TW200416232A - Norbornene derivative containing carbazol group and radical polymerization inducing reaction group and synthetic method thereof - Google Patents

Abstract

This invention provides a method, which uses norbornene halide, synthesized from cyclopentadiene and alkene containing halogen group, as a precursor to perform ring-opening metathesis with norbornene monomer containing carbazol group to prepare block copolymer thereof and further to graft acrylic monomers.

Description

200416232 V. Description of the invention (1) Field of the invention The present invention relates to another method for preparing monomers by extracting co-_orbornene derivatives, starting from the original norbornyl halide. Its polymer can further graft acrylic series. BACKGROUND OF THE INVENTION Ethylene metathesis polymerization (polymerization): f olefin is an important method in recent years in polymer material = molecular synthesis. For the synthesis of acyclic diene and alkynes, ring-opening metathesis polymerization and media development of cycloolefins are important for long-term polymerization. With the development of various new types, the synthesis of high-molecular materials, which have become important functional groups, is also one of the catalysts used in metathesis and molecular material synthesis methods. Organic gold is often present in polymerization but sensitive to functional groups. For example, crane (^ produced ^ water, and oxygen and the polymerization reaction are also compatible m m 烯 cycloolefins ring-opening metathesis polymerization catalyst, the bean 铧 metal catalyst for water is > from-α / contact Tolerance is better (VV ^: V /: ability) or compatible with 1QQfi ^ r, and it can even be polymerized in aqueous solution. . 9 In 1996, Gru bs · # person newly developed carbene coordination complex RU (CHPh) [P (C6HU) ^ d ring-opening metathesis polymerization non-t J, especially stable in air, can be carried out Polymerization of functional monomers. In addition, it has the characteristics of high polymerization rate and high molecular weight, and generally has the phenomenon of living polymerization (Hving polymerization). .

Page 4 200416232 V. Description of the invention (2) There are more and more related researches on ring-opening metathesis polymerization using cycloolefin derivatives as monomers, mainly side-chain liquid crystals, two steps synthesis Triblock copolymers, polymers with various functional groups introduced, where the introduction of functional groups makes the polymer have optoelectronic properties and biochemical activity. Polyorbornene and its derivatives were the first commercial products to be polymerized by ring-opening metathesis polymerization and were one of the important engineering plastics. Because of its good transparency, good impact resistance (rubber additives), wide temperature range, good mechanical properties and processability, it is widely used in lighting appliances, machinery, electronic parts, pipe fittings and food packaging. And its derivatives such as polymers of acids and esters have been used as photoresists in the electronics industry. The synthesis of a highly potential polymer material shows its importance. Brief description of the invention The present invention mainly synthesizes orthobornylfluorenyl chloride and a variety of orbornene derivatives in a high-pressure reactor by Diels-Alder reaction and introduces carbazolyl to synthesize monomers and polymers, and studies their polymerization Behavior and physical properties, have a deeper understanding and contribution to the related fields of ring-opening metathesis polymerization of orbornene derivatives. The block copolymer was prepared by ring-opening metathesis polymerization. Cyclopentadiene and propenylamine were used to perform Diles-Alder reaction in a high-pressure reactor to synthesize original norbornene methylamine and react with potassium carbazole to prepare monomers Carbazolyl-containing norbornene monomer (CbzNB). This monomer then undergoes ring-opening metathesis polymerization with rhenium metal complex catalyst, and forms a block copolymer with the original norbornene methane or bromine, and can change different [Μ] / [I ] Value (which

200416232 V. Description of the invention (3) [M]: monomer concentration, [I]: initiator concentration) to form polymers with different molecular weights and segments, and then hydrogenated to obtain hydrogenated block copolymerization Thing. Learn the physical properties of its polymerization mechanism and new materials (thermal stability, solubility, molecular weight, molecular weight distribution, and polymerization reaction mechanism). A block copolymer is formed from CbzNB and original norbornene methyl gas, and then grafted with methyl methacrylate, methyl acrylate, and styrene to prepare new functional polymer materials (including thermal properties, photoelectric properties, etc ...) .

The purpose of this case is to provide a polymer with orbornene terminal and synthesized with orbornenyl halide (I) as a starter, the structure of which is shown in (IV): 7 ~ CH2.VX (IV) Wherein X is one of C 1 and Br, M is one selected from the group consisting of methacrylate, methacrylic acid acrylate, styrene, and combinations thereof, and η is an integer of 1 to 50. Another object of the present case is to provide a copolymer which is prepared by ring-opening metathesis of a polymer with a probenbornene terminal as shown in (IV) and a carbazolyl-containing orthobornene monomer shown in (II) Formed after polymerization and has a structure like (V):

200416232

200416232 V. Description of the invention (5) The object has a structure like (V):

Among them, m, η, and p are integers of 50, X is Br or C 1, and M is one selected from the group consisting of fluorenyl acrylate, acrylate, styrene, and combinations thereof. Another object of the present case is to provide a poly-bornabornyl derivative containing side-linking branches, which has a structure such as (V I):

V CH2- (m female X (VI) where η and p are integers from 1 to 50, X is Br or C 1, and M is selected from fluorenyl acrylate, methyl acrylate, styrene, and One of the groups formed by the combination. Another object of the present case is to provide a copolymer having a structure such as (VII):

(VII)

200416232 V. Description of the invention (6) wherein m, η, and p are integers of 1 to 50, X is B r or C 1, and M is selected from the group consisting of methacrylate, acrylate, styrene, and One of the ethnic groups formed by the combination. Another object of the present case is to provide a polyorbornene derivative with a side-linking branch, which has a structure as shown in (VIII): ch2- (m seven X (VIII) where η and p are both 1 to 5 An integer of 0, X is Br or C, and BM is one selected from the group consisting of polyfluorenyl acrylate, polymethyl acrylate, polystyrene, and combinations thereof. Another object of the present invention is to provide a synthesis A method for a carbazolyl-containing polyorbornene dilute derivative, comprising the steps of: (1) synthesizing an orbornene-type halide from cyclopentadiene and an olefinic compound having a halogen group, wherein the orbornene-type halogenation The substance has a structure such as (I): ^ SCH2_X ① where X is one of C1 and one of them; (2) using the orbornene-type halide as a reactant to synthesize an orthobornene monomer containing a carbazolyl group;

200416232 V. Description of the invention (7) (3) Ring-opening metathesis polymerization of the original borneolene monomer containing carbazolyl group and original norbornene type halide to synthesize a prepolymer; and (4) halogenating the original norbornene The polymer and the prepolymer undergo a ring-opening metathesis reaction to form a block copolymer. According to the above concept, the halogen-containing olefinic compound is selected from one of propenyl chloride and propenyl bromide. According to the above conception, the carbazolyl-containing probenbornene type single system has a structure as shown in (I I):

According to the above concept, wherein the block copolymer has a structure such as (I I I):

Where m and η are integers from 1 to 50, and X is one of C1 and Br. According to the above concept, the ring-opening metathesis polymerization reaction is performed in a high vacuum system.

Page 10 200416232 V. Description of the invention (8) Another object of the present invention is to provide a method for synthesizing a copolymer by ring-opening metathesis polymerization using an original norbornene-type halide, such as ( I) Structure: ^ xCH2'x ® where X is one of Cl and Br.

According to the above-mentioned concept, a step is further included before the ring-opening metathesis (1) The probenbornene-type halide is synthesized from cyclopentadiene and an alkenyl compound having a functional group. According to the above concept, the olefinic compound having a halo group is selected from one of propene-based gas and propenyl bromide. According to the above conception, step (1) further includes a step (2), which uses the original borneol dilute halide as a reactant to synthesize a prosylbornyl monomer containing sialyl. According to the above conception, the carbazolyl-containing original norbornene-type single system has a structure as shown in (I I):

According to the above concept, the copolymer is a carbazole group-containing precursor

Page 11 200416232 V. Description of the invention (9) Borneene block copolymer, which has the structure of (I I I):

Wherein, m and η are integers of 50, and X is Br or C1. According to the above concept, the ring-opening metathesis reaction is performed in a high vacuum system. Another object of the present case is to provide a method for synthesizing a carbazolyl-containing orbornene derivative, the steps of which include: (1) synthesizing an orbornene-type halide from cyclopentadiene and an alkene compound having a halogen group; ; (2) synthesizing a carbazolyl-containing orthobornene monomer by using the probenbornene-type halide as a reactant; (3) using the carbazolyl-containing probenbornene monomer and a probenbornene-type halide Performing ring-opening metathesis polymerization to synthesize a prepolymer; and (4) subjecting the orbornene halide to the prepolymer to perform a ring-opening metathesis reaction to form a block copolymer. According to the above concept, the dilute compound having a halogen group is selected from one of propenyl chloride and propenyl bromide. According to the above concept, wherein the norbornene-type halide has a structure such as (I): Modal x ®

Page 12 200416232

Page 13 200416232 V. Description of the invention (11)-Description of the preferred embodiment Example 1. Synthesis of the original norbornene type halide The original norbornene dentate monomer can be prepared by Diels-Alder The reaction is synthesized in a high-pressure reactor. It is mainly produced by the action of cyclopentadiene (eye 1 open tad iene) and olefinic compounds with functional groups such as propenyl gas or propenyl bromide. Generally, a Diels-Alder reaction between an ailyi compound and cyclopentadiene requires j 80 ° C, and the boiling point of cyclopentadiene is 41 ° C. The reaction needs to be performed in a high-pressure reactor. And the reaction formula is as follows:

CH2 = CHCH2-X

X = Br, CI Take 50 grams of cyclopentadiene, equal equivalents of propylene chloride or propenyl chloride and 1 gram of hydroquinone, and place in a high-pressure reactor at a temperature of 180 ° C The reaction took 12 hours. Unreacted cyclopentafluorene and propenyl chloride or propylene bromide were vacuum-evacuated at room temperature under vacuum, and the original norbornene derivative was obtained after distillation. The boiling point distillation conditions are as follows: original norbornene chloride (NBMC1) is 54 ~ 56 ° (: / 11 mmHg and original norbornene bromide (from 81 to 75 to 7 8 ° C / 1 3 mmHg. Example) Preparation of CbzNB monomer containing carbazole group Add 12 grams of hydroxide and 30 grams of carbazol to 200 milliliters of xylene, and remove the water to obtain carbazol. Oxazole potassium salt. This dibenzobenzene is removed

Page 14 200416232 V. Description of the invention (12)-and replace it with DMF as a solvent, add 25 g of probenbornenyl chloride (5- to 10): 〇1116 1: 1 ^ 1-2-11〇1 ^ 〇1'1 ^ 1 ^) and refluxed for 12 hours. The refluxed solution was poured into 200 ml of water, and extracted three times with ethyl acetate at 100 milliliters each time. After the ethyl acetate, the extraction solvent, was distilled off, the residue was chromatographed on a silica gel column. Purification was performed by si 1 icage 1 c ο 1 um η chromatography, and the dike solution was a mixed solvent of ethyl acetate: n-hexane = 1: 6. The original borneol derivative with a leaf sigma group (endo / exo = 3: 2) having a melting point of 7 4 _ 7 can be obtained by recrystallization with n-hexane. The NMR results and identification are as follows: 13C NMR (CDCI3): ( 5 (ppm) = 1 40. 4, 1 38 · 3, 136 · 5, 136 · 1, 132 · 4, 125 · 5, 122 · 7, 120 · 1, 118 • 6, 108. 8, 50. 0 , 48 · 1, 47 · 0, 45. 0, 44. 5, 44 · 0, 42 · 6, 41. 8, 39 • 0, 38 · 6, 30 · 8, 30 · 5. 'IR (KBr pellet , cm ~ l); 1587 (v C = C, vinylic), 1647,1478 (v C = C, aromatic streching), 1324 (v CN), 745,718 (v CH, carbazo1e ring out of plane) 0 UV (THF ): λ max = 236.2nm, e = 4.19x 104Lmol-icm-i0 Elemental analysis: (C2QH19N) Calculated C: 8 7.87%, Ν: 5. · 12%. Found C: 87.58%, Η: 7.08 %, Ν: 5.31%. Example 3. Experimental Polymerization Behavior of Protobornenene Monomers Containing Carbazole Groups

200416232 V. Description of the invention (13) Ratio ([M]: [I]), get different number average molecular weight and molecule

量 DISTRIBUTION. In the verification of the living polymerization characteristics of the carbazole group-containing norbornene monomers, the change in the ratio of the concentration of the carbazole group-orbornene monomers to the catalyst concentration versus the number-average molecular weight and molecular weight distribution was achieved. It can be observed here that the molecular weight distribution of the resulting carbazole group-containing probenbornene polymer is between 1.2 and 1.3, and that the Changing the number average molecular weight to a linear correlation. By using the carbazole group-containing original norbornene monomer to change the catalyst concentration ratio, different numbers of average molecular weights and molecular weight distributions can be obtained with sigma sitting group-containing original norbornene polymers. It can be observed from Table 1 that the molecular weight distribution of the obtained carbazole group-containing probenbornene polymer is between 1.2 7 and 1. 2 9. Moreover, the number average molecular weight varies with the carbazole group-containing probenbornene The ratio of monomer concentration to catalyst concentration increased. Further, for the study of molecular weight, it is necessary to understand the chain transfer and the termination reaction of the chain to infer the behavior of the polymerization reaction.

Page 16 200416232 V. Description of the invention (14) Table I. Using {(: 1 疋 11 ((: 1 ^ 11) [? ((: 61111) 3] 2} catalyst, at 25 ^: change [M] / [I] value for ring-opening metathesis reaction a'b

[M] / [I] Yield c (%) Number Average molecular weight (theoretical value) Number average Molecular weight (measured value) Molecular weight distribution PDI

[M] / [I] Yield e (%) Number average molecular weight (theoretical value) Number average molecular weight (measured value) Molecular weight distribution PDI 100 97 27300 26400 1.29 300 98 81900 86000 1.27 700 98 191100 193000 1.28 1200 99 327600 328700 1.28 a · [Μ] = 0.23 3M, polymerization solvent: dichloromethane. b. Perform a GPC calibration curve with a polystyrene standard sample. c. Polymerization time is two hours. The experiment of adding the carbazole group-containing orbornene monomer in stages is helpful for understanding the polymerization behavior of the carbazole group-containing orbornene monomer. The catalyst complex {Cl 2Ru (CHPh) [P (C6Hn) 3] 2} was reacted with 50-fold equivalent of the original borneol monomer containing a carbazole group at room temperature for 1 hour. The 1-hour reaction solution was divided into three parts. After one part was taken out, the sample prepared by GPC after precipitation and drying was used to determine the molecular weight. The second part continued to be taken out after 5 hours of reaction, and then prepared into GPC after precipitation and drying. Molecular weight measurement

Page 17 200416232 V. Description of the invention (15) The final part is added with 750 times equivalent of the original borneol monomer containing carbazole group 'removed after 1 hour reaction' and also prepared by precipitation drying GPC samples were subjected to molecular weight determination. From the results of the molecular weight measurement, it was found that there was no significant difference between the molecular weight measured after 1 hour of reaction (Mn = 1 36 0 0 and PDI = 21) and the measured molecular weight of 6 hours after reaction (Mn = 1370 and 0). pDI = 丨 .25) ° In the third part, another 750 times equivalent of the original borneol monomer containing carbazole group is added to continue the reaction. The obtained polymer is prepared by GPC to prepare a GPC sample for molecular weight determination. The number average molecular weight Mn = 21970 0 and the molecular weight distribution pDl = 1 · 25. The peaks obtained by GPC were either 50-fold equivalents or 750-fold equivalents of the original norbornene monomers containing leaf n-groups. The polymer obtained after the reaction was a single peak. These results all show that the carbazole group-containing orbornene monomer has the property of living polymerization when the catalyst complex is used for ring-opening metathesis reaction. Example 4: Polymerization of block copolymers containing different segments of CbzNB and original ice, norbornene chloride (NBMC1) or original norbornene sulfonium bromide (NBMBr) The synthesis reaction formula and steps are as follows:

Page 18 200416232 V. Description of the invention (16)

Take 2.5 millimoles of CbzNB and dissolve it in 4 ml of dichloromethane, place it in a reaction bottle, connect to a high vacuum system, freeze-evacuate_seal tube-thaw, cycle three times. Take the catalyst {RuCl 2 (CHPh) [P (C6Hn) d 〇 g) in a dry box with argon, dissolve it in 1 ml of dichloromethane, and inject the cured monomer with an injection needle. The solution was evacuated. The reaction bottle was defused at room temperature, and after stirring for 200 minutes at room temperature of 200 million, the NBX (X = C1 or Br) monomer with a color of 0.5 millimolar remained red at the time of injection. After 12 hours, add ml of ethyl vinyl

vinyl ether) to terminate the polymerization reaction. The solution was precipitated at 50H. The polymer was dissolved in dichloromethane and reprecipitated once in chloroform to obtain a purified polymer, which was dried in the air at room temperature. 殁 二 广 一 钇 ^ Selected two monomers

200416232 V. Description of the invention (17) ^ Addition amount, block copolymers with different segments are polymerized. The obtained co-amplified compound was analyzed by 1H NMR, and 6.8 ppm to 8.2 ppm belonged to the peak of the yin group, and 0 · 5 ppm to 4 · 5 ppm belonged to the polyorbornene main chain ring. Special peak of lipid base. In the unhydrogenated segment copolymerization, 4 · 9 p p m to 5 · 8 p p m are characteristic peaks of double bonds on the main chain of polyorborneol, as shown in the first figure. Example 5: Hydrogenation of block copolymers containing different segments of C bz NB and NBX (X = C 1, B r). The original norbornene derivatives are polymerized by ring-opening metathesis polymerization with For materials with saturated double bonds, the thermal stability of the material will be reduced by the unsaturated double bonds of the main bond. Therefore, the unsaturated of the main chain can be hydrogenated to obtain a material with higher thermal stability. The g = group of the present invention has a benzene ring, so it cannot be directly hydrogenated with hydrogen, and it needs to be chemically nitrided. The synthetic reaction formula and steps are as follows:

200416232 V. Description of the invention (18) Take 0.2 g of polymer (CbzNB-b-ΝΒχ), 1.0 g of p-toluenesulfonylhydrazide, 20 ml of xylene, and put it in a 200 ml ampoule In addition, a small amount of antioxidant (BHT) is added. Connected to the high vacuum system, freeze-evacuate-sealed-thaw cycle three times. The reaction bottle was thawed at room temperature, heated to 120 ° C, and reacted until hydrogen was no longer generated, and stirred for about 3 hours. The reaction flask was cooled to room temperature, and the solution was precipitated in 500 ml of methanol to obtain a hydrogenated polymer. The hydrogenated polymer was dissolved in dichloromethane and reprecipitated in methanol to obtain a purified saturated polymer. The obtained product was identified by 忸 NMR from 6.8 ppm to 8.2 ppm, which is a characteristic peak belonging to the leaf saliva group, and 0.5 p p m to 4.5 p p m, which is a characteristic peak belonging to the cycloaliphatic group of the polyorbornene main chain, still exists. In the unhydrogenated copolymer, the characteristic peaks of 4.9 p p m to 5.8 p p m, which belong to the double bond on the main norbornene main chain, no longer exist after tritiation. Example 6: Heat of a block copolymer of unsalted leaf-salanyl group-containing original norbornene and pro-norbornene bromide and a hydrogenated carbazole group-containing original norbornene and pro-norbornene bromide block copolymer The stability analysis measures the thermal stability of the block copolymer of probenbornene and orbornene bromide containing carbazole groups and the copolymer after hydrogenation (as shown in the second figure). The block copolymers of the original borneol dilute with carbazole group and the original diborne bromine dilute bromine will begin to crack at about 300 ° C. The carbazole group-containing original norbornene and the original norbornene bromide have been argonized. Block copolymers will crack at about 4 ° C. From this, it can be seen that the block copolymers of dibenzyl bromide and dibenzylidene bromide that have been hydrolyzed have better thermal stability than non-hydrogenated leaf sigma group-containing orthobornyl bromide.

Page 21 200416232 V. Description of the invention (19) The second picture shows the copolymer of hydrogenated and unhydrogenated carbazole group-containing norbornene and original norbornyl bromide in nitrogen at 10 ° C / mi η Under the heating rate. a shows the temperature rise curve of unhydrogenated copolymer and b shows the hydrogenated copolymer. Example VII. Preparation of polymer with orbornene terminal The orbornene-type halide was further used as a starter to polymerize methyl methacrylate, methyl acrylate, and styrene to form a polymer with orbornene terminal Methyl acrylate, polymethyl acrylate, and polystyrene, as shown in chemical formula (IV): CH "MVX (IV) where X is Cl or Br, and M is methyl methacrylate, Methacrylate or styrene. When M is methyl acrylate, the polymethyl methacrylate polymer with orbornene terminal is obtained with the amount of methyl methacrylate added. Polymers with different molecular weights and molecular weight distributions are obtained. When the cuprous bromide, 2, 2'-bisperidine, probenbornene bromide and fluorenyl methacrylate (MMA) react, the molar number ratio is 1 · · 1: 1: 1 0, whose number average molecular weight is 1 1 2 6 7 9, weight average molecular weight is 16 0 8 7 5 and molecular weight distribution is 1. 4 2. If cuprous bromide, 2, 2 '- Molle reaction of bispyridine, orbornene bromide with fluorenyl methacrylate (MM A) Ratio of 1: 1: 1: 25, number average molecular weight of 190,382, a weight average molecular weight of 302,125 and a molecular weight distribution

200416232 V. Description of the invention (20) VIII: 8 deniers $: I ^ 'The greater the amount of methyl methacrylate added, the wider the distribution range of the obtained molecular fluorene. § 訄 is based on diethyl ether, which reflects the dehu tablet γ &, said to take eight private-丄 μ silly paid for the polyphenyl ethyl hydrate with the original norbornene terminal. The analysis of the media by GPC was τ / ι / _ 2, a & Knife, J, and the average molecular weight were set to 16 0 0 0 0 and the points were: 1, 2, 1. Its glass transition temperature T g was 107. (: (Measured by DSC, its molecular weight distribution is higher than that of polymethyl methacrylate with pro-norbornene terminus. On the right, pro-norbornene chloride (n〇rb〇rnene methy 丨 chlride, N / MC1 \ and The reaction of cuprous bromide and 2,2 dipyridine in toluene yielded lower yields. The 400MHz iHnMR spectrum (CDCI3) of the original norbornene-terminated polystyrene is shown in the third figure. (i) Preparation of bromo-containing polymethyl methacrylate [p〇ly (MMA) with norbornene methylene end group, NBM-PMMA-Br] with 1-Mole cuprous bromide [Cu ( I) Br], 1 millimolar of 2,2 '-bipyridine, 1 millimolar of norbornene methylene bromide (NMBMr), and 100 millimolar methylpropionic acid Methyl ester (MMA) was dissolved in 10 ml of toluene. After three freeze-pump-sealed-thaw cycles under a vacuum system, the reaction was stirred at 130 ° C for 12 hours. The product can be obtained by precipitation with methanol. The obtained polymer with polyorthomethacrylate at the end of norbornene is dissolved in tetrahydrofuran and then precipitated three times in methanol. The reaction formula is as follows: ·

Page 23 200416232 V. Description of the invention (21)

+ MMA C _ “— ^ NBM-PMMA-Br strip * Uses norbornene methylene chloride (NBMC1), evolved cuprous copper [Cu (I) Br], double σ ratio. (2, 2'-bipyridine) The reaction in toluene has a lower yield. The reaction formula is as follows:

Seven MMA

Cu (l) Br + 2,2, -bipyridine

NBM-PMMA-CI

(ii) Preparation of poly (styrene) with norbornene methylene end group (NBM-PSt-Br) with dilute end of raw borneol Take 0 · 3 8 grams of cuprous desertified cuprous, 1. 2 5 Double night for grams. (2,2'-1 ^ mouth 71 ^ (^ 116), 0.5 g of raw borneol dilute bromine and 8 g of styrene were dissolved in 10 ml of methylbenzyl, and three freeze-pumps under vacuum system- After the tube sealing-thawing cycle, the reaction was stirred at 130 ° C for 12 hours.

Page 24 200416232

V. Description of the invention After (22) hours, the product can be obtained after precipitation with methanol. After freeze-drying, the yield is 35%. The polystyrene polymer with the dilute end of the original borneol was dissolved in tetrahydrofuran and precipitated in methanol three times. By GPC analysis, the number average molecular weight was 16,000 and the molecular weight distribution (PDI) was 1.28. The reaction formula is as follows:

CH2-Br +

Styrene

Cu (l) Br + 2,2, -bipyridine ——-:-soil Ch ^ -fstyrenej ^ Br

NBM-PSt-Br If orthobenzene gas is used in combination with cuprous bromide and dipyridine in toluene to form chlorinated polystyrene with orbornene terminal end. If styrene, MM Α and Cu (I) Br, 2′2-biPyridine are added at the same time, a NBBr reaction can obtain a polymonomer containing both polystyrene and poly MMA and having a norbornene end. < The ring-opening metathesis and copolymerization reaction of the obtained brominated (or gas-containing) polystyrene with a probenbornene end and a probenbornene monomer containing a ° card σ sitting group is further subjected to a ring-opening metathesis copolymerization reaction to successfully synthesize carbazole The structure of the polyorbornene copolymer of the group and polystyrene is as follows:

Page 25

200416232 V. Description of the invention (23) CH2-* (Styrene) ^ Br

The copolymer of Poly (NBCbz / NBM-PSt) can be identified by E NMR, as shown in the fourth figure. The number average molecular weight is 399,900, and the molecular weight distribution is 1.30, and the yield is 9 5%. The polyorbornene copolymer containing carbazole group and polystyrene was measured by differential differential scanning thermal analyzer, and Tg = 1 105 ° C (polystyrene segment) and T g = 1 6 5 ° C (with carbazole group agglomerated orbornene segments). Further, poly (NBCbz / NBMPSt) can be obtained by using the hydrogenation method as in Example 5 to obtain poly (HNBCbz / NBMPSt). Its structure is as follows:

P

CH2- (styrene4jrBr can be obtained by 1H NMR spectrum at 4 · 6 ~ 5.8 ppm without signal, indicating that the hydrogenation is complete. Example VIII. Fluorescence spectroscopy measurement of carbazole group-containing original norbornene polymer, hydrogenated Azolyl

Page 26 200416232 V. Description of the invention (24) The fluorescence spectra of the original norbornene polymer and carbazole methacrylate polymer (Poly (N-vinyl carbazole) 'PVK). The carbazole group-containing probenbornene polymer (polyCbzNB) is excited by a light source of 3 3 0 nm to obtain a monomeric fluorescence spectrum at about 3 7 7 nm, and near the higher wavelengths (4 8 0 nm ) Will show a less intense fluorescence spectrum, which is caused by the formation of carbazole group dimers and being excited. The fluorescence spectrum of the hydrogenated probenbornene polymer containing the leaf group also has a monomer emission fluorescence spectrum at about 37, and a less intense fluorescence appears near the higher wavelength (480 nm). Spectrum, the intensity of the fluorescence emission spectrum of this excited dimer will be lower than that measured for the unhydrogenated carbazole group-containing probenbornene polymer. This is because the unsaturated double bond is saturated by the hydrogenation reaction. , So that f, mobility increases', which in turn reduces the chance of forming an excited dibody. However, it should be noted that neither the hydrogenated carbazole group-containing norbornene polymer (pOlyCbzNB nor the hydrogenated carbazole group-containing norbornene polymer) has a polyacrylic acid. Fluorescence spectra of excited dimers. The emission spectra of excited dimers of methylpropyl gamma ^ °° polymer were generated because the two soil diagrams were close to each other. Further, the carbazole-containing group was measured Block copolymers of Yinshua 片 Tablet Diluted with Probornyl Bromide, and Hydrogenated Spectra ^ 81 = Fluoroene ^ 原 of Raw Borneol Diluted with Raw Borneol Dilute Copolymer 1 (Shown) ° Original borneol with leaf stilbene groups and a number of segments of the original borneol light source 1-stage copolymer ('as close to ^^, will obtain a monomer emission fluorescence spectrum at about 37 7nm, In addition, the intensity of the "light spectrum" will appear at the smaller Chefannan wavelength (in the range of 45nm to 55nm), and the spectrum at this high wavelength is due to the carbazole group.

200416232 V. Description of the invention (25) Fluorescence spectrum of the enantiomeric copolymer of the original borneol dilute and original borneol dilute bromine caused by the formation of dimers and being excited. 0 The same is also true for 5 There is a monomer emission fluorescence spectrum at 7 7nm: 'and at a near wavelength (in the range of 4 50 n m'-550nm) a less intense fluorescence spectrum will also appear 5 This fluorescence spectrum intensity ratio The strength of the unhydrogenated block copolymers containing the original borneol dilute and the original norbornene bromide is slightly greater.5 This is because the unsaturated double bond is saturated by hydrogenation, which increases the activity. In addition, the polar and non-polar groups in the original borneol dilute block copolymers with carbodicarbonate groups were greatly rearranged by the molecular chain, which greatly increased the chance of exciting the formation of dimers. Group of raw borneol dilute polymers or hydrogenated The difference between the original norbornene polymers of the carbolazide group is in the range of 380 nm to 450nm.j has the same excited doublet emission fluorescence spectrum as the fluorene acrylic carbamaze polymer ( (As shown in the fifth figure) 0 and the emission fluorescence spectrum in the range of 3 8 0 η nr ^ 450nm is mainly due to the close proximity of the two leaf σ sitting groups > and the excitation of the doublet Dimer emission fluorescence spectra are different. Whether it is a hydrogenated or non-hydrogenated borneol-containing borneol dilute block copolymer, the molecular chain is due to the interaction between polar and non-polar groups. There will be rearrangement of the molecular chain. The rearrangement of the molecular chain itself will make the σσ sitting groups close to each other and is conducive to the formation of the dimer. Therefore, there will be a specific emission fluorescence spectrum at a specific wavelength position, that is, at 3 0 0 nm. The spectrum in the range of ~ 450 nm The groups are mutually close to each other in the range of 450 π m to 5 5 G n m. The optical spectrum is formed by the formation of the dimer. 〇 Example Example 9 Preparation of Nine Percent Borneene Halide Polymer

Page 28, 200416232 V. Description of the invention (26) Decomposition poly-i catalyst with ^ d scientific formula ^ "protobornene-type functional compound and ring-opening complex polymer of ^ structure, with ring metathesis polymerization The reaction forms a structure of pro-norbornene of formula (IX).

Where X is Br or C1. Instant

Phenene gas is dissolved in 5 ml of 1.3 x 1 0 to 3 mol of raw norbornene bromide or raw ice water and air. Take 〇. Chloromethane. Operate in a vacuum system, except for d (CHPh) [P (c6Hu) 3] Ite ^ ^ (^ 2 > < 10 ~ 6 ^ ^} ^ {RuC12 ^ ^ J 2 The catalyst is dissolved in 1 ml of monogas methane ,,, + human g reactor. The reaction was placed in the lice methane of the pen and the product obtained after the main reaction, M frozen = :, after stirring for 24 hours, precipitated with methanol and dried, yield About 70%. Halogen polymer is used to prepare polyorbornene. Example 10: Thin raw polymethyl methacrylate with raw borneol

Take 1 millimolar cuprous bromide, 丨 millimoles bispyridine, 丨 millimoles original norbornene bromide polymer and 100 millimoles methacrylic acid vinegar (μμα) in 10 milliliters of toluene in. After three cycles of congeal-pump-a-tube-thaw cycles in a vacuum system, the reaction was placed at 130 ° C and the reaction was searched out. After 2 hours, the product was obtained by immersing it in methanol. The obtained polystyrene polymer with pro-norbornene terminal ^ was dissolved in tetranitrofuran and then sunk in methanol three times. The reaction formula is as follows: κ ,,

Page 29 200416232 V. Description of the invention (27)

+ CH2-Br MMA U.-bipyridin ^

The reaction is further carried out without adding methylbenzyl, the reaction formula is as follows:

+ MMA ^^ bipyndine ^ iaine (', CH2-b “Reaction without solvent ^ cH ^ MMA ^ Br If used? Κ original borneol dilute gas and desertified cuprous, 2, 2'-double late σ is determined in toluene and The reaction is performed in a solvent-free manner, and the reaction is similar to that of polyorbornene bromide. Example 11: Preparation of hydrogenated aliphatic cyclic dentate polymer

The orbornene-type polymer having the structure of the chemical formula (I X) is hydrogenated to form a hydrogenated aliphatic cyclic polymer having the structure of the chemical formula (X).

X = Br, CI Take 0.5g of original norbornene bromide or probenbornene chloride and 0.75g of p-toluenesulfonylhydrazide hydrogenation agent and a little 2,6-di-tert-butyl -4 -2,6-ditertbutyl-4-methylphenol is dissolved in 50 ml of xylene and operated in a vacuum system to remove water and air. will

Page 30 200416232 V. Description of the invention (28) The reactor is stirred for 6 hours at 120 ° C, and the product can be obtained after freeze-drying. Example 12 Preparation of Polyorbornene Grafted Polymethyl Methacrylate

Take 1 millimolar cuprous bromide, 1 millimolar 2, 2'-bispyridine, 1 millimolar raw norbornene bromide polymer and 100 millimolar methyl methacrylate (MMA ) Dissolved in 10 ml of toluene. After three freeze-pump-sealed-thaw cycles in a vacuum system, the reaction was stirred at 130 ° C for 12 hours and then precipitated with methanol to obtain the product. The obtained polymethylmethacrylate polymer with a norbornene end was dissolved in tetrahydrofuran and then precipitated three times in methanol. Its synthetic reaction formula is as follows:

Cu (l) Br + 2,2, -bipyridine MMA-^ Benzene

The reaction is further carried out without adding toluene, and the reaction formula is as follows:

MMA

Cu (l) Br + 2,2'-bipyridine-^ Reaction without solvent

CH2 Ten MMA &!

Br

If polyorbornene chloride and cuprous bromide are used for the grafting reaction with 2,2 bispyridine, the reaction is similar to polyorbornene bromide. According to the examples in this case, it is known that the original borneol dilute polymer containing side-chain functional elements is beneficial.

Page 31 200416232 V. Description of the invention (29) Acrylic monomers can be grafted by the method of the present invention, which has not been disclosed before. Further utilizing the characteristics of living polymerization to form block copolymers with leaf π sitting groups, grafting acrylic monomers can obtain new high molecular materials. This case may be modified by people who are familiar with this technique, but they are not to be protected by the scope of the attached patent application.

Page 32 200416232 Brief description of the diagram The first picture, the 4 0 0 MHz β NMR chart (CDC1 s) of the original borneol and norbornene bromide block copolymers containing carbazole groups. Second diagram, TGA diagram (a) Block copolymer of probenbornene and probenbornene bromide containing carbazole groups; (b) hydrogenated probenbornene and probenbornene bromide containing carbazol groups Block copolymers under nitrogen at a temperature rise rate of 10 ° C / mi. The third figure, a 400 MHz NMR chart of polystyrene with orbornene-terminated polystyrene (CDCU. The fourth figure, a polyorbornene copolymer containing carbazole groups and polystyrene {Poly (NBCbz / NBM — PSt)} 400 MHz β NMR chart (CDCU.

Fifth figure, (a) Block copolymers of probenbornene and probenbornene bromide containing carbazole groups (dotted line); (b) hydrogenated probenbornene and probenbornene bromide containing carbazole groups The fluorescence spectrum of the block copolymer (solid line) has an excitation wavelength of 330 nm.

Page 33

Claims (1)

200416232 VI. Scope of patent application Scope of patent application 1. A polymer with orbornene terminal synthesized from orbornene-type halide (I) as a starter, the structure is shown in (IV): ^ feCH2 " x ① (IV) where X is one of C 1 and Br, M is one selected from the group consisting of methyl acrylate, methyl methacrylate, styrene, and combinations thereof, and η is 1 to 50 Integer. 2 · —A kind of copolymer, which is formed by ring-opening metathesis polymerization of the polymer with orbornene terminal as shown in (IV) and the carbazolyl-containing orbornene type monomer shown in (II) With a structure like (V): (Π) Page 34 200416232 Page 35 200416232 6. Scope of Patent Application Among them, m, η, and p are integers from 1 to 50, X is B r or C 1, and M is selected from the group consisting of methacrylate, methacrylate, styrene, and combinations thereof. One. 5. A kind of polyorbornene derivative containing side-linking branches, which has a structure like (V I) · CH2- (M-) FrX (VI) where η and p are integers of 50, X is Br or C 1, and M is selected from methyl acrylate, methyl acrylate, styrene, and combinations thereof One of the ethnic groups formed. 6. A kind of copolymer, which has a structure such as (V I I): Page 36 200416232 6. Scope of patent application One of the groups formed by methyl methacrylate, methyl acrylate, styrene and combinations thereof. 7. A kind of polyorbornene derivative containing side-linking branches, which has a structure such as (V I I): (ΥΠ) where m, η, and ρ are integers from 1 to 50, X is B r or C 1, and M is a group selected from the group consisting of methyl methacrylate, methyl acrylate, styrene, and combinations thereof one of them. 8 · A polyorbornene derivative containing a side-linking branch, which has a structure as shown in (V I I I): In 4 ch2-4m-^-x (yin), n and p are integers from 1 to 50, X is Br or C 1, and M is selected from the group consisting of methyl methacrylate, methyl acrylate, styrene, and One of the clans formed by the combination. A method for synthesizing a polyorborneol dilute derivative containing a leaf sigma group, the steps include:) synthesizing probenolone from cyclopentadiene and a halogen-containing olefinic compound Page 37 200416232 VI. Application scope Patent type halide, wherein the original norbornene type halide has a structure such as (I): 0) wherein X is one of C1 and Br ·; (2) using the orbornene-type halide as a reactant to synthesize a carbazolyl-containing orbornene monomer; (3) using the carbazolyl-containing Ring-opening metathesis polymerization of the original norbornene monomer and the original norbornene-type halide to synthesize a prepolymer; and (4) A ring-opening metathesis reaction is performed on the orbornene halide and the prepolymer to form a block copolymer. 10. The method according to item 9 of the scope of the patent application, wherein the halogen-containing olefinic compound is selected from one of propenyl chloride and propenyl bromide. 1 1. The method according to item 9 of the scope of the patent application, wherein the carbazolyl-containing probenbornene type single system has a structure as shown in (I I): 1 2. The method according to item 9 of the scope of patent application, wherein the block copolymer has a structure such as (I I I): Page 38 200416232 VI. Scope of Patent Application Where m and η are integers from 1 to 50, and X is one of C1 and Br. 1 3. The method according to item 9 of the scope of patent application, wherein the ring-opening complex decomposition polymerization reaction is performed in a high vacuum system. 14. The method according to item 9 of the scope of the patent application, wherein after step (4), an additional step (5) may be included, the step (5) is adding acrylic monomers to copolymerize with the block Grafting reaction was carried out to obtain an original borneol dilute derivative containing a side chain branch and a carbazole group. 15. The method according to item 14 of the scope of the patent application, wherein the orbornene derivative containing a side chain branch and a carbazole group has the following structure (V): 9η2 ^ 〇η2- (μ ^ χ (V) where m, n, and p are all integers from 1 to 50, X is Br or C 1, and M is selected from methyl methyl acrylate, methyl acrylate, One of the groups formed by styrene and its combinations. Page 39 200416232 6. Scope of patent application 1 6. —A method for synthesizing a copolymer by ring-opening metathesis polymerization using an original norbornene-type halide, wherein the dilute form of the original-bornbornen halide has a structure such as (I): X is one of C1 and Br. Λ 1 7. The method according to item 16 of the scope of patent application, wherein before the ring-opening metathesis, it further comprises a step (1) synthesizing the original borneol from cyclopentadiene and an olefinic compound having an ii-subsidyl group. Ethylene halide. 1 8. The method according to item 17 in the scope of the patent application, wherein the halogen-containing olefinic compound is selected from among propenyl chloride and propenyl bromide. According to the method, after step (1), a step (2) is further used to synthesize the original norbornyl dilute monomer containing a carbazolyl group by using the original norbornene type halide as a reactant. 20. The method according to item 19 of the scope of the patent application, wherein the carbazolyl-containing original borneol dilute single system has a structure as shown in (I I): 2 1. The method according to item 16 of the scope of patent application, wherein the copolymer Page 40 200416232 VI. The scope of patent application is the structure of a pro-norbornene enemy segment copolymer containing 17 bases: ⑽ It has (III) Among them, m and η are integers of 1 to 50, and X is one of Cl and Br. . 2 2. The method according to item 16 of the scope of patent application, wherein the ring-opening complex decomposition reaction is performed in a high vacuum system. 2 3 · —A method for synthesizing a carbazolyl-containing orbornene derivative, the steps of which include: (1) synthesizing an orbornene-type halide from cyclopentadiene and a halogen-containing olefinic compound; ( 2) Using the orthobornene-type halide as a reactant, synthesize an orthobornene monomer containing a carbazolyl group; (3) Performing an activity with the ortho-bornene monomer containing a carbazolyl group and an orbornene-type halide Ring-opening metathesis polymerization to synthesize a prepolymer; and (4) performing a ring-opening metathesis reaction on the orbornene halide and the prepolymer to form a block copolymer. 24. The method according to item 23 of the scope of the patent application, wherein the halogen-containing olefinic compound is selected from one of propenyl chloride and propenyl bromide. 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