Su'esu'ega Alualu i Luma ile Non-Isocyanate Polyurethanes
Talu mai lo latou faʻaofiina i le 1937, o mea polyurethane (PU) ua maua le tele o talosaga i vaega eseese e aofia ai felauaiga, fausiaina, petrochemicals, textiles, inisinia ma eletise, aerospace, soifua maloloina, ma faʻatoʻaga. O nei mea e faʻaaogaina i foliga e pei o palasitika foam, alava, elastomers, mea e le susu, paʻu faʻapipiʻi, paʻu, faʻapipiʻi, mea faʻapipiʻi ma sapalai faafomaʻi. O le PU masani o loʻo faʻapipiʻiina muamua mai le lua pe sili atu isocyanates faʻatasi ai ma polyols macromolecular ma faʻalautele filifili mole mole laiti. Peita'i, o le o'ona fa'atupu ole isocyanates e iai ni a'afiaga ogaoga i le soifua maloloina o tagata ma le si'osi'omaga; e le gata i lea e masani lava ona maua mai i le phosgene-o se mea e sili ona oona muamua-ma mea fa'atatau amine.
E tusa ai ma le tulituliloaina e le alamanuia o vailaʻau faʻaonapo nei i faiga faʻatupuina meamata ma gafataulimaina, ua faʻateleina le taulaʻi o tagata suʻesuʻe i le suia o isocyanates i punaʻoa faʻaleleia le siosiomaga aʻo suʻesuʻeina auala faʻapipiʻi fou mo polyurethanes non-isocyanate (NIPU). O lenei pepa o loʻo faʻaalia ai auala sauniuni mo le NIPU aʻo iloiloina le alualu i luma i ituaiga eseese o NIPU ma talanoaina o latou lumanaʻi lumanaʻi e maua ai se faʻamatalaga mo suʻesuʻega atili.
1 Fa'asologa o Polyurethanes e le-Isocyanate
O le fa'asologa muamua o fa'aputuga o karbamate mole mole maualalo e fa'aaoga ai monocyclic carbonates fa'atasi ma aliphatic diamines na tupu i fafo i le 1950s-fa'ailogaina se taimi taua i le non-isocyanate polyurethane synthesis. I le taimi nei, e lua auala autu mo le gaosia o le NIPU: O le mea muamua e aofia ai faʻaopoopoga faʻasolosolo gaioiga i le va o carbonates cyclic binary ma amines binary; O le lona lua e aofia ai le polycondensation tali e aofia ai le diurethane intermediates faʻatasi ma diols e faʻafaigofie ai fefaʻatauaiga i totonu o carbamates. Ole Diamarboxylate intermediates e mafai ona maua ile cyclic carbonate poʻo le dimethyl carbonate (DMC) auala; e fa'atatau i auala uma e tali atu e ala i vaega o le carbonic acid e maua mai ai galuega fa'atino.
O vaega o loʻo mulimuli mai o loʻo faʻamatalaina i luga o auala eseese e tolu e faʻapipiʻi ai le polyurethane e aunoa ma le faʻaaogaina o le isocyanate.
1.1Binary Cyclic Carbonate Auala
O le NIPU e mafai ona tu'ufa'atasia e ala i fa'aopoopoga fa'asolosolo e aofia ai le binary cyclic carbonate fa'atasi ma le amine binary e pei ona fa'aalia i le Ata 1.
Ona o le tele o vaega o le hydroxyl o lo'o iai i totonu o iunite fa'asolosolo i lona fausaga autu o filifili o lenei metotia e masani ona maua mai ai le mea e ta'ua o le polyβ-hydroxyl polyurethane (PHU). Leitsch et al., na atiina ae se faasologa o polyether PHUs e faʻaaogaina cyclic carbonate-terminated polyethers faʻatasi ma binary amines faʻatasi ai ma tamaʻi molelaʻau e maua mai le binary cyclic carbonates-faʻatusatusa nei mea i auala masani na faʻaaogaina mo le saunia o polyether PUs. O a latou su'esu'ega na fa'ailoa mai ai o vaega o le hydroxyl i totonu o PHU e faigofie ona fausia fa'amauga fa'ama'i fa'atasi ai ma atoms oona/okesene o lo'o i totonu o vaega vaivai/malosi; O fesuiaiga i vaega vaivai e a'afia ai le amio fa'apipi'i o le hydrogen fa'apea fo'i fa'ailoga vaeluaga o le microphase e a'afia ai uiga fa'atinoga atoa.
E masani ona faia i lalo o le vevela e sili atu i le 100 °C o lenei auala e leai ni mea e maua mai i le taimi o gaioiga e faʻafefe ai le susu aʻo tuʻuina atu oloa mautu e aunoa ma ni popolega faʻafefe ae o loʻo manaʻomia ni solvents faʻaletino e faʻaalia i le polarity malosi e pei o le dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DMF), ma isi.. Fa'aopoopo taimi fa'atupu fa'atupu i so'o se mea i le va o le tasi le aso se'ia o'o i le lima aso e masani ona maua mai ai le mamafa mole mole maualalo e masani ona pa'u i lalo ifo o fa'ailoga e tusa ma le 30k g/mol e fa'atupu ai le tele o le gaosiga o lu'itau ona o le tele o tau e mafua mai i tau maualuga. feso'ota'i i totonu fa'atasi ai ma le le lava o le malosi na fa'aalia e PHUs e maua mai e ui lava i fa'amoemoega fa'aoga e fa'asolo ai mea fa'apalapala fa'amaufa'ailoga fau mea manatua fau fa'apipi'i fa'apipi'i fofo fofo ma isi.
1.2Ala Monocylic Carbonate
Monocylic carbonate e tali sa'o ma le diamine e maua ai le dicarbamate o lo'o i ai vaega fa'ai'uga o le hydroxyl ona faia lea o feso'ota'iga fa'apitoa mo le transesterification/polycondensation fa'atasi ma le diols e iu ai ina fa'atupuina se NIPU fa'atusa fa'aleaganu'u tu'ufa'atasi o lo'o fa'aalia ile Ata 2.
O suiga e masani ona fa'aaogaina e aofia ai le ethylene & propylene carbonated substrates lea na fa'aaogaina ai e le 'au a Zhao Jingbo i le Beijing University of Chemical Technology ni diamine eseese e tali atu ai i latou fa'asaga i fa'alapotopotoga fa'ata'amilomilo na mua'i mauaina ni fa'alāpotopotoga eseese o le dicarbamate a'o le'i fa'agasolo atu i vaega fa'a'ele'ele e fa'aogaina ai le polytetrapolyethertheridiol-diol/culture. laina o oloa ta'itasi o lo'o fa'aalia ai mea fa'amanaia fa'amama/masini e o'o atu i luga mea liusuavai o lo'o fa'afefete solo i le lautele e fa'alautele atu e tusa ma le 125~161°C malosi mālosi e latalata i le 24MPa fua fa'alautele latalata ile1476%. Wang et al., fa'apena tu'ufa'atasiga fa'aopoopo e aofia ai le DMC fa'alua fa'atasi w/hexamethylenediamine/cyclocarbonated precursors fa'apipi'i fa'ama'i fa'amuta hydroxy mulimuli ane tu'uina atu i le biobased dibasic acids e pei o le oxalic/sebacic/acid adipic-acid-terephtalics ausia taunu'uga fa'ai'uga fa'aalia g13k~ malosi fa'amalosi e fesuisuia'i9~17 MPa fa'aumiumi eseese35%~235%.
Cyclocarbonic esters e fa'aoga lelei e aunoa ma le mana'omia o mea fa'aoso i lalo o tulaga masani fa'atumauina le vevela e tusa ma le 80° i le 120°C mulimuli ane transesterifications e masani ona fa'aogaina faiga fa'apipi'i fa'a-organotin e fa'amautinoa ai le lelei o le gaosiga e le sili atu i le200°. I tua atu o taumafaiga condensation e fa'atatau i mea fa'aoga o le diolic e mafai ona fa'ameamea le self-polymerization/deglycolysis fa'afaigofieina le fa'atupuina o taunu'uga mana'omia e fa'aalia ai metotia fa'anatura fa'alelei fa'alesiosiomaga e tele lava e maua mai ai toega methanol/laiti-molole-diolic ma fa'aalia ai isi mea tau alamanuia e aga'i i luma.
1.3Dimethyl Carbonate Auala
O le DMC e fai ma sui o le si'osi'omaga/e le o'ona e fa'aalia ai le tele o vaega galue malosi e aofia ai le methyl/methoxy/carbonyl configurations e fa'aleleia ai fa'amatalaga fa'agaioiga e matua mafai ai ona fa'aagaaga muamua e fegalegaleai sa'o ai le DMC fa'atasi ai ma diamine e fa'atupuina ai ni tama'i methyl-carbamate fa'amuta fa'alaua'itele mulimuli ane gaioiga fa'afefiloi fa'afefete. fa'aopoopo mea laiti filifili-fa'alautele-diolics/polyol lapopo'a e ta'ita'ia ai le tula'i mai o fausaga polymer o lo'o fa'atusalia e ala ile Ata3.
Deepa ma mataitusi tetele i luga o le dynamics taʻua i luga leveraging sodium methoxide catalysis orchestrating eseʻese faʻavae faʻavae mulimuli ane faʻapipiʻiina faʻalautele faʻauluulu faʻasologa faʻasolosolo faʻasologa tutusa vaega faigata tuʻufaʻatasiga maua le mamafa mole e tusa (3 ~ 20) x10^3g / molanning 1 vevela (0^3g/molanning 000% vevela vevela-3g/molanning) °C). Na filifilia e Pan Dongdong paiga faʻataʻitaʻiga e aofia ai le DMC hexamethylene-diaminopolycarbonate-polalcohols e iloa ai taunuʻuga mataʻina e faʻaalia ai le malosi-malosi metric oscillating10-15MPa faʻalauteleina ratios approaching1000% -1400%. O sailiga su'esu'e o lo'o si'osi'omia ai a'afiaga eseese e fa'alautele ai filifili na fa'aalia ai le fa'aogaina lelei o le fa'aogaina o butanediol/hexanediol pe a fa'atumauina le tutusa o numera atomika ma fa'atupuina le fa'aleleia atili o le tioata fa'atonu i filifili uma. Sa saunia e le vaega a Sarazin mea tu'ufa'atasia tu'ufa'atasia le lignin/DMC fa'atasi ma le hexahydroxytisafactory ℃ fa'atasi ma le hexahydroxytisafactmine. .Su'esu'ega fa'aopoopo e fa'atatau i le fa'atupuina o le non-isocyante-polyurea e fa'aogaina ai le fa'aogaina o le diazomonomer e fa'atatau i le fa'aogaina o vali fa'atatau e fa'atusalia fa'atusatusaga i luga ole vinyl-carbonaceous pa'aga e fa'amanino ai le tau-lelei/teletele auala e maua ai. fa'afitia mana'oga solvent ma fa'aiti'itia ai ala lapisi e fa'atapula'a na'o le methanol/laiti-molole-diolic effluent fa'avaeina fa'ameamea fa'atusa fa'atasi.
2 Vaega vaivai eseese ole polyurethane le isocyanate
2.1 Polyether polyurethane
Polyether polyurethane (PEU) e masani ona faʻaaogaina ona o le maualalo o le malosi faʻatasi o faʻamau eter i vaega vaivai toe fai iunite, faigofie suiga, sili ona lelei fetuutuunai vevela ma hydrolysis tetee.
Kebir et al. synthesized polyether polyurethane ma DMC, polyethylene glycol ma butanediol e pei o mea mata, ae o le mamafa molecular sa maualalo (7 500 ~ 14 800g / mol), Tg sa maualalo nai lo 0 ℃, ma le mea liusuavai sa maualalo foi (38 ~ 48 ℃) , ma o le malosi ma isi faʻailoga sa faigata ona faʻafetaui manaoga o le faʻaaogaina. O le vaega suʻesuʻe a Zhao Jingbo na faʻaaogaina ethylene carbonate, 1, 6-hexanediamine ma polyethylene glycol e faʻapipiʻi PEU, o loʻo i ai se mamafa mole o le 31 000g / mol, malosi tensile o 5 ~ 24MPa, ma elongation i le malologa o 0.9% ~ 1 388%. O le mamafa mole mole o le faasologa synthesized o polyurethanes manogi o le 17 300 ~ 21 000g / mol, o le Tg o le -19 ~ 10 ℃, o le mea liusuavai o le 102 ~ 110 ℃, o le malosi tensile o le 12 ~ 38MPa, ma le fua faʻaleleia toe faʻaleleia. o 200% elongation faifai pea o 69% ~ 89%.
O le vaega suʻesuʻe a Zheng Liuchun ma Li Chuncheng saunia le vaeluagalemu 1, 6-hexamethylenediamine (BHC) ma dimethyl carbonate ma 1, 6-hexamethylenediamine, ma polycondensation ma eseese molelaʻau saʻo filifili diols ma polytetrahydrofuranediols (Mn = 2 000). O se faasologa o polyether polyurethanes (NIPEU) faʻatasi ai ma le auala e le o le isocyanate na saunia, ma le faʻafitauli fesoʻotaʻiga o mea vavalalata i le taimi o le tali na foia. O le fausaga ma meatotino o le polyether polyurethane masani (HDIPU) saunia e le NIPEU ma le 1, 6-hexamethylene diisocyanate na faʻatusatusa, e pei ona faʻaalia i le Laulau 1.
| Fa'ata'ita'iga | Vaega faigata vaega vaega mamafa/% | mamafa mole/(g·mol^(-1)) | Fa'ailoga o le tufatufaina o le mamafa molekala | Malosi fa'amalosi/MPa | Elongation i le malologa/% |
| 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 |
Laulau 1
O fa'ai'uga i le Laulau 1 o lo'o fa'aalia ai o le eseesega o le fausaga i le va o le NIPEU ma le HDIPU e mafua ona o le vaega faigata. O le vaega o le urea e maua mai i le tali atu o le NIPEU o loʻo faʻapipiʻiina faʻafuaseʻi i le filifili mole mole vaega faigata, talepeina le vaega faigata e fausia ai faʻatonuga hydrogen, e mafua ai le vaivai o le hydrogen i le va o filifili mole o le vaega faigata ma le maualalo o le tioata o le vaega faigata. , e mafua ai le vavaeeseina o vaega maualalo ole NIPEU. O se taunuuga, o ana mea faʻainisinia e sili atu le leaga nai lo HDIPU.
2.2 Polyester Polyurethane
Polyester polyurethane (PETU) ma polyester diols e pei o vaega vaivai e lelei biodegradability, biocompatibility ma mea tau masini, ma e mafai ona faaaoga e saunia scaffolds inisinia tissue, o se mea biomedical ma faamoemoega sili talosaga. Polyester diols e masani ona fa'aogaina i vaega vaivai o le polybutylene adipate diol, polyglycol adipate diol ma le polycaprolactone diol.
Muamua, Rokicki et al. tali ethylene carbonate ma diamine ma diols eseese (1, 6-hexanediol,1, 10-n-dodecanol) e maua NIPU eseese, ae o le synthesized NIPU sa maualalo mole mamafa mamafa ma maualalo Tg. Farhadian et al. saunia polycyclic carbonate e faʻaaoga ai le suauʻu fatu o le sunflower e pei o mea mata, ona faʻafefiloi ma polyamines faʻavae, faʻapipiʻi i luga o se ipu, ma faʻamalolo i le 90 ℃ mo le 24 h e maua ai le thermosetting polyester polyurethane film, lea na faʻaalia ai le mautu lelei o le vevela. O le vaega su'esu'e a Zhang Liqun mai le Iunivesite o Tekonolosi i Saute Saina na fa'apipi'iina se fa'asologa o diamine ma cyclic carbonates, ona fa'apipi'i lea i le biobased dibasic acid e maua ai le biobased polyester polyurethane. Vaega su'esu'e a Zhu Jin i Ningbo Institute of Materials Research, Saina Academy of Sciences saunia diaminodiol vaega faigata e faaaoga ai le hexadiamine ma vinyl carbonate, ona polycondensation ma le bio-faavae unsaturated dibasic acid e maua ai se faasologa o polyester polyurethane, lea e mafai ona faaaogaina e pei o vali ina ua uma. fa'amalologa ultraviolet [23]. O le vaega suʻesuʻe a Zheng Liuchun ma Li Chuncheng faʻaaogaina adipic acid ma fa aliphatic diols (butanediol, hexadiol, octanediol ma decanediol) faʻatasi ai ma numera atomic carbon eseese e saunia ai le polyester diols tutusa e pei o ni vaega vaivai; O se vaega o le non-isocyanate polyester polyurethane (PETU), faaigoa i le numera o carbon atoms o aliphatic diols, na maua e ala i le liusua polycondensation ma le hydroxy-faamaufaailoga vaega malo prepolymer saunia e BHC ma diols. O mea fa'ainisinia o le PETU o lo'o fa'aalia i le Laulau 2.
| Fa'ata'ita'iga | Malosi fa'amalosi/MPa | Fa'aula'i fa'alava/MPa | Elongation i le malologa/% |
| 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 |
Laulau 2
O faʻaiʻuga e faʻaalia ai o le vaega vaivai o le PETU4 o loʻo i ai le maualuga o le carbonyl density, o le malosi malosi o le hydrogen faʻatasi ma le vaega faigata, ma le tikeri vavaeesega pito sili ona maualalo. O le tioata o vaega vaivai ma malo e faʻatapulaʻaina, e faʻaalia ai le maualalo o le liusuavai ma le malosi faʻamalosi, ae o le maualuga maualuga i le malologa.
2.3 Polycarbonate polyurethane
Polycarbonate polyurethane (PCU), aemaise aliphatic PCU, e sili atu le hydrolysis teteʻe, oxidation tetee, lelei mautu olaola ma biocompatibility, ma o loʻo i ai faʻamoemoega talosaga lelei i le fanua o biomedicine. I le taimi nei, o le tele o le NIPU saunia e faʻaaogaina polyether polyols ma polyester polyols e fai ma vaega vaivai, ma e itiiti ni lipoti suʻesuʻe i polycarbonate polyurethane.
Ole non-isocyanate polycarbonate polyurethane saunia e le vaega suʻesuʻe a Tian Hengshui i le Iunivesite o Tekonolosi i Saute Saina o loʻo i ai le mamafa mole mole e sili atu i le 50 000 g / mol. O le aʻafiaga o tulaga faʻaalia i luga o le mamafa mole mole o le polymer ua suʻesuʻeina, ae o ona mea faʻainisinia e leʻi lipotia. O le vaega su'esu'e a Zheng Liuchun ma Li Chuncheng na saunia le PCU e fa'aaoga ai le DMC, hexanediamine, hexadiol ma polycarbonate diols, ma fa'aigoaina le PCU e tusa ai ma le vaega tele o le vaega faigata e toe fai le iunite. O mea fa'ainisinia o lo'o fa'aalia i le Laulau 3.
| Fa'ata'ita'iga | Malosi fa'amalosi/MPa | Fa'aula'i fa'alava/MPa | Elongation i le malologa/% |
| 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 |
Laulau 3
O faʻaiʻuga e faʻaalia ai o le PCU e maualuga le mamafa o le mole, e oʻo atu i le 6 × 104 ~ 9 × 104g / mol, faʻafefeteina e oʻo atu i le 137 ℃, ma le malosi faʻamalosi e oʻo atu i le 29 MPa. O lenei ituaiga PCU e mafai ona faʻaaogaina a le o se palasitika malosi poʻo se elastomer, o loʻo i ai se faʻamoemoega faʻaoga lelei i le biomedical field (e pei o faʻainisinia faʻainisinia tagata poʻo mea faʻapipiʻi cardiovascular).
2.4 Polyurethane fa'atosina le isocyanate
Hybrid non-isocyanate polyurethane (hybrid NIPU) o le faʻaofiina o le epoxy resin, acrylate, silica poʻo siloxane vaega i totonu o le polyurethane molecular framework e fausia ai se fesoʻotaʻiga interpenetrating, faʻaleleia le faʻatinoga o le polyurethane poʻo le tuʻuina atu o le polyurethane galuega eseese.
Feng Yuelan et al. fa'afo'i le suau'u soya epoxy fa'aolaola fa'atasi ma CO2 e fa'apipi'i ai le pentamoni cyclic carbonate (CSBO), ma fa'afeiloa'i le bisphenol A diglycidyl eter (epoxy resin E51) fa'atasi ai ma vaega filifili sili malō e fa'aleleia atili ai le NIPU na faia e le CSBO fa'amausali ma amine. O le filifili mole o lo'o i ai se vaega filifili umi fetu'una'i ole oleic acid/linoleic acid. O loʻo i ai foʻi vaega sili atu o filifili filifili, ina ia maualuga le malosi faʻainisinia ma maualuga le malosi. O nisi tagata suʻesuʻe na faʻapipiʻiina foi ituaiga e tolu o le NIPU prepolymers ma furan pito vaega e ala i le fua-talatala tali o le diethylene glycol bicyclic carbonate ma diamine, ona tali atu lea i le polyester unsaturated e saunia ai se polyurethane vaivai ma le galuega faʻamalolo, ma iloa lelei le maualuga o le tagata lava ia. -fa'amalologa lelei ole NIPU vaivai. O le NIPU Hybrid e le gata e iai uiga o le NIPU lautele, ae e mafai foi ona sili atu le faʻapipiʻiina, faʻamaʻi faʻamaʻi ma le alkali, teteʻe solvent ma le malosi faʻainisinia.
3 Vaaiga
NIPU ua saunia e aunoa ma le faʻaogaina o le isocyanate oona, ma o loʻo suʻesuʻeina nei i le tulaga o le foam, faʻapipiʻi, faʻapipiʻi, elastomer ma isi oloa, ma o loʻo i ai le tele o avanoa faʻaoga. Ae ui i lea, o le tele oi latou e faʻatapulaʻa lava i suʻesuʻega falesuesue, ma e leai se gaosiga tele. I le faʻaopoopoga, faʻatasi ai ma le faʻaleleia atili o tulaga ola o tagata ma le faʻaauau pea o le faʻatupulaia o le manaʻoga, o le NIPU faʻatasi ma se galuega e tasi poʻo le tele o galuega tauave ua avea ma se faʻatonuga suʻesuʻega taua, e pei o le antibacterial, toe faʻaleleia e le tagata lava ia, foliga manatua, mumu afi, maualuga vevela ma fa'apea. O le mea lea, o le su'esu'ega i le lumana'i e tatau ona malamalama pe fa'afefea ona talepeina fa'afitauli autu o alamanuia ma fa'aauau pea ona su'esu'e le itu e saunia ai le NIPU galue.
Taimi meli: Aukuso-29-2024