon, neopentyl glycol, butyl ethyl Ucar 35,2,2-two (4-hydroxy phenyl) propane, hydroxypivalyl hydroxypivalate neopentyl alcohol ester, Resorcinol double hydroxyethyl ether, two (2-hydroxyethyl) ethers of quinhydrones, Resorcinol bis-hydroxypropyl ether, Resorcinol bis-hydroxypropyl ethyl ether, 2,5-ditert-butylhydro quinone, DPG, tripropylene glycol or Rutgers 612.
9. a kind of curing agent modified hexamethylene diisocyanate biuret according to claim 1 is characterized in that described water is deionized water or zero(ppm) water.
10. according to claim 1 a kind of curing agent modified 1; The hexamethylene-diisocyanate biuret is characterized in that described organic solvent is the ester class of vinyl acetic monomer, N-BUTYL ACETATE, ethylene glycol ether acetate, propylene glycol monomethyl ether acetate, methylcarbonate, diethyl carbonate, diphenyl carbonate, the ketone of acetone, butanone, cyclohexanone; Toluene, YLENE aromatic hydrocarbons; Dioxane, THF, N, dinethylformamide reaches wherein two or more mixture.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110028404 CN102617827B (en) | 2011-01-27 | 2011-01-27 | Curing agent modified 1,6-hexamethylene diisocyanate biuret (HDI biuret) and preparation method thereof |
| PCT/CN2011/078973 WO2012100532A1 (en) | 2011-01-27 | 2011-08-26 | Modified 1,6-hexamethylene diisocyanate biuret curing agent and preparation method therefor |
| DE112011101335.3T DE112011101335B4 (en) | 2011-01-27 | 2011-08-26 | Modified 1,6-hexamethylene diisocyanate biuret curing agent and a method of producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110028404 CN102617827B (en) | 2011-01-27 | 2011-01-27 | Curing agent modified 1,6-hexamethylene diisocyanate biuret (HDI biuret) and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102617827A true CN102617827A (en) | 2012-08-01 |
| CN102617827B CN102617827B (en) | 2013-10-30 |
Family
ID=46558068
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110028404 Expired - Fee Related CN102617827B (en) | 2011-01-27 | 2011-01-27 | Curing agent modified 1,6-hexamethylene diisocyanate biuret (HDI biuret) and preparation method thereof |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN102617827B (en) |
| DE (1) | DE112011101335B4 (en) |
| WO (1) | WO2012100532A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014098069A1 (en) * | 2012-12-20 | 2014-06-26 | Dic株式会社 | Resin composition for use as vapor-barrier adhesive, and laminate |
| CN105820302A (en) * | 2016-04-30 | 2016-08-03 | 华南理工大学 | Nonionic and anionic mixed waterborne polyurethane curing agent and preparation method thereof |
| CN111592635A (en) * | 2020-05-08 | 2020-08-28 | 深圳市前海博扬研究院有限公司 | Water-based polyurea curing agent and preparation method and application thereof |
| CN116041224A (en) * | 2023-01-31 | 2023-05-02 | 美瑞新材料股份有限公司 | Preparation method of hexamethylene diisocyanate biuret curing agent |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107793909B (en) * | 2017-10-21 | 2019-10-08 | 中海油常州涂料化工研究院有限公司 | A kind of aviation aircraft exterior skin Lacquer finish coating and preparation method thereof |
| CN107674553B (en) * | 2017-11-13 | 2020-01-21 | 中国海洋石油集团有限公司 | Coating system for outer skin of aviation aircraft and preparation method thereof |
| CN114853742B (en) * | 2022-05-13 | 2023-07-14 | 万华化学集团股份有限公司 | Preparation method and application of modified HDI uretdione curing agent |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3124605A (en) * | 1963-12-05 | 1964-03-10 | Biuret polyisocyanates | |
| US3358010A (en) * | 1964-03-11 | 1967-12-12 | Mobay Chemical Corp | Biuret polyisocyanates |
| US4051165A (en) * | 1969-06-19 | 1977-09-27 | Bayer Aktiengesellschaft | Preparation of biuret polyisocyanates |
| US4152350A (en) * | 1976-12-03 | 1979-05-01 | Bayer Aktiengesellschaft | Process for the preparation of polyisocyanates containing biuret groups |
| EP0035158A1 (en) * | 1980-02-29 | 1981-09-09 | Bayer Ag | Process for the preparation of polyisocyanates with a biuret structure |
| CN101274977A (en) * | 2007-03-29 | 2008-10-01 | 周建明 | Curing agent 1,6- hexamethylene diisocyanate prepolymer and preparation thereof |
| CN101475680A (en) * | 2008-05-21 | 2009-07-08 | 胡孝勇 | Method for synthesizing hexamethylene diisocyanate (HDI) biuret |
| CN101717571A (en) * | 2009-10-30 | 2010-06-02 | 华南理工大学 | Method for preparing non-toxic polyurethane curing agent with high solid content |
| CN101935448A (en) * | 2010-08-09 | 2011-01-05 | 江苏大象东亚制漆有限公司 | polyurethane curing agent and two-component polyurethane coating not containing benzene, methylbenzene or dimethylbenzene and TDI |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE637578A (en) * | 1962-09-19 | |||
| DD200888A1 (en) * | 1981-11-18 | 1983-06-22 | Gerhard Behrendt | METHOD FOR PRODUCING SOFT POLYURETHANE MOLDING MATERIALS |
| US4855490A (en) * | 1982-06-18 | 1989-08-08 | Mobay Corporation | Liquid polyisocyanate adduct mixtures possessing good compatibility with apolar solvents |
| DE3403277A1 (en) * | 1984-01-31 | 1985-08-01 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING POLYISOCYANATES WITH BIURET STRUCTURE |
| DE19505035A1 (en) * | 1995-02-15 | 1996-08-22 | Basf Ag | Process for the preparation of biisocyanate-containing polyisocyanates |
| DE19633404A1 (en) * | 1996-08-19 | 1998-02-26 | Basf Ag | Process for the production of polyisocyanates containing biuret groups from (cyclo) aliphatic diisocyanates |
| JP2005504137A (en) * | 2001-09-21 | 2005-02-10 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Preparation and use of biuret-containing polyisocyanates as crosslinking agents for coatings |
-
2011
- 2011-01-27 CN CN 201110028404 patent/CN102617827B/en not_active Expired - Fee Related
- 2011-08-26 WO PCT/CN2011/078973 patent/WO2012100532A1/en active Application Filing
- 2011-08-26 DE DE112011101335.3T patent/DE112011101335B4/en not_active Expired - Fee Related
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3124605A (en) * | 1963-12-05 | 1964-03-10 | Biuret polyisocyanates | |
| US3358010A (en) * | 1964-03-11 | 1967-12-12 | Mobay Chemical Corp | Biuret polyisocyanates |
| US4051165A (en) * | 1969-06-19 | 1977-09-27 | Bayer Aktiengesellschaft | Preparation of biuret polyisocyanates |
| US4152350A (en) * | 1976-12-03 | 1979-05-01 | Bayer Aktiengesellschaft | Process for the preparation of polyisocyanates containing biuret groups |
| EP0035158A1 (en) * | 1980-02-29 | 1981-09-09 | Bayer Ag | Process for the preparation of polyisocyanates with a biuret structure |
| CN101274977A (en) * | 2007-03-29 | 2008-10-01 | 周建明 | Curing agent 1,6- hexamethylene diisocyanate prepolymer and preparation thereof |
| CN101475680A (en) * | 2008-05-21 | 2009-07-08 | 胡孝勇 | Method for synthesizing hexamethylene diisocyanate (HDI) biuret |
| CN101717571A (en) * | 2009-10-30 | 2010-06-02 | 华南理工大学 | Method for preparing non-toxic polyurethane curing agent with high solid content |
| CN101935448A (en) * | 2010-08-09 | 2011-01-05 | 江苏大象东亚制漆有限公司 | polyurethane curing agent and two-component polyurethane coating not containing benzene, methylbenzene or dimethylbenzene and TDI |
Non-Patent Citations (3)
| Title |
|---|
| 彭丹等: "HDI类多异氰酸酯固化剂合成研究进展", 《化学与粘合》 * |
| 杨玲等: "用结晶硫酸钠和HDI合成缩二脲的工艺探讨", 《化学工业与工程》 * |
| 胡孝勇等: "HDI缩二脲聚氨酯固化剂合成与残余HDI的分离", 《涂料工业》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014098069A1 (en) * | 2012-12-20 | 2014-06-26 | Dic株式会社 | Resin composition for use as vapor-barrier adhesive, and laminate |
| JP5761460B2 (en) * | 2012-12-20 | 2015-08-12 | Dic株式会社 | Resin composition for water vapor barrier adhesive and laminate |
| CN105820302A (en) * | 2016-04-30 | 2016-08-03 | 华南理工大学 | Nonionic and anionic mixed waterborne polyurethane curing agent and preparation method thereof |
| CN105820302B (en) * | 2016-04-30 | 2018-09-14 | 华南理工大学 | A kind of nonionic and the mixed and modified water-based polyurethane curing agent of anion and preparation method thereof |
| CN111592635A (en) * | 2020-05-08 | 2020-08-28 | 深圳市前海博扬研究院有限公司 | Water-based polyurea curing agent and preparation method and application thereof |
| CN116041224A (en) * | 2023-01-31 | 2023-05-02 | 美瑞新材料股份有限公司 | Preparation method of hexamethylene diisocyanate biuret curing agent |
| CN116041224B (en) * | 2023-01-31 | 2024-02-13 | 美瑞新材料股份有限公司 | Preparation method of hexamethylene diisocyanate biuret curing agent |
Also Published As
| Publication number | Publication date |
|---|---|
| DE112011101335T5 (en) | 2013-04-04 |
| DE112011101335B4 (en) | 2016-10-27 |
| WO2012100532A1 (en) | 2012-08-02 |
| CN102617827B (en) | 2013-10-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102617827B (en) | Curing agent modified 1,6-hexamethylene diisocyanate biuret (HDI biuret) and preparation method thereof | |
| Patel et al. | Air-drying bio-based polyurethane dispersion from cardanol: Synthesis and characterization of coatings | |
| CN101274977B (en) | Curing agent 1,6- hexamethylene diisocyanate prepolymer and preparation thereof | |
| CN103059261B (en) | Modified diphenylmethane diisocyanate biuret curing agent and preparation method thereof | |
| CN109734864B (en) | Lignin-based polyurethane and preparation and application thereof | |
| CN101230124B (en) | Curing agent 4,4'-biphenyl methane diisocyanate prepolymer and preparation method thereof | |
| EP3305828B1 (en) | Polyester polyol, polyurethane resin, and production processes therefor | |
| CN102212182B (en) | Curing agent methylene diphenyl diisocyanate tripolymer and method for preparing same | |
| CN103709373B (en) | Ultra-branched polyurethane acrylate UV light-cured resin and preparation method thereof | |
| US11299614B2 (en) | Sustainable, energy-curable polyester polyols and coatings or rigid foams therefrom | |
| CN104892880B (en) | A kind of preparation method of the TDI tripolymer light curing agent of low free monomer content | |
| CN107082860B (en) | Self-emulsifying waterborne polyurethane curing agent and preparation method thereof | |
| CN101967222A (en) | Preparation method of epoxidized castor oil modified water-borne polyurethane | |
| CN101775120A (en) | Curing agent diisocyanate prepolymer and preparation method thereof | |
| US10189945B2 (en) | Method for producing light-coloured TDI-polyisocyanates | |
| CN105482762A (en) | Preparation method of reversed composite adhesive for food packaging | |
| CN103242254B (en) | Preparation method of HDI-TDI (Hexamethylene Diisocyanate-Toluene Diisocynate) polyurethane tripolymer | |
| EP3467001A1 (en) | Polyester resin comprising biomass-derived monomer and preparation method therefor, and powder paint composition comprising resin | |
| US8735495B2 (en) | Low-viscosity urethane system | |
| CN110483724A (en) | A kind of high branched structure hydrolysis wet polyurethane resin and preparation method thereof | |
| CN104479103B (en) | Polyurethane curing agent having high functionality, preparation method and use thereof | |
| WO2016174027A1 (en) | Polyurethane coverings having reduced water absorption and use thereof | |
| EP3027674B1 (en) | Process for preparing polycarbamate and reaction product thereof | |
| JP6661305B2 (en) | Carbamylation composition of monovalent metal-containing catalyst, polyol and urea compound, and carbamylation process using the same | |
| CN109897172A (en) | The preparation method and application of alkyd resin and polyurethane and acrylate modified alkyd resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| ASS | Succession or assignment of patent right |
Owner name: HUBEI UNIVERSITY OF ARTS AND SCIENCE Effective date: 20120705 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| C53 | Correction of patent of invention or patent application | ||
| CB02 | Change of applicant information |
Address after: 441003441003 No. 57 Zhongyuan Road, hi tech Zone, Hubei, Xiangyang Applicant after: XIANGYANG JINGXIN HUIMING CHEMICAL INDUSTRY Co.,Ltd. Address before: 441003 No. 45 Zhongyuan Road, Hubei, Xiangfan Applicant before: Xiangyang jingxin huiming Chemical industry Co.,Ltd. |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: APPLICANT; FROM: XIANGFAN JINGXIN HUIMING CHEMICAL INDUSTRY CO., LTD. TO: XIANGYANG JINGXIN HUIMING CHEMICAL INDUSTRY CO., LTD. |
|
| TA01 | Transfer of patent application right |
Effective date of registration: 20120705 Address after: 441003441003 No. 57 Zhongyuan Road, hi tech Zone, Hubei, Xiangyang Applicant after: XIANGYANG JINGXIN HUIMING CHEMICAL INDUSTRY Co.,Ltd. Co-applicant after: HUBEI University OF ARTS AND SCIENCE Address before: 441003441003 No. 57 Zhongyuan Road, hi tech Zone, Hubei, Xiangyang Applicant before: XIANGYANG JINGXIN HUIMING CHEMICAL INDUSTRY Co.,Ltd. |
|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: XIANGYANG JINGXIN HUIMING TECHNOLOGY CO., LTD. Free format text: FORMER NAME: XIANGYANG JINGXIN HUIMING CHEMICAL INDUSTRY CO., LTD. |
|
| CP03 | Change of name, title or address |
Address after: 441003 No. 57 Zhongyuan Road, hi tech Zone, Hubei, Xiangfan Patentee after: XIANGYANG JINGXIN HUI MING TECHNOLOGY CO.,LTD. Patentee after: HUBEI University OF ARTS AND SCIENCE Address before: 441003 No. 57 Zhongyuan Road, hi tech Zone, Hubei, Xiangyang Patentee before: XIANGYANG JINGXIN HUIMING CHEMICAL INDUSTRY Co.,Ltd. Patentee before: Hubei University of Arts and Science |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20131030 Termination date: 20210127 |