TW552274B - Epoxide-containing norbornene monomer and its polymer - Google Patents

Abstract

The invention is related to an epoxide-containing norbornene monomer, an epoxide-containing polynorbornene and its epoxide-containing copolynorbornene synthesized by ring-opening metathesis polymerization, and modifications of the epoxide-containing polynorbornene.

Description

552274 經濟部智慧財產局員工消費合作社印製 A7 五、發明說明（ί ) 發明背景： 聚原冰片稀（Polynorbomene)及其衍生物是第一個藉 由開環複分解聚合（Ring-opening Metathesis Polymerization，ROMP)之商業化產品，爲重要的工程塑 膠之一。因其透明性良好，耐衝擊性佳，廣泛之溫度使用 範圍，良好的機械特性，加工性。而被廣範地使用於形狀 記憶高分子、照明器具、機械、電子零件、管件、食品包 裝等。又其衍生物如含有酸及酯類的聚合物更被當作電子 產業的光阻劑。 聚原冰片稀（Polynorbomene)開環複分解聚合（Ringopening Metathesis Polymerization) ， 一般採用如鎢 （W) 、 鈦（Ti)、鉬（Mo)、鎊（Ru)等有機金屬化合物之觸 媒。而其中以1996年Gmbbs等人所開發的鎊碳烯配位觸媒 {Rua2(CHPh)[P(C6Hu)3]2}對於環烯類開環複分解聚合非常 有效，尤其在空氣中非常安定，甚至可進行具有極性官能機 單體之聚合。含環氧基團之高分子聚合物可用在黏著劑及表 面接枝上，其工業上之應用十分廣泛。 而本發明利用鐵碳烯配位{RuCl^CHPhXPCQHu%}爲觸 媒，利用開環複分解聚合(ROMP)的方法合成含環氧基團之 新型原冰片烯聚合物。 家標準（CNSM4規格⑽X 297公釐； --------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 552274 A7 B7 五、發明說明（2 ) 發明要旨 本發明揭示一種具有環氧基團的原冰片烯型化合物，其 結構式（I)爲：552274 Printed A7 by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the Invention (ί) Background of the Invention: Polynorbomene and its derivatives are the first to use Ring-opening Metathesis Polymerization, ROMP) is one of the important engineering plastics. Because of its good transparency, good impact resistance, wide temperature range, good mechanical properties and processability. It is widely used in shape memory polymers, lighting appliances, machinery, electronic parts, pipe fittings, and food packaging. Derivatives such as polymers containing acids and esters have been used as photoresists in the electronics industry. Polynorbomene Ringopening Metathesis Polymerization generally uses catalysts such as tungsten (W), titanium (Ti), molybdenum (Mo), pound (Ru) and other organometallic compounds. Among them, the pound carbene coordination catalyst {Rua2 (CHPh) [P (C6Hu) 3] 2} developed by GBMBs and others in 1996 is very effective for ring-opening metathesis polymerization of cycloolefins, especially very stable in air. Polymerization even with polar functional organic monomers is possible. High molecular polymers containing epoxy groups can be used in adhesives and surface grafting, and their industrial applications are very wide. The present invention synthesizes a new type of original norbornene polymer containing epoxy groups by using a ferrocarbene coordination {RuCl ^ CHPhXPCQHu%} as a catalyst and a method of ring-opening metathesis polymerization (ROMP). Home standard (CNSM4 specification ⑽ X 297 mm; -------- order --------- line (Please read the precautions on the back before filling out this page) 552274 A7 B7 V. Description of the invention ( 2) Summary of the Invention The present invention discloses an orbornene-type compound having an epoxy group, the structural formula (I) of which is:

(I) 其中R爲-〇或-(CH2)n-，其中〇5η^4的整數 本發明另揭示一種具有環氧基團側鏈的聚合物，其含 有化學式(II)之結構’(I) wherein R is -0 or-(CH2) n-, wherein 05η ^ 4 is an integer. The present invention also discloses a polymer having an epoxy group side chain, which contains the structure of formula (II) '

ch2-r-ch2ch-ch2χοκ (Π) 其中R爲-〇或-(CH2)n-，其中〇S64的整數 經濟部智慧財產局員工消費合作社印製 本發明更揭示一種具有烯基團側鏈的聚合物，其含有 化學式(III)之結構，ch2-r-ch2ch-ch2χοκ (Π) where R is -0 or-(CH2) n-, in which the integer of 064 is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The present invention further discloses a kind of A polymer containing a structure of formula (III),

丨—CH2— R—·CH2 CH—0—C—C = C Ho I II ι2 〇 OR2 Η (HI) 本紙張尺度適用中國國家標準（CNS)A4規格（210 χ 297公釐） n ϋ ϋ ϋ «ϋ I ϋ ϋ ^1 ϋ n n ϋ Λβ9 n I ϋ n ϋ H I ^1 n I .^1 ϋ ϋ ϋ n I— ϋ I (請先閱讀背面之注意事項再填寫本頁) 552274 A7 經濟部智慧財產局員工消費合作社印製丨 —CH2— R— · CH2 CH—0—C—C = C Ho I II ι2 〇OR2 HI (HI) This paper size applies to China National Standard (CNS) A4 (210 χ 297 mm) n ϋ ϋ ϋ «Ϋ I ϋ ϋ ^ 1 ϋ nn ϋ Λβ9 n I ϋ n ϋ HI ^ 1 n I. ^ 1 ϋ ϋ ϋ n I— ϋ I (Please read the notes on the back before filling out this page) 552274 A7 Wisdom of the Ministry of Economy Printed by the Property Agency Staff Consumer Cooperative

552274 A7 五、發明說明（牛） 其中R1爲-〇或-(CH2)n-，其中0S64的整數，及 R2爲Η或是CH3。 本發明亦揭示是一種具有四級胺基團側鏈的聚合物，其含 有化學式(VII)之結構’552274 A7 V. Description of the Invention (Bull) where R1 is -0 or-(CH2) n-, where the integer of OS64, and R2 is Η or CH3. The present invention also discloses a polymer having a side chain of a quaternary amine group, which has a structure of the chemical formula (VII) '

經濟部智慧財產局員工消費合作社印製 其中R1爲-0-或-(CH2)n-，其中〇S64的整數，及 R3爲 Η、CH3或C2H5 ; A·爲Cl·、Br·及CH3COO_。 發明之詳細說明 本案之目的係提供新的帶有環氧懸掛基團原冰片烯系 單體。進一步利用該單體可於開環聚合時，得到帶有環氧懸 掛基團聚原冰片烯系聚合物。此外，將該聚合物進一步氫 化，亦可製得具光學特性佳之高分子材料。 本發明除開發新原冰片烯系單體外，亦可配合其他原冰 片烯型單體製備新的共聚合物。至於其他原冰片烯系單體， 可舉出有：原冰片烯、及其烷基、亞烷基或芳香取代物，例 如有：2-原冰片烯、5-甲基-2-原冰片烯、5，6-二甲基-2-原 冰片烯、5-乙基-2-原冰片烯、5-丁基-2-原冰片烯、5-亞乙 基-2-原冰片烯、5-苯基-2-原冰片烯等；二環戊二烯、2，3-二羥基環戊二烯，及此等之甲基、乙基、丙基、丁基等的烷 基取代物。 -------------Mm (請先閱讀背面之注咅？事項再填寫本頁)Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs where R1 is -0- or-(CH2) n-, where integers of 64 and R3 are Η, CH3 or C2H5; A · is Cl ·, Br ·, and CH3COO_. DETAILED DESCRIPTION OF THE INVENTION The object of this case is to provide a new orthobornene monomer with an epoxy pendant group. Further use of this monomer can produce an orbornene polymer having an epoxy suspension group during ring-opening polymerization. In addition, by further hydrogenating the polymer, a polymer material having excellent optical characteristics can also be prepared. In addition to the development of new original norbornene-based monomers, the present invention can also be used with other original norbornene-type monomers to prepare new copolymers. As for the other norbornene-based monomers, there may be mentioned: norbornene, and alkyl, alkylene, or aromatic substitutes thereof; for example, 2-orbornene and 5-methyl-2-orbornene , 5,6-dimethyl-2-orbornene, 5-ethyl-2-orbornene, 5-butyl-2-orbornene, 5-ethylidene-2-orbornene, 5 -Phenyl-2-orbornene and the like; dicyclopentadiene, 2,3-dihydroxycyclopentadiene, and alkyl substituted products of methyl, ethyl, propyl, butyl and the like. ------------- Mm (Please read the note on the back? Matters before filling out this page)

-n ϋ ϋ I 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 552274 A7-n ϋ ϋ I This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 552274 A7

五、發明說明（f ) 經濟部智慧財產局員工消費合作社印製 又，该其他原冰片烯系阜體，亦可爲具有極性的取代基 者或有金屬原子之取代基者’至於此種取代者，可例示有： 氯、溴、氟之鹵素原子；甲氧羰基、乙氧親基、乙醯氧基等 酯型殘基；氰基；口比陡基等。 本發明之新原冰片烯系單體，係經由Diels-Alder(狄爾 斯-阿德耳)反應在180°C之高壓反應器中製備生成。Diels-Alder(狄爾斯-阿德耳)反應即爲將二烯類與烯類單體製成新 環烯類單體的反應。當然，本發明得到聚合物的方式並不限 定是以高壓反應器來進行。習知技藝中可進行Diels-Alder(狄爾斯-阿德耳)反應的方式，皆可在此被加以利用。 本發明所得到帶有環氧懸掛基團的新原冰片烯系單體，然後 可再藉由開環複分解聚合(ROMP)聚合該單體以形成新型之 聚合物。選擇性地，可利用烯基進行其他自由基反應來製備 聚合物。 複分解聚合反應條件 複分解觸媒 至於鎢及鉬系複分解觸媒可舉出有··此等金屬之鹵化 物，氧基鹵化物或氧基有機化合物，較具體可舉出有：六氯 化鎢、氧基氯化鎢、四氯化鎢、五氯化錦，氧化鉬乙醯基酉昔 酮酸酯等。另外有铑系複分解觸媒，本案最佳地使用 {C^RuCCHPhMPAHn：^}。V. Description of the invention (f) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, and the other pro-norbornene series is also a polar substituent or a substituent with a metal atom. Examples thereof include: halogen atoms of chlorine, bromine, and fluorine; ester residues such as methoxycarbonyl, ethoxyphile, and acetamyloxy; cyano; The new original norbornene-based monomer of the present invention is produced by a Diels-Alder reaction in a high-pressure reactor at 180 ° C. The Diels-Alder reaction is a reaction in which a diene and an olefinic monomer are made into a neocycloolefinic monomer. Of course, the manner in which the polymer is obtained by the present invention is not limited to a high-pressure reactor. The methods by which Diels-Alder reactions can be performed in conventional techniques can be used here. The neo-norbornene-based monomer having an epoxy pendant group obtained by the present invention can be polymerized by a ring-opening metathesis polymerization (ROMP) to form a new polymer. Alternatively, alkenyl groups can be used to perform other free radical reactions to prepare polymers. Metathesis polymerization reaction conditions Metathesis catalysts For tungsten and molybdenum-based metathesis catalysts, there are halides, oxyhalides, or oxyorganic compounds of these metals. More specifically, tungsten hexachloride, Tungsten oxychloride, tungsten tetrachloride, bromine pentachloride, molybdenum oxide ethanoxanthone, etc. In addition, there is a rhodium-based metathesis catalyst, and {C ^ RuCCHPhMPAHn: ^} is optimally used in this case.

SM 8 ^1 I; ϋ ϋ ϋ ϋ · n ϋ ϋ I ϋ ϋ H I ϋ ϋ I I I I I n I ί .1- n n n n _ϋ · n ϋ ϋ n n ϋ n - (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國 1 標準（CNS)A4規格（210 X 297公爱） 552274 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（6 ) 本發明之原冰片烯系單體之開環聚合’即使不採用溶劑 亦可能進行。惟該反應通常在惰性有機溶劑中實施。 至於所用之有機溶劑，宜爲烴系溶劑，其中，以可生成 溶解性優越的開環聚合物之環狀烴系溶劑爲尤宜。具體例可 舉出有：苯、乙基苯、甲苯、二甲苯等芳香族烴；正戊烷、 己烷、庚院等脂肪族烴；環戊烷、環己烷、甲基環己烷、二 甲基環己烷等之脂環族烴；二氯甲烷、二氯乙烷、二氯乙 烯、四氯乙烷、氯仿、二氯苯、三氯苯等鹵化烴等，亦可混 合此等之二種以上使用。又，溶劑對單體之使用量，通常爲 單體1重量份配溶劑1〜20重量份，而最佳爲配2〜10重量 份。 溫度 至於開環聚合之溫度條件並未予特別限定，通常爲_2(rc 〜100°C，較佳爲〇°C〜100°C，更佳爲選擇i〇c〜8(rc之任意 溫度。 聚合系之壓力 聚合壓力之條件爲0〜5〇公斤/平方公分。通常，以常壓 至10公斤/平方公分的範圍選擇爲最佳。 t ^系之籠罩氣 開環聚合係通常在氮氣或氬氣等惰性氣體籠罩氣中進 行。 9 t (請先閱讀背面之注意事項再填寫本頁) ^ ·11111111 I MV·----I---------------- 本紙張尺度適用中國國家標準（CNS)A4 ^Γ(210 X 297 ) 552274 A7SM 8 ^ 1 I; ϋ ϋ ϋ ϋ · n ϋ ϋ I ϋ ϋ HI ϋ ϋ IIIII n I ί .1- nnnn _ϋ · n ϋ ϋ nn ϋ n-(Please read the precautions on the back before filling this page) This paper size applies to China National Standard 1 (CNS) A4 (210 X 297 public love) 552274 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (6) The original norbornene-based monomer of the present invention The ring-opening polymerization is possible even without using a solvent. However, the reaction is usually carried out in an inert organic solvent. As the organic solvent to be used, a hydrocarbon-based solvent is preferred, and among them, a cyclic hydrocarbon-based solvent which can form a ring-opened polymer having excellent solubility is particularly preferred. Specific examples include aromatic hydrocarbons such as benzene, ethylbenzene, toluene, and xylene; aliphatic hydrocarbons such as n-pentane, hexane, and heptane; cyclopentane, cyclohexane, methylcyclohexane, Cycloaliphatic hydrocarbons such as dimethylcyclohexane; halogenated hydrocarbons such as dichloromethane, dichloroethane, dichloroethylene, tetrachloroethane, chloroform, dichlorobenzene, trichlorobenzene, etc., and these can also be mixed Use more than two kinds. The amount of the solvent used for the monomer is usually 1 to 20 parts by weight of the solvent and preferably 2 to 10 parts by weight of the solvent. Temperature The temperature conditions for the ring-opening polymerization are not particularly limited. Usually, it is _2 (rc ~ 100 ° C, preferably 0 ° C ~ 100 ° C, more preferably any temperature of i〇c ~ 8 (rc The pressure of the polymerization system The conditions of the polymerization pressure are 0 to 50 kg / cm². Generally, it is best to choose a range from normal pressure to 10 kg / cm². The ring-opening polymerization system of the shroud gas is usually under nitrogen. Or inert gas such as argon. 9 t (Please read the precautions on the back before filling this page) ^ · 11111111 I MV · ---- I ------------- --- This paper size applies to Chinese National Standard (CNS) A4 ^ Γ (210 X 297) 552274 A7

經濟部智慧財產局員工消費合作社印製Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

開環聚合物 本案所得之開環聚合物與共聚合物，其數目平均分子量 (Μη)爲10，000〜600，000，且分子量分布（Mw/Mn)(以下 簡稱PDI(分子量分怖）小於2。對該開環聚合物進行氫化反 應（習用於作光碟等的光學用材料）。由習知材料可知當分 子量分布範圍大於3時，則複折射率變大。然而，本案所得 之聚合物之PDI(分子量分怖)値小於2，因此具有較佳之光 學特性。開環聚合物之分子量及分子量分佈，係以四氫口夫 喃爲溶劑作凝膠層析儀（GPC)分析而測定。所得的開環聚 合物係採用一般的方法進行氫化反應，可較合適的使用做光 碟、光學透鏡、透明薄膜等的光學用材料。 實施例 以下舉出本案之最佳實施例以具體的說明本案，惟本案 並非僅爲此等實施例所限定者。 實施例一、合成末端含環氣某團之原冰片嫌單體(NBepoxv) 末端含環氧基團之原冰片烯單體(NBepoxy )可藉由狄爾 斯-阿德耳(Dids-Alder)反應在高壓反應器中合成，主要是以 環戊二烯(cyclopentadiene)以及帶有官能基的嫌類化合物丙 烯基甘油基***(allyl glycidyl ether)作用而生成。丙烯基甘 油基***(allyl glycidyl ether)爲本專題所使用之烯類，通常 丙烯混合物(allyl compound)與環戊二烯(cyclopentadiene)進行 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） 一^--------^---------^ (請先閱讀背面之注意事項再填寫本頁) 10 552274 A7 B7 五、發明說明（客） ------------- (請先閱讀背面之注意事項再填寫本頁) 狄爾斯-阿德耳(Diels-Alder)反應需要180°C，而環戊二烯 (cyclopentadiene)沸點41°C，丙烯基甘油基***(allyl glycidyl ether)沸點154t，因此反應需要在高壓反應器中進行。合成 之反應式及步驟如下： + ch2=chch2—〇-ch2 ch~ch2 _^厂。—αι2ς^：Η2 取50公克，環戊二烯(cyclopentadiene)與等當量數丙儲基甘 油基***(allyl glycidyl ether)及 1 公克氫酿(hydroquine)，置 於高壓反應器內，於18(TC下反應12小時。將所得液體在室 溫下以真空抽去未反應的環戊二烯(cyclopentadiene)和丙烯 基甘油基***(allyl glycidyl ether)。將所得的溶液，於真空 下蒸餾而得原冰片烯衍生物。NBepoxy蒸餾條件如下： NBepoxy ·· 63 〜64°C/毫米隶柱 所得的NBepoxy的紅外線吸收光譜圖，在1560公分4有 C=C的吸收，在1099公分4有C-0-C的吸收，在9〇5公分-1有環 氧乙基(oxirane)的吸收。 經濟部智慧財產局員工消費合作社印製 實施例二、合成末端含環氬某團之原冰片烯聚合物 【polv(NBep〇xv)l 合成末端含環氧基團之原冰片烯聚合物[P〇ly(NBepoxy)] 之反應式及步驟如下： 11 本紙張尺度適用中國國家標準（CNS)A4規格（21〇 X 297公釐） 552274Ring-opening polymers The ring-opening polymers and copolymers obtained in this case have a number average molecular weight (Mη) of 10,000 to 600,000, and a molecular weight distribution (Mw / Mn) (hereinafter referred to as PDI (molecular weight distribution)) 2. The ring-opened polymer is subjected to a hydrogenation reaction (commonly used as an optical material such as an optical disc). It is known from conventional materials that when the molecular weight distribution range is greater than 3, the complex refractive index becomes larger. However, the polymer obtained in this case The PDI (molecular weight distribution) 値 is less than 2, so it has better optical properties. The molecular weight and molecular weight distribution of the ring-opened polymer are determined by gel chromatography (GPC) analysis using tetrahydrofuran as a solvent. The obtained ring-opened polymer is subjected to a hydrogenation reaction by a general method, and can be more suitably used as an optical material such as an optical disc, an optical lens, a transparent film, etc. Examples The best examples of this case are listed below to specifically explain this case However, this case is not only limited by these examples. Example 1. Synthesis of NBepoxv monomer containing a certain group of ring gas at the end (NBepoxv) NBepoxy monomer containing an epoxy group at the end. ) Can be synthesized in a high-pressure reactor by the Diels-Alder reaction. It is mainly based on cyclopentadiene and allyl compounds with functional groups. glycidyl ether). Allyl glycidyl ether is the olefins used in this topic. Usually, allyl compounds and cyclopentadiene are used for this paper. CNS) A4 specifications (210 X 297 public love) One ^ -------- ^ --------- ^ (Please read the precautions on the back before filling this page) 10 552274 A7 B7 Five 、 Explanation (Customer) ------------- (Please read the notes on the back before filling this page) Diels-Alder reaction requires 180 ° C, The cyclopentadiene has a boiling point of 41 ° C and the allyl glycidyl ether has a boiling point of 154t, so the reaction needs to be performed in a high-pressure reactor. The reaction formula and steps for the synthesis are as follows: + ch2 = chch2—〇 -ch2 ch ~ ch2 _ ^ factory. —αι2ς ^: Η2 takes 50 grams, cyclopentadiene and equivalent number Allyl glycidyl ether and 1 gram of hydroquine were placed in a high-pressure reactor and reacted at 18 ° C for 12 hours. The resulting liquid was vacuum-evacuated at room temperature to remove unreacted rings. Cyclopentadiene and allyl glycidyl ether. The obtained solution was distilled under vacuum to obtain an original norbornene derivative. The NBepoxy distillation conditions are as follows: NBepoxy ··· The infrared absorption spectrum of NBepoxy obtained at 63 ~ 64 ° C / mm. It has an absorption of C = C at 1560 cm4 and an absorption of C-0-C at 1099 cm4. There is an absorption of oxirane at 905 cm-1. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Example 2. Synthesis of a probenbornene polymer containing a certain group of cycloargon at the end [polv (NBep〇xv) 〇ly (NBepoxy)] The reaction formula and steps are as follows: 11 This paper size applies the Chinese National Standard (CNS) A4 specification (21〇X 297 mm) 552274

經濟部智慧財產局員工消費合作社印製Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

實施例三、poly(NBepoxy)的氤化 取0.5克poly(NBepoxy)及2.75克甲苯磺基聯氨 toluenesulfonylhydrazide)之氫化劑及少許2，—叔丁基冬甲 基酚(2，6-di-tertbutyl-4-methylphenol)之抗氧化劑溶5〇晕:升 的二甲苯中。於真空系統下操作，除去水份及空氣。將反應 器於120°C下攪拌反應6小時，經冷凍乾燥後可得產物。反應 式如下 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） #--------訂---------線··------------------- (請先閱讀背面之注意事項再填寫本頁) 552274 A7 B7 經濟部智慧財產局員工消費合作社印製Example 3: Poly (NBepoxy) dehydration: 0.5 g of poly (NBepoxy) and 2.75 g of toluenesulfonylhydrazide toluenesulfonylhydrazide hydrogenation agent and a little 2, -tert-butyl orthomethylphenol (2,6-di- tertbutyl-4-methylphenol) antioxidant is dissolved in 50 ha: liter of xylene. Operate in a vacuum system to remove moisture and air. The reactor was stirred at 120 ° C for 6 hours, and the product was obtained after freeze-drying. The reaction formula is as follows: This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) # -------- Order --------- Line ·· ------ ------------- (Please read the notes on the back before filling out this page) 552274 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

五、發明說明（丨〇 ) CH2 )—CH2 CH-CH2 CH2 CH-C \〇/ CH-CH2 \〇/ 實施例四、Polv (NBepoxv)與氤化D〇lv (NBepoxv)之溶 解度測定 Poly (NBepoxy)與氫化-poly (NBepoxy)之溶解度列 於表冲。poly (NBepoxy)具有優異的溶解性。 表 lpoly (NBepoxy)與氫化-poly (NBepoxy)之溶解度 benzene Dichloro benzene toluene CH2C12 Xylene DMF DMSO NMP DMA THF 氫化前 + + Poly(Nbepoxy) + + + + + + ++ +— +— ++ + + + 氫化後 _ Poly(Nbepoxy) - 膨潤 一 — 膨潤 —— 膨潤 :於60°C溶解，+ —淤60°C部分溶解 :不 + + :室溫下溶解， 溶解 其中:benzene:苯，Dichloro-benzene:二氯基苯，Toluene:甲苯，CH2CI2: 二氯甲烷，Xylene:二甲苯，DMF: N，N-二甲基甲醯胺，DMSO:二甲亞 石風，NMP: N-甲基-2-口比口鋼，DMAc: N，N-二甲基乙醯胺，THF:四氫口夫喃。 實施例五、凝膠滲透層析儀(GPC)之測定 Poly(Nbepoxy)之不同M/Ι比的平均分子量及分子量分佈 如表2所示其中M/Ι比係指單體濃度對觸媒濃度比。 尺度適用中國國家標準（CNS)A4規格⑵〇 x 297公着 13 552274 A7 B7 五、發明說明（丨丨） 表2不同M/Ι比的平均分子量及分子量分佈 Μ/Ι 仏(克/莫耳） 分子量分佈 (Mw/Mn) 500 14980 1.65 1000 34870 1.66 2000 39950 1.67 4000 85490 1.85 Mw爲重量平均分子量而Mn爲數目平均分子重 經濟部智慧財產局員工消費合作社印製 實施例六、polv (NBepoxv)與氤化polv (NBepoxv)之运 熟差分析儀DSC測定 如poly (NBepoxy)並無觀察到玻璃轉化溫度Tg。但 氫化後之poly (NBepoxy)卻可觀察到熔點Tm。 本發明成功地合成末端含環氧基團之原冰片烯單體 (NBepoxy)，利用ROMP的方法{RuCl/CHPhXPCQHiAh} 爲觸媒，合成polyNBepoxy)。利用IR，W，及13CNMR鑑 定其結構。在NMR中，5.0-5.5ppm可觀察到開環聚合後主鏈 上雙鍵的存在。氫化前之poly (NBepoxy)可溶於一般的有 機溶劑（表1 )，但在氫化後，則不溶。改變不同的M/I 比，可得不同分子量之高分子聚合物。當M/I = 500碍，Mn = 14980，Mw/Mn二 1.65，而當Μ/Ι= 1000，Μη = 34870 , Mw/Mn=1.85。即隨著M/Ι的增加，分子量會增加，且分子 量分佈也些微的變大。DSC測定，在氫化前並沒有觀察到 _0--------β-------- (請先閱讀背面之注意事項再填寫本頁) -線丨一 ϋ ϋ ϋ I n -V. Description of the Invention (丨 〇) CH2) —CH2 CH-CH2 CH2 CH-C \ 〇 / CH-CH2 \ 〇 / Example IV. Determination of Solubility of Polv (NBepoxv) and Polyoxol (NBepoxv) Poly ( The solubility of NBepoxy) and hydrogenated poly (NBepoxy) is shown in the table. poly (NBepoxy) has excellent solubility. Table lpoly (NBepoxy) and hydrogenated-poly (NBepoxy) solubility benzene Dichloro benzene toluene CH2C12 Xylene DMF DMSO NMP DMA THF before hydrogenation + + Poly (Nbepoxy) + + + + + + + + + + + + + + + + After hydrogenation_ Poly (Nbepoxy)-Swelling-Swelling-Swelling: dissolve at 60 ° C, +-dissolve at 60 ° C Partially dissolve: not + +: dissolve at room temperature, dissolve of which: benzene: benzene, Dichloro-benzene : Dichlorobenzene, Toluene: Toluene, CH2CI2: Dichloromethane, Xylene: Xylene, DMF: N, N-dimethylformamide, DMSO: Dimethylphosphine, NMP: N-methyl-2 -Mouth-to-mouth steel, DMAc: N, N-dimethylacetamide, THF: tetrahydrooran. Example 5: Determination of gel permeation chromatography (GPC) The average molecular weight and molecular weight distribution of different M / I ratios of Poly (Nbepoxy) are shown in Table 2, where the M / I ratio refers to the monomer concentration versus the catalyst concentration ratio. Standards are applicable to China National Standard (CNS) A4 specifications 〇〇 297 Publication 13 552274 A7 B7 V. Description of the invention (丨 丨) Table 2 Average molecular weight and molecular weight distribution of different M / I ratios M / I 仏 (g / mol ) Molecular weight distribution (Mw / Mn) 500 14980 1.65 1000 34870 1.66 2000 39950 1.67 4000 85490 1.85 Mw is the weight average molecular weight and Mn is the number average molecular weight. Intellectual Property Bureau, Ministry of Economic Affairs, Employee Consumption Cooperative, Printed Example 6. Polv (NBepoxv) DSC measurements with tritium polv (NBepoxv) such as poly (NBepoxy) did not observe the glass transition temperature Tg. However, the melting point Tm was observed for the hydrogenated poly (NBepoxy). The present invention successfully synthesizes an orthonorbornene monomer (NBepoxy) containing an epoxy group at the end, and uses the method of Rump {RuCl / CHPhXPCQHiAh} as a catalyst to synthesize polyNBepoxy). The structure was identified by IR, W, and 13CNMR. In NMR, the presence of double bonds in the main chain after ring-opening polymerization was observed at 5.0-5.5 ppm. Poly (NBepoxy) before hydrogenation is soluble in common organic solvents (Table 1), but after hydrogenation, it is insoluble. By changing different M / I ratios, different molecular weight polymers can be obtained. When M / I = 500, Mn = 14980, Mw / Mn = 1.65, and when M / I = 1000, Mn = 34870, Mw / Mn = 1.85. That is, as M / I increases, the molecular weight increases, and the molecular weight distribution slightly increases. DSC measurement, no _0 -------- β -------- was observed before hydrogenation (please read the precautions on the back before filling this page) -line 丨 一 ϋ ϋ ϋ I n-

-ϋ n -I ϋ I 本紙張尺度適財國國家標準（CNS)A4規格（21{} χ挪公髮） 14 552274 A7 B7 五、發明説明（（2 )-ϋ n -I ϋ I The paper size is suitable for the national standard (CNS) A4 specification of the rich countries (21 {} χ Norwegian issued) 14 552274 A7 B7 V. Description of the invention ((2)

Tg，但氫化後，卻有一明顯之Tm，顯示氫化後結晶性變大。 (請先閱讀背面之注意事項再填寫本頁) 實施例七、製備含酉太酿胺基的原冰片烯不同鏈段夕嵌段共 聚合物 取原冰片烯甲胺（Norbomene methylene amine ) 20克， 献軒（Phthalic anhydride) 30克，氯仿80毫升，置於250毫 升三口瓶中，迴流12小時。旋轉蒸發移去氯仿，將固體含 酉太醯胺基的原冰片嫌(Norbomene phthalimide，NBMPI)於 正已烷中再結晶。所得NBMPI單體，熔點爲99至101°C。 -線： 經濟部智慧財產局員工消費合作社印製 進一步地，取2·5毫莫耳NBMPI溶於4毫升二氯甲烷中， 置於反應瓶中，接上高真空系統，冷凍-抽真空-封管-解 凍，循環三次。在通氬氣的乾燥手套箱中取觸媒 {RuCl2(CHPh)[P(C18H15)] 2} 2毫克，溶於1毫升二氯甲烷中， 以注射針打入固化的單體溶液中，再抽真空。將反應瓶於室 溫中解凍，於室溫（25t：)中攪拌3〇分鐘後。在顏色仍保 持紅色時將0.5毫莫耳之NBepoxy單體以注射針注入反應瓶 中。持續攪拌I2小時。加入0.1毫升乙基乙烯基醚（ethyl vinyl ether)終止聚合反應，將溶液注入於500毫升甲醇中 沈澱。將聚合物溶於二氯甲烷中，再沈澱於甲醇中，重複三 次，得精製聚合物，於室溫下真空乾燥。改變兩種單體的添 加量，聚合不同鏈段之嵌段共聚合物。所得之嵌段共聚合 物，以由W NMR分析得到酉太醯胺基上氫的位置在7.20到 7.71 ppm，此爲酉太醯胺基上氫的特性位置，而主鏈雙鍵 上氫的位置在5.23到5.51 ppm，此爲聚原冰片烯的特性位 15 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） · 552274 A7 五 經濟部智慧財產局員工消費合作社印製 發明説明（丨3 ) 置。IR圖在1590公分-1有開環後〇c的吸收，在1098公分-1 有C-0-C的吸收’在910公分4有環氧乙院基(oxirane)的吸 收。以凝膠層析儀（GPC)測聚合物之分子量與分子量分 佈。GPC等鑑定。以凝膠層析儀（GPC)測聚合物之分子量 與分子量分佈(PDI)。[M] / [I]=1000，i =271300，分子量分 佈（PDI)=1.67，Tg=ii7 °c，Td1G%=400 °C。反應式如下：Tg, but after hydrogenation, there is a significant Tm, indicating that the crystallinity becomes larger after hydrogenation. (Please read the precautions on the back before filling out this page) Example 7. Preparation of a block copolymer of different segments of orbornene containing proteolamine groups. Take 20 g of norbornomene methylene amine. 30 grams of Phthalic anhydride, 80 ml of chloroform, placed in a 250 ml three-necked flask and refluxed for 12 hours. The chloroform was removed by rotary evaporation, and the solid norbornem phthalimide (NBMPI) containing pentamidine group was recrystallized from n-hexane. The resulting NBMPI monomer has a melting point of 99 to 101 ° C. -Line: Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Further, take 2.5 millimoles of NBMPI in 4 ml of dichloromethane, place it in a reaction bottle, connect to a high vacuum system, and freeze-evacuate- Seal tube-thaw, cycle three times. Take 2 mg of the catalyst {RuCl2 (CHPh) [P (C18H15)] 2} in a argon-dried glove box, dissolve it in 1 ml of dichloromethane, and inject it into the solidified monomer solution with an injection needle. Vacuum. The reaction flask was thawed at room temperature and stirred at room temperature (25t :) for 30 minutes. While the color remained red, 0.5 mmol of NBepoxy monomer was injected into the reaction bottle with a syringe needle. Stirring was continued for 12 hours. 0.1 ml of ethyl vinyl ether was added to terminate the polymerization reaction, and the solution was poured into 500 ml of methanol to precipitate. The polymer was dissolved in dichloromethane and reprecipitated in methanol. This was repeated three times to obtain a purified polymer, which was dried under vacuum at room temperature. The block copolymers of different segments were polymerized by changing the addition amounts of the two monomers. According to W NMR analysis of the obtained block copolymer, the position of hydrogen on the acetaminophen group is 7.20 to 7.71 ppm, which is a characteristic position of the hydrogen on the acetaminophen group, and the position of hydrogen on the double bond of the main chain 5.23 to 5.51 ppm, which is the characteristic bit of polyorbornene. This paper size is in accordance with the Chinese National Standard (CNS) A4 specification (210X297 mm). 3) Set. The IR pattern has an absorption of 0c after the ring opening at 1590 cm-1, and an absorption of C-0-C at 1098 cm-1. The absorption of oxirane at 910 cm4. The molecular weight and molecular weight distribution of the polymer were measured by a gel chromatography (GPC). GPC identification. The molecular weight and molecular weight distribution (PDI) of the polymer were measured by a gel chromatography (GPC). [M] / [I] = 1000, i = 271300, molecular weight distribution (PDI) = 1.67, Tg = ii7 ° c, Td1G% = 400 ° C. The reaction is as follows:

^rCH2 - + NBMPI S +^ rCH2-+ NBMPI S +

〇—CH.CH—CH2 2 2\〇/ 氫化 PCy3 c-〇-CH.CH-CH2 2 2 \ 〇 / hydrogenated PCy3 c-

〇fC p=o〇fC p = o

CH2 CH2 〇-ch2ch-ch2 c/ p=〇 2、〇/ CH2 I 0-CH2 CH-CH2 將帶酉太胺基與環氧基的聚原冰片烯嵌段共聚合物溶於 四氫口夫口南中，以紫外線光譜儀測得其穿透度(tranSmittanCe) 爲94%，可見此種材料的透明性優良。 (請先閱讀背面之注意事項再填寫本頁) 線： 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 552274 A7 __B7 _ 五、發明說明（丨f ) 實施例八、製備含基與環氧基的聚原冰片烯不同鏈段 之嵌段共聚合物 將等莫耳之氫氧化鉀(K〇H)(12克)與咔唑（carbazole)(30 克)置於500毫升的反應瓶中，並加入200毫升的二甲苯 (xylene)，除水並除去二甲苯(xylene)得沛遗基鉀鹽。將口卡 口坐基鉀鹽置於N，N-二甲基甲醯胺(dimethylformamide)(DMF) 中，逐漸加入(25克)的原冰片烯甲氯並迴流12小時。將迴流 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 7 τ 丄 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 552274 A7 五、發明說明（IS )CH2 CH2 〇-ch2ch-ch2 c / p = 〇2, 〇 / CH2 I 0-CH2 CH-CH2 Dissolve polyorbornene block copolymer with fluorenylamino group and epoxy group in tetrahydrocyclopentane Nanzhong measured 94% of its transmittance (tranSmittanCe) with an ultraviolet spectrometer, showing that this material has excellent transparency. (Please read the precautions on the back before filling this page) Line: This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 552274 A7 __B7 _ V. Description of the invention (丨 f) Example 8. Preparation Block copolymers of different segments of polyorbornenyl groups containing epoxy groups and epoxy groups. Place equal molar potassium hydroxide (KOH) (12 g) and carbazole (30 g) at 500. In a milliliter reaction bottle, 200 milliliters of xylene was added to remove water and remove the xylene to obtain potassium potassium salt. Place the mouthpiece mouthwash potassium salt in N, N-dimethylformamide (DMF), gradually add (25 g) of norbornyl methyl chloride and reflux for 12 hours. Reflow (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 7 τ 丄 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 552274 A7 5 、 Explanation of invention (IS)

2H— 0—CH2 CH—CH + CH2 CH2 I 0-CH2 氫化 CH2 9H2 瓣 訂 線 將反應瓶於室溫中解凍，於室溫（25°c)中攪拌30分鐘 後。在顏色仍保持紅色時將〇·5毫莫耳之仰卬0兮單體以注射 針注入反應瓶中。持續攪拌12小時。加入ο·1毫升乙基乙烯 醚（ethyl vinyl ether)終止聚合反應’將彳谷液於笔升甲 醇中沈澱。將聚合物溶於二氯甲烷中，再沈澱於甲醇中，重 複三次，得精製聚合物，於室溫下真空乾燥。改變兩種單體 的添加量，聚合不同鏈段之嵌段共聚合物。所得之嵌段共聚 合物，以由W NMR分析得到口宋唑基上氫的位置在7.07到 7.95ppm此爲味邊基上氫的特性位置，而主鏈雙 鍵上氫的位置在5.09到5.51ppm，此爲聚原冰片烯的特性 位置。凝膠層析儀GPC測定。IR圖在1590公分^有開環後 C=C的吸收，在1099公分“有匕。/的吸收，在908公分―1有 環氧乙烷基(oxirane)的吸收。以凝膠層析儀（GPC)測聚合 物之分子量與分子量分佈。[Μ] / [Ι]=500，ϋ =14200，分2H— 0—CH2 CH—CH + CH2 CH2 I 0-CH2 hydrogenated CH2 9H2 flap Thread Thaw the reaction bottle at room temperature, and stir at room temperature (25 ° c) for 30 minutes. While the color remained red, 0.5 mmol of monomer was injected into the reaction flask with a syringe needle. Stirring was continued for 12 hours. Ο · 1 ml of ethyl vinyl ether was added to terminate the polymerization reaction ', and the barley solution was precipitated in penic methanol. The polymer was dissolved in dichloromethane and re-precipitated in methanol. This was repeated three times to obtain a purified polymer, which was dried under vacuum at room temperature. By changing the addition amounts of the two monomers, block copolymers of different segments were polymerized. The obtained block copolymer was obtained by W NMR analysis. The position of hydrogen on oroxazolyl group was 7.07 to 7.95 ppm. This is the characteristic position of hydrogen on odorant group, and the position of hydrogen on double bond of main chain was 5.09 to 5.51ppm, this is the characteristic position of polyorbornene. GPC determination by gel chromatography. The IR chart has an absorption of C = C after the ring opening at 1590 cm, an absorption of 1099 cm and an absorption of oxirane at 908 cm-1. Gel chromatography (GPC) measure the molecular weight and molecular weight distribution of the polymer. [Μ] / [Ι] = 500, ϋ = 14200, minute

子量分佈(PDI)=1.66，Tg=l57 °C ,10%Sub-quantity distribution (PDI) = 1.66, Tg = l57 ° C, 10%

=413 °C 本紙張尺度適用中國國家標準（CNS)A4規格（210 χ 297公f 18 552274 A7 〖兒明（ί6 ) 關於，帶非也基與環氧基的聚原冰片烯嵌段共聚合物 之電化學性質測定。帶pf連基與環氧基的聚原冰片烯嵌段 共聚合物溶於四氫□夫□南中的循環伏安圖（cyclic voltammetric waves)，掃描速度爲1〇〇亳伏/秒。由圖可 發現，在；L6伏特時具有電化學氧化狀態。即表示帶味座基 與環氧基的聚原冰片烯嵌段共聚合物帶有電化學活性。 關於帶味述基與環氧基的聚原冰片烯嵌段共聚合物之 透明度測定。係將帶味淡基與環氧基的聚原冰片烯嵌段共 聚合物溶於四氫口夫口南中，以紫外線光譜儀測得其穿透度 (transmittance)爲93%，可見此種材料的透明性優良。 經濟部智慧財產局員工消費合作社印製 實施例九、由末端含環氧基團之原冰片嫌聚合物 IPQlydVBepoxv)藤備末端含烯某之原冰片烯憨纟_ 取5克(0.05莫耳)NBepoxy溶於50毫升苯。加入3.6克 (〇·〇5莫耳）壓克力酸(acrylic acid)及0.005克(0.5莫耳) 氯化亞銅(CuCl)。於油浴溫度8(TC下，進行24小時反應。反 應結束後以甲醇進行沉澱，並洗去氯化亞銅（CuCl)，得白 色固體。經冷凍乾燥後，產率85%。合成之反應式及步驟如 CH2—CH一C一OH .= 413 ° C This paper is in accordance with Chinese National Standard (CNS) A4 (210 χ 297 male f 18 552274 A7) Er Ming (ί 6) About the copolymerization of polyorbornene block with epoxy group and epoxy group Determination of the electrochemical properties of polymers. Polyorbornene block copolymers with pf linker and epoxy groups were dissolved in cyclic voltammetric waves in tetrahydrofuran, with a scanning speed of 1.0. 〇 亳 volts / second. It can be found from the figure that there is an electrochemical oxidation state at L6 volts, which means that the polyorbornene block copolymer with odorous group and epoxy group has electrochemical activity. Determination of the transparency of polyorbornene block copolymers of odoryl and epoxy groups. The polyorbornene block copolymers with odorant groups and epoxy groups are dissolved in tetrahydrofuran The transmittance measured by ultraviolet spectrometer is 93%, which shows that the transparency of this material is excellent. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, Example IX. (Possible polymer IPQlydVBepoxv) Protobornylene containing olefin at the end of Fujibe纟 _ Take 5 grams (0.05 moles) of NBepoxy and dissolve in 50 ml of benzene. 3.6 grams (0.05 mol) of acrylic acid and 0.005 grams (0.5 mol) of cuprous chloride (CuCl) were added. The reaction was carried out at an oil bath temperature of 8 ° C for 24 hours. After the reaction was completed, precipitation was performed with methanol, and cuprous chloride (CuCl) was washed away to obtain a white solid. After freeze-drying, the yield was 85%. Synthetic reaction Formula and steps such as CH2-CH-C-OH.

CuCl ----------------- (請先閲讀背面之注意事項再填寫本頁) ch2 "ο dioxaneCuCl ----------------- (Please read the notes on the back before filling this page) ch2 " ο dioxane

19 > n I ϋ «Μ—- S國家標準（CNS)A4規格（210 X 297公釐） 552274 A7 B7 五、發明說明（丨7 ) 加入壓克力酸之改質所得末端含烯基之原冰片烯聚合物其紅 外線光譜分析（IR)如下所述：在1535公分-1有鏈上C=C的吸 收，在1099公分-1有ΟΟ-C的吸收。 實施例十、由末端含環氧基團之原冰片嫌聚合物 [poly(NBepoxv)l製備末端含四級胺基之原冰片懦聚合物 取1.81克(0.01莫耳)Nbepoxy溶於5毫升二甲苯(toluene)，加 熱至8(TC。加入1.05克(0.01莫耳）三甲基胺(TEA)及0.6克(0.01莫 耳）醋酸(aceticacid)。於油浴溫度8〇°C下，進行4小時反應。反應 結束後將溶濟抽乾，得黑色黏稠固體。經冷凍乾燥後，產率90 成之反應式及步驟如下： % 合19 > n I ϋ «M—-S National Standard (CNS) A4 specification (210 X 297 mm) 552274 A7 B7 V. Description of the invention (丨 7) Modified acrylic acid is added to the terminal containing alkenyl groups The infrared spectrum analysis (IR) of the original norbornene polymer is as follows: it has an absorption of C = C on the chain at 1535 cm-1, and an absorption of 0-C at 1099 cm-1. Example 10: Preparation of an original borneol polymer containing a tertiary amine group at the end from an original borneol polymer (poly (NBepoxv) l containing an epoxy group at the end) Take 1.81 g (0.01 mole) of Nbepoxy in 5 ml of two Toluene was heated to 8 ° C. 1.05 g (0.01 mole) of trimethylamine (TEA) and 0.6 g (0.01 mole) of aceticacid were added. The oil bath was performed at 80 ° C. 4 hours reaction. After the reaction, the solvent was drained to obtain a black viscous solid. After freeze-drying, the reaction formula and steps of 90% yield are as follows:

toluene + n(c2h5)3 - n acetic acidtoluene + n (c2h5) 3-n acetic acid

(請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 c2h5 加入TEA之改質所得末端含四級胺基之原冰片烯聚合 物，其紅外線光譜分析（IR)如下所述：在1530公分“有鏈上 c=c的吸收，在ι〇95公分-1有C-OC的吸收，在9〇1公分〃有環 氧乙院基（oxirane)的吸收。p〇ly(NBepoxy)在1591公分-1有開 環後OC的吸收，在1097公分-1有C-0-C的吸收，在903公分“ 有環氧乙烷基(oxirane)的吸收。此外，由DSC測定得到四級 化水溶性之末端含四級胺基之原冰片烯聚合物，在17WC存 20 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐） 552274 A7 B7 五、發明說明（丨β ) 冰片烯聚合物，在17.6°C存在一個Tg點。進一步測定其溶解度， 結果如下：所述末端含四級胺基之原冰片烯聚合物可溶於水及甲 醇，在甲苯、二氯甲烷、三氯甲院及四氯甲烷中，加熱到60°C仍是 部份溶解。在丙酮、四氫苯中完全不可溶。 本案得藉由熟悉此技藝之人士任施匠思而爲諸般修 飾，然皆不脫如附申請專利範圍所欲保護者。 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 21 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）(Please read the notes on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by c2h5. TEA-added modified TEA-containing original norbornene polymer with tertiary amine group at the end, its infrared spectrum analysis (IR) As follows: at 1530 cm, there is absorption of c = c on the chain, C-OC absorption at 1095 cm-1, and absorption of oxirane at 910 cm. P Oly (NBepoxy) has OC absorption after ring opening at 1591 cm-1, C-0-C absorption at 1097 cm-1, and "oxirane" absorption at 903 cm. In addition, quaternized water-soluble endorbornene polymers containing quaternary amine groups at the end were obtained by DSC measurement and stored at 17WC. 20 This paper size is applicable to China National Standard (CNS) A4 (210 x 297 mm) 552274 A7 B7 V. Description of the invention (丨 β) Borneene polymer has a Tg point at 17.6 ° C. The solubility was further measured, and the results were as follows: The orbornene polymer containing a tertiary amine group at the end was soluble in water and methanol, and heated to 60 ° in toluene, dichloromethane, chloroform and tetrachloromethane. C is still partially dissolved. Completely insoluble in acetone and tetrahydrobenzene. This case has to be modified by anyone who is familiar with this skill, but it is not inferior to those who want to protect the scope of the patent application. (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 21 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

Claims (1)

552^? 、、也瓜 ^552 ^?,, Also melon ^ 六、申請專利範圍 --200¾年〇2思12曰修正 • Η ,修司· 1.一種具有環氧基團的原冰片烯型化合物，其結構式（1)胃：Sixth, the scope of the patent application --200¾years, 02th, 12th amendments • 修正, repair · 1. a kind of orbornene compound with epoxy group, its structural formula (1) stomach: H2-〇-CH2-CH-/CH2 (I) 2.—種具有環氧基團側鏈的聚合物，其含有化學式(11) 之結構，、产H2-〇-CH2-CH- / CH2 (I) 2. A polymer having an epoxy group side chain, which contains the structure of the chemical formula (11). Ca—〇一 CH2 CH — CH: (Π) 3.—種具有烯基團側鏈的聚合物，其含有化學式(ΠΙ) 之結構，Ca—〇—CH2 CH — CH: (Π) 3. — A polymer having an alkenyl group side chain, which contains the structure of the chemical formula (ΠΙ), L-Chb—O—CH2 CH—0—c—q=：cH2 H R' (ΠΙ) (請先聞讀背面之注意事項再填寫本頁) Γ 其中R1爲H或是CH3 m. 經濟部智慧財產局員工消費合作社印製L-Chb—O—CH2 CH—0—c—q =: cH2 HR '(ΠΙ) (Please read the notes on the back before filling out this page) Γ where R1 is H or CH3 m. Intellectual property of the Ministry of Economic Affairs Printed by Bureau Consumers Cooperative 4.一種具有四級胺基團側鏈的聚合物，其含有化學式(IV) 之結構， (IV) 其中R1 爲Η、0¾ 或 QH5 ;以及A-爲cr、Br—及CH3COCT 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 552274 A8 B8 C8 D8 2002年09月J2日修正4. A polymer having a side chain of a quaternary amine group, which contains the structure of formula (IV), (IV) where R1 is Η, 0¾ or QH5; and A- is cr, Br— and CH3COCT. This paper is applicable to this paper China National Standard (CNS) A4 Specification (210X297 mm) 552274 A8 B8 C8 D8 Amended on September 2, 2002 結構structure 申請專利範圍 5.—種具有環氧基團側鏈的聚合物，其含有化學式(V)之結構 CH2—〇~CH2 CH-CH2 \〇/ (V) 6.—種具有烯基團側鏈的聚合物，其含有化學式(VI)之 Chfc—〇—CH2 CH—0—C — C = CH2 I II I , o OR1 H (VI) 其中R1爲H或是CH3。 7.—種具有四級胺基團側鏈的聚合物，其含有化學式(VII) 之結構， (請先閱讀背面之注意事項再填寫本頁)Patent application range 5.—A kind of polymer having an epoxy group side chain, which contains the structure of the chemical formula (V) CH2—0 ~ CH2 CH—CH2 \ 〇 / (V) 6.—A kind of side chain having an alkenyl group Polymer, which contains Chfc—O—CH2 CH—0—C — C = CH2 I II I, o OR1 H (VI) where R1 is H or CH3. 7.—A polymer with a quaternary amine group side chain, which contains the structure of chemical formula (VII), (Please read the precautions on the back before filling this page) (VII) 其中R1 爲Η、CH3 或 C2H5 ;以及A·爲cr、ΒΓ及CH3COO— 經濟部智慧財是局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）(VII) where R1 is Η, CH3 or C2H5; and A · is cr, ΒΓ, and CH3COO—printed by the Ministry of Economic Affairs ’Smart Consumer Finance Co., Ltd. Employees’ Cooperatives. The paper dimensions are in accordance with China National Standard (CNS) A4 (210X297 mm).