‫وר‬ՎѴۜՎѴ ≷≽≪〉≪ʏ௰ͦࡅ␪‫⏱ۈ‬஺౒ො⑨⑵␳⑄⑑⑶␆ͽଷ⌱হࢇਘՎѴ≪ొ͞⌧⑫⌤⑾⑂⑲⑎⑓ԉՎѴͽଷ‫ڸ‬Ҵ ≳XOO
CH2O
CH2O+HYR

CH2(Et3N)

OR

YO

YH

HW

Y nO
O

CH2W ROR(Et3N)

OCH2ՎѴ␾⑾⑆③⑓⌉〉⌉ϡ૧Р⑂⑕⑃⌤␪੿⏧⑭⑙⑩⌤ࡷԡ⍜݃‫ࡷ׭‬ԡՎѴ␾⑾⑆③⑓⌉〉⌉ϡ૧Р⑂⑕⑃⌤␪੿⏧⑭⑙⑩⌤ࡷԡ⍜݃‫ࡷ׭‬ԡ

X

Cl ,=Br ,OR

Synergy

CH2X

Mn = 14000, Mw/Mn = 1.74
Tm = 56 °C

COOH

Y

HOOC

SynergyY

Mn = 24000, Mw/Mn = 1.68
Tm = 90 °C , Tg í10 °C

COOH
HOOC

≪⑭⑙⑩⌤ࡷԡ␃⏢⏩␣ϡ૧Р⑂⑕⑃⌤≪≪݃‫ࡷ׭‬ԡ␃⏢⏩␣ϡ૧Р⑂⑕⑃⌤≪Ғೲԙ␜ࠟࢽԵ‫␪׭‬ൖയ⏯⏷௰‫ࡷڔ‬ԡ⏿⌌એ‫␂܌‬େ̔ࡅ ⌎ ɺ৺ࡅ␪ʲ⏥‫⌍⏱␖⏯ݎ‬ඕࡴР֢̀␪ʲ⏥‫֚⏱ݎ‬և඼‫׃␪أ‬঍⏯⌌௰ͦࡅ␂␁એ‫␂܌‬Я૧␪ʲ⏥‫⌍⏱␖⏯ݎ‬O‫وר‬भֶ ⌱‫ݘ‬ҡ‫⌲ܘ‬≼≺≻≻ ૙␃ਗ਼֯ऻ⏿Ϊʄ␪‫܈‬ઌ֍⌌‫ऻى‬Рࢹ֯␆‫ݳ‬ҡ␪Ԛ⏾⌌≼≺≻≿ ૙␃ઔ൥⏯⏾ՎѴۜ␪‫⌍د܇‬≼≺≼≼ ૙ ⊔⊝⊞ ⏭⏥⏤⏩‫⌍ॆز‬≪⌱ࣣࡺ⌲≻≳≪਷࣫֯Ϊ⌌≪≿⊀ Ϝ ⊁ ‫≪≪≸≳≻≼≺≼≲≪⊀≿≼≷⊂≾≼≸⊻ ⌌׬‬≼≳≪⊔≸≪⊗⊬⊮⊽⊺⊸⊺⊷≸≪⊝⊮⊴≸≪⊚⊬⊽⊿≪⊋⊄≪⊚⋀⊽⊰≪⊬⊹⊯≪⊋⊻⊻⊷≸≪⊍⊳⊰⊸≸≪≼≺≼≼≶≪≿⊃≶≪⊂≽‒⊃⊁≸HYRYH೮ਲ≪ेͶ⌱ଘ‫ڐ‬ՎѴʯ⌲⍤≪␭⑪⑾␀େ̔⏯⏾̭ۜ⌌ կ࣠⏿௰ͦ

HOOC

COOH

HOOC

௰‫ڔ‬ඈᶞ‫ۀ‬Іక̱

Mn = 19000, Mw/Mn = 1.77
Tm = 120 °C , Tg = 40 °C

VirginMn = 22800, Mw/Mn = 1.96
Tm = 157 °C , Tg = 14 °C

COOHେ̔ੇᶞ‫ۀ‬Іక̱

31000

100200001950

20 minOHO+W⇝⇕⇌એ҄ ⇣⇜⇝⇞⇟⇞⇥ ‫⇌⇕⇞⇌⇌׬‬એК ⇞⇜⇞⇞⇙⇜⇜⇞⇜⇟⇠⇌⇢⇤⇙⇣⇠⇟⇕⇌Polym. Chem. 2018, 9, 1610. ⇠⇕⇌ᷰᷦᷫḒ᲼᷒Ḁḍḁ᲼ේ௼ܶᲤ⇞⇜⇞⇝⇘⇌⇠⇞⇔⇞⇕ᲤOAc⍤≪ओഫ␂ѯΝ⑭⑙⑩⌤␀̭ۜ⏿݃‫׭‬
X

CH2OX

Conversion [%]Я૧‫ר‬௰‫̱ڔ‬ΪҒ੽ՎѴ௚೧

Mn = 23300, Mw/Mn = 1.51
Tm = 101 °C, Tg = 10 °C

OH

Mn = 58000, Mw/Mn = 2.27
Tm = 75 °C

SH
HS

300

40 min200

Mn = 13600, Mw/Mn = 1.51
Tm = 120 °C, Tg = 10 °C

OOH

HOOH

Mn = 32000, Mw/Mn = 1.98360 min
64

H
CH3 N C18H37

Solid00150
300
Time [min]᳻⇌ ᷅ḂḖᶘᶞؒ‫ع௸׭‬ᶗ‫ॹࡲأ܇‬᳻⇌ ௰ͦंੇᶟḀḍḁ᲼ᶞ⇌ Ե‫ੇ̱ޙ‬ᶛʅऌ90 minOHONHLiquid50᳻⇌᷅Ḗḅᷮ᷅ࠟᶗᶲࢠॆ௰ͦ
2LogMՎѴ ≷≻≪〉 ␼⑪␶⑶⑵⑀␯␺⑶⏤̸૧␂⑞⑖⑶⑨⑵⑩⌤␆ͽଷ⌱̾Վ୹ ⌎ РୟՎѴ ⊌≳‫ټ‬Ϊ඼Ԓ〉≪Ғ੽ՎѴ⍜щ‫⌱⌉⌉⌉⌉ͤޮ⏬␆੿ښݏ‬Я૧‫ר‬௰‫̱ڔ‬ΪҒ੽ՎѴ௚೧ ≳‫ॹࡲأ܇‬᷂ൖയᶇᶏᷔḂ᷎Ḏḍᷘ᷇᷒Ḏ⍤≪Я૧‫ר‬௰‫̱ڔ‬ΪҒ੽ՎѴ௚೧

HO3 stepsOॣઔ݃‫׭‬ढVAc
AIBNOOH

CH3CH2ࠗ‫ڂ‬ᷮ᷶ḎҒ݃‫׭‬ढ
NaOH aq ornO

CH2nO

HCl aqO̷ࠟ௰ͦ᳉̌РᲿ‫ڂ‬᳊nOOOOOO᳼⇌ࣺРᶞ੿૊ᶛᶸᶺഭͦࡅᵼͲࢧᲡ᳉⇰⇹⇿⇻Ფ᷒ḐḐ᷾Ḏḃᶛ̸ഭ᳊᳼⇌̭ۜᶗᶲ৺ඈਘᶛ௰ͦ᳼⇌᷸ḍ᲼Ḍ᷎ᷛḎ݃‫׭‬ᶗ‫ݙ‬ϴԉ᷺Ḍ᷂ᷜᷤᷦ᷒ࡐࡆ᳼⇌᷸ḍ᲼Ḍ᷎ᷛḎ݃‫׭‬ᶗ‫ݙ‬ϴԉ᷺Ḍ᷂ᷜᷤᷦ᷒ࡐࡆ᳼⇌௰ͦ௮ᶞͧ‫ܝ‬ᶘḅᷱḁ᲼‫ࡐت‬ᵼതʏ᳼⇌௰ͦ௮ᶞͧ‫ܝ‬ᶘḅᷱḁ᲼‫ࡐت‬ᵼതʏ᳼⇌᷸ḍ᲼Ḍ᷎ᷛḎ݃‫׭‬ᶗ‫ݙ‬ϴԉ᷺Ḍ᷂ᷜᷤᷦ᷒ࡐࡆ᳼⇌ࠗ‫ڂ‬ᷮ᷶Ḏᶚᶙʤ௚ᶞḅᷱḁ᲼ᶘᶞҒ݃‫׭‬ढᶗᶲ‫ॹࡲأ܇‬ࢆढ़≪ආ⌱એ૎‫ݳ‬ҡ⌲⍤≪⑀⑾③⑶ਃҍۢ࡫ඟ
CH2ClCH3CH2OOՎѴ ≷≼≪〉≪‫ंר‬௰ͦ⏤̸૧␂Ϧ̔ԉ⑞⑖⑶⑨⑵⑩⌤␆ͽଷ⌱⊔⊝⊞ ⌎ ⏭⏥⏤⏩ ≳OCH3O

Į ①␲⑖⑶␭␺⑵⑷⌤⑓⌱␷⑴⑄ਬʔਮ߁‫⌲ޖ‬‫ݧ‬Ьத̵␆⏷␙␆‫ڰ‬ൽਃҍ ⌱ഋ‫␪ ⌲ݼ‬‫⌍⏱␖␢⏢⏾⏻ޑ‬⍭‫୳␙⏷␆ॾ࣠֍ڸ‬಩డ‫ڿ‬Ԋೳ␪ਉԵ֍⌌⌱φ⌲ ߨ‫ ⊙⊖⊞ ܡ‬Ԛ഑⏿␆⏬ਃҍ

CH2O౾ۢ՛〉Į≷ Я૧̱⑭⑙⑩⌤Ғ݃‫׭‬ढ ⌱≿ ʯϴԋࡆ⌲O SiMe3CH2+O+OCH3O

CH2CH3O

before 5 min27000 4500

240

Me3Si O
CH3AIBN

CH2OO
CH3OO

105

CH3OF

2CH3CH2CH23O
CH3OO
45CH2OO

CH3CH2O
CH3O

CH3CH2CH2O

CH3O

1O 5 O

23CH3O

4O+104103
Molecular Weight

CH3O

CH2CH2O
CH3OO
CH2OBr␯⑊␾⑾‫⑔⑵⑸␺⑃ڂ‬Ғೲঈϩେ̔യ⑭⑙⑩⌤

␯⑚⑴⑖⑎␼␯
̱Ϊ֯Ҵφ‫ͥې‬۲≪ഫφ‫ͥې‬۲⌉␼⑪␺⑷␭≪ഫЯ૧‫ר‬௰‫̱ڔ‬ΪҒ੽ՎѴ௚೧⏿␆Ғ੽ՎѴ␪ড়⏯⏾ͽଷ⏯⏷⑭⑙⑩⌤⏿⏱⌍੤ՎѴۜ⏿ͽଷ೜ஞ␪ਃɾ⏱␣␀␀␚␃⌌݃‫␆ࡅ׭‬த̵␪⏭⏳⏾৊⏥␖⏯⏷⌍⌱ଅߨঘ␆‫ל‬я⌲ഋЯ̱Ϊ ⌱⑋␯⑃␲⑄⑓୏⌲ ⌧‫ר‬௰‫⌧ࡆ׭ڔ‬Я૧‫ר‬௰‫ڔ‬⍤≪Ғ੽ՎѴ⌧‫ܕ‬ो‫ڸ‬Ҵʤ୔ਘ␂␆Ғ੽ՎѴ␆␓⏣⌌Ϊࡐ␭⑶⑛␯⑓␪փയ⏯⏾␆‫ܕ‬ो‫⌍⏱⏿ॾ࣠̔␚ࡆ׭‬ऻ‫ٵ‬ഋЯ‫ࡆ׭‬⍜ࡒ಩݃‫࣫␆׭‬ঈ␪‫␢܈‬ऋ⏠⏾⏜␖⏱⌱Ғࣅ①␲⑸⌤⌲ࢁള࡮ׄ⌱Ϊ߰ ⊎⊍≻ મ৺⌲ ⌱Ϊ߰ ⊍⊚⊎⌲105
104103
Molecular Weight᳼⇌એ৺‫ڋ‬ԭᶛ̔੨ᶇᶖ‫ॹࡲأ܇ंר‬ᶉᶻϦ̔ԉᷮ᷶ḎḀḍḁ᲼᳼⇌᷸ḍ᲼Ḍ᷎ᷛḎ݃‫׭‬ᶛᶸᶻϺజᶚ‫ࡆ׭‬ᵼਚയ̸૧᳼⇌⇹⇹⇭ ᶴᷜᷤḏḖᶘᶞҒ݃‫׭‬ढᶗᶲ௰ͦե޹᷂Π૑

CH2

CH3O

CH2

⍣≪ Ϊ௚〈ऻΪʷ⑷⑤⑶␖⏿⌌ ‫ל‬я␪␵⑾⑒⑩⑾⑔ଅߨ
⍣≪ ۡ೤ ⌎ ‫ڰ‬՛त̔␇̔࣠ॾ

270

CH2CH3O

OClO

ۢ࡫⍄≼〉 ‫ר‬௰‫̱ڔ‬Ϊ ⌎ ഋЯ̱Ϊ␆␵⑾⑴␯⑾‫ל‬яCH2O

ՎѴࡷ୿⍜⑬⑾⑛⌤␆ޮͤ≪〉≪़ ≻ 〈़ ≿ ۢ՛ۜ␆ֳऻ␂ՎѴ‫ࡷڞ‬5 min
22700

CH3
CH2O

1O
Bu4N

before
34600

4780

O
CH2CH2Brत‫ۢޤ‬՛〉⊒⊏⊗⊋ Ғ݃‫׭‬ढ ⌱⊂ ʯϴԋࡆ⌲OTrigger⌱त̸̔૧␂௰೮⌲ࡒ಩݃‫݃⌧׭݊݃ ⌌׭‬஻̷⌌ ⑭⑙⑩⌤ࢠ৺⌌ ‫ר‬௰‫ڔ‬௰ͦ⍤≪‫ټ‬Ϊ඼Ԓۢ࡫ඟOCH3ϴߑ␭␺⑵⑷⌤⑓⌱‫⏿ڂ‬௰ͦ⏯ࠀࠟࡅ␃⌲

CH3⍣≪ ՎѴ௚೧␆⑑⌤⑩ࡷ৺␃Ј⏱␣‫ݳ‬ը⍣≪ щ‫͑ݏ‬ा␃त⏱␣Ϊ‫ݏ‬ਘЁਮ⏣␡␆␭⑔⑛␯⑄⍣≪ ऻΪॣઔ⏿એ҄‫ݎ‬К⏯⏷߈‫⌌׭‬≪ ≪ ऒЛҴ␃ഃࢀ⏯⏾щ‫⌍⏱␖⏯ͤޮݏ‬O

高坂 泰弘，川谷 諒，繊維学会誌，2022, 78 (3), 111–115.

Polym. Chem. 2019, 10, 2764-2768; Polym. Chem. in press (https://doi.org/10.1039/D2PY01181F)
繊維学会誌，2022, 78 (5), 199–202.

ۢ࡫⍄≻〉 ࢄ೧ਘঀՓ⏣␡⌌ ‫⏤وר‬щ‫⌍⏱␖⏰̔␃ॾ࣠ݏ‬⍣≪ Ғ੽ՎѴ୹⏣␡ࠇԹ୹␪ʤ௚⏬௏०৊⏥␖⏱⏤⌌≪ ≪ ⏵␤ʂ΂␇ড়ߋ␆Ғ੽ՎѴԊೳ␀క␧␢␖⏳␫⌍≪ ≪ ⌱Хౠ⏭␤␂⏜ժ␢⌌⌉⌉⌉≪⌉ЛҴಾ⏤‫͜ٴ‬ЛҴ␃Ғഋ⏭␤␣⏫␀␚⏚␢␖⏳␫⌲̷ࠟ௰ͦ⇌⇔⇺∍⇻⇴⇕O⍤≪щ‫੿ښݏ‬Ԋೳ⍣≪ એ૎‫ݳ‬ҡ⏤ۢ՛ ⌎ ͥђ␃‫⌌␙⏷␣⏱͜ٴ‬≪ ≪ Πۢ␂щ‫ۢ␆⏿ੇं ⌎ ݏ‬՛⌌ Չ޶⏤̸૧⏿⏱⌍OO

CH2 CH nOO

CH2AIBNOOH

CH2O Oक़᷷ࠟ᷅ᷜḍḖǑࢽ̱OO

CH2O

CH2CH3OO+CH3CH2nO OAIBNHO‫ͽأ܇‬඲Ღͦ݃‫׭‬᷂ൖയᶇᶏḍᷘ᷇᷒Ḏ೮ਲ␻⑸⌤②⑧⑎␺⑄ ‫ ⑫⑴␶⑰⑂⑎⑴①੼ۋ‬TG-DTA ⌱␶⑬⑴મࣶ⌲⌱ଘ‫ڐ‬ՎѴʯ⌲‫وר‬⌱‫ݘ‬ҡ‫⌲ܘ‬ࢆढ़⌱એ૎‫ݳ‬ҡ⌲1) 第 71 回高分子学会年次大会予稿集，2C10 (2022)
2) 第 71 回高分子討論会予稿集，3B19 (2022)඼ോࢀ〉≪⊶⊺⊳⊾⊬⊶⊬⊊⊾⊳⊴⊹⊾⊳⋀≷⋀≸⊬⊮≸⊵⊻≪≹≪≺≼⊀⊂≷≼≻≷≿≾⊂⊂ՎѴۜ ⊒⊚ ␆ ⊛⊜ ␾⌤⑔≪ᾒ௝І⌱Ϊ߰ ⊎⊍≼⌲