CN102428117B - 可由两种聚醚胺和预聚物制备的聚脲 - Google Patents
可由两种聚醚胺和预聚物制备的聚脲 Download PDFInfo
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- CN102428117B CN102428117B CN201080021700.9A CN201080021700A CN102428117B CN 102428117 B CN102428117 B CN 102428117B CN 201080021700 A CN201080021700 A CN 201080021700A CN 102428117 B CN102428117 B CN 102428117B
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- 229920002396 Polyurea Polymers 0.000 title claims abstract description 61
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 43
- 229920000570 polyether Polymers 0.000 claims abstract description 43
- 150000001412 amines Chemical class 0.000 claims abstract description 35
- 101100189913 Caenorhabditis elegans pept-1 gene Proteins 0.000 claims abstract description 27
- 108010088535 Pep-1 peptide Proteins 0.000 claims abstract description 26
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 99
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 81
- 238000002360 preparation method Methods 0.000 claims description 40
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 39
- 239000003054 catalyst Substances 0.000 claims description 30
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 229920001451 polypropylene glycol Polymers 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- -1 polyoxypropylene Polymers 0.000 claims description 18
- 150000002148 esters Chemical class 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 238000005507 spraying Methods 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- 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 7
- 239000000463 material Substances 0.000 claims description 7
- 239000007921 spray Substances 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 5
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 5
- 238000009472 formulation Methods 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 150000004982 aromatic amines Chemical group 0.000 claims description 3
- 101000782453 Homo sapiens Vacuolar protein sorting-associated protein 18 homolog Proteins 0.000 claims 4
- 102100035870 Vacuolar protein sorting-associated protein 18 homolog Human genes 0.000 claims 4
- 239000012948 isocyanate Substances 0.000 abstract description 10
- 229920005862 polyol Polymers 0.000 abstract description 10
- 150000003077 polyols Chemical class 0.000 abstract description 10
- 150000002513 isocyanates Chemical class 0.000 abstract description 8
- 239000004970 Chain extender Substances 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 30
- 238000000576 coating method Methods 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 8
- 125000003277 amino group Chemical group 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 6
- 230000021736 acetylation Effects 0.000 description 6
- 238000006640 acetylation reaction Methods 0.000 description 6
- 238000005576 amination reaction Methods 0.000 description 6
- 150000004985 diamines Chemical class 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 150000003141 primary amines Chemical class 0.000 description 6
- HGXVKAPCSIXGAK-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine;4,6-diethyl-2-methylbenzene-1,3-diamine Chemical compound CCC1=CC(CC)=C(N)C(C)=C1N.CCC1=CC(C)=C(N)C(CC)=C1N HGXVKAPCSIXGAK-UHFFFAOYSA-N 0.000 description 5
- 125000005702 oxyalkylene group Chemical group 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
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- 239000007858 starting material Substances 0.000 description 4
- WTFAGPBUAGFMQX-UHFFFAOYSA-N 1-[2-[2-(2-aminopropoxy)propoxy]propoxy]propan-2-amine Chemical compound CC(N)COCC(C)OCC(C)OCC(C)N WTFAGPBUAGFMQX-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
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- 229910052757 nitrogen Inorganic materials 0.000 description 3
- MBAUOPQYSQVYJV-UHFFFAOYSA-N octyl 3-[4-hydroxy-3,5-di(propan-2-yl)phenyl]propanoate Chemical compound OC1=C(C=C(C=C1C(C)C)CCC(=O)OCCCCCCCC)C(C)C MBAUOPQYSQVYJV-UHFFFAOYSA-N 0.000 description 3
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N ethyl trimethyl methane Natural products CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
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- 150000003335 secondary amines Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
- WZLFPVPRZGTCKP-UHFFFAOYSA-N 1,1,1,3,3-pentafluorobutane Chemical compound CC(F)(F)CC(F)(F)F WZLFPVPRZGTCKP-UHFFFAOYSA-N 0.000 description 1
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 description 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- RQEOBXYYEPMCPJ-UHFFFAOYSA-N 4,6-diethyl-2-methylbenzene-1,3-diamine Chemical compound CCC1=CC(CC)=C(N)C(C)=C1N RQEOBXYYEPMCPJ-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- IIGAAOXXRKTFAM-UHFFFAOYSA-N N=C=O.N=C=O.CC1=C(C)C(C)=C(C)C(C)=C1C Chemical compound N=C=O.N=C=O.CC1=C(C)C(C)=C(C)C(C)=C1C IIGAAOXXRKTFAM-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000013495 cobalt Nutrition 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical group OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical group CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920003226 polyurethane urea Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- BGXXXYLRPIRDHJ-UHFFFAOYSA-N tetraethylmethane Chemical compound CCC(CC)(CC)CC BGXXXYLRPIRDHJ-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N tolylenediamine group Chemical group CC1=C(C=C(C=C1)N)N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4866—Polyethers having a low unsaturation value
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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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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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
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- C08G18/08—Processes
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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
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- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/185—Catalysts containing secondary or tertiary amines or salts thereof having cyano 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
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- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3237—Polyamines aromatic
- C08G18/324—Polyamines aromatic containing only one aromatic ring
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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
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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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
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- C08G18/4825—Polyethers containing two hydroxy groups
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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
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- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
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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
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- C08G18/50—Polyethers having heteroatoms other than oxygen
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- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/02—Polyureas
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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
- C09D175/02—Polyureas
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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
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/50—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing nitrogen, e.g. polyetheramines or Jeffamines(r)
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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Abstract
本发明涉及一种可由以下组分制备的聚脲:a)包含以下物质的组分A:a1)5-40重量%至少一种聚醚胺1(PEA 1),其可由至少一种聚醚多元醇1(PEP 1)和至少一种胺1获得,其中PEP 1具有的当量≤500,a2)30-90重量%至少一种聚醚胺2(PEA 2),其可由至少一种聚醚多元醇2(PEP 2)和至少一种胺2获得,其中PEP 2具有的当量>500,a3)5-30重量%至少一种胺增链剂以及b)可由以下物质获得的预聚物组分B:b1)至少一种聚醚多元醇(PEP 3)和b2)至少一种异氰酸酯。
Description
本发明涉及可通过组分A与组分B反应制备的聚脲。组分A包含两种聚醚胺和胺增链剂,组分B为可由聚醚多元醇和异氰酸酯获得的预聚物。本发明聚脲优选作为喷雾配制剂制备。
DE-A 41 17 679涉及通过注射成型或反应性注射成型具有A面和B面的反应混合物制备聚氨酯/聚脲弹性体或聚脲弹性体的方法。这里,所用A面为聚异氰酸酯或具有异氰酸酯封端的聚氨酯预聚物。所用B面为多元醇或多胺和增链剂。多元醇使用双金属氰化物络合物催化剂(DMC催化剂)制备。多胺又通过用胺接枝多元醇制备。如果聚氨酯预聚物用于A面,则该预聚物基于二苯甲烷二异氰酸酯(MDI)与二醇、三醇或高分子量多元醇的反应。
US-B 6,797,798公开了一种包含准预聚物混合物组合物(组分A)和可与异氰酸酯反应的第二有机化合物(组分B)的反应产物的喷雾聚脲弹性体。这里,组分A包含中间体预聚物,其包含第一异氰酸酯组合物和可与异氰酸酯反应的第一有机化合物的反应产物。此外,组分A)包含第二异氰酸酯组合物。对于制备组分A)中存在的中间体预聚物,尤其可以使用多元醇,尤其是平均分子量为约1000-10000的聚醚二醇或聚醚三醇。适合作为组分B)的例如为包含平均分子量为2000-5000的胺封端的聚氧丙烯二胺的胺树脂(例如市售产品JEFFAMINE D-2000)或增链剂如市售产品ETHACURE100。然而,US-B 6,797,798不包括催化剂用于制备多元醇或聚醚多元醇的任何信息。
US-A 5,962,618公开了可由JEFFAMINE型胺树脂制备的其他喷雾聚脲弹性体。这些聚脲包含由异氰酸酯和含活性氢材料形成的准预聚物、胺树脂、增链剂、水和官能烷氧基硅烷的反应产物。
US-A 5,124,426中描述的喷雾聚脲弹性体包含作为组分A的异氰酸酯和作为组分B的胺封端的聚氧化烯多元醇以及增链剂。组分A又可以作为准预聚物形成,其中异氰酸酯与多元醇反应。用于制备组分A和B的多元醇还可以包含上述JEFFAMINE型胺树脂。
不同类型聚脲及其用途的综述可在B.Eling的文章(″Coatings″,ThePolyurethanes Book,D.Randall,S.Lee(编辑),John Wiley&Sons(2002),第363-378页)中找到。可用于聚脲制备的多元醇或聚醚多元醇例如描述于D.Sparrow的文章(″Polyols″;The Polyurethanes Book;D.Randall,S.Lee(编辑),John Wiley&Sons(2002),第89-112页)中。喷雾聚脲的制备方法的综述可以在D.J.Primeaux II的文章(Proceedings of the SPI,32ndAnnual Technical/Marketing Conference,San Francisco,California(1989年10月1日-4日),第126-130页)中找到。
因此,在现有技术中根本没有公开以两种组分之一可以使用就所用聚醚多元醇的当量而言不同的聚醚胺混合物制备聚脲。
本发明目的为提供可经由喷雾配制而制备的其他聚脲。与现有技术那些相比,新型聚脲应具有改进的机械性能和/或可以经济简单方式(成本降低)制备。
该目的通过可由以下组分制备的聚脲实现:
a)包含以下物质的组分A:
a1)5-40重量%至少一种聚醚胺1(PEA 1),其可由至少一种聚醚多元醇1(PEP 1)和至少一种胺1获得,其中PEP 1具有的当量≤500,
a2)30-90重量%至少一种聚醚胺2(PEA 2),其可由至少一种聚醚多元醇2(PEP 2)和至少一种胺2获得,其中PEP 2具有的当量>500,
a3)5-30重量%至少一种胺增链剂
以及
b)可由以下物质获得的预聚物组分B:
b1)至少一种聚醚多元醇(PEP 3)和
b2)至少一种异氰酸酯。
本发明聚脲具有的优点为A组分具有较低粘度并且聚脲,尤其是聚脲喷雾弹性体具有改进的机械性能,例如在其磨耗、其拉伸强度、其断裂伸长率和/或其抗进一步撕裂强度方面。此外,它们可以成本非常有效的方式制备。
在聚脲喷雾弹性体的制备过程中,有利的是A组分的粘度尽可能低以确保A和B组分的良好混合。此外,A和B组分中的反应性组分或所用聚醚多元醇具有至少2,通常2-3,常常(大约)2的标称官能度。聚醚多元醇或由其制备的聚醚胺的标称官能度通过已用于聚醚多元醇的特殊合成的起始剂分子(引发剂)的官能度确定或测定。由此可根据本发明制备基本上线性的聚脲聚合物,尤其是当两种组分a1)和a2)以及合适的话b)的官能度至少为2,优选(大约)2时。
在借助KOH催化剂制备聚醚多元醇如聚丙二醇的过程中,额外形成不饱和物(例如作为聚合过程中次要产物的末端不饱和化合物(一元醇)如烯丙醇)。在制备当量小于500的聚丙二醇的过程中,不饱和物的量很少,但在更高分子量多元醇情况下,形成显著量的不饱和物。这些不饱和物每个分子具有一个羟基(官能度为1)。虽然分子的标称官能度取决于所用起始剂分子为2、3或4,由于在现有技术聚合物情况下在聚合过程中形成的副产物(不饱和物)而(显著)小于标称官能度的实际(数均)官能度是显著的。在聚丙二醇的胺化反应中,不饱和物也被胺化。因此,聚醚胺也具有低于标称官能度的实际(真正)官能度。与此相反,在本发明聚醚多元醇或聚醚胺中,不饱和物(在聚合过程中的不饱和一元醇副产物)含量显著更低。因此,在本发明聚醚多元醇或聚醚胺的情况下,实际官能度相当于标称官能度。
然而,在具有线性结构的聚脲体系中,甚至少量的具有反应性基团的分子导致聚合物分子量显著降低。因此,由于存在该类单官能化合物而使性能受损。
然而,为了获得较大分子量聚合物,在现有技术中通常使用标称官能度为3的聚醚胺如聚醚胺T5000。加入三胺的缺点是A组分粘度由此显著增加。
另一方面,DMC催化剂也可以用于制备聚丙二醇。借助DMC催化剂制备的聚丙二醇通常包含非常少量的不饱和物。因此,对于这些丙二醇,实际官能度基本与标称官能度相同。已知催化剂用量取决于所制备多元醇的分子量。在制备高分子量多元醇中,仅需要两位数ppm范围内的少量催化剂,对于制备当量小于500的聚丙二醇,需要如此大量催化剂使得借助DMC催化剂制备该类多元醇在经济上不令人感兴趣。
本发明聚脲因此具有的优点是A组分具有低粘度并且在A组分与B组分反应过程中形成具有高分子量和良好性能的聚脲。
就本发明而言,以下定义适用:
羟基值(OH值):多元醇(聚醚多元醇)中羟基(OH基团)浓度的度量,以1克相应多元醇中羟基所相当的KOH的mg数表示。OH值经由常规方法DIN 53240测定。单位:mgKOH/g
当量:相当于数值56100除以OH值。
分子量:标称官能度乘以当量。
异氰酸酯指数:异氰酸酯的用量除以异氰酸酯的理论量乘以100。
不饱和值:多元醇(聚醚多元醇)中不饱和端基的(例如烯丙基)浓度的度量,
以1克多元醇中不饱和物的毫当量表示。单位:meq/g
总乙酰化度(acetylatability):反应性基团(-OH、-NH-、-NH2)浓度的度量,以1克聚醚胺中反应性基团所相当的KOH的mg数表示。单位:mgKOH/g
总胺值(胺数):氨基(叔、仲和伯)浓度的度量,以1克聚醚胺中反应性基团所相当的KOH的mg数表示。单位:mgKOH/g
胺化度:[总乙酰化度/总胺值]x 100%
标称官能度:相当于起始剂分子(引发剂)的官能度
可由组分A和组分B制备的本发明聚脲在下文更详细描述。本发明聚脲优选通过组分A与组分B反应制备。然而,合适的话还可以使用两种或更多种不同组分A和/或两种或更多种不同组分B。在本发明聚脲中,组分A与组分B的体积比通常为1∶1-1.5,优选1∶1-1.2,尤其是1∶1。合适的话,组分B也可以不足量使用。
该体系(聚脲)的异氰酸酯指数为80-150,优选90-130,进一步优选95-115。
组分A包含5-40重量%组分a1)、30-90重量%组分a2)和5-30重量%组分a3)。合适的话,其他组分也可以存在于组分A中。
组分a1)为至少一种聚醚胺1(PEA 1),其可由至少一种聚醚多元醇1(PEP 1)和至少一种胺1获得,其中PEP 1具有≤500的当量。
PEA 1通过本领域熟练技术人员已知的方法制备,其中PEP 1和胺1在升高温度和/或升高压力下在过渡金属催化剂以及合适的话氢气存在下反应。该反应可间歇进行,也可以连续进行。作为过渡金属催化剂,例如可以使用含铜或含镍催化剂。合适的胺1原则上为本领域熟练技术人员已知的任何胺,包括氨,其中该胺可以为伯胺或合适的话仲胺。优选使用氨作为胺1。根据组分a1)的聚醚胺例如可以商品名Polyetheramin D400由BASF SE(Ludwigshafen,德国)市购。Polyetheramin D400的标称官能度为2且分子量为400。PEA 1的标称官能度通常为2-4,优选2-3,尤其是2。
PEP 1的当量为≤500,优选50-500,尤其是100-400。PEP 1优选使用碱金属氢氧化物催化剂(MOH催化剂),尤其是使用氢氧化钾催化剂(KOH催化剂)制备。PEP 1的标称官能度通常为2-4,优选2-3,尤其是2。然而,制备PEA 2的其他工艺参数的选择可以不考虑制备PEA 1的相应其他工艺参数。
用于制备PEP 1的原料对本领域熟练技术人员是已知的,其他反应条件也如此。合适的原料通常为氧化烯或氧化烯混合物。这里,氧化烯借助在包含多个羟基的引发剂下的随机或逐步加成缩合而得到PEP 1。合适的氧化烯为氧化乙烯、氧化丙烯、氧化丁烯、氧化戊烯或亚芳烷基氧化物(aralkylene oxide)如氧化苯乙烯。所用氧化烯优选为氧化丙烯或其与至多20重量%氧化乙烯的混合物,尤其是氧化丙烯。合适的话可作为混合物使用的合适引发剂(起始剂或起始剂分子)为脂族三醇如甘油、丙氧基化甘油加合物、三甲基丙烷、三乙基丙烷或二醇如乙二醇、1,3-丙二醇或丁二醇。PEP 1优选为聚氧丙烯聚醚多元醇。
使用PEP 1使性能有利。例如,本发明聚脲的硬度和韧度由于加入PEP1而显著增加。
组分a2)为至少一种聚醚胺2(PEA 2),其可由至少一种聚醚多元醇2(PEP 2)和至少一种胺2获得,其中PEP 2具有>500的当量。
PEA 2与PEA 1的区别为在PEA 2制备过程中使用与在PEA 1相应制备过程中不同的聚醚多元醇(PEP 2)。然而,制备PEA 2的其他工艺参数如所用催化剂或胺对应于在制备PEA 1中使用的那些。然而,制备PEA 2的其他工艺参数的选择可以不考虑制备PEA 1的其他工艺参数。这也适用于相应的优选数据。因此,(例如)胺2的定义相当于胺1的定义,胺2优选为氨。PEA 2的标称官能度通常为2-4,优选2-3,尤其是2。
PEP 1和PEP 2尤其在其当量上不同,在PEP 2情况下当量为>500,优选550-10000,尤其是600-5000。PEP 2的标称官能度通常为2-4,优选2-3,尤其是2。PEP 2优选为聚氧丙烯聚醚多元醇。
PEP 2的制备通过本领域熟练技术人员已知的方法进行。用于制备PEP 2的原料,包括优选数据以及其他工艺参数对应于制备PEP 1的那些。然而,制备PEP 2的其他工艺参数的选择可以不考虑制备PEP 1的相应其他工艺参数。本领域熟练技术人员原则上知道如何制备不同当量的聚醚多元醇。虽然KOH催化剂也可以用于制备PEP 2,优选使用双金属氰化物络合物催化剂(DMC催化剂)制备PEP 2。合适的DMC催化剂是本领域熟练技术人员已知的。优选使用六氰基金属化锌(zinc hexacyanometallate)催化剂。
使用PEP 2使性能有利。例如,本发明聚脲的弹性和低温柔韧性由于加入PEP 2而显著增加。
组分a3)为至少一种胺增链剂。该胺增链剂可以为芳族或脂族的。市售脂族胺增链剂例如Baxxodur PC 136类型。芳族胺增链剂例如为3,5-二乙基-2,4-甲苯二胺、3,5-二乙基-2,6-甲苯二胺、异佛尔酮二胺、二甲硫基甲苯二胺、叔丁基甲苯二胺、1-甲基-3,5-二乙基-2,4-二氨基苯、1-甲基-3,5-二乙基-2,6-二氨基苯、3,5,3′,5′-四乙基-4,4′-二氨基二苯甲烷或其组合。市售芳族胺增链剂例如为DEDTA类型(二亚乙基甲苯二胺)的那些如LonzacureDEDTA 80、ETHACURE 100、ETHACURE 300或Unilink 4200。
组分B为预聚物且可由组分b1)和b2)获得。合适的话,其他组分也可以用于制备组分B。组分b1)为至少一种聚醚多元醇(PEP 3)。组分b2)为至少一种异氰酸酯。
PEP 3可以为任何所需聚醚多元醇,例如PEP 3可以为与PEP 1或PEP2相同的化合物。PEP 3的标称官能度通常为2-4,优选2-3,尤其是2。PEP 3优选对应于PEP 2的上述定义,包括各优选含义。因此,PEP 3同样优选为聚氧丙烯聚醚多元醇或使用DMC催化剂制备。PEP 3的当量同样优选为>500,优选550-10000,尤其是600-5000。
作为异氰酸酯(组分b2),可以使用本领域熟练技术人员已知的任何所需异氰酸酯。合适异氰酸酯例如描述于DE-A 10 2004 022 683中。该异氰酸酯可以为芳族或脂族的。合适的芳族异氰酸酯为二苯甲烷二异氰酸酯(MDI)、聚亚甲基聚苯基异氰酸酯(PMDI)、对亚苯基二异氰酸酯、亚萘基二异氰酸酯、液体碳二亚胺改性MDI或甲苯二异氰酸酯(TDI)。该异氰酸酯特别优选为MDI。优选的脂族异氰酸酯为异佛尔酮二异氰酸酯(IPDI)和四甲基二甲苯二异氰酸酯(TMXDI)。优选使用2,4′和4,4′-MDI的混合物。2,4′-MDI的比例优选为2-70重量%,尤其是30-60重量%。
组分B通常具有10-20的NCO值。
本发明的一个优选实施方案涉及一种可由如下组分制备的聚脲:
a)包含以下物质的组分A:
a1)5-40重量%至少一种聚醚胺1(PEA 1),其可由至少一种聚醚多元醇1(PEP 1)和至少一种胺1获得,其中PEP 1具有的当量≤500并且碱金属氢氧化物催化剂(MOH催化剂),尤其是氢氧化钾催化剂(KOH催化剂)用于制备PEP 1,
a2)30-90重量%至少一种聚醚胺2(PEA 2),其可由至少一种聚醚多元醇2(PEP 2)和至少一种胺2获得,其中PEP 2具有的当量>500并且双金属氰化物络合物催化剂(DMC催化剂)用于制备PEP 2,
a3)5-30重量%至少一种胺增链剂
以及
b)可由以下物质获得的预聚物组分B:
b1)至少一种聚醚多元醇(PEP 3),其中PEP 3具有的当量>500并且DMC催化剂用于制备PEP 3,和
b2)至少一种异氰酸酯。
本发明聚脲优选呈喷雾配制剂形式。聚脲可以为弹性体和/或涂料。本发明聚脲可通过常规制备方法如通过注射成型、反应性注射成型或借助喷雾配制方法,优选通过喷雾配制方法制备。
在本发明聚脲制备过程中,除了上述组分A和B外,还可以存在其他组分。这些其他组分可以预先与组分A和/或组分B混合或加入组分A和/或组分B中。合适的话,还可以将其他组分直接引入聚脲制备方法中。其他组分可以为单一组分或两种或更多种组分的混合物。其他组分例如包括推进剂如水和/或易挥发性有机物质如戊烷或氯仿、HCFC 141b、HFC-134a、HFC-245fa、HFC-365mfc或乙醚。类似地,惰性气体可以用作推进剂。除了推进剂外,还可以使用其他添加剂如染料、生物杀伤剂、增塑剂、脱模剂、填料、反应性和非反应性稀释剂、助粘剂、填料或颜料。碳酸亚丙酯用作反应性稀释剂,环氧硅烷用作助粘剂,碳酸钙用作填料,二氧化钛用作颜料。
因此,本发明还进一步提供一种制备本发明聚脲的方法,其中至少一种组分A与至少一种组分B反应。这优选为喷雾配制方法。该方法本身是本领域熟练技术人员已知的。
以下实施例阐述本发明聚脲及其制备方法。除非另有说明,全部比例以重量百分数给出(重量%)。
实施例
实施例1合成聚醚多元醇(多元醇1-多元醇3)
多元醇1(借助KOH催化剂):
该合成在清洁干燥的10升搅拌高压釜中进行。将0.525kg二丙二醇和0.034kg 47.5%KOH水溶液的溶液放入搅拌反应器中。反应器内容物在氮气下呈惰性,在减压和120℃下处理总共1小时并且干燥至水浓度为约0.02%。然后,将6.167kg氧化丙烯在4小时内计量加入。当计量加入完成时,后搅拌混合物至恒压并且然后将反应混合物在105℃和10毫巴下脱气。所得产物具有59mg KOH/g的OH值并且在进一步使用之前用500ppm作为抗氧化剂的Irganox 1135处理。多元醇1的不饱和值为0.048meq/g,当量为950。
多元醇2(借助DMC催化剂):
该合成根据DE 10 2004 047 406的实施例1在清洁干燥的10升搅拌高压釜中进行。将1.833kg起始剂化合物放入搅拌反应器中并用125ppm根据EP 0 862 947实施例1在表面活性剂存在下由乙酸锌和六氰基钴酸制备的多金属氰化物处理。该起始剂化合物为OH值为240mg KOH/g的双官能丙二醇丙氧基化物,其通过KOH催化剂在随后除去碱性催化剂下制备。
反应器内容物在氮气下呈惰性,并在减压和120℃下处理总共1小时。将6.167kg氧化丙烯在120℃下在4小时内计量加入。当计量加入完成时,后搅拌混合物至恒压并且然后将反应混合物在105℃和10毫巴下脱气。所得产物具有55mg KOH/g的OH值并且在进一步使用之前用500ppm作为抗氧化剂的Irganox 1135处理。多元醇2的不饱和值为0.003meq/g,当量为1020。
多元醇3(借助KOH催化剂):
该合成在清洁干燥的10升搅拌高压釜中进行。将2.56kg二丙二醇和0.034kg 47.5%KOH水溶液的溶液放入搅拌反应器中。反应器内容物在氮气下呈惰性,在减压和120℃下处理总共1小时并且干燥至水浓度为约0.02%。然后,将5.344kg氧化丙烯在4小时内计量加入。当计量加入完成时,后搅拌混合物至恒压并且然后将反应混合物在105℃和10毫巴下脱气。所得产物具有278mg KOH/g的OH值并且在进一步使用之前用500ppm作为抗氧化剂的Irganox 1135处理。多元醇3的不饱和值为0.004meq/g,当量为200。
实施例2合成聚醚胺(PPDA1-PPDA3)
在本发明实施例中,制备具有末端伯胺官能团的聚氧丙烯二胺。在其中实施例1的母体聚氧丙烯聚醚多元醇在升高温度和升高压力下在过渡金属催化剂存在下暴露于氨和氢气的方法中制备聚醚胺。该胺化步骤主要生产伯胺官能团,此时仲胺和叔胺含量基于该胺含量为小于1%。
连续操作的高压固定床反应器用500ml Ni/Co/ZrO2催化剂填充,该催化剂如EP-A 0 696 529所述制备(催化剂A)。将100g/h对应多元醇和210g/h液氨供入该反应器中。将催化剂温度调节为195℃并且反应器填充120巴氢气。将反应器出料在降压之后蒸馏以除去氨和水。
将标称官能度为2和OH值为59mg KOH/g的聚氧丙烯聚醚多元醇(来自实施例1的使用KOH催化剂的多元醇1)转化成具有末端伯胺官能团的聚氧丙烯二胺(PPDA1)。蒸馏残留物的胺值为57mg KOH/g。乙酰化值为61.5mg KOH/g。基于胺值和乙酰化值之比的胺化度为92.7%。
将标称官能度为2和OH值为55mg KOH/g的聚氧丙烯聚醚多元醇(来自实施例1的使用DMC催化剂的多元醇2)转化成具有末端伯胺官能团的聚氧丙烯二胺(PPDA2)。蒸馏残留物的胺值为50.7mg KOH/g。乙酰化值为54.0mg KOH/g。基于胺值和乙酰化值之比的胺化度为93.9%。
将标称官能度为2和OH值为278mg KOH/g的聚氧丙烯聚醚多元醇(来自实施例1的使用KOH催化剂的多元醇3)转化成具有末端伯胺官能团的聚氧丙烯二胺(PPDA3)。蒸馏残留物的胺值为247mg KOH/g。
实施例3合成根据组分B的预聚物
预聚物1由MDI和聚氧丙烯聚醚多元醇(来自实施例1的多元醇1)制备。MDI在每种情况下包含50重量%2,4′-异构体和4,4′-异构体(51.0重量%)。多元醇1的标称官能度为2且OH值为59mg KOH/g。其在作为催化剂的KOH(49重量%)存在下制备。多元醇1的不饱和值为0.048meq/g,当量为950。
预聚物2类似于预聚物1制备,但不同之处在于不使用多元醇1,而使用多元醇2,多元醇2的标称官能度为2且OH值为240mg KOH/g,使用DMC催化剂制备并且不饱和值为0.003meq/g。当量为1020。
预聚物1和2通过标准方法在80℃的批料温度和2小时的反应时间下制备。
实施例4制备聚脲
在以下实施例中,所用A组分为具有以下组分的基础配制剂:
聚醚胺2:PPDA1或PPDA2,在每种情况下为63.1重量%
聚醚胺1:PPDA3,为17.05重量%
胺增链剂:ETHACURE 100,为19.85重量%
ETHACURE 100为来自Albemarle Corporation的市售胺增链剂。其包含3,5-二乙基-2,4-甲苯二胺和3,5-二乙基-2,6-甲苯二胺的80/20混合物。
A组分(使用上述基础配制剂)与B组分(根据实施例3的预聚物之一)反应而得到聚脲喷雾配制剂(弹性体),其中使用100∶109的A组分与B组分混合比。这里在算数上得到104的异氰酸酯指数。所用喷雾装置为来自Graco的喷雾装置(Graco反应器E-XP 2-分配单元),其安装有Graco熔化喷枪,型号AR 2929。所用组分的温度为75℃,压力为160-170巴。将由此制备的聚脲喷雾至涂覆有脱模剂的塑料片(板)上。通过小心拉起涂层一角而从塑料片上取下聚脲涂层。
由此制备以下聚脲涂层(A-D):
表1
聚脲 | 聚脲 | 聚脲 | 聚脲 | |
A组分 | 涂层A | 涂层B | 涂层C | 涂层D |
PPDA1 | 63.1 | 63.1 | ||
PPDA2 | 63.1 | 63.1 | ||
PPDA3 | 17.05 | 17.05 | 17.05 | 17.05 |
Ethacure 100 | 19.85 | 19.85 | 19.85 | 19.85 |
B组分 | ||||
预聚物1 | 109 | 109 | ||
预聚物2 | 109 | 109 |
在各样品在室温和50%湿度下储存两周之后测量这些聚脲涂层的机械性能(见表2)。
表2
Claims (11)
1.一种可由以下组分制备的聚脲:
a)由以下物质组成的组分A:
a1)5-40重量%至少一种聚醚胺1(PEA1),其可由至少一种聚醚多元醇1(PEP1)和至少一种胺1获得,其中PEP1具有的当量≤500并且PEA1的标称官能度为2,
a2)30-90重量%至少一种聚醚胺2(PEA2),其可由至少一种聚醚多元醇2(PEP2)和至少一种胺2获得,其中PEP2具有的当量>500并且PEA2的标称官能度为2,
a3)5-30重量%至少一种芳族胺增链剂
以及
b)由以下物质获得的预聚物组分B:
b1)至少一种聚醚多元醇(PEP3),其中PEP3具有的当量>500且具有的标称官能度为2,和
b2)至少一种异氰酸酯。
2.根据权利要求1的聚脲,其中所述聚脲呈喷雾配制剂形式。
3.根据权利要求1或2的聚脲,其中双金属氰化物络合物催化剂(DMC催化剂)用于制备PEP2。
4.根据权利要求1或2的聚脲,其中DMC催化剂用于制备PEP3。
5.根据权利要求1或2的聚脲,其中碱金属氢氧化物催化剂(MOH催化剂)用于制备PEP1。
6.根据权利要求5的聚脲,其中所述MOH催化剂为氢氧化钾催化剂(KOH催化剂)。
7.根据权利要求1或2的聚脲,其中所述胺1或所述胺2为氨。
8.根据权利要求1或2的聚脲,其中PEP1、PEP2或PEP3为聚氧丙烯聚醚多元醇。
9.根据权利要求1或2的聚脲,其中所述异氰酸酯为二苯甲烷二异氰酸酯(MDI)。
10.一种制备根据权利要求1的聚脲的方法,其中至少一种组分A与至少一种组分B反应。
11.根据权利要求10的方法,其为喷雾配制方法。
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US20210363382A1 (en) * | 2018-09-20 | 2021-11-25 | Akzo Nobel Coatings International B.V. | Two-component coating composition, method for coating a substrate, coated substrate, and use of such coating composition for improving erosion resistance |
DE102019101729B4 (de) * | 2019-01-24 | 2022-07-07 | Jiuhua New Materials Technology Co., Ltd. | Verfahren zur Herstellung eines Polyurea-Formkörpers oder eines Polyurea-Formkörperteiles und entsprechendes Polyureaformteil |
CN111892863A (zh) * | 2019-05-06 | 2020-11-06 | 上海赛内特新材料科技有限公司 | 一种聚脲类防护涂料及其制备方法 |
CN110437725A (zh) * | 2019-08-14 | 2019-11-12 | 四川暄洋新材料科技有限公司 | 一种通过硅酸盐改性的聚醚胺聚氨酯防污涂料及其应用 |
CN110862761A (zh) * | 2019-11-19 | 2020-03-06 | 合众(佛山)化工有限公司 | 一种聚醚胺改性聚氨酯树脂水性功能涂料 |
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ES2436468T3 (es) | 2014-01-02 |
EP2432815A2 (de) | 2012-03-28 |
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WO2010133630A3 (de) | 2011-04-07 |
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