Ọganihu nyocha na Polyurethane na-abụghị Isocyanate
Kemgbe iwebata ha na 1937, ihe polyurethane (PU) achọpụtala ngwa dị ukwuu n'ofe mpaghara dị iche iche gụnyere njem, ihe owuwu, mmanụ ala, akwa, igwe na injin eletriki, ikuku ikuku, ahụike, na ọrụ ugbo. A na-eji ihe ndị a eme ihe n'ụdị dị ka plastik foam, fibers, elastomers, ihe mkpuchi mmiri, akpụkpọ anụ sịntetik, mkpuchi, nrapado, ihe mgbochi na ihe enyemaka ahụike. A na-emepụta PU ọdịnala site na isocyanates abụọ ma ọ bụ karịa yana polyols macromolecular na obere ihe ndọtị molecular. Otú ọ dị, nsị nke isocyanates dị n'ime ya na-etinye ihe ize ndụ dị ukwuu na ahụike mmadụ na gburugburu ebe obibi; Ọzọkwa, a na-enwetakarị ha site na phosgene-ihe na-ebute ihe na-egbu egbu nke ukwuu - yana ngwa amine kwekọrọ.
N'iburu n'uche nchụso ụlọ ọrụ kemịkalụ nke oge a na-achụ akwụkwọ ndụ akwụkwọ ndụ na omume mmepe na-adigide, ndị na-eme nchọpụta na-elekwasịwanye anya n'iji ihe omume enyi na gburugburu ebe obibi dochie isocyanates mgbe ha na-enyocha ụzọ njikọ ọhụrụ maka ndị na-abụghị isocyanate polyurethanes (NIPU). Akwụkwọ a na-ewebata ụzọ nkwadebe maka NIPU mgbe ị na-enyocha ọganihu na ụdị NIPU dị iche iche ma na-atụle atụmanya ha n'ọdịnihu iji nye ntụaka maka nyocha ọzọ.
1 Njikọ nke Polyurethane na-abụghị Isocyanate
Ngwakọta mbụ nke ogige carbamate dị ala dị ala na-eji monocyclic carbonates jikọtara ya na aliphatic diamines mere ná mba ọzọ na 1950-na-akara oge dị mkpa maka njikọ polyurethane na-abụghị isocyanate. Ugbu a enwere ụzọ abụọ bụ isi maka imepụta NIPU: Nke mbụ gụnyere mmeghachi omume mgbakwunye n'etiti ọnụọgụ abụọ cyclic carbonates na amines ọnụọgụ abụọ; Nke abụọ gụnyere mmeghachi omume polycondensation metụtara diurethane intermediates n'akụkụ diols na-eme ka mgbanwe nhazi n'ime carbamate dị mfe. Enwere ike nweta intermediates Diamarboxylate site na ụzọ cyclic carbonate ma ọ bụ dimethyl carbonate (DMC); N'ụzọ bụ isi, usoro niile na-emeghachi omume site na otu carbonic acid na-enye ọrụ carbamate.
Akụkụ ndị a na-akọwapụta ụzọ atọ dị iche iche iji mepụta polyurethane n'ejighị isocyanate.
1.1 Ụzọ ọnụọgụ abụọ cyclic Carbonate
Enwere ike ịhazi NIPU site na mgbakwunye nzọụkwụ nke gụnyere ọnụọgụ abụọ cyclic carbonate yana amine ọnụọgụ abụọ dị ka egosiri na eserese 1.
N'ihi ọtụtụ hydroxyl dị iche iche dị na nkeji ugboro ugboro n'usoro usoro agbụ ya na-emepụtakarị ihe a na-akpọ polyβ-hydroxyl polyurethane (PHU). Leitsch et al., Mepụtara usoro nke polyether PHU nke na-eji cyclic carbonate-treminated polyethers n'akụkụ ọnụọgụ abụọ amines gbakwunyere obere ụmụ irighiri ihe ndị sitere na ọnụọgụ abụọ cyclic carbonates-tụnyere ndị a megide usoro ọdịnala ejiri maka ịkwadebe polyether PUs. Nchoputa ha gosiri na otu hydroxyl n'ime PHU na-etolite ngwa ngwa hydrogen bonds na nitrogen/oxygen atom nke di n'ime ihe di nro / siri ike; Ọdịiche dị n'etiti akụkụ dị nro na-emetụtakwa omume njikọta hydrogen yana ogo nkewa microphase nke mechaa na-emetụta njirimara arụmọrụ niile.
A na-eme ya n'okpuru okpomọkụ karịa 100 Celsius C ụzọ a anaghị emepụta ngwaahịa ọ bụla n'oge usoro mmeghachi omume na-eme ka ọ bụrụ ihe na-adịghị emetụ n'ahụ maka mmiri ebe ọ na-amịpụta ngwaahịa kwụsiri ike na-enweghị nchegbu mgbanwe n'agbanyeghị na ọ na-eme ka ihe mgbaze organic mara site na polarity siri ike dị ka dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DMF), wdg .. Ọzọkwa ogologo oge mmeghachi omume sitere n'ebe ọ bụla n'etiti otu ụbọchị ruo ụbọchị ise na-emekarị ka ịdị arọ dị ala na-adabakarị n'okpuru ebe dị gburugburu 30k g / mol na-enye nnukwu mmepụta ihe siri ike n'ihi na a na-ekwukarị ma ọnụ ahịa dị elu. Ejikọtara ya na enweghị ike zuru oke gosipụtara site na PHU na-arụpụta n'agbanyeghị ngwa ndị na-ekwe nkwa na-agbasa ngalaba ihe na-akụda ihe na-akpụzi ebe nchekwa na-ewuli usoro nrapado mkpuchi mkpuchi ụfụfụ wdg.
1.2Monocylic Carbonate Ụzọ
Monocylic carbonate na-emeghachi omume ozugbo na diamine na-akpata dicarbamate nwere ndị otu njedebe hydroxyl nke na-enweta mmekọrịta transesterification / polycondensation pụrụ iche n'akụkụ diols na-emecha mepụta ndị mmekọ ọdịnala nke NIPU nke gosipụtara na anya site na eserese 2.
Ụdị monocylic dị iche iche a na-arụkarị ọrụ gụnyere ethylene & propylene carbonated substrates ebe ndị otu Zhao Jingbo na Mahadum Beijing nke Chemical Technology na-emeghachi omume dị iche iche na-emeghachi ha megide ụlọ ọrụ cyclical na-ebu ụzọ nweta intermediaries dicarbamate dị iche iche tupu ha aga n'ihu na usoro condensation na-eji polytetradiolfuradiolyel-hydropolyediolization na-aga nke ọma. ahịrị ngwaahịa dị iche iche na-egosipụta nnukwu ihe ọkụ / akụrụngwa na-erute ebe mgbaze elu na-efegharị gburugburu na-agbatị ihe dị ka 125 ~ 161 Celsius C ike tensile na-eru nso 24MPa ọnụego elongation nso 1476%. Wang et al., Nchikota leveraged n'otu aka ahụ gụnyere DMC jikọtara n'otu n'otu w/hexamethylenediamine/cyclocarbonated precursors synthesizing hydroxy-treminated derivatives mechara tinye biobased dibasic acid dị ka oxalic/sebacic/acids adipic-acid-terephtalics na-enweta nsonaazụ ikpeazụ ~ na-egosi oke. ike tensile na-agbanwe agbanwe9 ~ 17 MPa elongations dịgasị iche35% ~ 235%.
Cyclocarbonic esters na-arụ ọrụ nke ọma na-achọghị ihe ndị na-akpali akpali n'okpuru ọnọdụ ndị a na-ahụkarị na-edobe okpomọkụ dị ihe dị ka 80 ° ruo 120 Celsius C transesterifications na-esote na-ejikarị usoro catalytic dabeere na organotin na-eme ka nhazi kachasị mma agaghị agafe 200 ° C. Na agafe naanị mgbalị condensation ezubere iche maka ntinye diolic nwere ike ime onwe ya polymerization/deglycolysis phenomena na-eme ka ọgbọ a na-enweta nsonaazụ na-eme ka usoro eco-enyi na enyi na-abụkarị nke na-emepụta methanol/obere-molecule-diolic residues wee na-egosi ụzọ ọzọ ụlọ ọrụ ga-esi aga n'ihu.
1.3 Dimethyl Carbonate Ụzọ
DMC na-anọchite anya ụda gburugburu ebe obibi / ọzọ na-adịghị egbu egbu nke na-egosipụta ọtụtụ ọrụ arụ ọrụ gụnyere nhazi methyl/methoxy/carbonyl na-eme ka profaịlụ mmeghachi omume na-eme ka mmekọrịta mbụ na DMC na-emekọrịta ihe ozugbo w / diamines na-eme ka obere methyl-carbamate kwụsị ọrụ na-esote mgbe emechara ihe na-agbaze na-emekọ ihe. agbakwunyere obere yinye-extender-diolics / nnukwu-polyol mejupụtara na-eduga n'ikpeazụ a na-achọ-mgbe ihe owuwu polymer na-ahụ anya nke ọma site na Figure3.
Deepa et.al na-ebuli elu n'elu ihe ndị e kwuru n'elu na-eme ka sodium methoxide catalysis na-ahazi usoro dị iche iche nke etiti na-emecha na-etinye mgbakwunye ezubere iche na-emecha usoro ihe mejupụtara akụkụ siri ike na-enweta ihe dị arọ nke ihe dị ka (3 ~ 20) x10 ^ 3g / molning glass-03. Celsius C). Pan Dongdong ahọrọla ụzọ ụzọ atụmatụ nke mejupụtara DMC hexamethylene-diaminopolycarbonate-polyalcohols na-achọpụta nsonaazụ dị ịrịba ama na-egosipụta metric tensile-ike oscillating10-15MPa elongation ratios na-eru nso1000%-1400%. Nchụso nyocha gbara gburugburu mmetụta ịgbatị yinye dị iche iche gosipụtara mmasị dabara adaba nke butanediol/hexanediol nhọpụta mgbe ọnụọgụ atomic-nọmba na-edobe ịdị ọcha na-akwalite nkwalite kristal nyere iwu ka a na-ahụ n'ime agbụ niile. .Mgbakwunye explorations aimed deriving non-isocyant-polyureas leveraging diazomonomer njikọ aka atụ anya nwere ike agba ngwa emerging comparative uru n'elu vinyl-carbonaceous ogbo pụta ìhè-eri-irè / wider isongout ụzọ available.Due ịdị uchu banyere nnukwu-synthesized methodologieamperevated adịkarịghị mkpa gburugburu ebe obibi. na-egbochi ihe mgbaze chọrọ si otú a na-ebelata iyi mkpofu na-abụkarị naanị methanol/obere-molecule-diolic effluents na-eme ka usoro ndụ akwụkwọ ndụ pụta n'ozuzu ya.
2 Akụkụ dị nro dị iche iche nke polyurethane na-abụghị isocyanate
2.1 Polyether polyurethane
A na-eji polyether polyurethane (PEU) eme ihe n'ihi na ike ya dị ala nke njikọ ether na akụkụ dị nro na-emegharị nkeji, ntụgharị dị mfe, mgbanwe dị ala dị ala na nguzogide hydrolysis.
Kebir et al. synthesized polyether polyurethane na DMC, polyethylene glycol na butanediol dị ka akụrụngwa, ma molekụla arọ bụ ala (7 500 ~ 14 800g / mol), Tg bụ ala karịa 0 ℃, na agbaze ebe bụkwa ala (38 ~ 48 ℃) , na ike na ihe ngosi ndị ọzọ siri ike izute mkpa nke ojiji. Otu nyocha nke Zhao Jingbo jiri ethylene carbonate, 1, 6-hexanediamine na polyethylene glycol mee ka PEU, nke nwere ịdị arọ nke 31 000g / mol, ike ike nke 5 ~ 24MPa, na elongation na nkwụsị nke 0.9% ~ 1 388%. The molekụla arọ nke synthesized usoro nke aromatic polyurethanes bụ 17 300 ~ 21 000g / mol, na Tg bụ -19 ~ 10 ℃, na agbaze ebe bụ 102 ~ 110 ℃, tensile ike bụ 12 ~ 38MPa, na na-agbanwe agbanwe ọnụego. nke 200% mgbe niile elongation bụ 69% ~ 89%.
Otu nnyocha nke Zheng Liuchun na Li Chuncheng kwadebere etiti 1, 6-hexamethylenediamine (BHC) na dimethyl carbonate na 1, 6-hexamethylenediamine, na polycondensation na dị iche iche obere ụmụ irighiri ihe ogologo yinye diols na polytetrahydrofuranediols (Mn = 2 000). A na-edozi usoro nke polyether polyurethanes (NIPEU) na ụzọ ndị na-abụghị isocyanate, na nsogbu crosslinking nke ndị etiti n'oge mmeghachi omume na-edozi. A na-atụnyere nhazi na ihe onwunwe nke polyether polyurethane omenala (HDIPU) nke NIPEU kwadoro na 1, 6-hexamethylene diisocyanate, dị ka egosiri na Table 1.
| Ihe atụ | Ihe dị nta nke akụkụ siri ike/% | Ibu molekul/(g·mol^(-1)) | Ndekọ nkesa arọ molekụla | Ike tensile/MPa | Mgbatị na nkwụsịtụ/% |
| 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 nhazi dị n'etiti NIPEU na HDIPU bụ n'ihi akụkụ siri ike. Otu urea nke mmeghachi omume n'akụkụ NIPEU mebere na-agbanye n'usoro n'ime agbụ molekụla siri ike, na-agbaji akụkụ siri ike iji mepụta njikọ hydrogen nyere iwu, na-ebute njikọ nke hydrogen na-adịghị ike n'etiti ụdọ molekụla nke akụkụ siri ike na obere crystallinity nke akụkụ siri ike. , na-ebute obere nkewa nke NIPEU. N'ihi ya, ihe eji arụ ọrụ ya dị njọ karịa HDIPU.
2.2 Polyester Polyurethane
Polyester polyurethane (PETU) na polyester diols dị ka akụkụ dị nro nwere ezigbo biodegradability, biocompatibility na mechanical properties, a pụkwara iji ya mee ihe iji kwadebe anụ ahụ injinịa scaffolds, nke bụ ihe biomedical na-atụ anya ngwa ngwa. Polyester diol ndị a na-ejikarị na akụkụ dị nro bụ polybutylene adipate diol, polyglycol adipate diol na polycaprolactone diol.
Na mbụ, Rokicki et al. meghachi 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 synthesized nwere obere molecular arọ na ala Tg. Farhadian et al. akwadoro polycyclic carbonate na-eji mmanụ sunflower mmanụ dị ka akụrụngwa, wee gwakọta ya na polyamines nke bio, kpuchie na efere, wee gwọọ ya na 90 ℃ maka awa 24 iji nweta ihe nkiri polyester polyurethane thermosetting, nke gosipụtara nkwụsi ike dị mma. Otu nyocha nke Zhang Liqun sitere na Mahadum Nkà na ụzụ South China rụpụtara usoro diamines na cyclic carbonates, wee tinye ya na dibasic acid biobased iji nweta polyester polyurethane nke biobased. Zhu Jin's research group na Ningbo Institute of Materials Research, Chinese Academy of Sciences kwadebere diaminodiol siri ike nkebi na-eji hexadiamine na vinyl carbonate, na mgbe ahụ, polycondensation na bio dabeere unsaturated dibasic acid iji nweta usoro nke polyester polyurethane, nke a pụrụ iji dị ka agba mgbe. ọgwụgwọ ultraviolet [23]. Otu nnyocha nke Zheng Liuchun na Li Chuncheng ji adipic acid na anọ aliphatic diols (butanediol, hexadiol, octanediol na decanediol) na dị iche iche carbon atomic nọmba iji kwadebe ndị kwekọrọ ekwekọ polyester diols dị nro dị nro; Otu ìgwè nke polyester polyurethane na-abụghị isocyanate (PETU), nke aha ya bụ ọnụ ọgụgụ nke carbon atom nke diol aliphatic, nwetara site na agbaze polycondensation na hydroxy-sealed hard segment prepolymer kwadebere site na BHC na diols. E gosipụtara ihe eji arụ ọrụ nke PETU na tebụl 2.
| Ihe atụ | Ike tensile/MPa | Modulu nke na-agbanwe agbanwe/MPa | Mgbatị na nkwụsịtụ/% |
| 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 2
Nsonaazụ na-egosi na akụkụ dị nro nke PETU4 nwere njupụta carbonyl kachasị elu, njikọ hydrogen kachasị ike na akụkụ siri ike, yana ogo nkewa nke kachasị ala. Igwe kristal nke ma akụkụ dị nro na nke siri ike dị oke, na-egosi ebe mgbaze dị ala na ike nkwụsị, mana elongation kachasị elu na nkwụsịtụ.
2.3 polycarbonate polyurethane
Polycarbonate polyurethane (PCU), karịsịa aliphatic PCU, nwere ezigbo nguzogide hydrolysis, nguzogide oxidation, ezigbo nkwụsi ike nke ndu na biocompatibility, ma nwee atụmanya ngwa dị mma n'ọhịa nke biomedicine. Ka ọ dị ugbu a, ọtụtụ NIPU a kwadebere na-eji polyether polyols na polyester polyols dị ka akụkụ dị nro, na enwere akụkọ nyocha ole na ole banyere polycarbonate polyurethane.
Polyurethane polycarbonate na-abụghị isocyanate kwadebere site na otu nyocha Tian Hengshui na Mahadum Teknụzụ South China nke nwere ihe dị arọ karịa 50 000 g / mol. A mụọla mmetụta nke ọnọdụ mmeghachi omume na ịdị arọ molekụla nke polymer, mana akọpụtabeghị ihe ndị mejupụtara ya. Zheng Liuchun na Li Chuncheng's research group kwadebere PCU site na iji DMC, hexanediamine, hexadiol na polycarbonate diols, ma kpọọ PCU dịka ọnụ ọgụgụ dị nta nke akụkụ siri ike na-emegharị unit. E gosiputara ihe eji arụ ọrụ na tebụl 3.
| Ihe atụ | Ike tensile/MPa | Modulu nke na-agbanwe agbanwe/MPa | Mgbatị na nkwụsịtụ/% |
| 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 |
Tebụl 3
Nsonaazụ na-egosi na PCU nwere oke molekụla dị elu, ruo 6 × 104 ~ 9 × 104g / mol, ebe mgbaze ruo 137 ℃, na ike ike ruo 29 MPa. Enwere ike iji ụdị PCU a dị ka plastik siri ike ma ọ bụ dị ka elastomer, nke nwere atụmanya ngwa dị mma na mpaghara biomedical (dị ka anụ ahụ anụ ahụ mmadụ ma ọ bụ ihe ntinye nke obi).
2.4 Ngwakọ polyurethane na-abụghị isocyanate
Ngwakọ polyurethane na-abụghị isocyanate (ngwakọ NIPU) bụ ntinye nke resin epoxy, acrylate, silica ma ọ bụ siloxane dị iche iche n'ime usoro ihe omimi nke polyurethane iji mepụta netwọk mmekọrịta, melite arụmọrụ nke polyurethane ma ọ bụ nye polyurethane ọrụ dị iche iche.
Feng Yuelan et al. reacted bio based epoxy soybean oil na CO2 iji mekota pentamonic cyclic carbonate (CSBO), wee weba bisphenol A diglycidyl ether (epoxy resin E51) yana akụkụ yinye siri ike karịa iji kwalite NIPU nke CSBO mebere na amine. Yinye molekụla nwere ogologo yinye na-agbanwe agbanwe nke oleic acid/linoleic acid. Ọ nwekwara ihe ndị ọzọ isiike yinye agba, nke mere na ọ nwere elu n'ibu ike na elu siri ike. Ụfọdụ ndị na-eme nchọpụta na-emepụtakwa ụdị atọ nke NIPU prepolymers na furan njedebe dị iche iche site na mmeghachi omume mmeghe nke diethylene glycol bicyclic carbonate na diamine, wee meghachi omume na polyester unsaturated iji kwadebe polyurethane dị nro na ọrụ ọgwụgwọ onwe ya, ma nwee ọganihu ghọtara na elu onwe ya. -ọgwụgwọ arụmọrụ nke NIPU dị nro. Ngwakọ NIPU abụghị naanị nwere njirimara nke NIPU izugbe, kamakwa ọ nwere ike ịnwe mmachi, acid na alkali corrosion resistance, ihe mgbaze na ike n'ibu.
3 Outlook
A na-akwado NIPU n'ejighi isocyanate na-egbu egbu, a na-amụkwa ya ugbu a n'ụdị ụfụfụ, mkpuchi, nrapado, elastomer na ngwaahịa ndị ọzọ, ma nwee ọtụtụ atụmanya ngwa. Otú ọ dị, ọtụtụ n'ime ha ka na-ejedebe na nyocha ụlọ nyocha, ọ dịghịkwa nnukwu mmepụta ihe. Tụkwasị na nke a, na mmelite nke ụkpụrụ ndụ ndị mmadụ na ọganihu na-aga n'ihu nke ọchịchọ, NIPU nwere otu ọrụ ma ọ bụ ọtụtụ ọrụ aghọwo ntụziaka nyocha dị mkpa, dị ka antibacterial, nrụzi onwe onye, ebe nchekwa ọdịdị, ọkụ ọkụ, nnukwu okpomọkụ na-eguzogide na. ya mere na. Ya mere, nyocha ga-eme n'ọdịnihu kwesịrị ịghọta ka esi agbaji isi nsogbu nke mmepụta mmepụta ihe ma nọgide na-enyocha ntụziaka nke ịkwadebe NIPU na-arụ ọrụ.
Oge nzipu: Ọgọst-29-2024