Tsoelo-pele ea Lipatlisiso ka Non-Isocyanate Polyurethanes
Ho tloha ha li hlahisoa ka 1937, lisebelisoa tsa polyurethane (PU) li fumane lits'ebetso tse ngata ho pholletsa le mafapha a fapaneng a kenyeletsang lipalangoang, kaho, lik'hemik'hale tsa petrole, masela, boenjiniere ba mechine le motlakase, sefofane, tlhokomelo ea bophelo bo botle le temo. Lisebelisoa tsena li sebelisoa ka liforomo tse kang polasetiki ea foam, likhoele, li-elastomers, lisebelisoa tse thibelang metsi, letlalo la maiketsetso, likoahelo, likhomaretsi, lisebelisoa tsa ho betla le lisebelisoa tsa bongaka. PU ea setso ha e le hantle e entsoe ho tsoa ho li-isocyanate tse peli kapa ho feta hammoho le macromolecular polyols le li-extensions tse nyane tsa limolek'hule. Leha ho le joalo, chefo ea tlhaho ea isocyanate e baka likotsi tse kholo bophelong ba batho le tikolohong; ho feta moo, hangata li nkiloe ho phosgene-e leng selelekela sa chefo e ngata-le thepa e tala ea amine.
Ka lebaka la ts'ebetso ea morao-rao ea indasteri ea lik'hemik'hale ea mekhoa ea nts'etsopele e tala le e tsitsitseng, bafuputsi ba ntse ba tsepamisitse maikutlo ho nkela li-isocyanate sebaka ka lisebelisoa tse baballang tikoloho ha ba ntse ba hlahloba mekhoa e mecha bakeng sa non-isocyanate polyurethanes (NIPU). Pampiri ena e hlahisa mekhoa ea boitokiso bakeng sa NIPU ha e ntse e hlahloba tsoelo-pele mefuteng e fapaneng ea li-NIPU le ho buisana ka menyetla ea bona ea kamoso ea ho fana ka litšupiso bakeng sa lipatlisiso tse ling.
1 Synthesis ea Non-Isocyanate Polyurethanes
Tšimoloho ea pele ea lik'hemik'hale tse tlaase tsa limolek'hule tsa carbamate tse sebelisang monocyclic carbonates tse kopantsoeng le aliphatic diamines li etsahetse linaheng tse ling lilemong tsa bo-1950-e leng se bontšang nako ea bohlokoa ho ea ho non-isocyanate polyurethane synthesis. Hajoale ho na le mekhoa e 'meli ea mantlha ea ho hlahisa NIPU: Ea pele e kenyelletsa maikutlo a tlatsetso ka mehato lipakeng tsa binary cyclic carbonates le binary amines; ea bobeli e kenyelletsa karabelo ea polycondensation e kenyelletsang li-intermediate tsa diurethane hammoho le li-diol tse tsamaisang phapanyetsano ea sebopeho ka har'a carbamate. Li-intermediate tsa Diamarboxylate li ka fumanoa ka litsela tsa cyclic carbonate kapa dimethyl carbonate (DMC); ha e le hantle mekhoa eohle e sebetsa ka lihlopha tsa carbonic acid tse fanang ka ts'ebetso ea carbamate.
Likarolo tse latelang li hlalosa mekhoa e meraro e fapaneng ea ho etsa polyurethane ntle le ho sebelisa isocyanate.
1.1 Tsela ea Binary Cyclic Carbonate
NIPU e ka etsoa ka litlatsetso tse tsamaeang butle tse kenyelletsang binary cyclic carbonate hammoho le binary amine joalo ka ha ho bonts'itsoe ho Setšoantšo sa 1.
Ka lebaka la lihlopha tse ngata tsa hydroxyl tse teng ka har'a lihlopha tse pheta-phetoang ho latela sebopeho sa eona se seholo sa ketane mokhoa ona o atisa ho hlahisa se bitsoang polyβ-hydroxyl polyurethane (PHU). Leitsch et al., e hlahisitse letoto la polyether PHUs e sebelisang polyether ea cyclic carbonate-terinated hammoho le binary amines hammoho le limolek'hule tse nyane tse nkiloeng ho li-binary cyclic carbonates-ho bapisa tsena le mekhoa ea khale e sebelisoang ho lokisa li-PU tsa polyether. Liphuputso tsa bona li bontšitse hore lihlopha tsa hydroxyl ka har'a PHUs li theha maqhama a hydrogen habonolo ka liathomo tsa nitrogen / oksijene tse ka har'a likarolo tse bonolo / tse thata; phapang lipakeng tsa likarolo tse bonolo e boetse e ama boitšoaro ba hydrogen bonding hammoho le li-degree tsa karohano tsa microphase tseo hamorao li amang litšobotsi tsa ts'ebetso ka kakaretso.
Ka tloaelo ho etsoa ka tlas'a mocheso o fetang 100 ° C tsela ena ha e hlahise lihlahisoa nakong ea ts'ebetso ea ho itšoara ka tsela e etsang hore e se ke ea ameha ho mongobo ha e ntse e fana ka lihlahisoa tse tsitsitseng tse se nang likhathatso tse sa feto-fetoheng leha ho le joalo ho hlokahala lihlapolli tsa tlhaho tse khetholloang ke polarity e matla joaloka dimethyl sulfoxide (DMSO), N, N-dimethylformamide ka letsatsi le leng le le leng ho fihlela letsatsi le leng le le leng (DMF) fokotsa boima ba limolek'hule hangata bo oela ka tlase ho 30k g/mol e bakang tlhahiso e kholo e thata ka lebaka la litšenyehelo tse phahameng tse amanang le tsona hammoho le matla a sa lekaneng a hlahisoang ke li-PHUs le ha lits'ebetso tse ts'episang tse kenyelletsang libaka tse senyang li etsa mohopolo oa ho etsa litlolo tse khomaretsang joalo-joalo.
1.2 Tsela ea Monocylic Carbonate
Monocylic carbonate e sebetsana ka kotloloho le dicarbamate e hlahisang dicarbamate e nang le lihlopha tsa hydroxyl tse qetellang li sebelisana le litšebelisano tse khethehileng tsa transesterification/polycondensation hammoho le diols qetellong li hlahisa NIPU ka sebopeho se ts'oanang le balekane ba setso ba bonts'itsoeng ka pono ka Setšoantšo sa 2.
Mefuta e mengata ea monocylic e sebelisoang hangata e kenyelletsa li-substrates tsa ethylene le propylene carbonated moo sehlopha sa Zhao Jingbo Univesithing ea Beijing ea Chemical Technology se ileng sa sebetsana le li-diamine tse fapaneng tse li arabelang khahlano le mekhatlo e boletsoeng esale pele e ileng ea fumana li-intermediaries tse sa tšoaneng tsa dicarbamate pele li tsoela pele ka mekhahlelo ea condensation/polyminate e atlehileng ka ho sebelisa hydrochloride le polyethylene. sebopeho sa lihlahisoa tse fapaneng tse bonts'ang thepa e khahlang ea mocheso / ea mochini e fihlang holimo libakeng tse qhibidihang ho potoloha sebaka se ka bang 125 ~ 161°C matla a tsitsipano a fihlang sehlohlolong se haufi le litekanyetso tsa bolelele ba 24MPa tse haufi le 1476%. Wang et al., Metsoako e tšoanang e nang le matla a tšoanang e kenyelletsang DMC e kopantsoeng ka ho latellana w/hexamethylenediamine/cyclocarbonated precursors synthesizing derivatives ea hydroxy-terinated hamorao e ile ea hlahisoa ke biobased dibasic acids joalo ka oxalic/sebacic/acids adipic-acid-terephtalics e fihlelleng1300073007 matla a matla a fetoha9 ~ 17 MPa bolelele bo fapaneng35% ~ 235%.
Li-ester tsa Cyclocarbonic li sebetsa ka katleho ntle le ho hloka li-catalysts tlas'a maemo a tloaelehileng a ho boloka mocheso o fihlang ho 80 ho isa ho 120 ° C li-transesterifications tse latelang hangata li sebelisa mekhoa ea catalytic e thehiloeng ho organotin e netefatsang hore ts'ebetso e nepahetseng ha e fete200 °. Ka ntle ho matsapa a pholiso a shebaneng le litlatsetso tsa diolic tse khonang ho iketsetsa polymerization / deglycolysis liketsahalo tse nolofatsang liphetho tse lakatsehang li etsa hore mokhoa oa tlhaho o be bonolo o hlahisang methanol / masala a manyane a molek'hule-diolic kahoo a hlahisa mekhoa e meng e sebetsang ea indasteri ho ea pele.
1.3 Tsela ea Dimethyl Carbonate
DMC e emela mofuta o mong o sa utloahaleng oa tikoloho / o seng chefo o nang le likarolo tse ngata tse sebetsang tse kenyellelitsoeng methyl/methoxy/carbonyl e ntlafatsang profaele ea reactivity e nolofalletsang likamano tsa pele moo DMC e sebelisanang ka kotloloho le li-diamines ho theha li-intermediaries tse nyane tse felisitsoeng tsa methyl-carbamate tse lateloang ketso tse ling tsa ho qhibilihisa. li-small-chain-extender-diolics/tse kholoanyane-polyol tse etellang pele ho hlaha ha meaho ea polima e batloang ka tsela e nepahetseng ka Figure3.
Deepa et.al e kenyelelitsoe holim'a matla a boletsoeng ka holimo a leveraging sodium methoxide catalysis e hlophisang mefuta e fapaneng ea mahareng e ileng ea kenyelletsa likeketso tse lebisitsoeng ho fihlela sehlohlolong sa lihlopha tse lekanang le likarolo tse thata tse fihlelang boima ba limolek'hule bo ka bang(3 ~20)x10^3g/mol spanition ea khalase 0 ° C1 ° C1. Pan Dongdong e khethile li-pairings tsa leano tse nang le DMC hexamethylene-diaminopolycarbonate-polyalcohols tse hlokomelang liphetho tse hlokomelehang tse bonts'ang metrics ea matla a tensile oscillating10-15MPa karolelano ea bolelele e atamelang 1000% -1400%. Lipatlisiso tsa lipatlisiso tse mabapi le litšusumetso tse fapaneng tsa ho atolosa ketane li senotse likhetho tsa butanediol/hexanediol ha palo ea athomo e boloka ho lekana ho khothaletsa ntlafatso ea kristale e hlokometsoeng ho pholletsa le liketane. at230 ℃ .Litlhahlobo tse ling tse reretsoeng ho fumana li-non-isocyante-polyureas leveraging diazomonomer engagement li lebeletsoe ho sebelisa pente e ka bang teng ho hlahisa melemo ea ho bapisa ho feta li-vinyl-carbonaceous counterparts tse totobatsang katleho ea litšenyehelo/mekhoa e pharaletseng ea ho fumana mekhoa e fumanehang. maemo a phahameng a mocheso / moea o hloekileng a hlokomolohang litlhoko tsa mokelikeli ka tsela eo ho fokotsa metsi a litšila a nang le methanol / mahlaseli a manyane a molek'hule-diolic a theha li-paradigms tse tala ka kakaretso.
2 Likarolo tse fapaneng tse bonolo tsa non-isocyanate polyurethane
2.1 Polyether polyurethane
Polyether polyurethane (PEU) e sebelisoa haholo ka lebaka la matla a eona a ho kopanya a tlase a li-bond tsa ether ka likarolo tse bonolo tse pheta-phetoang, ho potoloha habonolo, ho feto-fetoha ha mocheso o tlase haholo le ho hanyetsa hydrolysis.
Kebir et al. polyether polyurethane e entsoeng ka DMC, polyethylene glycol le butanediol e le lisebelisoa tse tala, empa boima ba molek'hule bo ne bo le tlaase (7 500 ~ 14 800g / mol), Tg e ne e le ka tlaase ho 0 ℃, 'me ntlha ea ho qhibiliha le eona e ne e le tlaase (38 ~ 48℃),' me matla le litlhoko tse ling li ne li le thata ho finyella litlhoko tsa tšebeliso. Sehlopha sa lipatlisiso sa Zhao Jingbo se sebelisitse ethylene carbonate, 1, 6-hexanediamine le polyethylene glycol ho kopanya PEU, e nang le boima ba limolek'hule ba 31 000g/mol, matla a thata a 5 ~ 24MPa, le bolelele nakong ea khefu ea 0.9% ~ 1 388%. Boima ba limolek'hule tsa letoto la motsoako oa polyurethanes e nkhang hamonate ke 17 300 ~ 21 000g / mol, Tg ke -19 ~ 10 ℃, ntlha ea ho qhibiliha ke 102 ~ 110 ℃, matla a ho tsitsa ke 12 ~ 38MPa, 'me sekhahla sa ho hlaphoheloa sa 9% ke 9% e telele ke 20% e telele.
Sehlopha sa lipatlisiso sa Zheng Liuchun le Li Chuncheng se lokiselitse 1, 6-hexamethylenediamine (BHC) e bohareng e nang le dimethyl carbonate le 1, 6-hexamethylenediamine, le polycondensation e nang le limolek'hule tse fapaneng tse otlolohileng tsa ketane diols le polytetrahydrofuranediols (Mn = 2 000). Letoto la polyether polyurethanes (NIPEU) le tsela e seng isocyanate e ile ea lokisoa, 'me bothata ba ho tšela ba lipakeng nakong ea karabelo bo ile ba rarolloa. Sebopeho le thepa ea setso sa polyether polyurethane (HDIPU) se lokiselitsoeng ke NIPEU le 1, 6-hexamethylene diisocyanate li ile tsa bapisoa, joalokaha ho bontšitsoe ho Lethathamo la 1.
| Mohlala | Karolo e boima ea karolo e thata/% | Boima ba molek'hule/(g·mol^(-1)) | Lenane la kabo ea boima ba limolek'hule | Matla a ho tsieleha/MPa | Elongation nakong ea khefu/% |
| NIPEU30 | 30 | 74000 | 1.9 | 12.5 | 1250 |
| NIPEU40 | 40 | 66000 | 2.2 | 8.0 | 550 |
| HDIPU30 | 30 | 46000 | 1.9 | 31.3 | 1440 |
| HDIPU40 | 40 | 54000 | 2.0 | 25.8 | 1360 |
Lethathamo la 1
Liphetho ho Lethathamo la 1 li bontša hore phapang ea sebopeho pakeng tsa NIPEU le HDIPU e bakoa haholo ke karolo e thata. Sehlopha sa urea se hlahisoang ke karabelo ea lehlakore ea NIPEU e kenngoa ka mokhoa o sa reroang karolong e thata ea limolek'hule, ho senya karolo e thata ho theha likamano tse laetsoeng tsa haedrojene, ho fella ka litlamo tse fokolang tsa hydrogen pakeng tsa liketane tsa limolek'hule tsa karolo e thata le crystallinity e tlaase ea karolo e thata, e leng se fellang ka karohano e tlaase ea NIPEU. Ka lebaka leo, thepa ea eona ea mechine e mpe haholo ho feta HDIPU.
2.2 Polyester Polyurethane
Polyester polyurethane (PETU) e nang le polyester diol joalo ka likarolo tse bonolo li na le biodegradability e ntle, biocompatibility le thepa ea mochini, 'me e ka sebelisoa ho lokisa scaffolds tsa boenjiniere ba lisele, e leng thepa ea biomedical e nang le tebello e ntle ea ts'ebeliso. Li-polyester diol tse sebelisoang hangata likarolong tse bonolo ke polybutylene adipate diol, polyglycol adipate diol le polycaprolactone diol.
Pejana, Rokicki et al. e ile ea arabela ethylene carbonate ka diamine le diols tse fapaneng (1, 6-hexanediol,1, 10-n-dodecanol) ho fumana NIPU e fapaneng, empa NIPU e entsoeng e ne e e-na le boima bo tlaase ba molek'hule le Tg e tlaase. Farhadian et al. e lokisitse polycyclic carbonate e sebelisa oli ea peo ea soneblomo e le lintho tse tala, ebe e tsoakoa le li-polyamine tse thehiloeng ho bio, tse koahetsoeng ka poleiti, 'me li phekotsoe ka 90 ℃ bakeng sa lihora tse 24 ho fumana filimi ea thermosetting polyester polyurethane, e bontšang botsitso bo botle ba mocheso. Sehlopha sa lipatlisiso sa Zhang Liqun oa South China University of Technology se ile sa etsa letoto la li-diamine le cyclic carbonates, 'me sa kopanngoa ka biobased dibasic acid ho fumana biobased polyester polyurethane. Sehlopha sa lipatlisiso sa Zhu Jin Setsing sa Lipatlisiso sa Lintho tsa Ningbo, Sechaena sa Setsi sa Mahlale sa Machaena se lokiselitse karolo e thata ea diaminodiol e sebelisa hexadiamine le vinyl carbonate, ebe polycondensation e nang le bio-based unsaturated dibasic acid ho fumana letoto la polyester polyurethane, e ka sebelisoang e le pente ka mor'a phekolo ea ultraviolet [23]. Sehlopha sa lipatlisiso sa Zheng Liuchun le Li Chuncheng se sebelisitse adipic acid le li-aliphatic diols tse 'nè (butanediol, hexadiol, octanediol le decanediol) tse nang le linomoro tse fapaneng tsa carbon athomo ho lokisa li-polyester diols tse lumellanang e le likarolo tse bonolo; Sehlopha sa non-isocyanate polyester polyurethane (PETU), se reheletsoeng ka palo ea liathomo tsa carbon tsa aliphatic diol, se ile sa fumanoa ka ho qhibiliha ha polycondensation ka hydroxy-sealed hard segment prepolymer e lokisitsoeng ke BHC le diols. Thepa ea mochini ea PETU e bonts'itsoe ho Lethathamo la 2.
| Mohlala | Matla a ho tsieleha/MPa | Modulase oa elastic/MPa | Elongation nakong ea khefu/% |
| PETU4 | 6.9±1.0 | 36±8 | 673±35 |
| PETU6 | 10.1±1.0 | 55±4 | 568±32 |
| PETU8 | 9.0±0.8 | 47±4 | 551±25 |
| PETU10 | 8.8±0.1 | 52±5 | 137±23 |
Lethathamo la 2
Liphello li bontša hore karolo e bonolo ea PETU4 e na le carbonyl density e phahameng ka ho fetisisa, e matla ka ho fetisisa ea hydrogen bond le karolo e thata, le tekanyo e tlaase ka ho fetisisa ea karohano. The crystallization ea likarolo tse bonolo le tse thata li na le moeli, ho bonts'a ntlha e tlaase ea ho qhibiliha le matla a tsitsitseng, empa e telele e phahameng ka ho fetisisa nakong ea khefu.
2.3 Polycarbonate polyurethane
Polycarbonate polyurethane (PCU), haholo-holo PCU ea aliphatic, e na le khanyetso e ntle ea hydrolysis, khanyetso ea oxidation, botsitso bo botle ba likokoana-hloko le biocompatibility, 'me e na le litebello tse ntle tsa ts'ebeliso lefapheng la biomedicine. Hona joale, boholo ba NIPU e lokiselitsoeng e sebelisa polyether polyols le polyester polyols e le likarolo tse bonolo, 'me ho na le litlaleho tse fokolang tsa lipatlisiso ka polycarbonate polyurethane.
The non-isocyanate polycarbonate polyurethane e lokisitsoeng ke sehlopha sa lipatlisiso sa Tian Hengshui South China University of Technology e na le boima ba molek'hule bo fetang 50 000 g/mol. Tšusumetso ea maemo a karabelo holim'a boima ba molek'hule ea polymer e ithutiloe, empa thepa ea eona ea mochini ha e so tlalehe. Sehlopha sa lipatlisiso sa Zheng Liuchun le Li Chuncheng se ile sa lokisa PCU se sebelisa DMC, hexanediamine, hexadiol le polycarbonate diols, 'me sa reha PCU ho latela karolo e boima ea karolo e thata e pheta-phetoang. Thepa ea mochini e bonts'itsoe ho Lethathamo la 3.
| Mohlala | Matla a ho tsieleha/MPa | Modulase oa elastic/MPa | Elongation nakong ea khefu/% |
| PCU18 | 17±1 | 36±8 | 665±24 |
| PCU33 | 19±1 | 107±9 | 656±33 |
| PCU46 | 21±1 | 150±16 | 407±23 |
| PCU57 | 22±2 | 210±17 | 262±27 |
| PCU67 | 27±2 | 400±13 | 63±5 |
| PCU82 | 29±1 | 518±34 | 26±5 |
Lethathamo la 3
Liphetho li bonts'a hore PCU e na le boima bo phahameng ba limolek'hule, ho fihla ho 6 × 104 ~ 9 × 104g / mol, ntlha ea ho qhibiliha ho fihlela ho 137 ℃, le matla a ho tsitsa ho fihlela ho 29 MPa. Mofuta ona oa PCU o ka sebelisoa joalo ka polasetiki e thata kapa elastomer, e nang le tebello e ntle ea ts'ebeliso lefapheng la biomedical (joalo ka li-scaffolds tsa boenjiniere ba lisele tsa motho kapa lisebelisoa tsa ho kenya methapo ea pelo).
2.4 Hybrid non-isocyanate polyurethane
Hybrid non-isocyanate polyurethane (hybrid NIPU) ke kenyelletso ea lihlopha tsa epoxy resin, acrylate, silica kapa siloxane ka har'a moralo oa limolek'hule tsa polyurethane ho theha marang-rang a kenellang, ho ntlafatsa ts'ebetso ea polyurethane kapa ho fana ka mesebetsi e fapaneng ea polyurethane.
Feng Yuelan et al. ile a arabela bio-based epoxy soya oli le CO2 ho synthesize pentamonic cyclic carbonate (CSBO), 'me o ile a hlahisa bisphenol A diglycidyl ether (epoxy resin E51) le likarolo tse ling tse thata ketane ho ntlafatsa ka ho eketsehileng NIPU thehoa ke CSBO solidified le amine. Ketane ea molek'hule e na le karolo e telele ea ketane e tenyetsehang ea oleic acid / linoleic acid. E boetse e na le likarolo tse thata tsa ketane, e le hore e be le matla a phahameng a mochine le boima bo phahameng. Bafuputsi ba bang ba ile ba boela ba kopanya mefuta e meraro ea li-prepolymers tsa NIPU tse nang le lihlopha tsa ho qetela tsa furan ka karabelo ea ho bula lebelo la diethylene glycol bicyclic carbonate le diamine, 'me ka mor'a moo ba itšoara ka polyester e sa tsitsang ho lokisa polyurethane e bonolo e nang le ts'ebetso ea ho ipholisa,' me ka katleho e ile ea hlokomela katleho e phahameng ea ho ipholisa ea NIPU e bonolo. Hybrid NIPU ha e na feela litšobotsi tsa NIPU e akaretsang, empa hape e ka ba le ho khomarela hantle, acid le alkali corrosion resistance, ho hanyetsa solvent le matla a mochine.
3 Maikutlo
NIPU e lokiselitsoe ntle le tšebeliso ea isocyanate e chefo, 'me hajoale e ntse e ithutoa ka mokhoa oa foam, ho roala, sekhomaretsi, elastomer le lihlahisoa tse ling,' me e na le menyetla e mengata ea tšebeliso. Leha ho le joalo, boholo ba bona bo ntse bo lekanyelitsoe lipatlisisong tsa laboratori, 'me ha ho na tlhahiso e kholo. Ho phaella moo, ka ntlafatso ea litekanyetso tsa bophelo ba batho le kholo e tsoelang pele ea tlhokahalo, NIPU e nang le ts'ebetso e le 'ngoe kapa mesebetsi e mengata e fetohile tataiso ea bohlokoa ea lipatlisiso, tse kang antibacterial, ho itokisa, mohopolo oa sebopeho, ho thibela lelakabe, ho hanyetsa mocheso o phahameng joalo-joalo. Ka hona, lipatlisiso tsa nako e tlang li lokela ho utloisisa mokhoa oa ho rarolla mathata a mantlha a indasteri le ho tsoela pele ho lekola tataiso ea ho lokisa NIPU e sebetsang.
Nako ea poso: Aug-29-2024