Kev tshawb fawb nce qib ntawm Non-Isocyanate Polyurethanes
Txij li thaum lawv cov kev taw qhia nyob rau hauv 1937, polyurethane (PU) cov ntaub ntawv tau pom dav siv nyob rau hauv ntau yam sectors nrog rau kev thauj mus los, kev tsim kho, petrochemicals, textiles, mechanical thiab hluav taws xob engineering, aerospace, kev kho mob, thiab kev ua liaj ua teb. Cov ntaub ntawv no yog siv rau hauv cov ntaub ntawv xws li foam plastics, fibers, elastomers, waterproofing agents, hluavtaws tawv, coatings, adhesives, paving cov ntaub ntawv thiab cov khoom siv kho mob. Cov tsoos PU feem ntau yog tsim los ntawm ob lossis ntau dua isocyanates nrog rau macromolecular polyols thiab me me molecular saw extenders. Txawm li cas los xij, qhov muaj toxicity ntawm isocyanates ua rau muaj kev pheej hmoo loj rau tib neeg kev noj qab haus huv thiab ib puag ncig; Tsis tas li ntawd, lawv feem ntau yog muab los ntawm phosgene-ib qho tshuaj lom neeg ua ntej-thiab cov khoom siv amine raw.
Raws li kev lag luam tshuaj lom neeg niaj hnub nrhiav kev ua haujlwm ntsuab thiab kev tsim kho kom ruaj khov, cov kws tshawb fawb tau tsom mus rau kev hloov cov isocyanates nrog cov khoom siv zoo ib puag ncig thaum tshawb nrhiav cov kev sib txuas tshiab rau cov uas tsis yog isocyanate polyurethanes (NIPU). Daim ntawv no qhia txog txoj hauv kev npaj rau NIPU thaum tshuaj xyuas kev nce qib hauv ntau hom NIPUs thiab sib tham txog lawv cov kev cia siab yav tom ntej los muab kev siv rau kev tshawb fawb ntxiv.
1 Synthesis ntawm Non-Isocyanate Polyurethanes
Thawj qhov kev sib xyaw ua ke ntawm cov khoom hnyav molecular hnyav carbamate sib txuas siv monocyclic carbonates ua ke nrog aliphatic diamines tau tshwm sim txawv teb chaws hauv xyoo 1950 - cim lub sijhawm tseem ceeb ntawm non-isocyanate polyurethane synthesis. Tam sim no muaj ob txoj hauv kev tseem ceeb rau kev tsim NIPU: Thawj qhov cuam tshuam nrog kev sib txuas ntxiv ntawm binary cyclic carbonates thiab binary amines; Qhov thib ob entails polycondensation cov tshuaj tiv thaiv nrog diurethane intermediates nrog rau diols uas pab txhawb kev sib pauv hauv cov carbamates. Diamarboxylate intermediates tuaj yeem tau txais los ntawm kev sib tw cyclic carbonate lossis dimethyl carbonate (DMC) txoj kev; Hauv paus txhua txoj kev hnov mob los ntawm carbonic acid pawg yielding carbamate functionalities.
Cov ntu hauv qab no piav qhia txog peb txoj hauv kev sib txawv rau kev sib xyaw polyurethane yam tsis siv isocyanate.
1.1 Binary Cyclic Carbonate Txoj Kev
NIPU tuaj yeem ua ke los ntawm kev sib txuas ntxiv uas suav nrog binary cyclic carbonate txuas nrog binary amine raws li qhia hauv daim duab 1.
Vim muaj ntau pawg hydroxyl tam sim no nyob rau hauv rov qab units raws nws cov saw tseem ceeb cov qauv no feem ntau yields dab tsi yog hu ua polyβ-hydroxyl polyurethane (PHU). Leitsch li al., tau tsim ib tug series ntawm polyether PHUs siv cyclic carbonate-terminated polyethers nrog rau binary amines ntxiv rau me me molecules tau los ntawm binary cyclic carbonates-piv cov no tiv thaiv ib txwm siv rau kev npaj polyether PUs. Lawv qhov kev tshawb pom tau qhia tias cov pab pawg hydroxyl hauv PHUs tuaj yeem tsim cov ntawv cog lus hydrogen nrog nitrogen / oxygen atoms nyob rau hauv cov khoom muag / tawv; Kev hloov pauv ntawm cov ntu mos kuj cuam tshuam rau hydrogen bonding tus cwj pwm nrog rau microphase sib cais qib uas tom qab cuam tshuam rau tag nrho cov yam ntxwv ua haujlwm.
Feem ntau ua hauv qab qhov kub thiab txias tshaj 100 ° C txoj hauv kev no ua rau tsis muaj cov khoom lag luam thaum cov txheej txheem tshuaj tiv thaiv ua rau nws tsis hnov tsw mus rau noo noo thaum lub sij hawm yielding cov khoom ruaj khov tsis muaj kev txhawj xeeb tab sis xav tau cov kuab tshuaj organic uas muaj zog polarity xws li dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DMF), thiab lwm yam.. Ntxiv cov tshuaj tiv thaiv ncua sij hawm nyob qhov twg ntawm ib hnub mus txog rau tsib hnub feem ntau yields qis molecular luj feem ntau poob luv luv hauv qab qhov pib nyob ib ncig ntawm 30k g / mol rendering loj-scale ntau lawm nyuaj vim loj heev ob qho tib si cov nqi siab. txuam nyob rau hauv ua ke nrog tsis txaus lub zog uas tshwm sim los ntawm resultant PHUs txawm hais tias cov ntawv cog lus spanning damping khoom domains zoo nco constructs nplaum formulations txheej daws foams thiab lwm yam.
1.2 Monocylic Carbonate Txoj Kev
Monocylic carbonate reacts ncaj qha nrog diamine uas ua rau dicarbamate muaj hydroxyl kawg-pab pawg uas tom qab ntawd tau txais kev tshwj xeeb transesterification/polycondensation kev sib cuam tshuam nrog diols thaum kawg tsim ib qho NIPU structurally akin tsoos counterparts depicted visually ntawm daim duab 2.
Feem ntau ua hauj lwm monocylic variants suav nrog ethylene & propylene carbonated substrates nyob rau hauv Zhao Jingbo pab neeg ntawm Beijing University Of Chemical Technology koom nrog ntau hom diamines reacting lawv tawm tsam hais tias cyclical cov chaw pib tau txais ntau yam qauv dicarbamate intermediaries ua ntej mus rau condensation los ntawm cov txheej txheem dicarbamate kev ua Raws li cov khoom lag luam nthuav tawm cov khoom zoo thermal / cov cuab yeej cuab tam nce mus txog cov ntsiab lus melting hovering nyob ib ncig ntawm thaj tsam li ntawm 125 ~ 161 ° C tensile zog peaking ze 24MPa elongation tus nqi ze 1476%. Wang et al., zoo ib yam li kev sib txuas ua ke suav nrog DMC ua ke raws li w/hexamethylenediamine/cyclocarbonated precursors synthesizing hydroxy-terminated derivatives tom qab raug biobased dibasic acids xws li oxalic/sebacic/acids adipic-acid-terephtalics ntau yam kev ua tiav ~ 2. tensile zog fluctuating9 ~ 17 MPa elongations txawv ntawm 35% ~ 235%.
Cyclocarbonic esters koom nrog zoo yam tsis tas yuav tsum muaj cov catalysts nyob rau hauv cov xwm txheej uas tswj qhov kub thiab txias spans roughly 80 ° txog 120 ° C tom ntej transesterifications feem ntau yog siv organotin-based catalytic systems kom ntseeg tau tias kev ua haujlwm zoo tsis tshaj 200 °. Tshaj li qhov kev sib xyaw ua ke ntawm lub hom phiaj diolic inputs uas muaj peev xwm ua tus kheej-polymerization / deglycolysis phenomena ua kom yooj yim rau tiam neeg xav tau cov txiaj ntsig ua rau cov txheej txheem ua rau hauv eco-phooj ywg feem ntau yielding methanol / me me-molecule-diolic residues yog li nthuav tawm cov kev lag luam muaj txiaj ntsig mus rau tom ntej.
1.3 Dimethyl Carbonate Txoj Kev
DMC sawv cev rau ecologically suab / non-toxic lwm yam featuring ntau active functional moieties including methyl / methoxy / carbonyl configurations pab txhawb reactivity profiles ho ua rau thawj zaug kev koom tes uas DMC interacts ncaj qha w / diamines tsim me me methyl-carbamate terminated intermediaries ua raws li tom qab ntawd. ntxiv me-chain-extender-diolics/loj-polyol constituents ua rau qhov tshwm sim tshwm sim nrhiav-tom qab cov qauv polymer pom tau raws li daim duab 3.
Deepa et.al capitalized raws li aforementioned dynamics leveraging sodium methoxide catalysis orchestrating sib txawv intermediate formations tom qab koom lub hom phiaj extensions culminating series sib npaug zog-seg compositions attaining molecular luj approximating (3 ~ 20) x10 ^ 3g / spanning iav 2 (0. °C). Pan Dongdong xaiv cov kev sib tw zoo sib xws uas muaj DMC hexamethylene-diaminopolycarbonate-polyalcohols paub txog cov txiaj ntsig zoo tshaj plaws uas qhia cov tensile-strength metrics oscillating10-15MPa elongation ratios approaching1000%-1400%. Kev tshawb nrhiav nyob ib puag ncig sib txawv ntawm cov saw txuas txuas ntxiv tau nthuav tawm cov kev nyiam ua kom haum rau kev xaiv butanediol / hexanediol thaum atomic-number parity tuav tswj kev sib luag txhawb kev txiav txim crystallinity kev txhim kho pom thoob plaws hauv chains.Sarazin pawg npaj cov khoom sib xyaw ua ke nrog lignin / DMC nrog rau hexahydroxysattributes tom qab kev ua haujlwm 2. .Txoj kev tshawb nrhiav ntxiv txhawm rau muab cov uas tsis yog-isocyante-polyureas leveraging dizomonomer kev koom tes xav tias yuav muaj peev xwm pleev xim daim ntaub ntawv tawm los sib piv qhov zoo dua li cov vinyl-carbonaceous counterparts highlighting tus nqi-effectiveness/wide nrhiav avenues muaj.Due diligence hais txog cov bulkature-cov txheej txheem ua Environments negating cov kev xav tau hnyav li no txo qis cov dej khib nyiab feem ntau txwv tsuas yog methanol / me-molecule-diolic effluents tsim cov greener syntheses paradigms tag nrho.
2 Sib txawv mos ntu ntawm non-isocyanate polyurethane
2.1 Polyether polyurethane
Polyether polyurethane (PEU) yog dav siv vim nws tsis tshua muaj cohesion zog ntawm ether daim ntawv cog lus nyob rau hauv mos ntu rov ua dua units, yooj yim kev sib hloov, zoo heev tsis tshua muaj kub yooj thiab hydrolysis kuj.
Kebir et al. synthesized polyether polyurethane nrog DMC, polyethylene glycol thiab butanediol li raw cov ntaub ntawv, tab sis cov molecular hnyav yog tsawg (7 500 ~ 14 800g / mol), Tg yog qis dua 0 ℃, thiab lub melting point kuj tsawg (38 ~ 48 ℃) , thiab lub zog thiab lwm yam kev ntsuas tau nyuaj ua kom tau raws li qhov xav tau ntawm kev siv. Zhao Jingbo pawg tshawb fawb tau siv ethylene carbonate, 1, 6-hexanediamine thiab polyethylene glycol los ua ke PEU, uas muaj qhov hnyav ntawm 31 000g / mol, tensile lub zog ntawm 5 ~ 24MPa, thiab elongation ntawm tawg ntawm 0.9% ~ 1 388%. Qhov hnyav molecular ntawm cov synthesized series ntawm aromatic polyurethanes yog 17 300 ~ 21 000g / mol, Tg yog -19 ~ 10 ℃, lub melting point yog 102 ~ 110 ℃, tensile zog yog 12 ~ 38MPa, thiab elastic rov qab tus nqi ntawm 200% tas li elongation yog 69% ~ 89%.
Cov pab pawg tshawb fawb ntawm Zheng Liuchun thiab Li Chuncheng tau npaj cov tshuaj nruab nrab 1, 6-hexamethylenediamine (BHC) nrog dimethyl carbonate thiab 1, 6-hexamethylenediamine, thiab polycondensation nrog cov me me sib txawv molecules ncaj saw diols thiab polytetrahydrofuranediols (Mn = 2 000). Ib tug series ntawm polyether polyurethanes (NIPEU) nrog cov uas tsis yog-isocyanate txoj kev tau npaj, thiab cov crosslinking teeb meem ntawm intermediates thaum lub sij hawm cov tshuaj tiv thaiv tau daws. Cov qauv thiab cov khoom ntawm cov tsoos polyether polyurethane (HDIPU) npaj los ntawm NIPEU thiab 1, 6-hexamethylene diisocyanate tau muab piv, raws li qhia hauv Table 1.
| Qauv | Hard ntu pawg pawg /% | Molecular hnyav / (g·mol^(-1)) | Molecular Luj Distribution Index | Tensile zog / MPa | Elongation ntawm tawg /% |
| NPE 30 | 30 | 74000 ib | 1.9 | 12.5 ib | 1250 |
| NPE 40 | 40 | 6 6000 | 2.2 | 8.0 ib | 550 |
| HIPU 30 | 30 | 4 6000 | 1.9 | 31.3 | 1440 |
| HIPU40 | 40 | 5 4000 | 2.0 | 25.8 ib | 1360 |
Table 1
Cov txiaj ntsig hauv Table 1 qhia tias qhov sib txawv ntawm NIPEU thiab HDIPU feem ntau yog vim qhov nyuaj. Cov urea pab pawg tsim los ntawm sab cov tshuaj tiv thaiv ntawm NIPEU yog randomly embedded nyob rau hauv lub hard segment molecular saw, rhuav lub nyuaj segment los tsim hydrogen bonds, uas ua rau tsis muaj zog hydrogen bonds ntawm lub molecular chains ntawm lub hard segment thiab tsawg crystallinity ntawm lub hard segment. , uas ua rau qis theem sib cais ntawm NIPEU. Raws li qhov tshwm sim, nws cov khoom siv kho tshuab yog qhov phem dua li HDIPU.
2.2 Polyester Polyurethane
Polyester polyurethane (PETU) nrog polyester diols raws li cov khoom muag muag muaj biodegradability zoo, biocompatibility thiab txhua yam khoom, thiab tuaj yeem siv los npaj cov ntaub so ntswg engineering scaffolds, uas yog cov khoom siv biomedical nrog rau daim ntawv thov kev cia siab. Polyester diols feem ntau siv hauv cov khoom muag yog polybutylene adipate diol, polyglycol adipate diol thiab polycaprolactone diol.
Ua ntej, Rokicki et al. reacted ethylene carbonate nrog diamine thiab diols sib txawv (1, 6-hexanediol, 1, 10-n-dodecanol) kom tau txais NIPU sib txawv, tab sis cov synthesized NIPU muaj qhov hnyav molecular thiab qis Tg. Farhadian et al. npaj polycyclic carbonate siv sunflower noob roj raws li raw khoom, ces tov nrog bio-based polyamines, coated rau ntawm ib phaj, thiab kho ntawm 90 ℃ rau 24 h kom tau thermosetting polyester polyurethane zaj duab xis, uas pom zoo thermal stability. Cov pab pawg tshawb fawb ntawm Zhang Liqun los ntawm South China University of Technology tau tsim cov diamines thiab cyclic carbonates, thiab tom qab ntawd condensed nrog biobased dibasic acid kom tau txais biobased polyester polyurethane. Zhu Jin pawg tshawb fawb ntawm Ningbo Institute of Materials Research, Suav Academy ntawm Kev Tshawb Fawb tau npaj diaminodiol nyuaj ntu siv hexadiamine thiab vinyl carbonate, thiab tom qab ntawd polycondensation nrog bio-based unsaturated dibasic acid kom tau txais cov khoom siv polyester polyurethane, uas tuaj yeem siv los ua xim tom qab. Kev tiv thaiv ultraviolet [23] Cov pab pawg tshawb fawb ntawm Zheng Liuchun thiab Li Chuncheng siv adipic acid thiab plaub aliphatic diols (butanediol, hexadiol, octanediol thiab decanediol) nrog cov pa roj carbon monoxide sib txawv los npaj cov khoom sib xws polyester diols ua ntu mos; Ib pawg ntawm non-isocyanate polyester polyurethane (PETU), muaj npe tom qab tus naj npawb ntawm carbon atoms ntawm aliphatic diols, tau los ntawm melting polycondensation nrog hydroxy-sealed nyuaj ntu prepolymer npaj los ntawm BHC thiab diols. Cov khoom siv kho tshuab ntawm PETU tau qhia hauv Table 2.
| Qauv | Tensile zog / MPa | Elastic modulus/MPa | Elongation ntawm tawg /% |
| PEB 4 | 6.9±1.0 | 36±8 | 673 ib±35 |
| PEB 6 | 10.1±1.0 | 55±4 | 568 ib±32 |
| PEB 8 | 9.0 ib±0.8 ua | 47±4 | 551 ib±25 |
| PEB 10 | 8.8 ib±0.1 | 52±5 | 137±23 |
Rooj 2
Cov txiaj ntsig qhia tau hais tias qhov muag muag ntawm Petu4 muaj lub siab carboryl ntom, cov ntu muaj zog tshaj plaws nrog cov theem nyuaj, thiab theem qis tshaj ntu degree. Lub crystallization ntawm ob qho tib si mos thiab tawv ntu yog txwv, uas qhia tias tsis tshua muaj melting point thiab tensile lub zog, tab sis lub siab tshaj plaws elongation ntawm tawg.
2.3 Polycarbonate polyurethane
Polycarbonate polyurethane (PCU), tshwj xeeb tshaj yog aliphatic PCU, muaj zoo heev hydrolysis tsis kam, oxidation kuj, zoo lom neeg stability thiab biocompatibility, thiab muaj zoo daim ntawv thov kev cia siab nyob rau hauv lub teb ntawm biomedicine. Tam sim no, feem ntau ntawm cov npaj NIPU siv polyether polyols thiab polyester polyols ua ntu muag, thiab muaj ob peb cov ntaub ntawv tshawb fawb txog polycarbonate polyurethane.
Cov non-isocyanate polycarbonate polyurethane npaj los ntawm Tian Hengshui cov kev tshawb fawb pab pawg ntawm South China University of Technology muaj qhov hnyav molecular ntau dua 50 000 g / mol. Kev cuam tshuam ntawm cov tshuaj tiv thaiv ntawm qhov hnyav molecular ntawm cov polymer tau kawm, tab sis nws cov khoom siv tshuab tsis tau tshaj tawm. Zheng Liuchun thiab Li Chuncheng cov kev tshawb fawb pab pawg tau npaj PCU siv DMC, hexanediamine, hexadiol thiab polycarbonate diols, thiab hu ua PCU raws li qhov loj ntawm cov ntu nyuaj rov ua haujlwm. Mechanical zog muaj nyob rau hauv Table 3.
| Qauv | Tensile zog / MPa | Elastic modulus/MPa | Elongation ntawm tawg /% |
| PCU18 | 17±1 | 36±8 | 665 ib±24 |
| PCU33 | 19±1 | 107±9 | 656 ib±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 |
Table 3
Cov txiaj ntsig tau pom tias PCU muaj qhov hnyav molecular, mus txog 6 × 104 ~ 9 × 104g / mol, melting point txog 137 ℃, thiab tensile zog mus txog 29 MPa. Hom PCU no tuaj yeem siv los ua cov yas yas lossis cov elastomer, uas muaj cov ntawv thov zoo hauv thaj chaw biomedical (xws li tib neeg cov ntaub so ntswg engineering scaffolds lossis cov ntaub ntawv cog cov hlab plawv).
2.4 Hybrid non-isocyanate polyurethane
Hybrid non-isocyanate polyurethane (hybrid NIPU) yog kev taw qhia ntawm epoxy resin, acrylate, silica los yog siloxane pawg mus rau hauv lub polyurethane molecular molecular molecular molecular molecular molecular molecular qauv los tsim ib tug interpenetrating network, txhim kho kev ua tau zoo ntawm polyurethane los yog muab cov polyurethane sib txawv zog.
Feng Yuelan et al. reacted bio-raws li epoxy soybean roj nrog CO2 los ua ke pentamonic cyclic carbonate (CSBO), thiab qhia bisphenol A diglycidyl ether (epoxy resin E51) nrog cov saw nruj dua ntu kom txhim kho NIPU tsim los ntawm CSBO solidified nrog amine. Cov saw molecular muaj cov saw txuas ntev ntev ntawm oleic acid / linoleic acid. Nws kuj tseem muaj cov saw hlau nruj dua, kom nws muaj zog txhua yam thiab siab toughness. Qee cov kws tshawb fawb kuj tau tsim peb hom NIPU prepolymer nrog furan kawg pab pawg los ntawm kev qhib cov tshuaj tiv thaiv ntawm diethylene glycol bicyclic carbonate thiab diamine, thiab tom qab ntawd tau hnov mob nrog polyester tsis txaus los npaj ib qho mos polyurethane nrog kev kho tus kheej, thiab ua tiav kev paub txog tus kheej siab. - kho efficiency ntawm mos NIPU. Hybrid NIPU tsis yog tsuas yog muaj cov yam ntxwv ntawm NIPU, tab sis kuj tseem tuaj yeem ua kom zoo dua adhesion, acid thiab alkali corrosion kuj, hnyav tsis kam thiab txhua yam muaj zog.
3 Outlook
NIPU yog npaj tsis siv cov tshuaj lom isocyanate, thiab tam sim no tab tom kawm hauv daim ntawv ua npuas ncauj, txheej, nplaum, elastomer thiab lwm yam khoom, thiab muaj ntau yam kev cia siab rau daim ntawv thov. Txawm li cas los xij, feem ntau ntawm lawv tseem txwv rau kev tshawb fawb hauv chav kuaj, thiab tsis muaj kev tsim khoom loj. Tsis tas li ntawd, nrog kev txhim kho ntawm tib neeg cov qauv kev ua neej thiab kev loj hlob tsis tu ncua ntawm kev thov, NIPU nrog rau ib qho kev ua haujlwm lossis ntau lub zog tau dhau los ua cov kev tshawb fawb tseem ceeb, xws li tshuaj tua kab mob, kho tus kheej, zoo li nco, nplaim taws retardant, kub kub tsis kam thiab yog li ntawd. Yog li ntawd, kev tshawb fawb yav tom ntej yuav tsum nkag siab tias yuav ua li cas los ntawm cov teeb meem tseem ceeb ntawm kev lag luam thiab txuas ntxiv mus tshawb nrhiav cov kev taw qhia ntawm kev npaj ua haujlwm NIPU.
Post lub sij hawm: Aug-29-2024