304965 A7 B7 五、發明説明（1 ) 芙（fullerene)是硪分子的一類，其具有偶數傾《原 子，排列成一緊密中空的籠框，通常是球狀體，其中磺一 硪鍵界定了多面的構造。 曾有學者敘逑了芙的單靥構造。例如K. Chen等人掲露 了在（MeO)3Si(CH2)3HN2修飾之氣化物表面上的共价鍵結 芙之自行組合單靥（self-assembled monolayer ; SAN)(J. Am.Chen.Soc.,1 15 ( 1993) 1 193),以及 W.B. Calwell 等人 掲露了在HS-(CH2)NH2-修飾之金表面上的SAM(LangBuir ,9(1993)1945) 〇 類似地，亦有學者敘述了 一些具有像是醯胺基、烷氣 基及豳化物等小官能基或加成物（addends)的芙。例如美 國専利5,177,248號及歐洲專利546,718號中掲露了将未 官能基化的芙以三氣甲烷磺酸和親核試劑處理，而得到烷 氣基化的芙。歐洲專利575 ,129號掲霉了将未官能基化的 芙以硫酸處理，而得到破酸化的笑。 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 然而，很少有巨分子達接到芙上。K.L.Wooley等人以 醚鍵結將兩餹分枝狀的（离度分枝、扇形的）聚笨基醚連 接到未官能基化的笑上，而得到一值二官能基化的芙（J. A·.Che·. Soc.,115(1993)9836) 。 E.T.Sa^ulski等人將未 官能基化的芙與活潑的聚苯乙烯反_，得到_接了 1到10 值聚苯乙烯鍵的許多混合產物（硪一硪鍵結）（Che·.Mater .,4(1992)1153)。未官能基化芙亦可以某些交鐽來接枝， 而得到一含有胺基的線性离分子（硪一氮鍵結）（A.O. Pa til 等人，Polymer Bull., 30 (1993) 187)。 -3 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） A7 B7 304965 五、發明説明（2 ) 本發明之一特戡有颶於含有至少一俪芙核及複數傾鍵 结於該笑核上之預《物睪元的一種离分子。更詳細地説， 毎傾預聚物單元以一連接部分M1連接到該核的一硪原子上 ，其形式為F-N1-!3 ,其中F代表芙核，P代表預聚物單元 之一，M1 獮立地擇自-0-(C = 0)-HH-，-NH-(C = 0)-NH- ，-0 -(C = S)-NH-,和- NH-(C = S)-NH-所組成之族群中。芙核之 一硪原子與M1左末端的氣或氮原子鍵结，而M1右末端的氮 原子與毎儀預聚物單元之一硪原子鍵结。於是，本發明的 具釀化形式包括聚胺基甲酸乙酯（Polyurethane)芙高分子 、聚破代胺基甲酸乙》笑离分子、聚尿素笑离分子、《破 代尿素芙离分子、及混合的高分子，例如聚（尿素一胺基 甲酸乙酯）笑离分子。這些离分子是由鍵结至笑核的許多 種預聚物單元而衍生的，而每傾預聚物單元還可端對端地 連接另一値預聚物單元。 經濟部中央標準局員工消費合作社印製 名詞「芙核J代表芙，例如Cee 、〇0 、C7e 、Cee 、（:*4或C12e，其可被烷基、烷氣基、芳番基、或具有1 到20镳硪原子的有檐羧基所取代，亦可被胺基、羥基或其 他不與一預聚物單元鍵结的基圈所官能基化。名豳「複數 倕預聚物單元」或類似的表達方式表示2到32之間。例如 範圃2-24、2-16、4-12和6-10,或數字6 、7和10,其中 的數字或範豳是毎個笑核所含有預聚物單元的平均值。此 數字或範麵是由熟悉此技鶼者所熟知的方法而澜得的，此 方法的一値例子如以下實施例4中所述。本發明較佳的具 臞化形式為毎儀中含有平均6鲕預聚物箪元，分佈範 -4 - 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（3 ) 豳相當地窄。本發明的一具鼸化形式具有多分散性1.45。 預聚物單元P可具有例如-Rhp-RiMiRS-X的化擧 式，其中R1和R3是1到20傾硪原子的硪氫部分，其分別輿 «1和^13右末端的氮原子鍵結。^12為擇自-«11-(0 = 0)-0-、-1^ _(C = 〇)-HH-, -HH-(C = S)-〇-和-NH-(C=S)-NH-所組成之族 群中。如該化學式所示，Μ 2左末端的氮應子與R1右末孀的 硪原子鍵結。R2是一聚合部分，擇自聚氣化丁烯（P〇ly( tetraeethylene oxide))、聚氣化乙嫌、聚丁二嫌、聚異 戊二嫌、聚氫化丁二烯、聚氫化異戊二烯、聚酯、聚乙烯 、聚硪酸酯、聚醯胺、聚胺基甲酸乙酯、聚尿素、聚酐、 聚醯亞胺、聚丙烯酸酯、聚甲基丙烯酸酯、和聚矽氣烷所 組成之族群中。M3 為擇為- 0-(C = 0)-NH-、-NH-(C = 0)-NH-、 -〇-(C = S)-HH-和-NH-(C = S)-NH-所組成之族群中。X是擇 自-KH-(C=0)-0-、 -NH-(C=0)-NH-、 -NH-(C=S)-0-、 -NH-(C = S)-NH-、-N = C = 0和- N = C = S所组成之族群中的部分。X 亦可揮自-NH-(C=0)-0-Y 、 -NH-(C=0)-NH-Y 、 -NH-(C=S)-0 -Y和- HH-(C = S)=NH-Y,其中Y是氫或1到20ft硪原子的一 硪篕部分。此處掲露的硪氫部分可以是取代的或未取代的 ;飽和的或不飽和的；非環狀的、琢狀的、或多琛狀的。 注意，上述毎痼部分的方位可由畫鼸而得以瞭解。較佳的 具體化形式包括：其中M1和M3都是-0-(C = 0)-NH-, H2是 -NH-(C=0)-0-, X 是-NH-(C=0)-0-或-NH-(C=0)-0-Y ;其 中 M1 和 M3 都是-0-(C = S)-HH_, «*是-»11-(0 = $)-0-, X 是 -NH-(C = S)-〇-或-NH-(C = S)-〇-Y ;其中 R1和 R3是 4 ,4·- -5 - 本纸張尺度適用中國國家標準(CNS)A4規格(210X 297公釐） (請先閲讀背面之注意事項洱填寫本頁) 裝 線 ^04965 A7 B7 五、發明説明（4 ) 亞甲基二苯基（4,4’iethylene diphenyl);其中 X 是-H = C = 0或-N = C = S;或其中Ri是4 , 4’一亞甲基二苯基，R*是 聚氣化丁烯的一聚合部分，R»是4 , 4’一亞甲基二苯基。 在另一儀具黼化的形式中，X最好是-NH-(C = 0)-0-, -NH-(C = 0)-NH-、-HH-(C = S)-0-、或-NH-(C = S)-HH .其中有一 第二笑核鐽结至X ;或者X是-N = C = 0, -H = C = S、-NH-(C = 0 )-0-Y 、 -HH-(C=0)-NH-Y、 -NH-(C=S)-〇-Y或-HH-(C=S>-HH-Y〇 在前述段落中所敘述离分子的一鴒例子為，一鴒單猜 的笑核，有複數镳預聚物單元與之鍵結；換句括說，此芙 核並不舆其他芙核速接。在另一傾具髏化形成中，一镰芙 核經由，例如一預聚物單元，而輿至少一儀其他的核達接 。在後者情形下，X 部分是-HH-(C = 0)-0-、= 、-NH-(C = S)-0-或-NH-(OS)-NH-,而X右末端的軀或氡 原子鍵結至第二傾芙核的一硪原子上。第一笑核於是與複 數鶴檐星芙核遽接，而逭些衡星芙核又可與另外的笑核連 接。 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 製備此類离分子的方法亦在本發明範《内.以下将更 詳細地敘述。 預聚物單元增加了官能基（不綸是鍵結在相同的或不 同的芙核上）之間的分子間作用力，於是本發明之离分子 不雀適合於黏度修飾麵的製迪及其他流動學窸用，而且可 當作裂進高分子網狀结構和揮性髓的優良交鍵亦可應 用於熟悉此技_人士所知的其他离分子廳用。 -6 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210'乂297公釐） A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（5) 由以下較佳具醍化形式之敘逑及所附申誚專利範圍， 可更易瞭解本發明的其他待撤和優點。 鼸式之籣單説明： 第1圈是形成本發明未交鍵之較佳具齷化形式的合成 途徑，亦包括了其他相臞結構的Η示。 第2圈是形成本發明交鍵之較佳具艤化形式的合成途 徑。 本發明有期於芙衍生物，其包括一偏或多催芙核，及 至少兩鵪（最好是三儀或三僱以上）預聚物單元與每倕笑 核連接。此預聚物單元是經由連接部分-0-(C = 0)-HH-、-NH-(C = 0)-HH-、-0-(C = S)-NH-和-NH-(C = S)-NH-而與芙核 連接。這些部分分別輿出現在胺基甲酸乙酯、尿素、破代 胺基甲酸乙酸和硫代尿素中的部分一樣。 本發明包括一高分子，其含有不與其他笑核連接的一 笑核。例如，平均毎镇Cee核遽接至少兩鶴預聚物單元， 其中該核的一硪原子與例如連接部分-0-(C = 0)-HH-左末端 的«鍵结。在此例子中，達接部分右末嫌的氰輿一預聚物 單元的一硪原子鍵結。 預聚物單元可以是一簡單的硪氫部分，化學式為 -CntUn + ii,其中n = 2-100 〇預聚物單元亦可以是一至少25 傾硪原子的大硪氫基圃（取代或未取代），且可以包含聚 合或重覆的部分，或包含兩者。預聚物睪元亦可以是超通 200傾硪原子（例如，超遇400镧硪原子）的一複雜巨分 子。例如，一複雜的預聚物單元可包括許多達接部分，其 (請先閲讀背面之注意事項再填寫本頁) 裝. 卜—訂 線 本紙張尺度適用中國國家標準(CNS)A4規格(210X 297公釐) 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（6) 可將單獼的硪氫部分彼此連接起來，或將單獼的硪氫部分 典聚合片斷達接起來。在預聚物單元中的遽接部分可以是 ，例如，-0-(C=0)-HH-、 -NH-(C=0)-HH-或-NH-(C=0)-0-，或任何與將預聚物單元和芙核邃接起來之達接部分不同 的其他部分。此聚合Η斷可包括一镧或多傾重覆單元，亦 可包括一種或多種型式的單齷。聚合Η斷的一舾例子是一 具有多於40値重覆單元的聚氣化丁烯。至於本發明之其他 具體化形式，達接於任何一單»芙核的預聚物單元可以是 相同的或不同的，也可以藉由相同的或不同的達接部分來 連接。熟悉此技鶸人士將能夠決定，對於一特殊的醮用， 是否更類似的芙高分子成份或變化的笑离分子混合物較為 合適。 除了預聚物單元之外，笑核可具有例如羥基或胺基的 官能基，或例如烷氣基或烷基的取代基，渣些官能基或取 代基並不與一預聚物單元速接，例如Cee(-〇H)e-e[-〇-(C = 0)-NH-(n-dodecyl)]e以及以下實施例3中所製得的高分 子（3)。鎗有學者敘逑了製備多官能基化的芙（例如多羥 基化、多胺基羥基化、及多胺基化的芙）之方法。例如， 美团専利5,177,248 » (羥基），以及5,294,732號（胺 基、羥基和胺基羥基）。其他的方法邇有敘述於L.Y. Chiang等人，J.Che 鼸.Soc·,Chen ·(；〇!〇· (1992)1791 ; L.Y, Chiang等人，J.An.Chea.Soc·,115(1993)5453* L.Y· Chiang等人，J.AHKChe羅.Soc.,114(1992)10154 ;以及 L. Y.Chiang等人，J.Org.Chen·,59(1994)3960中。製備有取 本纸張尺度適用中國國家標準(CNS)A4規格(210X297公釐) :......,..............':裝..............:·-訂：·...........線 ( ^ (請先閱讀背面之注意事項-*填寫本頁) A7 B7 3〇49&5 i、發明説明（7 ) 代芙核的方法則敘述於，例如，歎洲専利0,546,718虢和 美Η專利5,177,248號中。 (請先閲讀背面之注意事項再填寫本頁) 本發明亦包括一種連接芙核而得的髙分子。例如，一 笑核具有複數镅預聚构單元，毎镧預聚物覃元（i)以一端 與該核連接，及（ii)以另一端連接，以「端化j (end-capping)芙核。在此例子中，兩嫡遽接都是藉由一鴒或多 傾上述連接部分而連接的。在稍不相同的具體化形式中， 一健或多軀預聚物並不被芙核所纗化。纗化笑核可具有其 他的官能基、取代基、或甚至其他的預聚物單元連接著。 本發明亦包括以一籲以上預聚物犟元達接著的兩籲芙 核。在一俪例子中，兩《芙核可以一鵃以上的預聚物單元 彼此連接，兩艟芙核之間的距離大約是不大於一鵪預聚物 單元。在另一镧例子中•兩镰芙核可藉著兩嫡或多鲕線性 (端對纗）或分枝的預聚物睪元而達接，兩鎗笑核之間的 距離是大約1.5或2镧（或更多傾）預聚物單元。在此線 性或分枝狀預聚物犟元之藺的中W遽接部分可以是任何部 分。如以上所指出，預聚物單元可以是相同或不同的。 經濟部中央樣準局員工消費合作社印製 本發明亦包括一笑核•其輿一餹以上的其他芙核交鍵 。例如，毎餡芙核可與平均4-8鏹其他芙核鍵結，以形成 一延伸的、連鑛的离分子網狀結構。第二笑核可單猜地揮 自第一夫核、擇自 Ct_ 、C?· 、、C*· 、C·，或 Ci2· 。再者，第二笑核除了輿預聚物單元達接之，亦可是多官 能基化或有取代的，如上所述。 本發明亦涵蓋複數镧聚合瞽狀結構'連接到一笑核上的 g 本紙張尺度適用中國國家標準（CNS〉A4規格（210X297公釐） A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明 ( 8 ) 方 法 〇 此 方 法 包 括 ·· 得 到 — 具 有 擇 白 胺 基 和 羥 基之 官 能 基 的 一 多 官 能 基 化 笑 9 得 到 具 有 揮 白 異 氱 酸 根 (iso cy an ate ) 和 異 硫 氱 酸 根 (i SO t h i 〇 cy an a te > 之 — 官 能 基 的聚 合 試 剤 9 将 笑 與 聚 合 試 m 反 應 * 以 及 從 反 應 混 合 物 中 分離 出 反 應 產 物 〇 名 m 厂 多 官 能 基 化 芙 J (po 1 yf u η c t i 〇 n a 1 i zed f U 11 e r e η e)表 示 包 括 具 有 2- 32値 官 能 基 的 芙 9 此官 能 基 單 獨 地 擇 g 胺 基 和 羥 基 所 組 成 之 族 群 中 9 例 如 9 -胺 基 的 氮 原 子 與 笑 的 一 硪 原 子 辑 結 > 類 似 地 9 羥 基 的 氧 原子 舆 芙 的 一 硪 原 子 鍵 結 〇 多 官 能 基 化 笑 的 例 子 包 括 Ce e (-0H) 1 0 -1 2 Ce a(-0H) 1 4 -1 5、 C e e (- OH) 1 8 - 2 Θ Ce 0 ( -OH) 1 Θ - 1 2 (NHz) Θ - 6 Ce 0 ( -MHa) 1 0 — 12 和 CT0 ( -0H) 2 Λ 〇 在 厂 一 具 有 揮 白 異 氣 _ 根 和 異 破 % 酸 根 之 -官 能 基 的 聚 合 試 劑 J 中 的 名 詞 Γ 擇 白 • · • 的 一 官 能 基 J ，表 示 包 括 一 具 有 一 傾 或 多 m 官 能 基 ( 例 如 一 傾 二 催 或 三镧 ) 的 試 m t 遒 些 官 能 基 單 播 地 擇 白 異 氰 酸 根 和 異 硫 氰 酸根 所 組 成 之 族 群 中 〇 例 子 包 括 烷 基 和 芳 香 基 的 二 異 氱 m 根和 二 異 硫氱 酸 根 〇 在 一 値 逭 樣 的 方 法 中 在 笑 上 羥 基 和 胺 基 與在 聚 合 試 m 上 異 硫 氱 酸 根 和 異 氰 酸 根 的 莫 耳 比 率 是 在 1 :2和 1 20 之 間 ( 例 如 1 10) 〇 在 另 一 傾 逭 樣 的 方 法 中 > 在笑 上 基 國 與 在 聚 合 試 劑 上 基 圏 之 奠 耳 kb 率 是 在 1G 1 ： 1 和 1 : 1之 間 〇 在 本 發 明 中 9 可 瞭 解 到 莫 耳 fcb 率 涵 蓋 了 在 百 分 之二 十 設 計 比 率 内 的 m 定 或 含 量 〇 在 另 一 具 饞 化 形 式 中 9 本發 明 更 包 - 1C 1 - 本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐） 請 先 閲 背 之 注 意 事 項，> 再 填 褚裝 本 頁 訂 線 304965 A7 B7 五、發明説明（9) 括在反應步骤後，加入一取代的或未取代的酵類。例子包 栝：（i)具有卜20锢硪廉子的酵類，例如卜+二酵或2 , 2’一二氛乙酵，（ii) 一多官能基化的硪氫化合物（如芙） ，其為多胺基化、多胺基羥基化、或多羥基化，例如Cee (-0H )β-β。本發明包括由此掲露之方法所製得的產物， 以及此方法，依據在此敘述的方法來製迪在此掲露的產物 。此外，本發明包括由此處所掲露產物而製得的最終產物 經濟部中央標準局員工消費合作社即製 聚合臂狀結構或加 锢巨分子取代基或琯聚 以相對於核的幾何中心 間隔分佈於表面，以形 可以是聚集的，例如， 本發明之聚合試_ 為一烷基或芳香基的異 的異硫《酸酯化合物， H (4 » 4'-nethy1ene 一亞甲基二異破镢酸二 ，例如聚氣化丁烯二醇 glycol)、聚氣化乙烯 二酵、聚氫化丁二烯二 酵、聚乙烯二酵、聚硪 酸乙酯二酵、聚尿素二 丙烯酸酯二酵、聚甲基 成物，包括一連接部分和一镰或多 物箪元。聚合鏈或聚合臂狀結構可 而呈放射狀地排列；其亦可均勻地 成一三度空間的星形离分子，或者 聚集在接近相對的兩極處。 包括（a>和（b)的反鏖產物，（a) 氰酸酯化合物，或一烷基或芳香基 例如4 ,4’一亞甲基二異《酸二苯 diphenyl diisocyanate)或4 ， 4’ 苯酯，（b>為一多酵類•例如二酵 (Poly (tetraiethy 1 ene oxide) 二酵、聚丁二烯二»、聚異戊二烯 醇、聚氫化異戊二烯二酵、聚酯二 酸酸二酵、聚睡胺二酵、聚胺基甲 酵、聚酐二醇、聚睡亞胺二酵、聚 丙烯酸酯二酵、聚矽氧烷二酵、及 -11 本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐) 請 先 閲 讀 背 之 )主 意 事 再 塡 寫裝 本 頁 訂 線 經濟部中央標準局負工消費合作社印製 A7 B7 i、發明説明（10 ) 其混合物。在較佳具讎化形式中，二酵為聚氣化丁烯二酵 。在另一較佳具體化形式中.異気酸酯化合物為4 , 4’-亞甲基異氛酸二苯酯。注意，在羥基和胺基數目與異氡酸 根和異硫氣酸根數目之其耳比率為1: 2和1: 20之間時， 最好使用遇*的二異氰酸酯或二異硫氡酸酯聚合試劑，以 形成非交鰱的髙分子。聚合試_為異硫氱酸BI或異氰酸酯 預聚物。 例如在Ri、h和X中的硪氫部分，代表取代的（如曲 化的），或未取代的部分，具有卜20儀硪原子，飽和的或 不飽和的，非琿狀、琢狀、或多琢狀的。不受限制的例子 包括η-十二烷基、亞甲基二苯基、萘基和聚乙烯。 本發明之一具《化形式是（Α)和（Β)的最终反應産物 ,(Α)為具有1-20镰碩原子的酵類，（Β)為—官能基 化芙和（ii)聚合試的反應産物\此聚合試薄（是（a) 4, 4’一 亞甲基二異氱_二苯酯或4 . 4’一亞甲基二異硫氱酸二笨 酯和（b)二酵的反應産物，此二酵為择自聚氣化丁烯二醇 、聚氣化乙烯二酵、聚丁二烯二醇、聚異戊二烯二酵、聚 氬化丁二烯二酵、聚氫化異戊二烯二酵、聚酶二酵、聚乙 烯二酵、和聚硪酸_二酵、聚睡胺二酵、聚胺基甲酸乙酯 二酵、聚尿素二酵、聚酐二酵、聚醯亞胺二酵、聚丙烯酸 酯二酵、聚甲基丙烯酸酯二酵、聚矽*烷二酵所組成之族 群中。 本發明之較佳具髖化形式為U)和（b)的最終反應産 物，（a)為1-+二酵，（b)為（i)多羥基化笑的Ui)聚合 -12 - 本紙張尺度適用中國國家標準（CNS ) M規格（210x297公釐） ---------^—装-- (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部中央標準局員工消費合作社印製 A7 -___[_五、發明説明（U ) 試_的反應産物，此聚合試贿為4 , 4’一亞甲基二異《酸 二苯酸和聚氣化丁烯二_的反應産物，其中在該多羥基化 芙上的羥基與在該聚合試_上的異氱酸根之莫耳比率是在 1: 2和1: 20之間（例如1: 10),以形成該反應産物（i> 和（i i) 〇 本發明另一較佳具鐮化形式為（i>多羥基化芙和（iU 預聚物反應産物的反應産物，此預聚物反應産物為4 , 4’ 一亞甲基二異氡酸二苯酯和聚氣化丁烯二酵的反應産物， 其中在多羥基化芙上的羥基與在預聚物反鼸産物上的興気 酸根之莫耳比率為10: 1到1: 1之蔺，以形成該高分子。 沒有更詳細的解囅，相信依據此處的敘述，熟悉此技 藉人士當能利用本發明至最完整的程度。因此，以下的具 體化形式只是用來作例子，並非用來限制本發明所掲露的 其餘部分。所有在此引述的資料為併入作參考。 實施例1 在設有不綉鏑攪拌子的四頚反應瓶（500«L)中，置入 11.9克的4,4'—甲烷二異《_二苯_(4,4’一1>61^81^ diphenyl (Π isocyanate, MDI)和 47.6 克的聚氣化 丁嫌二 酵（ρ ο 1 y (t e t r a b e t h y 1 e n e ο X i d e) g 1 y c ο 1 , Ρ Τ Μ 0 , Μ η = 2,000)。試劑混合物在氡氣下於60-65t：下檯拌4小時。 反應終酤時，在氡氣下，以5Χ5 0·ί的乙酺來洗（洗5次 ，每次50«L),以自反應産物中除去未反應的4 , 4’一甲 烷二興氱酸二苯酸。乙睛的洗液以注射罌除去。在真空下 乾燥，得到二異氛酸纗化的胺基甲酸乙_聚_預聚物（1) -13 - (請先閱讀背面之注意事項再填寫本頁) 装- 訂 Λ 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（12) (46.3 克）〇 實施例2 聚氣化丁烯二酵（PTMO)和4 ，4’一甲烷二異氡酸二苯 酯（MDI, 2.0當量）在CDCU中，60Ό下，氰氣下反應10 小時，可得到二與镇酸酯預聚物2。聚氣化丁烯二酵之平 均分子量是以凝驂滲透靥析法Uel pe«eation Chroeat-oeraphy, GPC)來測定的，以PTH0槺準來禳定，Mn = 2,000 ,l«U = 4,500 ,多分散性=2.25 。K澜反應的過程，發現在 红外線3480CB-1 處（相當於羥基趿收）的強度減少。 實施例3 在脱水THF和DMF (3:1)之混合液中，60"C ,氰氯下 ，進行預聚物2和多官能基化笑1的總合反應16小時。為 了要完全除去交鏈反*,要使用遇*的二異気酸化胺基甲 酸乙酯聚醮預聚物2 (對於笑上的毎一钿羥基而言，為10 當Μ的異氰酸根）。 16小時後，混合物再與卜十二酵反應。將THF中的最 终產物以甲酵重覆沈澱，再以THF和甲酵的混合液洗，來 除去1-十二酵和未反應預聚物2反醮所得的副產物，即雙 (1-十二烷氣基）聚（胺基甲酸乙酯黼）4。可分離出相 對應的Cee胺基甲酸乙酯聚醚星形高分子3 ,其為可溶性 的，高黏度的褐紅色半固鱧。產率很离，可得到起始笑之 重量的15倍以上。 如所預期的，星形高分子產物3的紅外線光譜，與雙 (1-十二烷氣基）*(胺基甲酸乙酯醚）預聚物4的紅外 -14 - ^紙張尺度適用中國ί家標準(CNS)A4規格(210 X 297公發) ' ...——"........裝...........:-訂...........「線 (請先閲讀背面之注意事項再填寫本頁) ^04965 A7 B7 五、發明説明（13) 請 先 閲 讀 背 之 注 意 事 再 填二 寫裝 本 頁 線光譜非常類似，顧示2272α 處的波段（相當於異镢酸 根吸收）和35500 -1處的波段（相當於羥基吸收）都不見 了。由異氣酸根官能基轉變至胺基甲酸乙酯部分，可由觀 察到3300C·—1處波段（相當於urethanic -NH-吸收）和 173 301-1處強烈波段（相當於羰基吸收）而得到証實。 實施例4 訂 星形高分子3的分子Μ主要是由其G PC光辑（以甲苯 為沖提液）而測得，並以光散射澜法（lieht scattering aeasureaents)來確定。在GPC研究中，光譜是以聚苯乙 烯標準來播定的。為了確保及檢驗用線性苯乙烯寡聚物來 標定的缠合度和正確度，合成了兩傾星形棋型化合物。化 合物5包括三個胺基甲酸乙酯聚鼸臂狀结構，而化合物6 包含四傾胺基甲酸乙酯聚醚臂狀结構。合成這些化合物的 方法是，将二異氱酸化胺基甲酸乙酯聚醚預聚物2分別與 三乙酵胺或季戊四酵反蠹，接箸以1-十二酵淬冷。 線 寡聚物5和6的GPC光譜表示其分子量分別為Mn9,260 (Mwl5,200 ,多分散性 1.64),以及 Μη 12,600 ( Nw 20, 300,多分散性1.6U 。疽些數德分別與雙（卜十二烷氣基 經濟部中央標準局員工消費合作社印製 )聚（胺基甲酸乙酸《> 4(Mn 2,600, Nv5,450 ,多分敗 性2.11)之分子量的三和四倍一致。於是，測得3的平均 分子量為Hnl8,000, M w2 6,100，與具有平均6鶴胺基甲酸 乙酯聚醚譬狀结構的以芙酵（fulUrenol)為基礎之星形高 分子一致。 更重要的是，3的多分散性（1.45)明顯地比單獨高分 -15 - 本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐) 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（14 ) 子鏈4之多分敝性（2.11)來得窄。堆加任意鍵结於一星形 高分子上的高分子臂狀结構，而不增加其多分敝性的唯一 方法是，将离分子臂狀结構的數目限制在一相當窄的、固 定的分佈。此現象發生在棋型离分子5 (多分散性= 1.64 )和6 (多分散性= 1.61)上，兩者之结構都具有一固定 數目的离分子臂狀結構。G PC數據亦證明，具有固定數目 离分子臂狀結構的星形高分子之多分敝性值，傾向於比原 本單獼的高分子罾狀結構的多分敝性值來得低。 資施例5 在結構3、4、5、6中重覆四亞甲基（tetranethylene) PTMO單元之平均數目亦可由1H NMR光譜研究而拥|知。在MDI 一衍生之胺基甲酸乙酯部份中兩種型式的芳香霣子之化學 轉移（chemical shift )可確定為在 7 7.08 ( d, J = 10 Hz)和7.28 ( d, J = 10Hz )。每群波峰的強度與在圃示 1中所示一离分子臂狀结構中的8偏質子一致。因此，逭 些芳香質子和在PTMO部份中之氣化亞甲基質子（7 3.40 ) 或未氣化亞甲基質子（7 1.62)之間稹分比率之值，使得可 對PTMO之平均分子量作正確估計。结果，可知毎傾PTMO Η 斷含有42蕕四亞甲基重覆單元。這表示，在聚胺基甲酸乙 _醚4中的每僱离分子蓍狀結構，其分子量分別為3,920 或3,790 ,此值在4之分子董Μη(2,600)和Mw(5,450)之 間。再者，此分析可知3的平均分子董為2.4X104。 奮施例6 星形高分子3有一値未被預期的物理性質，邸其在低 -16 - 本纸張尺度適用中國國家標準(CNS)A4規格(210X 297公釐) .…：I»...............裝…： ( (請先閲讀背面之注.意事項再塡寫本頁)304965 A7 B7 5. Description of the invention (1) Fullerene is a kind of molecular, which has an even number of atoms, arranged in a tight hollow cage, usually a sphere, in which a sulfo-bond defines a multifaceted structure. Some scholars once described Fu's Shanyu structure. For example, K. Chen et al. Revealed a self-assembled monolayer (SAN) (J. Am. Chen. Co., Ltd.) on the surface of (MeO) 3Si (CH2) 3HN2 modified covalent bonds. Soc., 1 15 (1993) 1 193), and WB Calwell et al. Exposed SAM on the surface of HS- (CH2) NH2-modified gold (LangBuir, 9 (1993) 1945). Similarly, there are Scholars have described some compounds with small functional groups or additions such as amide groups, alkane groups, and compound compounds. For example, U.S. Patent No. 5,177,248 and European Patent No. 546,718 disclose the treatment of unfunctionalized lotions with tri-gas methanesulfonic acid and nucleophiles to obtain alkylated lotions. European Patent No. 575, 129 has treated the unfunctionalized lotus with sulfuric acid, and has a broken acidic smile. Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) However, few giants have received it. KLWooley et al. Used ether linkage to connect two branched (divided branched, fan-shaped) polybenzyl ethers to the unfunctionalized laughter, and obtained a one-valued bifunctionalized fur (J . A .. Che .. Soc., 115 (1993) 9836). ETSa ^ ulski et al. Reversed the unfunctionalized fu and active polystyrene to obtain a number of mixed products with polystyrene bonds of 1 to 10 values (Qia-Qia bond) (Che · .Mater ., 4 (1992) 1153). Unfunctionalized sulfonates can also be grafted with certain crosslinks to obtain a linear ionophore (amino nitrogen bond) containing amine groups (A.O. Pa til et al., Polymer Bull., 30 (1993) 187). -3-This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X 297mm) A7 B7 304965 V. Description of the invention (2) One of the special features of the present invention is that it contains at least one core and plural tilt keys It is a kind of dissociative element that is prefaced on the laughing core. In more detail, each prepolymer unit is connected to one atom of the core with a connecting part M1 in the form of F-N1-! 3, where F represents the core and P represents one of the prepolymer units , M1 is selected from -0- (C = 0) -HH-, -NH- (C = 0) -NH-, -0- (C = S) -NH-, and -NH- (C = S ) -NH- in the ethnic group. One of the nucleus of the nucleus is bonded to the gas or nitrogen atom at the left end of M1, and the nitrogen atom at the right end of M1 is bonded to one of the atom atoms in each of the prepolymer units. Thus, the brewed form of the present invention includes polyurethane (Polyurethane) polymer, polydebrominated urethane, laughter molecule, polyurea laugher molecule, "broken urea splitter molecule, and Mixed macromolecules, such as poly (urea monocarbamate) laughing molecules. These ionomers are derived from many kinds of prepolymer units bonded to the laugh core, and the prepolymer unit per tilt can also be connected to another prepolymer unit end-to-end. The Ministry of Economic Affairs, Central Bureau of Standards and Staff Employee Cooperative printed the noun "Fuhe J stands for Fu, such as Cee, 〇0, C7e, Cee, (: * 4 or C12e, which can be alkyl, alkane, arylfanyl, or It is substituted by eaves carboxyl groups with 1 to 20 atoms and can also be functionalized by amine groups, hydroxyl groups or other base rings that are not bonded to a prepolymer unit. The name is "plural prepolymer unit" Or a similar expression means between 2 and 32. For example, Fanpu 2-24, 2-16, 4-12 and 6-10, or the numbers 6, 7 and 10, where the number or Fan Bin is a laughing core The average value of the prepolymer units contained. This number or profile is derived from a method well known to those skilled in the art. An example of this method is described in Example 4 below. The present invention is preferred The specific form is that each instrument contains an average of 6 oolitic prepolymers, and the distribution range is -4-This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) Employee consumption of the Central Standards Bureau of the Ministry of Economic Affairs Printed by cooperatives A7 B7 V. Description of the invention (3) Bin is quite narrow. One of the chemical forms of the present invention has a polydispersity of 1.45. The unit P may have the chemical formula of -Rhp-RiMiRS-X, for example, where R1 and R3 are 1 to 20 tilt hydrogen atoms of the hydrogen atom, which are bonded to nitrogen atoms at the right end of «1 and ^ 13, respectively. ^ 12 is selected from-«11- (0 = 0) -0-, -1 ^ _ (C = 〇) -HH-, -HH- (C = S) -〇- and -NH- (C = S) -NH- group. As shown in the chemical formula, the nitrogen atom at the left end of M 2 is bonded to the atom at the right end of R1. R2 is a polymerized part, selected from polygasified butene (P〇 ly (tetraeethylene oxide)), polygasified ethylene, polybutadiene, polyisoprene, polyhydrogenated butadiene, polyhydrogenated isoprene, polyester, polyethylene, polyacrylic acid ester, polyacrylic acid Amine, Polyurethane, Polyurea, Polyanhydride, Polyimide, Polyacrylate, Polymethacrylate, and Polysilazane. M3 is selected as-0- (C = 0) -NH-, -NH- (C = 0) -NH-, -〇- (C = S) -HH- and -NH- (C = S) -NH-. X is Select from -KH- (C = 0) -0-, -NH- (C = 0) -NH-, -NH- (C = S) -0-, -NH- (C = S) -NH-, -N = C = 0 and-N = C = part of the group of S. X can also be swept from -NH- (C = 0) -0-Y, -NH- (C = 0) -NH-Y, -NH- (C = S) -0-Y, and -HH- (C = S) = NH-Y, where Y is hydrogen or 1 to 20 ft of a kiln part of a net. Here, the exposed hydrogen moiety may be substituted or unsubstituted; saturated or unsaturated; non-cyclic, cut-shaped, or multi-shaped. Note that the orientation of the aforesaid part can be understood from the painting. Preferred embodiments include: where M1 and M3 are both -0- (C = 0) -NH-, H2 is -NH- (C = 0) -0-, X is -NH- (C = 0) -0- or -NH- (C = 0) -0-Y; where M1 and M3 are both -0- (C = S) -HH_, «* 是-» 11- (0 = $)-0-, X is -NH- (C = S) -〇- or -NH- (C = S) -〇-Y; where R1 and R3 are 4, 4,--5-This paper scale is applicable to China National Standards (CNS ) A4 specification (210X 297 mm) (please read the precautions on the back first and fill in this page) Threading ^ 04965 A7 B7 5. Description of the invention (4) Methylene diphenyl (4,4'iethylene diphenyl); Where X is -H = C = 0 or -N = C = S; or where Ri is 4, 4'-methylenediphenyl, R * is a polymerized part of polygasified butene, R »is 4 , 4'-methylene diphenyl. In another instrumentalized form, X is preferably -NH- (C = 0) -0-, -NH- (C = 0) -NH-, -HH- (C = S) -0- , Or -NH- (C = S) -HH. One of the second nucleus nucleus to X; or X is -N = C = 0, -H = C = S, -NH- (C = 0)- 0-Y, -HH- (C = 0) -NH-Y, -NH- (C = S) -〇-Y or -HH- (C = S> -HH-Y. An example of a molecule is a smile core with a single guess, which has a plurality of ytterbium prepolymer units bonded to it; in other words, this core is not connected with other cores quickly. In the formation of a chemical, a sickle core passes through, for example, a prepolymer unit, and at least one other core is connected. In the latter case, the X part is -HH- (C = 0) -0-, =, -NH- (C = S) -0- or -NH- (OS) -NH-, and the body or radon atom at the right end of X is bonded to a atom in the second tilting nucleus. The first laugh nucleus is then Connected to multiple Heyan Xingfu cores, and some Hengxingfu cores can be connected to another laugh core. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) Such ionomer methods are also within the scope of the present invention. It will be described in more detail. The prepolymer unit increases the intermolecular force between the functional groups (polyester is bonded to the same or different core), so the ionomer of the present invention is not suitable for viscosity modification It can be used for surface preparation and other fluidics applications, and can be used as an excellent cross-link to break into the polymer network structure and volatility. It can also be used in other ionomer halls known to those skilled in this technology. -6 -This paper scale is applicable to China National Standard (CNS) A4 specification (210 'x 297 mm) A7 B7 Printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs V. Description of invention (5) The following is a description of the preferred form With the scope of the attached patent application, it is easier to understand other pending and advantageous features of the present invention. The description of the mongolian style sheet: The first circle is the synthesis route that forms the preferred cross-linked form of the present invention. Included are the indications of other phase structures. Circle 2 is the preferred synthetic route for the formation of the cross-links of the present invention. The present invention is expected to be derived from furan derivatives, which include one or more nuclei, and at least Two quails (preferably three instruments or more than three hires The prepolymer unit is connected to each laugh core. This prepolymer unit is connected via the connecting part -0- (C = 0) -HH-, -NH- (C = 0) -HH-, -0- (C = S) -NH- and -NH- (C = S) -NH- are connected to the nucleus. These parts are the parts that appear in ethyl carbamate, urea, decomposed carbamate acetic acid and thiourea The same. The present invention includes a polymer that contains a smile core that is not connected to other smile cores. For example, on average, the Cee nucleus is connected to at least two crane prepolymer units, in which one atom of the nucleus is bonded to «, for example, the left end of the connecting part -0- (C = 0) -HH-. In this example, a single atom of the cyano-prepolymer unit at the right end is connected. The prepolymer unit can be a simple hydrogen segment, the chemical formula is -CntUn + ii, where n = 2-100. The prepolymer unit can also be a large hydrogen base of at least 25 atoms (substitute or not) Substitute), and may contain polymerized or repeated parts, or both. The prepolymer test element may also be a complex macromolecule that exceeds 200 atoms (e.g., meets 400 lanthanum atoms). For example, a complex prepolymer unit may include many access parts, which (please read the precautions on the back before filling out this page). BU—The paper size of the binding book is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) A7 B7 printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (6) The hydrogen atoms of mono-cylinders can be connected to each other, or the typical hydrogen-polymerized fragments of the mono-cylinders can be connected. The connected portion in the prepolymer unit may be, for example, -0- (C = 0) -HH-, -NH- (C = 0) -HH- or -NH- (C = 0) -0- , Or any other part that is different from the connection part that connects the prepolymer unit and the core. The polymerized H-fracture may include a lanthanum or multi-tilt repetitive unit, and may also include one or more types of mono-clamps. An example of polymerization H off is a polygasified butene with more than 40 repeat units. As for other specific forms of the invention, the prepolymer units connected to any single core can be the same or different, or they can be connected by the same or different connection parts. Those who are familiar with this technique will be able to decide whether for a particular application, it is more similar to the polymer composition or the changed mixture of laughing molecules. In addition to the prepolymer unit, the nucleus may have a functional group such as a hydroxyl group or an amine group, or a substituent such as an alkane group or an alkyl group. These functional groups or substituents are not fast-connected to a prepolymer unit. For example, Cee (-〇H) ee [-〇- (C = 0) -NH- (n-dodecyl)] e and the polymer (3) prepared in Example 3 below. Some scholars have described the method of preparing polyfunctionalized vesicles (such as polyhydroxylated, polyamino hydroxylated, and polyamine-based vesicles). For example, Meituan special 5,177,248 »(hydroxyl), and 5,294,732 (amino group, hydroxyl group and amino hydroxyl group). Other methods are described in LY Chiang et al., J. Che Mitsui. Soc., Chen. (; 〇! 〇. (1992) 1791; LY, Chiang et al., J. An. Chea. Soc., 115 ( 1993) 5453 * LY · Chiang et al., J. AHK Che Luo. Soc., 114 (1992) 10154; and LYChiang et al., J. Org. Chen ·, 59 (1994) 3960. The paper was prepared. The scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm): ..., .................. ': installed ... ....:-order: · ........... line (^ (please read the precautions on the back-* fill in this page) A7 B7 3〇49 & 5 i. Description of invention ( 7) The method of Daifu Nucleus is described in, for example, Tan Zhouli 0,546,718 and US Patent No. 5,177,248. (Please read the notes on the back before filling this page) The invention also includes a high-level connection with Fu Nu Molecule. For example, a smiling nucleus has a plurality of americium prepolymerized structural units, each lanthanum prepolymer Qin Yuan (i) is connected to the nucleus at one end, and (ii) is connected at the other end to "end-capping" The core. In this example, the two joints are connected by one or more inclination of the above connection parts. In the sterilized form, the one- or multi-body prepolymer is not degraded by the fu nucleus. The degraded nucleus can have other functional groups, substituents, or even other prepolymer units. The present invention also This includes two cores followed by one or more prepolymers, Yuanda. In one example, two cores can be connected to each other by more than one prepolymer unit, and the distance between the two cores is about No more than one quail prepolymer unit. In another lanthanum example • Two sickle cores can be accessed by two heirlooms or multiple oolitic (end-to-end) or branched prepolymer test elements, two shots laughing The distance between the cores is about 1.5 or 2 lanthanum (or more inclined) prepolymer units. Here, the linear or branched prepolymers can be any part of the linking element. As shown above It is pointed out that the prepolymer units can be the same or different. Printed by the Employee Consumer Cooperative of the Central Bureau of Prospects of the Ministry of Economic Affairs. The invention also includes a smile core and other cross-bonds with more than one core. For example, each filling core is approved Bond with an average of 4-8 Pb other nucleus to form an extended, ore-bearing molecular network junction . The second laugh core can be single guessed from the first husband core, selected from Ct_, C? ·,, C * ·, C ·, or Ci2 ·. Furthermore, the second laugh core is up to Then, it may also be multifunctional or substituted, as described above. The present invention also covers a plurality of lanthanum polymer-like structures' connected to a smile core g This paper scale is applicable to the Chinese National Standard (CNS> A4 specification (210X297 Mm) A7 B7 Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (8) Method 〇 This method includes · Get-a polyfunctionalized group with functional groups of selective white amine groups and hydroxyl groups 9 Get Of iso cy an ate and isothiocylate (i SO thi occy an a te >-functional group polymerization test 9) will react with the polymerization test m * and separate from the reaction mixture Out of the reaction product 〇m m plant polyfunctional sulfonate J (po 1 yf u η cti 〇na 1 i zed f U 11 ere η e) means including Fu 9 having a 2-32-value functional group. This functional group is independently selected from the group consisting of 9 amine groups and hydroxyl groups. For example, the nitrogen atom of 9-amine group is combined with the one atom of laughter > One atom bonding of oxygen atom Yufu. Examples of polyfunctionalized laughter include Ce e (-0H) 1 0 -1 2 Ce a (-0H) 1 4 -1 5, C ee (-OH) 1 8 -2 Θ Ce 0 (-OH) 1 Θ-1 2 (NHz) Θ-6 Ce 0 (-MHa) 1 0 — 12 and CT0 (-0H) 2 Λ Isobroken% acid radical-the functional group of the polymerization reagent J, the noun Γ select white • · • a monofunctional group J, said that includes a one or more m functional group (for example, a dip or trilanthanum) test mt These functional groups are selected by unicast white isocyanate and isothiocyanate. Examples include diisopropyl radicals and diisothioglycate radicals of alkyl and aromatic groups. In the same method, the molar ratio of hydroxyl groups and amine groups to isothiothioate and isocyanate groups on the polymerization test is between 1: 2 and 1 20 (for example, 1 10). In another In the method of sampling, the kb rate of the base ring on the base of Xiaoxiao and the base of the polymerization reagent is between 1G 1: 1 and 1: 1. In the present invention, 9 the molar fcb rate can be understood Covers the value of m within 20% of the design ratio or content. In another greedy form 9 The invention is more packaged-1C 1-This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm ) Please read the precautions first, and then fill in this page. 304965 A7 B7. 5. Description of the invention (9) Include a substituted or unsubstituted yeast after the reaction step. Examples include: (i) enzymes with Bu 20 seeds, such as Bu + two enzymes or 2, 2'-dihydrogen fermentation, (ii) a polyfunctionalized hydrogen compound (such as Fu) , Which is polyaminolated, polyaminohydroxylated, or polyhydroxylated, such as Cee (-0H) β-β. The present invention includes products made by this method of dew, as well as this method, according to the method described here to make the products of this dew. In addition, the present invention includes the final product made from the products exposed here. It is prepared by the Ministry of Economic Affairs Central Standards Bureau employee consumer cooperatives. It is made of polymeric arm structures or immobilized macromolecular substituents or polymerized to be spaced relative to the geometric center of the core. On the surface, the shape can be aggregated, for example, the polymerization test of the present invention is an iso-isothiosulfate compound of an alkyl or aromatic group, H (4 »4'-nethy1ene monomethylene diisobroken Dicarboxylic acid, such as poly (gasified butenediol glycol), poly (gasified ethylene) fermentation, poly (hydrogenated butadiene) fermentation, polyethylene fermentation, polyethyl acetate fermentation, polyurea diacrylate fermentation 、 Polymethyl compounds, including a connecting part and a sickle or multi-object element. The polymer chain or polymer arm structure can be arranged in a radial manner; it can also be uniformly formed into a three-dimensional space star-shaped molecule, or gathered near the opposite poles. Including (a > and (b) anti-silver products, (a) cyanate compounds, or an alkyl or aromatic group such as 4,4'-methylene diisodicarboxylic acid diphenyl diisocyanate) or 4, 4 'Phenyl ester, (b > is a multi-enzyme • such as second enzyme (Poly (tetraiethy 1 ene oxide) second enzyme, polybutadiene di », polyprenyl alcohol, polyhydroprenyl isoprene, Polyester diacid diacid fermentation, polyamino amine fermentation, polyamino formaldehyde fermentation, polyanhydride glycol, polyimide di fermentation, polyacrylic acid fermentation, polysiloxane fermentation, and -11 paper The standard is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm), please read the back first) the idea and then write this page and book this line. A7 B7 i printed by the Ministry of Economic Affairs Central Standards Bureau Consumer Cooperative Co. ) Its mixture. In the preferred form of acetylation, the second enzyme is polygasified butene. In another preferred embodiment, the isomeric ester compound is 4, 4'-methylene isomer Diphenyl acid. Note that it is best when the ratio of the number of hydroxyl groups and amine groups to the number of isodonate and isothiolate is between 1: 2 and 1: 20 Use the diisocyanate or diisothio radon polymerization reagent that meets * to form the non-carp silver carp molecule. The polymerization test is isothio bisacrylic acid BI or isocyanate prepolymer. For example, in Ri, h and X The hydrogen moiety represents a substituted (such as curved) or unsubstituted moiety, with 20 atoms or less, saturated or unsaturated, non-Hun-shaped, cut-shaped, or multi-cut. Unrestricted Examples include η-dodecyl, methylene diphenyl, naphthyl and polyethylene. One of the present invention has the final reaction products of (Α) and (Β), (Α) has 1- The enzyme of 20 Si Shuo atoms, (B) is the reaction product of the functional group and (ii) the polymerization test \ This polymerization test is thin (is (a) 4, 4'-methylene diisopropyl _ diphenyl The reaction product of ester or 4.4′-methylene diisothiothioic acid dibenzyl ester and (b) two fermentation, this two fermentation is selected from polygasification butenediol, polygasification ethylene two fermentation, poly Butadiene diol, polyisoprene two fermentation, polyargonated butadiene two fermentation, polyhydrogenated isoprene two fermentation, polymerase two fermentation, polyethylene two fermentation, and polyacid _ two fermentation, Polypyramid The group consisting of polyurethane secondary fermentation, polyurea secondary fermentation, polyanhydride secondary fermentation, polyimide secondary fermentation, polyacrylic acid secondary fermentation, polymethacrylate secondary fermentation, polysilicane dual fermentation The preferred reaction product of the present invention has the final reaction products of U) and (b), (a) is 1- + dye, (b) is (i) polyhydroxylated xiao Ui) polymerization-12 -This paper scale is applicable to the Chinese National Standard (CNS) M specifications (210x297mm) --------- ^ — installed-- (please read the precautions on the back before filling this page) to set the Central Standard of the Ministry of Economic Affairs A7 -___ [_ V. Invention description (U) trial_ reaction product printed by the Consumer Cooperative of the Bureau, the polymerization trial bribe is 4, 4'-methylene diiso-acid dibenzoic acid and polygasified butene The reaction product of II_, in which the molar ratio of the hydroxyl group on the polyhydroxylated Fu to the isomerate on the polymerization test is between 1: 2 and 1: 20 (eg 1: 10), to The reaction product (i > and (ii) is formed. Another preferred form of the present invention is the reaction product of (i > polyhydroxylated fu and (iU prepolymer reaction product, the prepolymer reaction product is 4 , 4 'The reaction product of diphenyl monomethylene diisoradate and polygasified butene fermentation, in which the hydroxyl group on the polyhydroxylated sulfonate and the molybdenum molybdate on the reaction product of the prepolymer The ratio is 10: 1 to 1: 1, to form the polymer. Without a more detailed explanation, I believe that according to the description here, those skilled in the art should be able to use the present invention to the fullest extent. Therefore, the following specific forms are only used as examples and are not intended to limit the rest of the disclosure. All materials cited here are incorporated by reference. Example 1 In a four-bronze reaction bottle (500 «L) equipped with a non-embroidered dysprosium stirrer, 11.9 grams of 4,4'-methane diiso" _diphenyl_ (4,4'-1 1 > 61 ^ 81 ^ diphenyl (Π isocyanate, MDI) and 47.6 grams of poly-gasified butyrate (ρ ο 1 y (tetrabethy 1 ene ο X ide) g 1 yc ο 1, Ρ Τ Μ 0, Μ η = 2,000) The reagent mixture is under radon gas at 60-65t: mixed for 4 hours under the stage. At the end of the reaction, under radon gas, it is washed with 5 × 50 · L of ethyl chloride (wash 5 times, 50 «L each time), To remove unreacted 4,4'-methanedioxanic acid dibenzoic acid from the reaction product. The washing solution of acetonitrile is removed by injecting poppy. It is dried under vacuum to obtain diisocyanic acid carbamic acid ethyl acetate _Poly_Prepolymer (1) -13-(Please read the precautions on the back before filling this page) Binding-Order Λ This paper size is applicable to China National Standard (CNS) Α4 specification (210Χ297mm) Central Standard of the Ministry of Economic Affairs A7 B7 printed by the Bureau ’s Consumer Cooperatives V. Description of the invention (12) (46.3 g) 〇Example 2 Polygasified butene fermentation (PTMO) and 4,4′-methane diiso radon diphenyl ester (MDI, 2.0 when ) In the CDCU, react at 60 ° C for 10 hours under cyanogen gas to obtain di- and sedate prepolymer 2. The average molecular weight of poly-gasified butene dienzyme is based on the permeation and precipitation method Uel pe «eation Chroeat -oeraphy, GPC), determined by PTH0 standard, Mn = 2,000, l «U = 4,500, polydispersity = 2.25. In the process of Klan reaction, it was found that the intensity of infrared light 3480CB-1 (equivalent to hydroxyl trapping) decreased. Example 3 In a mixed solution of dehydrated THF and DMF (3: 1), the total reaction of prepolymer 2 and polyfunctionalized Xiao 1 was carried out at 60 ° C under cyanogen chloride for 16 hours. In order to completely remove the cross-linked anti- *, the * -diisocyanated urethane polyprepolymer 2 (for isocyanate of 10 μM for each hydroxy group on the smile) is used. . After 16 hours, the mixture reacted with Buddlease again. The final product in THF is repeatedly precipitated with formazan, and then washed with a mixed solution of THF and formazan to remove the by-product obtained from the reaction of 1-dodecanoate and unreacted prepolymer 2 and the bis (1- Dodecane gas group) poly (urethane sulfonate) 4. The corresponding Cee urethane polyether star polymer 3 can be isolated, which is a soluble, high-viscosity brown-red semi-solid snake. The yield is very far away, and more than 15 times the weight of the initial laugh can be obtained. As expected, the infrared spectrum of the star-shaped polymer product 3, and the infrared -14 of the bis (1-dodecane gas group) * (ethyl carbamate ether) prepolymer 4-^ Paper scale applicable China ί National Standard (CNS) A4 specification (210 X 297 public) '...---- " ........ installed ...........:-subscribe ..... ...... "Line (please read the precautions on the back before filling in this page) ^ 04965 A7 B7 5. Description of the invention (13) Please read the precautions on the back and then fill in two to write this page The line spectrum is very similar , The band at 2272α (corresponding to isotonic acid absorption) and the band at 35500 -1 (corresponding to hydroxy absorption) are gone. The conversion of the functional group from isozonate to ethyl carbamate can be observed 3300C · -1 band (equivalent to urethanic-NH-absorption) and 173 301-1 strong band (equivalent to carbonyl absorption) were confirmed. Example 4 The molecular M of the star polymer 3 is mainly determined by its G PC light series (using toluene as the eluent) was measured and determined by the lieht scattering aeasureaents. In the GPC study, the spectrum was based on polystyrene standards In order to ensure and verify the entanglement and accuracy of the linear styrene oligomer to calibrate, a two-pointed star-shaped chess compound was synthesized. Compound 5 includes three urethane-polyamide arm structures, Compound 6 contains an arm-like structure of polyether tetraethyl urethane. The method of synthesizing these compounds is to diethylate polyisocyanate urethane polyether prepolymer 2 with triethylamine or pentaerythritol respectively. Fermentation reaction, followed by quenching with 1-dodecanase. The GPC spectra of linear oligomers 5 and 6 indicate that their molecular weights are Mn9,260 (Mwl5,200, polydispersity 1.64), and Mn 12,600 (Nw 20 , 300, polydispersity 1.6U. These are several poly- (carbamic acid acetic acid "> 4 (Mn 2,600, Nv5, 450, multi-point failure 2.11) The molecular weights are three and four times the same. Therefore, the average molecular weight of 3 is measured as Hnl8,000, M w2 6,100, and the average structure of 6 hexyl carbamate polyether The star polymer based on fulUrenol is consistent. More importantly, the polydispersity of 3 (1. 45) Significantly higher score -15-this paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) A7 B7 printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of invention (14) Sub-chain 4 Most of them are narrow (2.11). The only way to stack polymer arm-like structures arbitrarily bonded to a star-shaped polymer without increasing its multiplicity is to limit the number of isolated molecular arm-like structures to a fairly narrow, fixed distribution. This phenomenon occurs on chess-type ionomers 5 (polydispersity = 1.64) and 6 (polydispersity = 1.61), both of which have a fixed number of ionomer arm structures. The G PC data also proves that the multivalued value of star polymers with a fixed number of molecular arm-like structures tends to be lower than the multivalued value of the original single-molecule polymer-like structure. Example 5 The average number of repeating tetranethylene PTMO units in structures 3, 4, 5, and 6 can also be known from 1H NMR spectroscopy studies. The chemical shifts of the two types of aromatic dips in the MDI-derived ethyl carbamate can be determined at 7 7.08 (d, J = 10 Hz) and 7.28 (d, J = 10 Hz) . The intensity of each group of peaks is consistent with the 8 partial protons in the molecular arm structure shown in Figure 1. Therefore, the value of the fractional ratio between some aromatic protons and gasified methylene protons (7 3.40) or ungasified methylene protons (7 1.62) in the PTMO part makes it possible to determine the average molecular weight of PTMO Make a correct estimate. As a result, it can be seen that each tilt PTMO H-block contains 42 repeat units of tetramethylene tetramethylene. This means that the molecular weight of each yarrow-like structure in polyethylcarbamate 4 is 3,920 or 3,790, which is between the molecular weight of Mn 4 (2,600) and Mw (5,450). Furthermore, this analysis shows that the average molecular weight of 3 is 2.4 × 104. Fenshi Example 6 The star polymer 3 has an unexpected physical property, and its low -16-this paper scale applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) ....: I ». .............. Pretend…: ((Please read the note on the back. Note before writing this page)
、tT 線 經濟部中央標準局員工消費合作社印繁 A7 B7_ 五、發明説明（15 ) 粗下有不尋常的熱性霣。雖然3之分子量是線性聚胺基甲 酸乙酯醚4的6倍，3的玻鳙_移謳度（Tg)是-671Q . 只 比 4(-71t：)、5(-70t：)、6(-69Ό)之 Tg 略离一些（Tg 是由 DSC·形計算得 >。從嫌性结構4到5 (三镇臂狀結構之星 形）和6(四鵪鹭狀结構之星形），然後到六鹤臂狀结構的 星形离分子3,其玻璃轉移湛度有条统的、_次的壜加情 形。 實施例7 關於PTMO之鰱軟化瀑度，將3、4、5、6在顛似的 »度範_内加熱，分別為21*0(34.3"8)、22<0<45.3<1/8) 、231〇(43.5«1“）和231〇(42.7<1/8),四锢离分子都會變為 一期狀物質。在加熱後，所有四儀离分子都願示出寡聚 PTNO鍵之再結晶的相似熱性質。然而線性离分子4之再结 晶轉移較強，為-25tM45.0J/g>,其他的星形离分子3、 5、6則只有中度到弱的轉移，分別為-31T、-29Ό、-31 υ。遒些數擔表示，在C*_分子上的毎鵃离分子臂狀結構 ，與原本線性离分子4類似地，對於粗度的變勘嫌立地反 應。由於3、5、6的星狀外形，离分子臂狀结構之再结 晶能力明顯地減少。 實施例8 在設有不锈銅檯拌子的四頸反窸瓶（500iL)中，置入 11.9克的4, 4’一甲烷二異《酸二苯醣（MDI)和47.6克的聚 氣化丁烯二酵（PTNO, Nn = 2,000> 。試_混合物在《氣、 6Θ-65Τ下攪拌，反鼴4小時。反鼴終黏時，在《氣下， -17 - 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) 装· 、1Τ 經濟部中央標隼局員工消費合作社印製 A7 ---__ 五、發明説明（16 ) 以5x 50»L的乙谓來洗（洗5次，毎次50iL),以自反應産 物中除去未反竈的4· 4’——甲烷二異《酸二苯_。乙請的 洗掖以注射器除去。在稟空下乾燥，得到二異氰酸纗化的 胺基甲酸乙酯聚醚預聚物（46.3克）。 在遽接有一冷凝器和鈍氣産生器的反鼴瓶A(250iL)中 ，置入二異«酸端化的胺基甲酸乙酯聚鰱預聚物（25克>、 _水四氫味喃（90*L ,以納蒸皤）、和二甲基甲醯胺（10*L ,以分子篩乾嫌）。混合物在室溫下攪拌，直到二異«酸 端化的胺基甲酸乙釀聚醚預聚物完全溶解為止。在另一籲 反應瓶B(50«L)中，多羥基化笑衍生物（芙酵.1.5克）溶於 二甲基甲醯胺（25iL)中，且此溶液以4埃分子篩乾燥2天 。在Β瓶中的芙酵溶液然後倒入反應瓶Α中。所得混合物 在氡氣下，60-65t!下，攪拌16小時。反應5小時内，此 溶液變成凝顧。在氮氣下讓溶劑蒸發，得到橡0樣的膜。 將此膜在甲酵中懸浮，並在室溫下以超音波水浴處理30分 鑪。在6010下除去甲酵並於稟空下乾燥，得到芙酵交鏈的 聚胺基甲酸乙酯網狀结構之産物（2 3克）。 實施例9 将笑酵1, (^(01〇1_-1*舆二異氰酸化胺基甲酸乙_ 聚醚預聚物2 (對於笑酵上的毎翻羥基而言，為1.0當ft 的異氰酸根 >,在無水THF和DMF(3: 1>混合液中，於60t! 、氘氣下反應16小畤，可製得离分子網狀结構。二興糲酸 化預聚物2之製法為，將聚（氣化丁烯）二酵（PTHO)和4 ,4’一甲烷二興氯酸二苯酯（MDI, 2.0當量）在CDC13中、 -18 一 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） (請先閲讀背面之注意事項再填寫本頁), TT line, the Ministry of Economic Affairs, Central Bureau of Standards, Employee and Consumer Cooperatives A7 B7_ V. Description of the invention (15) There is an unusually hot character. Although the molecular weight of 3 is 6 times that of linear polyurethane ether 4, the degree of 3 glass-breasted _ migration (Tg) is -671Q. Only 4 (-71t :), 5 (-70t :), 6 The Tg of (-69Ό) is slightly off (Tg is calculated by DSC · shape>. From the suspected structure 4 to 5 (the star of the three-armed structure) and 6 (the star of the four-quail-shaped structure) , And then to the six-armed star-shaped molecule 3 of the arm-shaped structure, and its glass transfer degree is orderly and orderly. Example 7 Regarding the softening degree of the silver carp of PTMO, 3, 4, 5, 6Heating in the reversed »degree range_, respectively 21 * 0 (34.3 " 8), 22 < 0 < 45.3 < 1/8), 231〇 (43.5« 1 ″) and 231〇 (42.7 <; 1/8), the four-molecule molecules will become one-stage substances. After heating, all the four-molecule molecules are willing to show the similar thermal properties of the recrystallization of the oligomeric PTNO bond. The crystallization transfer is strong, which is -25tM45.0J / g >, the other star ion molecules 3, 5, 6 only have moderate to weak transfer, which are -31T, -29Ό, -31 υ. Represents that the arm-like structure of each molecule on the C * _ molecule is different from the original linear molecule 4 Ground, to respond to site changes of roughness. Due to the star shape of 3, 5, and 6, the recrystallization ability of the molecular arm structure is significantly reduced. Example 8 In the neck bottle (500iL), put 11.9 grams of 4, 4 'monomethane diisodioic acid diphenyl sugar (MDI) and 47.6 grams of polygasified butene difermentase (PTNO, Nn = 2,000>). Test _ the mixture is stirred under "gas, 6Θ-65T, and reacted for 4 hours. When the anti-mole is finally sticky, under" gas, -17-This paper scale applies the Chinese National Standard (CNS) Α4 specification (210X297 mm) ( Please read the precautions on the back and then fill out this page), installed, 1T printed by the Ministry of Economic Affairs, Central Standard Falcon Bureau Employee Consumer Cooperative A7 ---__ V. Description of invention (16) Washed with 5x 50 »L Wash 5 times, 50iL each time) to remove the unreacted 4 · 4 '-methane bis-isoacid "acid diphenyl _ from the reaction product. The washing and removal of the B please remove it with a syringe. Dry under air to obtain Diisocyanate urethane polyether prepolymer (46.3 g). In the reverse-bottle A (250iL) with a condenser and a passive gas generator Place diiso «acid-terminated urethane polycarp prepolymer (25g>, _water tetrahydroflavor (90 * L, sodium steamed), and dimethylformamide ( 10 * L, dried with molecular sieve). The mixture is stirred at room temperature until the diisocyanate-terminated polyether prepolymer is completely dissolved. In another reaction flask B (50 «L), the polyhydroxylated laughter derivative (furan.1.5 g) was dissolved in dimethylformamide (25iL), and the solution was dried with 4 Angstrom molecular sieve for 2 days . The fermented solution in the bottle B is then poured into the reaction bottle A. The resulting mixture was stirred under radon at 60-65 t! For 16 hours. Within 5 hours of reaction, this solution became a gaze. The solvent was evaporated under nitrogen to obtain a rubber-like film. The membrane was suspended in formazan and treated in an ultrasonic water bath for 30 minutes at room temperature. The formazan was removed at 6010 and dried under air, to obtain a product of a urethane cross-linked network structure (23 g). Example 9 Xiaoji 1, (^ (01〇1_-1 * and diisocyanated urethane _ polyether prepolymer 2 (for the hydroxyl group on the laughing yeast, 1.0 ft Isocyanate>, in a mixture of anhydrous THF and DMF (3: 1>), reacted for 16 hours under 60t! And deuterium gas to produce a molecular network structure. Dioxing acidified prepolymer 2 The manufacturing method is to combine poly (gasified butene) diacid (PTHO) and 4,4′-methane dichlorodiphenyl chlorate (MDI, 2.0 equivalents) in CDC13, -18 for a paper scale applicable to Chinese national standards (CNS) Α4 specification (210Χ297mm) (Please read the precautions on the back before filling this page)
、1T 經濟部中央標準局員工消費合作社印製 A7 ___ B7 五、發明説明（1*7 ) 60¾、氮氣下反應。所使用之聚（氣化丁烯）二酵之平均分 子量經測得為Νη 2,000，Mw4,500，多分散性2.25。 在異 氱酸根-羥基進行縮合反應前，芙酵先在真空、下預 乾嫌24小時。將DNF-THF溶液以分子篩（4埃）乾燥2天，以 除去反應介質中的水份。監测反應的遇程，發現在3480c·-1 處羥基吸收波段的強度渐減。在起初幾小時内，會發現漸 漸有凝醪的形成。在反應終點時，以甲醇在超音波處理下 ，將殘餘的異氮酸根官能基淬冷。在溶薄！蒸發及繼之的在 真空下乾燥後，分離出相對應的[Οβ]芙酵交鏈聚胺基甲 酸乙酯7 ,其為厚的自支撐膜。 此交鍵芙酵聚胺基甲_乙_產物7之红外線光譜顯示 出，相對於異氡酸根吸收的2272c·-1波段不見了，且3550 cm — 1處的羥基吸收有明顯的減少。異氡酸根轉變為胺基甲 酸乙酯，可經由觀察到330 0cm-1處的波段（相當於urethanic -NH-吸收）和1733c·-1處的強烈波段（相當於羰基吸收） 而得到證實。 實施例10 离度交鍵聚胺基甲酸乙酯7在低溫下的熱性質是很值 得注意的。為了促進7和其線性高分子之物理性質的鬭聪 性，將1-十二醇（2.0當量）與二異氮酸酯預聚物2在60 t 下反應，合成出雙（1-十二烷氣基）聚（胺基甲酸乙酯醚）4 Ο 有趣的是，由DSC·中看出，7的玻璃轉移溫度為-7 0 t：,與4的Tg(-71t)非常近似。7的PTMO鏈軟化溫度為 -19 - 本纸張尺度適用中國國家標準(CNS)A4規格(210X 297公釐） (請先閲讀背面之注.意事項再填寫本頁) 裝 線_ A7 B7 五、發明説明（18 ) 7t!,再结晶溫度為-321C,其值都比4來得小· 4的PTHO 鰱軟化漏度為22C,再結晶纒度為-2510 。迪些現象表示 (請先閲讀背面之注意事項再填寫本頁) ,在受到«度變化膨響下•化合物綱狀结構7之C··分子 上所化學建接耱的每镧聚胺基甲酸乙釀鰱都是玀立反應着 的。 實施例11 使用平黏探針法（flat-point probe)來研究7的熱機 械性霣。在两始《度-701C畤（輿其Tg—致 > ,發現到高分 子的體積變大。在-331到-201：下（此時7的再结晶轉移 發生），离分子的黼積幾乎為固定的。在更离租下會引起 線性熱蟛脹之前，大約在51C下的ΡΤΜ0鐽軟化轉移，使得 离分子的鱷積陡然增加。再者，在固定力作用下，直到約 191t,才有离分子膜被探針熱穿捶的情形發生。 實施例12 在设有冷凝器和鈍氣産生器的反應瓶A(250BL)中，置 入二異氡酸蠼化的胺基甲酸乙酸聚醚預聚物（25克，遍置） 經濟部中央標準局員工消費合作社印製 或一異氣酸蟵化的胺基甲酸乙酯聚醚預聚物25克、無水四 氫呋_(9θ·ί,以鎸蒸鏞 >、以及二甲基甲睡胺（10bL ,以 4埃分子飾乾嫌2天然後，在室滬下，将B瓶中的芙酵溶 液倒入反應庙A中。所得混合物於氡氣、60-6 5C下，攪拌 16小時。反應終黏時，加入1-十二酵（4.0克），以在每軀 興気酸端化的預聚物鐽端形成胺基甲酸乙酯官能基，瀣度 維持在為60T；。1小時後，反應産物以甲酵和四氫呋喃（ 3: 1)之混合掖重覆地洗，並於601?下真空乾燥。可得到 -20 - 本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐) SG4S65 A 7 _B7 五、發明説明（19) 以芙為基礎的星形聚（胺基甲酸乙麵一醚），其為黑褐色的 半固齷（2.3克）。 其池具黼化形式 由以上敘逑，熟悉此技鏟人士當能很容易地確知本發 明的主要特撖，並且，在不《離本發明之精神和範醻下， 可以将本發明作各種改變和改良，以迪應各種用途和情況 。因此，其他具釅化形式亦涵蓋於本發明之申謫専利範圃 内。 (請先閲讀背面之注.意事項再填寫本頁) 裝 線 經濟部中央標準局員工消費合作社印製 1 2 本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐)1. Printed by the employee consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. A7 ___ B7 5. Description of the invention (1 * 7) 60¾, react under nitrogen. The average molecular weight of the poly (gasified butene) yeast used was measured to be η 2,000, Mw 4,500, and polydispersity 2.25. Before the isomerate-hydroxyl group undergoes a condensation reaction, Furan is pre-dried under vacuum for 24 hours. The DNF-THF solution was dried with molecular sieves (4 Angstroms) for 2 days to remove water from the reaction medium. Monitoring the course of the reaction, it was found that the intensity of the hydroxyl absorption band gradually decreased at 3480c · -1. Within the first few hours, you will notice the formation of mash. At the end of the reaction, the residual isocyanate functional groups were quenched with methanol under ultrasonic treatment. Melting thin! After evaporation and subsequent drying under vacuum, the corresponding [Οβ] fermented cross-linked polyurethane ethyl ester 7 is isolated, which is a thick self-supporting membrane. The infrared spectrum of this cross-linked polyglucosamine_B_product 7 shows that the 2272c · -1 band relative to the absorption of isodonate is missing, and the hydroxyl absorption at 3550 cm -1 is significantly reduced. The conversion of isodonate to ethyl carbamate can be confirmed by observing the band at 330 0 cm-1 (equivalent to urethanic-NH-absorption) and the strong band at 1733c · -1 (equivalent to carbonyl absorption). Example 10 The thermal properties of the ion-crosslinked polyurethane 7 at low temperatures are worth noting. In order to promote the smartness of the physical properties of 7 and its linear polymer, 1-dodecyl alcohol (2.0 equivalents) and diisocyanate prepolymer 2 were reacted at 60 t to synthesize bis (1-dodecane) Alkyl) poly (urethane ether) 4 Ο Interestingly, as seen from DSC ·, the glass transition temperature of 7 is -7 0 t: very similar to the Tg (-71t) of 4. The PTMO chain softening temperature of 7 is -19-This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) (please read the note on the back. Please fill in this page before filling in the notes) Threading_ A7 B7 5 3. Description of the invention (18) 7t !, the recrystallization temperature is -321C, and its value is lower than 4. The PTHO silver carp softening leakage of 4 is 22C, and the recrystallization temperature is -2510. Describe some phenomena (please read the precautions on the back and then fill out this page), under the «degree change swelling ring» compound structure 7 C, the molecule is chemically built on each lanthanum polycarbamic acid All the silver carp are responsive. Example 11 The flat-point probe method was used to study the thermomechanical index of 7. In the two beginnings of "degree-701C" (Yi Tg-consistent), it was found that the volume of the polymer became larger. Under -331 to -201: (at this time, the recrystallization transfer of 7 occurred), the ionized product It is almost fixed. Before it will cause linear thermal expansion under more off-lease, the PTM0 softening transfer at about 51C makes the alligator accumulation of the ion molecules increase suddenly. Furthermore, under the action of fixed force, until about 191t, Only when the molecular membrane is thermally pierced by the probe. Example 12 In reaction bottle A (250BL) equipped with a condenser and a passive gas generator, diiso radon acidified carbamic acid acetic acid was placed Polyether prepolymer (25g, overlaid) 25g, anhydrous tetrahydrofuran_ (9θ) printed or monoisocyanate polyether prepolymer printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs · Ί, 鎸 邛 鉛>, and dimethylmethanamine (10bL, decorated with 4 Angstrom molecules for 2 days. Then, in the room under the Shanghai, pour the fermented solution in the B bottle into the reaction temple A The resulting mixture was stirred for 16 hours under radon gas at 60-6 5C. When the reaction was finally viscous, 1-dodecanoate (4.0 g) was added to promote radon acid in each body. The terminal of the terminalized prepolymer forms a functional group of ethyl carbamate, and the degree is maintained at 60T ;. After 1 hour, the reaction product is repeatedly washed with a mixture of formazan and tetrahydrofuran (3: 1), and Vacuum dry at 601 ?. Available -20-This paper scale is applicable to China National Standard (CNS) A4 specification (210X297 mm) SG4S65 A 7 _B7 5. Description of the invention (19) Star-based poly (amine) based on Fu Carbamic acid ethyl ether monoether), which is a black-brown semi-solid (2.3 g). Its pooling form is described above. Those familiar with this shovel can easily confirm the main features of the present invention, In addition, without departing from the spirit and scope of the present invention, the present invention can be changed and improved to meet various uses and situations. Therefore, other forms of conciseness are also covered by the scope of the present invention. (Please read the note on the back. Matters needing attention before filling in this page) Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 1 2 The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm)