Inqubekela phambili Yocwaningo kuma-Polyurethanes angewona ama-isocyanate
Kusukela kwethulwa kwabo ngo-1937, izinto zokwakha i-polyurethane (pu) zithole izicelo ezibanzi emikhakheni ehlukahlukene kufaka phakathi izinto zokuhamba, ukwakhiwa, ama-petrochemicals, izindwangu, i-aerosperical Engineering, i-aerosperical Engineering, i-aerospe, kanye nezolimo. Lezi zinto zokwenziwa zisetshenziswa ngamafomu afana nama-foam plastitics, imicu, ama-lastomers, ama-ejenti angavikeleki, isikhumba sokwenziwa, ukumboza, ukunamathela, izinto zokwelashwa. I-PU yendabuko ngokuyinhloko yahlanganiswa kusuka kuma-isocyanates amabili noma ngaphezulu kanye nama-macromolecular polyols kanye nabasanda kungena kuma-molecular chain elevers. Kodwa-ke, ubuthi bemvelo be-isocyanates bubeka engcupheni enkulu empilweni yabantu nasendaweni; Ngaphezu kwalokho zithathwe ngokujwayelekile kusuka ku-phosgene - isisekelo esinobuthi esinobuthi kakhulu - nezinto ezihambelana nezinto ezihambelana ne-Amine.
Ngokukhanyiswa komkhakha wamakhemikhali wanamuhla wokuthuthuka kwentuthuko eluhlaza okwesikhashana, abacwaningi baqhubeka begxile ekubambeni okufakwa esikhundleni ngezinsizakusebenza ezinobungane bemvelo ngenkathi behlola imizila yenovel ye-polyurethanes (NIPU). Leli phepha lingenisa izindlela zokulungiselela i-NIPU ngenkathi ibukeza intuthuko ezinhlotsheni ezahlukahlukene ze-nipus futhi ngixoxa ngamathemba abo esikhathi esizayo ukunikeza ireferensi yocwaningo olwengeziwe.
Ukuhlanganiswa okungu-1 kwama-polyurethanes angewona ama-isocyanate
Ukuhlanganiswa kokuqala kwezindawo eziphansi ze-molecular izimbotshana ezisebenzisa ama-monocyclic carbonate kuhlangene ne-aliphatic diamered kwenzeke phesheya ngo-1950s okumaka umzuzu ongeyona i-pollyuselane. Njengamanje kunezindlela ezimbili zokuqala zokukhiqiza i-NIPU: Okokuqala kubandakanya ukusabela kokungezwani okuzayo phakathi kwe-Binary Coury Carctionates kanye nama-Binary Amonnes; Okwesibili kubandakanya ukusabela kwe-polycondenmation okubandakanya i-Diurethane Intermediates kanye namaDiols asiza ukushintshaniswa kwesakhiwo ngaphakathi kwama-carbamates. I-DiamaarBoxylate Intermediates ingatholakala nge-Carclic Carbonate noma imizila ye-DIMETHYL CACBONATE (DMC); Ngokuyisisekelo zonke izindlela ziphendula nge-CarBonic Acid Bround zithela ukusebenza kwezimoto.
Lezi zingxenye ezilandelayo zichaze ngezindlela ezintathu ezihlukile zokuvumelanisa i-polyurethane ngaphandle kokusebenzisa i-isocyanate.
1.1Binary Cyclic Carbonate Route
I-NIPU ingahle ihlolwe ngokungezwa okuzayo okubandakanya i-kanambambili cyclic carbonate ehlanganiswe nge-binary Amine njengoba kuboniswe kuMfanekiso 1.
Ngenxa yamaqembu amaningi we-hydroxyl akhona ngaphakathi kwamayunithi aphindaphindwayo ngesandla sawo esikhulu se-chain sesakhiwo le ndlela ngokuvamile ithela i-polyβ-hydroxyl polyurethane (PHRE). I-Leitsch et al., Yathuthukisa uchungechunge lwe-polyther pus esebenzisa ama-polsethers anqanyulwa yi-cyclic kanye nama-molecule kanambambili ama-molecule ama-molecule amancane asuselwa kuma-cyclic carbonates asetshenziselwa ukulungiselela ama-polyther pus. Ukutholwa kwazo kuveze ukuthi amaqembu e-hydroxyl ngaphakathi kwama-phus avela kalula ama-hydrogen bond ngama-nitrogen / oksijini athomu akhiwe ngaphakathi kwezingxenye ezithambile / ezinzima; Ukuhlukahluka phakathi kwezingxenye ezithambile kuthonya futhi nokuziphatha kwe-hydrogen Bonding kanye nama-degree ama-microphase okulandelayo athinta izici zokusebenza ezijwayelekile.
Imvamisa eyenziwe ngaphansi kwamazinga okushisa adlula okungu-100 ° C Le ndlela ayikhiqizi ngemikhiqizo ngezikhathi ezithile ezenza ukuthi ingenele amaphola angenayo (DMF), njll. Kuze kube yilapho izinsuku ezinhlanu zivame ukuveza izinsimbi eziphansi zamangqamuzana ezivame ukuwa ngaphansi kwemibundu ezungeze ama-30k g / mol anikeze amandla amakhulu atholakele ngenxa yezizinda eziphakemeyo ezihlotshiswe ngazo ukumiswa kwememori yokwakha ama-foolutions njll..
Umzila we-1.2monkerlic carbonate indlela
I-Monocylic Carbonate isabela ngqo nge-dicarbamate ephumela ama-DICARBAMATID ATHOLA I-HYDROXYL EMERTION OFTRAMETSHESHEKILE UKUTHOLAKALA NGOKUGCINWA KWAMAHHALA / POLYCOMPENTENATION BANDLA
Ukuhlukahluka okusetshenziswayo kwe-monocylic kufaka phakathi i-ethylene & prepene carbrated substrates lapho iqembu laseBeijing University of Chemical Deports benza izikhalazo ezibucayi zokuthola izigaba ezahlukahlukene ezisebenzisa i-polytetrahydroforurediol / polyther-diols Ukuvuselela ukwakheka okuphumelelayo kwemigqa yomkhiqizo okubonisa izindawo ezihlaba umxhwele ze-thermal / mechanical ezifinyelela phezulu kwamaphoyinti ancibilikayo azulazula anweba amazinga acishe acishe abe yi-Cishe amakhono asondele ku-Founding Coud1476%. I-Wang et al., Ukuhlanganiswa okuphelele okubandakanya i-DMC kubhangqiwe ngokulandelana w / hexamethylediamine / sebacic / acid adipic-acid adipic-acid adipic-acid adipic-acid adipic-acid adipic-acid adipic-acid adipic-acid adipic-acid adipic-acid adipic-acid adipic-acid adrephtalics okuthola amabanga okugcina I-EncompPassing13k ~ 28k g / mol tensile amandla amandla eguqukayo9 ~ 17 MPA Elongations ahlukahlukanehluko35% ~ 235%.
I-cyclocarbonic esters ibandakanyeka ngempumelelo ngaphandle kokudinga ama-catalysts ngaphansi kwezimo ezijwayelekile ukulondolozwa kwezinga lokushisa okungu-RETALL80 ° I-C Transestem ajwayele ukusebenzisa ama-organin-based Catalytic aqinisekisa ukucubungula okuphezulu okungaphezulu kwe-accoup200 °. Ngaphandle kwemizamo yokuvuselela ukuqondisa okokufaka kwe-diolioliolization / i-deglycolysis Penomena yenza izizukulwane ezifunwa yimiphumela ye-volemes Methodes evumela i-methanol / izinsalela ezincane ze-molecule-dioliolic ngale ndlela yethula ezinye izindlela ezisebenzayo zezimboni eziqhubekela phambili.
1.3Dimethyl Carbonate Route
I-DMC imele enye indlela enomsindo wezemvelo / ongelona ubuthi equkethe ama-moieties amaningi asebenzayo asebenzayo asebenzayo we-methyl / methoxy / carbonyl ukucushwa kokuvumelanisa okunika amandla amaphrofayili okuqala we-methyl-carbamate aqeda ngokuqondile ama-methyl-carberate aqediwe ngezenzo ezikuncibilikayo ezisetshenziswayo Ama-diolics ama-diolics amancane / ama-diolics amancane
I-Deenta Et.al eyakhelwe amandla okuvela ku-Dynamics averaging sodium methongide catalysis ukwakheka okuhlukahlukene okuningana okubandakanya ukunwetshwa kwezinsimbi ezinqunyiwe ezinqunyiwe I-PAN DONGDOng ekhethiwe amasu okubhangqa aqukethe i-DMC hexamethylene-diamencohols ukubona imiphumela ebabazekayo ekhombisa ama-metrile-cell metric oscillating10% -1400%. Ukuphikelela okuphathelene nokuphenya amathonya ahlukile - Ukunwebeka okuvezwa okuveziwe okucatshangelwa kahle i-Butanediol / Hexanediol okukhethiwe lapho i-Atomic-Partity ilondoloze izivumelwano zeCrystancil ezihlanganiswe ne-hexahydroxyamine ekhombisa ukucubungula okusekelwayo kwe-mechahydroxyamine I-AT230 ℃ .Addorations Exporations okuhlose ukutholwa okungekho-socyante-polyureas I-Loveling Diazomonomer Engagulamevement Izicelo Zokuhlobisa Izindleko Zokulinganisa ngaphezulu kwezindlela zokulinganisa ze-vinyl Izidingo ngaleyo ndlela zinciphise ukusakaza imfucumfucu kakhulu elilinganiselwe kuphela i-methanol / ama-molecule-diafliolic anfluents asungula ama-greener syntheres paradigms jikelele.
Izingxenye ezi-2 ezihlukene ezithambile ze-non-isocyanate polyurethane
2.1 Ama-polythea polyurethane
I-Polythert Polyurethane (Peu) isetshenziswa kabanzi ngenxa yamandla awo aphansi ama-cohesion aphansi ama-ether amabhondi ezingxenyeni ezithambile eziphindaphindwayo amayunithi, ukujikeleza okulula, ukuguquguquka okuhle kakhulu kwe-hydrolysis.
Kebir et al. I-Synthessed Polythene Polyurethane ene-DMC, i-polyethylene glycol kanye ne-butanediol njengezinto zokwakha eziluhlaza, kepha isisindo samangqamuzana sasiphansi (7 500 ~ 14 800g / mol), futhi amandla nezinye izimbotshana kwakunzima ukufeza izidingo zokusebenzisa. Iqembu lokucwaninga leZhao Jingbo lalisebenzisa i-ethylene Carbonate, 1, 6-hexanediamine ne-polyethylene glycol ukuvumelanisa iPeu, enesisindo samangqamuzana esingu-31 000rg / i-24MPA yamandla angu-5 ~ 24MPA, Isisindo se-molecular sochungechunge lwezinhlangano zama-polyurethanes amnandi yi-17 300 ~ 21 000g / i-TG ~ 102 ~ 110 ~ 10 ~ 38mpa, kanye nezinga lokubuyisa okuqhubekayo lingu-69% ~ 89% ~ 89%.
Iqembu elicwaningayo leZheng Liuchun neLi Chuncheng lilungiselele okuphakathi nendawo 1, 6-hexamethylessiane (BHC) nge-Dimethyl Uchungechunge lwama-polytheap polyurethanes (iNipeu) ne-non-isocyanate yalungiswa, futhi inkinga yokuwela yabaphakathi phakathi nokusabela kwaxazululwa. Ukwakheka kanye nezakhiwo zendabuko ye-polyeane polyurethane (HDIPU) elungiselelwe yiNipeu no-1, 6-hexamethylene diisocyate kuqhathaniswa, njengoba kukhonjisiwe kuThebula 1.
| Imbonakaliso | Ingxenye enkulu yengxenye yengxenye /% | Isisindo se-molecular / (g·mol ^ (- 1)) | Inkomba yokusabalalisa isisindo molecular | Amandla we-Tensile / MPA | Ukunwebeka ngekhefu /% |
| Nipeu30 | 30 | I-74000 | 1.9 | 12.5 | Oku-1250 |
| Nipeu40 | 40 | I-66000 | 2.2 | 8.0 | I-550 |
| HDIPU30 | 30 | I-46000 | 1.9 | 31.3 | 1440 |
| HDIPU40 | 40 | I-54000 | I-2.0 | 25.8 | I-1360 |
Ithebula 1
Imiphumela etafuleni 1 ikhombisa ukuthi umehluko wesakhiwo phakathi kweNipeu neHDIPU ikakhulukazi ngenxa yengxenye enzima. I-Urea Pro Group ekhiqizwa ukusabela okuhlangenwe nakho kweNipeu ifakwe ngokungahleliwe ku-Hard segment chain molecular chain, okuholela ekuhlolweni kwamakhekhe we-hydrogen phakathi kwengxenye ye-hydrogen yengxenye enzima kanye ne-crystaltaltipy ephansi ye-napeu. Ngenxa yalokhu, izakhiwo zalo zemishini zimbi kakhulu kune-HDIPU.
2.2 Polyester Polyurethane
I-Polyester Polyurethane (PEPU) ene-polyester diols njengoba izingxenye ezithambile zine-biodegradability enhle, i-biocomtic kanye nezakhiwo zemishini, futhi zingasetshenziswa ukulungiselela izicubu zobunjiniyela zezinto ezinhle kakhulu. Ama-polyester diols asetshenziswa kakhulu ezingxenyeni ezithambile yi-polybutylene adiol diol, polyglycol adiol diol ne-polycapropactone diol.
Phambilini, rokicki et al. Uphendule i-ethylene Carbonate ene-diamline kanye ne-diols ehlukene (1, 6-hexanediol, 1, 10-n-dodecanol) ukuthola i-nipu ehlukile, kepha i-nipu esetshenzisiwe yayinesisindo esiphansi se-molecular kanye ne-TG ephansi. Farhadian et al. I-Carbonate elungiselelwe i-polycyclic usebenzisa i-sunflower HEMBEOWER Amafutha, bese ixutshwa nama-polyamines asuselwa kwi-bio, futhi yelaphe ku-240 ℃ ukuze uthole i-polyester polyurethane ifilimu, ekhombisa ukuqina okuhle okushisayo. Iqembu lokucwaninga leZhang Liqun laseNingizimu China University of Technology Synthessived ochungechungeni lwama-diamenes kanye ne-cyclic carbonates, bese livumelana ne-bibased acid ukuthola i-polyester polyurethane. Iqembu likacwaningo lukaZhu Jin eSingbo Institute of Materies Research, Chinese Academy of Science alungiselelwe i-DibadiaDiol Hard ingxenye ye-Dibadiamine usebenzisa uchungechunge lwe-pibasimine ne-vinyl carbonase, olungasetshenziswa njengopende ngemuva kokuphulukiswa kwe-ultraviolet [23]. Iqembu lokucwaninga leZheng Liuchun kanye neLi Chuncheng lisebenzise i-adipic acid nama-aliphatic diols (i-butanediol, i-hexadiol, i-octanediol ne-decanediol) ngezinombolo ezihlukile ze-carbon atolic ukulungiselela izingxenye ezihambisanayo ze-polyester njengezingxenye ezithambile; Iqembu le-polyeretester polyethane (Pepu), eliqanjwe ngegama lama-athomu e-carbon ama-aliphatic diols, latholakala ngokuncibilika kwe-polycondensation nge-hydroxy-sailed arvin segment prepolymer elungiselelwe yi-BHC kanye Diols. Izakhiwo zemishini zePetu zikhonjiswa kuThebula 2.
| Imbonakaliso | Amandla we-Tensile / MPA | I-Elastic Modulus/ MPA | Ukunwebeka ngekhefu /% |
| Petu4 | 6.9±1.0 | 36±8 | I-673±35 |
| Petu6 | I-10.1±1.0 | 55±4 | 568±32 |
| Petu8 | 9.0±0.8 | 47±4 | 551±25 |
| Petu10 | 8.8±0.1 | 52±5 | 13±23 |
Ithebula 2
Imiphumela ikhombisa ukuthi ingxenye ethambile yePetu4 ine-carbonyl density ephezulu kakhulu, isibopho esinamandla kunazo zonke se-hydrogen enengxenye enzima, kanye neziqu ezisezingeni eliphansi kakhulu zesigaba sokuhlukaniswa. I-crystallization yazo zombili izingxenye ezithambile nezilukhuni zilinganiselwe, zibonisa iphuzu eliphansi elincibilikayo namandla ashubile, kodwa kunwebeka okuphezulu kakhulu ngekhefu.
2.3 polycarbonane polyurethane
I-Polycarbonate Polyurethane (PCU), ikakhulukazi i-Aliphatic PCU, inokumelana kahle ne-hydrolysis, ukumelana kwe-oxidation, ukuqina okuhle kwemvelo kanye nokuqina kwemvelo, futhi kunamathemba amahle esicelo emkhakheni we-biomedicine. Njengamanje, iningi le-niPu elilungiselelwe lisebenzisa ama-polytheate polyols kanye nama-polyester polyols njengezingxenye ezithambile, futhi kunemibiko embalwa yocwaningo ngePolycarbonate Polyurethane.
I-polycarbonate polycarbonate polyurethane elungiselelwe yiqembu elicwaninga nguTian Hengshui eSouth China University of Technology linesisindo samangqamuzana esingama-50 000 g / mol. Ithonya lezimo zokusabela ezimeni ze-moleemale ze-polymer selifundzelwe, kodwa izici zalo zemishini azizange zibikwe. Iqembu le-Zheng Liuchun kanye neLi Chuncheng's Research Group alungiselelwe i-PCU elungiselelwe i-DMC, i-Hexanediamine, i-Hexadiol nePolycarbonate Diols, ne-PCU ngokunegama ngokusho kwengxenye enkulu ye-Hard Ingxenye ephindaphindwayo. Izakhiwo zemishini zikhonjiswa kuThebula 3.
| Imbonakaliso | Amandla we-Tensile / MPA | I-Elastic Modulus/ MPA | Ukunwebeka ngekhefu /% |
| I-PCU18 | 17±1 | 36±8 | I-665±24 |
| I-PCU33 | 19±1 | I-107±9 | I-656±33 |
| I-PCU46 | 21±1 | I-150±16 | 407±23 |
| I-PCU57 | 22±2 | 210±17 | 262±27 |
| I-PCU67 | 27±2 | 400±13 | 63±5 |
| I-PCU82 | 29±1 | 518±34 | 26±5 |
Ithebula 3
Imiphumela ikhombisa ukuthi i-PCU inesisindo esiphakeme samangqamuzana, kuze kufike ku-6 × 104 ~ 9 × 104g / mol, ikhombe incibilize kuze kube yi-137 ℃, kanye namandla ashubile afinyelela ku-29 MPA. Lolu hlobo lwe-PCU lungasetshenziswa njengepulasitiki eqinile noma njenge-elastomer, enethemba lesicelo esihle ensimini ye-biomedical (njengezinto ezisetshenziswayo zezicubu zabantu).
2.4 hybrid non-isocyanate polyurethane
I-Hybrid non-isocyanate polyurethane (hybrid nipu) ukwethulwa kwe-epoxy resin, i-acrylate, i-silica noma amaqembu e-siloxane kuhlaka lwe-polyurethane moleculane ukwakha inethiwekhi ye-interpenetane, ngcono ukusebenza kwe-polyurethane noma unikeze imisebenzi ehlukene ye-polyurethane.
UFeng Youen et al. I-Bio-based bepoxy soybean oyela nge-CO2 ukuvumelanisa i-pentamoc cyclic carbonate (CSBO), futhi wethule i-bisphenol i-diglycidyl ether (epoxy resin e51) ngezingxenye ze-nipu eziqinile ukuze uthuthukise i-NIPU eyenziwe nge-anine. I-cleach molecular iqukethe ingxenye ende ye-chain chain ye-oleic acid / linoleic acid. Iphinde iqukethe izingxenye eziqinile ze-chain, ukuze inamandla aphezulu emishini kanye nobunzima obuphezulu. Abanye abacwaningi bahlanganisa izinhlobo ezintathu ze-NIPU Premolymers ngamaqembu okugcina we-furan ngokusebenzisa ukusabela kwesilinganiso kwe-diethylene glycol Carbonal Carbonate Carbonate ye-diethylene, bese besabela nge-polyester ethambile ukulungiselela umsebenzi othambile we-nipu. I-Hybrid Nipu ayigcini nje ngezimpawu ze-General Nipu, kepha futhi ingahle ibe nokuphikiswa okungcono, i-acid kanye ne-alkali yokuphikiswa, ukumelana nokuqina komzimba namandla okusebenza ngomshini.
3 umbono
UNipu ulungiselelwe ngaphandle kokusebenzisa i-assocyanate enobuthi, futhi njengamanje ufundwa ngendlela ye-foam, ukunamathela, ukunamathela, i-elastomer neminye imikhiqizo, futhi enamathemba ahlukahlukene wesicelo. Kodwa-ke, iningi labo lisakhawulelwe ekucwaningweni kwelebhu, futhi akukho ukukhiqizwa okukhulu. Ngaphezu kwalokho, ngokuthuthuka kwamazinga okuphila kwabantu kanye nokukhula okuqhubekayo kwesidingo, uNipu ngomsebenzi owodwa noma imisebenzi eminingi esephenduke indlela ebalulekile yocwaningo, njenge-antibacterial, ubuyiseli, ukumelana nokushisa okuphezulu nokunye. Ngakho-ke, ucwaningo lwesikhathi esizayo kufanele lubhekise ukuthi ungazibeka kanjani ezinkingeni ezisemqoka zokuthuthuka kwezimboni futhi uqhubeke nokuhlola ukuqondiswa kokulungiselela i-NIPU esebenzayo.
Isikhathi sePosi: Aug-29-2024