TW434263B - Graft copolymer of syndiotactic styrene/para-alkylstyrene copolymer - Google Patents

Abstract

The present invention provides a graft copolymer of a syndiotactic styrene/para-alkylstyrene copolymer, having the formula of wherein R1 and R2 are independently selected from the group consisting of hydrogen, alkyl, primary and secondary haloalkyl; X is a functional group selected from a group containing halogen, oxygen, sulfur, silicon, nitrogen, carbon, phosphorus, and mixtures thereof; Y is a polymer moiety; a ranges from 10 to 30000; b ranges from 0 to 30000; c ranges from 0 to 30000; and d ranges from 1 to 30000. In comparison with a syndiotactic styrene polymer, the compatibility of the graft copolymer of syndiotactic styrene/para-alkylstyrene copolymer of the present invention with other polymers is improved. Also, the graft copolymer of the present invention can serve as a compatibilizer for a polymer blend.

Description

434263 A7 B7 V. Description of the invention (1) The present invention relates to a kind of graft copolymers of syndiotactic styrene / para-alkylstyrene copolymers. 〇Parylene Syndiotactic polystyrene (sPS) is widely used commercially. However, it has the disadvantage of poor adhesion to other materials (such as copper for PC circuit boards). Also, SPS is not compatible with other polymers. Therefore, it is necessary to improve the physical properties of traditional para-polyethylene.

Chung et al., In U.S. Patent No. 5,543,484, disclose a functionalized (X-olefin / p-alkylstyrene copolymer. First, an α-olefin is copolymerized with p-alkylstyrene. -The introduction of alkylstyrene into α-dilute hydrocarbon polymers will generate benzyl protons. This benzyl proton can easily perform many chemical reactions under mild reaction conditions, so it can be used in benzyl A functional group is introduced at the position. Then, the ot-olefin / p-alkylstyrene copolymer is subjected to a functionalization reaction, so that the benzyl protons on the p-alkylstyrene unit are functionalized. Functionalization can improve the physical properties of the original olefin polymer. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page)

Powers et al., In U.S. Patent No. 5,548,029, disclose a para-alkylstyrene / isoolefin graft copolymer. In a similar manner, the isoolefin and p-alkylstyrene are first copolymerized, and then the p-alkylstyrene / isoolefin copolymer is subjected to a functionalization reaction such that benzyl on the p-alkylstyrene unit Matrix protons are functionalized. Similarly, the physical properties of the original isoolefin polymer can be improved by such functionalization. In the Powers patent, in order to improve the isoolefin / p-alkylbenzene, the paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) A7 B7 434263 5. Description of the invention (2) Ethylene copolymer and other Polymer compatibility, such as compatibility with thermoplastic polymers, can be reused with grafting techniques. That is, a thermoplastic polymer is partially grafted onto a functionalized copolymer. Furthermore, such a graft copolymer can also be used as a compatibilizer for blending polymers. To date ', no graft copolymer of para-styrene / p-alkylene copolymer has been developed. An object of the present invention is to solve the above problems and to provide a graft copolymer of a para-styrene / p-alkylstyrene copolymer. Compared with the para-styrene polymer, the graft copolymer of the para-styrene / p-alkylstyrene copolymer of the present invention has better compatibility with other polymers. Furthermore, the graft copolymer of the para-styrene / p-alkylstyrene copolymer of the present invention can be used as the compatibilizer of the blended polymer, so the compatibility of the blended polymer with other polymers can be improved. , And improve the impact resistance and elongation of the blended polymer, and the physical properties of the original polymer in the blended polymer can still be maintained. In order to achieve the above-mentioned object, the graft copolymer of the para-styrene / p-alkylstyrene copolymer of the present invention has the following chemical formula-(-CH2—-CH CH — CH- ^ (CH2— CH Price ~~ (-CH2—CH-^-

丨 D {^ C I ---- 110-- (Please read the precautions on the back before filling in this page). Order by the Central Working Group

r2-c-h R1

r2-c-x R1 r2-c-y R1

(I R1 and R2 are independently selected from fluorene, alkyl, primary and secondary halide papers. MIg (| CNS) A4 ^ (210X297 ^ ·) '? .Fi- 43426 A7 B7 Central Bureau of Standards, Ministry of Economic Affairs Printed by the Shelley Consumer Cooperative 5. In the group consisting of the (3) base (haloalky 丨), it is preferable that R1 and R2 are independently selected from the oxygen 'Ct · 5 burning base' and Cw-grade and secondary In the group consisting of halogenated groups, X is a functional group. It is selected from the group consisting of halogen, metal, oxygen, sulfur, stone, nitrogen, carbon, functional groups and mixtures thereof. Y is a In the polymer portion, a is 10 to 30,000, b is 0 to 30,000, c is 0 to 30,000, and d is 1 to 30,000. The polymer preferably has a number average molecular weight of at least 1,000 or more. The para-styrene of the present invention is prepared. The general methods of graft copolymers of p-alkyl styrene copolymers will be described as follows. Grafting technology can be divided into two categories: " graft-from " and " graft-on ". Refers to para-styrene / p-alkylene styrene copolymer and a monomer using anionic polymerization, cationic polymerization, anion or cation Ring-opening polymerization or radical polymerization for graft polymerization. For example, via anionic polymerization: ..... —-In--II ^^^^ 1 I (Please read the precautions on the back first (Fill in this page again.) · 'Ordering line 0 This paper size is applicable to Chinese National Standard (CNS) A4 specification (210 X 297 mm) 4342S3 Α7 Β7 V. Description of the invention (4 _ ^ ch2ch)-(-ch2ck-)

sBuLi

Anionic TMEDA polymerizatbn

iH3

Or a functionalized (eg brominated) para-styrene / p_alkylstyrene copolymer and a monomer via cationic polymerization: —CH2CK) ^ (-CH2CH ~ j

x '‘/ y — (-^ 20 ^^ 201 + ^ AgCl〇4 ^ Cationic _ AgBr polymerization

J ------ IJIO ~ | (Please read the precautions on the back before filling in this page) Λ: H2Br

Or use the living radical polymerization reaction to connect the monomer to the para-styrene / ρ-alkylstyrene copolymer to become a graft copolymer: CHaCK ^ CH2CH-) ^-— (-〇Η2〇Η ^ 〇Η2ΟΗ-] ^-Living Free Radical -► Polymerization

-Printed by the Central Consumers Bureau of the Ministry of Economic Affairs

H2Br

〉 H2 graft-on technology is the functionalization of functionalized para-styrene / p-alkylstyrene copolymers and functionalities on para-styrene / ρ · alkylstyrene copolymers that can be functionalized with this. One of the basic reactions is that the polymers react with each other, and this paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm). Line 0 · Printed by the Bayer Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 34263 A7 _B7 V. Description of the invention (5 ) Grafting is achieved by linking the polymer with the functionalized para-ethylene / p-alkylstyrene copolymer. Therefore, Y in Chemical Formula (I) may be a polymer selected from anionic polymerizable monomers, cationic polymerizable monomers, anionic ring-opening or cationic ring-opening monomers, and free-radically polymerizable monomers. And copolymers. Specific examples of anionically polymerizable monomers include conjugated diene, vinyl aromatic compounds, vinyl unsaturated benzylamine, acephthylene'9-acrylcarbazole, propionitrile, Methacrylonitrile, organic cyanate, acrylate, methacrylate, alkyl acrylates, alkyl methacrylates, glycidyl methacrylate ), Vinyl pyridines, etc., or mixtures thereof. Specific examples of the cationically polymerizable monomer are vinyl aromatic compounds, vinyl ethers, and vinyl. Carbohydrate (N-vinylcarbazole), isobutylene, etc., can also be used as a mixture. Specific examples of anionic ring-opening or cationic ring-opening monomers are cyclic ethers, sulfides, lactones, lactams, N-carboxyanhydrides, etc., and mixtures thereof may also be used. . Examples of radically polymerizable monomers are vinyl aromatic compounds, conjugated dienes, acrylates, alkyl acrylates, alkyl acrylates, alkyl methacrylates, vinyl acetates, and the like. Mixture 0 8 ----- IHI9L. (Please read the precautions on the back before filling in this page}. Alignment 〇 This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 4342 ^ 3 A7 B7 Economy Printed by the Consumer Standards Cooperative of the Ministry of Standards and Standards of the People's Republic of China 5. Description of the invention (6) The general method for preparing the functionalized para-styrene / p-alkylstyrene copolymer of the present invention will be described as follows. Styrene and para- The reaction of f-based styrene monomer is taken as an example. First, these two monomers are copolymerized using a metallocene compound as a catalyst. The catalyst system may also include an activating catalyst (f-CH2CH). ^ (-CH2CH ^-metallocene MAO CH3 ch3 cocatalyst), such as methyl aluminoxane. Where each x and y is the mole fraction (%) of the corresponding monomer, x + y = 100 . Suitable metallocene catalysts are delocalized (deloc alized) π bond part, but has a restricted three-dimensional structure. This catalyst can be interpreted as a metal coordination complex, which has a metal element of group IVB-VIB and a non-localized π of restricted three-dimensional structure Bonding portion. Such catalysts are described in U.S. Patent Nos. 4,542,199; 4,530,914; 4,665,047; 4,752,597; 5,026,798; and 5,272,236. Preferred catalyst complexes include zirconium complexes and titanium Coordination compounds can have one or two cyclopentadienyl derivatives. Suitable activation catalysts can be fluorenyl aluminoxane (ΜΑΟ), trialkyl aluminum, dialkyl aluminum) 'Inert and non-coordinating anion salts, or mixtures thereof. Trialkylaluminum can be trimethylaluminum, triethylaluminum, tripropylaluminum,

! ^ \ " iο ~~ (Please read the note on the back side before filling in this page) Alignment 〇 This paper size is applicable to China National Standards (CNS > A4 size (210X297 mm) 434263 A7 B7 V. Description of the invention (7) Isopropyl, tributyl, triisobutyl aluminum (TIB A), etc. "The salts of inert and non-coordinating anions may be borate salts. Borates suitable for use in the present invention include N , N-dimethyl anilinium tetrakis (pentafluorophenyl) borate], triphenyl carbeniumtetrakis (pentafluorophenyl ) borate], trimethyl ammonium tetrakis- (pentafluorophenyl) borate], ferrocene (pentafluorophenyl) borate] , Dimethyl ferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate], etc. The better match is A Alumoxane, or a mixture of trialkylaluminum and borate. Printed by Shelley Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs (please read the precautions on the back of this page before filling out this page) For monomers, catalyst ingredients, and The preferred diluent for the polymerization reaction can be ordinary aliphatic and aromatic hydrocarbons, which can be used alone or in combination, such as propane, butane, pentane, cyclopentane, hexane'toluene, heptane Alkane, isooctane and so on. Generally speaking, in the polymerization reaction of the present invention, styrene and p-fluorenylstyrene are mixed uniformly in a copolymerization reactor in the presence of a catalyst, and the reaction temperature is about 0. (: To 100 ° C. The polymerization reaction is carried out in an inert gas atmosphere and substantially free of water vapor. The advantage of styrene / p-methylstyrene copolymer is that the Paper size applies to Chinese National Standard (CNS) A4 (210X297 mm). Printed by Shellfish Consumer Cooperative, Central Standards Bureau, Ministry of Economic Affairs, printed 434263 A7 -------- B7 __ 5. Description of the invention (8) Styrene unit The benzyl matrix on the substrate can be easily converted into various functional groups in a mild reaction state, such as -COOH, _OH, _NH2, -Cl, -Br, -M, COOM (M is a metal such as Li, Na, K , Ca, etc.) The functionalization reaction that can be carried out on the benzyl matrix of most organic compounds is also applicable to the benzyl matrix on p-methylstyrene. The following two chemical formulas, namely para-position The bromination and carboxylation reactions of styrene / p-alkylstyrene copolymers are used to illustrate the functionalization reaction of the benzyl protons on para-p-hexene / p-alkylstyrene copolymers.

------------- io- — (Please read the note ^ on the back before filling this page) Order COOH benzyl matrix on para-styrene / p-alkylstyrene copolymer Among the functionalization reactions, the halogenation and metallization reactions are the most important. The halogenation reaction produces benzyldentin, and benzylnan is a very active electrophile, which can be reacted into various functional groups through nucleophilic substitution reactions. The metallization reaction produces a benzyl anion on the p-alkylstyrene unit, which can react to many other functional groups. As a matter of fact, dentinization and 11-line 9 paper sizes are applicable to China National Standard (CMS) A4 specifications (210 > < 297 mm) Printed by Shellfish Consumer Cooperative, Central Standards Bureau, Ministry of Economic Affairs, 43426 3 A7 ~ ~~~ ~ ________ B7 V. Description of the invention (9) ~ — The metalized para-ethyl / p-phenylene styrene copolymer can react to almost all organic functional groups. So 'direct reaction via unfunctionalized para-paraben / p-alkyl styrene copolymer' or via dentin or metallization of para-paraben / p-alkylstyrene copolymer The functional group X in the reaction formula IX may be a beta energy group containing halogen, metal, oxygen, sulfur, silicon, nitrogen, carbon, or phosphorus, or a mixture thereof. The functional group X at the benzyl position is also described in U.S. Pat. Nos. 5,543,484 (Chung, et al.); 5,548,029 (Powers, et al.); And 5,162,445 (powers, et al) There are detailed reveals. Specific examples of the metal-containing functional group X are an alkali metal or an alkaline earth metal. Examples of the oxygen-containing functional group X include alkoxides, phenoxides, and earboxylates, which are obtained by replacing a halogen ion on a benzyl group with -0-. Examples of the sulfur-containing functional group X include thiolates, thiophenolates, thioethers, thiocarboxylates, dithiocarboxylates, sulfur glands Thioureas, dithiocarbamates, xanthates, and thiocyanates, which are obtained by replacing halogen ions on the base with -S-. Examples of the functional group X containing Shixi include silanes and halosilanes, which are obtained by replacing halogen ions on the base with -Si-. This paper size applies to China National Standards (CNS) A4 specification (2 丨 0 > < 297 Gongchu) -------- ^-Io--Order ---,-line 〇I (Please read first Note on the back, please fill in this page again) 434263 Printed A7 B7 by Zhengong Consumer Cooperative of Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (1) Examples of functional groups containing broken X include malonates' cyanide The cyanides' and CR33 and R3 are an organic group, which is obtained by replacing a halogen ion on a benzyl group with -C-. Examples of nitrogen-containing functional groups X include amides, amines, carbazoles, phthalimides, pyridines' maleimides ( maleimides), cyanates, which are obtained by replacing a halogen ion on a benzyl group with -N-. Examples of the functional group X containing a phosphine are, for example, phosphines. , Which is obtained by replacing the-ion on the benzyl group with -P-. In the following, the content, methods, and features of the present invention will be further explained through several embodiments, but it is not intended to limit the present invention. The scope of the present invention shall be based on the scope of the attached patent application. Synthesis of dendritic poly (styrene-co-co-alkylstyrene) Example 1: Synthesis of para-poly (styrene-co-para-methylstyrene) Purified para-methyl under nitrogen 35 ml of styrene monomer (hereinafter abbreviated as pMS) and 315 ml of styrene monomer (hereinafter abbreviated as SM) were charged into a 1 L metal reaction vessel, and then 2.8 ml of a 10 wt0 / 〇 alumoxane (MAO) solution was charged into the reaction Device. After the reaction vessel was heated to 70 ° C, the pentamethylcyclopentadienyldimethoxy '(m) [cP * Ti (OMe) 2] catalyst was added 0.0208 mmol, and the reaction was carried out for 60 minutes with hydrogen After the reaction was terminated with sodium / methanol solution, soxhlet extraction was used to 'extract with methanol as solvent for 24 hours' to obtain 86 g of product. The 13 paper sizes of the copolymer are applicable to the Chinese National Standard (CNS) A4 specification (21〇 ×: 297 mm) ---------- ο__ (Please read the note $ on the back before filling this page } T 'S. 434263 Printed by A7 B7, Shellfish Consumer Cooperatives, Central Standards Bureau, Ministry of Economic Affairs 5. Description of the invention (n) In terms of physical property analysis, NMR analysis shows that the pMS content is 12 mole percent; the melting point after DSC analysis is 239 ° C; by GPC analysis, the weight average molecular weight is 1,526,000, the number average molecular weight is 741,000, and the molecular weight distribution is 2.06. The properties and results of other copolymers are shown in Table 1. Example 2 The steps are the same as described in Example 1, but changed The amount of catalyst and aluminoxane (MAO) was used. The results are shown in Table 1. Example 3 A para-styrene copolymer was prepared in the same manner as in Example 1. The catalyst was changed to the one described in US Patent No. 5,644,009. The catalyst system used. The results are shown in Table 1. "Examples 4 to 6 Except the reactor was changed to a 1L glass reactor to polymerize para-ethylene copolymers at 0.1 kg / cm2G of hydrogen, the remaining methods and implementations Example 3 is the same. The results are shown in Table 1. 会 施The 7 steps are the same as described in Example 1, but a 100 liter reactor was used, and the amount of reactants was changed. The results are shown in Table 1. Example 8 The steps are the same as described in Example 1, but at 0.4 kg / cm2G of hydrogen. The reaction was carried out under pressure, and the results are shown in Table 1. The paper size applies the Chinese National Standard (CNS) A4 ^ grid (21〇 > < 297). I. oI—--(Please read the note on the back first Please fill in this page again)-Order 0.4 342 ^ S ^: A7 B7 — '— ~ — _ V. Description of the invention (12) Table 1 贲 Example SM (ml) pMS (ml) Catalyst (mmol) MAO (ml) Reaction time fmin) Melting point pMS content (mol%) in CO Mw Mw / Mn copolymer 1 315 35 0,0208 2.8 60 239 1.53χ106 2.06 12 2 315 35 0.0384 6.2 60 232 3.4x10s 1.87 17 3 295 5 0.019 3.2 270 259 12xl05 6.1 5 4 397 3 0.0208 8,4 30 271 7.8xl05 1.68 1 5 315 35 0.0384 62 40 236 2.4x10s 9.32 15 6 200 200 0.0416 9.0 300 1.12x10s 2.93 58 7 45 L 5L 1,8 500 120 235 9.4x10s 2.04 7 8 * 300 33 0.008 1.5 30 242.8 1.57x10s 2.4 10 ———— ο— (Please read the precautions on the back before filling this page) —. Order

* Functionalization of 1-5mL 22wt% TIBA hanging poly (stupid ethylene-co-p-alkane) has been functionalized. Example 9: Para-poly (stupid ethylene-co-p-fluorenylstyrene) (sPS- pMS) was oxidized by taking 20 g of para-poly (styrene-co-p-methylphenylhexyl) (syndiotactic poly (styrene, methylstyrene): hereinafter referred to as sPS-pMS) (SM = 83%) : pMS = 17%) was placed in a 2L three-necked round bottom flask and 600 ml of o-dichlorobenzene (〇DCB; o-dichlorobenzene) was added as a solvent. The three necks of the round-bottomed bottle were respectively connected to a mechanical stirrer, a serum stopper and condensation 15 This paper size applies the Chinese National Standard (CNS) M specification (2i0x29 " 7mm) -line 0— · Printed by the Beige Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 434263, A? B7 Employees of the Central Standards Bureau of the Ministry of Economic Affairs Cooperatives have cracked V. Invention Description (13) Tube. First, stir in an oil bath at 120 ° C until the sPS-pMS is completely dissolved. Add 300ml of glacial acetic acid slowly and reduce the temperature to maintain the reaction temperature to 100 ° C. 20 mole% concentration of the catalyst acetic acid #cobalt acetate tetrahydrate and 60mole% relative to the pMS content in SPS-pMS Sodium bromide was added to the round bottom, and oxygen was introduced at a rate of 1 L / min for 2 hours. After cooling, the reaction solution was poured into methanol, and the precipitated polymer was collected by filtration and heated with hot water / methanol. The mixed solution was washed twice, washed twice with methanol, and then extracted with a Soxhlet extractor for 20 hours with methanol, and then dried. The absorption of -CHO and -COOH groups was observed from the 1H NMR spectrum. The results are shown in Table 2. The total oxidation rate (Total oxidation) represents the mole% of the original starting polymer (Sps_pMS), and PDI represents the molecular weight distribution index (p0yydispersity index). Example 9 'However, the amount of catalyst and sodium bromide was changed, and the reaction time was changed. The results are shown in Table 2. Example 12 shows that 20 g of para-poly (styrene-co-p-fluorenylstyrene) obtained in Example 7 was used in the same experimental procedure as in Example 9 'to change the reaction time to control the molecular weight. The results are shown in Table 2. ° 16 The size of this paper is in accordance with China National Standards (CNS) M specifications (2 × 297 × 297 mm) (Please read the precautions on the back before filling this page) 6. 434263 A7 ______B7 V. Description of the invention (14) Table 2 Example Reaction time (h) Co: NaBr (mole% of pMS) Total oxidation (%) Mn PDI Tm (° C) Tg (° C) 9 2hr 20:60 9.27 16000 2.29 185.28 98.74 10 lhrSOn 10:40 3.61 45000 2.28 225.82 96.92 11 1.5 hr 10:40 3.32 58000 1.98 223.45 95.26 12 3.0 hr 20:40 6.20 43000 1.76 228.0 93.67 13 1.5 hr 20:40 6.15 289000 2.32 235.5 93.22 (Please read the notes on the back first (Fill in this page again.) Printed in Example 14: 35.9 g of sPS-pMS bromide scale by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. The sPS-pMS obtained in Example 6 was placed in a round-bottom flask, and the round-bottom flask was surrounded by aluminum foil. Then, add 450ml of CC14, 49.6g of NBS, and 1.7g of BPO, and install a condenser tube. Heat under reflux for 43 hours under nitrogen using an oil bath. Then pour this polymer solution into an isopropanol solvent. Precipitation, the resulting polymer was water and isopropyl Cleaning. The brominated polymer was vacuum-dried at 60 ° C using a vacuum system to obtain 49.3 g of the brominated polymer. From 1H-NMR, it was found that 75% of the chemical shift of para-CH3 had been converted to the chemical shift of -CH ^ Br at 4.4 ppm. Example 15: 2.5g of sPS-pMS bromide scale. The sPS-pMS obtained in Example 2 was placed in a round-bottomed flask. 17 This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) t54263'ii A7 B7 V. Description of the invention (15) j 〇 ~ |--(Please read the precautions on the back before filling in this page) Add 200ml C6H5C1 and install the condenser tube, and heat to 120 ° C under nitrogen by oil bath heating Make the SPS-pMS completely dissolved and then return to 75 ° C. Take 0.1ml of bromine (50% para-CH3 amount), add C6H5C1 and dilute to 1ml, put it into a dropper tube surrounded by aluminum foil, and irradiate with a 90W bulb. Round-bottomed flask and the bromine solution in the dropper tube was added dropwise to the round-bottomed flask within 20 minutes, and then this polymer solution was poured into a methanol solution containing sodium hydroxide to precipitate. Alcohol cleaning. The brominated polymer was vacuum-dried at 60 ° C using a vacuum system to obtain 2.58 g of the brominated polymer. From 1H-NMR, 43% of the chemical shift of para-CH3 had been converted to 4.4 ppm- CH2Br chemical shift. Example 16: Carboxylation of sPS-pMS 6. The Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs printed 3 g of the dried sPS-pMS obtained in Example 6 into a 300 ml round-bottomed flask, and added 100 under a nitrogen atmosphere. ml of purified and dried cyclohexane, heated to 60 ° C to dissolve, and then gradually cooled to 0 ° C, 10.4 ml of s-BuLi (1.3M) and 4.1 ml of TMEDA were mixed first, and then this brown red The solution was taken out of the solution injected into the sPS-pMS with a syringe, slowly raised the temperature to 60 ° C for 3 hours, and then cooled to room temperature. 150 ml of THF saturated with CO 2 was added to the reaction flask, and CO 2 was continuously introduced for 1.5 hours to carry out the carboxylation reaction. Finally, the reaction was terminated with methanol and the polymerization reaction product was precipitated with methanol. The obtained polymer was dissolved in THF and reused in isopropyl. Isopropyl alcohol (IPA; isopropyl alcohol) was used to dry the polymer Shen Dian. The FT-IR analysis showed an absorption peak of carboxyl (00) at 1718 cm-1. From the DSC analysis, it was found that the Tg (glass transition temperature) was 18 This paper size applies to Chinese National Standard (CNS) A4 specification (210 × 297 cm) A7 434263 B7 V. Description of the invention (16) 5.5 ° C. Example 17: Silanization of sPS-pMS Take 0.5 g of the carboxylated sPS-pMS obtained in Example 15 and add 5 ml of THF to dissolve it. Add 1 ml of (CH3) 3SiCl and 0.5 ml of Et3N, and heat to reflux for 30 minutes. The reaction solution was poured into a large amount of methanol solvent to precipitate, and the polymer was collected by filtration, washed with methanol, and dried. From the 1H-NMR spectral analysis, it was found that the chemical shift of -Si (CH3) 3 was 0.09 ppm. Example 18 for preparation of edge copolymers: sPS-pMS-g-Polystyrene Take 1.04 g of sPS-pMS (containing 10 mol% para-styrene) (made in Example 8) and put it into a 300 ml round bottom flask Then, 150 ml of purified and dried cyclohexane was added, and 30 ml of cyclohexane was distilled out by distillation. Take 1.5 ml of TMEDA and 3.8 ml of sec-Butyllithium (1.3M in cyclohexane) and mix this deep-gray solution into the SPS-pMS / cyclohexane solution, keeping the reaction temperature at 35 ° C and continuously stir the reaction for 20 hours. "Transfer this round-bottomed flask to the glove box, wash and rinse with n-pentanol repeatedly, add 100 ml of n-pentane courtyard, and then remove this round-bottomed flask from the glove box. Use a long needle to purify 10 ml. The styrene was added to the round-bottomed flask and kept stirring at room temperature for 30 minutes. A large amount of methanol was added to stop the reaction and the polymerization was collected by filtration. This polymer was extracted with methyl ethyl ketone (MEK) at room temperature. Centrifuged 19 paper sizes are applicable to China National Standard (CNS) A4 specifications (210X297 mm) i: 11 -I-i-: =-I ^^^ 1 _ (Please read the precautions on the back before Fill out this page) Order_ 6. Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives, A7 I342§3 B7 V. Description of the invention (17) The method separates and dissolves soluble and insoluble polymers, and finally insoluble Graft copolymer SPS-pMS-g-Polystyrene in MEK 6.2 g 3.3 g of polystyrene homogeneous polymer falling on MEK Example 19 · sPS-pMS-g-Polybutadiene 2.0 g of sPS-pMS (containing 5 mol% para-styrene) (obtained from Example 3) was placed in a 300 ml round bottom 150 ml of purified and dried cyclohexane was added to the flask, and 50 ml of cyclohexane was distilled out by distillation. Take 1.5 milligrams of TMEDA and 3.8 milliliters of sec-Butyllithium (1.3M in cyclohexane), and then add this deep-scraped solution to the SPS-pMS / cyclohexane solution, keeping the reaction temperature 55 ° (: and continuously stirring the reaction 20 hours. Transfer this round-bottomed flask to the glove box, wash repeatedly with n-pentanol, purge and drain, add 100 ml n-pentyl-burn, then remove this round-bottomed flask from the glove box, and use vacuum transfer to transfer 4.0 A gram of purified 1,3 butadiene (1,3-butadiene) was added to a round-bottomed flask and stirred at room temperature for 6 hours. Then, methanol was added to stop the reaction and a large amount of acetone was added to allow the polymer to precipitate, and collected by filtration. Polymer. The homogeneous polymer of 1,3 butadiene in this polymer was extracted by continuous extraction with n-pentane at room temperature for 24 hours. The soluble and insoluble polymers were separated by centrifugation and drained. Finally, 3.08 g of SPS-pMS-g-Polybutadiene insoluble in n-pentane and 1.83 g of polybutadiene homopolymer soluble in n-pentane were obtained. The analysis results from 1H-NMR showed that SPS-pMS-g-Polybutadiene Contains 50.7 mol% of 1,3 Butadiene. 20 This paper size applies Chinese National Standard (CNS) A4 specification (210X297mm)!; 丨, 1〇 ~ | (Read the precautions on the back before filling in this page) Order 0. Central Ministry of Economic Affairs Printed by the Consumer Bureau of the Standards Bureau 4 342 ^ 3 A1 B7 Printed by the Central Bureau of Standards of the Ministry of Economy Shellfish Consumer Cooperatives 5. The Invention Description (18) Example 20: sPS-pMS-g-PMMA Take 2.0 grams of sPS-pMS ( Contains 5mol% para-phenylethylamidine) (obtained from Example 3) Put into a 300ml round-bottomed flask and add 150ml purified and dried cyclohexane, then steam out 50ml of the cyclohexanone by steaming sticks Take 1.1 milligrams of TMEDA and 2.9 milliliters of sec_ Butyllithium (1 '3M in cyclohexane) and mix this deep-colored solution into the sPS-pMS / cyclohexane solution. Keep the reaction temperature 55 and continuously stir the reaction for 20 hours. This round-bottomed flask was transferred into a glove box, washed repeatedly with n-pentanol, filtered, and drained. After adding 100 ml of n-flame, the round flask was removed from the glove box. Using a long needle, 8 ml of purified methyl propionate Ester (methylmethacrylate) was added to the round bottom flask and protected. Stir at room temperature for 5 hours, then add methanol to stop the reaction and allow the polymer to settle down. Collect the polymer by filtration. At room temperature, use acetone to extract the homomethyl PMMA homopolymer PMMA from this polymer to The soluble and insoluble polymers were separated by centrifugation and dried. Finally, 2.2 g of acetone-insoluble SPS-pMS-g-PMMA and 0.3 g of acetone-soluble homopolymer of methyl methacrylate were obtained. From the results of W-NMR, sPS-pMS-g-PMMA contained 10.1 mol% PMMA. Example 21 1 sPS-pMS-g-Polyisoprene Take 0.7 g of sPS-pMS (containing 15 mol% para-styrene) (obtained from Example 6) and put it into a 300 ml Schlenk round-bottomed flask and add 100 ml of purified and dried Cyclohexane, distilling 50ml of cyclohexane 21 [I 丨 丨 " Γιοι (Please read the precautions on the back before filling out this page) / -β Line 9 · This paper size applies to Chinese national standards (CNS ) Α4 specification (2〗 0X297 mm) Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 4342 ^ 3 A7 B7 V. Description of the invention (19) Alkanes are distilled out. Take 2.4 M of TMEDA and 5 ml of 36 ° Butyllithium (1.3 M in cyclohexane) and then add this dark brown solution to the SPS-pMS / cyclohexane solution. Keep the reaction temperature at 75 ° (: and stir the reaction continuously for 20 hours. The Schienk round-bottomed flask was transferred into a glove box, washed repeatedly with n-pentane, and dried under vacuum. After adding 100 ml of n-pentane, the Schlenk-shaped round flask was removed from the box, and 4 grams of purified Isoprene was added to the Schlenk round-bottomed flask and kept at room temperature for 48 hours, and then a large amount of methanol was added to stop the reaction and allow the polymer to settle. The polymer was collected by filtration. Continuously using n-pentane at room temperature The isoprene homopolymer in this polymer was extracted for 24 hours, and the soluble and insoluble polymers were separated by centrifugation and dried. Finally, sPS-pMS- g-Polyisoprene and isoprene homopolymer that are soluble in n-pentane. Analysis of sPS-pMS starting materials by high temperature gel permeation chromatography (Waters GPC 150CV) Mw = 240,600, PDI = 9.3; sPS- Mw = 5 for pMS-g-Polybutadiene 56,400, PDI = 8.1.

f Example 22: sPS-pMS-g-PtBMA Take 1.0 g of sPS-pMS (obtained from Example 8) and put it into a 250 mL round-bottomed flask, and then add 50 mL of purified and dried cyclohexane. Take 1.4 mL · of TMEDA and 1.1 mL of n-butyllithium (2'5 M in hexane) and then add this mixed solution to the SPS-pMS / cyclohexane solution 'to keep the reaction temperature at 60. (: And continuously stir the reaction for 4 hours. Move this round-bottomed flask into the glove box, wash repeatedly with n-pentane, filter, and dry, add 20 ml of n-22 (please read the precautions on the back before filling this page) Γ I centimeter 7 9 2 The central government bureau of the Ministry of Economic Affairs of the Offshore Consumer Cooperative Press 43426g of sand A7 B7 V. Description of the invention (20) The appearance and 1.0 g of t-butylmethacrylate were added to the round bottom After inside the bottle, remove the round bottom bottle from the glove box and keep it at room temperature for 48 hours. Then add 10 ml of methanol with a long needle to stop the reaction. After stirring for 5 minutes, pour into a large amount of methanol to precipitate the polymer and collect by filtration. Polymer β was continuously extracted with acetone at room temperature for 24 hours. The homogeneous polymer tert-butyl methacrylate PtBMA was extracted from the polymer. Finally, 1.163 g of sPS-pMS-g-PtBMA insoluble in acetone and 0.158 g of a homopolymer of T-based acrylate f-ester soluble in acetone. Through FT-IR analysis, it can be found that SPS-pMS-g-PtBMA has carbonyl group (00) absorption at 1 725 cm · 1, which can be determined by 1H-NMR. Calculate the content of PtBMA in sPS-pMS-g-PtBMA It is 9_3 mol%.

Example 23: sPS-pMS-g-PTHF Take 1.0 g of sPS-pMS-Br (containing 2 mol% bromine) and put it into a 250 mL jacketed reactor, then add 15 mL of purified and dried THF (tetrahydrofuran), Use a cold; East cycle machine to reduce the reactor temperature to -15 ~ 20. 〇Take 5 ml of THF and 8.76 mg of anhydrous AgBF4 (silver tetrafluoroborate) in the gloves and remove the gloves immediately. Cool to -30 ~ 40oC with liquid IL. Use a long needle to add this solution to the SPS-pMS-Br / THF solution and keep the reaction temperature. Stir the reaction at -15 ~ 20 ° C for 20 minutes', then raise the temperature to -3 ° C and continue to stir the reaction for 24 hours. 3 ml of methanol was added to stop the reaction, and then a large amount of methanol was added to precipitate the polymer, and the polymer was collected by filtration. At room temperature, ethanol was used to extract the THF homogeneous polymer from this polymer, and the soluble and insoluble 23 paper sizes were GM A4 (210X297 mm) by centrifugation- -------- ^ 〇-I (please read the notes on the back before filling out this page); Booking line 〇- 闹 # M Jibu Central Ladder Bureau Bureau Consumer Consumption Co., Ltd. India Benben is more knowledgeable Supplementary amendments to the "Creation Instructions" of the Patent Specification No. 25 (Date of revision: 89.9, 7) V. Creation Instructions (21) The polymer was separated and dried, and finally spS-pjy [Sg-PTHF2.34 g insoluble in ethanol was obtained Through FT-IR analysis, it can be found that there are characteristic absorption peaks of ethers (-C-0-C-) at 1112 cm · 1.

Example 24: SPS-pMS containing hydroxyl group Weigh 0.51 g of brominated sP (S-co-4MS) and add 40 ml of a THF / Toluene (volume ratio = V1) solution to a double-mouthed reaction flask. The upper opening device condenses Tube, the other-the opening is sealed with a serum plug. Nitrogen was bubbled in and heated in an oil bath, and the temperature of the oil bath was set to 80 t. After about 5 hours, it was seen that the polymer powder was dissolved. Reduce the temperature of the oil bath to 60 t, slowly add 40 ml of the aqueous reaction solution * with a syringe, and continue to stir. At this time, it is a turbid solution mixed with the aqueous phase and the organic phase. After adding the aqueous phase solution, it was heated again. The temperature of the oil bath was set at 80 ° C, and the reaction time was 21 hours. After the reaction is completed, the reaction solution in the reaction flask is poured into 200 mi of methanol to precipitate the polymerization product. The precipitated polymerization product was washed three times with a 10/0 HCl aqueous solution and a 10% methanol aqueous solution, respectively. 'The product was collected by filtration and dried under vacuum at 70 ° C for 16 hours. The method of preparing Dididan solution should be 4.06g NaOH and 35ml of pure water. Stir and dissolve it, put it in a double p reaction bottle, pass nitrogen at one end, seal with a serum stopper, and slowly drip with a syringe. 4.0 ml of CH3COOH was added and finally 1.0 ml of phase transfer catalyst Bu4NOH was added. The polymerization product was dissolved in CDC13 at 25 ° C. (: When the spectrum of 1H-NMR is measured, the chemical shifts of the para-styrene copolymer with the starting material deserted and the hydroxyl-functional para-styrene copolymer with the para-styrene copolymer can be seen. The chemical shift of benzyllic proton (sPS-C6H5_-CHrBr) is located at 4.42ppm, and the chemical shift of esterified intermediate product (sPS_C () H5_CHrOCOCH3) is at 5,000ppm; and The hydroxyl-containing para-styrene copolymer (sPS_C6H5_CHrOH) obtained after hydrolysis has a phenyl hydrogen. The chemical shift is at 4_54ppm. The reaction equation and some experimental results are shown below: 24 (revised page) This paper is scaled to the standard of the National Offshore Ladder (CNS) A4 gauge (21〇X; 297 mm) (please read the note on the back of Jing before filling this page)

4342 No .: ^ 7110125 Patent Specification "Creation Note" V. Creation Note (22) Supplementary amendments (Date of amendment: 89.9.7) Attachment ^ ch2_ch ^ ch2_ch_ ^ ch2_ch ^ _I \] H3 CH2Br

CH3COO'Na (Bu) 4NT〇H ') refluxI ten CH2—CH ^ _ ^ CH2 one CH person

h2_o_c_ch3 (Please read the note on the back before filling this page) (Bu) 4N OH "

Ministry of Economic Affairs, Central Bureau of Economic Affairs, Industrial Policy, Consumer Cooperatives, India, OH ", refkix ch2—ch ^ _ ^ ch2 Table 3. Reaction conditions

Reaction No Brominated SPS-pMS CH3COOH NaOH Bu4NOH Rxn (g) (ml) (g) (ml) (hr) LJC-027 0.5 2.0 8.39 1.0 20 LJC-028 0.5 4.0 8.49 2.0 17 LJC-029 0.5 2.0 7.94 1.0 16 LJC-030 0.5 1.0 3.95 0.3 4.5 LJC-031 0.5 4.0 4.06 1.0 21

25 (Amendment page) The paper standard is applicable to China and Fujian National Standards (CNS > Α4 specification (21〇 > < 297mm)) Supplementary amendment to the "creation description" of Patent Specification No. 087110125 (Date of amendment: 89.9.7 ) V. Creation instructions (23) Table 4. Product analysis results--1 ~--------- Reaction No Base content (mol%) Tg (° C) Tm (° C) —ΔΗ | ( J / g) LJC-027 1.29 90 205 18.83 LJC-028 1.28 91 201 14.53 LJC-029 1.53 89 202 18.99 LJC-030 — 0.65 93 203 8.79 1 LJC-031 2.1 88 1S8 9.83 Attachment (please read the note on the back first) $ Item, please fill in this page) Example 25: Amination reaction of sPS-pMS, Ministry of Economic Affairs, Ministry of Economic Affairs, 6-Central Bureau Staff Consumer Cooperative, India Benben Weighing l.lg brominated SPS and 40mL THF / Toluene (v / v = l / l) In a 250ml double-necked reaction flask, a condenser tube is opened at the upper end, and the other opening is sealed with a serum stopper. Pass in nitrogen, heat and stir with an oil bath method to dissolve the oil bath temperature at 80 ° C, Heat for about 0.5 hours to dissolve the polymer. Reduce the temperature of the oil bath to 60 ° C, and then slowly add 5 ml of isopropyl alcohol (IPA) containing 0.17 g of diethanolamine (DEA) using a syringe. Stir. Pass nitrogen and heat the oil bath to 90 ° C (Reflux temperature). After 16 hours of reaction, pour the reaction solution into about 200 ml of methanol to precipitate the polymerization products. The polymer products that are precipitated are then mixed at 50% ( ν / ν) methanol solution was washed 3 times, and the product was collected by filtration and dried under vacuum at 70 ° C for 16 hours. From the results of 1H-NMR analysis, the chemical shift of the methylene group of the starting material SPS-C ^ -CIVBr was found. The position is 4.42ppm, and the product is analyzed by iH-NMR to find that the chemical shift is 3.54ppm, which is the chemical shift of SPS-C6H5-CHrN- (CH2CH2〇H) 2, and 2 63ppm is our Qishou-Nuzhou? 2 Chemical shift. The reaction formula and experimental results are as follows: "26 (revised page) This paper is used in the standard _ sleepy home standard (0 posts > input 4 specifications (210 parent 297 mm) '' --- _ ^ 42 @ 磨 087110125 Patent Specification Supplementary Amendment to "Creation Instructions" (Date of revision: 89.9.7) V. Creation Instructions (24)?!

CH2Br HN (CH2CH2OH) 2

ch2n,, ch2ch2oh, ch2ch2oh (Please read Note 11 ^ on the back before filling in this I) * 1Τ Table 5. Amination reaction conditions and results

Rxn. No sPS-pMS (g) I PA (ml) DEA (g) Rxn time (hr) Amine hydroxyl (%) Tg (° C) Tm rc) ΔΗ (J / g) LJC-045 1.0 10 2.61 19 2.1 99 240 10.7 LJC-047 1.1 5 2.74 15 2.2 98 240 6.8 LJC-048 1.1 2 1.10 15 2.2 240 12..0 LJC-056 1.1 5 0.59 16 2.0 101 240 14.0 LJC-057 1.1 3 0.35 16.5 1.6 101 241 14.0 LJC -058 1.1 5 0.17 16 1.8 99 237 9.4 LJC-059 1.1 2 0.07 16 2.4 97 238 15.2 Seal of the Ministry of Economic Affairs, Central Bureau of Standards, and Industrial Engineering Cooperative, India Example 26: The etherification reaction of sPS-pMS weighs 3 g Brominated SPS and 50 ml of toluene were placed in a 250 ml double-necked reaction flask. The upper end was equipped with a condenser tube, and the other opening was sealed with a serum stopper. Nitrogen was bubbled in, heated in an oil bath, and dissolved by stirring. The temperature of the oil bath is 100 ° C to dissolve the polymer, reduce the temperature of the oil bath to 60 ° C, and then slowly add 20ml of 0.5g potassium hydroxide and 0.3g 27 using a syringe (correction page)逋 Use Chinese National Standard Feng (CNS) A4 Specification (210X297 mm) 34 ^^^-Supplemental Amendment to "Creation Note" of Patent Specification No. 087110125 (Date of revision: 89.9.7) V. Creation Note (25) Annex I CH3 (OCH2CH2) 3OH in methanol solution, then add 5mi of Bu4NOH and continue stirring, oil bath heated to 90 ° C (Reflux temperature), after 16 hours of reaction, pour the reaction solution into about 200ml methanol The polymer product was precipitated by precipitation. The precipitated polymer product was washed with a 50% (v / v) methanol aqueous solution three times, and the product was collected by filtration and dried under vacuum at 70 ° C for 16 hours. From the analysis results of 1H-NMR, It was found that the chemical shift of the sulfenyl group of the starting material sps_c6H5-CH2-Br was 4_42 ppm, and the product after the etherification reaction was analyzed by ih-NMR. (CH2Qfl20) 3CH3 chemical shift, which is removed by the reaction of brominated SPS-pMS with CH3 (OCH2CH2) 3OH The results of hydrogenation. Example 27: sPS-pMS-g-polycaprolactone Printed by the Bayer Consumer Cooperative of the Central Slope Bureau of the Ministry of Economic Affairs *. (Please read the precautions on the back before filling out this page) It will contain 2.78 mol% pMS. sPS-pMS was placed in a 300ml round-bottomed flask, and purified cyclohexane was added to the round-bottomed flask. TEDA and 11-Butyllithium (1.6M in cyclohexane) were added in a fixed ratio and mixed, and this dark brown solution was added to SPS-pMS. In a cyclohexane solution, the reaction temperature was maintained at 5 ° C. and the reaction was continuously stirred for 15 hours. The round-bottomed flask was moved into a glove box and repeatedly washed with n-pentane, filtered, 100 nl of n-pentane was added, and the round-bottomed flask was removed from the glove box. The purified caprolactone was added to a round-bottomed flask using a long needle, and the graft polymerization reaction was performed at room temperature for 30 minutes. After stopping the reaction, a large amount of methanol was added to stop the reaction and the polymer was collected by filtration. The polymer was acetone Extraction is performed at room temperature. The soluble and insoluble polymers are separated by centrifugation and dried. Finally, acetone-insoluble SPS-pMS-g-polycaprolactone and polycaprolactone soluble in acetone are obtained. One homogeneous polymer. NMR spectrum of the obtained graft copolymer • 28 (revised page) «Minjia Rare Standards & CNS > A4 Specification (210X297 mm) 43426 | 087110125 Patent Supplementary amendments to "Creation Instructions" in the manual (Date of revision: 89.9.7) V. Creation Instructions (26) Figures can be observed at 2.24ppm and 4.06ppm, respectively, two methylene (CHP) and The chemical shift of (CH2OO) and the chemical shift of (CHP) overlap with the chemical shift of the methyl group of p-fluorenylstyrene of para-ethylene copolymer, both are 2.24 ppm, so the degree of grafting The calculation is to use the integrated area of hydrogen on CH200 and the integrated area of hydrogen on the benzene ring to calculate 'the more polycaprolactone is connected, the more the area of chemical shift at 4.06 ppm will increase. ‘Please read the note on the back page t. Table 6. Effect of metallization reaction time changes on SPS-co-4-MS graft polymerization

Reaction condition Graft copolymers Ex. No. £ -CL (ml) Rxn Time (hr) NMR (mole%) Tm (° C) ΔΗ (J / g) Mw 0921 247 30.1 5040 035A 0.1 15 7 206 18.0 5350 046A 0.1 1 7 236 17.0 0921, containing 2.78 mole% of p-methystyrene (calculated by H-NMR). Deprotonated condition: (PMS): [nBu Li]: [TEMA] = 1: 10: 10; reaction temperature: 50 ° C, 15hr, solvent: cyclohexane. SIH standard for paper use: <CNS &gt; A4 Specifications (210X297 mm) Supplementary amendments to the "creation instructions" of Patent Specification No. 087110125 of the Ministry of Economic Affairs, Industrial and Commercial Cooperatives, 43 42 6 3 (Date of amendment: 89.9.7) V. Creation Instructions (27) Annex I The Central Government of the Ministry of Economic Affairs, Japan Industrial Cooperatives Cooperative Association Table 7. The effect of changes in the concentration of caprolactone monomers on the graft polymerization of SPS-co-4-MS Reaction condition Graft copolymers Ex. No. ε-CL RxnTime NMR Tm ΔΗ (ml) (hr) (mole%) (° C) (J / g) 0605 ~-243 27.0 040Α 0.1 1.0 7 234 0.5 040Β 0.3 0.5 18 236 0.4 040C 0.5 0.5 27 236 0.2 0605, $ p-methystyrenel3mole % (NMR). Deprotonated condition: [PMS]: [nBu Li): [TEMDA] = 1: 10: 10; reaction temperature 50 ° C, Ihr, solvent: cyclohexane ° Table 8. Variation of caprolactone monomer concentration Effect on the graft polymerization of SPS-co-4-MS I II Μί. '. Ί'ΙΙΒί ^ ί1 · quot; 1 , 1, ~ ίίϋΒ ^ ΜΒίίΜ1 »· ί !! · ΐΐΐι ^ ί · t — Exp. No. Reaction condition graft copolymers ε-CL (ml) Rxn Time (hr) NMR (mole%) Tm (° C) Δ H (J / g) asPS-pMS (Xc%) 0921 247 30.1 03 5A 0.1 0.5 7 209 9.3 33.4 038B 0.2 0.5 10 207 8.4 31.4 038C 0.3 0.5 16 206 6.0 24.0 035B 1 0.5 65 200 2.0 20.1 0921 with p-methystyrene 2.78 mole% (; iHNMR :). Metallization reaction conditions: [PMS]: [nBuLi]: [丁 £ 1 \ «) 八] = 1: 1〇: 1〇; reaction temperature 50 ° 〇, 15111 :, solvent: cyclohexane» 0.5hr graft polymerization The solvent was n-pentane and Acetone was used to extract PoliCaproiactone. a. Xc (sps—co_4- MS) [ΔΗ ^ π.ρς ^ / (ΔΗ sPS-co-4-MsX ^^ PS-CO- ^ MS)] ^ 100% (Please note the items on the back first Refill this page) 30 (revised page) Standards for the two papers used in this paper standard (CNS &gt; Α4 size (210X297 mm) Attachment Printed by the Bayon Consumer Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs, 342δ # 087110125 Supplementary amendment to the "creation description" of the patent specification (Date of revision: 89.9.7) V. Creation description (28) Example 28: sPS-pMS-g-polyisoprene Take 0.7 g of sPS-co-4-MS-g-Polyisoprene (Containing 15 mole ° / 〇 unsaturated double bond) put into a 300m 丨 Sclilenk round bottom flask, add 100ml of cyclohexane, and then add 3-Chloroperoxybenzoic acid, the amount of 3-Chloroperoxybenzoic acid can be as required Adjust, keep the reaction temperature at room temperature, and continuously stir the reaction for 2 hours. Pour this polymer solution into methanol to precipitate and repeatedly wash, filter, and vacuum dry. SPS-pMS-g-polyisoprene After epoxidation , Its FT-1R spectrum can clearly see the specific absorption peaks of the epoxy groups of 91〇11- | and 1710011-1. Inverse 8-0] ^ 13 € 11 Spectral circle, chemical shift 145.2ppm is the position of alpha carbon on the benzene ring of para-polystyrene '125-128ppm 疋 belongs to the chemical shift of carbon on the soil, 41.1 ppm and 43.9ppm belong to para-polystyrene Specific absorption peaks of Ling carbon and T carbon. The l3C NMR spectrum of sPS_pMS_g_polyis〇prene 'in addition to the chemical shift of [sps-C0-4-MS], a new chemical shift is obviously added, 110Ppm is the chemical of CHp Shift, 1475ppm is the chemical shift of c. The nCNMR spectrum of sPS-pMS-g-po 丨 yiSOprene after epoxidation shows that the chemical shift of 110ppm has disappeared, and the chemical shift is 54 ~ 60ppm2 The specific peak of the newly formed epoxy group is shown in the figure. The IH spectrum of spS_pMS, 6.5 ~ for the stupid ring, the chemical conversion of 2.4 ppm is the p-methylphenyl stilbene methyl age shift, SPS-PMS-gPolilypreprene IHNMR spectrum, after adding the graft bond of isoprene, it can be found that a new chemical shift is added between 5.6 and 4.8 ppm, which is a hydrogenation hybrid of isoprene unsaturated double bond. Sps_pMS_g_pGlyisGp_ After the epoxidation reaction, the NMR light is still visible, but the chemical woman can be seen 5 6 to 4.8 ppm 敎, and a chemical shift belonging to an epoxy group occurs near a chemical shift of 2-5 ppm. _____31 (correction page) S® home kneading rate (CNS) A4 «^ (21GX 297 mm j --------- (please read the back note of the West first and then fill this page)

Attachment 1 3 4? 6 ^. W ^ 'Shang087110125 Patent Specification "Creation Note" Supplementary amendment (Date of revision 89.9.7) V. Creation Note (29) Table 9. Response time vs. sPS-pMS-g Effect of -PIP Epoxidation Reaction Exp. No. Time (h) Converion (mole%) Tm (° C) ΔΗ I (J / g) 056 0 238.7 14.6 058A 2 54.4 241.3 21.2 058B 4 63.8 240.1 15.1 058C 6 73 237.4 11.4 058D 10 86.4 236.2 11: 7 05 8E 24 91.8 236.7 11.3 The solvent is CHC13, and the reaction temperature is polyisoprene at room temperature: MCPBA = 1: 2 (Please read the precautions on the back before filling in this X). Although the present invention has been disclosed in the preferred embodiment as above, 'but it is not intended to limit the present invention. Any person skilled in the art' does not depart from the spirit and scope of the present invention. Changes and retouching can be made, so the scope of protection of the present invention shall be determined by the scope of the attached patent application. 32 (Revised page) This paper uses Chinese National Standards (CNS) Α4 Grid (210X2 Magic mm)

Claims (1)

Report "Amended Patent Scope" of Patent Specification No. 10125 (Date of revision: 89.9 · 7) 1 Application for a patented graft copolymer of acetophenone / p-sereneacetofluorene copolymer, which has CH2-CH- a CH2—CH- R2— b CH2—CH- Γ R2-Bu CHo-CH · R2—C—Y d (I) Printed by the Central Government Bureau of the Ministry of Economic Affairs and Industrial Cooperatives, where R and R2 are independently selected from hydrogen 'alkyl, primary and secondary haloalkyl In the group, X is a functional group, and it is selected from the group consisting of functional groups containing _ primes, metals, oxygen, sulfur, stone, nitrogen, hydrogen, and fluorene, and mixtures thereof, and γ is a grafted polymer moiety. , A is 10 to 15000, b is 0 to 2000, c is 0 to 2000, and d is 1 to 2000 2. The graft copolymer described in the first item of the patent application scope, which is _ prime. 3. The graft copolymer according to item 1 of the scope of patent application, wherein χ is an alkali metal or an alkaline earth metal. 4. The graft copolymer according to item 1 of the scope of the patent application, wherein χ is selected from the group consisting of alkoxides, phenoxides, and carboxyiates. 5. The graft copolymer as described in item 1 of the scope of the patent application, where χ is selected from alkanesulfurs 33 (revised page) ^ 'This paper size is applicable to a solid household kneading (CNS) A4 specification (210X297) (Please read the note f on the back before filling this page). I. &quot; Attachment IV. Ministry of Economic Affairs 4-printed by Zhengong Consumer Cooperative of the Central Standard Vehicle Bureau 4 34i2: © 3.! · No. 087110125 Amendments to the “Scope of Patent Application” of the patent specification (Date of amendment: 89.9.7), scope of patent application (thiolates), thiophenolates, ^^^^ (thioethers), thiocarboxylates Dithiocarboxylates, thioureas, thioureas, dithiocarbamates, xanthates, and thiocyanates. 6. The graft copolymer according to item 1 of the patent application scope, wherein χ is selected from the group consisting of silanes and halosilanes. 7. The graft copolymer described in item 1 of the scope of patent application, wherein χ is selected from the group consisting of malonates, cyanides, and CR33, and R3 is an organic group . 8. The graft copolymer according to item 1 of the scope of the patent application, wherein χ is selected from anudes, amines, carbazois, phthalimides ), ° than ° in the group of pyridines' maleimides and cyanates. 9. The graft copolymer according to item 1 of the scope of the patent application, wherein χ is a phosphine. 10. The graft copolymer as described in item 1 of the scope of Shenying's patent, wherein Ri and R2 are independently selected from the group consisting of hydrogen 'C] · 5 alkynyl, and Cm-grade and second-order halogenated halides. in. 11. The graft copolymer according to item 1 of the scope of patent application, which is obtained by reacting in the presence of a cyclopentadienyl metal compound (metallocene) catalyst. 12. The graft copolymer as described in claim 1 of the patent scope, wherein the number average molecular weight of the polymer is at least 1,000. 13. The graft copolymer as described in item 1 of the scope of the patent application, wherein Y is a monomer selected from the group consisting of an anion-polymerizable monomer, a cationic-polymerizable monomer, an anion-opening or cationic ring-opening monomer, 34 (Correction page) This paper uses Zhonggu_Home Slope (CNS) specifications (210 &gt; &lt; 297mm) (Please read the precautions on the back before filling out this page) 4 豸 42 豸 豸 8711〇 Amended version of Patent Application Park No. 125 (Date of revision: 89.9.7) Attachment 4: The Ministry of Economic Affairs Central Government Bureau, patent application scope, and polymers and copolymers of free-radically polymerizable monomers In the ethnic group. The graft copolymer according to item 1 of the application, wherein γ is an anionic polymerizable monomer. 15 'The graft copolymer as described in item 14 of the scope of the patent application, wherein the anionically polymerizable monomer is selected from a co-roller's ethyl aceto aromatic compound, a vinyl unsaturated amine, and a wife (acenaphthylene), 9-acrylcarbazole, acrylonitrile, methacryl guess, organic cyanate esters, methacrylates, alkyl acrylates, alkyl acrylates Groups of alkyl methacrylates, glycidyl methacrylate, vinyl pyridines, and mixtures thereof. 16. The graft copolymer as described in item 13 of the scope of the patent application, wherein the cationically polymerizable monomer is a selective vinyl aromatic compound, vinyl ethers, and ethyl ether. (N-vinylcarbazole), isobutene, and mixtures thereof. 17. The graft copolymer according to item 13 of the scope of the patent application, wherein the anionic ring-opening or% ion-ring-opening monomer is a free-ring cyclic ether, sulfjdes, lactam, and linamine 'N-carboxyanhydrides and their mixtures. 1S. The graft copolymer as described in item 13 of the scope of the patent application, wherein the free-radically polymerizable monomer is a selective ethylenic aromatic compound, a total of two dilute, acrylate, methyl propyl (please first Read the note on the back and fill in this page) 'Packed in dilute acid brewed' alkyl acrylate ', fluorenyl alkyl acrylate, vinyl acetate, and mixtures. 35 (Revised page) The specifications of this sheet are applicable to Zhongli® Home Standard (CNS) 4 specifications (210X297 mm). Additional "Creation Instructions" (Date of revision: 89.9, 7) V. Creation Instructions (21) The polymer was separated and drained, and finally spS-pjy [Sg-PTHF2.34 g insoluble in ethanol was obtained, via FT- According to IR analysis, a characteristic absorption peak of ethers (-C-0-C-) was found at 1112 cm · 1. Example 24: SPS-pMS containing hydroxyl group Weigh 0.51 g of brominated sP (S-co-4MS) and add 40 ml of a THF / Toluene (volume ratio = V1) solution to a double-mouthed reaction flask. The upper opening device condenses Tube, the other-the opening is sealed with a serum plug. Nitrogen was bubbled in and heated in an oil bath, and the temperature of the oil bath was set to 80 t. After about 5 hours, it was seen that the polymer powder was dissolved. Reduce the temperature of the oil bath to 60 t, slowly add 40 ml of the aqueous reaction solution * with a syringe, and continue to stir. At this time, it is a turbid solution mixed with the aqueous phase and the organic phase. After adding the aqueous phase solution, it was heated again. The temperature of the oil bath was set at 80 ° C, and the reaction time was 21 hours. After the reaction is completed, the reaction solution in the reaction flask is poured into 200 mi of methanol to precipitate the polymerization product. The precipitated polymerization product was washed three times with a 10/0 HCl aqueous solution and a 10% methanol aqueous solution, respectively. 'The product was collected by filtration and dried under vacuum at 70 ° C for 16 hours. The method of preparing Dididan solution should be 4.06g NaOH and 35ml of pure water. Stir and dissolve it, put it in a double p reaction bottle, pass nitrogen at one end, seal with a serum stopper, and slowly drip with a syringe. 4.0 ml of CH3COOH was added and finally 1.0 ml of phase transfer catalyst Bu4NOH was added. The polymerization product was dissolved in CDC13 at 25 ° C. (: When the spectrum of 1H-NMR is measured, the chemical shifts of the para-styrene copolymer with the starting material deserted and the hydroxyl-functional para-styrene copolymer with the para-styrene copolymer can be seen. The chemical shift of benzyllic proton (sPS-C6H5_-CHrBr) is located at 4.42ppm, and the chemical shift of esterified intermediate product (sPS_C () H5_CHrOCOCH3) is at 5,000ppm; and The hydroxyl-containing para-styrene copolymer (sPS_C6H5_CHrOH) obtained after hydrolysis has a phenyl hydrogen. The chemical shift is at 4_54ppm. The reaction equation and some experimental results are shown below: 24 (revised page) This paper is scaled to the standard of the National Offshore Ladder (CNS) A4 gauge (21〇X; 297 mm) (please read the note on the back of Jing before filling this page) 4342 No .: ^ 7110125 Patent Specification "Creation Note" V. Creation Note (22) Supplementary amendments (Date of amendment: 89.9.7) Attachment ^ ch2_ch ^ ch2_ch_ ^ ch2_ch ^ _I \] H3 CH2Br CH3COO'Na (Bu) 4NT〇H ') refluxI ten CH2—CH ^ _ ^ CH2 one CH person h2_o_c_ch3 (Please read the note on the back before filling this page) (Bu) 4N OH &quot; Ministry of Economic Affairs, Central Bureau of Economic Affairs, Industrial and Consumer Cooperatives, India, OH &quot;, refkix ch2—ch ^ _ ^ ch2 Table 3. Reaction Conditions Reaction No Brominated SPS-pMS CH3COOH NaOH Bu4NOH Rxn (g) (ml) (g) ( ml) (hr) LJC-027 0.5 2.0 8.39 1.0 20 LJC-028 0.5 4.0 8.49 2.0 17 LJC-029 0.5 2.0 7.94 1.0 16 LJC-030 0.5 1.0 3.95 0.3 4.5 LJC-031 0.5 4.0 4.06 1.0 21 25 (Amendment page) The paper standard is applicable to China and Fujian National Standards (CNS &gt; Α4 specification (21〇 &gt; &lt; 297mm)) Supplementary amendment to the "creation description" of Patent Specification No. 087110125 (Date of amendment: 89.9.7 ) V. Creation instructions (23) Table 4. Product analysis results--1 ~--------- Reaction No Base content (mol%) Tg (° C) Tm (° C) —ΔΗ | ( J / g) LJC-027 1.29 90 205 18.83 LJC-028 1.28 91 201 14.53 LJC-029 1.53 89 202 18.99 LJC-030 — 0.65 93 203 8.79 1 LJC-031 2.1 88 1S8 9.83 Attachment (please read the note on the back first) $ Item, please fill in this page) Example 25: Amination reaction of sPS-pMS, Ministry of Economic Affairs, Ministry of Economic Affairs, 6-Central Bureau Staff Consumer Cooperative, India Benben Weighing l.lg brominated SPS and 40mL THF / Toluene (v / v = l / l) In a 250ml double-necked reaction flask, a condenser tube is opened at the upper end, and the other opening is sealed with a serum stopper. Pass in nitrogen, heat and stir with an oil bath method to dissolve the oil bath temperature at 80 ° C, Heat for about 0.5 hours to dissolve the polymer. Reduce the temperature of the oil bath to 60 ° C, and then slowly add 5 ml of isopropanol containing 0.17 g of diethanolamine (DEA) using a syringe. IPA) and keep stirring. Pass nitrogen and heat the oil bath to 90 ° C (Reflux temperature). After 16 hours of reaction, pour the reaction solution into about 200 ml of methanol to precipitate the polymerization products. The polymerization products that are precipitated are separately It was washed three times with a 50% (ν / ν) methanol solution, and the product was collected by filtration and dried under vacuum at 70 ° C for 16 hours. From the results of 1H-NMR analysis, the methylene group of the starting material SPS-C ^ -CIVBr was found. The chemical shift of the product was 4.42ppm. The product was found to have a chemical shift of 3.54ppm by iH-NMR analysis, which is the chemical shift of SPS-C6H5-CHrN- (CH2CH2〇H) 2, and 2 63ppm is the same. The chemical shift of the state 洱 ⑽2. The reaction formula and experimental results are as follows: "26 (Revised page) This paper is in use _ sleepy home standard (0 Posts> Enter 4 specifications (210 parent 297 mm)” — -_ ^ 42 @ 磨 087110125 Patent Specification "Creation Explanation" Supplementary Modification _ (Revision Date: 89.9.7) V. Creation Explanation (24)?! CH2Br HN (CH2CH2OH) 2 ch2n,, ch2ch2oh, ch2ch2oh (please read the note 11 ^ on the back before filling in this I) * 1T Table 5. Amination reaction conditions and results Rxn. No sPS-pMS (g) I PA (ml) DEA (g ) Rxn time (hr) Amine hydroxyl (%) Tg (° C) Tm rc) ΔΗ (J / g) LJC-045 1.0 10 2.61 19 2.1 99 240 10.7 LJC-047 1.1 5 2.74 15 2.2 98 240 6.8 LJC-048 1.1 2 1.10 15 2.2 240 12..0 LJC-056 1.1 5 0.59 16 2.0 101 240 14.0 LJC-057 1.1 3 0.35 16.5 1.6 101 241 14.0 LJC-058 1.1 5 0.17 16 1.8 99 237 9.4 LJC-059 1.1 2 0.07 16 2.4 97 238 15.2 Seal of the Ministry of Economic Affairs, Central Bureau of quasi-government, Industrial Engineering Cooperative Cooperative, Example 26: The etherification reaction scale of sPS-pMS takes 3 g of brominated sPS and 50 ml of toluene in a 250 ml double-necked reaction bottle, and the upper opening device Condensation tube, the other opening is sealed with a serum plug. Nitrogen was bubbled in, heated in an oil bath, and dissolved by stirring. The temperature of the oil bath is 100 ° C to dissolve the polymer, reduce the temperature of the oil bath to 60 ° C, and then slowly add 20ml of 0.5g potassium hydroxide and 0.3g 27 using a syringe (correction page)逋 Use Chinese National Standard Feng (CNS) A4 Specification (210X297 mm) 34 ^^^-Supplemental Amendment to "Creation Note" of Patent Specification No. 087110125 (Date of revision: 89.9.7) V. Creation Note (25) Annex I CH3 (OCH2CH2) 3OH in methanol solution, then add 5mi of Bu4NOH and continue stirring, oil bath heated to 90 ° C (Reflux temperature), after 16 hours of reaction, pour the reaction solution into about 200ml methanol The polymer product was precipitated by precipitation. The precipitated polymer product was washed with a 50% (v / v) methanol aqueous solution three times, and the product was collected by filtration and dried under vacuum at 70 ° C for 16 hours. From the analysis results of 1H-NMR, It was found that the chemical shift of the sulfenyl group of the starting material sps_c6H5-CH2-Br was 4_42 ppm, and the product after the etherification reaction was analyzed by ih-NMR. The chemical shift of (CH2Qfl20) 3CH3 is the reaction of brominated SPS-pMS with CH3 (OCH2CH2) 3OH. Results of the removal of hydrogen bromide. Example 27: sPS-pMS-g-polycaprolactone Printed by the Bayer Consumer Cooperative of the Central Slope Bureau of the Ministry of Economic Affairs *. (Please read the precautions on the back before filling this page) will contain 2.78 mol % pMS of SPS-pMS was placed in a 300 ml round bottom flask, and purified cyclohexane was added to the round bottom flask. TEDA and 11-Butyllithium (1.6M in cyclohexane) were added in a fixed ratio and mixed, and then this dark brown solution was added. In the SPS-pMS / cyclohexane solution, the reaction temperature was maintained at 5 ° C. and the reaction was continuously stirred for 15 hours. The round bottom flask was moved into a glove box, washed repeatedly with n-pentane, filtered, 100 nl of pentane was added, and then the round bottom flask Remove the glove box. Use a long needle to add the purified caprolactone to the round bottom flask, and perform graft polymerization at room temperature for 30 minutes. After stopping the reaction, add a large amount of methanol to stop the reaction and filter the polymer to collect it. The product was extracted with acetone at room temperature, and the soluble and insoluble polymers were separated by centrifugation and dried. Finally, acetone-insoluble SPS-pMS-g-polycaprolactone and acetone-soluble Polycaprolactone homogeneous polymer. NMR spectrum of the obtained graft copolymer • 28 (correction page) «Min Jiaxiu Zhun &lt; CNS &gt; A4 Specification (210X297 mm) 43426 | 087110125 Patent Supplementary amendments to "Creation Instructions" in the manual (Date of revision: 89.9.7) V. Creation Instructions (26) Figures can be observed at 2.24ppm and 4.06ppm, respectively, two methylene (CHP) and The chemical shift of (CH2OO) and the chemical shift of (CHP) overlap with the chemical shift of the methyl group of p-fluorenylstyrene of para-ethylene copolymer, both are 2.24 ppm, so the degree of grafting The calculation is to use the integrated area of hydrogen on CH200 and the integrated area of hydrogen on the benzene ring to calculate 'the more polycaprolactone is connected, the more the area of chemical shift at 4.06 ppm will increase. '' Please read the note on the back page t. Table 6. Effect of metallization reaction time change on the SPS-co-4-MS graft polymerization reaction Condition Graft copolymers Ex. No. £ -CL (ml) Rxn Time (hr ) NMR (mole%) Tm (° C) ΔΗ (J / g) Mw 0921 247 30.1 5040 035A 0.1 15 7 206 18.0 5350 046A 0.1 1 7 236 17.0 0921, including p-methystyrene 2.78 mole% (丨 H-NMR calculation ). Deprotonated condition: (PMS): [nBu Li]: [TEMA] = 1: 10: 10; reaction temperature: 50 ° C, 15hr, solvent: cyclohexane. SIH standard for paper use: <CNS &gt; A4 Specifications (210X297 mm) Supplementary amendments to the "creation instructions" of Patent Specification No. 087110125 of the Ministry of Economic Affairs, Industrial and Commercial Cooperatives, 43 42 6 3 (Date of amendment: 89.9.7) V. Creation Instructions (27) Annex I The Central Government of the Ministry of Economic Affairs, Japan Industrial Cooperatives Cooperative Association Table 7. The effect of changes in the concentration of caprolactone monomers on the graft polymerization of SPS-co-4-MS Reaction condition Graft copolymers Ex. No. ε-CL RxnTime NMR Tm ΔΗ (ml) (hr) (mole%) (° C) (J / g) 0605 ~-243 27.0 040Α 0.1 1.0 7 234 0.5 040Β 0.3 0.5 18 236 0.4 040C 0.5 0.5 27 236 0.2 0605, $ p-methystyrenel3mole % (NMR). Deprotonated condition: [PMS]: [nBu Li): [TEMDA] = 1: 10: 10; reaction temperature 50 ° C, Ihr, solvent: cyclohexane ° Table 8. Variation of caprolactone monomer concentration Effect on SPS-co-4-MS Graft Polymerization I II Μί. '. Ί'ΙΙΒί ^ ί ·· 1 &quot; 1—, 1, ~ ίίϋΒ ^ ΜΒίίΜ1 »· ί !! · ΐΐΐι ^ ί · t — Exp.No. Reaction condition graft copolymers ε-CL (ml) Rxn Time (hr) NMR (mole%) Tm (° C) Δ H (J / g) asPS-pMS (Xc%) 0921 247 30.1 03 5A 0.1 0.5 7 209 9.3 33.4 038B 0.2 0.5 10 207 8.4 31.4 038C 0.3 0.5 16 206 6.0 24.0 035B 1 0.5 65 200 2.0 20.1 0921, Contains p-methystyrene 2.78 mole% (; iHNMR :). Metallization reaction conditions: [PMS]: [nBuLi]: [丁 £ 1 \ «) 八] = 1: 1〇: 1〇; reaction temperature 50 ° 〇, 15111 :, solvent: cyclohexane» 0.5hr graft polymerization The solvent was n-pentane and Acetone was used to extract PoliCaproiactone. a. Xc (sps—co_4- MS) [ΔΗ ^ π.ρς ^ / (ΔΗ sPS-co-4-MsX ^^ PS-CO- ^ MS)] ^ 100% (Please note the items on the back first Refill this page) 30 (revised page) Standards for the two papers used in this paper standard (CNS &gt; Α4 size (210X297 mm) Attachment Printed by the Bayon Consumer Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs, 342δ # 087110125 Supplementary amendment to the "creation description" of the patent specification (Date of revision: 89.9.7) V. Creation description (28) Example 28: sPS-pMS-g-polyisoprene Take 0.7 g of sPS-co-4-MS-g-Polyisoprene (Containing 15 mole ° / 〇 unsaturated double bond) put into a 300m 丨 Sclilenk round bottom flask, add 100ml of cyclohexane, and then add 3-Chloroperoxybenzoic acid, the amount of 3-Chloroperoxybenzoic acid can be as required Adjust, keep the reaction temperature at room temperature, and continuously stir the reaction for 2 hours. Pour this polymer solution into methanol to precipitate and repeatedly wash, filter, and vacuum dry. SPS-pMS-g-polyisoprene After epoxidation , Its FT-1R spectrum can clearly see the specific absorption peaks of the epoxy groups 91001- | and 1710011-1. Inverse 8-0] ^ 13 € View 11 Spectral circle, chemical shift of 145.2ppm is the position of alpha carbon on the benzene ring of para-polystyrene '125-128ppm 疋 is the chemical shift of carbon on the soil, 41.1 ppm and 43.9ppm are para-positions Specific absorption peaks of carbon and T carbon in polystyrene. The l3C NMR spectrum of SPS_pMS_g_p〇lyis〇prene 'in addition to the chemical shift of [sps-C0-4-MS], a new chemical shift is obviously added, 110Ppm It is the chemical shift of CHp, and 1475ppm is the chemical shift of c. The nCNMR spectrum of sPS-pMS-g-po 丨 yiSOprene after the epoxidation reaction shows that the chemical shift of 110ppm has disappeared, and the chemical shift of 54 ~ 60ppm2 is the newly formed epoxy-specific peak. IH spectrum of spS_pMS, 6.5 ~ for the stupid ring, the chemical conversion of 2.4ppm is the para-phenylacetophenidyl methyl group age shift, SPS-PMS- IHNMR spectrum of gPOlyisoprene. After adding the isoprene graft bond, it can be found that a new chemical shift is added between 5.6 and 4.8 ppm. This is a hydrogenated compound that is an isoprene unsaturated double bond. shift. sPS_pMS_g_pGlyisGp_ After the epoxidation reaction, the NMR light is still visible. It can be seen that the chemical compound is 56 ~ 4.8ppm 敎, and a chemical shift belonging to the epoxy group appears near the chemical shift of 2-5ppm. _____31 (correction page) S® home kneading rate (CNS) A4 «^ (21GX 297 mm j --------- (please read the back note of the West first and then fill this page) Attachment 1 3 4? 6 ^. W ^ 'Shang087110125 Patent Specification "Creation Note" Supplementary amendment (Date of revision 89.9.7) V. Creation Note (29) Table 9. Response time vs. sPS-pMS-g Effect of -PIP Epoxidation Reaction Exp. No. Time (h) Converion (mole%) Tm (° C) ΔΗ I (J / g) 056 0 238.7 14.6 058A 2 54.4 241.3 21.2 058B 4 63.8 240.1 15.1 058C 6 73 237.4 11.4 058D 10 86.4 236.2 11: 7 05 8E 24 91.8 236.7 11.3 The solvent is CHC13, and the reaction temperature is polyisoprene at room temperature: MCPBA = 1: 2 (Please read the precautions on the back before filling in this X). Although the present invention has been disclosed in the preferred embodiment as above, 'but it is not intended to limit the present invention. Any person skilled in the art' does not depart from the spirit and scope of the present invention. Changes and retouching can be made, so the scope of protection of the present invention shall be determined by the scope of the attached patent application. 32 (Amendment page) This paper uses the Chinese National Standards (CNS) Α4 grid (210X2 magic mm) No. © 1〇125 Patent Specification "Amendment of Patent Application" (Revision Date: 89.9 · 7) 1 patent application Fanyuan acetophenone / p-serene copolymer, which has the following CH2-CH- a CH2—CH- R2— b CH2—CH- Γ R2-Bu CHo-CH · R2—C—Y d (I) Printed by the Central Government Bureau of the Ministry of Economic Affairs and Industrial Cooperatives, where R and R2 are independently selected from hydrogen 'alkyl, primary and secondary haloalkyl In the group, X is a functional group, and it is selected from the group consisting of functional groups containing _ primes, metals, oxygen, sulfur, stone, nitrogen, hydrogen, and fluorene, and mixtures thereof, and γ is a grafted polymer moiety. , A is 10 to 15000, b is 0 to 2000, c is 0 to 2000, and d is 1 to 2000 2. The graft copolymer described in the first item of the patent application scope, which is _ prime. 3. The graft copolymer according to item 1 of the scope of patent application, wherein χ is an alkali metal or an alkaline earth metal. 4. The graft copolymer according to item 1 of the scope of the patent application, wherein χ is selected from the group consisting of alkoxides, phenoxides, and carboxyiates. 5. The graft copolymer as described in item 1 of the scope of the patent application, where χ is selected from alkanesulfurs 33 (revised page) ^ 'This paper size is applicable to a solid household kneading (CNS) A4 specification (210X297) (Please read the note f on the back before filling this page). I. &quot; Attachment IV. Ministry of Economic Affairs 4-printed by Zhengong Consumer Cooperative of the Central Standard Vehicle Bureau 4 34i2: © 3.! · No. 087110125 Amendments to the “Scope of Patent Application” of the patent specification (Date of amendment: 89.9.7), scope of patent application (thiolates), thiophenolates, ^^^^ (thioethers), thiocarboxylates Dithiocarboxylates, thioureas, thioureas, dithiocarbamates, xanthates, and thiocyanates. 6. The graft copolymer according to item 1 of the patent application scope, wherein χ is selected from the group consisting of silanes and halosilanes. 7. The graft copolymer described in item 1 of the scope of patent application, wherein χ is selected from the group consisting of malonates, cyanides, and CR33, and R3 is an organic group . 8. The graft copolymer according to item 1 of the scope of the patent application, wherein χ is selected from anudes, amines, carbazois, phthalimides ), ° than ° in the group of pyridines' maleimides and cyanates. 9. The graft copolymer according to item 1 of the scope of the patent application, wherein χ is a phosphine. 10. The graft copolymer as described in item 1 of the scope of Shenying's patent, wherein Ri and R2 are independently selected from the group consisting of hydrogen 'C] · 5 alkynyl, and Cm-grade and second-order halogenated halides. in. 11. The graft copolymer according to item 1 of the scope of patent application, which is obtained by reacting in the presence of a cyclopentadienyl metal compound (metallocene) catalyst. 12. The graft copolymer as described in claim 1 of the patent scope, wherein the number average molecular weight of the polymer is at least 1,000. 13. The graft copolymer as described in item 1 of the scope of the patent application, wherein Y is a monomer selected from the group consisting of an anion-polymerizable monomer, a cationic-polymerizable monomer, an anion-opening or cationic ring-opening monomer, 34 (Correction page) This paper uses Zhonggu_Home Slope (CNS) specifications (210 &gt; &lt; 297mm) (Please read the precautions on the back before filling out this page) 4 豸 42 豸 豸 8711〇 Amended version of Patent Application Park No. 125 (Date of revision: 89.9.7) Attachment 4: The Ministry of Economic Affairs Central Government Bureau, patent application scope, and polymers and copolymers of free-radically polymerizable monomers In the ethnic group. The graft copolymer according to item 1 of the application, wherein γ is an anionic polymerizable monomer. 15 'The graft copolymer as described in item 14 of the scope of the patent application, wherein the anionically polymerizable monomer is selected from a co-roller's ethyl aceto aromatic compound, a vinyl unsaturated amine, and a wife (acenaphthylene), 9-acrylcarbazole, acrylonitrile, methacryl guess, organic cyanate esters, methacrylates, alkyl acrylates, alkyl acrylates Groups of alkyl methacrylates, glycidyl methacrylate, vinyl pyridines, and mixtures thereof. 16. The graft copolymer as described in item 13 of the scope of the patent application, wherein the cationically polymerizable monomer is a selective vinyl aromatic compound, vinyl ethers, and ethyl ether. (N-vinylcarbazole), isobutene, and mixtures thereof. 17. The graft copolymer according to item 13 of the scope of the patent application, wherein the anionic ring-opening or% ion-ring-opening monomer is a free-ring cyclic ether, sulfjdes, lactam, and linamine 'N-carboxyanhydrides and their mixtures. 1S. The graft copolymer as described in item 13 of the scope of the patent application, wherein the free-radically polymerizable monomer is a selective ethylenic aromatic compound, a total of two dilute, acrylate, methyl propyl (please first Read the note on the back and fill in this page) 'Packed in dilute acid brewed' alkyl acrylate ', fluorenyl alkyl acrylate, vinyl acetate, and mixtures. 35 (Revised page) This sheet size is applicable to Zhongli® Home Kneading Standard (CNS) 厶 4 (210X297 mm)