TWI271411B - Norbornene derivative containing carbazole group to initiate radical polymerization and synthetic process thereof - Google Patents

Abstract

The invention provides a halogen-containing norbornene, which can be used as an initiator for radical polymerization. Synthesis of halogen-containing norbornene was accomplished by using cyclopentadiene and allyl halide. Ring-opening metathesis copolymerization of the halogen-containing norbornene and norbornene monomer containing carbazole group was carried out to prepare diblock copolymers. Furthermore, a method for preparing grafted the diblock copolymers with acrylate monomer is also provided.

Description

1271411 玖, invention description: [Technical field to which the invention belongs], the present invention relates to providing an original borneol halide as a starting material, preparing an original borneol derivative and a polymer thereof and further grafting an acrylic monomer The method. ~ [Prior Art] Olefin metathesis polymerization is an important method in polymer synthesis. In recent years, in the synthesis of polymer materials, ring-opening metathesis polymerization of cycloolefins and metathesis polymerization of acyclic diene and acetylenes have become increasingly important. With the development of various new catalysts, more and more polymer materials with various functional groups have been synthesized, which has become one of the important methods for synthesizing molecular materials. Organometallic catalysts have been used in metathesis polymerization for some time, but there are often restrictions on the polymerization of monomers with functional groups, and moisture and oxygen are also quite sensitive to polymerization. For example, tungsten (W) 'titanium (Ti), molybdenum (Mo) and ruthenium (RU) and other metal compounds are the catalysts for ring-opening metathesis polymerization of rings and olefins, in which metal catalysts are used for moisture and oxygen. Stabiliity or compatibility is preferred to carry out the polymerization even in an aqueous solution. For example, in 1996, Grubbs et al. newly developed a carbon-diluted coordination catalyst {Cl2Ru(CHph)[p(C6Hn)3]2} is very effective for ring-opening metathesis polymerization of cycloolefins, especially in air. Polymerization with a functional group monomer can be carried out. In addition, it has a high polymerization rate and a high molecular weight property, and generally has a living polymerization. There are more and more researches on ring-opening metathesis polymerization using cycloolefin derivatives as monomers, mainly with side chain liquid crystals, and two-step (twdsteps) synthesis of triblock (tdblock) copolymers. Various functional group-introduced polymers 'wherein the introduction of functional groups gives the polymer photoelectric and biochemical activity. Polynorbornene and its derivatives are the first I27l4ll commercial/commercial products by open-loop metathesis polymerization, which is one of the important engineering plastics. It is widely used in lighting fixtures, machinery, electronic parts, and food packaging because of its good transparency, good impact (rubber additive), wide temperature range, good mechanical properties and processability. Further, derivatives such as acids and ester polymers are more suitable as photoresists for the electronics industry. The synthesis of a promising polymer material is even more important. SUMMARY OF THE INVENTION The present invention mainly introduces carbazole groups by diels_Aider reaction of borneolene methyl gas and various norbornene derivatives, and extracts monomers and polymers from high-pressure reactors, and studies their polymerization behavior and physical properties. For a more in-depth understanding of the field of open-loop metathesis polymerization of the original ice II and He organisms. Preparation of money co-polymer by ring-opening metathesis polymerization, using 'Ϊ = dilute and propylene base gas or bromine' in a high pressure reactor Diles_Alder = synthesis of raw borneol methylamine, and reaction with (d) potassium salt to kill monomer Flavored medium monomer (CbZNB). The monomer is then metathesized with the base metal of the ruthenium metal complex, and the block formed by the formation of the original borneol or bromine. The ring can be changed by ring-opening metathesis polymerization to change the value of the monomer. Concentration, starting agent concentration), forming a variety of different I: if polymers 'hydrogenated to obtain hydrogenated blocks a total of two: Xu 1 〇 its polymerization rhyme and new materials of the material ten (heat stability) , = sub-quantity, molecular weight distribution, and polymerization mechanism). : From the knee second trial t original borneol methyl chloride to form a block copolymer, and then grafted a jiajiu u μ r seven &#布 I, olefin, a new functional polymer 枓 (including thermal properties) , photoelectric properties, etc.). Sub-5^CH2'x #ι所t provides a polymer which is based on the original borneol-type dentate (1) as the starting point of the original borneolene, and its structure is as shown in (ιν).: ( I) 1271411 ^1^7~CH24MkX (iv) ^ is one of Cl and Br, and M is a group selected from the group consisting of polymethyl acrylate, methyl methacrylate, polystyrene, and combinations thereof. ^一和quot;), 'n is an integer of 150~18〇〇. Another purpose of the demonstration is to provide a copolymer, which is the original polymer of (Iv) and the original polymer of (Iv) The carbazolyl-containing, norbornene-type monomer is formed by ring-opening metathesis polymerization and has a structure of (V):

(V)

', medium, m is an integer of 50 to 1200, 11 is an integer of 1050 to 1800, and P is an integer of 1 to 3, X is Bi^c1, and m is selected from polymethyl methacrylate and polyacrylic acid. One of the groups formed by vinegar, polystyrene and combinations thereof. Another object of the present invention is to provide a block copolymerization of a side chain containing branches as in (III).

1271411 wherein 'm is an integer from 5 〇 to 12 00, η is an integer from 1050 to 1800, and χ is Br or Cl. A further object of the present invention is to provide a block copolymerized article comprising a side chain branch having a structure as in (V).

Where 'm is an integer from 50 to 1200,! ! An integer of 1050 to woo and an integer of ρ of 1 to 3, X is Br or Cl, and Μ is selected from the group consisting of polymethyl methacrylate, polymethyl acrylate, polystyrene, and combinations thereof. One. '

CH2-(m^-X (VI) = medium, η is an integer of 1〇5〇~uoo and p is an integer of 1~3, χ 2Br or M is selected from polymethyl methacrylate, polyacrylic acid One of the groups formed by 曱-曰, polystyrene, and combinations thereof. The result of the combination is to provide a copolymer having (νπ)

(VII) 111 is an integer of 50 to 1200, η is an integer of 1050 to 1800, 1271411, and p is 1 3, and the number of 'X is Br or Cl,] viAip is white for methyl methacrylate, Acrylic review # iVL horse is selected from one of methacrylic. a group formed by hydrazine, the present ethylene, and a combination thereof. Derivatization: The ii:: series provides a poly-borne borneol containing a side-linked branch which has a structure as shown in (VIII):

Ch2-(m-)^x J: Φ , . lncA 丨丨 (νπΐ)

An integer of Br or Cl::Γ〇 and an integer of 1 to 3, X ester, polystyrene, and t are formed from polymethyl methacrylate, polyacrylic acid methylated ethylene, and combinations thereof. one. A further object of the present invention is to provide a method for forming a olefin derivative, the steps comprising: a card-based H-illusion (1) = % pentadiene and a dentate-based olefinic borneol-type halide, 1 The structure of the middle 嗲 shoulder, Yong Hw Shangcheng 3' (1): The original borneol (4) compound has a female ^^ch2-x (I) where X is one of Cl and Br; (2) the original borneol type letter The compound is a reactant, the original borneol monomer; and the 3 oxime group (3): the original borneol-containing borneol-containing monomer and the original are subjected to ring-opening metathesis polymerization to synthesize a prepolymer, and a window (4) The raw borneol halide is reacted with the prepolymer to form a block copolymer. According to the above concept, the olefinated person having a dentate group is derived from one of propylene chloride and propylene bromide. "The system and the right view" wherein the carbazolyl-containing ortho-ene monomer has the structure shown in (II): Early body 1271411

According to the above concept, wherein the block copolymer has a structure as follows:

Wherein m is an integer from 50 to 1200, and 11 is an integer from 1〇5〇 to 18〇〇, which is C1 and Br. According to the above concept, the ring-opening metathesis polymerization is carried out under an empty system. Another object of the present invention is to provide a method for synthesizing a copolymer by depolymerization of a raw borneol-type halide into a ring-opening compound, wherein the raw ice-type halide has a structure of (I):

The X system is one of C1 and Br. According to the above concept, wherein the step (1) is further carried out by cyclopentadiene and a dentate-containing olefinic compound, the bornene-type halide is further included before the ring-opening metathesis. According to the above concept, the halogen group-containing olefin compound is selected from one of propylene-based gas and acryl bromide. According to the above concept, the step (1) further comprises a step (2) of synthesizing the orthoquinone-containing precursor 271411 borneol monomer. The borneol type single system According to the above concept, the ruthenium containing ruthenium has a structure as shown in (II):

According to the above concept, wherein the copolymer is a swain-containing borneol block copolymer having a structure of:

Wherein, m is an integer of 50 to 1200, an integer of 1050 to 18 ,, and X is one of C1 and Br. According to the above concept, the ring opening metathesis reaction is carried out under a high vacuum system. '

A further object of the present invention is to provide a method for synthesizing a flavonoid derivative containing a scented α-sodium group, the steps of which include: (1) synthesizing a norbornene type with a cyclopentanthene and a halogen-containing rare compound a halide; (2) synthesizing a carbazolyl-containing ornidyl monomer with the ornidyl-type sulphate as a reactant; (3) using the carbazolyl-containing borneol monomer and the original borneol type The halide is subjected to ring-opening metathesis polymerization to synthesize a prepolymer; and (4) the original borneol compound is subjected to ring-opening metathesis reaction with the prepolymer to form a block copolymer. 11 1271411 According to the above concept, the servant of the olefinic propylene and the propylene group with the 卣1 Λ ^ 国 。 ^. s system selection According to the above concept, wherein the norbornene type compound has the structure (I) as structure: ^^ch2-x I) wherein the X system is one of C1 and Br. According to the above concept, the azole-containing raw borneol has a structure as shown in (II):

According to the above concept, wherein the block copolymer has (如)

Wherein m is an integer of 50 to 1200, n is an integer of 1 〇 5 〇 to 18 χ, and χ is one of Cl and Br. According to the above concept, wherein the ring-opening metathesis polymerization reaction is carried out under a high vacuum system. This case can be further explained by the following examples and illustrations. [Embodiment] 12 1271411 Example 1 Synthesis of raw borneol-type halide The norbornene-type monomer monomer can be synthesized in a high-pressure reactor by a Diels-Alder reaction. It is mainly produced by the action of cyclopentadiene (CyCl〇Pentadiene) and a functional group-containing olefinic compound, propenyl chloride or propylene bromide. Usually, the propylene compound (impound) and the cyclopentadiene are subjected to the Diels Alder reaction, which requires i8〇C, and the cyclopentadiene has a boiling point of 41 ° C. The reaction is carried out in a high pressure reactor and the reaction formula is as follows: :

〇 + CH2=CHCH2-X -►

X=Br, CI Take 50 g of cyclopentadiene, an equivalent amount of propylene or propylene bromide and 1 g of hydroquinone (Hydr〇qUinone), placed in a high pressure reactor at a temperature of 1 80 C (5) Reaction for 12 hours. The resulting liquid was vacuum-extracted with unreacted cyclopentadiene and propylene-based gas or propylene-based bromine at room temperature, and distilled to give the original borneol. The boiling point distillation conditions are as follows: · The original borneol chloride () is 54~56 C / 11 汞mHg and the original borneol bromide (nbmb ~ 78 ° C / 13 mm Hg. ^

Example 2: Preparation of carbazole group-containing raw borneol monomer (CbzNB) 12 grams of potassium hydroxide and 3 gram of carbazole 2 oxime in xylene, water can be obtained to obtain carbazole Potassium salt. The dimethyl hydride was removed and replaced with DMF as a solvent. Into the carbazole potassium salt DMF solution t, 25 g of raw borneol chloride (5_chl〇r〇methyi_2__b__ sub-reflux was added for 1*2 hours. The solution after refluxing Pour into 2 ml of water, and extract twice with 100 ml of ethyl acetate. Evaporate the solution (silica ger; 〇I^ chromatography) for purification. The dyke solution is ethyl acetate·n-hexane = 13 A mixed solvent of 1271411 1 : 6 and recrystallized from n-hexane to obtain a fluorenyl group-derived norbornene derivative (endo/ex〇 = 3:2) having a melting point of 74-76 ° C. NMR results and identification As follows: 13C NMR (CDC13): (ppm) = 140.45138.3, 136.5, 136. 1,132·4,125·5,122 ·7,120.1,118.6,108.8,50.0,4 8.1,47.0,4 5.0, 44· 5,44·0,42.6541·833 9·0,3 8·6,3 0·8,30·5. IR (KBr pellet.cm·1) ;1587 ( v 〇= c5vinylic ) J647J4 78 ( c=c5aromatic Streching) ,1324 ( y Cn) ?745?718 ( v c-H9carbazole ring out of plane) 〇UV( THF) · λ max= 23 6.2nm5 ε = (lQxH^LmoldcnT1. Elemental analysis: (C2〇H19N ) Calculated C: 87.87%, Η: 7·01%, Ν ·5.12%. Found C: 87.58%, η: 7·08%, N: 5.31% 〇 Example 2: Experimental polymerization behavior of the original borneol group containing carbazole group. Changing the reaction monomer concentration to the catalyst concentration ratio ([Mp [I]), different number average molecular weights and molecular weight distributions are obtained. When verifying the living polymerization characteristics of the raw borneol-containing monomer containing the group, it is beneficial. The original ice of the salivary group (4) The change of the ratio of the ratio to the number average molecular weight and the molecular weight distribution to reach the following: The molecular weight of the obtained carbazole-containing borneol polymer is observed to be between dt and b匕'. And the change in the ratio of the concentration of the original borneol monomer concentration of the ° card group is linearly related to the number average molecular weight. The use of the carbazole group of the original borneol monomer to the catalyst concentration ratio is changed to a different number. The average molecular weight and the molecular weight distribution of the taste-containing pyrenoidene polymer. It can be observed from Table 1 that the obtained carbazole-containing group average molecular weight increases with the increase of the ratio of the original ratio of the taste-containing salivary group: It repeats a single "; real 1271411 reaction type m ) is about 100 to 1200. Further, the study of molecular weight must understand the chain transfer and the chain termination reaction to elicit the behavior of the polymerization reaction. Table 1. Using {Cl2Ru(CHPh)[P(C6Hu)3]2} catalyst, changing at 25 °C [M] [M]/[I] Yield c; %) Number average molecular weight (theoretical) 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 Polymerization solvent: di-methane. b. Gpc calibration curve with polystyrene standard sample c·polymerization time of two hours. The experiment of adding the original borneol monomer containing the scented saliva group in stages helps to understand the polymerization behavior of the original borneol monomer containing the carbazole group. The catalyst conjugate was reacted with 50 equivalents of the lanthanide group-containing ornidyl monomer at room temperature for a few hours. The reaction will be divided into three parts: the solution is divided into three parts, and the part is taken out, and dried by precipitation: the sample prepared by GPC is used for the determination of the molecular weight, and the second part is further taken out after the reaction, and is prepared by precipitation and drying. The sample was made into Gpc; the amount was measured, and the last part was added with 750-fold equivalents of the scorpion-containing group = f hydrophenene monomer, which was taken out after 1 hour of reaction, and also subjected to precipitation dry welding to prepare GPC. The sample was subjected to molecular weight determination. As determined by molecular weight = it can be found that the molecular weight measured by the reaction for 1 hour (Mn = 136 〇〇 and 6 hours after the reaction is not very large ((10) (4) · and PDI: = 1.25). The third part is added 75 〇. The equivalent of 15 1271411 of the carbazole group-containing raw ice precipitate was dried and formulated into GPC-like: continue the reaction. The obtained polymer was subjected to the amount of Μ n = 2 i 9 7 〇〇 and the molecular weight was determined. Points;: , ▲ distribution of pDl = 1 25, push J: de-sub- (ie, the reaction of the fourth embodiment of the m) •;; two-fold unit in 50 times the equivalent or add 75 times the equivalent of (4) The base::: peak, regardless of the peak, the polymer obtained after the reaction is a single peak. i; the carbene-containing borneol group of the original borneol single unit ^ t two,, ° ° fruit shows that the reaction has the characteristics of living polymerization Open-loop double decomposition

== Polymerization of block copolymers containing different fractions of CbzNB and raw borneol (10) (10) or the original 4 quaternary odor (NBMBr). The synthesis reaction and steps are as follows:

2.5 耄 Mo Er CbzNB was dissolved in 4 liters of digas methane, placed in a reaction ,, connected to a high vacuum system, frozen _ vacuumed, sealed tube _ thawed, cycled one person. The catalyst was taken in a dry argon-filled glove box (dry b〇x), dissolved in 1 ml of di-methane, injected into the solidified monomer solution with an injection needle, and evacuated. The reaction 16 1271411 bottle was thawed at room temperature, stirred at room temperature for 25 〇c for 3 minutes, and 0.5 mM NBX (x=C1 or ΒΓ) monomer was injected into the reaction needle while the color remained red. In the bottle. After stirring for 12 hours, the polymerization was terminated by the addition of ethyl vinyl ether. The solution was precipitated in 5 Torr of methanol. The polymer was dissolved in dioxane and reprecipitated in decyl alcohol to "repeated twice" to obtain a purified polymer which was dried under vacuum at room temperature. The addition amount of the two monomers is selected to polymerize the block copolymers of different segments. The obtained block copolymer was analyzed by iH NMR, and 68 ppm to 82 ppm was characteristic peak of the carbazole group, and 〇 5 ppm to 45 ppm was a characteristic peak of the polynorbornene main chain cycloaliphatic group. In the unhydrogenated block copolymerization, 49 ppm to Lu 5 ·8ρριη belong to the characteristic peak of the double bond on the polynorbornene main chain, as shown in the first figure. Therefore, it has been explained from Table 1 in the foregoing Example 3 that the polymer synthesized by using CbzNB can be controlled by the change of [Μ]/[Ι], which is the following structure:

::[M]/[I]=100, in Table 1, we can know that the number of polymers is flat! / knife is 26400', after calculation, it can be known that the repeating unit (melon) is about = and ^ Qing [I] = 12 GG, from the table - the number of polymers is 328700, and the repeating unit (m) is about 12 〇〇. Another example is as follows: The number average molecular 4 13_polymer disclosed in Example 3 has a m of about 50. Example 5: Hydropolymerization of a segmented co-polymer containing a mixture of CbzNB and NBX (X=cl Br) in different segments of the original borneol derivative. The polymer obtained by ring-opening metathesis polymerization is mainly a material of 17 1271411 unsaturated double bond. The unsaturated double bond of the chain reduces the heat of the material, so that the unsaturated double bond of the main chain is hydrogenated to obtain a material having two-direction thermal stability. The functional group of the present invention has a benzene ring and thus cannot be directly hydrogenated with hydrogen, and is chemically hydrogenated. The reaction formula and steps of the synthesis are as follows:

The polymer (CbzNB_b-NBX) was 0.2 g, p-tolnenesulfonylhydrazide (1.0 g), diphenylbenzene 2 ml, placed in a 200 ml ampule, and a small amount of antioxidant (BHT) was added. Connect to a high vacuum system, freeze-vacuum, seal, and thaw cycle three times. The reaction flask was thawed in the chamber =, heated to 12 (TC, until the hydrogen was no longer produced, stirred for about 3 hours. The reaction flask was cooled to room temperature, and the solution was precipitated in 5 ml of methanol to obtain hydrogenated a polymer obtained by dissolving the hydrogenated polymer in di-methane and reprecipitating it in decyl alcohol to obtain a purified saturated polymer. The obtained product was identified by NMR to 8.2 ppm to 8.2 ppm of a characteristic peak belonging to the carbazole group. And the characteristic peaks of 聚.5PPm to 4.5PPm belonging to the polynorbornene main chain cycloaliphatic group still exist. 49 ppm to 58 ppm of the unhydrogenated block copolymer belongs to the characteristic peak of the original bond of the original norbornene main chain to hydrogenation. After that, it has ceased to exist. , '' Example 6, unhydrogenated carbazole group-containing borneolene and original borneol bromine embedded 18 1271411 ^ and a total of I compound and gasification containing 吟 σ sitting group original embedded Thermal stability analysis of segment copolymers The measurement of borneol and norbornene bromine contains the thermal stability of the (4) group of raw borneol thin and the original borneol dilute complex and the hydrogenated copolymer (eg second The polybutene group containing the carbazole group and the original borneol bromide are not included. The cracking will begin, and the block copolymer of the original borneol flavonene bromide containing m nitriding has a better thermal stability than the unchlorinated group. The original borneol? Unhydrogenated carbazole-containing borneolene-divorced co-polymers in nitrogen, 1 (rate at rc/min. a table of unhydrogenated 'b) hydrogenated copolymers, temperature rise curve. Example 7 Preparation of a polymer with a norbornene-terminated polymer The original borneol-type compound is further used as a starter to polymerize methyl methacrylate, methyl acrylate and styrene to form a raw hail; The terminal polymethyl methacrylate, polymethyl acrylate and polystyrene (IV) are shown as: (IV) wherein X is Cl or Br'M is methyl methacrylate, acrylic acid Methacrylate or styrene. However, when X is C1, the polymerization effect on methyl acrylate and styrene is far less than when X is Βγ. When Μ is methyl acrylate, the resulting borneolene is obtained. The end of the polymethyl methacrylate polymer, with the addition of f-based methyl acrylate To obtain polymers with different molecular weights and molecular weight distributions. When bromide steel, 1271411 2 = number is compared with dimethicone and methyl methacrylate (_) (about 112700, 1. 1〇) 'The average number of molecular weights is 1 12679 (about 112700), the weight average molecular weight is 16〇875 160900) and the molecular weight distribution is 1 (about desertified steel, 2,...:, raw borneol 曰) The molar ratio is 1:1:1:25, the number of cytographs:=, is 190382 (about 19〇4〇〇), and the weight average molecular weight knife (two about 21). . And the molecular weight distribution is 158, which is 1811. It can be seen that the amount of methyl methacrylate added has a broader molecular weight distribution range. When the cockroach is styrene, the reaction is obtained as the polymer with the end of norbornene. By means of GPC analysis, the average number of points (10) τ ΛΊ ΛΊ a, push, η is about 1 different. Its glass transition temperature: (measured by DSC) has a molecular weight distribution narrower than that of the original borneol-enhanced poly(methyl acrylate). If nobornene methyl chloride (NBMC1) is used in combination with cuprous bromide and 2 2, _ ^ bite in toluene, the yield is low. The 400 MHz h NMR spectrum (CDC13) of the dilute end of the original borneol is shown in the third figure. (i) Preparation of bromopolymethyl methacrylate with endobornene end [p〇ly (MMA) with n〇rb〇rnene methylene end group, NBM-PMMA-Br] 1 mol of bromide Copper [Cu(I)Br], 1 millimolar double sigma (2,2'_biPyridine),! The n〇rb〇rnene methylene bromide (NBMBr) was dissolved in 10 ml of toluene with 1 mM of methyl methacrylate (MMA). After three freeze-pump-seal-thaw-thaw cycles under a vacuum system, the reaction was placed at l3 (the reaction was stirred for 12 hours at rc temperature, and the product was precipitated with methanol. The resulting polypyrene having a base of norbornene was obtained. The methyl acrylate polymer was dissolved in tetrahydrotetramine and then killed three times in methanol 20 1271411. The reaction formula is as follows:

CH2-Br + MMA

ΟΗ2~(ΜΜΑ)ηΒΓ NBM-PMMA-Br

NBMC1) reacts with cuprous bromide [Cu(I)Br] and bipyridine (2,2,-bipyridine) in 曱 _ stupid, resulting in lower yield. Its reaction formula is as follows:

Ch2-ci + MMA

NBM-PMMA-CI () with the preparation of the original borneol, the base of polystyrene methylene end group, NBM-PSt-Br] preparation of 〇 · 3 8 grams of cuprous bromide, 1 2 5 The grams of 2,2'-bipyridine, 5 g of raw borneol bromide and 8 g of styrene are dissolved in 10 ml of toluene, and after three cycles of freezing-suction-sealing in a vacuum system - After the thawing cycle, the reaction was stirred at a temperature of 13 ° C for 12 hours, and then the product was obtained after immersion in methanol, and after cooling, the yield was 35 % after drying in the east. The polymer of polystyrene with a thin end of the original borneol was dissolved in tetrahydroanthracene and precipitated three times in methanol. By number analysis, the number average molecular weight was 60000 and the molecular weight distribution (PDI) was 1.28, which was estimated to be about 153 Å by GPC analysis. Its reaction formula is as follows: 21 1271411

CH2-Br +

Styrene

Cu(l)B "+2,2'_bipyridine NBM-PSt-Br If the original borneol chloride is reacted with cuprous bromide or bipyridine in indole benzene, the yield is low. If styrene, MMA and Cu(I)Br, 2,2'-bipyridine ' NBBr reaction can obtain a polymonomer with polystyrene and poly-MMA and having a norbornene terminal. The resulting bromo-containing bromo (or chlorine-containing) The polystyrene and the carbazole group-containing raw borneol monomer are further subjected to ring-opening metathesis copolymerization, and the polynorbornene copolymer structure containing carbazole group and polystyrene can be successfully synthesized as follows:

The copolymer obtained from Poly(NBCbz/NBM-PSt) can be identified by iH NMR as shown in the fourth figure. The number average molecular weight was 39,000 and the molecular weight distribution was 1.30, and the yield was 95%, which gave a p of about 2.5. The polynorbornene copolymer containing carbazole group and polystyrene was subjected to differential differential scanning thermal analyzer to obtain Tg = 105 ° C (polystyrene segment) and Tg = 165X: (containing carbazole) The group is a poly-borne borneol segment). Further, p〇ly(NBCbz/NBM-PSt) can be obtained by the method of hydrogen as in Example 5, 12 1271411, to obtain poly(HNBCbz/NBMPSt), and its structure is as follows:

From the 1H NMR spectrum, a signal of 4.6 to 5.8 ppm was obtained, indicating that the hydrogenation was completed. Example 8 Fluorescence Spectrometric Analysis The borneazole group-containing raw borneol polymer, the hydrogenated carbazole-containing borneol polymer, and the poly(N-vinyl carbazole), PVK were measured. ) Fluorescence spectrum.原 原 唾 唾 之 之 之 之 之 以 以 以 以 以 以 以 以 以 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾 唾The less intense fluorescent light, which is caused by the formation and excitation of the carbazole group. The fluorescence spectrum of the hydrogenated carbazole-containing ortho-norbornene polymer also has a monomeric emission spectroscopy spectrum at about 377 nm, and at a near higher wavelength, a less intense fluorescence spectrum appears. Bulk, monoterpene, and strength will be more concentrated than unhydrogenated carbazole-containing borneolene

The intensity measured by the object is smaller. This I 1 Γ 坆疋 because the unsaturated double bond is reduced by the hydrogenation reaction, the activity of the ruthenium is increased, and the formation of the excited double body is reduced. Unhydrogenated carbazole group-containing material (polyCbzNB), 啖熹p gas from humans, sub-cylinder =... polymer excited double-body radiation camp light ^. B a 'carbazole polymer excited double body The generation of the fluorescing spectroscopy is caused by the close proximity of the two carbazole groups. Further, the block copolymer of the original borneolene and the norbornene bromine of each of the carbazole groups in 23 1271411 is hydrogenated. : The base of the original group of borneol and the original borneolene block. The fluorescence spectrum of the secret store (as shown in the fifth figure). Contains the original borneol of the cardinal group, borneol bromide The block copolymer (p〇lyCbzNB_d_NBBr), if excited by a 33 〇nm source, will have an emission spectrum of approximately monomer, and will be close to a higher wavelength (in the range of 450 nm to 550 nm). See the less intense fluorescence spectrum, and the spectrum at this high wavelength is _ because of the formation of the carbazole group To the excitation, the fluorescent fluorene of the block copolymer of the original borneolene group and the original borneol bromide has been hydrogenated, and likewise, the monomer fluorescing spectrum is also at about 377 nm, and A near-higher wavelength (in the range of 45 〇 nm to 550 nm) also exhibits a less intense fluorescence spectrum, which is stronger than the unhydrogenated carbazole-containing group = raw borneol and norbornene. The intensity measured by the block copolymer of bromine is slightly larger because the unsaturated double bond is saturated by hydrogenation, so that the activity is increased, and the block of the original borneol group containing the carbazole group is further The polar and non-polar groups in the polymer are self-rearranged by the molecular chain, which greatly increases the chance of formation of the excited dimer. The un-hydrogenated carbazole-containing borneolene polymer or the hydrogenated carbazole-containing group The original borneol polymer of the group is different in the range of 3 8 〇 11111~45 〇 11111, and has the same excitation double-body fluorescing spectroscopy spectrum as the methacrylic acid carbazole polymer (as shown in the fifth figure) Generation of radioactive spectroscopy in the range of 3 8 〇 nm # ～450 nm, the main If the two cymbal groups are close to each other, it is different from the twin-body excited double-body fluorescing spectroscopy. Whether it is hydrogenated or unhydrogenated carbazole group-containing borneol oxime copolymerization Between the molecular chains, due to the interaction between the polar and non-polar groups, the molecular chain will self-rearrange. The self-rearrangement of the molecules will make the carbazole groups close to each other, which is also beneficial to the double The formation of the body 'so there is a specific emission fluorescence spectrum at a specific wavelength position, that is, in the range of 380 nm to 450 nm, the spectrum is close to each other due to carbazole groups, and the spectrum is due to double body formation in the range of 45 〇 nm to 550 nm. 24 1271411 Example 9 Preparation of the original borneol olefin polymer The original borneol-type halide and the ring-opening complex catalyst having the structure of the formula (1) were subjected to ring-opening metathesis polymerization to form a pro-form. The borneolene polymer has the structure shown in (IX) below.

Wherein X is Br or C1. That is, i.kio-3 Moore of the original borneol bromide or norbornene chlorinated in 5 ml of di-methane. Operate under a vacuum system to remove moisture and air. Take 0.001 g (1 2χ1〇_6 mol) of {ΓΙιΚ^γΗΡΙιΠΡβ6!^)3]2} The catalyst is dissolved in i ml of di-methane and injected into the reactor. The reaction was allowed to stand at room temperature, and after stirring for 24 hours, the product was obtained by precipitation with methanol. After lyophilization, the yield was about 7 %. The borneol is exemplified in the tenth embodiment, and the raw borneol halide polymer is used to prepare the poly-branched methyl polyacrylic acid for the purpose of taking 1 millimole of cuprous bromide, 1 millimole of bipyridine, and 丨1 The original borneol bromine polymer of the ear and 1 mM of methyl methacrylate (mma) are dissolved in hydrazine). After three times of aging under the λ-vacancy system, after the venting-sealing-thawing cycle, the reaction was placed at a temperature of 130 °C for 2 hours, and then the product was obtained by methanol. The obtained polymer with the original borneolene " polystyrene is dissolved in tetrahydrofuran and then dissolved in methanol. The reaction formula is as follows:

CH〗 - Br

MMA

Cu(l)Br + 2,2'-bipyridine ------ sub-benzene reaction 25 1271411 Further, the reaction is carried out without adding toluene, and the reaction formula is as follows:

\Ύ^ + _A lcH2_Br No solvent reaction if °H2~(-MMA3p-Br::聚原冰片#chlorine with cuprous bromide, 2,2,_bipyridine in toluene", bath reaction The reaction is similar to that of polynorbornene bromide. 实施 Example 11 Preparation of hydrogenated aliphatic cyclic halide polymer ♦ Raw borneol (4) polymer with chemical formula (() structure) Hydrogenation y has a chemical formula (χ A hydrogenated aliphatic cyclic polymer of the structure.

(X) 氢化 5 5g of norbornene bromide or norbornene chloride and 0.75g of a hydrogenated agent of pt〇luenesulf〇nylhydrazide Ditertbutyl_4-methylphenol) 4 : = agent in 50 ml of xylene, operating under vacuum system, business soil knife and work gas. The reactor was stirred at 120 ° C for 6 hours, and the product was obtained by drying the sea-cooled image. , 1 case 12, hydrogenated raw borneol halide polymer to prepare poly-original flavonol grafted polymethyl methacrylate to take 1 millimol of cuprous bromide, 丨 莫 2 2 , _bipyridine, ,, the ear of the original borneol bromine polymer and 1 〇〇 mM methacrylic acid age, in 1 〇 ml of toluene. After three times of cooling under a vacuum system ~ after the gas-sealing-thaw cycle, the reaction was stirred at 130 ° C and 26 1271411 for 12 hours, after methanol precipitation, the product was obtained. The polymethyl methacrylate polymer was dissolved in hydrogen three times at the end of the methylene. Its synthetic reaction formula is as follows:

CH2—Br "+ ΜΜΑ + 2,2,-biPyridint

Further allowing the reaction to proceed without adding toluene

The reaction formula of CHo-Br cH2~fMMA3^Br is as follows: Π + MMa ^(DBr + 2,2>-bipyridine No solvent reaction

The reaction of CH2-(-MMA^Br with polynorbornene chloride, cuprous bromide and 2,2,_dipyridyl-branched reaction is similar to that of poly-formal borneol. The examples in this example show that the side chain contains The original borneol polymer of the element can be grafted with the monomer of the acrylic series by the method of the present invention, and this reveals that it utilizes the characteristics of living polymerization to form a block copolymer having a group. Materials, grafted acrylic series of monomers can be obtained a new high-second material. The mouth of this case can be used by those who are familiar with this skill, and for all those who do not care for the scope of the patent application. ^ [Simple description of the diagram] The first figure, 400MHz 4 NMR chart (CDC13) of the original borneol group containing the carbazole group and the original borneol bromide block. ', ° The second figure, TGA figure (a) contains The original borneol of the salivary group is thin and the original borneol is inferior = block copolymer; (b) the original borneol thin plate of the (4) group has been hydrogenated. The block bromo block copolymer is under nitrogen. (rc/min heating rate:, the third figure, with 4 〇〇MHz of the original borneol end polystyrene 1H 1^^ 尺 Figure 27 1271411 (CDC13 The fourth figure, a 400MHz 1H NMR image of the poly-borne borneol thin copolypolymer {Poly(NBCbz/NBM-PSt) containing carbazole group and polystyrene (CDC13). The fifth figure, (a) contains a leaf raft Co-formed borneol and original borneol co-polymer (dashed line); (b) hydrogenated carbazole-containing, stinky squalor borneol block copolymer (solid line); borneol thin and original length For _. camp..., its excitation wave

28

Claims (1)

Pick-up, patent application scope: 1. A polymer with a raw terminal of the original borneol-type halide (I) as a starting agent, and its structure is as follows: (I) The raw borneol formed by the film is ^XCH2_X (I) (IV Wherein X is one of Cl and Br, and Μ is a white stone selected from the group consisting of Δmethylpropionic acid formazan, styrene, and a combination thereof, and is an integer of from 1050 to 1800. a 4 2.-copolymer formed by the mono-metathesis polymerization of the original borneol compound represented by (IV) and the carbazole group-containing borneolene group represented by (II). Has a knot like (V): Ή% (Π) Wherein m is an integer of 50 to 1200, η is an integer of ι〇50 to 18〇〇, and P is an integer of 1 to 3, and X is Br*C is selected from methyl methacrylate and methyl acrylate. , stupid ethylene and their combination formed by two groups. 29 1271411 3 . A block copolymer comprising a side chain branch having a structure such as (111) Wherein m is an integer of 50 to 12 00, η is an integer of 1050 to 180 0, and X is Br or C1. 4. A block copolymer comprising a side chain branch having a structure as in (V): Wherein 'in is an integer of 50^~^1200, η is an integer from 1050 to 1800, and ρ is an integer from 1 to 3, and X is Br or C is selected from decyl methacrylate, methyl acrylate, and benzene. One of the ethnic groups formed by ethylene and combinations thereof. A rare form of poly-borne borneol containing a side-linked branch having the structure of (VI): CH2KX (VI) wherein η is an integer of 1〇5〇~1800 and ρ is an integer of i~3, χ, Br or C1, and Μ is selected from decyl methacrylate, decyl acrylate, stupid ethylene and Combine one of the ethnic groups formed. 6. A copolymer having a structure such as (νπ): (VII) 1271411 Wherein m is an integer of 50 to 1200, n is 1〇5〇~18〇〇, and P is an integer of 1 to 3 'X is 汾 or α, M A = :”, acetoacetate, ethylene And a combination thereof. 7. A poly-bornene derivative containing a side-linked branch, having the structure: having (VII) (VII): wherein m is an integer of 50 to 1200, n is an integer of 1〇5〇 to 18〇〇, and Ρ is an integer of 1 to 3, X is Br or C1, and Μ is selected from the group consisting of One of two groups formed by esters, methyl acrylate, styrene, and combinations thereof. , 8 polynorbornene derivatives containing side-linking branches having the structure as shown: V J In ch24m-^-x (VIII), B ^ is an integer of 10 50 to 18 00 and p is an integer of 1 to 3, χ 1 ' or Cl, and μ is selected from methyl methacrylate and methyl acrylate. , 31 And one of the ethnic groups formed by the combination thereof. The method for synthesizing a carbazole-containing poly raw borneol comprises: a method for flavonoids, wherein the step (1) is a cyclopentene and a halogen-containing borneic borneol-type halide, wherein the strontium ore, ', s synthesis of the original (1) structure · · Thai original borneol thin toothed with _CH2-X (I) wherein X is one of Cl and Br; (7) Raw borneol thinning dentate is the reactant, meridene monomer; oleo 3 carazole violent (3) with carbazole-containing The original ice-moon sputum entry rod „ e _ 八 w 月 烯 早 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 „ „ „ „ „ „ „ „ „ „ „ „ „ „ „ „ „ „ „ „ „ The reaction forms a segment of the copolymer pre-form for ring-opening metathesis. 10. The compound according to the scope of claim 9 is selected from the group consisting of propylene: the method and the dentate-containing one. And propylene bromide according to the method of the item 'wherein the (tetra) quinone-type early system has the structure as shown in (11). ch2~n (II) 12 · According to the method of claim 9, wherein the block has a structure of (ΠΙ): 32 (III) 1271411 CH2 - X is an integer from 1050 to 1800. Eight is an integer of 50 to 12 、, and X is one of C1 and Br. The method of claim 9, wherein the open-loop complex split reaction is carried out under a helium vacuum system. The method of the above, wherein the step η is a step (5), wherein the step (5) is carried out by adding an acrylic series copolymer to carry out a graft reaction to obtain a raw borneol having a side-linking column-seat group. Alkene derivative. The method of claim 14, wherein the ortho-formene derivative having a pendant group has the following (V) CH2—(Μ甘X where m is 5〇~12〇〇Mdu & (V) and P is an integer of 1~3, n is 1050~1800 integer I -7 < integer, X is Br哎C1,1U, methyl ester, methyl acrylate, and di J are selected from one of methyl ruthenium. The group formed by bismuth ethylene and its combination is more than 16 Type deuteration: a structure in which ring-opening metathesis polymerization is carried out in a method in which the ortho-normene type halide has a (I) shirt replacement page where the X system is one of C1 and Br. 1 7 · According to the application The method of the patented Fan Yishang is further described before the decomposition of the compound, wherein the ring-opening compound is alkalized two:: two (1) is a cyclopentadiene and a method described in the item Y, wherein _ one of them. The D system is selected from the group consisting of acryloyl chloride and acryl bromide, etc. 19. According to the application of Patent No. 7, the method described in the above paragraph (1), and the method of the step (1), The human A ( 2 ) is a raw material containing the borneoyl halide as a reactant, and the carbazolyl-containing raw borneol 20 is synthesized according to the scope of the patent application; Method, wherein the single original dilute borneol system containing the carbazolyl structure as shown having the ⑼. Ch2-n (Π) 2 1 · According to the method of applying for a patent, the father of the r mw, the raw borneol block copolymer having the structure of (III) : Wherein, m is a slave of 50 to 1200, ^ ^ ^ ^ old hair number, n is an integer of 1050 to 1800, and X is one of C1 and Br. (III) 2 2 · According to the scope of the patent application 篦 ^ y, the method described in paragraph 16, wherein the open-loop metathesis reaction is carried out under a high vacuum system. 34 feelings τ 23. A method for synthesizing a raw borneol derivative containing a carbaryl group, the step comprising: (1) 2 cyclopentadiene and a olefinic borneol-type sulphate-based sulphate; (2): the raw borneol thin-formed compound is a reactant, the original borneol monomer; f-based (3) active ring-opening metathesis polymerization of the carbazole-containing raw borneol monomer and raw ice Synthetic prepolymerized character Nanhua (4) The original borneol halide is reacted with the prepolymer to form a -block copolymer.仃 裱 裱 24. 24. 24. According to the method described in claim 23, the olefinic compound is selected from the group consisting of acryloyl chloride. Long-standing acryl bromide wherein, according to the method described in claim 23, the hair styling halide has the structure of (1): /, 〒 the borneol (I) wherein X is C1 and B r One. 26. According to the method described in claim 23 of the patent application, 占 gt; π , · 六' A, the mouth card 29 ch2-n: The base norbornene type single system has a structure as shown in (Π). (Π) 27. The method of claim 23, wherein the #段4 polymer has the structure of (III): 1271411 Wherein m is an integer of 50 to 1200, η is an integer of 1050 to 1800, and X is one of C1 and Br. 28. The method of claim 23, wherein the ring opening metathesis polymerization is carried out under a high vacuum system. 36