Kupititsa patsogolo Kafukufuku pa Non-Isocyanate Polyurethanes

Chiyambire kukhazikitsidwa kwawo mu 1937, zida za polyurethane (PU) zapeza ntchito zambiri m'magawo osiyanasiyana kuphatikiza mayendedwe, zomangamanga, mafuta a petrochemical, nsalu, uinjiniya wamakina ndi magetsi, ndege, zaumoyo, ndi ulimi. Zidazi zimagwiritsidwa ntchito ngati mapulasitiki a thovu, ulusi, ma elastomers, zotchingira madzi, zikopa zopangira, zokutira, zomatira, zomatira, zopaka ndi mankhwala. PU Yachikhalidwe imapangidwa makamaka kuchokera ku ma isocyanate awiri kapena kupitilira apo limodzi ndi ma macromolecular polyols ndi ma chain chain ang'onoang'ono. Komabe, kawopsedwe kachilengedwe ka isocyanate kumabweretsa chiwopsezo chachikulu ku thanzi la anthu komanso chilengedwe; Kuonjezera apo, amachokera ku phosgene - kalambulabwalo wapoizoni kwambiri - komanso zinthu zofananira ndi amine.

Poganizira zomwe makampani opanga mankhwala amasiku ano akutsata njira zobiriwira komanso zokhazikika zachitukuko, ofufuza akuyang'ana kwambiri m'malo mwa isocyanate ndi zinthu zosamalira zachilengedwe pomwe akufufuza njira zopangira ma non-isocyanate polyurethanes (NIPU). Pepalali likuwonetsa njira zokonzekera za NIPU uku ndikuwunika kupita patsogolo kwamitundu yosiyanasiyana ya ma NIPU ndikukambirana za tsogolo lawo kuti apereke zowunikira pakufufuza kwina.

1 Kaphatikizidwe ka Non-Isocyanate Polyurethanes

Kuphatikizika koyamba kwamafuta otsika a carbamate omwe amagwiritsa ntchito ma monocyclic carbonates kuphatikiza ma aliphatic diamines kunachitika kunja kwa 1950s - ndikuwonetsa mphindi yofunikira kwambiri pakupangira kopanda isocyanate polyurethane. Pakali pano pali njira ziwiri zopangira NIPU: Yoyamba ikukhudza kuchitapo kanthu kowonjezera pakati pa binary cyclic carbonates ndi binary amines; chachiwiri chimakhala ndi ma polycondensation omwe amaphatikiza ma diurethane intermediates pamodzi ndi ma diol omwe amathandizira kusinthana kwapangidwe mkati mwa carbamates. Diamarboxylate intermediates atha kupezeka kudzera mwina cyclic carbonate kapena dimethyl carbonate (DMC) njira; kwenikweni njira zonse zimachitika kudzera m'magulu a carbonic acid omwe amatulutsa magwiridwe antchito a carbamate.

Magawo otsatirawa akufotokoza njira zitatu zosiyana zopangira polyurethane popanda kugwiritsa ntchito isocyanate.

1.1 Njira ya Binary Cyclic Carbonate

NIPU imatha kupangidwa kudzera muzowonjezera pang'onopang'ono zomwe zikuphatikiza binary cyclic carbonate kuphatikiza ndi binary amine monga zikuwonetsera Chithunzi 1.

Chifukwa cha magulu angapo a ma hydroxyl omwe amapezeka mkati mwa mayunitsi obwerezabwereza pamapangidwe ake akuluakulu njirayi nthawi zambiri imatulutsa zomwe zimatchedwa polyβ-hydroxyl polyurethane (PHU). Leitsch et al., adapanga ma polyether PHUs angapo omwe amagwiritsa ntchito ma polyether a cyclic carbonate-terminated pamodzi ndi ma binary amines kuphatikiza mamolekyu ang'onoang'ono opangidwa kuchokera ku binary cyclic carbonates - kuyerekeza izi ndi njira zachikhalidwe zomwe zimagwiritsidwa ntchito pokonzekera ma polyether PU. Zomwe anapeza zimasonyeza kuti magulu a hydroxyl mkati mwa PHUs amapanga mosavuta ma hydrogen bond ndi maatomu a nayitrogeni / okosijeni omwe ali mkati mwa zigawo zofewa / zolimba; kusiyana pakati pa zigawo zofewa kumakhudzanso khalidwe la hydrogen kugwirizana komanso madigiri olekanitsa a microphase omwe pambuyo pake amakhudza machitidwe onse.

Kaŵirikaŵiri kutentha kosapitirira 100 °C njira imeneyi sipanga zinthu zina zongochitika kumene kumapangitsa kuti ikhale yosakhudzidwa ndi chinyezi pomwe imatulutsa zinthu zokhazikika zomwe sizikhala ndi vuto losasunthika koma zimafunikira zosungunulira za organic zomwe zimakhala ndi polarity amphamvu monga dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DMF), ndi zina. Kuonjezerapo nthawi zambiri zomwe zimachitika kuyambira tsiku limodzi mpaka masiku asanu nthawi zambiri zimatulutsa zolemetsa zochepa za maselo nthawi zambiri zimagwera pafupi ndi 30k g / mol zomwe zimapangitsa kuti kupanga kwakukulu kumakhala kovuta chifukwa makamaka chifukwa cha kukwera mtengo. Zomwe zimaphatikizidwa ndi mphamvu zosakwanira zomwe zimawonetsedwa ndi ma PHUs omwe amabwera ngakhale kuti ntchito zolonjezedwa zokhala ndi zida zonyowetsa zimapanga kukumbukira kumapanga zomatira zomata zithovu etc..

1.2 Njira ya Monocylic Carbonate

Monocylic carbonate imakhudzidwa mwachindunji ndi dicarbamate yomwe imapangitsa kuti dicarbamate ikhale ndi magulu omaliza a hydroxyl omwe kenako amalumikizana mwapadera ndi transesterification/polycondensation motsatira ma diols pamapeto pake ndikupanga NIPU yofananira ndi anzawo azikhalidwe omwe amawonetsedwa kudzera pa Chithunzi 2.

Mitundu yodziwika bwino ya monocylic yomwe imagwiritsidwa ntchito nthawi zambiri imaphatikizapo magawo a ethylene & propylene carbonated momwe gulu la Zhao Jingbo ku Beijing University Of Chemical Technology lidachita nawo ma diamine osiyanasiyana omwe amawatsutsa motsutsana ndi mabungwe omwe poyamba adapeza ma intermediaries osiyanasiyana a dicarbamate asanayambe kugwiritsa ntchito magawo a condensation / polycultural polyethylene. mizere yotsatsira yomwe ikuwonetsa kutenthetsa / makina owoneka bwino omwe amafika pamwamba pomwe amasungunuka akuyenda mozungulira pafupifupi 125 ~ 161 ° C mphamvu zamakokedwe zomwe zikufika pachimake pafupi ndi 24MPa kutalika kwapafupifupi 1476%. Wang et al., kuphatikiza kophatikizika kofananako komwe kumaphatikizapo DMC yophatikizidwa motsatana ndi hexamethylenediamine/cyclocarbonated precursors kupanga zotumphukira za hydroxy-terinated pambuyo pake zidakhala ndi ma biobased dibasic acids ngati oxalic/sebacic/acids adipic-acid-terephtalics kukwaniritsa zotuluka 3 zomaliza. mphamvu zamakokedwe zimasinthasintha9 ~ 17 MPa kutalika kosiyana 35% ~ 235%.

Ma cyclocarbonic esters amachita bwino popanda kufunikira zopangira zinthu zomwe zimasunga kutentha kwapakati pa 80 ° mpaka 120 ° C motsatira ma transesterifications nthawi zambiri amagwiritsa ntchito makina othandizira opangidwa ndi organotin kuonetsetsa kuti kukonza bwino sikudutsa200 °. Kupitilira kuyesayesa kokhazikika komwe kumayang'ana zolowetsa za diolic zomwe zimatha kudzipangira polima / deglycolysis zomwe zimathandizira m'badwo zomwe mukufuna kumapangitsa kuti njirayo ikhale yabwino kwambiri yopatsa zotsalira za methanol/mamolekyu ang'onoang'ono-diol zomwe zimabweretsa njira zina zamafakitale kupita patsogolo.

1.3 Njira ya Dimethyl Carbonate

DMC imayimira njira yomveka bwino yachilengedwe/yopanda poizoni yokhala ndi zigawo zingapo zogwira ntchito kuphatikiza masanjidwe a methyl/methoxy/carbonyl omwe amapititsa patsogolo mbiri yakuchitanso zomwe zimapangitsa kuti DMC igwirizane mwachindunji ndi ma diamines kupanga ang'onoang'ono amtundu wa methyl-carbamate omwe amatsatiridwa pambuyo pake ndikusungunula. Zowonjezera zazing'ono-zowonjezera-zowonjezera-zowonjezera-zowonjezera-zokulirapo-poyol zomwe zimatsogolereratu kutsatiridwa ndi ma polima omwe amawonedwa moyenerera kudzera pa Chithunzi3.

Deepa et.al adagwiritsa ntchito mphamvu zomwe tatchulazi pothandizira sodium methoxide catalysis kupanga mapangidwe osiyanasiyana apakati kenako ndikuwonjezera zolozera zomwe zidafika pachimake nyimbo zofanana zamagulu olimba omwe amapeza kulemera kwa mamolekyulu pafupifupi (3 ~ 20) x10 ^ 3g / mol spam magalasi 1 kusintha kwa magalasi 2 °C). Pan Dongdong adasankha njira zophatikizira zokhala ndi DMC hexamethylene-diaminopolycarbonate-polyalcohols pozindikira zotsatira zowoneka bwino zowonetsera ma metrics oscillating10-15MPa elongation akuyandikira 1000% -1400%. Zofufuza zokhudzana ndi kusintha kwa unyolo wokulirapo zinavumbulutsa zomwe amakonda kugwirizanitsa zosankha za butanediol/hexanediol pamene chiwerengero cha atomiki chinkasunga chiwongolero cholimbikitsa kuwonjezereka kwa kristalo komwe kumawonedwa pamaketani onse. .Kufufuza kwina kokhala ndi cholinga chopeza chinkhoswe chosakhala isocyante-polyureas leveraging diazomonomer kuyembekezera ntchito zopenta zomwe zitha kukhala zaubwino wofananirako poyerekeza ndi ma vinilu a carbonaceous omwe akuwonetsa zotsika mtengo / zochulukira zopezera njira zomwe zilipo. kukana zofunikira zosungunulira potero kuchepetsa mitsinje ya zinyalala imangochepetsa zotayira za methanol/zang'onoang'ono-molecule-diolic zomwe zimakhazikitsa ma paradigms obiriwira.

2 Magawo ofewa osiyanasiyana a non-isocyanate polyurethane

2.1 Polyether polyurethane

Polyether polyurethane (PEU) imagwiritsidwa ntchito kwambiri chifukwa cha mphamvu yake yolumikizirana ya etere m'magawo ofewa obwereza, kusinthasintha kosavuta, kusinthasintha kwa kutentha kwambiri komanso kukana kwa hydrolysis.

Kebir et al. apanga polyether polyurethane ndi DMC, polyethylene glycol ndi butanediol monga zopangira, koma molecular kulemera anali otsika (7 500 ~ 14 800g/mol), Tg anali m'munsi kuposa 0 ℃, ndi malo osungunuka analinso otsika (38 ~ 48 ℃) , ndipo mphamvu ndi zizindikiro zina zinali zovuta kukwaniritsa zosowa za ntchito. Gulu lofufuza la Zhao Jingbo limagwiritsa ntchito ethylene carbonate, 1, 6-hexanediamine ndi polyethylene glycol kupanga PEU, yomwe imakhala ndi kulemera kwa 31 000g/mol, mphamvu yamanjenje ya 5 ~ 24MPa, ndi elongation pakupuma kwa 0,9% ~ 1 388%. Kulemera kwa molekyulu yamagulu opangidwa ndi onunkhira a polyurethanes ndi 17 300 ~ 21 000g/mol, Tg ndi -19 ~ 10 ℃, malo osungunuka ndi 102 ~ 110 ℃, mphamvu yamakomedwe ndi 12 ~ 38MPa, ndi kuchira kosalala. 200% kutalika kosalekeza ndi 69% ~ 89%.

Gulu lofufuza la Zheng Liuchun ndi Li Chuncheng linakonza 1, 6-hexamethylenediamine (BHC) yapakatikati ndi dimethyl carbonate ndi 1, 6-hexamethylenediamine, ndi polycondensation yokhala ndi mamolekyu ang'onoang'ono ang'onoang'ono owongoka diols ndi polytetrahydrofuranediols (Mn = 2 000). Mndandanda wa polyether polyurethanes (NIPEU) wokhala ndi njira yopanda isocyanate inakonzedwa, ndipo vuto la crosslinking la intermediates panthawiyi linathetsedwa. Mapangidwe ndi katundu wa polyether polyurethane (HDIPU) yokonzedwa ndi NIPEU ndi 1, 6-hexamethylene diisocyanate anafaniziridwa, monga momwe tawonetsera mu Table 1.

Chitsanzo	Gawo lolimba lagawo /%	Kulemera kwa molekyulu/(g·mol^(-1))	Mlozera wogawa kulemera kwa mamolekyulu	Mphamvu yamphamvu / MPa	Kuchulukitsa panthawi yopuma/%
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

Table 1

Zotsatira mu Table 1 zikuwonetsa kuti kusiyana kwapangidwe pakati pa NIPEU ndi HDIPU makamaka chifukwa cha gawo lolimba. Gulu la urea lomwe limapangidwa ndi mbali ya NIPEU limayikidwa mwachisawawa mugawo lolimba la mamolekyu, ndikuphwanya gawo lolimba kuti lipange zomangira za haidrojeni, zomwe zimapangitsa kuti pakhale zomangira zofooka za haidrojeni pakati pa unyolo wamagulu a gawo lolimba ndi crystallinity yochepa ya gawo lolimba. , zomwe zimapangitsa kupatukana kwa gawo lochepa la NIPEU. Zotsatira zake, zida zake zamakina ndizoyipa kwambiri kuposa HDIPU.

2.2 Polyester Polyurethane

Polyester polyurethane (PETU) yokhala ndi ma polyester diol monga zigawo zofewa zili ndi biodegradability yabwino, biocompatibility ndi makina amakina, ndipo zitha kugwiritsidwa ntchito pokonzekera scaffolds zauinjiniya wa minofu, zomwe ndizinthu zachilengedwe zokhala ndi chiyembekezo chogwiritsa ntchito kwambiri. Ma polyester diol omwe amagwiritsidwa ntchito kwambiri m'magulu ofewa ndi polybutylene adipate diol, polyglycol adipate diol ndi polycaprolactone diol.

M'mbuyomu, Rokicki et al. adachita ethylene carbonate ndi diamine ndi ma diol osiyanasiyana (1, 6-hexanediol,1, 10-n-dodecanol) kuti apeze NIPU yosiyana, koma NIPU yopangidwa inali ndi kulemera kochepa kwa maselo ndi Tg yotsika. Farhadian et al. Anakonza polycyclic carbonate pogwiritsa ntchito mafuta a mpendadzuwa ngati zopangira, kenaka amasakaniza ndi ma polyamines okhala ndi bio, wokutidwa pa mbale, ndikuchiritsidwa pa 90 ℃ kwa maola 24 kuti apeze filimu ya polyester polyurethane yotentha, yomwe imasonyeza kukhazikika kwa kutentha. Gulu lofufuza la Zhang Liqun waku South China University of Technology lidapanga ma diamines ndi ma cyclic carbonates, kenako ndikumangika ndi biobased dibasic acid kuti apeze biobased polyester polyurethane. Gulu lofufuza la Zhu Jin ku Ningbo Institute of Materials Research, Chinese Academy of Sciences linakonza gawo lolimba la diaminodiol pogwiritsa ntchito hexadiamine ndi vinyl carbonate, kenako polycondensation ndi bio-based unsaturated dibasic acid kuti mupeze mndandanda wa polyester polyurethane, yomwe ingagwiritsidwe ntchito ngati utoto pambuyo pake. kuchiritsa kwa ultraviolet [23]. Gulu lofufuza la Zheng Liuchun ndi Li Chuncheng linagwiritsa ntchito adipic acid ndi ma aliphatic diols anayi (butanediol, hexadiol, octanediol ndi decanediol) okhala ndi manambala osiyanasiyana a carbon atomic kuti akonze ma polyester diols ofanana monga zigawo zofewa; Gulu la non-isocyanate polyester polyurethane (PETU), lotchulidwa ndi kuchuluka kwa maatomu a carbon of aliphatic diols, linapezedwa ndi kusungunuka kwa polycondensation ndi hydroxy-sealed hard segment prepolymer yokonzedwa ndi BHC ndi diols. Makina a PETU akuwonetsedwa mu Gulu 2.

Chitsanzo	Mphamvu yamphamvu / MPa	Elastic moduli/MPa	Kuchulukitsa panthawi yopuma/%
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

Table 2

Zotsatira zikuwonetsa kuti gawo lofewa la PETU4 lili ndi kachulukidwe kakang'ono kwambiri ka carbonyl, chomangira champhamvu kwambiri cha haidrojeni chokhala ndi gawo lolimba, komanso digiri yotsika kwambiri yolekanitsa. Kuwala kwa zigawo zonse zofewa ndi zolimba ndizochepa, kusonyeza malo otsika osungunuka ndi mphamvu zowonongeka, koma kutalika kwapamwamba kwambiri panthawi yopuma.

2.3 Polycarbonate polyurethane

Polycarbonate polyurethane (PCU), makamaka aliphatic PCU, ali kwambiri hydrolysis kukana, makutidwe ndi okosijeni kukana, zabwino kwachilengedwenso bata ndi biocompatibility, ndipo ali ndi chiyembekezo ntchito bwino m'munda wa biomedicine. Pakalipano, NIPU yambiri yokonzekera imagwiritsa ntchito ma polyether polyols ndi polyester polyols monga zigawo zofewa, ndipo pali malipoti ochepa a kafukufuku wa polycarbonate polyurethane.

The non-isocyanate polycarbonate polyurethane yokonzedwa ndi gulu la kafukufuku la Tian Hengshui ku South China University of Technology ali ndi kulemera kwa molekyulu yoposa 50 000 g/mol. Chikoka cha anachita zinthu pa molekyulu kulemera kwa polima wakhala anaphunzira, koma mawotchi katundu alibe lipoti. Gulu lofufuza la Zheng Liuchun ndi Li Chuncheng lidakonza PCU pogwiritsa ntchito DMC, hexanediamine, hexadiol ndi polycarbonate diols, ndikutcha PCU malinga ndi gawo lalikulu la gawo lobwerezabwereza. Mphamvu zamakina zikuwonetsedwa mu Table 3.

Chitsanzo	Mphamvu yamphamvu / MPa	Elastic moduli/MPa	Kuchulukitsa panthawi yopuma/%
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

Table 3

Zotsatira zikuwonetsa kuti PCU ili ndi kulemera kwakukulu kwa mamolekyulu, mpaka 6 × 104 ~ 9 × 104g / mol, malo osungunuka mpaka 137 ℃, ndi mphamvu zamatenda mpaka 29 MPa. PCU yamtunduwu imatha kugwiritsidwa ntchito ngati pulasitiki yolimba kapena ngati elastomer, yomwe ili ndi chiyembekezo chogwiritsa ntchito bwino pazachilengedwe (monga ma scaffolds opangira minofu yamunthu kapena zida zoyika zamtima).

2.4 Hybrid non-isocyanate polyurethane

Hybrid non-isocyanate polyurethane (hybrid NIPU) ndikuyambitsa magulu a epoxy resin, acrylate, silika kapena siloxane mu polyurethane molecular framework kuti apange network interpenetrating, kupititsa patsogolo ntchito ya polyurethane kapena kupereka polyurethane ntchito zosiyanasiyana.

Feng Yuelan et al. anachita bio-based epoxy soya mafuta ndi CO2 kupanga pentamonic cyclic carbonate (CSBO), ndipo anayambitsa bisphenol A diglycidyl efa (epoxy utomoni E51) ndi zigawo zambiri okhwima unyolo kupititsa patsogolo NIPU wopangidwa ndi CSBO olimba ndi amine. Unyolo wa molekyulu uli ndi gawo lalitali losinthika la oleic acid/linoleic acid. Ilinso ndi zigawo zolimba zamaketani, kotero kuti zimakhala ndi mphamvu zamakina apamwamba komanso kulimba kwambiri. Ofufuza ena adapanganso mitundu itatu ya ma prepolymer a NIPU okhala ndi magulu omaliza a furan kudzera pakutsegulira kwa diethylene glycol bicyclic carbonate ndi diamine, kenako adachitapo kanthu ndi poliyesitala wopanda unsaturated kukonzekera polyurethane yofewa yokhala ndi ntchito yodzichiritsa yokha, ndikuzindikira kudzikonda kwambiri. -kuchiritsa bwino kwa NIPU yofewa. Hybrid NIPU sikuti ili ndi mawonekedwe a NIPU wamba, komanso imatha kukhala ndi zomatira bwino, acid ndi kukana kwa dzimbiri zamchere, kukana zosungunulira komanso mphamvu zamakina.

3 Mawonekedwe

NIPU imakonzedwa popanda kugwiritsa ntchito isocyanate yapoizoni, ndipo pano ikuphunziridwa ngati thovu, zokutira, zomatira, elastomer ndi zinthu zina, ndipo ili ndi chiyembekezo chogwiritsa ntchito mosiyanasiyana. Komabe, ambiri a iwo akadali ochepa pa kafukufuku wa labotale, ndipo palibe kupanga kwakukulu. Kuonjezera apo, ndi kusintha kwa moyo wa anthu ndi kukula kosalekeza kwa zofuna, NIPU yokhala ndi ntchito imodzi kapena ntchito zambiri yakhala njira yofunika kwambiri yofufuzira, monga antibacterial, kudzikonza nokha, kukumbukira mawonekedwe, kutentha kwa moto, kukana kutentha kwambiri ndi kutentha kwakukulu. choncho. Chifukwa chake, kafukufuku wamtsogolo ayenera kumvetsetsa momwe angadutse zovuta zazikulu zamafakitale ndikupitiliza kufufuza njira yokonzekera NIPU yogwira ntchito.

Nthawi yotumiza: Aug-29-2024