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 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) 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) 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 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 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) '

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 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 552274 A7

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 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

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

Ring-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

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

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

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 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, 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 +

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

〇fC p = o

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 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

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

= 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 ----------------- (Please read the notes on the back before filling this page) ch2 " ο dioxane

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 acid

(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 ^?,, Also melon ^ 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. A polymer having an epoxy group side chain, which contains the structure of the chemical formula (11). 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 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. 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 structure 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) 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).