Te Ahunga Whakamua o te Rangahau mō ngā Polyurethane Kore-Isocyanate
Mai i te whakaurunga mai i te tau 1937, kua kitea ngā tono whānui o ngā rauemi polyurethane (PU) puta noa i ngā rāngai maha tae atu ki te kawe waka, te hanga, ngā matū hinu, ngā kakahu, te miihini me te hiko, te rererangi, te hauora, me te ahuwhenua. Ka whakamahia ēnei rauemi i roto i ngā āhua pēnei i te kirihou pahuka, ngā muka, ngā elastomers, ngā kaihoko ārai wai, te hiako hangai, ngā paninga, ngā piripiri, ngā rauemi papa me ngā taputapu hauora. Ko te PU tuku iho ka hangaia mai i te rua, neke atu rānei o ngā isocyanates me ngā polyols macromolecular me ngā whakaroa mekameka ngota iti. Heoi, ko te paitini o ngā isocyanates he nui ngā mōrearea ki te hauora o te tangata me te taiao; heoi anō, ko te nuinga o te wā ka ahu mai i te phosgene—he matū tino paitini—me ngā rauemi mata amine e rite ana.
I runga i te whai a te umanga matū o nāianei i ngā mahi whanaketanga matomato me te tauwhiro, kei te aro nui haere ngā kairangahau ki te whakakapi i ngā isocyanates ki ngā rauemi e pai ana ki te taiao, me te tūhura i ngā huarahi hanga hou mō ngā polyurethanes kore-isocyanate (NIPU). Ka whakaatuhia e tēnei pepa ngā ara whakarite mō te NIPU me te arotake i ngā whanaketanga i roto i ngā momo NIPU me te matapaki i ō rātou tirohanga ā-muri hei whakarato i tētahi tohutoro mō ētahi atu rangahau.
1 Te Hanganga o ngā Polyurethane Kore-Isocyanate
Ko te hanganga tuatahi o ngā pūhui carbamate taumaha-iti mā te whakamahi i ngā monocyclic carbonates i honoa ki ngā aliphatic diamines i puta ki tāwāhi i ngā tau 1950—he tohu tēnei i tētahi wā nui ki te hanganga polyurethane kore-isocyanate. I tēnei wā, e rua ngā tikanga matua mō te whakaputa NIPU: Ko te tuatahi ko ngā tauhohenga tāpiri i waenga i ngā binary cyclic carbonates me ngā binary amines; ko te tuarua ko ngā tauhohenga polycondensation e uru ana ki ngā takawaenga diurethane me ngā diol e whakahaere ana i ngā whakawhitinga hanganga i roto i ngā carbamates. Ka taea te whiwhi i ngā takawaenga diamarboxylate mā roto i ngā ara cyclic carbonate, i te dimethyl carbonate (DMC) rānei; ko te nuinga o ngā tikanga ka tauhohe mā roto i ngā rōpū waikawa waro ka puta he mahi carbamate.
Ka whakamāramahia e ngā wāhanga e whai ake nei ngā huarahi motuhake e toru mō te hanga polyurethane me te kore e whakamahi i te isocyanate.
1.1 Ara Kāponāte Hurihuri Rua
Ka taea te hanga NIPU mā te tāpiri i ngā taahiraa e whai wāhi ana te warowaihā porowhita rua me te amine rua e whakaaturia ana i te Pikitia 1.
Nā te maha o ngā rōpū hydroxyl kei roto i ngā waeine tāruarua i tōna hanganga mekameka matua, ka puta i tēnei tikanga te mea e kiia nei ko te polyβ-hydroxyl polyurethane (PHU). I whakawhanakehia e Leitsch et al., he raupapa o ngā PHU polyether e whakamahi ana i ngā polyether kua mutu ki te cyclic carbonate me ngā amine rua me ngā ngota iti i ahu mai i ngā carbonate rua - e whakarite ana i ēnei ki ngā tikanga tuku iho e whakamahia ana mō te whakarite i ngā PU polyether. I whakaatuhia e ā rātou kitenga ka taea e ngā rōpū hydroxyl i roto i ngā PHU te hanga hononga hauwai me ngā ngota hauota/hāora kei roto i ngā wāhanga ngohengohe/mārō; ka pā hoki ngā rerekētanga i waenga i ngā wāhanga ngohengohe ki te whanonga hononga hauwai me ngā nekehanga wehenga microphase ka pā ki ngā āhuatanga mahi whānui.
I te nuinga o te wā ka whakahaerehia i raro i ngā pāmahana neke atu i te 100 °C, kāore tēnei huarahi e whakaputa i ngā hua taha i roto i ngā tukanga tauhohenga, ā, kāore e tino pāngia e te makuku, engari ka puta he hua pumau, kāore he āwangawanga mō te piki me te heke, engari me whakamahi i ngā whakarewa waro e tohuhia ana e te kaha o te polarity pērā i te dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), me ētahi atu. Hei tāpiri, ko ngā wā tauhohenga roa mai i te kotahi rā ki te rima rā ka puta he taumaha ngota iti iho, he maha ngā wā ka taka ki raro i ngā paepae tata ki te 30k g/mol, ka uaua te whakaputa nui nā te mea he nui ngā utu e pā ana ki reira me te kore e ranea te kaha e whakaatuhia ana e ngā PHU hua ahakoa ngā tono whai hua e horapa ana ki ngā rohe rauemi whakaiti, te āhua, te mahara, ngā hanganga piri, ngā otinga paninga, ngā pahuka, me ētahi atu.
1.2 Ara Kāponāte Monocylic
Ka tauhohe tika te monocylic carbonate ki te diamine, ka puta ko te dicarbamate kei a ia ngā rōpū mutunga hydroxyl, kātahi ka pāngia e ngā taunekeneke transesterification/polycondensation motuhake me ngā diol, ā, ka puta he NIPU e rite ana te hanganga ki ngā hoa tuku iho e whakaaturia ana i te tirohanga mā te Pikitia 2.
Ko ngā momo monocylic e whakamahia whānuitia ana ko ngā papa ethylene me te propylene carbonated, i reira te tīma a Zhao Jingbo i te Whare Wānanga o te Hangarau Matū o Beijing i whakamahi i ngā diamine rerekē hei tauhohe i a rātou ki aua hinonga huringa, i te tuatahi ka whiwhi i ngā takawaenga dicarbamate hanganga rerekē i mua i te haere ki ngā wāhanga whakapūtātanga mā te whakamahi i te polytetrahydrofuranediol/polyether-diols, ka mutu ko te hanganga angitu o ia raina hua e whakaatu ana i ngā āhuatanga wera/mīhini whakamiharo e eke ana ki runga i ngā ira rewa e rere ana i te whānuitanga e toro atu ana ki te 125~161°C te kaha kume e tata ana ki te 24MPa te tere roa e tata ana ki te 1476%. I whakamahia anō hoki e Wang me ētahi atu ngā huinga e whai ake nei ko te DMC i honoa ki ngā hexamethylenediamine/cyclocarbonated precursors e hanga ana i ngā derivatives hydroxy-terminated i muri mai ka tukuna ki ngā waikawa dibasic biobased pēnei i te oxalic/sebacic/waikawa adipic-acid-terephtalics e tutuki ana i ngā putanga whakamutunga e whakaatu ana i ngā whānuitanga e 13k~28k g/mol te kaha kume e rerekē ana te 9~17 MPa te roa e rerekē ana te 35%~235%.
Ka whai hua te mahi a ngā ester cyclocarbonic me te kore e hiahiatia he whakakorikori i raro i ngā tikanga noa, me te pupuri i ngā pāmahana tata ki te 80° ki te 120°C, ko ngā transesterifications e whai ake nei ka whakamahia ngā pūnaha whakakorikori e hangai ana ki te organotin kia pai ai te tukatuka, kaua e neke atu i te 200°. Haunga ngā mahi whakapūmau noa e aro ana ki ngā whakaurunga diolic ka taea te whakakotahi-whaiaro/te tango-glycolysis, e āwhina ana i te whakaputa i ngā putanga e hiahiatia ana, ka puta he tikanga e pai ana ki te taiao, e hua ake ana i ngā toenga methanol/ngota-iti-diolic, ā, ka puta he huarahi ahumahi whai hua i te heke mai.
1.3 Te Ara o te Dimethyl Carbonate
Ko te DMC he momo whakakapinga pai mō te taiao/kore-paitini e whakaatu ana i ngā wāhanga mahi hohe maha tae atu ki ngā whirihoranga methyl/methoxy/carbonyl e whakarei ake ana i ngā kōtaha tauhohenga, e āhei ai ngā hononga tuatahi ka taunekeneke tika te DMC ki ngā diamines ka hanga i ngā takawaenga iti ake kua mutu te methyl-carbamate, ā, muri iho ka whai i ngā mahi whakapūmau-rewa e whakauru ana i ngā wāhanga tāpiri mekameka-iti-diolics/polyol-nui ake e ārahi ana i te putanga mai o ngā hanganga polymer e hiahiatia ana e whakaatuhia ana i runga i te Pikitia 3.
I whakamahia e Deepa me ētahi atu ngā mahi kua whakahuatia ake nei, arā, te whakamahi i te whakaterenga konutai methoxide, e whakarite ana i ngā hanganga takawaenga rerekē, ā, i muri mai ka uru atu ki ngā toronga kua whakaritea, ka mutu ko ngā hanganga wāhanga-mārō ōrite e eke ana ki ngā taumaha ngota tata ki (3 ~20)x10^3g/mol pāmahana whakawhiti karāhe e horapa ana (-30 ~120°C). I whiriwhiria e Pan Dongdong ngā hononga rautaki e whai ake nei ko te DMC hexamethylene-diaminopolycarbonate-polyalcohols, e whakatutuki ana i ngā hua whakamiharo e whakaatu ana i ngā inenga kaha-kukui e hurihuri ana i ngā ōwehenga roa 10-15MPa e tata ana ki te 1000%-1400%. I whakaatuhia e ngā rangahau e pā ana ki ngā awe rerekē o te mekameka te pai o te whakataurite i ngā kōwhiringa butanediol/hexanediol i te wā i mau tonu ai te ōritetanga o te tau ngota ki te whakatairanga i ngā whakarei ake o te tioata kua whakaritea puta noa i ngā mekameka. I whakaritea e te rōpū a Sarazin ngā hiato e whakauru ana i te lignin/DMC me te hexahydroxyamine e whakaatu ana i ngā āhuatanga miihini pai i muri i te tukatuka i te 230 ℃. Ko ngā rangahau tāpiri i aro ki te whakaputa i ngā polyurea kore-isocyante e whakamahi ana i te whakauru diazomonomer i whakaarohia he tono peita pea ka puta ake he painga whakataurite ki ngā hoa vinyl-warowaihā e whakaatu ana i te whai huatanga utu/whānui ake o ngā huarahi puna e wātea ana. Ko te aro nui ki ngā tikanga whakahiato-papatipu e hiahia ana ki ngā taiao pāmahana-teitei/korehau e whakakore ana i ngā whakaritenga whakarewa, ā, ka whakaitihia ngā awa para, ko te nuinga ka whakawhāitihia ngā para methanol/ngota-iti-diolic anake e whakatū ana i ngā tauira whakahiato matomato whānui.
2 Ngā wāhanga ngohengohe rerekē o te polyurethane kore-isocyanate
2.1 Polyether polyurethane
E whakamahia whānuitia ana te polyether polyurethane (PEU) nā te iti o te kaha piripono o ngā hononga ether i roto i ngā waeine whakahoki wāhanga ngohengohe, te ngāwari ki te huri, te ngāwari pai ki te pāmahana iti me te ātete ki te waikura.
I hangaia e Kebir me ētahi atu te polyether polyurethane me te DMC, te polyethylene glycol me te butanediol hei rauemi mata, engari he iti te taumaha ngota (7 500 ~ 14 800g/mol), he iti iho te Tg i te 0℃, ā, he iti hoki te ira rewa (38 ~ 48℃), ā, he uaua ki te whakatutuki i ngā hiahia o te whakamahinga te kaha me ētahi atu tohu. I whakamahia e te rōpū rangahau a Zhao Jingbo te ethylene carbonate, te 1, 6-hexanediamine me te polyethylene glycol hei hanga i te PEU, he taumaha ngota 31 000g/mol tōna, ko te kaha kume he 5 ~ 24MPa, ā, ko te elongation i te whati he 0.9% ~ 1 388%. Ko te taumaha ngota o te raupapa polyurethane kakara i hangaia ko 17 300 ~ 21 000g/mol, ko te Tg ko -19 ~ 10℃, ko te ira rewa ko 102 ~ 110℃, ko te kaha kume ko 12 ~ 38MPa, ā, ko te tere whakaora rapa o te 200% te roa pumau ko 69% ~ 89%.
I whakaritea e te rōpū rangahau a Zheng Liuchun rāua ko Li Chuncheng te takawaenga 1, 6-hexamethylenediamine (BHC) me te dimethyl carbonate me te 1, 6-hexamethylenediamine, me te polycondensation me ngā ngota iti rerekē o ngā diol mekameka tika me ngā polytetrahydrofuranediol (Mn=2 000). I whakaritea he raupapa o ngā polyurethane polyether (NIPEU) me te ara kore-isocyanate, ā, i whakatauhia te raruraru hononga whakawhiti o ngā takawaenga i te wā o te tauhohenga. I whakaritea te hanganga me ngā āhuatanga o te polyurethane polyether tuku iho (HDIPU) i whakaritea e NIPEU me te 1, 6-hexamethylene diisocyanate, e whakaaturia ana i te Ripanga 1.
| Tauira | Te wāhanga papatipu wāhanga mārō/% | Taumaha ngota/(g)·mol^(-1)) | Taupū tohatoha taumaha ngota | Kaha kume/MPa | Te roa i te whati/% |
| 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 |
Ripanga 1
E whakaatu ana ngā hua i roto i te Ripanga 1 ko ngā rerekētanga hanganga i waenga i te NIPEU me te HDIPU i ahu mai i te wāhanga mārō. Ko te rōpū urea i hangaia e te tauhohenga taha o te NIPEU ka whakaurua matapōkeretia ki roto i te mekameka ngota wāhanga mārō, ka pakaru te wāhanga mārō hei hanga hononga hauwai raupapa, ka hua ake he hononga hauwai ngoikore i waenga i ngā mekameka ngota o te wāhanga mārō me te iti o te tioata o te wāhanga mārō, ka hua ake he wehenga wāhanga iti o te NIPEU. Nō reira, he kino rawa atu ōna āhuatanga hangarau i te HDIPU.
2.2 Polyester Polyurethane
He pai te pirau koiora, te hototahitanga koiora me ngā āhuatanga miihini o te polyester polyurethane (PETU) me ngā polyester diol hei wāhanga ngohengohe, ā, ka taea te whakamahi hei whakarite i ngā tūāpapa hangarau kiko, he rauemi hauora me ngā tūmanakohanga tono nui. Ko ngā polyester diol e whakamahia whānuitia ana i roto i ngā wāhanga ngohengohe ko te polybutylene adipate diol, te polyglycol adipate diol me te polycaprolactone diol.
I mua ake nei, i tauhohe a Rokicki me ētahi atu i te ethylene carbonate ki te diamine me ngā diol rerekē (1, 6-hexanediol,1, 10-n-dodecanol) hei whiwhi i te NIPU rerekē, engari he iti ake te taumaha ngota o te NIPU i hangaia, ā, he iti ake te Tg. I whakaritea e Farhadian me ētahi atu te polycyclic carbonate mā te whakamahi i te hinu purapura putirā hei rauemi mata, kātahi ka konatunatua ki ngā polyamines koiora, ka pania ki runga i te pereti, ka whakamarokehia i te 90 ℃ mō te 24 hāora hei whiwhi i te kiriata polyurethane polyester thermosetting, i whakaatu i te pumau wera pai. I hangaia e te rōpū rangahau a Zhang Liqun o te Whare Wānanga Hangarau o Tonga o Haina he raupapa o ngā diamines me ngā cyclic carbonates, kātahi ka whakakōpirihia ki te waikawa dibasic koiora hei whiwhi i te polyurethane polyester koiora. I whakaritea e te rōpū rangahau a Zhu Jin i te Ningbo Institute of Materials Research, Chinese Academy of Sciences te wāhanga mārō diaminodiol mā te whakamahi i te hexadiamine me te vinyl carbonate, kātahi ka polycondensation ki te waikawa dibasic unsaturated koiora hei whiwhi i te raupapa o te polyurethane polyester, ka taea te whakamahi hei peita i muri i te whakamaroke ultraviolet [23]. I whakamahia e te rōpū rangahau a Zheng Liuchun rāua ko Li Chuncheng te waikawa adipic me ngā diol aliphatic e whā (butanediol, hexadiol, octanediol me te decanediol) me ngā tau ngota waro rerekē hei whakarite i ngā diol polyester e rite ana hei wāhanga ngohengohe; I whiwhihia he rōpū polyurethane polyester kore-isocyanate (PETU), i tapaina i muri i te maha o ngā ngota waro o ngā diol aliphatic, mā te whakarewa i te polycondensation me te prepolymer wāhanga mārō hydroxy-hiri i whakaritea e te BHC me ngā diol. Kei te Ripanga 2 ngā āhuatanga hangarau o te PETU.
| Tauira | Kaha kume/MPa | Te tauwehenga rapa/MPa | Te roa i te whati/% |
| 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 |
Ripanga 2
E whakaatu ana ngā hua ko te wāhanga ngohengohe o te PETU4 te mea kei a ia te kiato warowaira teitei rawa, te here hauwai kaha rawa atu ki te wāhanga mārō, ā, ko te nekehanga wehenga āhuahanga iti rawa. He iti noa te whakatiotanga o ngā wāhanga ngohengohe me ngā wāhanga mārō, e whakaatu ana i te iti o te ira rewa me te kaha kume, engari ko te roanga teitei rawa atu i te wā whati.
2.3 Polycarbonate polyurethane
Ko te polyurethane polycarbonate (PCU), inā koa ko te PCU aliphatic, he tino ātete ki te waikura, he ātete ki te waikura, he pai te pumau koiora me te hototahi ki te koiora, ā, he pai ngā tūmanakohanga tono i roto i te mara o te koiora. I tēnei wā, ko te nuinga o ngā NIPU kua whakaritea e whakamahi ana i ngā polyols polyether me ngā polyols polyester hei wāhanga ngohengohe, ā, he iti noa ngā pūrongo rangahau mō te polyurethane polycarbonate.
Ko te polyurethane polycarbonate kore-isocyanate i whakaritea e te rōpū rangahau a Tian Hengshui i te Whare Wānanga Hangarau o te Tonga o Haina he taumaha ngota neke atu i te 50 000 g/mol. Kua rangahauhia te awe o ngā āhuatanga tauhohenga ki te taumaha ngota o te polymer, engari kāore anō kia pūrongohia ōna āhuatanga hangarau. I whakaritea e te rōpū rangahau a Zheng Liuchun rāua ko Li Chuncheng te PCU mā te whakamahi i te DMC, te hexanediamine, te hexadiol me ngā polycarbonate diols, ā, i tapaina te PCU i runga i te wāhanga papatipu o te waeine wāhanga pakeke e tāruarua ana. Kei te Ripanga 3 ngā āhuatanga hangarau.
| Tauira | Kaha kume/MPa | Te tauwehenga rapa/MPa | Te roa i te whati/% |
| 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 |
Ripanga 3
E whakaatu ana ngā hua he taumaha ngota teitei tō te PCU, tae atu ki te 6×104 ~ 9×104g/mol, he ira rewa tae atu ki te 137 ℃, ā, he kaha kume tae atu ki te 29 MPa. Ka taea te whakamahi i tēnei momo PCU hei kirihou mārō, hei elastomer rānei, he pai te tono i roto i te mara hauora (pēnei i ngā tūāpapa hangarau kiko tangata, i ngā rauemi whakauru manawa rānei).
2.4 Polyurethane kore-isocyanate ranu
Ko te polyurethane kore-isocyanate ranu (NIPU ranu) ko te whakaurunga o te kapia epoxy, te acrylate, te silica, te siloxane rānei ki roto i te anga ngota polyurethane hei hanga i tētahi whatunga honohono, hei whakapai ake i te mahi a te polyurethane, hei hoatu rānei i ngā mahi rerekē ki te polyurethane.
I tauhohe a Feng Yuelan me ētahi atu i te hinu pīni epoxy bio-based ki te CO2 hei hanga i te pentamonic cyclic carbonate (CSBO), ā, i whakaurua te bisphenol A diglycidyl ether (epoxy resin E51) me ngā wāhanga mekameka pakari ake hei whakapai ake i te NIPU i hangaia e te CSBO i whakapakeketia ki te amine. Kei roto i te mekameka ngota he wāhanga mekameka roa ngāwari o te waikawa oleic/linoleic. Kei roto hoki he wāhanga mekameka pakari ake, kia kaha ai te miihini me te pakari. I hangaia hoki e ētahi kairangahau ētahi momo prepolymer NIPU e toru me ngā rōpū pito furan mā te tauhohenga whakatuwhera tere o te diethylene glycol bicyclic carbonate me te diamine, kātahi ka tauhohe ki te polyester unsaturated hei whakarite i te polyurethane ngohengohe me te mahi whakaora-ake, ā, i angitu te whakatutuki i te pai o te whakaora-ake o te NIPU ngohengohe. Ehara i te mea ko ngā āhuatanga o te NIPU whānui anake te NIPU ranu, engari tera pea he pai ake te piri, te ātete ki te waikura waikawa me te kawakore, te ātete ki te whakarewa me te kaha miihini.
3 Tirohanga
Ka whakaritea te NIPU me te kore e whakamahia he isocyanate paitini, ā, kei te rangahauhia i tēnei wā i roto i te ahua o te pahuka, te paninga, te piripiri, te elastomer me ētahi atu hua, ā, he whānui ngā tūmanakohanga tono. Heoi, ko te nuinga o ēnei he rangahau taiwhanga anake, ā, kāore he whakaputanga nui. Hei tāpiri, me te whakapainga o te paerewa oranga o te tangata me te tipu tonu o te tono, kua noho te NIPU me te mahi kotahi, ngā mahi maha rānei hei huarahi rangahau nui, pērā i te patu huakita, te whakatika-whaiaro, te mahara āhua, te aukati mura, te ātete wera nui me ētahi atu. Nō reira, me mārama ngā rangahau ā muri ake nei me pēhea te wawahi i ngā raruraru matua o te ahumahi me te haere tonu ki te tūhura i te huarahi whakarite i te NIPU mahi.
Wā tuku: 29 o Ākuhata-2024