Ọganihu Nnyocha na Polyurethanes Na-abụghị Isocyanate
Kemgbe e webatara ha na 1937, ihe ndị e ji polyurethane (PU) mee abụrụla ihe dị iche iche a na-eji eme ihe n'ọtụtụ ebe dịka njem, ihe owuwu, ihe ndị e ji petrochemicals, ákwà, injinia igwe na eletriki, ụgbọelu, nlekọta ahụike, na ọrụ ugbo. A na-eji ihe ndị a eme ihe n'ụdị dịka plastik ụfụfụ, eriri, elastomers, ihe ndị na-egbochi mmiri, akpụkpọ anụ sịntetik, ihe mkpuchi, ihe nrapado, ihe ndị e ji pave mee na ihe ndị e ji agwọ ọrịa. A na-emepụta PU ọdịnala site na isocyanates abụọ ma ọ bụ karịa yana polyols macromolecular na obere ihe ndọtị nke molekul. Agbanyeghị, nsí dị n'ime nke isocyanates na-akpata nnukwu ihe egwu nye ahụike mmadụ na gburugburu ebe obibi; ha na-esikarị na phosgene—ihe na-akpata nsí dị ukwuu—na ihe ndị e ji amine mee.
N'ihi mbọ ụlọ ọrụ kemịkalụ nke oge a na-agba iji mepụta usoro mmepe ndụ ndụ na nke na-adịgide adịgide, ndị nchọpụta na-elekwasị anya nke ukwuu n'iji ihe ndị na-adịghị ize ndụ gburugburu ebe obibi dochie isocyanates ka ha na-enyocha ụzọ mmepụta ọhụrụ maka polyurethanes na-abụghị isocyanate (NIPU). Akwụkwọ a na-ewebata ụzọ nkwadebe maka NIPU ebe ọ na-enyocha ọganihu dị iche iche na ụdị NIPU dị iche iche ma na-atụle atụmanya ha n'ọdịnihu iji nye ntụaka maka nyocha ọzọ.
1 Njikọ nke Polyurethanes Na-abụghị Isocyanate
Mmekọrịta mbụ nke obere ihe ndị dị arọ nke carbamate site na iji monocyclic carbonates jikọtara ya na aliphatic diamines mere na mba ofesi na afọ 1950 - nke na-egosi oge dị mkpa maka njikọta polyurethane na-abụghị isocyanate. Ugbu a, e nwere ụzọ abụọ bụ isi maka imepụta NIPU: Nke mbụ gụnyere mmeghachi omume mgbakwunye nzọụkwụ n'etiti binary cyclic carbonates na binary amines; nke abụọ gụnyere mmeghachi omume polycondensation nke gụnyere diurethane intermediates n'akụkụ diols nke na-eme ka mgbanwe nhazi dị mfe n'ime carbamates. Enwere ike nweta diarboxylate intermediates site na ụzọ cyclic carbonate ma ọ bụ dimethyl carbonate (DMC); ụzọ niile na-emeghachi omume site na otu carbonic acid na-enye ọrụ carbamate.
Ngalaba ndị a na-akọwa ụzọ atọ dị iche iche esi emepụta polyurethane na-ejighị isocyanate.
1.1 Ụzọ Binary Cyclic Carbonate
Enwere ike iji usoro nzọụkwụ tinye NIPU dịka egosiri na Foto 1.
N'ihi ọtụtụ otu hydroxyl dị n'ime nkeji ndị na-emegharị n'akụkụ nhazi isi ya, usoro a na-emepụta ihe a na-akpọ polyβ-hydroxyl polyurethane (PHU). Leitsch et al., mepụtara usoro PHU polyether na-eji polyethers carbonate-endated cyclic yana binary amines tinyere obere molekul sitere na binary cyclic carbonates - na-atụnyere ha na usoro ọdịnala eji eme nkwadebe polyether PUs. Nchọpụta ha gosiri na otu hydroxyl dị n'ime PHUs na-etolite njikọ hydrogen ngwa ngwa na atọm nitrogen/oxygen dị n'ime akụkụ dị nro/siri ike; mgbanwe dị n'etiti akụkụ dị nro na-emetụtakwa omume njikọ hydrogen yana ogo nkewa microphase nke na-emesịa metụta njirimara arụmọrụ zuru oke.
A na-eme ya n'okpuru okpomọkụ karịrị 100 Celsius C n'ụzọ a anaghị emepụta ihe ndị ọzọ n'oge usoro mmeghachi omume, nke na-eme ka ọ ghara inwe mmetụta na mmiri ma na-emepụta ngwaahịa kwụsiri ike na-enweghị nsogbu mgbanwe mana ọ dị mkpa ihe mgbaze organic nke ejiri ike dị ka dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), wdg mara. Ọzọkwa, oge mmeghachi omume agbatịkwuru site n'otu ụbọchị ruo ụbọchị ise na-ebute obere ibu molekul, na-adakarị n'okpuru oke ihe dịka 30kg/mol, nke na-eme ka mmepụta buru ibu sie ike n'ihi nnukwu ọnụ ahịa abụọ ahụ jikọtara ya na ike na-ezughị oke nke PHUs na-arụpụta n'agbanyeghị ngwa ndị na-ekwe nkwa gbasara mpaghara ihe ndị na-emebi ihe, nhazi ebe nchekwa, nhazi ihe mkpuchi, ụfụfụ wdg.
1.2 Ụzọ Carbonate Monocylic
Monocylic carbonate na-emeghachi omume ozugbo na diamine nke nwere dicarbamate nwere hydroxyl end-groups nke na-eme mmekọrịta pụrụ iche nke transesterification/polycondensation yana diols n'ikpeazụ na-emepụta NIPU yiri ọdịnala ndị a na-egosi anya site na Foto 2.
Ụdị monocylic ndị a na-ejikarị eme ihe gụnyere ihe ndị e ji ethylene na propylene carbonated substrates ebe ndị otu Zhao Jingbo na Mahadum Chemical Technology nke Beijing tinyere ọtụtụ diamines iji meghachi omume megide ihe ndị ahụ na-agbanwe agbanwe na mbụ na-enweta ụdị dicarbamate dị iche iche tupu ha agaa n'ihu na usoro condensation site na iji polytetrahydrofuranediol/polyether-diols, nke mechara mepụta usoro ngwaahịa dị iche iche, na-egosipụta ihe ndị dị egwu na-ekpo ọkụ/usoro, na-eru elu ebe agbaze agbaze gburugburu, na-agbatị ihe dị ka 125 ~ 161°C ike nrụgide, na-eru nso 24MPa, ọnụego ogologo dị ihe dị ka 1476%. Wang na ndị otu ya, njikọta ndị nwere ike itinye aka n'otu aka ahụ gụnyere DMC jikọtara ọnụ na hexamethylenediamine/cyclocarbonated precursors na-emepụta ihe ndị na-eme ka hydroxy kwụsịchaa nke mechara bụrụ dibasic acid dị ka oxalic/sebacic/acids adipic-acid-terephthalics na-enweta nsonaazụ ikpeazụ na-egosi oke nke gụnyere ike nrụgide 13k ~ 28k g/mol na-agbanwe agbanwe9 ~ 17 MPa na-agbanwe agbanwe35% ~ 235%.
Ndị Cyclocarbonic esters na-arụ ọrụ nke ọma n'enweghị ihe ndị na-akpali akpali n'okpuru ọnọdụ nkịtị, na-ejigide okpomọkụ dị ihe dịka 80° ruo 120°C, transesterifications ndị na-esote na-ejikarị sistemụ catalytic dabere na organotin na-ahụ na nhazi kacha mma agaghị agafe 200°. Karịa naanị mgbalị condensation na-elekwasị anya na ntinye diolic nwere ike ịmepụta onwe-polymerization/deglycolysis ihe omume na-eme ka mmepụta ihe achọrọ pụta ìhè na-eme ka usoro ahụ bụrụ nke na-enye gburugburu ebe obibi ihe fọdụrụ nke na-enye methanol/obere-molecule-diolic si otú a na-enye nhọrọ ụlọ ọrụ bara uru na-aga n'ihu.
Ụzọ 1.3Dimethyl Carbonate
DMC na-anọchite anya nhọrọ ọzọ dị mma/anaghị egbu egbu nke nwere ọtụtụ akụkụ ọrụ na-arụ ọrụ gụnyere nhazi methyl/methoxy/carbonyl na-eme ka profaịlụ mmeghachi omume dịkwuo mma nke na-enye ohere ka mmekọrịta mbụ dị mfe ebe DMC na-emekọrịta ozugbo na diamines na-emepụta obere ndị ogbugbo methyl-carbamate kwụsịrị, wee soro ya, ihe ndị na-agbaze agbaze nke gụnyere obere ihe ndị mejupụtara obere yinye-extender-diolics/nnukwu-polyol na-eduga n'ọdịdị polymer achọrọ nke a na-ahụ anya site na Foto3.
Deepa et.al jiri usoro ndị a kpọtụrụ aha mee ihe nke ọma site n'iji sodium methoxide catalysis na-ahazi ụdị dị iche iche dị iche iche, na-emesịa na-etinye ndọtị ndị a na-elekwasị anya, na-emecha na-eru usoro nhazi siri ike nhata, na-eru oke molekul dị ihe dị ka (3 ~ 20) x 10^ 3g/mol, okpomọkụ mgbanwe iko nke na-agafe (-30 ~ 120°C). Pan Dongdong họọrọ njikọ atụmatụ nke gụnyere DMC hexamethylene-diaminopolycarbonate-polyalcohols, na-enweta nsonaazụ dị ịrịba ama na-egosipụta usoro ike nrụgide na-agbagharị 10-15MPa, oke ogologo na-eru nso 1000%-1400%. Nnyocha ndị e mere gbasara mmetụta dị iche iche nke ịgbasa agbụ gosiri mmasị ndị a na-ahọrọ nke ọma site n'ịhazi nhọrọ butanediol/hexanediol mgbe nha nha atọm nọgidere na-enwe nha nhata na-akwalite mmụba kristal a na-ahụ n'usoro n'usoro n'ime agbụ niile. Otu Sarazin kwadebere ngwakọta ndị na-ejikọta lignin/DMC yana hexahydroxyamine na-egosi njirimara igwe na-eju afọ mgbe nhazi ya gasịrị na 230℃. Nnyocha ndị ọzọ ezubere iji nweta ndị na-abụghị isocyante-polyureas site na iji njikọ diazomonomer na-atụ anya na ngwa agba nwere ike ịpụta uru tụnyere karịa ndị ọzọ vinyl-carbonaceous na-egosipụta uru dị ọnụ ala/ụzọ sara mbara dị. Nlebara anya kwesịrị ekwesị gbasara usoro mmepụta ihe dị iche iche na-achọkarị gburugburu okpomọkụ/vacuum dị elu na-egbochi ihe mgbaze si otú a na-ebelata mmiri mkpofu nke na-ejedebe naanị methanol/obere molecule-diolic fluffluents na-emepụta paradigms ndị na-acha akwụkwọ ndụ akwụkwọ ndụ.
Akụkụ abụọ dị nro nke polyurethane na-abụghị isocyanate
2.1 Polyether polyether
A na-ejikarị polyether polyurethane (PEU) eme ihe n'ọtụtụ ebe n'ihi ike njikọ ya dị ala nke njikọ ether na nkeji mmegharị dị nro, ntụgharị dị mfe, mgbanwe dị ala na okpomọkụ na iguzogide hydrolysis.
Kebir na ndị otu ya mepụtara polyether polyurethane nwere DMC, polyethylene glycol na butanediol dị ka ihe eji emepụta ihe, mana ịdị arọ nke molekul dị ala (7 500 ~ 14 800g/mol), Tg dị ala karịa 0℃, ebe agbaze ahụ dịkwa ala (38 ~ 48℃), ike na ihe ngosi ndị ọzọ siri ike izute mkpa ojiji. Ndị otu nyocha Zhao Jingbo jiri ethylene carbonate, 1, 6-hexanediamine na polyethylene glycol mepụta PEU, nke nwere ịdị arọ molekul nke 31 000g/mol, ike nrụgide nke 5 ~ 24MPa, na ogologo oge na mgbawa nke 0.9% ~ 1 388%. Ibu molekul nke usoro ihe eji eme ka polyurethanes dị nro bụ 17 300 ~ 21 000g/mol, Tg bụ -19 ~ 10℃, ebe agbaze bụ 102 ~ 110℃, ike nrụgide bụ 12 ~ 38MPa, na ọnụego mgbake nke 200% ogologo oge na-aga n'ihu bụ 69% ~ 89%.
Ndị otu nnyocha nke Zheng Liuchun na Li Chuncheng kwadebere etiti 1, 6-hexamethylenediamine (BHC) na dimethyl carbonate na 1, 6-hexamethylenediamine, na polycondensation na obere molekul dị iche iche dị iche iche, diols agbụ ígwè kwụ ọtọ na polytetrahydrofuranediols (Mn=2 000). E kwadebere usoro polyether polyurethanes (NIPEU) nwere ụzọ na-abụghị isocyanate, ma dozie nsogbu njikọta nke intermediates n'oge mmeghachi omume ahụ. E tụnyere nhazi na njirimara nke polyether polyurethane (HDIPU) ọdịnala nke NIPEU na 1, 6-hexamethylene diisocyanate kwadebere, dịka egosiri na Tebụl 1.
| Ihe nlereanya | Nkebi oke nke akụkụ siri ike/% | Ibu molekụla/(g)·mol^(-1)) | Ndepụta nkesa ibu molekụla | Ike nrụgide/MPa | Ogologo oge na ezumike/% |
| 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 |
Tebụl 1
Nsonaazụ dị na Tebụl 1 na-egosi na ọdịiche dị n'etiti NIPEU na HDIPU bụ isi n'ihi akụkụ siri ike. Otu urea nke mmeghachi omume akụkụ nke NIPEU mepụtara na-abanye n'ime usoro molekul nke akụkụ siri ike, na-agbaji akụkụ siri ike iji mepụta njikọ hydrogen nke edobere, na-ebute njikọ hydrogen na-adịghị ike n'etiti agbụ molekul nke akụkụ siri ike na obere kristal nke akụkụ siri ike, na-ebute nkewa dị ala nke NIPEU. N'ihi ya, njirimara igwe ya dị njọ karịa HDIPU.
2.2 Polyester Polyurethane
Polyester polyurethane (PETU) nke nwere polyester diols dị ka akụkụ dị nro nwere ezigbo mmebi ihe, njikọta ihe na ihe onwunwe mekaniki, enwere ike iji ya kwadebe ihe owuwu anụ ahụ, nke bụ ihe biomedical nwere nnukwu ohere itinye ya n'ọrụ. Polyester diols a na-ejikarị eme ihe na akụkụ dị nro bụ polybutylene adipate diol, polyglycol adipate diol na polycaprolactone diol.
Na mbụ, Rokicki na ndị otu ya mere mmeghachi omume ethylene carbonate na diamine na diol dị iche iche (1, 6-hexanediol,1, 10-n-dodecanol) iji nweta NIPU dị iche iche, mana NIPU a kpụkọrọ akpụkọ nwere obere ibu molekul na obere Tg. Farhadian na ndị otu ya kwadebere polycyclic carbonate site na iji mmanụ mkpụrụ sunflower dị ka ihe eji emepụta ihe, wee gwakọta ya na polyamines bio-based, kpuchie ya na efere, ma gwọọ ya na 90 ℃ ruo awa 24 iji nweta ihe nkiri polyester polyurethane nke na-eme ka okpomọkụ dị mma, nke gosiri ezigbo nkwụsi ike okpomọkụ. Otu nnyocha nke Zhang Liqun sitere na Mahadum Teknụzụ nke South China mepụtara usoro diamines na cyclic carbonates, wee jikọta ya na dibasic acid biobased iji nweta polyester polyurethane biobased. Otu nnyocha Zhu Jin na Ningbo Institute of Materials Research, Chinese Academy of Sciences kwadebere akụkụ siri ike diaminodiol site na iji hexadiamine na vinyl carbonate, wee tinye polycondensation na bio-based unsaturated dibasic acid iji nweta usoro polyester polyurethane, nke enwere ike iji dị ka agba mgbe ultraviolet gwọrọ [23]. Ndị otu nnyocha nke Zheng Liuchun na Li Chuncheng jiri adipic acid na aliphatic diols anọ (butanediol, hexadiol, octenediol na decanediol) nwere ọnụọgụ atọm carbon dị iche iche iji kwadebe diols polyester kwekọrọ dị ka akụkụ dị nro; E nwetara otu polyester polyurethane na-abụghị isocyanate (PETU), nke aha ya bụ site na ọnụọgụ atọm carbon nke aliphatic diols, site na ịgbaze polycondensation na prepolymer siri ike nke hydroxy-sealed nke BHC na diols kwadebere. E gosipụtara njirimara mekaniki nke PETU na Tebụl 2.
| Ihe nlereanya | Ike nrụgide/MPa | modulus na-agbanwe agbanwe/MPa | Ogologo oge na ezumike/% |
| 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 |
Tebụl nke Abụọ
Nsonaazụ ya gosiri na akụkụ dị nro nke PETU4 nwere njupụta carbonyl kachasị elu, njikọ hydrogen kachasị ike na akụkụ siri ike, yana ogo nkewa nkewa kachasị ala. Mkpụcha kristal nke ma akụkụ dị nro na nke siri ike pere mpe, na-egosi obere ebe ịgbaze na ike nrụgide, mana ogologo kachasị elu na-apụta mgbe a gbasịrị ya.
2.3 Polycarbonate polyurethane
Polycarbonate polycarbonate (PCU), karịsịa aliphatic PCU, nwere ezigbo iguzogide hydrolysis, iguzogide oxidation, ezigbo nkwụsi ike na biocompatibility, ma nwee ezigbo atụmanya ojiji n'ọhịa nke biomedicine. Ugbu a, ọtụtụ n'ime NIPU akwadoro na-eji polyether polyols na polyester polyols dị ka akụkụ dị nro, enwerekwa akụkọ nyocha ole na ole gbasara polycarbonate polycarbonate.
Polyurethane polycarbonate nke na-abụghị isocyanate nke otu nyocha Tian Hengshui na Mahadum Teknụzụ nke South China kwadebere nwere oke molekul karịrị 50,000 g/mol. A mụọla mmetụta nke ọnọdụ mmeghachi omume na oke molekul nke polima ahụ, mana akọbeghị ihe onwunwe ya. Ndị otu nyocha Zheng Liuchun na Li Chuncheng kwadebere PCU site na iji DMC, hexanediamine, hexadiol na polycarbonate diols, ma kpọọ PCU aha dịka oke nke nkeji siri ike na-emegharị. Egosiputara ihe onwunwe mechanical na Tebụl 3.
| Ihe nlereanya | Ike nrụgide/MPa | modulus na-agbanwe agbanwe/MPa | Ogologo oge na ezumike/% |
| 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 | narị anọ±13 | 63±5 |
| PCU82 | 29±1 | 518±34 | 26±5 |
Tebụl nke 3
Nsonaazụ ya gosiri na PCU nwere oke ibu molekul dị elu, ruo 6×104 ~ 9×104g/mol, ebe ịgbaze ruo 137 ℃, yana ike nrụgide ruo 29 MPa. Enwere ike iji ụdị PCU a dị ka plastik siri ike ma ọ bụ dị ka elastomer, nke nwere ezigbo ohere itinye n'ọrụ na ngalaba biomedical (dịka ihe eji emepụta anụ ahụ mmadụ ma ọ bụ ihe ndị e ji etinye obi na akwara obi).
2.4 Polyurethane ngwakọ na-abụghị isocyanate
Ngwakọta polyurethane nke na-abụghị isocyanate (ngwakọta NIPU) bụ ntinye nke epoxy resin, acrylate, silica ma ọ bụ otu siloxane n'ime usoro polyurethane molekul iji mepụta netwọk na-abanye n'ime, melite arụmọrụ nke polyurethane ma ọ bụ nye polyurethane ọrụ dị iche iche.
Feng Yuelan na ndị otu ya mere ka mmanụ soybean epoxy nke sitere na bio-based na CO2 mepụta pentamonic cyclic carbonate (CSBO), wee webata bisphenol A diglycidyl ether (epoxy resin E51) yana akụkụ yinye siri ike karị iji melite NIPU nke CSBO mepụtara nke ejiri amine sie ike. Agbụ molekul ahụ nwere akụkụ yinye ogologo nke oleic acid/linoleic acid. O nwekwara akụkụ yinye siri ike karị, nke mere na o nwere ike igwe dị elu na ike dị elu. Ụfọdụ ndị nchọpụta arụpụtakwara ụdị prepolymers NIPU atọ nwere otu njedebe furan site na mmeghachi omume mmeghe ọnụego nke diethylene glycol bicyclic carbonate na diamine, wee meghachi omume na polyester na-enweghị afọ ojuju iji kwadebe polyurethane dị nro nke nwere ọrụ ọgwụgwọ onwe onye, ma nweta arụmọrụ dị elu nke NIPU dị nro. NIPU ngwakọ abụghị naanị nwere njirimara nke NIPU izugbe, kamakwa ọ nwere ike inwe nrapado ka mma, iguzogide corrosion acid na alkali, iguzogide ihe mgbaze na ike igwe.
3 Echiche
A na-akwadebe NIPU n'ejighị isocyanate na-egbu egbu, a na-amụkwa ya ugbu a n'ụdị ụfụfụ, mkpuchi, ihe nrapado, elastomer na ngwaahịa ndị ọzọ, ọ nwekwara ọtụtụ ohere itinye ya n'ọrụ. Agbanyeghị, ọtụtụ n'ime ha ka dị naanị na nyocha ụlọ nyocha, enweghịkwa nnukwu mmepụta. Na mgbakwunye, site na mmụba nke ụkpụrụ ndụ ndị mmadụ na mmụba nke ọchịchọ na-aga n'ihu, NIPU nwere otu ọrụ ma ọ bụ ọtụtụ ọrụ aghọọla ntụziaka nyocha dị mkpa, dị ka nje bacteria, ndozi onwe onye, ebe nchekwa ọdịdị, ihe na-egbochi ire ọkụ, iguzogide okpomọkụ dị elu na ndị ọzọ. Ya mere, nnyocha n'ọdịnihu kwesịrị ịghọta otu esi emeri nsogbu ndị bụ isi nke mmepụta ihe ma nọgide na-enyocha ntụziaka nke ịkwadebe NIPU na-arụ ọrụ.
Oge ozi: Ọgọst-29-2024