CN110963944A - Novel low-free TDI polyurethane curing agent containing fluorocarbon chains and preparation method thereof - Google Patents
Novel low-free TDI polyurethane curing agent containing fluorocarbon chains and preparation method thereof Download PDFInfo
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- CN110963944A CN110963944A CN201911208930.5A CN201911208930A CN110963944A CN 110963944 A CN110963944 A CN 110963944A CN 201911208930 A CN201911208930 A CN 201911208930A CN 110963944 A CN110963944 A CN 110963944A
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- Prior art keywords
- curing agent
- reaction
- rotary evaporation
- alcohol amine
- methanol
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 84
- 239000004814 polyurethane Substances 0.000 title claims abstract description 64
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 64
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 114
- -1 alcohol amine Chemical class 0.000 claims abstract description 56
- 238000013006 addition curing Methods 0.000 claims abstract description 42
- 239000004970 Chain extender Substances 0.000 claims abstract description 26
- 239000012948 isocyanate Substances 0.000 claims abstract description 25
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 25
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000007259 addition reaction Methods 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 95
- 238000003756 stirring Methods 0.000 claims description 37
- 238000010438 heat treatment Methods 0.000 claims description 25
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 claims description 22
- 230000002829 reductive effect Effects 0.000 claims description 22
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 17
- 238000004821 distillation Methods 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 16
- 239000003963 antioxidant agent Substances 0.000 claims description 12
- 230000003078 antioxidant effect Effects 0.000 claims description 12
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical compound NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 12
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 8
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 5
- OJZQOQNSUZLSMV-UHFFFAOYSA-N (3-aminophenyl)methanol Chemical compound NC1=CC=CC(CO)=C1 OJZQOQNSUZLSMV-UHFFFAOYSA-N 0.000 claims description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 4
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 3
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 claims description 3
- GIXHHVDNJZSLBZ-UHFFFAOYSA-N n-butylbutan-1-amine;phosphoric acid Chemical compound OP(O)(O)=O.CCCCNCCCC GIXHHVDNJZSLBZ-UHFFFAOYSA-N 0.000 claims description 3
- ADJMNWKZSCQHPS-UHFFFAOYSA-L zinc;6-methylheptanoate Chemical compound [Zn+2].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O ADJMNWKZSCQHPS-UHFFFAOYSA-L 0.000 claims 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 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- KCWDJXPPZHMEIK-UHFFFAOYSA-N isocyanic acid;toluene Chemical class N=C=O.N=C=O.CC1=CC=CC=C1 KCWDJXPPZHMEIK-UHFFFAOYSA-N 0.000 claims description 2
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 2
- 229940011051 isopropyl acetate Drugs 0.000 claims description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000004606 Fillers/Extenders Substances 0.000 claims 1
- 239000007983 Tris buffer Substances 0.000 claims 1
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000001723 curing Methods 0.000 abstract description 49
- 239000003973 paint Substances 0.000 abstract description 31
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 27
- 239000011737 fluorine Substances 0.000 abstract description 27
- 229910052731 fluorine Inorganic materials 0.000 abstract description 27
- 238000000576 coating method Methods 0.000 abstract description 21
- 239000011248 coating agent Substances 0.000 abstract description 17
- 239000000126 substance Substances 0.000 abstract description 12
- 239000002253 acid Substances 0.000 abstract description 11
- 239000003513 alkali Substances 0.000 abstract description 9
- 229920005989 resin Polymers 0.000 abstract description 9
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 7
- 238000001035 drying Methods 0.000 abstract description 6
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- 238000001953 recrystallisation Methods 0.000 abstract description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000004922 lacquer Substances 0.000 abstract description 2
- 239000002023 wood Substances 0.000 abstract description 2
- 238000007039 two-step reaction Methods 0.000 abstract 1
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- 239000000178 monomer Substances 0.000 description 12
- 238000010276 construction Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
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- 230000007797 corrosion Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
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- TUMXZMGATGHISZ-UHFFFAOYSA-N 1,1,1,2,3,3-hexafluoropentane-2,4-diol Chemical compound CC(O)C(F)(F)C(O)(F)C(F)(F)F TUMXZMGATGHISZ-UHFFFAOYSA-N 0.000 description 5
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- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
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- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- QSGUUPSHTLCZAS-UHFFFAOYSA-N 1,3,5-tris(2-methylbutan-2-yl)triazinane Chemical compound CC(CC)(N1NN(CC(C1)C(CC)(C)C)C(CC)(C)C)C QSGUUPSHTLCZAS-UHFFFAOYSA-N 0.000 description 3
- PRPAGESBURMWTI-UHFFFAOYSA-N [C].[F] Chemical group [C].[F] PRPAGESBURMWTI-UHFFFAOYSA-N 0.000 description 3
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- 150000004812 organic fluorine compounds Chemical class 0.000 description 3
- RGASRBUYZODJTG-UHFFFAOYSA-N 1,1-bis(2,4-ditert-butylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C RGASRBUYZODJTG-UHFFFAOYSA-N 0.000 description 2
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- 238000004448 titration Methods 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
- 238000005829 trimerization reaction Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/02—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from isocyanates with formation of carbamate groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/04—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—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
- C08G18/7843—Nitrogen containing -N-C=0 groups containing urethane groups
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- 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
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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- Chemical & Material Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a novel fluorocarbon chain-containing polyurethane addition curing agent and a preparation method thereof. The method comprises the following steps: perfluor propylene oxide and alcohol amine are subjected to two-step reaction under the condition of taking methanol as a solvent, N, N-di (2-hydroxy-perfluoropropyl) alcohol amine containing three hydroxyl groups is prepared by rotary evaporation and recrystallization, N, N-di (2-hydroxy-perfluoropropyl) alcohol amine is used as a chain extender for reacting with isocyanate, and the N, N-di (2-hydroxy-perfluoropropyl) alcohol amine and the isocyanate are subjected to addition reaction under the mixed catalysis condition of the solvent and a catalyst to obtain the fluorine-containing carbon chain polyurethane addition curing agent with the solid content of 75%. The curing agent has strong tolerance and good quick-drying performance, can be widely applied to surface coating of wood lacquer, waterproof coating, anticorrosive coating and the like when being matched with polyhydroxy resin components, and endows a paint film with better hardness and acid and alkali resistance chemical properties.
Description
Technical Field
The invention belongs to the field of synthesis and preparation of a coating additive curing agent, and particularly relates to a novel low-free TDI polyurethane curing agent containing fluorocarbon chains and a preparation method thereof.
Background
Polyurethane coatings, also known as urethane coatings, refer to coatings that contain a significant number of urethane linkages in the paint film. It is a new material developed gradually in the middle of the twentieth century, and in the synthesis of polyurethane coatings, urethane paint films are generally obtained by crosslinking and curing isocyanate groups (-NCO) and hydroxyl resin groups (-OH). The epoxy resin can not only provide aesthetic properties such as color and luster, but also protect materials from being damaged by the environment, has wide construction range, can be mixed and matched with various hydroxyl resins for use, and has wide application prospect in industry, agriculture, scientific research and national life.
Curing agents, also known as hardeners, curing agents or setting agents, are a class of substances or mixtures that enhance or control the curing reaction. The resin curing is carried out by carrying out chemical reactions such as condensation, ring closure, addition or catalysis to enable the thermosetting resin to generate an irreversible change process, and the curing is completed by adding a curing agent. The curing agent is an indispensable additive, and the curing agent is required to be added when the curing agent is used as a binder, a coating and a casting material, otherwise, the resin cannot be cured. The variety of the curing agent has great influence on the mechanical property, heat resistance, water resistance and corrosion resistance of the cured product. The TDI-TMP is a polyurethane curing agent which is commonly used at home and abroad at present, and the discovered addition product of the TDI-TMP has over sixty years of history, is improved and developed for more than half a century, and becomes the curing agent which is most widely applied in polyurethane two-component coatings at home and abroad. The composite material has the advantages of excellent comprehensive performance, proper curing rate, good storage performance, good heat resistance, moderate film forming strength and the like. The TDI monomer content of products in developed countries such as Europe and America can reach 0.5 percent, and the products are colorless transparent liquid. Among the most representative products, Desmodur L75, a TDI-TMP adduct produced by Bayer in Germany, Takenate L-75, a TDI-TMP adduct produced by Mitsui Japan, AK-75, a TDI-TMP adduct produced by Korea, a free value of < 0.5%, a solid content of 75%, a tolerance of >3, and a paint film drying time of about 1.5 hours after mixing with a main paint. At present, the tolerance of the curing agent is relatively low, the curing construction time is long, the use scenes are limited due to the hardness, the acid and alkali corrosion resistance and the like, the modification for increasing the tolerance of long-chain alcohol to the curing agent is performed, and few documents aim at the improvement of the paint film performance of the curing agent.
The fluorine-containing polyurethane resin is a high molecular material with special functions, Bayer reports the fluorine-containing polyurethane material firstly in 1947, fluorine atoms in an organic fluorine compound determine the special performance of the fluorine-containing polyurethane resin, fluorine elements are elements with the strongest electronegativity in the periodic table of elements, the radius of the fluorine elements is the smallest atom except hydrogen atoms, and the decomposition heat of fluorine-containing polymers is smaller; the C-F bond is short and large in bond energy, so that the chemical and thermal stability of the organic fluorine compound is improved; fluorine atoms connected with the main chain in the fluorine-containing polymer are distributed spirally along the C-C bond main chain, so that the main chain of the polymer is tightly shielded and is prevented from being directly acted by external factors, such as light, water, oxygen, chemicals and the like, and the weather resistance, oxidation resistance and corrosion resistance of organic fluorine can be effectively improved; the organic fluorine compound has low intermolecular cohesion, small molecular acting force of the air and polymer interface, low surface free energy and small surface friction coefficient, and endows the organic fluorine polymer with excellent water resistance, oil resistance and wear resistance.
At present, there are many methods for modifying paint with fluorine, and the paint film performance can be effectively improved by introducing fluorocarbon chains, patent CN 108977072a discloses a method for preparing fluorocarbon paint modified with fluorocarbon chain resin mixture, which comprises adding copolymerized fluoroolefin, such as Tetrafluoroethylene (TFE), Chlorotrifluoroethylene (CTFE), vinylidene chloride (VDF), vinyl chloride (VF) and the like, as basic units to homopolymerize or copolymerize homopolymer or copolymer, mixing and stirring, adding dodecylbenzene sulfonic acid and silicone oil, feeding into a colloid mill for reaction for 2-4h, adding redox initiator, and mixing with curing agent composition, thereby obtaining paint film with short curing time, high curing efficiency and strong adhesive force. Patent CN 109734918A discloses a fluorine siliconThe preparation method of the isocyanate curing agent comprises the steps of dehydrating perfluorohexyl alcohol and hydroxypropyl fluorosilicone oil monomers, then dropwise adding the dehydrated perfluorohexyl alcohol and hydroxypropyl fluorosilicone oil monomers into polyisocyanate, adding a catalyst for reaction to obtain the curing agent with fluorosilicone isocyanate, and matching with the strong base acrylic resin for construction, the curing agent has excellent chemical stability, atmospheric aging resistance and low surface performance. Patent CN 110028651a discloses a preparation method of fluorocarbon modified isocyanate curing agent for powder coating, which directly reacts fluorocarbon isocyanate with polyester polyol and chain extender under the condition of organic metal catalyst, and finally uses methyl ethyl ketoxime as a sealant to obtain fluorocarbon chain modified isocyanate curing agent, thus increasing hardness, wear resistance, high gloss and weather resistance of the coating. Patent CN 10102907a discloses a preparation method of a fluorine-silicon block chain polymer type marine antifouling paint, which uses a ternary fluorine-silicon bond block copolymer as a base material, and mixes with an auxiliary agent, a pigment and a solvent to obtain the marine antifouling paint with low surface energy, high solvent resistance and stable antifouling effect. Patent CN 103992242B provides a preparation method of fluorinated isocyanate and acrylic copolymer emulsion thereof, wherein, fluorinated alcohol reacts with diisocyanate monomer to obtain fluorinated isocyanate intermediate, the intermediate reacts with hydroxyalkyl acrylate, and then emulsion polymerization is carried out with conventional acrylate to obtain organic fluorine modified polyurethane-acrylate copolymer emulsion, which increases the compatibility among monomers, improves the stability of the synthesized copolymer emulsion, and has better performance in the aspects of water resistance and acid resistance, but the emulsion copolymerization modification process is complex and the application condition is limited. Patent CN 103396722A discloses a water-based UV-curable fluorine-alcohol-modified epoxy resin coating, which is prepared by reacting fluorine-containing hydroxyl-terminated substance with diisocyanate to obtain monoisocyanate-terminated fluorine-containing isocyanate by using a solution polymerization method, and carrying out directional grafting reaction on epoxy resin containing hydroxyl groups to prepare fluorine-alcohol-modified epoxy resin FnEP, further by maleic acid rod monomer with FnAnd (3) carrying out EP reaction to prepare the water-based ultraviolet-curable fluorine alcohol modified epoxy resin, and mixing the resin with water after salifying to prepare the UV-curable coating with excellent heat resistance, weather resistance, stain resistance and low-temperature quick curing performance. Patent CN 103865026B providesA preparation method of an organic fluorine-silicon modified polyurethane emulsion containing a fluorine carbon chain comprises the steps of using isophorone diisocyanate as a hard segment, using a mixture of polytetrahydrofuran ether dihydric alcohol and hydroxyl silicone oil as a soft segment, adding dimethylolpropionic acid and fluorine-containing dihydric alcohol as chain extenders, and adding deionized water and a secondary chain extender for high-speed dispersion to obtain the organic fluorine-modified polyurethane emulsion. Fluorine is applied to the coating in many aspects, but the modification of a two-component chain extender is not performed, the preparation process is complex, the construction condition of the modified coating is limited, the problems that the construction condition of fluorine modification is limited and the performance of a TDI-TMP addition curing agent is poor and the like can be solved by modifying the chain extender with fluorine, and the modification of the chain extender curing agent in the coating has important significance for improving the performance of a coating by adding a fluorine carbon chain segment.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a novel fluorocarbon chain-containing polyurethane addition curing agent and a preparation method thereof. The polyurethane addition curing agent containing fluorocarbon chains provided by the invention is a high-tolerance, corrosion-resistant and quick-drying two-component fluorine-containing polyurethane paint curing agent.
Aiming at the problems that the existing isocyanate addition curing agent has long curing time and the traditional addition curing agent has tolerance and the curing agent film hardness is limited, the invention provides the addition curing agent containing the fluorocarbon chain and the preparation method thereof. The invention aims to introduce the fluorine-containing long carbon chain polyol as a chain extender of isocyanate to replace the traditional mode of a polyol chain extender, and then combine the fluorine-containing carbon chain extender with an isocyanate monomer to obtain the fluorine-containing carbon chain polyurethane addition curing agent, which can increase the tolerance of curing agent components, shorten the curing time of two-component polyurethane coating and simultaneously improve the hardness, acid resistance, alkali resistance and waterproof property of a paint film.
The purpose of the invention is realized by at least one of the following technical solutions.
The invention provides a synthetic method of a fluorine-containing carbon chain extender, which comprises the steps of adding perfluoroepoxypropane and alcohol amine to obtain N, N-bis (2-hydroxy-perfluoropropyl) alcohol amine with a fluorine carbon chain, and further reacting the N, N-bis (2-hydroxy-perfluoropropyl) alcohol amine with isocyanate to obtain a novel fluorine-containing carbon chain curing agent, wherein the alcohol amine can be one or more of amino methanol, ethanolamine or 3-amino benzyl alcohol, and the molecular formula is as follows:
wherein the R group can be methylene, ethylene and toluene groups.
The invention provides a preparation method of a fluorocarbon chain-containing polyurethane addition curing agent, which comprises the following steps:
(1) adding perfluoroepoxypropane and alcohol amine into methanol, and carrying out first heating reflux reaction under the stirring state (the speed is controlled at 150-200rpm) to obtain a product after first heating;
(2) putting the product obtained after the first heating in the step (1) into a rotary evaporator for first rotary evaporation to remove excessive amino methanol or ethanolamine or 3-amino benzyl alcohol, methanol and water to obtain a product obtained after the first rotary evaporation, adding the product obtained after the first rotary evaporation into a reaction kettle, adding perfluoroepoxypropane and methanol, and carrying out a second heating reflux reaction under a stirring state to obtain a product obtained after the second heating;
(3) transferring the product obtained after the second heating in the step (2) into a rotary evaporator again for second rotary evaporation to remove methanol, and obtaining the N, N-bis (2-hydroxy-perfluoropropyl) alcohol amine chain extender;
(4) adding the N, N-bis (2-hydroxy-perfluoropropyl) alcohol amine chain extender obtained in the step (3) into a reaction kettle under the protective atmosphere, adding an organic solvent and an antioxidant, uniformly mixing to fully dissolve all substances, adding isocyanate and a catalyst to obtain a mixture, and heating to perform an addition reaction under the stirring state (the stirring speed is controlled at 100-200rpm) to obtain a product of the addition reaction;
(5) and (4) adding a terminating agent into the product of the addition reaction in the step (4), carrying out the termination reaction in a stirring state, cooling to 40 ℃, filtering and discharging to obtain the fluorocarbon chain-containing polyurethane addition curing agent.
Further, the alcohol amine in the step (1) is one of amino methanol, ethanolamine and 3-amino benzyl alcohol; the mass ratio of the perfluoro propylene oxide to the alcohol amine is 1: 1-3; the mass ratio of the methanol to the alcohol amine is 1: 1-3; the rotating speed of the step (1) in the stirring state is 150-200 rpm; the temperature of the first heating reflux reaction is 40-50 ℃, and the time of the first heating reflux reaction is 2-8 h. The methanol is industrial grade methanol. The alcohol amine can also be in the form of an aqueous solution.
Further, the first rotary evaporation in the step (2) is reduced pressure distillation, the temperature of the first rotary evaporation is 50-80 ℃, the time of the first rotary evaporation is 1-4h, and the pressure of the first rotary evaporation is-0.07 to-0.1 Mpa; the mass ratio of the perfluoro propylene oxide in the step (2) to the alcohol amine in the step (1) is 1: 1-3; the mass ratio of the methanol in the step (2) to the alcohol amine in the step (1) is 1: 2-4.
Further, the rotation speed in the stirring state in the step (2) is 150-.
Further, the second rotary evaporation in the step (3) is reduced pressure distillation, the temperature of the second rotary evaporation is 50-80 ℃, the time of the second rotary evaporation is 1-4h, and the pressure of the second rotary evaporation is-0.07-0.1 Mpa.
Preferably, the N, N-bis (2-hydroxy-perfluoropropyl) olamine chain extender in the step (3) can be further purified by recrystallization from chloroform.
The structural formula of the N, N-bis (2-hydroxy-perfluoropropyl) alcohol amine chain extender in the step (3) is shown as follows:
wherein R may be one of methylene, ethylene and toluene groups.
The steps (1) to (3) are the preparation of the chain extender of the adduct N, N-bis (2-hydroxy-perfluoropropyl) alcohol amine, and the reaction formula is as follows:
wherein R is methyl or ethyl or phenyl.
Further, the protective atmosphere in the step (4) is a nitrogen atmosphere; the organic solvent is more than one of N, N-dimethylformamide, cyclohexanone, acetone, butanone, ethyl acetate, butyl acetate, isopropyl acetate and N-propyl acetate; the mass ratio of the organic solvent to the N, N-bis (2-hydroxy-perfluoropropyl) alcohol amine chain extender is 1: 1-3.
In step (4), the antioxidant is at least one of tris (2, 4-di-tert-butylphenyl) phosphite, pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], N-bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, and bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, the antioxidant is at least one of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and hydrogenated phenylmethane diisocyanate, the catalyst is at least one of zinc isooctoate, tributyl phosphorus, tributyl tin oxide, triethylene diamine, 2,4, 6-tris (dimethylaminomethyl) phenol, 1,3, 5-tris (dimethylpropyl) hexahydrotriazine, the catalyst is at least one of zinc isooctanoate, tributyl phosphorus, tributyl tin oxide, triethylene diamine, 2,4, 6-tris (dimethylaminomethyl) phenol, and 1,3, 5-tris (dimethylpropyl) hexahydrotriazine, and the weight ratio of the isocyanate to N, N-dihydroxy-propyl) alcohol is 1: 5.
Further, the stirring speed in the stirring state in the step (4) is 100-200rpm, and the temperature of the addition reaction is 50-80 ℃; the addition reaction is carried out until the mass fraction of NCO functional groups in the mixture is 12-13.0%.
Preferably, the catalyst in step (4) may be added in two stages.
Preferably, the addition reaction of step (4) may be carried out in two stages. Adding partial catalyst in the first stage, titrating the content of NCO functional groups by di-n-butylamine according to 1-1.5g of the catalyst every 0.5-1h, and entering the second stage when the NCO mass fraction is 15.0-16.0%. And (3) supplementing the rest catalyst, taking 1-1.5g of catalyst every 1 hour, titrating the content of NCO functional groups by using di-n-butylamine, and adding a terminator to stop the reaction when the mass fraction of NCO is 12.0-13.0%.
In the step (5), adding a terminating agent for terminating reaction after the NCO functional group in the mixture is reduced to a specific value (mass fraction is 12-13.0%), and obtaining the fluorocarbon chain-containing polyurethane addition curing agent.
Further, the terminating agent in the step (5) is more than one of phosphoric acid, benzoyl chloride, methyl p-toluenesulfonate, dimethyl sulfate, di-n-butylamine phosphate and anhydrous hydrogen chloride; the mass of the terminator is 0.05 to 0.2 weight percent of the mass of the product of the addition reaction; the temperature of the termination reaction is 50-80 ℃, and the time of the termination reaction is 1-3 h; the stirring rate for terminating the reaction was 100-. The terminator is a trimerization terminator.
The above steps (4) to (5) are the preparation of the fluorocarbon chain-containing polyurethane addition curing agent, and the reaction formula is as follows:
the invention provides a fluorocarbon chain-containing polyurethane addition curing agent prepared by the preparation method, wherein the content of NCO is 10.0-12.0%, and the solid content is 75%.
The curing agent has strong tolerance and good quick-drying performance, can be widely applied to surface coating of wood lacquer, waterproof coating, anticorrosive coating and the like when being matched with polyhydroxy resin components, and endows a paint film with better hardness and acid and alkali resistance chemical properties.
Compared with the prior art, the invention has the following advantages and effects:
(1) according to the preparation method of the fluorocarbon chain-containing polyurethane addition curing agent provided by the invention, in the synthetic process of the fluorocarbon chain, the perfluorinated propylene oxide is added to mainly play a role in introducing the fluorocarbon chain to provide a fluorocarbon structure, so that three influences are exerted on a coating film: firstly, the chemical stability of strong acid and strong base resistance of organic fluorine is utilized and simultaneously used as a hard segment of a paint film, so that the acid and alkali chemical corrosion resistance and the paint film hardness of the paint film are improved; secondly, the introduction of the long fluorocarbon chains increases the relative molecular mass of the adduct curing agent, increases the hardness of a paint film, reduces the reaction curing time and improves the construction efficiency; thirdly, the introduced fluorocarbon chain reduces the polarity of the chain extender, improves the miscibility with a non-polar solvent, improves the tolerance of dimethylbenzene under the condition of not adding long-chain alcohol for modification, and does not reduce the NCO value due to adding the long-chain alcohol and better cooperate with the main paint for construction;
(2) according to the preparation method of the fluorocarbon chain-containing polyurethane addition curing agent, the hydramine is added, so that on one hand, a hydroxyl chain extending group can be provided, the content of hydroxyl of a chain extender is met, the NCO value of the polyurethane addition curing agent is ensured, and the hardness of a paint film is improved by increasing the crosslinking density during curing. Meanwhile, after the alcohol amine is synthesized, primary amine is converted into tertiary amine. The tertiary amine has the strong electronegativity effect, provides a catalytic site in the process of combining with isocyanate, can effectively accelerate the reaction rate, promotes the combination of a chain extender and an isocyanate monomer, further reduces the content of the isocyanate monomer while shortening the reaction time, and reduces the toxicity caused by overhigh free isocyanate monomer due to incomplete reaction;
(3) according to the preparation method of the fluorocarbon chain-containing polyurethane addition curing agent, methanol is selected as a solvent in the synthesis of the fluorocarbon chain extender, and the methanol is a polar solvent, so that the ring-opening reaction of epoxy bonds is facilitated under the condition that the methanol is used as the solvent, the perfluoro epoxypropane component with fluorocarbon chains and the grafting reactant alcohol amine component can react more fully and more quickly under the condition that the methanol solvent is present, and in addition, the boiling point of the methanol is lower, and the methanol can be evaporated and removed after the reaction is finished. Therefore, the methanol can be used as a promoting solvent for the synthesis reaction of the chain extender, and the reaction rate is improved;
(4) the preparation method of the fluorocarbon chain-containing polyurethane addition curing agent provided by the invention has the advantages that Toluene Diisocyanate (TDI) is used as a carrier of isocyanate functional groups, alcohol amine is used as a grafted intermediate connector, fluorocarbon chain-containing organic perfluoroepoxypropane is used as a modified chain extender for enhancing a functional structure, so that the relative molecular mass of key substances of a curing agent main body is increased, the quick-drying rate is increased, the tolerance is improved, the content of free isocyanate monomers is more effectively reduced through a two-step isocyanate dripping mode, the reaction is more sufficient, the molecular weight of a product is increased, the vapor pressure of molecules is reduced, and the toxicity of the product is further reduced;
(5) the fluorocarbon chain-containing polyurethane addition curing agent provided by the invention can replace the traditional TDI-TMP curing agent, shortens the construction time, improves the hardness of a paint film, improves the water resistance and the acid and alkali corrosion resistance of the paint film, does not need constructors to search for a new formula and a new formula ratio, and reduces the cost of replacing a main paint and searching for the new formula due to the replacement of the curing agent.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Example 1
In a reaction kettle, according to the weight ratio of the formula, respectively adding 100g of methanol, 104g of perfluoroepoxypropane and 158g of amino methanol into the kettle, starting stirring (the rotating speed is 175rpm) and refluxing, raising the temperature to 45 ℃ to start the reaction, stopping the reaction after 6h of the reaction, transferring the reaction into a rotary evaporator to perform reduced pressure distillation under the condition of 60 ℃/0.1 MPa, after the methanol and the amino methanol are completely evaporated, transferring the primary product into the reaction kettle, adding 125g of perfluoroepoxypropane and 50g of methanol, starting stirring (the rotating speed is 175rpm) and raising the temperature to 65 ℃ to continue the reaction, continuing transferring the reaction into the rotary evaporator to perform reduced pressure distillation under the condition of 60 ℃/0.1 MPa after 4h of the reaction, recrystallizing and purifying by using chloroform to finally obtain 196g of the N, N-bis (2-hydroxy-perfluoropropyl) methanol adduct. The reaction mixture was charged into a reaction vessel, to which were added 121g of ethyl acetate and 0.8g of tris (2, 4-di-t-butylphenyl) phosphite, 6.5g of tributyl phosphorus was added with stirring (185 rpm), and 293g of toluene diisocyanate was added after dissolution. And (3) detecting the NCO value, wherein the NCO value reaches 15.6% after 3.5h, adding 2g of tributyl phosphorus catalyst, continuously detecting the NCO value, wherein the NCO value reaches 12.9% after 3h, mixing 4.5g of phosphoric acid (serving as a terminator) into 42g of ethyl acetate, continuously reacting for 1h, cooling to 40 ℃, discharging, and packaging to obtain the novel fluorocarbon chain-containing polyurethane addition curing agent. The percent NCO content was determined as HG/T2409-1992; the solids content was determined according to GB/T2793-1995; the tolerance of the xylene is tested by xylene titration, namely the ratio of the mass of the xylene to the mass of the sample when the xylene is white and turbid; the color number is determined by adopting a platinum-cobalt color number; the viscosity was measured at 25 ℃ using a rotary viscometer according to GB/T2794-1995; TDI free value monomer free content was determined according to GB/T18446-2009. The parameters of the novel fluorocarbon chain-containing polyurethane addition curing agent prepared in example 1 are shown in table 1 below.
TABLE 1
Example 2
In a reaction kettle, according to the weight ratio of the formula, respectively adding 105g of methanol, 99g of perfluoropropylene oxide and 147g of amino methanol into the kettle, starting stirring (the rotation speed is 165rpm) and refluxing, heating to 40 ℃ to start reaction, stopping the reaction after 5h of reaction, transferring the reaction into a rotary evaporator to perform reduced pressure distillation under the condition of 60 ℃/0.1 MPa, after the methanol and the amino methanol are completely evaporated, transferring the primary product into the reaction kettle, adding 115g of perfluoropropylene oxide and 45g of methanol, starting stirring (the rotation speed is 165rpm) and heating to 65 ℃ to continue the reaction, transferring the reaction into the rotary evaporator to perform reduced pressure distillation under the condition of 60 ℃/0.1 MPa after 5h of reaction, recrystallizing and purifying by using chloroform to finally obtain 186g of N, N-bis (2-hydroxy-perfluoropropyl) methanol adduct. 112g of ethyl acetate and 0.6. 0.6g N g of N-bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine were put into a reaction vessel, stirred (rotation speed: 175rpm) was started, 4.3g of tributyl phosphorus was mixed, and 258g of toluene diisocyanate was added after dissolution. And (3) detecting the NCO value, wherein the NCO value reaches 15.2% after 3.5h, adding 1.8g of zinc isooctanoate, continuously detecting the NCO value, wherein the NCO value reaches 13.0% after 3h, mixing 3.3g of methyl p-toluenesulfonate (serving as a terminator) into 38g of ethyl acetate, continuously reacting for 1.5h, cooling to 40 ℃, discharging, and packaging to obtain the novel fluorocarbon chain-containing polyurethane addition curing agent. The parameters of the novel fluorocarbon chain-containing polyurethane addition curing agent prepared in example 2 are shown in table 2 below, and the method and standard of the related test are referred to in example 1.
TABLE 2
Example 3
In a reaction kettle, according to the weight ratio of the formula, respectively adding 140g of methanol, 114g of perfluoropropylene oxide and 179g of ethanolamine, starting stirring (185 rpm) and refluxing, heating to 50 ℃ to start the reaction, stopping the reaction after 7h of reaction, transferring to a rotary evaporator for reduced pressure distillation under the condition of 60 ℃/-0.1MPa, after methanol and amino methanol are completely evaporated, transferring the initial product to the reaction kettle, adding 136g of perfluoropropylene oxide and 68g of methanol, starting stirring (185 rpm) and heating to 70 ℃ to continue the reaction, after 6h of reaction, transferring to the rotary evaporator for reduced pressure distillation under the condition of 60 ℃/-0.1MPa, recrystallizing and purifying by using chloroform to finally obtain 228g of N, N-bis (2-hydroxy-perfluoropropyl) ethanol adduct, putting the adduct into the reaction kettle, adding 144g of butyl acetate and 1g of tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester antioxidant, starting stirring (185 rpm) to obtain the value of 2, adding 6 g-bis (2-4-hydroxy-perfluoropropyl) propionate) pentaerythritol ester, after starting stirring to obtain the value of 5g of 2, after adding the new type polyurethane curing agent, detecting the value of 5g of 5h, adding the polyurethane, adding the new type polyurethane curing agent, detecting the polyurethane, adding the polyurethane, and detecting the polyurethane, adding the polyurethane, adding the polyurethane curing agent, the polyurethane, and the polyurethane, wherein the polyurethane, the polyurethane with the polyurethane, the polyurethane with the polyurethane, the polyurethane with the polyurethane, the.
TABLE 3
Example 4
In a reaction kettle, according to the weight ratio of the formula, 150g of methanol, 119g of perfluoroepoxypropane and 186g of ethanolamine are respectively added into the kettle, stirring (the rotation speed is 165rpm) and refluxing are started, the temperature is raised to 50 ℃ to start the reaction, the reaction is stopped after 6h of reaction and is transferred into a rotary evaporator to be subjected to reduced pressure distillation under the condition of 60 ℃/-0.1MPa, after the methanol and the amino methanol are completely evaporated, an initial product is transferred into the reaction kettle, 142g of perfluoroepoxypropane and 77g of methanol are added, stirring (the rotation speed is 165rpm) is started, the temperature is raised to 70 ℃ to continue the reaction, after 6h of reaction, the initial product is transferred into the rotary evaporator to be subjected to reduced pressure distillation under the condition of 60 ℃/-0.1MPa, recrystallization and purification are performed by using chloroform, 289g of N, N-bis (2-hydroxy-perfluoropropyl) ethanol adduct is finally obtained, butyl acetate 162g and tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester antioxidant are added into the reaction kettle, after the initial product is subjected to be subjected to recrystallization and purified, after the final obtaining 289g of N, N-bis (2-hydroxy-perfluoropropyl) ethanol adduct, butyl acetate, the initial product is added into the reaction kettle, the initial product is added into the reaction kettle, the urethane antioxidant is added with 2-4-hydroxy-4-hydroxy-4-hydroxy-4-hydroxy-4-hydroxy.
TABLE 4
Example 5
In a reaction kettle, according to the weight ratio of the formula, respectively adding 100g of methanol, 109g of perfluoropropylene oxide and 390g of ethanolamine into the kettle, starting stirring (the rotating speed is 175rpm) and refluxing, raising the temperature to 45 ℃ to start the reaction, stopping the reaction after 4h of reaction, transferring the reaction into a rotary evaporator to perform reduced pressure distillation under the condition of 60 ℃/0.1 MPa, transferring the primary product into the reaction kettle after the methanol and the amino methanol are completely evaporated, adding 131 g of perfluoropropylene oxide and 50g of methanol, starting stirring (the rotating speed is 175rpm) and raising the temperature to 70 ℃ to continue the reaction, transferring the reaction into the rotary evaporator to perform reduced pressure distillation under the condition of 60 ℃/0.1 MPa after 7h of reaction, recrystallizing and purifying by using chloroform to finally obtain 235g of N, N-bis (2-hydroxy-perfluoropropyl) ethanol adduct. Adding 148g of butyl acetate and 1.2g of bis (2.4-di-tert-butylphenyl) pentaerythritol diphosphite antioxidant into a reaction kettle, starting stirring (185 rpm), mixing 6g of triethylene diamine, beginning to drop 345g of toluene diisocyanate, detecting the NCO value, after 5 hours, enabling the NCO value to reach 15.8%, adding 5g of triethylene diamine, beginning to detect the NCO value, after 2 hours, enabling the NCO value to reach 13.0%, mixing 5g of benzoyl chloride (serving as a terminator) into 50g of ethyl acetate, continuously reacting for 1 hour, cooling to 40 ℃ and discharging to obtain the novel fluorocarbon chain-containing polyurethane addition curing agent. The parameters of the novel fluorocarbon chain-containing polyurethane addition curing agent prepared in example 5 are shown in table 5 below, and the methods and standards of the related tests are referred to in example 1.
TABLE 5
Example 6
In a reaction kettle, according to the weight ratio of the formula, respectively adding 120g of methanol, 129g of perfluoropropylene oxide and 402g of ethanolamine into the kettle, starting stirring (the rotating speed is 175rpm) and refluxing, heating to 40 ℃ to start reaction, stopping the reaction after 5h of reaction, transferring into a rotary evaporator for reduced pressure distillation under the condition of 60 ℃/0.1 MPa, after the methanol and the amino methanol are completely evaporated, transferring the primary product into the reaction kettle, adding 142g of perfluoropropylene oxide and 69g of methanol, starting stirring (the rotating speed is 175rpm) and heating to 70 ℃ to continue the reaction, transferring into the rotary evaporator for 6h of reaction, carrying out reduced pressure distillation under the condition of 60 ℃/0.1 MPa, recrystallizing and purifying by using chloroform to finally obtain 277g of N, N-bis (2-hydroxy-perfluoropropyl) ethanol adduct. 153g of butyl acetate and 1.5g of bis (2.4-di-tert-butylphenyl) pentaerythritol diphosphite antioxidant are added into a reaction kettle, stirring is started (the rotating speed is 175rpm) to mix 7g of 1,3, 5-tris (dimethylpropyl) hexahydrotriazine, after the mixture is dissolved, 382g of toluene diisocyanate is added, the NCO value is detected, after 5.5 hours, the NCO value reaches 15.7%, 5g of triethylene diamine is added, the NCO value is continuously detected, after 3 hours, the NCO value reaches 12.9%, 6g of di-n-butylamine phosphate (used as a terminator) is mixed into 55g of ethyl acetate, the reaction is continuously carried out for 1.5 hours, the temperature is reduced to 40 ℃, and the novel fluorocarbon chain-containing polyurethane addition curing agent is obtained. The parameters of the novel fluorocarbon chain-containing polyurethane addition curing agent prepared in example 6 are shown in table 6 below, and the methods and standards of the related tests refer to example 1.
TABLE 6
Comparative example:
a commercially available TDI-TMP polyurethane addition curing agent was used as a comparative example, and the product specifications are shown in Table 7 below, the method of testing and the standards are referred to in example 1.
TABLE 7
The novel fluorocarbon chain-containing polyurethane addition curing agent in the examples and the commercially available TDI-TMP polyurethane addition curing agent in the comparative examples were prepared into two groups of polyurethane coatings with alkyd resin according to the NCO: OH ratio of 1:1 (molar ratio), the paint viscosity was adjusted to 20s (coating-4 cups, 23 + -2 ℃) with butyl acetate diluent, and the coatings were sprayed on the surface of tin plate, and the curing tack-free and finger-pressure-dry times, i.e., the time taken from the start of the construction until the paint was not touched with the hand and the time taken for the finger to press the surface of the paint film after spraying without leaving a fingerprint, were tested. And then standing for 24 hours at 25 ℃ and 50% humidity, and testing the hardness, the adhesive force and the acid and alkali resistance. The hardness is measured according to GB/T6739-2006; adhesion was determined according to GB/T9286-1998; tack-free time and tack-free time were determined according to GB/T1728-1979; the acid and alkali resistance was determined according to GB/T1763-1989. The test results are shown in table 8 below.
TABLE 8
As can be seen from Table 8, the novel fluorocarbon chain-containing polyurethane addition curing agent provided by the embodiment is used in combination with the main paint, so that the physical properties of the hardness and the adhesive force of the paint film can be improved, the acid and alkali resistance and chemical corrosion resistance are enhanced, the drying time of the paint film is reduced, and the construction efficiency and the film forming performance of the paint film are effectively improved.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.
Claims (10)
1. A preparation method of a novel fluorocarbon chain-containing polyurethane addition curing agent is characterized by comprising the following steps:
(1) adding perfluoroepoxypropane and alcohol amine into methanol, and carrying out first heating reflux reaction under a stirring state to obtain a first heated product;
(2) performing primary rotary evaporation on the product subjected to primary heating in the step (1) to obtain a product subjected to primary rotary evaporation, adding the product subjected to primary rotary evaporation into a reaction kettle, adding perfluoroepoxypropane and methanol, and performing secondary heating reflux reaction under a stirring state to obtain a product subjected to secondary heating;
(3) performing secondary rotary evaporation on the product obtained after the secondary heating in the step (2) to obtain an N, N-bis (2-hydroxy-perfluoropropyl) alcohol amine chain extender;
(4) adding the N, N-bis (2-hydroxy-perfluoropropyl) alcohol amine chain extender obtained in the step (3) into a reaction kettle under a protective atmosphere, adding an organic solvent and an antioxidant, uniformly mixing, adding isocyanate and a catalyst to obtain a mixture, and heating under a stirring state to perform an addition reaction to obtain a product of the addition reaction;
(5) and (4) adding a terminating agent into the product of the addition reaction in the step (4), and carrying out termination reaction under a stirring state to obtain the fluorocarbon chain-containing polyurethane addition curing agent.
2. The method for preparing a novel fluorocarbon chain-containing polyurethane addition curing agent according to claim 1, wherein the alcohol amine in step (1) is one of amino methanol, ethanolamine and 3-aminobenzyl alcohol; the mass ratio of the perfluoro propylene oxide to the alcohol amine is 1: 1-3; the mass ratio of the methanol to the alcohol amine is 1: 1-3; the rotating speed of the step (1) in the stirring state is 150-200 rpm; the temperature of the first heating reflux reaction is 40-50 ℃, and the time of the first heating reflux reaction is 2-8 h.
3. The method for preparing the novel fluorocarbon chain-containing polyurethane addition curing agent according to claim 1, wherein the first rotary evaporation in the step (2) is reduced pressure distillation, the temperature of the first rotary evaporation is 50 ℃ to 80 ℃, the time of the first rotary evaporation is 1 to 4 hours, and the pressure of the first rotary evaporation is-0.07 to-0.1 Mpa; the mass ratio of the perfluoro propylene oxide in the step (2) to the alcohol amine in the step (1) is 1: 1-3; the mass ratio of the methanol in the step (2) to the alcohol amine in the step (1) is 1: 2-4.
4. The method for preparing a novel fluorocarbon chain-containing polyurethane addition curing agent as claimed in claim 1, wherein the rotation speed in the stirring state in step (2) is 150-200rpm, the temperature of the second heating reflux reaction is 65-70 ℃, and the time of the second heating reflux reaction is 2-8 h.
5. The method for preparing the novel fluorocarbon chain-containing polyurethane addition curing agent according to claim 1, wherein the second rotary evaporation in step (3) is reduced pressure distillation, the temperature of the second rotary evaporation is 50 ℃ to 80 ℃, the time of the second rotary evaporation is 1 to 4 hours, and the pressure of the second rotary evaporation is-0.07 to-0.1 Mpa.
6. The method for preparing the novel fluorocarbon chain-containing polyurethane addition curing agent according to claim 1, wherein the protective atmosphere in the step (4) is a nitrogen atmosphere; the organic solvent is more than one of N, N-dimethylformamide, cyclohexanone, acetone, butanone, ethyl acetate, butyl acetate, isopropyl acetate and N-propyl acetate; the mass ratio of the organic solvent to the N, N-bis (2-hydroxy-perfluoropropyl) alcohol amine chain extender is 1: 1-3.
7. The method of claim 1, wherein the antioxidant in step (4) is one or more selected from tris (2, 4-di-tert-butylphenyl) phosphite, pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], N-bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, and bis (2, 4-di-tert-butylphenyl) pentaerythrityl diphosphite, wherein the isocyanate is one or more selected from toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and hydrogenated phenylmethane diisocyanate, and wherein the mass ratio of the isocyanate to N, N-bis (2-hydroxy-perfluoropropyl) alkanolamine extender is 1: 0.5-1, the antioxidant is 0.1-0.3% by mass of the mixture, and the catalyst is one or more selected from zinc isooctanoate, tributyl phosphorus, tributyl tin oxide, triethylene diamine, 2,4, 6-tris (2-hydroxy-perfluoropropyl) ethanolamine, and the antioxidant is 1.3-0.3% by mass of the mixture.
8. The method for preparing a novel fluorocarbon chain-containing polyurethane addition curing agent as claimed in claim 1, wherein the stirring speed in the stirring state in step (4) is 100-200rpm, and the temperature of the addition reaction is 50-80 ℃; the addition reaction is carried out until the mass fraction of NCO functional groups in the mixture is 12-13.0%.
9. The method for preparing a novel fluorocarbon chain-containing polyurethane addition curing agent according to claim 1, wherein the terminating agent in step (5) is one or more of phosphoric acid, benzoyl chloride, methyl p-toluenesulfonate, dimethyl sulfate, di-n-butylamine phosphate, and anhydrous hydrogen chloride; the mass of the terminator is 0.05 to 0.2 weight percent of the mass of the product of the addition reaction; the temperature of the termination reaction is 50-80 ℃, and the time of the termination reaction is 1-3 h; the stirring rate for terminating the reaction was 100-.
10. A novel fluorocarbon chain-containing polyurethane addition curing agent obtained by the production method according to any one of claims 1 to 9, characterized by having an NCO content of 10.0 to 12.0% and a solid content of 75%.
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