Kufambira Mberi Kwekutsvaga PamaPolyurethane Asiri eIsocyanate
Kubva pazvakatanga kushandiswa muna 1937, zvinhu zve polyurethane (PU) zvave zvichishandiswa zvakanyanya muzvikamu zvakasiyana-siyana zvinosanganisira kutakura, kuvaka, petrochemicals, machira, mechanical nemagetsi engineering, aerospace, healthcare, uye kurima. Zvinhu izvi zvinoshandiswa mumhando dzakadai semapurasitiki efoam, fibers, elastomers, waterproofing agents, synthetic dehwe, coatings, adhesives, paving materials uye medical supplies. PU yechinyakare inonyanya kugadzirwa kubva kuma isocyanates maviri kana anopfuura pamwe chete nema macromolecular polyols uye small molecular chain extenders. Zvisinei, chepfu ye isocyanates inokonzera njodzi huru kuhutano hwevanhu nenharaunda; uye zvakare inowanzo torwa kubva ku phosgene - chinhu chine chepfu yakawanda - uye amine raw materials anoenderana nayo.
Zvichienderana nekutsvaga kuri kuitwa neindasitiri yemakemikari yemazuva ano yekuvandudza zvakatipoteredza, vaongorori vari kuramba vachinyanya kutarisisa pakushandisa isocyanates nezvinhu zvisingakuvadzi nharaunda uku vachitsvaga nzira itsva dzekugadzira ma polyurethanes asiri isocyanate (NIPU). Pepa iri rinosuma nzira dzekugadzirira NIPU uku vachiongorora kufambira mberi mumhando dzakasiyana dzeNIPU uye vachikurukura nezveramangwana ravo kuti vape ruzivo rwekutsvagisa kwakawanda.
1 Kugadzirwa kweNon-Isocyanate Polyurethanes
Kugadzirwa kwekutanga kwemakemikari ecarbamate ane huremu hwakaderera achishandisa monocyclic carbonates pamwe chete ne aliphatic diamines kwakaitika kunze kwenyika muma1950—zvichiratidza nguva inokosha yekugadzirwa kwe non-isocyanate polyurethane. Parizvino kune nzira mbiri huru dzekugadzira NIPU: Yokutanga inosanganisira kuwedzera nhanho pakati pe binary cyclic carbonates ne binary amines; yechipiri inosanganisira polycondensation reactions inosanganisira diurethane intermediates pamwe chete ne diols dzinobatsira kuchinjana kwechimiro mukati me carbamates. Diamarboxylate intermediates inogona kuwanikwa kuburikidza ne cyclic carbonate kana dimethyl carbonate (DMC) routes; nzira dzese dzinoita kuburikidza ne carbonic acid groups dzinoburitsa carbamate functionalities.
Zvikamu zvinotevera zvinotsanangura nzira nhatu dzakasiyana dzekugadzira polyurethane pasina kushandisa isocyanate.
1.1 Nzira yeBinary Cyclic Carbonate
NIPU inogona kugadzirwa kuburikidza nekuwedzera nhanho nhanho kunosanganisira binary cyclic carbonate yakabatana nebinary amine sezvakaratidzwa muMufananidzo 1.
Nekuda kwemapoka akawanda ehydroxyl ari mukati memayuniti anodzokorora pamwe chete nechimiro chayo chikuru cheketani, nzira iyi inowanzo buritsa chinonzi polyβ-hydroxyl polyurethane (PHU). Leitsch et al., vakagadzira nhevedzano yepolyether PHUs vachishandisa cyclic carbonate-terminated polyethers pamwe chete ne binary amines pamwe nemamorekuru madiki anobva mu binary cyclic carbonates—vachienzanisa izvi nenzira dzechinyakare dzinoshandiswa pakugadzira polyether PUs. Zvavakawana zvakaratidza kuti mapoka ehydroxyl ari mukati mePHUs anogadzira nyore nyore hydrogen bonds nemaatomu enitrogen/oxygen ari mukati mezvikamu zvakapfava/zvakaoma; kusiyana pakati pezvikamu zvakapfava kunokanganisawo maitiro ehydrogen bonding pamwe nemadhigirii ekuparadzanisa microphase izvo zvinozokanganisa hunhu hwese hwekushanda.
Kazhinji kacho, tembiricha dzinopfuura 100°C hadziburitse zvimwe zvinhu panguva yekuita reaction, zvichiita kuti isanyanya kunzwa hunyoro uku ichiburitsa zvinhu zvakagadzikana zvisina dambudziko rekushanduka-shanduka asi zvinoda organic solvents ine strong polarity senge dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), nezvimwewo. Uyezve, nguva yakareba yekuita reaction inotangira pakati pezuva rimwe kusvika mazuva mashanu inowanzoburitsa huremu hwakaderera hwemamorekuru, kazhinji inoderera pasi pemiganhu inosvika 30k g/mol, zvichiita kuti kugadzirwa kukuru kuve kwakaoma nekuda kwemitengo yakakwira inobatanidzwa nayo, pamwe nekusakwana kwesimba rinoratidzwa nePHUs, kunyangwe mashandisirwo akanaka anosanganisira damping material domains, shape memory constructions, adhesive formulations, coating solutions, foams, etc..
1.2 Nzira yeMonocylic Carbonate
Monocylic carbonate inosangana zvakananga nediamine inoburitsa dicarbamate ine hydroxyl end-groups iyo inobva yasangana ne transesterification/polycondensation interactions pamwe chete nema diols zvichizopedzisira zvagadzira NIPU yakafanana neyakajairika inoratidzwa nemufananidzo 2.
Mhando dze monocylic dzinonyanya kushandiswa dzinosanganisira ethylene & propylene carbonated substrates apo timu yaZhao Jingbo kuBeijing University Of Chemical Technology yakashandisa ma diamond akasiyana-siyana achiarwisa pakurwisa zvinhu izvi zvakatanga nekugadzira dicarbamate intermediaries dzakasiyana-siyana vasati vapinda muzvikamu zvekuomarara vachishandisa polytetrahydrofuranediol/polyether-diols, zvichiguma nekubudirira kwekugadzirwa kwezvigadzirwa zvine hunhu hwekupisa hunoshamisa/hwemakanika hunosvika kumusoro panzvimbo dzekunyunguduka dzichikwira kusvika pa125~161°C, simba rekusimba richikwira kusvika pa24MPa, richisvika pa1476%. Wang nevamwe vake, vakashandisawo DMC pamwe chete ne/hexamethylenediamine/cyclocarbonated precursors vachigadzira hydroxy-terminated derivatives, vakazopedzisira vashandisa biobased dibasic acids se oxalic/sebacic/acids, adipic-acid-terephtalics achieving final outputs, vachiratidza mazinga akakomberedza 13k~28k g/mol tensile strengths fluctuating9~17 MPa elongations variable35%~235%.
Maester eCyclocarbonic anoshanda zvakanaka pasina kushandisa macatalyst mumamiriro ezvinhu akajairwa, achichengetedza tembiricha inosvika 80° kusvika 120°C, ma transesterification anotevera anowanzo shandisa masisitimu e catalytic akavakirwa pa organotin zvichiita kuti kugadziriswa kwakanakisa kusapfuure 200°. Kunze kwekungoedza kudzikamisa mvura kunotarisa ma diolic inputs anokwanisa kuzvigadzirisa ega/deglycolysis phenomena zvichiita kuti pave nemigumisiro inodiwa inoita kuti nzira iyi ive neushamwari nezvakatipoteredza, ichipa methanol/molecule-diolic residues, nokudaro ichipa dzimwe nzira dzeindasitiri dzinoshanda.
1.3 Nzira yeDimethyl Carbonate
DMC inomiririra imwe nzira inoshanda/isina chepfu ine zvikamu zvakawanda zvinoshanda zvinosanganisira methyl/methoxy/carbonyl configurations inowedzera reactivity profiles zvichigonesa zvikuru kubatana kwekutanga apo DMC inosangana zvakananga ne/diamines ichigadzira methyl-carbamate intermediaries diki dzakapera mushure mezvo zvichizotevera zviito zvekunyungudutsa-kunyungudutsa zvinosanganisira zvimwe zvikamu zve small-chain-extender-diolics/larger-polyol zvichikonzera kubuda kwezvimiro zve polymer zvinotsvakwa zvichiratidzwa zvinoenderana neMufananidzo 3.
Deepa nevamwe vakashandisa nzira dzataurwa pamusoro apa vachishandisa sodium methoxide catalysis vachironga mafomu akasiyana-siyana epakati, zvichizobatanidza ma extensions akatarwa, zvichiguma nekuumbwa kwakafanana kwezvikamu zvakaoma, zvichisvika pakurema kwemamorekuru, tembiricha yekuchinja kwegirazi inosvika (3 ~ 20) x 10^3g/mol (-30 ~ 120°C). Pan Dongdong yakasarudza ma pairings anosanganisira DMC hexamethylene-diaminopolycarbonate-polyalcohols, zvichiita kuti pave nemigumisiro inooneka inoratidza tensile-strength metrics oscillating 10-15MPa elongation ratios inosvika 1000%-1400%. Kuferefeta kwakaitwa pamusoro pesimba rekuwedzera kwecheni kwakaratidza kuti zvaunofarira zvinogadzirisa sarudzo dzebutanediol/hexanediol zvakanaka apo atomic-number parity yakaramba yakafanana uye ichikurudzira kuwedzerwa kwekristaro kwakarongwa kwakaonekwa mumaketani ese. Boka raSarazin rakagadzira macomposites anobatanidza lignin/DMC pamwe chete nehexahydroxyamine achiratidza hunhu hwakanaka hwemakanika mushure mekugadzirwa pa230℃. Kumwe kuongorora kwakanangana nekuwana non-isocyante-polyureas vachishandisa diazomonomer entability yaitarisira kuti paint applications dzinogona kubuda zvakanaka kupfuura vinyl-carbonaceous counterparts zvichiratidza kushanda kwemari/nzira dzakafara dzekuwana dziripo. Kuongorora kwakakodzera maererano nenzira dzakagadzirwa nehukuru kazhinji kunoda kuti nzvimbo dzakakwira-tembiricha/vacuum dzisave nezvinodiwa zve solvent nokudaro zvichideredza marara anoyerera zvakanyanya anongogumira methanol/small-molecule-diolic effluents zvinogadzira maparadigms egreen syntheses.
2 Zvikamu zvakasiyana-siyana zvakapfava zve polyurethane isina isocyanate
2.1 Polyether polyurethane
Polyether polyurethane (PEU) inoshandiswa zvakanyanya nekuda kwesimba rayo shoma rekubatana kwe ether bonds muzvikamu zvakapfava zvekudzokorora, kutenderera kuri nyore, kuchinjika kwakanaka kwekupisa kwakaderera uye kuramba hydrolysis.
Kebir nevamwe vake vakagadzira polyether polyurethane neDMC, polyethylene glycol uye butanediol sezvinhu zvakagadziriswa, asi huremu hwemamorekuru hwaive hwakaderera (7 500 ~ 14 800g/mol), Tg yaive yakaderera pane 0℃, uye nzvimbo yekunyunguduka yaive yakadererawo (38 ~ 48℃), uye simba nezvimwe zviratidzo zvaive zvakaoma kusangana nezvinodiwa zvekushandisa. Boka rekutsvagisa raZhao Jingbo rakashandisa ethylene carbonate, 1, 6-hexanediamine uye polyethylene glycol kugadzira PEU, ine huremu hwemamorekuru hwe31 000g/mol, simba rekudhonza re5 ~ 24MPa, uye kureba pakuputsika kwe0.9% ~ 1 388%. Huremu hwemamorekuru emhando dzakagadzirwa dzearomatic polyurethanes i17 300 ~ 21 000g/mol, Tg i -19 ~ 10℃, nzvimbo yekunyunguduka i102 ~ 110℃, simba rekudhonza i12 ~ 38MPa, uye mwero wekupora we200% constant elongation i69% ~ 89%.
Boka rekutsvagisa raZheng Liuchun naLi Chuncheng rakagadzira intermediate 1, 6-hexamethylenediamine (BHC) ne dimethyl carbonate uye 1, 6-hexamethylenediamine, uye polycondensation nemamorekuru madiki akasiyana ma straight chain diols uye polytetrahydrofuranediols (Mn=2 000). Nhevedzano ye polyether polyurethanes (NIPEU) ine non-isocyanate route yakagadzirwa, uye dambudziko re crosslinking re intermediates panguva ye reaction rakagadziriswa. Maumbirwo uye hunhu hwe traditional polyether polyurethane (HDIPU) yakagadzirwa neNIPEU uye 1, 6-hexamethylene diisocyanate zvakaenzaniswa, sezvakaratidzwa muTafura 1.
| Muenzaniso | Chikamu chehuremu hwakaoma/% | Huremu hwemamorekuru/(g)·mol^(-1)) | Nhamba yekugoverwa kwehuremu hwemamorekuru | Simba rekudhonza/MPa | Kureba panguva yekutyoka/% |
| 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
Zvakabuda muTafura 1 zvinoratidza kuti musiyano uripo pakati peNIPEU neHDIPU unonyanya kukonzerwa nechikamu chakaoma. Boka reurea rinogadzirwa nerutivi rweNIPEU rinoiswa mucheni yemamorekuru echikamu chakaoma, richityora chikamu chakaoma kuti chigadzire mabhondi ehydrogen akarongwa, zvichikonzera mabhondi ehydrogen asina simba pakati pemaketani emamorekuru echikamu chakaoma uye crystallinity yakaderera yechikamu chakaoma, zvichikonzera kuparadzaniswa kweNIPEU kwechikamu chakaderera. Nekuda kweizvozvo, hunhu hwayo hwemakanika hwakaipa zvikuru kupfuura HDIPU.
2.2 Polyester Polyurethane
Polyester polyurethane (PETU) ine polyester diols sezvikamu zvakapfava ine kugona kuora kwemuviri, inoenderana nemuviri uye ine hunhu hwemakanika, uye inogona kushandiswa kugadzira ma tissue engineering scaffolds, inova chinhu chekurapa chine mukana wekushandiswa zvakanaka. Polyester diols dzinowanzoshandiswa muzvikamu zvakapfava ndi polybutylene adipate diol, polyglycol adipate diol uye polycaprolactone diol.
Pakutanga, Rokicki nevamwe vake vakashandisa ethylene carbonate nediamine uye diols dzakasiyana (1, 6-hexanediol,1, 10-n-dodecanol) kuti vawane NIPU dzakasiyana, asi NIPU yakagadzirwa yaive nehuremu hwakaderera uye Tg yakaderera. Farhadian nevamwe vake vakagadzira polycyclic carbonate vachishandisa mafuta embeu yezuva sezvinhu zvakabikwa, ndokuzosanganiswa ne bio-based polyamines, yakafukidzwa neplate, uye yakacheneswa pa90 ℃ kwemaawa makumi maviri nemana kuti iwane thermosetting polyester polyurethane film, iyo yakaratidza kugadzikana kwakanaka kwekupisa. Boka rekutsvagisa raZhang Liqun kubva kuSouth China University of Technology rakagadzira nhevedzano ye diamines uye cyclic carbonates, uye ndokuzosanganiswa ne biobased dibasic acid kuti iwane biobased polyester polyurethane. Boka rekutsvagisa raZhu Jin paNingbo Institute of Materials Research, Chinese Academy of Sciences rakagadzira diaminodiol hard segment vachishandisa hexadiamine uye vinyl carbonate, uye ipapo polycondensation ne bio-based unsaturated dibasic acid kuti iwane nhevedzano ye polyester polyurethane, iyo inogona kushandiswa sependi mushure mekupiswa kwe ultraviolet [23]. Boka rekutsvagisa raZheng Liuchun naLi Chuncheng rakashandisa adipic acid uye ma aliphatic diol mana (butanediol, hexadiol, octanediol uye decanediol) ane manhamba akasiyana eatomu ekabhoni kugadzirira ma polyester diols anoenderana sezvikamu zvakapfava; Boka re non-isocyanate polyester polyurethane (PETU), rakatumidzwa zita rehuwandu hwemaatomu ekabhoni e aliphatic diols, rakawanikwa nekunyungudutsa polycondensation ne hydroxy-sealed hard segment prepolymer yakagadzirwa ne BHC nema diols. Hunhu hwe PETU hunoratidzwa muTafura 2.
| Muenzaniso | Simba rekudhonza/MPa | Modulus yakasununguka/MPa | Kureba panguva yekutyoka/% |
| 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
Zvakabuda zvinoratidza kuti chikamu chakapfava chePETU4 chine huwandu hwakanyanya hwecarbonyl density, hydrogen bond yakasimba nechikamu chakasimba, uye low phase separation degree. Kuumbwa kwezvikamu zvakapfava nezvisimba kwakaderera, zvichiratidza pokunyunguduka kwakaderera uye simba rekudhonza, asi kureba kwakanyanya pakuputsika.
2.3 Polycarbonate polyurethane
Polycarbonate polyurethane (PCU), kunyanya aliphatic PCU, ine simba rakanaka rekudzivirira hydrolysis, simba rekudzivirira oxidation, simba rakanaka rehupenyu uye kushanda pamwe chete, uye ine mikana yakanaka yekushandisa mumunda we biomedicine. Parizvino, yakawanda yeNIPU yakagadzirwa inoshandisa polyether polyols uye polyester polyols sezvikamu zvakapfava, uye hapana mishumo mishoma yekutsvagisa pamusoro pe polycarbonate polyurethane.
Polyurethane isina isocyanate polycarbonate yakagadzirwa neboka rekutsvagisa raTian Hengshui kuSouth China University of Technology ine huremu hwemorekuru hunopfuura 50 000 g/mol. Kukanganiswa kwemamiriro ekuita kwemuviri pahuremu hwemorekuru hwepolymer kwakadzidzwa, asi hunhu hwayo hwemakanika hahuna kutaurwa. Boka rekutsvagisa raZheng Liuchun naLi Chuncheng vakagadzira PCU vachishandisa DMC, hexanediamine, hexadiol uye polycarbonate diols, uye vakatumidza PCU zvichienderana nechikamu chehukuru hwechikamu chakaoma chinodzokorora. Hunhu hwemakanika hunoratidzwa muTafura 3.
| Muenzaniso | Simba rekudhonza/MPa | Modulus yakasununguka/MPa | Kureba panguva yekutyoka/% |
| 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
Zvakabuda zvinoratidza kuti PCU ine huremu hwakawanda hwemamorekuru, kusvika 6×104 ~ 9×104g/mol, poindi yekunyunguduka inosvika 137 ℃, uye simba rekudhonza rinosvika 29 MPa. Rudzi urwu rwePCU runogona kushandiswa sepurasitiki yakasimba kana se elastomer, iyo ine mukana wakanaka wekushandiswa mumunda wezvekurapa (senge mascaffolds ekugadzira matishu evanhu kana zvinhu zvemoyo zvinoiswa).
2.4 Polyurethane yeHybrid isina isocyanate
Hybrid non-isocyanate polyurethane (hybrid NIPU) kuisirwa kwe epoxy resin, acrylate, silica kana siloxane groups mu polyurethane molecular framework kuti vagadzire network inopindirana, kuvandudza mashandiro e polyurethane kana kupa polyurethane mabasa akasiyana.
Feng Yuelan nevamwe vake vakashandisa mafuta epoxy soybean ane bio-based neCO2 kugadzira pentamonic cyclic carbonate (CSBO), uye vakaunza bisphenol A diglycidyl ether (epoxy resin E51) ine zvikamu zve chain zvakasimba kuti vawedzere kuvandudza NIPU yakaumbwa neCSBO yakasimbiswa neamine. Cheni yemolecular ine chikamu chakareba che chain chinochinjika che oleic acid/linoleic acid. Inewo zvikamu zve chain zvakasimba, zvekuti ine simba re mechanical uye kusimba kwakanyanya. Vamwe vaongorori vakagadzirawo marudzi matatu eNIPU prepolymers ane furan end groups kuburikidza ne rate-opening reaction ye diethylene glycol bicyclic carbonate uye diamine, uye vakazoshandisa unsaturated polyester kugadzira soft polyurethane ine self-healing function, uye vakabudirira kuona high self-healing efficiency ye soft NIPU. Hybrid NIPU haina chete hunhu hwe general NIPU, asi inogonawo kuva nekunamatira kuri nani, acid ne alkali corrosion resistance, solvent resistance uye mechanical strength.
3 Maonero
NIPU inogadzirwa pasina kushandisa isocyanate ine chepfu, uye parizvino iri kudzidzwa muchimiro chefuro, coating, glue, elastomer nezvimwe zvigadzirwa, uye ine mikana yakawanda yekushandisa. Zvisinei, mazhinji acho achiri kungotsvaga murabhoritari, uye hapana kugadzirwa kukuru kuri kuitwa. Pamusoro pezvo, nekuvandudzwa kwemararamiro evanhu uye kukura kuri kuramba kuchienderera mberi kwekuda, NIPU ine basa rimwe chete kana mabasa akawanda yave nzira yakakosha yekutsvagisa, senge antibacterial, kuzvigadzirisa, kurangarira chimiro, kudzoreredza moto, kuramba kupisa zvakanyanya nezvimwewo. Saka, tsvakiridzo yeramangwana inofanira kunzwisisa maitirwo ekupedza matambudziko makuru eindasitiri uye kuramba ichiongorora nzira yekugadzirira NIPU inoshanda.
Nguva yekutumira: Nyamavhuvhu-29-2024