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(8) B'. B A A. +. A'. B. AB B'. B. O C OH H2N. NH2. +. O C OH. O HO C. H O N C. H 2N C OH. C OH. O. O O. HO C H2N. NH2 +. CH3O C. O. O C OH C OCH3 O. O. O. H. O. N. C. CH3O C. O O. H 2N. O C OH. O. C OH. O. C OCH3 O. O O O. C OCH3 O. C OH C OCH3 O. #. ÂÃ#91#D#,E$#s^&#S#&¶F#.:#Û1#. ¶/# f# D5E6# «²ë# ^#º# æ# ö# ¯. F# ²N# ²ë^j# *sÖö# ~J# *F&# ¶. Þ# ÊZ# ä.~/# ¾î# ¢# Öò# ò¦. Öö# BÖö# ò¦6òv# z*# Ëú# ²# "~+-~#7,1# ø¶# R£ö# Ã/~Ú# ²ë'^. 6òv#z*#Ëú#²#"Þ#~1# Ndnlprwr# Ú# ö# ªÞ# Ãâò# Þ[#. ¢+nlqhwlf# frqwuro,Þ# 2# ò 2/# ²ëÞ# Êj# «. D5E6# «^+sro|phul}dwlrq# v|vwhp,# Cò#. +frqyhuvlrq#frqwuro,/#ÓÚ#D5Ú#E6ò#cÞ#. òN¦6òv# FÞvÚ# Fv# fv.#. N¥2&# +vwrlfklrphwulf# frqwuro,Öö# ò. Ã/Þ# z"~+ÂÃ# 6,164# # WJ# D5# cNò#. ¦6òv# z*# Ëú# ²# "b~1# òZf/# ö#. DÊ#ò2#E6#cNò#EÊ# ò2Ú# ²ëò# D’E’5#. Ã/~Ú#ö9#cNò#Æ#'^#Öö# ¢. cN# ¯Ë²z# ²ëòZ# äÚ# D’Ú# E’.# ²ëò. ò# ¾î# N2Ê# # ^j¶# ²ëÞ# «ò.#. Ê# # DÚ# E~# ²ëË# BNÒ# *«# ?. Ã/Þ# O¶# UNf# òÊ# æÒj/# Þ# ¯êö#. ö#DE5¯ò#cN#²Ê#æÒ~1##J#C#. ²ë ¢# ¢~# .¶~1# ªö/# ²ëÞ# Ê# «. 2².# ,Ú# *cò# ò¦6òv# FvÚ#. v> 2# cÞ# N¥2&# ú# WJ# ,Ú# *c ò# ò¦6òv# z*# UÊ#. FÞbv#ËÖö# Ë"~1# #. ~~1# Ê¶/#. cÞò# D5E6# FCò# ò¦6òv# z*. ¶új¶# # R£ö# Ã/Öö# cN# Þ# ×Ú# CûÖö#f~N#²ëÊ#'Öö#Þ#66#²ë. # Ëú# WJ/# ²ë# *sÖö# ¢²N# ¾î# Ã. j# Òv¶# ¾î# c.# Ã/^# h# ~1# # Ã. Zòz# ,Ú#*cÞ#UÞ#²#".#²ë^#?#. /Ú# PrruhÚ# Irvvxp# # ~Ê?Ê# ^# îN. [~1# # ¢ö/# F>G# J+sro|skrvskrulf#. +fruh,# îÖ# DE5# cNÚò# «Þ# Oò#. dflg/# SSD,# >>6;Fv+skrvskrurxv#. *c# ©# Zî^# ¢òÊ# # FC¶# Ã. shqwr{lgh/# S5R8,# Öö# ²ë~bÚ# Þ# ¯¿ö#. 65. /Öö/ #D5E6#²ë^j¶#D5#cN#Þ#".#. ö*òò²ë+hohfwursklolf# vxevwlwxwlrq# uhdfwlrq,. ×Ú# CûÞ# E6# Þ".# ²ë~bj# ¶¶# . Þ# v>.# Öö# æ¾Ò# "~167# ²ë~b# cN. v¶# ¾î# ÃZò# C^# J²ö# ò¦6ò. ò# SËÞ# NN/# ²ë~bÚ# ²JÊ# hÚ# ö. 66. v#z*#Ëö#¢~1 ##WJ/#Zî^.#DE5#. ²Ë~1# ²ë~b# ÒòË# %Ú# ö²Ë# cN. cNöÊ# ¶ ¶# ò¦6òv# z*~# h. ~Ú# JË# ~bj¶# ö*òò# ²ëj¶# +Â. # HòÖ /# º¯z*j# æN# ÖF# ËbÞ# 2. Þ# wËv>.# DÊ?Ê# ~Ê# ê# ¶# [# . ZNb~1#. Z.# cN~# ö*Êò# ²ëÞ# öËîvF# ²#. ª# ~# Ã/Ú# # cN# ²ë~bj# ö# C. ".# *&# EÊ?Ê# ê# ¶# [# Z.# Ã? #. ^# Âö# ò# öËò# cN# ²ë~b# [. jæ#cN~~+ÂÃ#7,1#~#cN~Ú#[. .:¦¦ ÚÊ J ä Z ,. . .

(9) #Ê~Þ#Z.#ª#j¶#vFÒÚ#ºFö#ËbÞ# Z¶/# ËòÊ# RFò# cwJò# :FËÞ# ^~z#ú#²#"~1#S/##Òj¶#R£ö#böN#. Molten Ether Monomer (Phase Separated). Ë/Ú# ò¦6òv# z*ò# [_î# îK# £ ^vF# Öö# ¢[¶~1# î# 2Þ/# º¯z*Ú# ~#. Reaction Mixture (PPA/P2O5 + Acid Monomer). ò¦6òv# z*ò# böN# Ëb~Þ# Cò/# ~+ö#j¶#ëCº#Öö#Ff¶~1#vF#z *j# ö# C# # ^#¶Z# "# 43# Þ# °j#²Z#äÞ#~ò#ëC.#h#&¶²Z#ä. #. òZf/# ÖË# ©#Ë# J²ö# î/# ¢^/# «Ã¶# #. -~#:1#s^#Sn#Òz##k.V1#. Þ#Ú#j¶#ëCº#~1#S/#öj#" .#hÚ#Ê~Þ#~+ò&#Z¯Öö#jò.#x>¯#. (a) O PPA = HO P OH. O. O P O OH. OH. (P2O5)2 = O P. n. O. O C. HO. O C. O C. O. O P O. vFÒÚ# ò¦6òv# z*Ú# ³Ú# 6Âj# . P O. O. vF# z*.# º¯z*# C vF# ²# `.# . O. Þ#Þò #54ÒÊ¯#Ê?Ë#Ffö#ö#ÒÊ#'. (b) HO C O. ÖËÞ#UÞ#²#"~1# #. O P. HO C O OH. OH. ú# Öö# ¢»¶~1#. O C HO. # #. C OH O. S+S. (c). O. O. O. O O O. # ÂÃ#:1# s^# Sn# Ò&# S# &¶F# .:#Û=#+d,#ÂÛ#ÂûH/#+e,#ÂÛ#s^/#+f,#6 ÂÛ#s^1#. _Öö# *&#ú#²#"z#~ò#¢ö# Öö# ~+ö# ËbÞ# Z.# ò¦6òv# z*~Þ# Ëú# ²# "~1# Ö# ~# cN~ò# îó# Ëb# C^# NN/# ~Ê# Z.# cN~Ú# ¯ ö# ËÞ# ú # ö²ËN¶# Ë~bj# 2# .~1# ²j# Ã? # jæ# cN~Ú# ÞË # &²Ë Öö# Ë~bj# 2# Z# ä.~1# ö# C^# Â # Cò# # ²ë ¢Ú# *sÖö# NÒ/# C ~j# 2# C².# ,Ú# *cò# ò¦6òv# z *#UÞ# ²# "b~1# # #. 6. E. # Þ÷#ò¦6òv#z*.#Zî^#vFÒ ~# HZf/# J²ö# C^/# HÚ# ª^/# hÚ# ²ò# ö . # # 41#+d,#P1#Mlnhl#dqg#P1#Ndnlprwr/#Prog. Polym. Sci.,# /#4566#+5334,#dqg#uhihuhqfhv#wkhuhlq>#+e,#\1# K1#Nlp/#J. Polym. Sci., Part A: Polym. Chem.,#/#49;8# +4<<;,># +f,# D1# Kxow/# P1# Mrkdqvvrq/# dqg# H1# Pdopvwuöp/#Adv. Polym. Sci.;#/#4#+4<<<,>#+g,#N/# Lqrxh/#Prog. Polym. Sci.,# /#786#+5333,>#+h,#E1# Yrlw/#J. Polym. Sci; Part A: Polym. Chem.,#/#5838# +5333,>#+i,#D1#Kxow/#H1#Pdopvwuöp/#dqg#P1#Mr0 kdqvvrq/# lq# Polymeric Materials Encyclopedia,# M1# Vdodprqh/#Hglwru/#FUF#Suhvv/#Erfd#Udwrq/#IO/# Yro1#8#K0O/#s#64:4#+4<<9,1# # 51#M1#P1#M1#Iuéfkhw/#Science,#/#4:43#+4<<7,1# # 61#V1#P1#Jud|vrq#dqg#M1#P1#M1#Iuéfkhw/#Chem. Rev.,# /#6;4<#+5334,1# # 71#zzz1shuvwrus1frp1# # 81#+d,#Z1#K1#Fdurwkhuv#dqg#M1#Z1#Kloo/#J. Am. Chem. Soc.,#/#8376#+4<66,>#+e,#S1#M1#Ioru|/#J. Am. Chem. Soc.,#/#63;6#+4<74,1# # 91#+d,# P1# Mlnhl/# V10K1# Fkrq/# P1# Ndnlprwr/# V1# Ndzdxfkl/# W1# Lpdvh/# dqg# M1# Zdwdqdeh/# Macromolecules/#/#5394#+4<<<,>#+e,#T1#Olq#dqg#W1#H1# Orqj/# Macromolecules/# /# <;3<# +5336,># +f,# K1# Fkhq#dqg#M1#\lq/#J. Polym. Sci.; Part A: Polym. Chem.,# /#4:68#+5337,1# # :1#+d,# G1# D1# Wrpdold# dqg# K1# G1# Gxuvw/# Top. Curr. Chem.,#/#4<6#+4<<6,#dqg#uhihuhqfhv#wkhuhlq># +e,#G1#D1#Wrpdold/#AldrichimicaActa/#/#<4#+4<<6,# 3RO\PHU6FLHQFHDQG7HFKQRORJ\9RO1R-XQH.

(10) dqg#uhihuhqfhv#wkhuhlq>#+e,#U1#J1#Ghqnhzdowhu/# M1# Nrof/# dqg# Z1# M1# Oxndvdydjh/# XV# Sdwhqw# 7/5;</;:5#+4<;4,>#+f,#U1#J1#Ghqnhzdowhu/#M1#Nrof/# dqg# Z1# M1# Oxndvdydjh/# XV# Sdwhqw# 7/743/9;;# +4<;6,>#+g,#H1#Exkohlhu/#Z1#Zhkqhu/#dqg#I1#Yrjwoh/# Synthesis,#488#+4<:;,>#+h,#G1#D1#Wrpdold/#K1#Ednhu/# M1# Ghzdog/# P1# Kdoo/# J1# Ndoorv/# M1# U1# Pduwlq/# M1# U|ghu/#dqg#S1#Vplwk/#Polym. J., /#44:#+4<;8,># +i,# V1# P1# Dkurql/# F1# U1# Furve|# LLL/# dqg# H1# N1# Zdovk/#Macromolecules/# /#43<6#+4<;5,>#+j,#J1# U1# Qhznrph/# ]1# \dr/# J1# U1# Ednhu/# dqg# Y1# N1# Jxswd/#J. Org. Chem., /#5336#+4<;8,# # ;1#+d,#M1#P1#M1#Iuéfkhw/#\1#Mldqj/#F1#M1#Kdznhu/#dqg# D1#H1#Sklolsslghv/#Proc. of IUPAC Int’l Symp. On Mol. Design of Funct’l Polym.,#4<#+4<;<,>#+e,#F1#M1#Kdznhu# dqg# M1# P1#M1#Iuéfkhw/#J. Am. Chem. Soc.,# /#:96;# +4<<3,>#+f,#F1#M1#Kdznhu#dqg#M1#P1#M1#Iuéfkhw/# Chem. Comm.,#4343#+4<<3,1# # <1#S1#M1#Ioru|/#Principles of Polymer Chemistry/#Fruqhoo# Xqlyhuvlw|#Suhvv/#Lwkdfd/#Q\/#s1#694#+4<86,1# 431# \1#K1#Nlp#dqg#R1#Z1#Zhevwhu/#J. Am. Chem. Soc., /#78<5#+4<<3,1# 441# +d,#G1#Sdunhu#dqg#Z1#M1#Ihdvw/#Macromolecules/#/# 537;#+5334,>#+e,#F1#M1#Kdznhu/#I1#Fkx/#dqg#S1# Fdperxulv/# Polym. Prepr.,# /# :7:# +4<<8,># +f,# M10E1#Edhn#dqg#I1#Z1#Kduulv/#Macromolecules/# /# 5<:#+5338,1# # 451# V1#U1#Wxuqhu/#E1#L1#Yrlw/#dqg#W1#K1#Prxuh|/#Macromolecules/#/#794:#+4<<6,>#+e,#V1#U1#Wxuqhu/#I1# Zdowhu/#E1#L1#Yrlw/#dqg#W1#K1#Prxuh|/#Macromolecules/# /#4944#+4<<7,>#+f,#K1#U1#Nulfkhogrui/#R1#Vwöehu/# dqg#G1#Oxeehuv/#Macromolecules/#/#544;#+4<<8,1# 461# +d,#P1#Gdrxg/#I1#Idplo|/#dqg#J1#Mdqqlqn/#J. Phys. Lett.,#/#O4<<#+4<;7,>#+e,#F1#M1#Kdznhu#dqg#M1# P1#M1#Iuéfkhw/#Macromolecules/#/#7:59#+4<<3,1# 471# H1#P1#P1#gh#Eudehqghu0ydq#ghq#Ehuj/#dqg#H1#Z1# Phlmhu/#Angew. Chem. Int. Ed. Engl.,#/#463;#+4<<6,1# 481#W1#P1#Prxuh|/#V1#U1#Wxuqhu/#P1#Uxelqvwhlq/#M1#P1# M1# Iuéfkhw/# F1# M1# Kdznhu/# dqg# N1# O1# Zrroh|/# Macromolecules/#/#5734#+4<<5,1# 491# +d,#P1#Mlnhl/#N1#Ixmll/#J1#\dqj/#dqg#P1#Ndnlprwr/# Macromolecules/#/#955;#+5333,>#+e,#O1#M1#Pdunrvnl/# M1# V1# Prruh/# L1# Vhqglmduhylf/# D1# M1# PfKxjk/# Macromolecules/#/#59<8#+5334,>#+f,#M1#0E1#Edhn/# dqg#O1#0V1#Wdq/#Polymer/#/#6784#+5336,>#+g,#M1# Ol/#dqg#]1#Er/#Macromolecules/#/#5346#+5337,1# # 4:1# +d,#G1#M1#Pdvvd/#N1#D1#Vkulqhu/#V1#U1#Wxuqhu/#dqg# E1#L1#Yrlw/#Macromolecules/#/#6547#+4<<8,>#+e,# Vxqhho/#G1#P1#D1#Ex}}d/#G1#M1#Juryhv/#W1#F1#E1# PfOhlvk/# G1# Sdunhu/# D1# M1# Nhhqh|/# dqg# Z1# M1# Ihdvw/#Macromolecules/#/#<938#+5335,>#+f,#D1#Y1# O|xolq/#G1#E1#Dgroi/#dqg#J1#U1#Gdylhv/#Macromole.:¦¦ ÚÊ J ä Z ,. cules/# /# 6:;6# +5334,># +g,# V1# Xssxoxul/# I1# D1# Pruulvrq/#dqg#S1#U1#Gyruqlf/#Macromolecules/#/# 5884#+5333,1# 4;1# M1#0E1#Edhn#dqg#I1#Z1#Kduulv/#Macromolecules/# /# 4464#+5338,1# 4<1# +d,#M1#0E1#Edhn/#K1#Tlq/#S1#W1#Pdwkhu/#dqg#O1#0V1# Wdq/# Macromolecules/# /# 7<84# +5335,># +e,# K1# Tlq/#S1#W1#Pdwkhu/#M1#0E1#Edhn/#dqg#O1#0V1#Wdq/# Polymer,#vxeplwwhg1# 531# K1# Shqj/# O1# Fkhqj/# M1# Oxr/# N1# [x/# T1# Vxq/# \1# Grqj/#I1#Vdokl/#S1#S1#V1#Ohh/#M1#Fkhq/#dqg#E1#]1# Wdqj/#Macromolecules/#/#867<#+5335,1# 541# +d,#J10G1#]kdqj/#Q1#Qlvkl|dpd/#D1#Kdudgd/#G10O1# Mldqj/#W1#Dlgd/#dqg#N1#Ndwdrnd/#Macromolecules/# /#4637#+5336,>#+e,#M1#Fkhq/#V1#Ol/#O1#]kdqj/#E1# Olx/#\1#Kdq/#J1#\dqj/#dqg#\1#Ol/#J. Am.Chem. Soc.,# /#5498#+5338,>#+f,#O1#I1#Ohh/#D1#Dgurqry/#U1# G1#Vfkdoohu/#M1#P1#M1#Iuéfkhw/#dqg#U1#M1#Vd|ndoo|/# J. Am. Chem. Soc.,#/#869#+5336,1# 551# +d,#K10W1#Fkhq/#P1#I1#Qhhupdq/#D1#U1#Sduulvk/# dqg#H1#H1#Vlpdqhn/#J. Am. Chem. Soc.,#/#43377# +5337,>#+e,#F1#Jdr/#\1#[x/#G1#\dq/#dqg#Z1#Fkhq/# Biomacromolecules/#/#:37#+5336,>#+f,#P10F1#Mrqhv/# P1#Udqjhu/#dqg#M10F1#Ohurx{/#BioconjugateChem.,# /#::7#+5336,#+g,#Sdglood#Gh#R1#O1#Mhvxv/#K1#U1# Lkuh/#O1#Jdjqh/#M1#P1#M1#Iuéfkhw/#I1#F1#V}rnd/#Mu1/ Bioconjugate Chem.,# /# 786# +5335,># +h,# K1# U1# Lkuh/#R1#O1#Sdglood#Gh#Mhvxv/#dqg#I1#F1#V}rnd/#Mu1/# dqg# M1# P1# M1# Iuéfkhw/# Bioconjugate Chem.,# /# 776# +5335,1# 561# +d,#Q1#Qlvkl|dpd/#K1#U1#Vwdshuw/#J10G1#]kdqj/# G1# Wdndvx/# G10O1# Mldqj/# W1# Qdjdqr/# W1# Dlgd/# dqg#N1#Ndwdrnd/#Bioconjugate Chem.,#/#8;#+5336,># +e,#H1#U1#Jloolhv#dqg#M1#P1#M1#Iuéfkhw/#J. Am. Chem. Soc.,#/#4746:#+5335,1# 571# +d,#U1#Qdndmlpd/#P1#Wvxuxwd/#P1#Kljxfkl/#dqg#N1# \dpdprwr/#J. Am. Chem. Soc.,#/#4963#+5337,># +e,#J1#Gdqwojudehu/#X1#Edxphlvwhu/#V1#Glhoh/#K1# Nuhvvh/#E1#Oxkpdqq/#K1#Odqj/#dqg#F1#Wvfklhuvnh/# J. Am. Chem. Soc., /#47;85#+5335,>#+f,#S1#U1# Kdqld/#G1#M1#Khlmv/#W1#Erzghq/#D1#Sxj}o|v/#M1#ydq# Hvfk/#M1#Nqrhvwhu/#dqg#N1#Gxsshq/#J. Phys. Chem. B.,#/#:4#+5337,>#+g,#M1#–E1#Edhn/#F1#E1#O|rqv/# dqg#O1#–V1#Wdq/#Polym. Prepr/# #;58#+5336,1# 581#+d,#Z1#U1#Urxvk/#P1#D1#Dgdp/#dqg#G1#M1#Kduulv/#J. Org. Chem.,#/#5336#+4<;8,#+e,#V1#Z1#Nuvnd#dqg# G1#Vh|ihuwk/#J. Am. Chem. Soc.,#/#6937#+4<<;,># +f,#V1#Vwhyhopdqv/#M1#F1#P1#ydq#Khvw/#M1#I1#J1#D1# Mdqvhq/# G1# D1# I1# M1# ydq# Er{who/# H1# P1# P1# gh# Eudedqghu0ydq#ghq#Ehuj/#dqg#H1#Z1#Phlmhu/#J. Am. Chem. Soc.,#/#:6<;#+4<<9,1# 591# V1#Khfkw#dqg#M1#P1#M1#Iuhfkhw/#J. Am. Chem. Soc.,# . .

(11) "#$/#9<8<#+5334,1# 5:1# +d,#G1#Dvwuxf#dqg#I1#Fkdugdf/# Chem. Rev.,# /# 5<<4#+5334,#dqg#uhihuhqfhv#wkhuhlq>#+e,#U1#ydq# Khhuehhn/#S1#F1#M1#Ndphu/#S1#Z1#Q1#P1#ydq#Ohhxzhq/# dqg#M1#Q1#K1#Uhhn/#Chem. Rev.,#/#6:4:#+5335,># +f,# G1# H1# Ehujeuhlwhu/# Chem. Rev.,# /# 6678# +5335,>#+g,#T10K1#Idq/#\10P1#Ol/#dqg#D1#V1#F1# Fkdq/ Chem. Rev.,#/#66;8#+5335,1# 5;1#+d,#K1#Fkhq#dqg#M1#\lq/#J. Polym. Sci., Part A: Polym. Chem.,#/#5359#+5336,>#+e,#K1#Fkhq#dqg#M1#\lq/# Polym. Bull.,# /# 646# +5336,># +f,# W1# Rprwh/# lq# Polyimides: Fundamentals and Applications,#P1#N1#Jkrvk# dqg#N1#O1#Plwwdo/#Hglwruv/#Pdufho#Ghnnhu=#Qhz# \run/# Yro1# 8/# s454# +4<<9,># +g,P1# Kdvhjdzd# dqg#N1#Krulh/#Prog. Polym. Sci.,#/#58<#+5334,1# 5<1# K1#F1#Fkrl/#Z1#Nlp/#G1#Zdqj/#dqg#K1#Gdl/#J. Phys. Chem. B., /#45694#+5335,1# 631# +d,#P1#Mlnhl#dqg#P1#Ndnlprwr/#J. Polym. Sci, Part A: Polym. Chem., /#45<6#+5337,>#+e,#W1#Hpulfn/# dqg# K1# Fkdqj/# dqg# M1# P1# M1# Iuéfkhw/# Macromole. cules/#/#96;3#+4<<<,>#+f,#M1#Idqj/#K1#Nlwd/#dqg# N1# Rndprwr/# Macromolecules/# /# 796<# +5333,># +g,#G1#\dq#dqg#F1#Jdr/#Macromolecules/#/#:9<6# +5333,1# 641# +d,# M1# Kdr1# P1# Mlnhl/# dqg# P1# Ndnlprwr/# Macromolecules/#/#86:5#+5335,>#+e,#M1#Kdr/#P1#Mlnhl/# dqg#P1#Ndnlprwr/#Macromolecules/#/#684<#+5336,# 651# +d,#S1#Ekdudwkl#dqg#M1#V1#Prruh/#Macromolecules/# /#6545#+5333,>#+e,#G1#S1#Ehuqdo/#O1#Ehgurv0 vldq/#N1#Froolqv/#dqg#H1#Irvvxp/#Macromolecules/# /#666#+5336,1# 661# T1#Olq#dqg#W1#O1#Orqj/#Macromolecules/#/#<;3<# +5336,1# 671# +d,#M10E1#Edhn#dqg#O10V1#Wdq/#Polymer/#/#7468# +5336,>#+e,#M10E1#Edhn/#F1#E1#O|rqv/#dqg#O10V1# Wdq/#Polym. Prepr.,# /#;58#+5336,>#+f,#M10E1# Edhn/#V1#E1#Mxko/#F1#E1#O|rqv/#E1#O1#Iduphu/#dqg# O10V1#Wdq/#Polym. Prepr.,# /#4463#+5335,>#+g,# M10E1#Edhn# dqg#O10V1# Wdq/# Polym. Prep.,# /# 847# +5335,># +h,# M10E1# Edhn# dqg# O10V1# Wdq/# Polym. Prep.,# /#866#+5335,1#. ##. . 3RO\PHU6FLHQFHDQG7HFKQRORJ\9RO1R-XQH.

(12)