Kufambira mberi kwekutsvakurudza pane Non-Isocyanate Polyurethanes
Kubva pavakaunzwa muna 1937, polyurethane (PU) zvinhu zvakawana mashandisirwo akawandisa muzvikamu zvakasiyana zvinosanganisira zvekufambisa, kuvaka, petrochemicals, machira, mainjiniya nemagetsi, aerospace, hutano, uye zvekurima. Zvinhu izvi zvinoshandiswa mumhando dzakadai semapurasitiki efuro, faibha, elastomers, maajenti ekudzivirira mvura, matehwe ekugadzira, machira, zvinonamira, zvekupaza zvinhu uye zvekurapa. Yechinyakare PU inonyanya kugadzirwa kubva maviri kana anopfuura isocyanates pamwe ne macromolecular polyols uye madiki mamorekuru cheni inotambanudza. Nekudaro, iyo inherent chepfu ye isocyanates inoisa njodzi huru kune hutano hwevanhu uye nharaunda; uyezve iwo anowanzo kutorwa kubva kuphosgene-yakanyanya muchetura precursor-uye inoenderana amine mbishi zvinhu.
Tichifunga nezve indasitiri yemakemikari yemazuva ano kutsvaga kwegirinhi uye kusimudzira maitiro, vaongorori vari kuwedzera kutarisisa kutsiva isocyanates nezviwanikwa zvine hushamwari kwezvakatipoteredza vachiongorora nzira dzemanovel synthesis ye-non-isocyanate polyurethanes (NIPU). Iri bepa rinosuma nzira dzekugadzirira dzeNIPU uku uchiongorora kufambira mberi mumhando dzakasiyana dzeNIPU uye kukurukura nezveramangwana ravo rekupa chirevo chekuenderera mberi nekutsvaga.
1 Synthesis yeNon-Isocyanate Polyurethanes
Yekutanga synthesis yeyakaderera molecular uremu carbamate makomisheni achishandisa monocyclic carbonates akasanganiswa nealiphatic diamines yakaitika kunze kwenyika muma1950s-ichicherekedza nguva yakakosha kune isiri-isocyanate polyurethane synthesis. Parizvino pane nzira mbiri dzekutanga dzekugadzira NIPU: Yekutanga inosanganisira nhanho yekuwedzera maitiro pakati pebinary cyclic carbonates nemabinary amines; yechipiri inosanganisira polycondensation maitiro anosanganisira diurethane epakati padivi pemadhiori anofambisa shanduko yemaitiro mukati mecarbamates. Diamarboxylate intermediates inogona kuwanikwa kuburikidza ne cyclic carbonate kana dimethyl carbonate (DMC) nzira; zvakanyanya nzira dzese dzinoita kuburikidza nekabhoni asidhi mapoka anoburitsa carbamate functionalities.
Zvikamu zvinotevera zvinotsanangura nzira nhatu dzakasiyana dzekugadzira polyurethane pasina kushandisa isocyanate.
1.1Binary Cyclic Carbonate Route
NIPU inogona kugadzirwa kuburikidza nenhanho yekuwedzera inosanganisira bhinari cyclic carbonate yakasanganiswa nebinary amine sezvakaratidzwa mumufananidzo 1.
Nekuda kweakawanda mahydroxyl mapoka aripo mukati anodzokorora mayuniti pamwe neiyo huru cheni chimiro nzira iyi inowanzo buritsa inonzi polyβ-hydroxyl polyurethane (PHU). Leitsch et al., yakagadzira nhevedzano yepolyether PHUs inoshandisa cyclic carbonate-terminated polyethers padivi pebinary amines pamwe nemamorekuru madiki anotorwa kubva kumabhinari cyclic carbonates-achienzanisa aya nemaitiro echinyakare anoshandiswa kugadzira polyether PUs. Zvavakawana zvakaratidza kuti mapoka ehydroxyl mukati mePHUs anoumba nyore hydrogen bond nenitrogen/oxygen maatomu ari mukati mezvikamu zvakapfava/zvakaoma; misiyano pakati pezvikamu zvakapfava zvakare inokanganisa hydrogen bonding maitiro pamwe neiyo microphase yekuparadzanisa madhigirii ayo anozokanganisa maitiro ese ekuita.
Kazhinji inoitwa pasi petembiricha inodarika 100 °C nzira iyi haigadzirise zvigadzirwa panguva yekuita maitiro zvichiita kuti isanzwe kunyorova uku ichiburitsa zvigadzirwa zvakatsiga zvisina kugadzikana asi zvichidikanwa zvinonyungudutsa zvinonyungudutsa zvine simba rakasimba senge dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DMF), nezvimwewo . yakabatana mairi pamwe nekusakwana simba rinoratidzwa nezvinozoitika maPHUs kunyangwe achivimbisa maapplication anotora anonyorovesa zvinhu madomasi chimiro chendangariro chinovaka anonamira maumbirwo ekuputira mafoam nezvimwe.
1.2Monocylic Carbonate Nzira
Monocylic carbonate inobata zvakananga nediamine zvichiita kuti dicarbamate iwane hydroxyl end-groups iyo inobva yasangana nehunyanzvi transesterification/polycondensation kupindirana padivi pemadhiyori inozopedzisira yagadzira NIPU yakarongeka yakafanana neyechinyakare vamwe vanoratidzwa zvinoonekwa kuburikidza neMufananidzo 2.
Anowanzo shandirwa monocylic akasiyana anosanganisira ethylene & propylene carbonated substrates umo timu yaZhao Jingbo kuBeijing University ye Chemical Technology yakaita madhiamine akasiyana siyana achiapindura achipesana neakataurwa masangano ekutanga akawana akasiyana dicarbamate intermediaries asati aenderera kune condensation nhanho ichishandisa kana imwe polyucultation yepolyiculture. mitsara yechigadzirwa inotaridza zvinokatyamadza zvekupisa/makina zvivakwa zvinosvika kumusoro zvinonyungudika zvichitenderera zvichitenderera kureba zvinosvika 125 ~ 161°C masimba ekusimba achikwira padyo ne24MPa elongation rates iri pedyo ne1476%. Wang et al., misanganiswa yakafanana yakasimudzwa inosanganisira DMC yakapetwa zvakateerana w/hexamethylenediamine/cyclocarbonated precursors synthesizing hydroxy-terminated derivatives gare gare yakaisa biobased dibasic acids se oxalic/sebacic/acids adipic-asidi-terephtalics inobudirira 12007 dhizaini yekupedzisira. simba rekusimba richichinja9 ~ 17 MPa elongations inosiyana35% ~ 235%.
Cyclocarbonic esters inobata zvinobudirira pasina kuda macatalysts pasi pemamiriro akajairwa kuchengetedza tembiricha inosvika 80 ° kusvika 120 ° C anotevera transesterifications anowanzo shandisa organotin-based catalytic masisitimu inova nechokwadi chekugadzirisa kusapfuudza200 °. Kupfuura kungoyedza kuedza kwakanangana nezvinopinza diolic inokwanisa-yega-polymerization/deglycolysis chiitiko kufambisa chizvarwa chinodiwa mhedzisiro inopa maitiro echisikigo eco-hushamwari achiburitsa methanol / diki-morekuru-diolic zvisaririra zvichipa zvinogoneka maindasitiri mamwe maindasitiri achifambira mberi.
1.3 Dimethyl Carbonate Nzira
DMC inomiririra ecologically inonzwika/isina-chepfu imwe nzira ine akawanda anoshanda anoshanda zvikamu zvinosanganisira methyl/methoxy/carbonyl zvigadziriso zvinosimudzira reactivity profiles zvinogonesa kudyidzana kwekutanga uko DMC inopindirana zvakananga w/madhiamine ichigadzira diki methyl-carbamate inogumiswa vapomeri inoteedzerwa mushure mekunyunguduka-kukanganisa zviito. mamwe madiki-cheni-extender-diolics/hombe-polyol zvinotungamira zvinozoitika zvakatsvakwa-mushure mepolymer zvimiro zvinoonekwa zvinoenderana kuburikidza neFigure3.
Deepa et.al capitalized pamusoro pezvambotaurwa dynamics leveraging sodium methoxide catalysis orchestrating akasiyana epakati maumbirwo achizobatanidza anonangwa ekuwedzera anoguma akatevedzana akaenzana akaoma-segment zvinyorwa zvinosvika mamolecular uremu akaenzana (3 ~ 20) x10 ^ 3g/s mol spar girazi kushandura 02 °C). Pan Dongdong yakasarudza nzira dzekubatanidza dzinosanganisira DMC hexamethylene-diaminopolycarbonate-polyalcohols vachiona mhedzisiro inoratidzira kusimba-simba metrics oscillating10-15MPa elongation ratios inoswedera ku1000% -1400%. Zvitsvagiro zvekuongorora zvakatenderedza kwakasiyana cheni-kuwedzera pesvedzero zvakaratidza zvaunofarira kubatanidza butanediol/hexanediol sarudzo apo atomiki-nhamba parity yakachengetedza kuenzana ichikurudzira yakaraira crystallinity ekuwedzera inocherechedzwa mumaketani.Boka raSarazin rakagadzira zvinoumba zvinosanganisa lignin/DMC padivi pehexating hydroxyamine dhimoni pamashure pehexating hydroxyamine dhimoni. .Kuwedzera kuongorora kwakanangana nekuwana isiri-isocyante-polyureas leveraging diazomonomer engagement inotarisirwa inogona kuve yependi zvikumbiro zvinobuda zvakanakira kuenzanisa pamusoro pevinyl-carbonaceous anofananidzira zvinoratidzira mutengo-unobudirira/hwakawanda sourcing nzira dziripo.Nekuda kushingairira maererano nezvakawanda-synthesized mitoo yakawanda necuvacumu-yakawanda kuregeredza zvinonyungudutsa zvinodikanwa nokudaro kuderedza hova dzemarara kunonyanya kuganhurirwa chete methanol/diki-morekuru-diolic effluents zvinogadzira greener syntheses paradigms zvachose.
2 Zvikamu zvakapfava zvakasiyana zve-non-isocyanate polyurethane
2.1 Polyether polyurethane
Polyether polyurethane (PEU) inoshandiswa zvakanyanya nekuda kwesimba rayo rakaderera rekubatana kweether zvisungo muchikamu chakapfava chekudzokorora zvikamu, kutenderera kuri nyore, kuchinjika kwakadzika kwakadzika uye hydrolysis kuramba.
Kebir et al. synthesized polyether polyurethane neDMC, polyethylene glycol uye butanediol semidziyo yakabikwa, asi molecular huremu hwaive hwakaderera (7 500 ~ 14 800g/mol), Tg yaive yakaderera pane 0℃, uye nzvimbo yekunyunguduka yaive yakadzikira (38 ~ 48 ℃) , uye simba uye zvimwe zviratidzo zvakanga zvakaoma kusangana nezvinodiwa zvekushandisa. Boka retsvakurudzo raZhao Jingbo rakashandisa ethylene carbonate, 1, 6-hexanediamine uye polyethylene glycol kugadzira PEU, ine huremu hwemamolecular hunosvika 31 000g/mol, kusimba kwe5 ~ 24MPa, uye kurebesa pakupera kwe0.9% ~ 1 388%. Huremu hwemamorekuru eiyo synthesized series yearomatic polyurethanes ndeye 17 300 ~ 21 000g/mol, iyo Tg iri -19 ~ 10 ℃, nzvimbo yakanyunguduka i102 ~ 110 ℃, simba rekusimba i12 ~ 38MPa, uye chiyero chekudzoreredza. ye200% inogara yakareba ndeye 69% ~ 89%.
Boka rekutsvagisa raZheng Liuchun naLi Chuncheng vakagadzira yepakati 1, 6-hexamethylenediamine (BHC) ine dimethyl carbonate uye 1, 6-hexamethylenediamine, uye polycondensation ine akasiyana mamorekuru madiki akatwasuka ketani diols uye polytetrahydrofuranediols (Mn = 2 000). Yakatevedzana yepolyether polyurethanes (NIPEU) ine isiri-isocyanate nzira yakagadziriswa, uye dambudziko rekuyambuka repakati panguva yekupindura rakagadziriswa. Mamiriro uye zvimiro zvechinyakare polyether polyurethane (HDIPU) yakagadzirwa neNIPEU uye 1, 6-hexamethylene diisocyanate yakaenzaniswa, sezvakaratidzwa muTable 1.
| Muenzaniso | Chikamu chakaoma chikamu chikamu /% | Huremu hwemorekuru/(g·mol^(-1)) | Molecular weight distribution index | Tensile simba/MPa | Elongation panguva yekuzorora/% |
| 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 |
Tafura 1
Mhedzisiro muTafura 1 inoratidza kuti misiyano yemaitiro pakati peNIPEU neHDIPU inonyanya kukonzerwa nechikamu chakaoma. Boka reurea rinogadzirwa nedivi rekuita reNIPEU rakaiswa zvisina tsarukano muchikamu chakaomarara cheni, ichityora chikamu chakaomarara kuti chigadzire mabhondi ehydrogen akaodha, zvichikonzera husina simba hwehydrogen zvisungo pakati pemaketani emamorekuru echikamu chakaoma uye yakaderera crystallinity yechikamu chakaoma. , zvichikonzera kuparadzaniswa kwechikamu cheNIPEU. Nekuda kweizvozvo, maitiro ayo emagetsi akanyanya kuipa kupfuura HDIPU.
2.2 Polyester Polyurethane
Polyester polyurethane (PETU) ine polyester diols sezvikamu zvakapfava zvine yakanaka biodegradability, biocompatibility uye michina zvivakwa, uye inogona kushandiswa kugadzirira tishu engineering scaffolds, inova zvinhu zvebiomedical zvine tarisiro huru yekushandisa. Polyester diols anowanzoshandiswa muzvikamu zvakapfava polybutylene adipate diol, polyglycol adipate diol uye polycaprolactone diol.
Pakutanga, Rokicki et al. yakaita ethylene carbonate ine diamine uye diols dzakasiyana (1, 6-hexanediol,1, 10-n-dodecanol) kuti iwane NIPU yakasiyana, asi NIPU yakasanganiswa yakanga ine yakaderera molecular huremu uye yakaderera Tg. Farhadian et al. akagadzira polycyclic carbonate achishandisa mafuta emaringazuva semafuta echiringazuva, obva asanganiswa nebio-based polyamines, akaputirwa mundiro, uye akaporeswa pa90 ℃ kwemaawa makumi maviri nemana kuti awane thermosetting polyester polyurethane firimu, rairatidza kugadzikana kwekupisa. Boka rekutsvagisa raZhang Liqun kubva kuSouth China University of Technology rakagadzira akateedzana diamines uye cyclic carbonates, ndokuzodzoreredzwa nebiobased dibasic acid kuti vawane biobased polyester polyurethane. Zhu Jin's research group kuNingbo Institute of Materials Research, Chinese Academy of Sciences yakagadzira diaminodiol hard segment vachishandisa hexadiamine uye vinyl carbonate, uyezve polycondensation ine bio-based unsaturated dibasic acid kuti iwane akatevedzana epolyester polyurethane, inogona kushandiswa sependi mushure. ultraviolet kurapa [23]. Boka rekutsvagisa raZheng Liuchun naLi Chuncheng vakashandisa adipic acid uye mana aliphatic diol (butanediol, hexadiol, octanediol uye decanediol) ine nhamba dzakasiyana dzeatomu dzekabhoni kugadzirira anowirirana polyester diols sezvikamu zvinyoro; Boka reisina-isocyanate polyester polyurethane (PETU), rakatumidzwa zita rehuwandu hweatomu kabhoni yealiphatic diols, rakawanikwa nekunyungudusa polycondensation neiyo hydroxy-yakavharwa yakaoma segment prepolymer yakagadzirwa neBHC uye diols. Iyo mechanic properties yePETU inoratidzwa muTafura 2.
| Muenzaniso | Tensile simba/MPa | Elastic modulus/MPa | Elongation panguva yekuzorora/% |
| 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 |
Tafura 2
Mhedzisiro yacho inoratidza kuti chikamu chakapfava chePETU4 chine yakanyanya carbonyl density, iyo yakasimba yehydrogen bond ine yakaoma segment, uye yakaderera chikamu chekuparadzanisa dhigirii. Iyo crystallization yeese ari maviri akapfava uye akaoma segment ane mashoma, anoratidza yakaderera kunyungudika uye kusimba kusimba, asi iyo yakakwirira elongation panguva yekuzorora.
2.3 Polycarbonate polyurethane
Polycarbonate polyurethane (PCU), kunyanya aliphatic PCU, ine yakanakisa hydrolysis kuramba, oxidation kuramba, kugadzikana kwakanaka kwebiological uye biocompatibility, uye ine yakanaka tarisiro yekushandisa mumunda webiomedicine. Parizvino, mazhinji eNIPU akagadzirira anoshandisa polyether polyols uye polyester polyols sezvikamu zvakapfava, uye kune mishumo mishoma yekutsvagisa papolycarbonate polyurethane.
Iyo isiri-isocyanate polycarbonate polyurethane yakagadzirwa neboka retsvakurudzo raTian Hengshui kuSouth China University of Technology ine huremu hwemamorekuru hunodarika 50 000 g/mol. Kupesvedzera kwemamiriro ekuita pane huremu hwema molecular yepolymer kwakadzidzwa, asi maitiro ayo emagetsi haana kutaurwa. Zheng Liuchun naLi Chuncheng's boka rekutsvagisa rakagadzira PCU vachishandisa DMC, hexanediamine, hexadiol uye polycarbonate diols, uye vakatumidza PCU maererano nehukuru chikamu chechikamu chakaoma chinodzokorora unit. Iyo mechanical properties inoratidzwa muTafura 3.
| Muenzaniso | Tensile simba/MPa | Elastic modulus/MPa | Elongation panguva yekuzorora/% |
| 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 |
Tafura 3
Mhedzisiro yacho inoratidza kuti PCU ine huremu hwemamorekuru, inosvika 6 × 104 ~ 9 × 104g/mol, nzvimbo yakanyunguduka inosvika 137 ℃, uye kusimba kwesimba kusvika ku29 MPa. Rudzi urwu rwePCU runogona kushandiswa sepurasitiki yakaoma kana se elastomer, ine tarisiro yakanaka yekushandisa mumunda webiomedical (senge scaffolds yeinjiniya yemunhu kana zvinhu zvemoyo nevascular implant).
2.4 Hybrid isiri-isocyanate polyurethane
Hybrid non-isocyanate polyurethane (hybrid NIPU) ndiko kuunzwa kwe epoxy resin, acrylate, silica kana siloxane mapoka mu polyurethane molecular framework kuti iite interpenetrating network, kuvandudza kushanda kwe polyurethane kana kupa polyurethane mabasa akasiyana.
Feng Yuelan et al. reacter bio-based epoxy soybean oil ne CO2 kuti igadzire pentamonic cyclic carbonate (CSBO), uye yakaunza bisphenol A diglycidyl ether (epoxy resin E51) ine mamwe macheni akaomarara kuti awedzere kuvandudza NIPU yakaumbwa neCSBO yakasimbiswa neamine. Iyo molecular chain ine refu inoshanduka cheni chikamu cheoleic acid / linoleic acid. Iyo ine zvakare yakawanda yakaomesesa cheni zvikamu, zvekuti ive yakakwira mechanic simba uye yakakwirira kuoma. Vamwe vaongorori vakagadzirawo marudzi matatu eNIPU prepolymers nemapoka ekupedzisira efuran kuburikidza nechiyero-kuvhura maitiro ediethylene glycol bicyclic carbonate uye diamine, uye ndokuita ne polyester isina unsaturated kugadzirira yakapfava polyurethane ine kuzvirapa basa, uye nekubudirira kuziva iyo yakakwirira. -kuporesa kushanda kweNIPU yakapfava. Hybrid NIPU haingove nehunhu hweNIPU chete, asi zvakare inogona kunge iine zvirinani kunamatira, asidhi uye alkali corrosion resistance, solvent resistance uye simba remagetsi.
3 Outlook
NIPU inogadzirwa pasina kushandiswa kwechepfu isocyanate, uye parizvino iri kudzidzwa muchimiro chefuro, kukoira, kunamira, elastomer nezvimwe zvigadzirwa, uye ine tarisiro yakawanda yekushandiswa. Nekudaro, mazhinji acho achiri akaganhurirwa kutsvagurudzo yerabhoritari, uye hapana kugadzirwa kwakakura. Pamusoro pezvo, nekuvandudzwa kwemararamiro evanhu uye nekuenderera mberi kwekukura kwekuda, NIPU ine basa rimwechete kana akawanda mabasa yave yakakosha kutungamira kwekutsvaga, senge antibacterial, kuzvigadzirisa, ndangariro yechimiro, kudzoreredza kwemoto, kupisa kwakanyanya uye kupisa. zvichingodaro. Naizvozvo, tsvakiridzo yeramangwana inofanirwa kubata nzira yekupfuura nemumatambudziko akakosha ekusimudzira maindasitiri uye kuenderera mberi nekuongorora gwara rekugadzirira NIPU inoshanda.
Nguva yekutumira: Aug-29-2024