Iterambere ry'ubushakashatsi kuri Polyurethane zitari izosianati
Kuva byatangira gukoreshwa mu 1937, ibikoresho bya polyurethane (PU) byakoreshejwe cyane mu nzego zitandukanye zirimo ubwikorezi, ubwubatsi, peteroli, imyenda, ubwubatsi bw'imashini n'amashanyarazi, iby'indege, ubuvuzi, n'ubuhinzi. Ibi bikoresho bikoreshwa mu buryo nka pulasitiki ya foam, fibre, elastomer, ibikoresho bikingira amazi, uruhu rw'ubukorikori, irangi, kole, ibikoresho byo ku meza n'ibikoresho by'ubuvuzi. PU gakondo ikorwa ahanini mu isocyanate ebyiri cyangwa nyinshi hamwe na polyols macromolecular na small molecular chain extenders. Ariko, uburozi bw'isocyanate butera ingaruka zikomeye ku buzima bw'abantu n'ibidukikije; kandi akenshi bikomoka kuri fosgene - ikintu gitera uburozi bwinshi - hamwe n'ibikoresho fatizo bya amine bihuye na byo.
Mu rwego rwo guharanira iterambere rirambye kandi rirambye, abashakashatsi bakomeje kwibanda ku gusimbuza isocyanates umutungo kamere utangiza ibidukikije mu gihe bashakisha inzira nshya zo gukora polyurethane zitari isocyanates (NIPU). Iyi nyandiko igaragaza inzira zo gutegura NIPU mu gihe hasuzumwa iterambere mu bwoko butandukanye bwa NIPU no kuganira ku mahirwe yazo y'ejo hazaza kugira ngo haboneke icyitegererezo cy'ubushakashatsi burambuye.
1 Guhuza Polyurethanes Zitari Isocyanate
Ikorwa rya mbere ry’ibinyabutabire bya karubomatike bifite uburemere buke hakoreshejwe karubomatike imwe ivanze na diamine ya aliphatic ryabaye mu mahanga mu myaka ya 1950—bikaba ari igihe cy’ingenzi mu ikorwa rya polyurethane idakoresha isocyanate. Ubu hariho uburyo bubiri bw’ibanze bwo gukora NIPU: Ubwa mbere bukubiyemo kongeramo intambwe hagati ya karubotini zigenda zihinduka na amine zigenda zihinduka; ubwa kabiri bukubiyemo uburyo bwa polycondensation burimo diurethane intermediates hamwe na diols zoroshya ihererekanya ry’imiterere muri karubomati. Diarboxylate intermediates zishobora kuboneka binyuze mu nzira za karubomatike cyangwa dimethyl carbonate (DMC); mu by’ukuri uburyo bwose bushobora gukora binyuze mu matsinda ya aside karubotiki atanga imikorere ya karubomatike.
Ibice bikurikira bikubiyemo uburyo butatu butandukanye bwo gukora polyurethane nta gukoresha isocyanate.
1.1 Inzira ya Kaboneti Igendanwa mu Gihembwe
NIPU ishobora gukorwa binyuze mu kongeramo intambwe zirimo binary cyclic carbonate ihujwe na binary amine nk'uko bigaragara ku Ishusho ya 1.
Bitewe n'amatsinda menshi ya hydroxyl aba mu bice bisubiramo ku miterere y'uruhererekane rw'ingenzi, ubu buryo bukunze gutanga icyo bita polyβ-hydroxyl polyurethane (PHU). Leitsch et al., bakoze urukurikirane rwa polyether PHUs bakoresheje polyethers za cyclic carbonate-terminated polyethers hamwe na binary amines hamwe na molekile nto zikomoka kuri binary cyclic carbonates—bagereranya ibi n'uburyo gakondo bukoreshwa mu gutegura polyether PUs. Ibyo bavumbuye byagaragaje ko amatsinda ya hydroxyl muri PHUs akora byoroshye imigozi ya hydrogen hamwe na atome za azote/okisijeni ziri mu bice byoroshye/bikomeye; itandukaniro riri hagati y'ibice byoroshye naryo rigira ingaruka ku mikorere ya hydrogen bond ndetse no ku gipimo cyo gutandukanya microphase, ibyo bikaba bigira ingaruka ku mikorere rusange.
Ubusanzwe ikorwa munsi y’ubushyuhe burenze 100 °C, iyi nzira nta bivange itanga mu gihe cy’ibikorwa byo gusubiza bituma idakunda ubushuhe mu gihe itanga ibintu bihamye nta kibazo cyo guhinduka ariko igasaba ibintu bisukura ibinyabuzima birangwa na polarity ikomeye nka dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DMF), nibindi. Byongeye kandi, igihe cyo gusubiza kiri hagati y’umunsi umwe kugeza ku minsi itanu akenshi gitanga uburemere buke bwa molekile akenshi bugabanuka munsi y’umurongo ugera kuri 30k g/mol bigatuma umusaruro munini ugorana bitewe ahanini n’ibiciro binini bijyana nabyo hamwe n’imbaraga zidahagije zigaragazwa na PHUs nubwo hari gahunda nziza zirimo damping material domains shape memory constructs adhesive solutions coating solutions foams nibindi.
1.2 Inzira ya Monocylic Carbonate
Karubone monocylic ihura neza na dicarbamate ikomoka kuri diamine ifite amatsinda ya hydroxyl, hanyuma igakora interactions zihariye za transesterification/polycondensation hamwe na diols, amaherezo zigatanga NIPU isa n’iya gakondo igaragara ku ishusho ya 2.
Ubwoko bwa monocylic bukunze gukoreshwa burimo ethylene na propylene carbonated substrates aho itsinda rya Zhao Jingbo ryo muri Kaminuza ya Beijing y’Ikoranabuhanga ry’Ubutabire ryakoresheje diamine zitandukanye zibagiraho ingaruka kuri ibyo bintu bihindagurika byabanje kubona imiterere itandukanye ya dicarbamate mbere yo gukomeza ku cyiciro cyo guhumeka hakoreshejwe polytetrahydrofuranediol/polyether-diols bikarangira neza imiterere y’ibicuruzwa bigaragaza imiterere itangaje y’ubushyuhe/mekanike ikagera hejuru aho ishonga izamuka igera hafi ya 125 ~ 161°C imbaraga zo gukurura zizamuka hafi ya 24MPa hafi ya 1476%. Wang n'abandi, bahuje uburyo bwo gukoresha DMC hamwe n'ibice bya hexamethylenediamine/cyclocarbonated precursors bihuza ibikomoka kuri hydroxy-terminated derivatives, nyuma bashyiramo aside dibasic zishingiye kuri bio nka oxalic/sebacic/acides, aside adipic-terephtalics, bagera ku musaruro wa nyuma, bigaragaza ingano ikubiyemo 13k ~ 28k g / mol, imbaraga zo gukurura zihindagurika, 9 ~ 17 MPa, uburebure butandukanye na 35% ~ 235%.
Esters za Cyclocarbonic zikora neza nta catalysts zikeneye mu bihe bisanzwe, ariko ubushyuhe buri hagati ya 80° na 120°C, transesterifications zikurikiraho zikoresha sisitemu za catalytic zishingiye kuri organotin, zigatuma gutunganya neza bitarenze 200°. Uretse imbaraga zo gushonga gusa, zigamije kwishyiramo diolic, zishobora kwikoraho/gukuraho glycolysis, bigatuma habaho umusaruro wifuza, bituma uburyo bworoshye bwo kubungabunga ibidukikije, cyane cyane butanga methanol/molecule nto-diolic residues, bityo bugatanga ubundi buryo bwo gukora mu nganda.
1.3 Inzira ya Dimethyl Carbonate
DMC igaragaza uburyo bwo guhindura ibintu mu buryo buzira ibidukikije/butari uburozi bufite ibice byinshi bikora birimo imiterere ya methyl/methoxy/carbonyl yongera imiterere ya reactivity bigatuma habaho ibikorwa bya mbere aho DMC ikorana neza na diamines ikora intermediates nto za methyl-carbamate zirangiye hanyuma ibikorwa byo gushonga birimo ibindi bice bito bya polymer-extender-diolics/polyol nini biganisha ku miterere ya polymer ishakishwa igaragazwa neza n'Ishusho ya 3.
Deepa n'abandi bashingiye ku miterere yavuzwe haruguru bakoresheje sodium methoxide catalysis itunganya imiterere itandukanye hagati nyuma ikoresha inyongera zigamije kugera ku bice bikomeye bingana n'ibice bigera ku buremere bwa molekile bugera kuri (3 ~ 20) x 10 ^ 3g / mol ubushyuhe bw'impinduka mu kirahuri bugera kuri (-30 ~ 120°C). Pan Dongdong yatoranyije uburyo bwo guhuza bugizwe na DMC hexamethylene-diaminopolycarbonate-polyalcohols, bibonera ibisubizo bifatika bigaragaza ibipimo by'imbaraga zo gukurura bihindagurika 10-15MPa elongation ratios yegera 1000% - 1400%. Ibikorwa by’ubushakashatsi ku ngaruka zitandukanye zo kwaguka k’uruhererekane byagaragaje ko ibyo abantu bakunda bihuza neza uburyo butanediol/hexanediol ihitamo iyo umubare wa atome uhagaze neza, bigatuma habaho kongera imiterere ya kristali mu miyoboro. Itsinda rya Sarazin ryateguye ibinyabutabire bihuza lignin/DMC hamwe na hexahydroxyamine bigaragaza imiterere ishimishije ya mekanike nyuma yo gutunganya kuri 230℃. Ubushakashatsi bw’inyongera bwari bugamije kubona ibintu bitari isocyante-polyurea bikoresheje diazomonomer, byateganyaga ko hashobora gukoreshwa irangi rishobora kugaragaramo inyungu zigereranywa ugereranije n’ibindi binyabutabire bya vinyl-carbonaceous, bigaragaza uburyo bwo kugabanya ikiguzi/uburyo bwagutse bwo kurikuramo. Isuzuma ryimbitse ku buryo bwo gukora ibintu byinshi akenshi risaba ahantu hashyushye cyane/hadafite umwuka uhagije, bigatuma hagabanywa imyanda igabanya gusa imyanda ya methanol/molecule nto-diolic ishyiraho uburyo bwo gukora ibintu buto muri rusange.
Ibice 2 bitandukanye byoroshye bya polyurethane idakoresha isocyanate
2.1 Polyeteri polyurethane
Polyether polyurethane (PEU) ikoreshwa cyane kubera imbaraga nke zo guhuza ether mu bice byoroshye, kuzunguruka byoroshye, ubushobozi bworoshye bwo koroshya ubushyuhe no kurwanya hydrolysis.
Kebir n'abandi bakoze polyether polyurethane bakoresheje DMC, polyethylene glycol na butanediol nk'ibikoresho fatizo, ariko uburemere bwa molekile bwari buke (7 500 ~ 14 800g / mol), Tg yari munsi ya 0℃, kandi aho gushonga na ho hari hasi (38 ~ 48℃), kandi imbaraga n'ibindi bimenyetso byari bigoye guhaza ibyifuzo byo gukoresha. Itsinda ry'ubushakashatsi rya Zhao Jingbo ryakoresheje ethylene carbonate, 1, 6-hexanediamine na polyethylene glycol kugira ngo bakore PEU, ifite uburemere bwa molekile bwa 31 000g / mol, imbaraga zo gukurura za 5 ~ 24MPa, n'uburebure ku kigero cya 0.9% ~ 1 388%. Uburemere bwa molekile y’uruhererekane rwa aromatike ya polyurethane ni 17 300 ~ 21 000g / mol, Tg ni -19 ~ 10℃, aho gushonga ni 102 ~ 110℃, imbaraga zo gukurura ni 12 ~ 38MPa, naho igipimo cyo kugarura ubushyuhe cya 200% cy’uburebure buhoraho ni 69% ~ 89%.
Itsinda ry’ubushakashatsi rya Zheng Liuchun na Li Chuncheng ryateguye intermediate 1, 6-hexamethylenediamine (BHC) hamwe na dimethyl karubone na 1, 6-hexamethylenediamine, hamwe na polycondensation hamwe na molekile nto zitandukanye za diols z’uruhererekane rw’imiyoboro igororotse na polytetrahydrofuranediols (Mn = 2 000). Hateguwe urukurikirane rwa polyether polyurethanes (NIPEU) zifite inzira idahinduka isocyanate, maze ikibazo cyo guhuza intermediates mu gihe cyo gukora reaction cyakemutse. Imiterere n’imiterere ya polyether polyurethane (HDIPU) gakondo yakozwe na NIPEU na 1, 6-hexamethylene diisocyanate byaragereranyijwe, nk’uko bigaragara mu mbonerahamwe ya 1.
| Urugero | Igice gikomeye cy'uburemere/% | Uburemere bwa molekile/(g)·mol^(-1)) | Igipimo cy'ikwirakwizwa ry'uburemere bwa molekile | Imbaraga zo gukurura/MPa | Kureshya igihe cyo kuruhuka/% |
| 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 |
Imbonerahamwe ya 1
Ibisubizo biri mu mbonerahamwe ya 1 bigaragaza ko itandukaniro riri hagati ya NIPEU na HDIPU riterwa ahanini n'igice gikomeye. Itsinda rya urea rikomoka ku buryo butunguranye bwa NIPEU ryinjizwa mu muyoboro wa molekile w'igice gikomeye, rigaca igice gikomeye kugira ngo habeho imiyoboro ya hydrogen itunganijwe, bigatuma imiyoboro ya hydrogen idakomeye hagati y'imiyoboro ya molekile w'igice gikomeye n'ubutare buke bw'igice gikomeye, bigatuma NIPEU itandukana mu byiciro bike. Kubera iyo mpamvu, imiterere yayo ya mekanike iba mibi cyane kurusha HDIPU.
2.2 Polyester Polyurethane
Polyester polyurethane (PETU) ifite polyester diols nk'ibice byoroshye ifite ubushobozi bwo kwangirika neza, ikora neza kandi ifite ubushobozi bwo gukora, kandi ishobora gukoreshwa mu gutegura ibyuma bitunganya imiterere y'umubiri, ikaba ari ibikoresho bya siyansi bifite amahirwe menshi yo gukoreshwa. Polyester diols zikunze gukoreshwa mu bice byoroshye ni polybutylene adipate diol, polyglycol adipate diol na polycaprolactone diol.
Mbere yaho, Rokicki n'abandi bakoranye na ethylene carbonate na diamine na diol zitandukanye (1, 6-hexanediol, 1, 10-n-dodecanol) kugira ngo babone NIPU zitandukanye, ariko NIPU yakozwe yari ifite uburemere buke bwa molekile na Tg nkeya. Farhadian n'abandi bateguye polycyclic carbonate bakoresheje amavuta y'ibihwagari nk'ibikoresho fatizo, hanyuma bavanga na polyamines zishingiye kuri bio, basiga ku isahani, hanyuma bavurwa ku bushyuhe bwa 90 ℃ mu gihe cy'amasaha 24 kugira ngo babone polyester polyurethane film ya thermosetting, yagaragaje ubushyuhe bwiza. Itsinda ry'ubushakashatsi rya Zhang Liqun ryo muri Kaminuza y'Ikoranabuhanga y'Ubushinwa y'Epfo ryakoze urukurikirane rwa diamines na cyclic carbonates, hanyuma bavanga aside dibasic ishingiye kuri bio kugira ngo babone polyester polyurethane ishingiye kuri bio. Itsinda ry'ubushakashatsi rya Zhu Jin ryo muri Ningbo Institute of Materials Research, Chinese Academy of Sciences ryateguye diaminodiol hard segment rikoresheje hexadiamine na vinyl carbonate, hanyuma polycondensation na bio-based unsaturated dibasic acid kugira ngo babone urukurikirane rwa polyester polyurethane, ishobora gukoreshwa nk'irangi nyuma yo gukaraba ultraviolet [23]. Itsinda ry’ubushakashatsi rya Zheng Liuchun na Li Chuncheng ryakoresheje aside adipike na dioli enye za aliphatic (butanediol, hexadiol, octanediol na decanediol) zifite imibare itandukanye ya atome ya karuboni kugira ngo zitegure dioli za polyester zijyanye nazo nk'ibice byoroshye; Itsinda rya polyester polyurethane itari isocyanate (PETU), ryitiriwe umubare wa atome za karuboni za dioli za aliphatic, ryabonetse binyuze mu gushonga polycondensation hamwe na hydroxy-sealed hard segment prepolymer yateguwe na BHC na dioli. Imiterere ya PETU igaragara mu mbonerahamwe ya 2.
| Urugero | Imbaraga zo gukurura/MPa | Moduli ya elastic/MPa | Kureshya igihe cyo kuruhuka/% |
| 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 |
Imbonerahamwe ya 2
Ibisubizo bigaragaza ko igice cyoroshye cya PETU4 gifite ubucucike bwa karubonili bwinshi cyane, isano ikomeye ya hydrogen n'igice gikomeye, hamwe n'urugero rwo hasi rwo gutandukana kw'ibice. Uburyo ibice byoroshye n'ibikomeye bihindukamo ni bike, bigaragaza aho gushonga hasi n'imbaraga zo gukurura, ariko uburebure bwinshi mu gihe cyo gucika.
2.3 Polyurethane ya Polycarbonate
Polycarbonate polyurethane (PCU), cyane cyane aliphatic PCU, ifite ubushobozi bwo kurwanya hidrolisise neza, irwanya ogisijeni, ihamye neza mu binyabuzima kandi ihura neza n’ibinyabuzima, kandi ifite amahirwe meza yo gukoreshwa mu rwego rw’ubuvuzi bw’ibinyabuzima. Muri iki gihe, NIPU nyinshi zateguwe zikoresha polyether polyols na polyester polyols nk’ibice byoroshye, kandi hari raporo nke z’ubushakashatsi kuri polycarbonate polyurethane.
Polyurethane idafite isocyanate polycarbonate yakozwe n'itsinda ry'ubushakashatsi rya Tian Hengshui muri Kaminuza y'ikoranabuhanga y'Amajyepfo y'Ubushinwa ifite uburemere bwa molekile burenga 50 000 g / mol. Ingaruka z'imiterere y'ibisubizo ku buremere bwa molekile ya polymer zarakozweho ubushakashatsi, ariko imiterere yayo ya mashini ntabwo yagaragajwe. Itsinda ry'ubushakashatsi rya Zheng Liuchun na Li Chuncheng ryateguye PCU bakoresheje DMC, hexanediamine, hexadiol na polycarbonate diols, maze bise PCU hakurikijwe igice cy'uburemere bw'igice gikomeye gisubiramo. Imiterere ya mashini igaragara mu mbonerahamwe ya 3.
| Urugero | Imbaraga zo gukurura/MPa | Moduli ya elastic/MPa | Kureshya igihe cyo kuruhuka/% |
| 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 |
Imbonerahamwe ya 3
Ibisubizo bigaragaza ko PCU ifite uburemere bwinshi bwa molekile, kugeza kuri 6 × 104 ~ 9 × 104g / mol, aho gushonga kugera kuri 137 ℃, n'imbaraga zo gukurura kugeza kuri 29 MPa. Ubwo bwoko bwa PCU bushobora gukoreshwa nk'ipulasitiki ikomeye cyangwa nk'icyuma gikingira, gifite amahirwe menshi yo gukoreshwa mu rwego rw'ubuvuzi (nk'ibice by'umubiri by'abantu cyangwa ibikoresho byo guteranya indwara z'umutima).
2.4 Polyurethane ivanze idasesanyati
Polyurethane idasenya (hybrid non-isocyanate polyurethane) ni ukwinjizwa kwa epoxy resin, acrylate, silica cyangwa siloxane mu buryo bwa molekile ya polyurethane kugira ngo habeho urusobe rw’imiyoboro ihuza, kunoza imikorere ya polyurethane cyangwa guha polyurethane imikorere itandukanye.
Feng Yuelan n'abandi bakoranye amavuta ya soya ya epoxy ashingiye kuri bio hamwe na CO2 kugira ngo bakore pentamonic cyclic carbonate (CSBO), kandi bashyizeho bisphenol A diglycidyl ether (epoxy resin E51) hamwe n'ibice bikomeye by'urunigi kugira ngo barusheho kunoza NIPU yakozwe na CSBO ivanze na amine. Urunigi rwa molekile rufite igice kirekire cy'urunigi rworoshye cya aside oleic / linoleic acid. Rufite kandi ibice bikomeye by'urunigi, ku buryo rufite imbaraga nyinshi za mekanike n'ubukomere bwinshi. Bamwe mu bashakashatsi banakoranye ubwoko butatu bwa prepolymer za NIPU hamwe n'amatsinda ya furan binyuze mu buryo bwo gufungura bwa diethylene glycol bicyclic carbonate na diamine, hanyuma bagakora polyester idasembuye kugira ngo bategure polyurethane yoroshye ifite imikorere yo kwivura, kandi babonye neza ubushobozi bwo kwivura bwa NIPU yoroshye. Hybrid NIPU ntabwo ifite imiterere ya NIPU rusange gusa, ahubwo ishobora no kugira uburyo bwo gufatana neza, kurwanya aside na alkali, kurwanya solvent n'imbaraga za mekanike.
3 Ishusho
NIPU itegurwa hatabayeho gukoresha isocyanate y'uburozi, kandi ubu irimo kwigwa mu buryo bwa furo, irangi, kole, elastomer n'ibindi bicuruzwa, kandi ifite amahirwe menshi yo kuyikoresha. Ariko, inyinshi muri zo ziracyari ubushakashatsi bwa laboratwari gusa, kandi nta musaruro munini uhari. Byongeye kandi, hamwe no kunoza imibereho y'abantu no kwiyongera guhoraho kw'abakenewe, NIPU ifite imikorere imwe cyangwa myinshi yabaye icyerekezo cy'ingenzi cy'ubushakashatsi, nko kurwanya bagiteri, kwisana, kwibuka imiterere, kudakoresha umuriro, kurwanya ubushyuhe bwinshi n'ibindi. Kubwibyo, ubushakashatsi bw'ejo hazaza bugomba gusobanukirwa uburyo bwo guca ibibazo by'ingenzi by'inganda no gukomeza gushakisha icyerekezo cyo gutegura NIPU ikora.
Igihe cyo kohereza: Kanama-29-2024