Iterambere ryubushakashatsi kuri Non-Isocyanate Polyurethanes

Kuva ryatangizwa mu 1937, ibikoresho bya polyurethane (PU) byabonye ibisabwa byinshi mu nzego zitandukanye zirimo ubwikorezi, ubwubatsi, peteroli, imiti, imyenda, imashini n’amashanyarazi, icyogajuru, ubuvuzi, n’ubuhinzi. Ibi bikoresho bikoreshwa muburyo nka plastiki ya furo, fibre, elastomers, ibikoresho bitarinda amazi, uruhu rwubukorikori, impuzu, ibifunga, ibikoresho bya kaburimbo nibikoresho byubuvuzi. Gakondo PU ikomatanyirizwa cyane cyane muri isocyanate ebyiri cyangwa nyinshi hamwe na macromolecular polyol hamwe na molekile ntoya. Nyamara, uburozi bwihariye bwa isocyanates buteza ingaruka zikomeye kubuzima bwabantu no kubidukikije; ikindi kandi mubisanzwe bakomoka kuri fosgene-uburozi bukabije - hamwe nibikoresho bya amine bihuye.

Ukurikije inganda zikora imiti zigezweho zikurikirana ibikorwa byiterambere kandi birambye, abashakashatsi barushijeho kwibanda mugusimbuza isocyanate hamwe n’ibidukikije byangiza ibidukikije mu gihe bashakisha inzira zerekana uburyo bushya bwa polyurethanes itari isocyanate (NIPU). Uru rupapuro rutangiza inzira zo gutegura NIPU mugihe harebwa iterambere mubyiciro bitandukanye bya NIPU no kuganira kubyerekezo byabojo hazaza kugirango bitange ibisobanuro byubushakashatsi.

1 Synthesis ya Non-Isocyanate Polyurethanes

Synthesis ya mbere yuburemere buke bwa karbamate ikoresheje karubone ya monocyclic ihujwe na diamine ya alifatique yabereye mumahanga mu myaka ya za 1950 - ibyo bikaba ari umwanya wingenzi kuri synthesis ya polyurethane itari isocyanate. Kugeza ubu hariho uburyo bubiri bwibanze bwo kubyara NIPU: Iya mbere ikubiyemo intambwe yo kongera intambwe hagati ya binary cyclic carbone na binine amine; icya kabiri gikubiyemo reaction ya polycondensation irimo abahuza diurethane hamwe na diol yorohereza guhanahana imiterere muri karbamate. Abahuza ba Diamarboxylate barashobora kuboneka binyuze mumashanyarazi ya karubone cyangwa karubone ya dimethyl (DMC); mubyukuri uburyo bwose bwitwara binyuze mumatsinda ya acide karubone itanga imikorere ya karbamate.

Ibice bikurikira birasobanura uburyo butatu butandukanye bwo guhuza polyurethane udakoresheje isocyanate.

1.1 Inzira ya Cycle Carbone Inzira

NIPU irashobora guhuzwa binyuze mubyongeweho byongeweho birimo binary cyclic carbone ikomatanya hamwe na amine binini nkuko bigaragara mumashusho 1.

Bitewe nitsinda ryinshi rya hydroxyl riboneka mubice bisubiramo imiterere yuruhererekane rwibanze ubu buryo butanga icyo bita polyβ-hydroxyl polyurethane (PHU). Leitsch n'abandi, yateguye urukurikirane rwa PHUs ikoresha polyeteri ya cyclicique ya karubone irangiye hamwe na amine ya binary hiyongereyeho molekile ntoya ikomoka kuri binary cyclic carbone-ugereranije nuburyo gakondo bukoreshwa mugutegura PUs nyinshi. Ubushakashatsi bwabo bwerekanye ko amatsinda ya hydroxyl muri PHU akora byoroshye guhuza hydrogène hamwe na atome ya azote / ogisijeni iri mu bice byoroshye / bikomeye; Guhindagurika mubice byoroheje nabyo bigira ingaruka kumyitwarire ya hydrogène kimwe na dogere ya microphase itandukanya nyuma bigira ingaruka kumikorere rusange.

Ubusanzwe bikozwe munsi yubushyuhe burenga 100 ° C iyi nzira ntishobora kubyara ibicuruzwa mugihe cyibikorwa byogukora bigatuma itita cyane kubushuhe mugihe bitanga umusaruro uhamye udafite impungenge z’imihindagurikire ariko bikenera umusemburo kama urangwa na polarite ikomeye nka dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DMF), nibindi. bifitanye isano muri yo hamwe imbaraga zidahagije zerekanwa na PHU zivuyemo nubwo zitanga ibyiringiro zikoresha ibintu bitandukanya ibintu domeni ishusho yibuka yubaka ibyubaka bifata ibisubizo bifata ibisubizo nibindi ..

1.2 Inzira ya Carbone ya Monocylic

Monocylic carbone ikora neza na diamine bivamo dicarbamate ifite hydroxyl ya nyuma-matsinda hanyuma ikagira imikoranire yihariye ya transesterifike / polycondensation iherekejwe na diol amaherezo ikabyara NIPU muburyo busa nabagenzi gakondo bagaragajwe muburyo bwa 2.

Ubwoko bwa monocylic busanzwe bukoreshwa harimo na Ethylene & propylene karubone ya substrate aho itsinda rya Zhao Jingbo muri kaminuza ya Beijing ya kaminuza y’ikoranabuhanga ry’imiti ryashizeho diamine zitandukanye zibasubiza ku bigo by’imikino yabanje kubona ibice bitandukanye bya dicarbamate mbere yo gukomeza mu byiciro byifashishwa na polytetrahydrofuranediol / polyether-diol. Imirongo yibicuruzwa byerekana ibintu bitangaje byubushyuhe / ubukanishi bugera hejuru yo gushonga hejuru yizunguruka igera ku ntera igera kuri 125 ~ 161 ° C imbaraga zingana zingana na 24MPa yo kuramba igera kuri 1476%. Wang n'abandi. imbaraga zingutu zihindagurika9 ~ 17 MPa kurambura bitandukanye 35% ~ 235%.

Imisozi ya Cyclocarbonique ikora neza idasabye catalizator mubihe bisanzwe bikomeza ubushyuhe bugera kuri 80 ° kugeza kuri 120 ° C nyuma ya transesterifasiyo ikurikira ikoresha sisitemu ya catalitiki ya organotine itanga uburyo bwiza bwo gutunganya butarenze 200 °. Usibye imbaraga zokwegeranya gusa zigamije kwinjiza diolike ishoboye kwikorera-polymerisation / deglycolysis ibintu byorohereza ibisekuruza byifuzwa bitanga uburyo bukoreshwa mubidukikije byangiza ibidukikije ahanini bitanga methanol / ibisigisigi bito-bya molekile-diolike bityo bikerekana ubundi buryo bukomeye bwinganda butera imbere.

1.3Dimethyl Carbone Inzira

DMC yerekana ibidukikije byumvikana neza / bidafite uburozi burimo ibintu byinshi bikora bikora birimo methyl / mitoxy / carboneyl iboneza byongera imyirondoro ya reaction ituma ibikorwa byambere bitangira DMC ikorana na w / diamine ikora methyl-karbamate ntoya yarangije gukurikira nyuma yibikorwa byo gushonga bikubiyemo inyongera ntoya-urunigi-rwagutse-diolika / ibinini-binini bya polyol biganisha ku kugaragara kwa nyuma gushakishwa nyuma yimiterere ya polymer igaragara ukurikije amashusho3.

Deepa et.al yanditseho imbaraga zimaze kuvugwa zikoresha sodium methoxide catalizike itegura ibice bitandukanye bigizwe nyuma hanyuma igahuza iyaguka igasozwa nuruhererekane rugizwe nibice bigoye bigera ku bipimo bya molekuline bigereranya (3 ~ 20) x10 ^ 3g / mol ubushyuhe bwikirahure buringaniye (-30 ~ 120) ° C). Pan Dongdong yahisemo ingamba zifatika zigizwe na DMC hexamethylene-diaminopolycarbonate-polyalcohol ibona ibisubizo bitangaje byerekana imbaraga zingirakamaro zingana na 10-15MPa ibipimo byo kurambura bigera ku 1000% -1400%. Iperereza ryakozwe ryerekeranye ningaruka zinyuranye zagutse zagaragaje ibyifuzo byatoranijwe neza guhuza butanediol / hexanediol mugihe uburinganire bwa atomic numero bwagumanye uburinganire buteza imbere kongererwa imbaraga za kristu zagaragaye muminyururu yose. Itsinda rya Sarazin ryateguye ibice bihuza lignin / DMC hamwe na hexahydroxyamine yerekana ibimenyetso bya tekinike nyuma yo gutunganywa kuri230 ℃ .Ubushakashatsi bwiyongereye bugamije kuvana non-isocyante-polyureas gukoresha diazomonomer gusezerana byateganijwe ko hashobora gukoreshwa amarangi agaragara ugereranije na vinyl-karubone ya bagenzi babo bagaragaza uburyo bukoreshwa neza / inzira zagutse zituruka kuboneka. guhakana ibisabwa kugirango habeho kugabanya imyanda yiganjemo ahanini methanol / ntoya-ya-molekile-diolike yimyanda ishyiraho icyatsi kibisi muri rusange.

2 Ibice bitandukanye byoroshye bya polyurethane itari isocyanate

2.1 Polyurethane

Polyetherthane (PEU) ikoreshwa cyane kubera imbaraga zayo zo guhuza imbaraga za ether mugace koroheje gisubiramo, kuzunguruka byoroshye, ubushyuhe buke bwo guhinduka no kurwanya hydrolysis.

Kebir n'abandi. synthesized polyether polyurethane hamwe na DMC, polyethylene glycol na butanediol nkibikoresho fatizo, ariko uburemere bwa molekile bwari buke (7 500 ~ 14 800g / mol), Tg yari munsi ya 0 and, naho gushonga nabyo byari bike (38 ~ 48 ℃) , n'imbaraga nibindi bipimo byari bigoye guhuza ibikenewe gukoreshwa. Itsinda ry’ubushakashatsi bwa Zhao Jingbo ryakoresheje karubone ya Ethylene, 1, 6-hexanediamine na polyethylene glycol mu guhuza PEU, ifite uburemere bwa molekuline ya 31 000g / mol, imbaraga zingana na 5 ~ 24MPa, no kurambura ikiruhuko cya 0.9% ~ 1 388%. Uburemere bwa molekuline yuruhererekane rwa polyurethanes ya aromatic ni 17 300 ~ 21 000g / mol, Tg ni -19 ~ 10 ℃, aho gushonga ni 102 ~ 110 ℃, imbaraga za tensile ni 12 ~ 38MPa, nigipimo cyo gukira kwa elastique ya 200% ihoraho ni 69% ~ 89%.

Itsinda ry’ubushakashatsi rya Zheng Liuchun na Li Chuncheng ryateguye hagati ya 1, 6-hexamethylenediamine (BHC) hamwe na karubone ya dimethyl na 1, 6-hexamethylenediamine, na polycondensation hamwe na molekile ntoya itandukanye ya diol na polytetrahydrofuranediols (Mn = 2 000). Hateguwe uruhererekane rwa polyurethanes (NIPEU) hamwe n'inzira itari isocyanate, maze ikibazo cyo guhuza abahuza mugihe cya reaction cyakemutse. Imiterere n'imiterere ya polyurethane gakondo (HDIPU) yateguwe na NIPEU na 1, 6-hexamethylene diisocyanate yagereranijwe, nkuko bigaragara mu mbonerahamwe ya 1.

Icyitegererezo	Igice kinini cyigice /%	Uburemere bwa molekile / (g·mol ^ (- 1))	Indangagaciro yo gukwirakwiza uburemere	Imbaraga zingana / MPa	Kurambura 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 1

Ibisubizo biri mu mbonerahamwe ya 1 byerekana ko itandukaniro ryimiterere hagati ya NIPEU na HDIPU biterwa ahanini nigice gikomeye. Itsinda rya urea ryatewe no kuruhande rwa NIPEU ryinjijwe mu buryo butunguranye mu ruhererekane rukomeye rwa molekuline, rucamo igice gikomeye kugira ngo ribe imigozi ya hydrogène itumijwe, bikavamo imigozi ya hydrogène idakomeye hagati y'iminyururu ya molekile yo mu gice gikomeye ndetse na kristu ntoya yo mu gice gikomeye. , bivamo gutandukanya icyiciro cya NIPEU. Nkigisubizo, imiterere yubukanishi ni mbi cyane kurenza HDIPU.

2.2 Polyester Polyurethane

Polyester polyurethane (PETU) hamwe na polyester diol nkibice byoroheje bifite biodegradabilite nziza, biocompatibilité hamwe nubukanishi, kandi birashobora gukoreshwa mugutegura ingirabuzimafatizo za tissue, ni ibikoresho bya biomedical bifite amahirwe menshi yo gukoreshwa. Dioles ya polyester ikunze gukoreshwa mubice byoroshye ni polybutylene adipate diol, polyglycol adipate diol na diol polycaprolactone.

Mbere, Rokicki n'abandi. yakoresheje karubone ya Ethylene hamwe na diamine na diol zitandukanye (1, 6-hexanediol, 1, 10-n-dodecanol) kugirango ibone NIPU itandukanye, ariko NIPU ikomatanya yari ifite uburemere buke bwa molekile na Tg yo hepfo. Farhadiyani n'abandi. yateguye karubone ya polyisikike ikoresheje amavuta yimbuto yizuba nkibikoresho fatizo, hanyuma ikavangwa na bioamine ishingiye kuri bio, igashyirwa ku isahani, hanyuma igakira kuri 90 ℃ kuri 24 h kugirango ibone firime ya polyester polyurethane yerekana ubushyuhe bwiza. Itsinda ry’ubushakashatsi rya Zhang Liqun wo muri kaminuza y’ikoranabuhanga y’Ubushinwa ry’Ubushinwa ryashushanyije urukurikirane rwa diamine na karubone ya cyclicale, hanyuma ruhuza aside aside ya dibasike kugira ngo ibone polyester polyurethane. Itsinda ry’ubushakashatsi bwa Zhu Jin mu kigo cy’ubushakashatsi cya Ningbo, Ishuri Rikuru ry’Ubumenyi ry’Ubushinwa ryateguye igice gikomeye cya diaminodiol ukoresheje hexadiamine na karubone ya vinyl, hanyuma polycondensation hamwe na bio ishingiye kuri bio idahwitse kugira ngo ibone urukurikirane rwa polyester polyurethane, rushobora gukoreshwa nk'irangi nyuma. gukiza ultraviolet [23]. Itsinda ry’ubushakashatsi rya Zheng Liuchun na Li Chuncheng bakoresheje aside ya adipic na diole enye ya alifatique (butanediol, hexadiol, octanediol na decanediol) hamwe n’imibare itandukanye ya karubone atome kugirango bategure diole ihuye n’ibice byoroshye; Itsinda rya polyesterthane itari isocyanate polyurethane (PETU), ryitiriwe umubare wa atome ya karubone ya diol ya alifatique, ryabonetse mugushonga polycondensation hamwe na hydroxy-ifunze igice gikomeye prepolymer yateguwe na BHC na diol. Imiterere ya mashini ya PETU irerekanwa mumeza 2.

Icyitegererezo	Imbaraga zingana / MPa	Modulus/ MPa	Kurambura 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 2

Ibisubizo byerekana ko igice cyoroshye cya PETU4 gifite ubwinshi bwa karubone, isano ya hydrogène ikomeye hamwe nigice gikomeye, hamwe nicyiciro cyo hasi cyo gutandukana. Korohereza ibice byombi byoroshye kandi bikomeye bigarukira, byerekana aho gushonga hasi hamwe nimbaraga zingana, ariko kuramba cyane kuruhuka.

2.3 Polyakarubone polyurethane

Polyakarubone polyurethane (PCU), cyane cyane PCU ya alifatique, ifite hydrolysis irwanya cyane, irwanya okiside, ituze ry’ibinyabuzima hamwe na biocompatibilité, kandi ifite ibyifuzo byiza mubijyanye na biomedicine. Kugeza ubu, ibyinshi muri NIPU byateguwe bifashisha polyole polyole na polyester polyole nkibice byoroshye, kandi hariho raporo nke zubushakashatsi kuri polyakarubone polyurethane.

Polyurethane itari isocyanate polyurethane yateguwe nitsinda ry’ubushakashatsi bwa Tian Hengshui muri kaminuza y’ikoranabuhanga y’Ubushinwa ifite uburemere burenze 50 000 g / mol. Ingaruka yimiterere yimiterere yuburemere bwa molekuline ya polymer yarizwe, ariko imiterere yubukanishi ntabwo yatangajwe. Itsinda ry’ubushakashatsi rya Zheng Liuchun na Li Chuncheng bateguye PCU bakoresheje DMC, hexanediamine, hexadiol na polyakarubone, kandi bita PCU ukurikije igice kinini cy’igice gisubiramo igice. Imiterere yubukorikori irerekanwa mu mbonerahamwe ya 3.

Icyitegererezo	Imbaraga zingana / MPa	Modulus/ MPa	Kurambura 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 3

Ibisubizo byerekana ko PCU ifite uburemere buke bwa molekile, kugeza kuri 6 × 104 ~ 9 × 104g / mol, gushonga kugera kuri 137 and, nimbaraga zikomeye kugeza kuri MPa 29. Ubu bwoko bwa PCU burashobora gukoreshwa haba nka plastiki itajenjetse cyangwa nka elastomer, ifite ibyifuzo byiza byo gukoresha mubuzima bwa biomedical medicine (nkibikoresho byubwubatsi bwa tissue scafolds cyangwa ibikoresho byimitsi yumutima).

2.4 Hybrid itari isocyanate polyurethane

Hybrid itari isocyanate polyurethane (hybrid NIPU) ni kwinjiza amatsinda ya epoxy resin, acrylate, silika cyangwa siloxane mumikorere ya molekile ya polyurethane kugirango habeho urusobe rwuzuzanya, kunoza imikorere ya polyurethane cyangwa guha polyurethane imirimo itandukanye.

Feng Yuelan n'abandi. yakoresheje amavuta ya soya ya epoxy ya bio hamwe na CO2 kugirango ashushanye pentamonic cyclic carbone (CSBO), maze ashyiraho bisphenol A diglycidyl ether (epoxy resin E51) hamwe nuduce twinshi twumunyururu kugirango turusheho kunoza NIPU yashizweho na CSBO ikomera hamwe na amine. Urunigi rwa molekile rurimo urunigi rurerure rworoshye rwa acide oleic / aside linoleque. Irimo kandi ibice byinshi byumunyururu, kuburyo bifite imbaraga zubukanishi hamwe nubukomere bukabije. Abashakashatsi bamwe kandi bahujije ubwoko butatu bwa NIPU prepolymers hamwe nitsinda ryanyuma rya furan binyuze muburyo bwo gufungura igipimo cya diethylene glycol bicyclic carbone na diamine, hanyuma bakitwara hamwe na polyester idahagije kugirango bategure polyurethane yoroshye hamwe nibikorwa byo kwikiza, maze bamenya neza kwishira hejuru. -gukiza imikorere ya NIPU yoroshye. Hybrid NIPU ntabwo ifite ibiranga NIPU rusange gusa, ahubwo irashobora no kugira neza, aside hamwe na alkali irwanya ruswa, irwanya imbaraga nimbaraga za mashini.

3 Ibitekerezo

NIPU yateguwe idakoresheje isocyanate yuburozi, kandi kuri ubu irimo kwigwa muburyo bwa furo, gutwikira, gufatira, elastomer nibindi bicuruzwa, kandi ifite ibyifuzo byinshi byo gusaba. Nyamara, inyinshi murizo ziracyagarukira gusa mubushakashatsi bwa laboratoire, kandi nta musaruro munini uhari. Byongeye kandi, hamwe no kuzamura imibereho yabantu no gukomeza kwiyongera kwicyifuzo, NIPU ifite umurimo umwe cyangwa imirimo myinshi yabaye icyerekezo cyingenzi cyubushakashatsi, nka antibacterial, kwikosora, kwibuka imiterere, kubika umuriro, kurwanya ubushyuhe bwinshi no n'ibindi. Kubwibyo, ubushakashatsi buzaza bugomba gusobanukirwa nuburyo bwo guca mubibazo byingenzi byinganda kandi bigakomeza gushakisha icyerekezo cyo gutegura NIPU ikora.

Igihe cyo kohereza: Kanama-29-2024