CN116731381A - 一种含二氧化碳加合物的液态发泡剂 - Google Patents
一种含二氧化碳加合物的液态发泡剂 Download PDFInfo
- Publication number
- CN116731381A CN116731381A CN202310551793.5A CN202310551793A CN116731381A CN 116731381 A CN116731381 A CN 116731381A CN 202310551793 A CN202310551793 A CN 202310551793A CN 116731381 A CN116731381 A CN 116731381A
- Authority
- CN
- China
- Prior art keywords
- polyamine
- polyamine polymer
- adducts
- solvent
- blowing agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004088 foaming agent Substances 0.000 title claims description 28
- 239000007788 liquid Substances 0.000 title abstract description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical class O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title description 136
- 229920000642 polymer Polymers 0.000 claims abstract description 122
- 229920000768 polyamine Polymers 0.000 claims abstract description 117
- 239000004604 Blowing Agent Substances 0.000 claims abstract description 50
- 239000002904 solvent Substances 0.000 claims abstract description 44
- 238000005187 foaming Methods 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 239000006260 foam Substances 0.000 claims abstract description 19
- 125000003277 amino group Chemical group 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 11
- 125000004429 atom Chemical group 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 229920002873 Polyethylenimine Polymers 0.000 claims description 28
- -1 alcohol amine Chemical class 0.000 claims description 24
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- 125000005647 linker group Chemical group 0.000 claims description 17
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 15
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 15
- 239000011496 polyurethane foam Substances 0.000 claims description 15
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 12
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical group NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 11
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 10
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 10
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 10
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims description 9
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 8
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 7
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 7
- 235000011187 glycerol Nutrition 0.000 claims description 7
- 229920000083 poly(allylamine) Polymers 0.000 claims description 7
- 229920001451 polypropylene glycol Polymers 0.000 claims description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- 229960004063 propylene glycol Drugs 0.000 claims description 7
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 claims description 6
- 150000002009 diols Chemical class 0.000 claims description 6
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 6
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims description 6
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 5
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 5
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 150000001721 carbon Chemical group 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims 2
- 229940035437 1,3-propanediol Drugs 0.000 claims 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims 2
- 235000013772 propylene glycol Nutrition 0.000 claims 2
- 229960005150 glycerol Drugs 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 239000006185 dispersion Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000001569 carbon dioxide Substances 0.000 description 67
- 229910002092 carbon dioxide Inorganic materials 0.000 description 67
- 238000000034 method Methods 0.000 description 17
- 229920002635 polyurethane Polymers 0.000 description 14
- 239000004814 polyurethane Substances 0.000 description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- 230000002209 hydrophobic effect Effects 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 6
- 150000002513 isocyanates Chemical class 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000002390 rotary evaporation Methods 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 229920000333 poly(propyleneimine) Polymers 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 239000008240 homogeneous mixture Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- JLHTVZLEHOQZBM-UHFFFAOYSA-N 1-bromo-2-isocyanatoethane Chemical compound BrCCN=C=O JLHTVZLEHOQZBM-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000002666 chemical blowing agent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000007922 dissolution test Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000004665 fatty acids Chemical group 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000010952 in-situ formation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- JDNTWHVOXJZDSN-UHFFFAOYSA-N iodoacetic acid Chemical compound OC(=O)CI JDNTWHVOXJZDSN-UHFFFAOYSA-N 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 239000004620 low density foam Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3275—Hydroxyamines containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3278—Hydroxyamines containing at least three hydroxy groups
- C08G18/3281—Hydroxyamines containing at least three hydroxy groups containing three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6644—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6655—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
-
- 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
- C08G2101/00—Manufacture of cellular products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
本发明公开了一种含多胺聚合物的CO2加合物的液态发泡剂,由CO2加合物和溶剂组成;该CO2加合物由多胺聚合物和CO2组成,CO2和多胺聚合物以加合物的形式存在;或所述CO2加合物由接枝改性多胺聚合物和CO2组成,CO2和多胺聚合物主链以加合物的形式存在;所述多胺聚合物为分子链中含有4个及以上胺基的聚合物,胺基所连原子为碳原子,其结构为直链、支化、超支化中的至少一种,分子量大于200。加入发泡混合物为液体,在发泡体系中分散度高,发泡效果好。该溶剂为反应性溶剂,可以和发泡体系中的其它物质发生化学反应,成为泡沫的一部分。
Description
技术领域
本发明涉及发泡剂的技术领域,具体涉及一种含二氧化碳(CO2)加合物的液态发泡剂。
背景技术
聚氨酯泡沫广泛用于沙发、床垫、汽车坐垫、冰箱、管道和建筑保温等领域。一般而言,聚氨酯泡沫的生产往往需要大量的发泡剂,传统的发泡剂为低沸点氯氟烃(CFC)和氢氯氟烃(HCFC)化合物,其结构中含有氯原子,会破坏臭氧层;目前使用的发泡剂包括不含氯不破坏臭氧层的氢氟碳(HFC)化合物和含氟烯烃(HFO)化合物,但前者具有很强的温室效应,是造成全球变暖的元凶之一,后者在大气中的分解产物含三氟醋酸(CF3COOH)和氢氟酸(HF),有可能造成酸污染,破坏生态环境。常见的发泡剂还包括烷烃类发泡剂(例如环戊烷),这类发泡剂的性能与HFO类似,虽然对环境影响较小,但存在易燃易爆的风险。
由多胺聚合物和CO2反应形成加合物,该加合物受热可释放CO2用于聚氨酯发泡。该发泡剂的优点是室温下可以将CO2固定在多胺聚合物中,并可与聚氨酯原料混合,克服了气态CO2难以贮存在发泡原料中的缺点。在聚氨酯发泡过程中,该发泡剂吸收反应热,释放CO2用于发泡。这类发泡剂为固体,在聚氨酯原料中难以分散。中国专利CN 103965470 A公开了疏水改性聚乙烯亚胺的CO2加合物发泡剂,所用的疏水链为聚丙二醇链或烷基链,疏水改性一定程度上提高了发泡剂在聚氨酯原料中的分散性。中国专利CN 112457520A采用将疏水改性的聚乙烯亚胺和聚醚多元醇混合,然后吸收CO2原位生成疏水改性聚乙烯亚胺的CO2加合物发泡剂,该发泡剂以纳米颗粒的形式存在于聚醚多元醇中。这种方法大大提高了该发泡剂的分散性,但是也提高了发泡混合物的粘度,造成使用不便;粘度过高,有可能阻碍气泡的生长,甚至造成气泡破裂,导致发泡失败。
实际上,传统的聚氨酯发泡剂都是液态,很容易和其他液态原料混合,用于发泡。现有的CO2加合物发泡剂都是固态,使用起来很不方便。开发液态的CO2加合物发泡剂既可以保留CO2加合物发泡剂的环境友好的特点,又可以增加施工的方便性。
发明内容
本发明人针对现有的多胺聚合物的CO2加合物发泡剂使用不方便的特点,积极寻找其溶剂,希望开发出液态的CO2加合物发泡剂体系。该发泡剂为CO2加合物,分子结构上含有烷基铵正离子和氨基甲酸根负离子组成的两性离子(为亲水结构),一般的有机溶剂是难以溶解该发泡剂的。水可以溶解多胺聚合物的CO2加合物。但是水本身也是聚氨酯的发泡剂,引入过多的水,会导致所生成的聚合物结构中生成大量的脲键,泡沫变脆。同时水和多胺聚合物的CO2加合物发泡剂同时存在一个体系中,会给泡沫配方设计带来牵制。例如,为了得到低密度的泡沫,需要加大发泡剂用量;如果发泡剂中存在水,必然会加大水的用量,而水的增加就会增大异氰酸酯的用量,使泡沫变脆。也就是说密度低而软的泡沫就很难制备出来。另外,一般情况下多胺聚合物的CO2加合物发泡剂是需要疏水改性的(为了提高该发泡剂在聚氨酯原料中的分散能力;同时接枝改性会提高位阻,避免多胺聚合物释放CO2发泡以后形成的自由氨基和异氰酸酯过多的反应,这会导致泡沫交联密度过大,也会导致泡沫变脆),疏水改性后在水中的溶解度会下降很多。因此,单纯的水作为多胺聚合物的CO2加合物发泡剂的溶剂是不合适的。
本发明人仔细研究了多胺聚合物的CO2加合物的分子结构,发现该结构所含的烷基铵正离子和氨基甲酸根负离子均可以形成氢键,于是积极探索含羟基和氨基的化合物作为多胺聚合物的CO2加合物的溶剂的可行性。经过大量探索,发现碳原子数≤8,羟基和氨基总数为2~5的醇、胺和/或醇胺可以溶解多胺聚合物的CO2加合物。同时所述的醇、胺和/或醇胺还可以和聚氨酯的原料之一异氰酸酯反应,成为聚氨酯泡沫制品的一部分。因此,所述的醇、胺和/或醇胺一方面溶解多胺聚合物的CO2加合物发泡剂(即多胺聚合物的CO2加合物发泡剂),使其该发泡剂可以和液态的聚氨酯原料充分混合,在泡沫制备过程中起到发泡剂的作用;同时所述的醇、胺和/或醇胺还可以与异氰酸酯反应,起到扩链剂的作用,最终成为泡沫材料的一部分。
本发明的目的之一是提供一种含CO2加合物的液态发泡剂,该发泡剂至少由CO2加合物和溶剂组成。所述CO2加合物由多胺聚合物和CO2组成,CO2和多胺聚合物以加合物的形式存在;或所述CO2加合物由接枝改性多胺聚合物和CO2组成,CO2和多胺聚合物主链以加合物的形式存在;所述多胺聚合物为分子链中含有4个及以上胺基的聚合物,胺基所连原子为碳原子,其结构为直链、支化、超支化中的至少一种,分子量大于200。所述溶剂为碳原子数≤8,羟基和氨基总数为2~5的醇、胺和/或醇胺组成;且为反应性溶剂,即溶剂既可以溶解所述CO2加合物,又可以与发泡体系中的其它物质发生化学反应,成为泡沫的一部分。
所述多胺聚合物包括但不限于聚乙烯亚胺,聚丙烯亚胺,聚丁烯亚胺、聚乙烯胺、聚烯丙胺中的至少一种;所述接枝改性多胺聚合物可以接枝有以下侧链的至少一种:
(1)所述侧链为聚乙二醇、聚环氧丙烷、聚氧杂环丁烷、聚四氢呋喃或聚硅氧烷,且聚合度至少为1;
(2)所述侧链含有三甲基硅烷基;
(3)所述侧链含有碳原子数为1到22的烃基;
(4)所述侧链含有碳原子数为1到22的含氟烷基。
具体地,上述接枝侧链可以为聚乙二醇、聚环氧丙烷、聚氧杂环丁烷和聚四氢呋喃等聚醚齐聚物,或者聚硅氧烷,含有至少一个重复单元,结构举例为:
其中m至少为1,n为1到4的正整数,Q和T为接枝侧链和多胺聚合物的主链之间的联接基团。该联接基团Q和T属于可替换的基团,可以选取的基团有:
上述接枝多胺聚合物的接枝侧链还可以含有硅烷,其结构可以为:
T为侧链和多胺聚合物主链之间的联接基团,T可以为:
上述接枝多胺聚合物的接枝侧链还可以含有碳原子数为1到22的烃基,含有至少一个不饱和键,其结构举例为:
CnH2n-1-M-,
其中n为1到22的整数,M为疏水侧链和多胺聚合物的主链之间的联接基团。该联接基团M属于可替换的基团,M可以直接为共价键或酰胺键。
上述接枝多胺聚合物的接枝侧链还可以含有碳原子数为1到22的烷基或含氟烷基,其结构举例为:
CnH2n+1-mFm-M-,
其中n为1到22的整数,m为0或1到43的整数,M为接枝侧链和多胺聚合物主链之间的联接基团。该联接基团M属于可替换的基团,M可以直接为共价键或酰胺键,还可以选取以下基团:
需要指出的是,上述接枝侧链和多胺聚合物的主链之间的联接基团Q、T和M等均属于可替换基团,本领域的技术熟练人员还可以选取其他基团进行替代,在此不一一列举。
至于上述接枝多胺聚合物的具体制备方法,可以将带接枝侧链的缩水甘油醚和多胺聚合物在乙醇溶液中反应,得到接枝改性的多胺聚合物。其中带疏水链的缩水甘油醚的结构为:
其中m至少为1,n为1到4的正整数,这种方法制备的接枝多胺聚合物侧链与主链之间的联接基团为Q1;带疏水链的缩水甘油醚的结构还可以为:
其中m为0或正整数,这种方法制备的接枝多胺聚合物侧链与主链之间的联接基团为T;带疏水链的缩水甘油醚的结构还可以为:
其中n为1到22的整数,m为0或1到43的整数,这种方法制备的接枝多胺聚合物侧链与主链之间的联接基团为M2。
还可以采用带环氧基的烷基或带环氧基的含氟烷基和多胺聚合物在乙醇溶液中反应,得到接枝多胺聚合物。其中的带环氧基的烷基或含氟烷基的结构可以为:
其中n为1到22的整数,m为0或1到43的整数,这种方法制备的接枝多胺聚合物侧链与主链之间的联接基团为M1。
还可以采用如下方法来制备上述接枝多胺聚合物:首先将烷氧基聚醚齐聚物分别与碘乙酸和2-溴异氰酸乙酯反应得到卤代烃封端的产物,反应如下(其中m至少为1,n为1到4的正整数):
上述反应是以烷氧基聚丙二醇齐聚物为例,其中的重复单元还可以是聚乙二醇、聚氧杂环丁烷和聚四氢呋喃的重复单元。
其次将上述卤代烃封端产物和多胺聚合物反应,脱去卤化氢,得到N取代疏水改性聚乙烯亚胺(侧链与主链之间的联接基团为Q2或Q3)。
还可以用烷烃或含氟烷烃的溴代物或碘代物与多胺聚合物发应,来制备上述接枝多胺聚合物。其中的溴代物或碘代物的结构可以为:
CnH2n+1-mFm-Br,或CnH2n+1-mFm-I,
其中n为1到22的整数,m为0或1到43的整数。这种方法制备的接枝多胺聚合物侧链与主链之间的联接基团为共价键。
还可以用烷基或含氟烷基羧酸与多胺聚合物反应制备来制备上述接枝多胺聚合物。其中的羧酸的结构可以为:
CnH2n+1-mFm-COOH,
其中n为1到22的整数,m为0或1到43的整数。这种方法制备的接枝多胺聚合物侧链与主链之间的联接基团为酰胺键。
还可以用不饱和脂肪酸与多胺聚合物发应制备来制备上述接枝多胺聚合物。其中的脂肪酸的结构可以为:
CnH2n-1-M-,
其中n为1到22的整数。这种方法制备的接枝多胺聚合物侧链与主链之间的联接基团M为酰胺键。
所有这些反应都是已知化学反应,其具体制备方法可以参阅现有公开的技术,如专利文献CN 108355472 A。
另外,在本发明提供的接枝多胺聚合物的制备方法中,所述接枝多胺聚合物的接枝度以多胺聚合物的N原子计为1~45mol%。优选地,所述接枝多胺聚合物的接枝度以多胺聚合物的N原子计为3~20mol%。通常情况下,接枝多胺聚合物接枝度越大,越有利于其在溶剂中的溶解,但接枝率过大,会使接枝多胺聚合物与CO2反应的氨基数量下降,使接枝多胺聚合物CO2加合物中的CO2含量下降,从而使发泡能力下降。
具体地,本发明所述的CO2加合物液态发泡剂中的溶剂为乙二醇、1,2-丙二醇、1,3-丙二醇、丁二醇,戊二醇,甘油、乙醇胺、二乙醇胺、三乙醇胺、乙二胺、1,2-丙二胺、1,3-丙二胺、一缩二乙二醇、二甘醇胺当中的至少一种;所述丁二醇为1,4-丁二醇或1,4-丁二醇的含两个羟基的任一同分异构体,所述戊二醇为1,5-戊二醇或1,5-戊二醇的含两个羟基的任一同分异构体。其中乙二醇、乙醇胺、二乙醇胺和三乙醇胺溶解性较好。而乙二醇价格较为便宜,常常作为首选溶剂。
当乙二醇和其他含羟基和/或氨基的小分子混合时,也可以有很好的溶解效果,所述其他含羟基和/或氨基的小分子为1,2-丙二醇、1,3-丙二醇、甘油、丁二醇、戊二醇、己二醇、乙醇胺、二乙醇胺、三乙醇胺、乙二胺,1,2-丙二胺,1,3-丙二胺,丁二胺、一缩二乙二醇、二甘醇胺、二乙烯三胺、三乙烯四胺、四乙烯五胺当中的至少一种;所述丁二醇、戊二醇和己二醇为相应二醇的含两个羟基的任一同分异构体;所述丁二胺为1,4-丁二胺或1,4-丁二胺的含两个氨基的任一同分异构体。当乙二醇和其他含羟基和/或氨基的小分子混合时,乙二醇的质量百分含量最好不小于50%。
需要说明的是,本发明所述的含CO2加合物的液态发泡剂还可以含有水,水的用量不超过所述含CO2加合物的液态发泡剂中溶剂质量的40%。水本身也是聚氨酯材料的一种化学发泡剂,水也有一定的溶解作用。但如果水的用量过大,不利于疏水链接枝的多胺聚合物的CO2加合物的溶解;同时水的用量过大,也会导致所制备的泡沫性能变脆。
本发明的另一目的是提供所述含CO2加合物的液态发泡剂用于制备聚氨酯泡沫的用途。在使用所述含CO2加合物的液态发泡剂的过程中可以预先将聚氨酯泡沫的其他液态组分,如匀泡剂、催化剂等也加入其中,这仍然属于本发明的保护范围,因为这些助剂本身不能溶解所述CO2加合物,只是和所述液态发泡剂形成了均匀的混合物。
本发明与现有技术相比,具有以下积极效果:
1、本发明提供液态的含多胺聚合物的CO2加合物发泡剂,可以和液态的聚氨酯原料充分混合,解决了固态的多胺聚合物的CO2加合物难以在聚氨酯原料中分散的问题,便于多胺聚合物的CO2加合物作为环保发泡剂在聚氨酯泡沫中的应用。
2、本发明提供的含多胺聚合物的CO2加合物液态发泡剂中的溶剂,分子结构中含有羟基和/或氨基,可以和异氰酸酯反应,成为泡沫结构的一部分,避免溶剂成为可挥发物污染环境。
附图说明
附图1为接枝多胺聚合物制备实施例(1)~(21)中制备接枝多胺聚合物所用到的侧链原料的化学结构式。
具体实施方式
为了使本发明的目的、技术方案和技术效果更加清楚,以下结合具体实施例,对本发明作进一步的详细说明,需要说明的是,所有这些实施例均是为了进一步说明本发明,不得理解为对本发明的限制。本领域技术人员根据上述本发明内容对本发明作出的一些非本质的改进和调整仍属于本发明的保护范围。
接枝多胺聚合物的制备实施例
在进行具体实施例描述之前,先对本发明所述的接枝多胺聚合物的制备进行说明。本发明所述的多胺聚合物是分子结构中含有氨基的聚合物,包括但不限于聚乙烯亚胺(PEI),聚丙烯亚胺(PPI),聚丁烯亚胺(PBI),其分子结构分别为氨基之间间隔2、3、4个亚甲基,当然间隔5,6个亚甲基的多胺聚合物也是可以的(这些聚亚烷基胺可以有线性、支化和超支化等结构变化),只不过亚甲基越多,吸收CO2的氨基含量就相对减少了,单位质量的发泡剂的发泡能力就下降了。另外,聚乙烯胺(PEA)和聚烯丙胺(PAA)这些含伯胺基的多胺聚合物也是可以用的。其结构如下所示:
本发明所述的多胺聚合物可以接枝侧链,以增加其CO2加合物在聚氨酯原料中的分散性,所述侧链包括但不限于以下至少一种:
(1)所述侧链为聚乙二醇、聚环氧丙烷、聚氧杂环丁烷、聚四氢呋喃或聚硅氧烷,且聚合度至少为1;
(2)所述侧链含有三甲基硅烷基;
(3)所述侧链含有碳原子数为1到22的烃基;
(4)所述侧链含有碳原子数为1到22的含氟烷基。
所述接枝侧链的接枝度可以根据需要变化,可以在1~45%之间变化。
具体地,所合成的接枝改性多胺聚合物的结构见表1。其中理论接枝度都是通过接枝有侧链的氨基和主链上的所有氨基的摩尔比计算得到的,实际接枝度是通过核磁谱图中侧链和主链有关质子信号的面积比计算得到的。需要说明的是,表中样品代号由侧链和多胺聚合物的代号组成,如5%C8-PEI,其中5%C8表示侧链为含8个碳原子的烷基链,5%表示侧链的设计接枝度(即理论接枝度),PEI表示多胺聚合物为聚乙烯亚胺,侧链的来源为C8-EPO,其结构见图1。其它样品的代号意义类似,有些样品有两种接枝侧链,则分别列出各自侧链的理论接枝度和侧链代号,所有侧链的来源均列在图1中。多胺聚合物的代号为:PEI聚乙烯亚胺,PPI聚丙烯亚胺,PBI聚丁烯亚胺,PEA聚乙烯胺,PAA聚烯丙胺。除PEA和PAA外,其余多胺聚合物有线性、支化或超支化的结构变化。
表1
接枝多胺聚合物制备实施例(1)~(16)、(20)和(21)的工艺条件和步骤如下:将相应的多胺聚合物加入反应釜中,并向反应釜中加入乙醇,使多胺聚合物的质量浓度约为10%,在搅拌条件下将多胺聚合物完全溶解,然后加入相应的缩水甘油醚化合物(表1,侧链原料),使侧链的理论接枝度符合表1所列数值,在50℃搅拌反应15小时,然后旋蒸除去乙醇;先在旋蒸后的产物中加入10体积份的石油醚,以溶解产物以及未反应的缩水甘油醚类化合物,然后加入以石油醚体积份计1/3的蒸馏水,以析出接枝改性的多胺聚合物;再用石油醚洗涤析出后的多胺聚合物至少三次,然后旋蒸除去石油醚并干燥至恒重即可得到产物。
接枝改性多胺聚合原料制备实施例(17)的工艺条件和步骤如下:取以聚乙烯亚胺的重复单元计量1摩尔份的该聚乙烯亚胺溶于氯仿,使其质量浓度约为10%,然后加入0.03摩尔份的C17H33-COOH(图1)和N,N'–羰基二咪唑(CDI),理论接枝率为3%。然后在回流条件下搅拌反应12小时,用饱和食盐水萃取3次,取氯仿层,在50℃下旋蒸除去溶剂,最后在75℃的烘箱中烘干,得到提纯的疏水链接枝的聚乙烯亚胺产物3%C17H33-PEI。
接枝改性多胺聚合物原料制备实施例(18)的工艺条件和步骤如下:取以聚乙烯亚胺的重复单元计量1摩尔份的该聚乙烯亚胺溶于氯仿,使其质量浓度约为10%,然后加入0.2摩尔份的C2F3-I(表1),回流反应3小时,冷却至室温,用与氯仿等体积的5%的氢氧化钠水溶液萃取反应混合物三次,去掉水层,水洗直到水层pH值为中性,用无水硫酸钠干燥有机层,40℃真空旋转蒸发除掉溶剂,得相应的疏水链改性的聚乙烯亚胺20%C2F3-PEI。
接枝多胺聚合物原料制备实施例(19)的工艺条件和步骤如下:取以聚乙烯亚胺的重复单元计量1摩尔份的该聚乙烯亚胺溶于氯仿,使其质量浓度约为10%,然后加入0.45摩尔份的C4-Br(表1),回流反应6小时,冷却至室温,用与氯仿等体积的5%的氢氧化钠水溶液萃取反应混合物三次,去掉水层,水洗直到水层pH值为中性,用无水硫酸钠干燥有机层,40℃真空旋转蒸发除掉溶剂,得相应的疏水链改性的聚乙烯亚胺45%C4-PEI。
由表1可知各产物的实际接枝度和理论接枝度是很接近的,说明接枝反应进行得很完全。理论接枝度是通过侧链摩尔数和主链氮原子摩尔数之比计算而得,实际接枝度是通过核磁谱图中侧链和主链有关质子信号的面积比计算得到的。由表1可知,各产物疏水链的接枝度在1~45%之间。
实施例1~37
本组实施例将接枝多胺聚合物(见表1)制备成相应的CO2加合物,然后将其溶于相应的溶剂中(见表2)形成含多胺聚合物的CO2加合物的液态发泡剂。其中多胺聚合物的CO2加合物的制备方法为:取1质量份的多胺聚合物(来源列于表2,带括号的数字指表1的序号)溶于乙醇得到10%质量浓度的多胺聚合物溶液,放入密闭的反应釜内,通入0.5MPa的CO2反应5小时,得到白色沉淀,过滤除掉溶剂,然后40℃真空干燥3天,然后放入密闭反应釜内通入0.5MPa的CO2保压2天,得到多胺聚合物的CO2加合物,以该加合物作为溶质溶于表2所示的相应溶剂中。需要指出的是表2中实施例33~37的多胺聚合物没有接枝侧链。
表2中的溶质百分含量是指该溶质能够溶解的最大百分质量含量。具体的测试方法为:取50mL的离心管,加入0.5g的表2所列的多胺聚合物的CO2加合物(即溶质)粉末,然后加入3g的相应溶剂(见表2,其中的丁二醇、戊二醇和己二醇为直链二醇,丁二胺为1,4-丁二胺;当采用两种及上物质作混合溶剂时,该物质后的数值为该物质的质量百分数),用超声波(KQ-300DE型数控超声波清洗器,昆山市超声仪器有限公司)处理10分钟,使固体分散到液体中,放入30℃恒温水浴中静置,待固体完全溶解,形成透明液体,再加入0.5g的溶质粉末,反复操作,直至体系中有不溶解的固体物质,记录此时的溶质与溶剂质量之比,选取此不溶解点的质量与前一次溶解点的质量的平均值再次进行溶解测试。若溶解,则测试此溶解点与不溶解点的中间质量的溶解性;若不溶解,则测试此不溶解点与前一溶解点的中间质量的溶解性。如此反复此操作,直到不溶解点和前一溶解点的溶质质量差值占前一溶解点的溶质质量的百分数小于2%,则该前一溶解点质量视为最大溶解质量,该质量占溶液总质量的百分比为表2所列的溶质百分含量(显然误差小于2%)。需要指出的是,虽然表2中的丁二醇、戊二醇、己二醇为直链二醇,丁二胺为直链二胺,但如果采用带支链的相应二醇或二胺替代也是可以的,所得溶质百分含量稍有波动,和相应直链二醇或二胺的数值相比,波动小于10%。
表2中实施例3~10采用同一种多胺聚合物(10%C8-PEI)的CO2加合物作溶质溶于不同的溶剂;可以看出,乙二醇的溶解度相对较高。加上乙二醇价格便宜,因此乙二醇应该是多胺聚合物的CO2加合物的良溶剂,未接枝的多胺聚合物的CO2加合物溶解性更好,质量浓度达66%(实施例33)。
表2
从表2的数据可知,乙二醇、丙二醇、乙醇胺、二乙醇胺、三乙醇胺的溶解度相对较大(实施例1~18),甘油、丁二醇、戊二醇、乙二胺、1,2-丙二胺和1,3-丙二胺的溶解度相对较小。显然,乙二醇、1,2-丙二醇、1,3-丙二醇、丁二醇,戊二醇,甘油、乙醇胺、二乙醇胺、三乙醇胺、乙二胺、1,2-丙二胺、1,3-丙二胺、一缩二乙二醇、二甘醇胺等都有比较可观的溶解度(质量百分含量大于20%),他们的混合溶剂也是很好的溶剂(见实施例19~37)。另外,己二醇、丁二胺、二乙烯三胺、三乙烯四胺和四乙烯无胺单独作为溶剂时,溶解度较小,其溶质百分含量小于10%,但当它们和其他溶剂混合时,所得混合溶剂表现出了较高的溶解度,说明不同溶剂之间有一定的协同作用,如实施例21、24、25、29和30所示。
实施例20、27、32和34还采用了水作为溶剂的一个组分,有机溶剂和水组成的混合溶剂也有比较好的效果,水的用量可以达到混合溶剂质量的40%。
需要说明的是,表2所列的含多胺聚合物的CO2加合物的液态发泡剂中的溶质(即多胺聚合物的CO2加合物)的含量达到了该溶质的最大百分含量,实际使用中,溶质的用量可以小于最大百分含量。
应用实施例1–5
本应用实施例选取接枝多胺聚合物的CO2加合物溶液(实施例2、4、11和12)来制备相应的聚氨酯泡沫,配方如表3所示(此配方只用于说明不同发泡剂的发泡效果,可以根据不同的使用目的,对发泡配方进行调整)。
表3
在表3中,聚酯多元醇为聚己二酸丁二醇乙二醇酯(丁二醇和乙二醇用量摩尔比1:1),分子量约1500g/mol,羟值76.2mgKOH/g,来自Sigma公司;丙三醇来自成都长联化工试剂有限公司;辛酸亚锡和三乙烯二胺来自成都高端聚合物科技有限公司;匀泡剂BL-8530来自上海麦豪新材料科技有限公司;PM-200为多亚甲基多苯基异氰酸酯,来自万华化学集团股份有限公司,–NCO含量为30.5~32.0%。表中来源的例2指的是实施例2(见表2),以此类推。
制备含不同发泡剂的聚氨酯泡沫,配方如表3所示。对照例1(简称对1)不外加发泡剂,靠原料中的微量水发泡。将发泡剂溶液和其他白料组分按照配方比例混合,800r/min机械搅拌30s后加入黑料,然后1800r/min的机械搅拌15s,让泡沫自然生长,待泡沫顶部不黏手时即完成发泡,得到聚氨酯泡沫。
由于表3中的发泡剂是接枝多胺聚合物的CO2加合物的乙二醇溶液,可以很方便的和其他组分的混合。应用实施例1~4所制备的泡沫的密度远远小于对照样,说明发泡剂确实起到了发泡的作用。应用实施例5在应用实施例4的基础上加了0.1质量份的水作为额外的发泡剂(水占发泡剂中乙二醇溶剂的10%,占水和乙二醇总量的9.1%),由于水会消耗异氰酸酯,因此PM-200的用量也相应增加了。应用实施例5的密度进一步下降了,且密度也小于单纯用水作发泡剂的对照样2(对2),说明水和实施例12的发泡混合物共同起到了发泡作用。
在应用实施例5中,将发泡剂水直接和实施例12的发泡混合物混合,得到了均匀的发泡混合物。这说明在实际使用本发明所述溶剂溶解多胺聚合物的CO2加合物发泡剂的时候,水是可以加到本发明所述溶剂中的,所加的水也起到发泡剂的作用,这样的使用方式也属于本发明的保护范围。
需要指出的是,本发明所列举的聚氨酯泡沫配方只是为了验证本发明所制备的可释放二氧化碳的改性多胺聚合物发泡剂与溶剂形成的均匀混合物可以用于聚氨酯泡沫的制备,不能理解为对本发明制备的发泡剂材料以及溶剂的使用范围的限制。聚氨酯泡沫的形成过程是一个放热反应,所放出的热量正好用于释放本发明制备的发泡剂中的二氧化碳。因此本发明所制备的发泡剂材料及溶剂体系可以用于各种聚氨酯泡沫之中。
以上所述仅为本发明的实施例而已,并不用于限制本发明,对于本领域的技术人员来说,本发明可以有各种更改和变化。凡在本发明的精神和原则之内所做的任何修过、等同替换、改进等,均应包含在本发明的权利要求范围之内。
Claims (10)
1.一种发泡剂,其特征在于,该发泡剂至少由CO2加合物和溶剂组成;
所述CO2加合物由多胺聚合物和CO2组成,CO2和多胺聚合物以加合物的形式存在;或所述CO2加合物由接枝改性多胺聚合物和CO2组成,CO2和多胺聚合物主链以加合物的形式存在;所述多胺聚合物为分子链中含有4个及以上胺基的聚合物,胺基所连原子为碳原子,其结构为直链、支化、超支化中的至少一种,分子量大于200;
所述溶剂为碳原子数≤8,羟基和氨基总数为2~5的醇、胺和/或醇胺组成;且为反应性溶剂,即溶剂既可以溶解所述CO2加合物,又可以与发泡体系中的其它物质发生化学反应,成为泡沫的一部分。
2.根据权利要求1所述的发泡剂,其特征在于,该发泡剂还可以含有水,水的用量不超过所述溶剂和水的总质量的40%。
3.根据权利要求1所述的发泡剂,其特征在于,所述溶剂为乙二醇、1,2-丙二醇、1,3-丙二醇、丁二醇,戊二醇,甘油、乙醇胺、二乙醇胺、三乙醇胺、乙二胺、1,2-丙二胺、1,3-丙二胺、一缩二乙二醇、二甘醇胺当中的至少一种;所述丁二醇为1,4-丁二醇或1,4-丁二醇的含两个羟基的任一同分异构体,所述戊二醇为1,5-戊二醇或1,5-戊二醇的含两个羟基的任一同分异构体。
4.根据权利要求3所述的发泡剂,其特征在于,所述溶剂组成至少含有两组分,组分一为乙二醇,组分二为1,2-丙二醇、1,3-丙二醇、甘油、丁二醇、戊二醇、己二醇、乙醇胺、二乙醇胺、三乙醇胺、乙二胺,1,2-丙二胺,1,3-丙二胺,丁二胺、一缩二乙二醇、二甘醇胺、二乙烯三胺、三乙烯四胺、四乙烯五胺当中的至少一种;所述丁二醇、戊二醇和己二醇为相应二醇的含两个羟基的任一同分异构体;所述丁二胺为1,4-丁二胺或1,4-丁二胺的含两个氨基的任一同分异构体。
5.根据权利要求4所述的发泡剂,其特征在于,所述乙二醇质量分数≥50%。
6.根据权利要求1所述的发泡剂,其特征在于,所述多胺聚合物包括但不限于聚乙烯亚胺,聚丙烯亚胺,聚丁烯亚胺、聚乙烯胺、聚烯丙胺。
7.根据权利要求6所述的发泡剂,其特征在于,所述多胺聚合物为聚乙烯亚胺。
8.根据权利要求6所述的发泡剂,其特征在于,所述多胺聚合物含有侧链,所述侧链为下述情况至少一种:
(1)所述侧链为聚乙二醇、聚环氧丙烷、聚氧杂环丁烷、聚四氢呋喃或聚硅氧烷,且聚合度至少为1;
(2)所述侧链含有三甲基硅烷基;
(3)所述侧链含有碳原子数为1到22的烃基;
(4)所述侧链含有碳原子数为1到22的含氟烷基。
9.根据权利要求6所述的发泡剂,所述聚环氧丙烷含有其中,m为1~15的整数,n为1~6的整数;所述聚硅氧烷链含有/>其中,m为0~10的整数,T为所述聚硅氧烷链与所述接枝改性聚乙烯亚胺的主链的联接基团,T的结构可以为/>
10.根据权利要求1~9任一项所述的发泡剂,用于制备聚氨酯泡沫的用途。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310551793.5A CN116731381A (zh) | 2023-05-16 | 2023-05-16 | 一种含二氧化碳加合物的液态发泡剂 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310551793.5A CN116731381A (zh) | 2023-05-16 | 2023-05-16 | 一种含二氧化碳加合物的液态发泡剂 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN116731381A true CN116731381A (zh) | 2023-09-12 |
Family
ID=87903516
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202310551793.5A Pending CN116731381A (zh) | 2023-05-16 | 2023-05-16 | 一种含二氧化碳加合物的液态发泡剂 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN116731381A (zh) |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4500656A (en) * | 1983-04-05 | 1985-02-19 | Bayer Aktiengesellschaft | Process for the preparation of a cellular polyurethane |
CA1199147A (en) * | 1981-10-31 | 1986-01-07 | Werner Rasshofer | Non-crystalline polyamine/carbonic acid salt compositions, a process for their preparation and their use for the production of polyurethane ureas, especially foamed coatings |
WO1998055528A1 (de) * | 1997-06-03 | 1998-12-10 | Bayer Aktiengesellschaft | Verfahren zur herstellung von geschlossenzelligen polyurethan-hartschaumstoffen mit geringer wärmeleitfähigkeit |
JP2011037951A (ja) * | 2009-08-07 | 2011-02-24 | Tosoh Corp | ポリウレタンフォーム製造用の発泡性添加剤、及びそれを用いた硬質ポリウレタンフォームの製造方法 |
CN102803325A (zh) * | 2009-04-24 | 2012-11-28 | 东曹株式会社 | 用于制造聚氨酯泡沫的发泡性添加剂、以及使用该发泡性添加剂的硬质聚氨酯泡沫的制造方法 |
CA3025030A1 (en) * | 2016-06-02 | 2017-12-07 | Shandong University Of Technology | Organic amine salt compounds having co2-donating anions and their use as foaming agent |
CN109867767A (zh) * | 2017-12-05 | 2019-06-11 | 补天新材料技术有限公司 | 二氧化碳与有机胺相结合使用的聚氨酯发泡方法 |
CN110023363A (zh) * | 2016-11-25 | 2019-07-16 | 科思创德国股份有限公司 | 一种制备开孔硬质聚氨酯泡沫的方法 |
CN110023364A (zh) * | 2016-11-25 | 2019-07-16 | 科思创德国股份有限公司 | 开孔硬质聚氨酯泡沫的制备方法 |
CN113121865A (zh) * | 2020-01-16 | 2021-07-16 | 四川大学 | 可释放二氧化碳的聚氨酯发泡混合物的制备方法及其应用 |
CN114507362A (zh) * | 2022-03-17 | 2022-05-17 | 四川大学 | 喷雾法制备改性聚乙烯亚胺二氧化碳加合物微球发泡剂 |
-
2023
- 2023-05-16 CN CN202310551793.5A patent/CN116731381A/zh active Pending
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1199147A (en) * | 1981-10-31 | 1986-01-07 | Werner Rasshofer | Non-crystalline polyamine/carbonic acid salt compositions, a process for their preparation and their use for the production of polyurethane ureas, especially foamed coatings |
US4500656A (en) * | 1983-04-05 | 1985-02-19 | Bayer Aktiengesellschaft | Process for the preparation of a cellular polyurethane |
WO1998055528A1 (de) * | 1997-06-03 | 1998-12-10 | Bayer Aktiengesellschaft | Verfahren zur herstellung von geschlossenzelligen polyurethan-hartschaumstoffen mit geringer wärmeleitfähigkeit |
CN102803325A (zh) * | 2009-04-24 | 2012-11-28 | 东曹株式会社 | 用于制造聚氨酯泡沫的发泡性添加剂、以及使用该发泡性添加剂的硬质聚氨酯泡沫的制造方法 |
JP2011037951A (ja) * | 2009-08-07 | 2011-02-24 | Tosoh Corp | ポリウレタンフォーム製造用の発泡性添加剤、及びそれを用いた硬質ポリウレタンフォームの製造方法 |
CA3025030A1 (en) * | 2016-06-02 | 2017-12-07 | Shandong University Of Technology | Organic amine salt compounds having co2-donating anions and their use as foaming agent |
CN110023363A (zh) * | 2016-11-25 | 2019-07-16 | 科思创德国股份有限公司 | 一种制备开孔硬质聚氨酯泡沫的方法 |
CN110023364A (zh) * | 2016-11-25 | 2019-07-16 | 科思创德国股份有限公司 | 开孔硬质聚氨酯泡沫的制备方法 |
CN109867767A (zh) * | 2017-12-05 | 2019-06-11 | 补天新材料技术有限公司 | 二氧化碳与有机胺相结合使用的聚氨酯发泡方法 |
CN113121865A (zh) * | 2020-01-16 | 2021-07-16 | 四川大学 | 可释放二氧化碳的聚氨酯发泡混合物的制备方法及其应用 |
CN114507362A (zh) * | 2022-03-17 | 2022-05-17 | 四川大学 | 喷雾法制备改性聚乙烯亚胺二氧化碳加合物微球发泡剂 |
Non-Patent Citations (4)
Title |
---|
GUO, ZHI,等: "Homogeneous polyurethane foaming systems containing polyester diol, ethylene glycol, and alkylated polyethylenimine-CO2 adducts", 《JOURNAL OF APPLIED POLYMER SCIENCE》, vol. 140, no. 31, 27 May 2023 (2023-05-27), pages 54320 * |
LI, ZHAOJIAN,等: "Polyurethane foams co-blown by water and alkylated polyethylenimine-CO2 adducts: An additive or antagonistic effect?", 《JOURNAL OF CELLULAR PLASTICS》, vol. 59, no. 5, 31 December 2023 (2023-12-31), pages 361 - 377 * |
LIU, CHAO,等: "Towards green polyurethane foams via renewable castor oil-derived polyol and carbon dioxide releasing blowing agents from alkylated polyethylenimines", 《POLYMER》, vol. 116, 5 May 2017 (2017-05-05), pages 240 - 250, XP029987677, DOI: 10.1016/j.polymer.2017.03.079 * |
符腾,等: "辛基改性聚乙烯亚胺CO2加合物的聚氨酯硬泡应用", 《聚氨酯工业》, vol. 32, no. 6, 31 December 2017 (2017-12-31), pages 38 - 40 * |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5671212B2 (ja) | ポリオール混合物の貯蔵安定性を改善するための新しいタイプの相溶化剤 | |
US7939574B2 (en) | Foamed isocyanate-based polymer having improved hardness properties and process for production thereof | |
KR910004899B1 (ko) | 친수성 폴리우레탄/폴리우레아 스폰지의 제조방법 | |
CN112457520B (zh) | 聚氨酯发泡混合物的制备方法及其应用 | |
CN107880306B (zh) | 疏水改性聚乙烯亚胺发泡剂 | |
EP2430061B1 (en) | Silicone surfactant for use in polyurethane foams prepared using vegetable oil based polyols | |
CN113121865B (zh) | 可释放二氧化碳的聚氨酯发泡混合物的制备方法及其应用 | |
MXPA06013159A (es) | Dispersantes depolieteralcanolamina. | |
CN114507362B (zh) | 喷雾法制备改性聚乙烯亚胺二氧化碳加合物微球发泡剂 | |
BR112012029753B1 (pt) | método para absorver líquidos hidrofóbicos, e, uso de uma espuma de poliuretano | |
WO2002010189A2 (en) | Dendritic macromolecule with improved polyether polyol solubility and process for production thereof | |
AU2001282733A1 (en) | Dendritic macromolecule with improved polyether polyol solubility and process for production thereof | |
CN116731381A (zh) | 一种含二氧化碳加合物的液态发泡剂 | |
CN116769120A (zh) | 一种含芳香环的多胺聚合物用于可释放二氧化碳发泡剂 | |
CN116731382A (zh) | 一种二氧化碳型潜发泡剂的溶剂 | |
Da et al. | Polyurethane foaming with CO2 adducts from C8 alkyl grafted polyethyleneimines: Optimization of the grafting rate and application of the blowing agents | |
CN116535726A (zh) | 一种可吸收二氧化碳的液态混合物用于聚氨酯泡沫 | |
CN116535727A (zh) | 含聚酯多元醇和二氧化碳加合物的液态发泡混合物 | |
CN113929864B (zh) | 一种阻燃保温型聚氨酯材料 | |
Long et al. | Climate‐friendly polyurethane blowing agent based on a carbon dioxide adduct from palmitic acid grafted polyethyleneimine | |
CN116790020A (zh) | 含芳香环多胺聚合物的二氧化碳加合物发泡剂及应用 | |
CN115636974B (zh) | 一种碳酸钙包裹的聚乙烯亚胺的二氧化碳加合物发泡剂 | |
EP0153031B1 (en) | Polyether polyol compositions and their use in polyurethane production | |
CN116874867A (zh) | 一种主链含醚键的多胺聚合物的二氧化碳加合物发泡剂 | |
CN116854934A (zh) | 环氧卤丙烷扩链的多胺聚合物的二氧化碳加合物发泡剂 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |