TW434264B - Functionalized syndiotactic styrene/para-alkylstyrene copolymer - Google Patents

Abstract

The present invention provides a functionalized syndiotactic styrene/para-alkylstyrene copolymer, having the formula of (I) wherein R1 and R2 are independently selected from the group consisting of hydrogen, alkyl, primary and secondary haloalkyl, X is a functional group is selected from the group consisting of a functional group containing a halogen, a metal, oxygen, sulfur, silicon, nitrogen, carbon, phosphorus, and mixtures thereof, a ranges from 10 to 30000, b ranges from 0 to 30000, and c ranges from 1 to 30000. In comparison with the unfunctionalized syndiotactic styrene polymer, the functionalized syndiotactic styrene/p-alkylstyrene copolymer of the present invention has a better adhesion to many substrates and a better compatibility with other polymers.

Description

A7 4342B4 B7_______ 5. Description of the invention (1) The present invention relates to a functionalized syndiotactic styrene / p-alkyls1 (yrene copolymer). 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. Moreover, SPS is not compatible with other functional polymers. Therefore, it is necessary to improve the physical properties of traditional para-polystyrene.

Chung et al., In U.S. Patent No. 5,543,484, disclose a functionalized alpha-olefin / p-alkylstyrene copolymer. First, an? -Olefin is copolymerized with p-alkylstyrene. The introduction of p-alkylstyrene into α-olefin polymers will produce benzyl protons. This narrow matrix can easily perform many chemical reactions under mild reaction conditions. A functional group is introduced at the position of. Then, the α-olefin / p-alkylene copolymer is functionalized so that the benzyl protons on the p-alkylene styrene unit are functionalized. By such functionalization, the physical properties of the original dilute hydrocarbon polymer can be improved.

Powers et al., U.S. Patent No. 5,548,029, discloses a p-alkylene / isoolefin graft copolymer. In a similar manner, the iso-olefin and p-alkylbenzene are first copolymerized ', and then the p-alkylstyrene / isoalkylene copolymer is functionalized so that the The benzyl proton is functionalized. Similarly, the physical properties of the original hetero-lean hydrocarbon polymer can be improved by such functionalization. To this day, no functionalized p-phenylene has been developed / 4 This standard applies to China National Standard (CNS) A4 specifications (2-Gongchu) (Please read the precautions on the back before filling this page) — Printed by the Ministry of Standards Bureau of the Central Bureau of Standards, printed by the Consumers' Cooperative ^ 14264 ΓΤ —__ ^ V. Description of the Invention (2) ~ --- p-Alkyl Styrene Copolymer. The object of the present invention is to solve the above-mentioned problems and provide a functionalized para-styrene / p-alkyl benzene copolymer. Compared with the unfunctionalized para-styrene polymer, the functionalized para-styrene / p-phenylene polymer of the present invention has better adhesion to many substrates, and The compatibility of other polymers is also better. In order to achieve the above-mentioned objective, the functionalized p-styrene / p-phenylene copolymer of the present invention has the following chemical formula

The Consumers' Cooperative Printing Stand R1 (I) of the Central Standards Bureau of the Ministry of Economic Affairs, where R and R are independently selected from the group consisting of nitrogen, radicals, and primary and secondary halogen radicals (haloaikyl), preferably with R2 Independently selected from the group consisting of hydrogen 'Cw alkyl' and (^ _5-grade and secondary haloalkyl, X is a functional group, which is selected from the group consisting of halogen, metal, oxygen, sulfur, and stone, In the group consisting of the functional group of nitrogen 'carbon' phosphorus and mixtures thereof, a is 10 to 30,000, b is 0 to 30,000, and c is 1 to 30,000. The polymer preferably has a number average molecular weight of at least 1,000 or more. Paper size applies Chinese National Standard (CNS) A4 specification (210X29? Mm) 4342§4 A7 B7 V. Description of the invention (3) Preparation of functionalized para-styrene / p-alkylstyrene copolymer of the present invention The general method will be described as follows. Take the reaction of styrene and p-methylstyrene monomer as an example. First, using metallocene as a catalyst, these two monomers are co-^^ The catalyst system is also May include activating cocatalysts, such as amyl | Oxygen appearance (methyi ai ^ inoxane).

Wherein each X and y is the Mohr fraction (❶ /.) Of the corresponding monomer, x + y = 100. A suitable amyl metal catalyst has a delocalized π-bonded portion 'and a restricted three-dimensional structure. This catalyst can be interpreted as a metal coordination complex having a metal element of Group IVB-VIB and a non-localized π-bonded portion of a restricted stereostructure. This type of catalyst is printed in the Shell Standard Consumer Cooperative of the Central Bureau of Standards of the United States Patent Department (please read the "背面" on the back before filling in this page) 4,542,199; 4,530,914; 4,665,047; 4,752,597; Nos. 5,026,798; and 5,272,236. Preferred catalyst complexes include complexes of titanium and titanium ', which may have one or two cyclopentadienyl derivatives. Suitable activation catalysts can be methylalumoxane (ΜΑΟ), trialkyl aluminum (dialkyl aluminum), dialkyl aluminum, inert and the paper size applies to the Chinese National Standard (CNS) Λ4 specification UlOX297 (Mm) 43426 A7 B7 Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Bei Gong Xiao F Cooperative, V. Description of the invention (4) Salts of non-coordinating anions, or mixtures thereof. Examples of trisalamides include trimethylsaurus, triethylsam, tripropylsau, triisopropyl_'dibutylsau 'and diisobutyl | lu (trjjs〇butyl aluminum; TIB A). Salts of inert and non-coordinating anions may be borates. Suitable naphthalates for use in the present invention include N, N-dimethyl anilinium tetrakis (pentafluorophenyl) borate] > Pentafluorobenzyl) mono acid salt [triphenyl carbenium tetrakis (pentafluorophenyl) borate], trimethyl ammonium tetrakis (pentafluorophenyl) borate [trimethyl ammonium tetrakis- (pentafluorophenyl) orate], ferrocene (pentafluorobenzene Ferrocenium tetrakis (pentafluorophenyl) borate], dimethyl ferrocenium tetrakis (pentafluorophenyl) borate, dimethyl ferrocenium tetrakis (pentafluorophenyl) borate, siiver Tetrakis (pentafluorophenyl) borate] and other activated catalysts are preferably methylalumoxane, or a mixture of trialkylaluminum and shed salt. The preferred diluent for monomers, catalyst components, and polymerization reactions can be ordinary aliphatic and aromatic hydrocarbons, which can be used alone or in a mixture of 'e.g., propane, butane, and pentane' rings. Pentane, hexane, toluene, heptane, isooctane and the like. Generally speaking, the polymerization reaction of the present invention is to mix stupid ethylene and p-fluorenylstyrene in a copolymerization reactor in the presence of a catalyst, and the reaction temperature is about 0 ° C to 100 ° C. between. The polymerization reaction is inert gas. The paper size applies to the Chinese national standard (CNS > A4 specification (2〗 0X297 mm) (Please read the precautions on the back before filling this page). Order 01. 4342β4 Α7 Β7 V. Description of the invention (5). It is carried out in a bulk atmosphere, and in a condition substantially free of water vapor. The advantage of the styrene / p-methylstyrene copolymer is that the benzyl matrix on the p-methylstyrene unit can be mild In the reaction state, it can be easily converted into various functional groups, 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 for the benzyl matrix of organic compounds can also be applied to the benzyl matrix on p-fluorenylstyrene. Two chemical formulas, namely, para-styrene / p-alkyl Bromination and carboxylation reactions of styrene copolymers to illustrate the functionalization of the benzyl matrix on para-styrene / p-alkylstyrene copolymers. (Please read the precautions on the back before filling this page )

(-ch2ch) ^-ch2ch {-ch2ch) ^-(-ch2ch ·

Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs

metallation and carboxylation

Among the functionalization reactions of benzyl protons on para-styrene / p-alkylbenzyl ethylene copolymers, the prime and metallization reactions are the most important. The halogenation reaction will produce benzyl halogen, and benzyl halogen is a very active electrophilic test. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 4342§4 A7 B7 V. Description of the invention (6) Electrophiles can react to various functional groups via nucleophilic substitution reactions. The metallization reaction produces a benzyl anion on the p-alkylstyrene unit, which can react to many other functional groups. In fact, the halogenated and metallized para-ethylene / p-alkylstyrene copolymers can react to almost all organic functional groups. Thus, via a direct reaction of an unfunctionalized para-hexene / p-alkylstyrene copolymer, or via a functionalized or metallized para-styrene / p-alkylstyrene copolymer The functional group X in the chemical formula (I) may be a functional group containing halogen, metal, oxygen, sulfur, silicon, nitrogen, carbon, or phosphorus, or a mixture thereof. The functional group X at the base position is also detailed in U.S. Patent Nos. 5,543,484 (Chung, etal.); 5,548,029 (Powers, et al.); And 5,162,445 (Powers, et al.) Revelation. 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 carboxylates, which are obtained by substituting a halogen ion on the main group with -0. Printed by the Central Government Bureau of the Ministry of Economic Affairs-X. Consumer Cooperatives (please read the notes on the back to complete this page) Examples of functional groups X containing sulfur include thiolates, thiophenolates , Thioethers, thiocarboxylates, dithiocarboxylates, thioureas, dithiocarbamates, xanthates, and cyanothiones (Thiocyanates) 'It is obtained by replacing halogen ions on the vehicle base with -S-. This paper size applies the Chinese National Standard {CNS) A4 specification (210X297 mm) 434264 A7 _B7_ V. Description of the invention (7) Examples of functional groups X containing Shixi include silanes and halogenated silanes ( halosilanes), which are obtained by replacing halogen ions on a benzyl group with -Si-. Examples of the carbon-containing functional group X include malonates' cyanides and CR33. R3 is an organic group which is obtained by replacing a halogen ion on a benzyl group with -C ·. Examples of the nitrogen-containing functional group X include amides, amines, and carbamide. 〇31 ^ & 2168), phthalimides, pyridines, maleimides, cyanates, which are based on the benzyl group The above halogen ions were replaced with the obtained ones. Examples of the functional group X containing lin include phosphines. It is obtained by replacing the halogen ion on the benzyl group with -P-. In the following, the content, methods, and features of the present invention will be further described 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. Example 1: Synthesis of para-poly (styrene-co-para- stilbene styrene) printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Distillation (#Read the precautions on the back first, then fill out this page) under nitrogen 35 ml of purified p-methylstyrene monomer (hereinafter referred to as pMS) and 315 ml of styrene monomer (hereinafter referred to as SM) were charged into a 1 L metal reaction container, and then 2.8 ml of 10 wt. /. The alumoxane (MAO) solution was charged into the reactor. After the reaction vessel was heated to 70 ° C, then pentafluorenylcyclopentadienyl dioxotitanium (III) [Cp * Ti (OMe) 2] catalyst 0.0208 mmol was added, and the reaction was carried out for 60 minutes with sodium hydroxide. After the reaction was terminated by a methanol / methanol solution, Soxhlet extraction was used again, and after extraction with methanol as a solvent for 24 hours, 86 g of a product was obtained. Analysis of physical properties of copolymers 10 This paper size applies to Chinese National Standard (CNS) A4 specifications (210 × 297 Gongchu) Μ2δ4 Α7 Β7

Description of the invention (8) The melting point is 239 after analysis. (:; GPC analysis is 1,526,000, number average molecular weight is above, and NMR analysis, where pMS content is u mole percentage; dsc 'wherein weight average molecular weight 741,000, molecular weight distribution 2.06. Other copolymers The properties and results are shown in Table 1. Example 2 The steps are the same as those described in Example 1, but the amount of catalyst and aluminoxane (MA0) was changed. The results are shown in Table 1. Example 3 The same use as in Example 1 The para-styrene copolymer was prepared by using the catalyst system used in US Pat. No. 5,644,009. The results are shown in Table 1. Examples 4 to 6 except that the reactor was changed to The 1L glass reactor was polymerized with para-styrene copolymer under hydrogen 0.1 kg / cm2G, and the remaining method was the same as that in Example 3. The results are shown in Table 1. Example 7 The steps are the same as those described in Example 1 ' However, using a 100-liter reactor and changing the amount of reactants, the results are shown in Table 1. This paper size applies the Chinese National Standard (CNS) Λ4 specification (210X297 mm) 434264 A7 B7 V. Description of the invention (9) Table 1 Example SM (ml) pMS (ml) catalyst (mmol) MAO (ml) Reaction time (min) Melting point (° C) pMS content (mol%) in Mw Mw / Mn copolymer 1 315 35 0.0208 2.8 60 239 1.53xl06 2.06 12 2 315 35 0.0384 6,2 60 232 3.4xl05 1.87 17 3 300 50 0.0215 2,4 60 226 6.12x10s 6.42 1 1 4 397 3 0.0208 8.4 30 271 7.8x10s 1.68 1 5 315 35 0.0384 6.2 40 236 2.4xl05 9,32 15 6 200 200 0.0416 9.0 300 1.12 xl05 2.93 58 7 45 L 5 L 1.8 500 120 235 9.4xl05 204 7 (Please read the note on the back before filling out this page) Ordering the stamp of the employee consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Example 8: Poly (Polystyrene) -Co-p-methylstyrene (sPS-pMS) oxidation 20 g of para-poly (styrene-co-p-fluorenylstyrene) (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 (ODCB; o-dichlorobenzene) was added as a solvent. The three necks were respectively connected to a mechanical stirrer, a serum stopper and a condenser. Stir in an oil bath at 120 ° C until the sPS-pMS is completely dissolved. 300 ml of glacial acetic acid was slowly added, and the reaction temperature was reduced to 100 ° C. The catalyst cobalt acetate tetrahydrate and 60 mole ° / 〇 odor were added at a concentration of 20 mole% relative to the pMS content in SPS-pMS. Chemicals 12 This paper is in accordance with the Chinese national standard {CNS) A4 (210X297 mm) 4342S4 A7 B7 5. Description of the invention (10) (sodium bromide) is added to the round bottom bottle, and oxygen is introduced at a rate of 1L / min. 2 hours. After cooling, the reaction solution was poured into methanol, and the precipitated polymer was collected by filtration, washed twice with a hot water / methanol mixed solution, washed twice with methanol, and 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 (polydispersity index). Examples 9 and 10 The experimental steps are the same as those in Example 8, but the amount of catalyst and sodium bromide is changed, and the reaction time is changed. The results are shown in Table 2. Examples 11 and 12 20 g of para-poly (styrene-co-p-fluorenylstyrene) obtained in Example 7 were used. The experimental procedure was the same as that in Example 8. The molecular weight was controlled by changing the reaction time. The results are shown in Table 2. Table 2 (Please read the note 1 on the back before filling in this page)

P Order Printing Example of the Central Government Bureau of Standards, Shellfish Consumer Cooperative, Co., Ltd. Response time Co: NaBr (mole% of pMS) Total oxidation (%) Mn PDI Tm (° C) Tg (° C) 8 2hr 20:60 9.27 16000 2.29 185.28 98.74 9 lhr50m 10:40 3.61 45000 2.28 225.82 96.92 10 1 · 5 hr 10:40 3.32 58000 1.98 223.45 95.26 11 3.0 hr 20:40 6.20 43000 1.76 228.0 93.67 12 1,5 hr 20:40 6.15 289000 2.32 235.5 93.22 13 This paper size applies to China National Standard (CNS) A4 (210XW7 mm) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 434a @ 4 A7 B7 V. Description of the invention (11) Example 13: Bromination of sPS-pMS Weigh 35.9g of the SPS-pMS obtained in Example 6 into a round-bottomed flask, and round it; | The flask was enclosed in an aluminum box, and 450ml of CC14, 49.6g of NBS, and 1.7g of ΒPO were added, respectively, and a condenser was used. The oil bath was heated under reflux for 43 hours under nitrogen, and then the polymer solution was poured into an isopropanol solvent to precipitate. The obtained polymer was washed with water and isopropanol, respectively. 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 a chemical shift of -CiisBr at 4.4 ppm. Example 14: 2.5 g of sPS-pMS bromide scale The sPS-pMS obtained in Example 2 was placed in a round-bottomed flask, 200 ml of C6H5Cl was added and a condenser was installed, and heated to 120 ° C under nitrogen using an oil bath heating method. 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 it to 1ml, put it into a dropper tube surrounded by aluminum foil, and irradiate with a 90W bulb The round bottom flask was charged dropwise with the bromine solution in the dropper tube within 20 minutes, and then the polymer solution was poured into a methanol solvent 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 15: Carboxylation of sPS-pMS Take 3 g of the dried sPS-pMS obtained in Example 6 into a 300 ml round-bottomed flask, and add 100 ml of purified and dried cyclohexane under a nitrogen atmosphere. China National Standard (CNS) A4 specification (210X297 mm) — K——1 --- LP! (Please read the following: the matters on the back before filling out this page) Order attachments, MiJl Consumer Cooperatives, Central Government Bureau of the Ministry of Economic Affairs 3426 | 〇87110126 Patent Specification “Creation of Creation” Supplementary amendment (Date of revision: 89.9.7) V. Creation Instructions (12) Heat to 60C to make it decompose 'and then gradually cool to 10.4ml s_BuLi (1.3M ) And 4.1ml TMEDA are mixed first, and then this brown-red solution is taken out of the syringe and injected into the sporopic solution of spg_pMs. 'Slowly raise the temperature to 60C to react for 3 hours, and then cool to room temperature. 150 ml of THF saturated with CO 2 was added to the reaction flask and the CO 2 reaction was continuously introduced for 5 hours to carry out the amination reaction. Finally, the reaction was terminated with methanol and the polymerization reaction product was precipitated with methanol. The polymer was re-dissolved in THF and the polymer was precipitated with isopropyl alcohol (IpA; isopropyl alcohol). The polymer was precipitated and dried. The FT-IR analysis showed an absorption peak of carboxyl group (C = 0) at the position of i718cm-1. From the analysis chart of DSC, it was found that Dingg (glass transition temperature) increased by 5 5 ° C. Example 16: 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 lmKCHASiCl and 0.5 ml of Et #, 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. The optical f-analysis of 'H-NHR showed that the chemical shift of -Si (CH3) 3 was 0.09 ppm. .

Example 17: SPS-pMS containing hydroxyl group Weigh 0.5 lg of brominated sP (S-co-4MS) and add 40 ml of THF / Toluene (volume ratio = 1/1) solution to a two-necked reaction flask, with the upper end open The condensate tube is installed, and the other opening is sealed with a serum plug. Nitrogen was passed in, and the oil bath was heated and stirred, and the oil bath temperature was set to 80. 〇After about 5 hours, the polymer powdei • was seen to dissolve. Reduce the temperature of the oil bath to 60 ° C, slowly add 40 ml of the aqueous phase 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. The water phase solution was added and heated again, and the temperature of the oil bath was set at 80. (^, Reverse 15 (correction page) This paper uses China® home broadcast standard & CNS > A4 size (210X297 mm) 1L ~ Bu | —— (Please read the note 1P on the back before filling in this page)

• 、 1T Attachment 4342 ^ 41 087110126 Patent Specification Supplementary Amendment (Date of revision: 89, 9.7) V. Creation Note (B) should take 21 hours. After the reaction is completed, the reaction solution in the reaction flask is poured into 2000 m of methanol to precipitate the polymerization product. The precipitated polymerization product was washed three times with a 1% HC1 aqueous solution and a 10% methanol aqueous solution, and the product was collected by filtration and dried under vacuum at 70 for 16 hours. # 相 反应 溶 垫 * is prepared by taking 4.06g of NaOH and 35ml of pure water locust and dissolving it 'in a double-mouthed reaction bottle'. One end is vented with nitrogen and the other end is sealed with a serum stopper; 4.0ml is slowly dripped into the syringe. CH3COOH, finally add 1.0ml of phase transfer catalyst Bu4NOH. The polymerization product was dissolved in CDC13, and the chemistry of 1H-NMR was measured at 25 ° C. Displacement changes. The chemical shift of phenyl hydrogen (benZyi 丨 c pr〇t〇n, sps_c6H5-CI ^ -Br) in the starting material is located at 4.42ppm. The esterified intermediate product (Sps-C6H5-Ci ^- 〇COCH3) The chemical shift of its phenyl hydrogen is at 5.00ppm; and the hydroxyl group-containing para-styrene copolymer (sPS-C6HrCH2-OH) obtained after hydrolysis is at a chemical shift of phenyl hydrogen at 4.54ppm Office. The reaction equation and some experimental results are as follows: (Please read the notes on the back before filling in this page) Order, 七 CHjH 廿 CH, 丨 妖 叫 -⑶ 士 6

Cli ,, CO〇W Printed by the Ministry of Economic Affairs, China Bureau of Industrial and Commercial Cooperatives: Η2Β ·

CNS (210 × 297 mm) 41416 | 087110126 Patent Specification "Additional Amendments" (Revised Date: 89.9.7) V. Creation Instructions (14) Attachment Table 3. Reaction No. Bromination SPS-pMS (g) CH3COOH (ml) NaOH (g) Bu4NOH (ml) Rxn Time (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 1 LJC-031 0.5 4.0 4.06 1.0 21 Table 4. Product analysis results Reaction No hydroxyl 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 LJC-031 2.1 88 188 9.83 ^ in ^^^ 1 ^^^ 1 ^ i · — ^ In ^^^ 1 ^^ 1 (#Read the notes on the back and fill in this note) Example 18: Amination reaction of sPS-pMS Printed by the Central Labor Bureau of the Ministry of Economic Affairs l_lg Deodorized SPS and 40ml THF / Toluene (v / v = l / l) in a 250ml double-necked reaction flask. The upper end is equipped with a condenser tube, and the other opening is sealed with a serum stopper. Nitrogen was passed in, and the oil was heated and dissolved by stirring. The temperature of the oil bath is 80t. Heat it for about 0.5 hours to dissolve the polymer. Reduce the temperature of the oil bath to 60 ° C. Then slowly add 5ml of 0.1ml of diethanolamine (DEA) with a syringe. Isopropyl alcohol (IPA) and continuous mixing. Nitrogen was passed, and the oil bath was heated to 90 ° C (Reflux temperature). After 16 hours of reaction, the reaction solution was poured into about 200 ml of methanol to precipitate a polymerization product. The precipitated polymer product is 50% (v / v) __π mifm ___ This paper size is applicable to China National Standards (CNS) A4 specifications (210X297 cm) 3 4 Attachment I 42g I 087110126 Patent Specification "Additional amendments _____ — (Revision date: 89.9.7) V. Creation instructions (15) Wash the methanol solution 3 times, filter and collect the product, and dry it under vacuum at 70t for 16 hours. From the results of 1H-NMR analysis, it can be found that the chemical shift of the methylene group of the starting material SPS <: 6H5_CHrBr is 4.42 PPm, and the chemical shift of the product by 1H-NMR analysis shows that the chemical shift is 3'54 ppm 'as SPS-C6HrCHrN- (CH2CH2 〇H) 2 chemical shift, and 2 63 卯 claw shell sPS-C ^ -CTVN-tq ^ CHpH) 2 chemical shift. The reaction formula and experimental results are as follows: (Please complete the notes on the back of the product before completing this I). Table 5. Conditions and results of the amination reaction.

Rxn. No SPS-pMS (g) I PA (ml) DEA (8) Rxn time (hr) Amine hydroxyl (%) Tg (° C) Tm (° C) ΔΗ (J / g) LJC-045 1.0 10 2.61 19 2.1 99 240 10.7 LJC-047 \ A 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

—_____ 18 (revised TF page $ ^ 浪 尤 1 逋 uses 0 standard in the garden (CNS) Α4 specifications {210X297 mm > "Creation Explanation" of the patent specification No. 087110126 of the Central Liangzhun Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, Inc. Supplementary amendments __. —_ (Date of revision: 89.9.7) V. Creative Instructions (16) Example 19: Etherification scale of sPS-pMS Take 3 g of brominated sPS and 50 ml of toluene in a 250 ml double-mouthed reaction bottle In the middle, the upper end is equipped with a condenser tube, and the other-the opening is sealed with a serum plug. Pass through the record, heat by oil bath and search for dissolution. The temperature of the oil bath is 100 ° C, the polymer is dissolved, and the oil bath The temperature was reduced to 6 (rc), and then a syringe was used to slowly add 20 ml of a methanol solution containing 0.5 g of potassium hydroxide and 0.3 g (: Η3 ((χΉ2αΐ2; > 3〇ΡΙ), and then add 5ml of Bu4NOH and continue stirring The oil bath was heated to 90 t (Reflux temperature). After 16 hours of reaction, the reaction solution was poured into about 200 ml of methanol to precipitate a polymerization product. The polymer products that were precipitated were then mixed at 50% (v / v) Washed with methanol aqueous solution 3 times, collected the product by filtration and then dried at 70. (: under vacuum for 6 hours. From 1H-NMR The analysis results showed that the chemical shift of the methylene group of the starting material spS_C6HrCHrBr was 4.42 ppm. After the analysis of the product after the etherification reaction, it was found that the chemical shift at 3.3 ppm was SPS-C6HrCH2-0- ( The chemical shift of CH2CH20) 3CH3 is the result of the removal of hydrogen bromide by the reaction of brominated sPS-pMS with CH3 (OCH2CH2) 3OH. Although the present invention has been disclosed above in the preferred embodiment, it is not intended to limit the present invention. Invention, anyone skilled in the art can make changes and retouching without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention shall be determined by the scope of the attached patent application. Du Xiaoyu uses the Chinese Standard for Homelessness (CNS) A4 (210X297 mm) --.- IΓ ----- II (Please read the note on the back before filling in this section) Order:

Claims (1)

Deleted the amendment of "Patent Application Fan Jr. Wai" of the Patent Specification No. 26 (Date of amendment: 89.9.7) Attachment 4 «Printed by the Central Ministry of Economy and Trade, Industrial and Commercial Cooperatives 6. Application for Patent Park 1. A functionalization The para-styrene / p-alkylstyrene copolymer has the following chemical formula: '/, R1, Α wherein R and R2 are independently selected from the group consisting of hydrogen, alkyl, primary and secondary haloalkyl, and X is a functional group selected from halogen-containing metal, oxygen In the group consisting of sulfur, stone, nitrogen, carbon, scale functional groups and mixtures thereof, a is 10 to 15000, b is 0 to 2000, and c is 1 to 2000. 2. The functionalized para-styrene / p-alkylstyrene copolymer 'as described in item 丨 of the patent application, wherein X is a halogen. 3. The functionalized para-benzyl ethylene / p-alkylphenyl ethyl fluorene copolymer 'described in item i of the scope of the patent application, where X is an alkali metal or an alkaline earth metal. 4. The functionalized para-stilbene / para-stilbene ethene compound as described in item 1 of the scope of the patent application, where X is selected from alkoxides, phenoxides, In the group of carbaxyiates. 20 (Revised page) (Please read the precautions before writing this page) 4T * t ;. J This paper ruler and GM Zhonggu 11 companies (CNS) A4 size (210x297 mm) Annex IV Ministry of Economy Revised “Scope of Patent Application” of the Patent Specification No. 10126 of the Sinopec Bureau of Shellfish Consumer Cooperatives (Revision Date: 89.9.7) β, Patent Application Range 5. Functionalization as described in item i of the patent application range P-phenylene / p-alkylstyrene copolymers, where X is selected from thiolates, thiophenolates, thioethers, and thiocarboxylates , Dithiocarboxylates, thioureas, dithiocarbamates, xanthates, and thiocyanates. 6. If applying for a patent The functionalized para-styrene / p-alkylstyrene copolymer described in Fanyuan Item 1 wherein X is selected from the group consisting of JM silanes and halosilanes. 7. The functionalized para-phenylethyl ethene / p-alkylstyrene copolymer described in item 1 of the scope of the patent application, wherein X is selected from malonates, cyanides, In the group consisting of CR and CR33, R3 is an organic group. 8. The functionalized para-styrene / p-alkylstyrene copolymer as described in item 1 of the scope of the patent application, wherein X is selected from amides, amines, and leaves ( carbazoles, phthalimides, ° ratio β (pyridines), maleimides, cyanates. 9. The functionalized para-p-ethylene / p-alkylstyrene copolymer as described in item 1 of the scope of the patent application, wherein X is a phosphine. 10. The functionalized para-styrene / p-alkylstyrene copolymer described in item 1 of the scope of the patent application, wherein R1 and R2 are independently selected from hydrogen, CN5 alkyl 'and < ^ _ 5 — The first and second iS alkyl groups. 21 (Revised page) This paper size is in Chinese National Standard (CNS) A4 (210〆297mm) ---- r— > —.-. Ί ---- r Pack-(please first Note on the back of the occasional reading, please fill in this page, and then fill in this page): Yes> Attachment 4 Revised "Scope of Patent Application" of Patent Specification No. 4342: ®_087110126 by the Central Rubbing Bureau of the Ministry of Economy (Date of revision: 89.9 .7) 6. Scope of Patent Application 11. The functionalized para-styrene / p-alkylstyrene copolymer described in item 1 of the scope of patent application, which is based on cyclopentadienyl metal compound (metallocene) Obtained in the presence of the catalyst. 12. The functionalized para-phenylene vinyl / p-alkylene styrene copolymer 'described in item 1 of the scope of the patent application, wherein the number average molecular weight of the polymer is at least. 22 (Revised page) This paper size is applicable to the Central Solid State Government (CNS) standard (210X297 mm) {Please read the notes on the back before filling in this card) Attachment: MiJl Consumer Cooperatives, Ministry of Economic Affairs, Central Government Bureau, MiJl Consumer Cooperative, Yinjia No. 3426 | 〇87110126 Patent Specification Supplementary Amendment (Date of amendment: 89.9.7) V. Creation Instructions (12) Heat to 60C to make it dew ' Gradually lower the temperature to 10.4ml s_BuLi (1.3M) and 4.1ml TMEDA before mixing this brown-red solution with a syringe and injecting it into the spg_pMs solution. Slowly raise the temperature to 60C for 3 hours and then cool To room temperature. 150 ml of THF saturated with CO 2 was added to the reaction flask and the CO 2 reaction was continuously introduced for 5 hours to carry out the amination reaction. Finally, the reaction was terminated with methanol and the polymerization reaction product was precipitated with methanol. The polymer was re-dissolved in THF and the polymer was precipitated with isopropyl alcohol (IpA; isopropyl alcohol). The polymer was precipitated and dried. The FT-IR analysis showed an absorption peak of carboxyl group (C = 0) at the position of i718cm-1. From the analysis chart of DSC, it was found that Dingg (glass transition temperature) increased by 5 5 ° C. Example 16: 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 lmKCHASiCl and 0.5 ml of Et #, 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. The optical f-analysis of 'H-NHR showed that the chemical shift of -Si (CH3) 3 was 0.09 ppm. . Example 17: SPS-pMS containing hydroxyl group Weigh 0.5 lg of brominated sP (S-co-4MS) and add 40 ml of THF / Toluene (volume ratio = 1/1) solution to a two-necked reaction flask, with the upper end open The condensate tube is installed, and the other opening is sealed with a serum plug. Nitrogen was passed in, and the oil bath was heated and stirred, and the oil bath temperature was set to 80. 〇After about 5 hours, the polymer powdei • was seen to dissolve. Reduce the temperature of the oil bath to 60 ° C, slowly add 40 ml of the aqueous phase 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. The water phase solution was added and heated again, and the temperature of the oil bath was set at 80. (^, Reverse 15 (correction page) This paper uses China® home broadcast standard & CNS > A4 size (210X297 mm) 1L ~ Bu | —— (Please read the note 1P on the back before filling in this Pages), 1T Attachment No. 4342 ^ 41 087110126 Patent Specification "Creation Explanation" Supplemental amendment (Date of revision: 89, 9.7) V. Creation Explanation (B) The response time should be 21 hours. After the reaction is completed, the reaction solution in the reaction bottle Pour into 2000m of methanol to precipitate the polymerization product. The precipitated polymerization product is washed 3 times with 1% HC aqueous solution and 10% methanol aqueous solution, and the product is collected by filtration and dried under vacuum at 70 for 16 hours. The preparation method of #phase reaction dissolving blanket * is: take 4.06g NaOH and 35ml pure water locust and mix and dissolve 'put in a double-mouthed reaction bottle' with nitrogen at one end and seal with a serum stopper at the other end; slowly drop 4.0 with a syringe. ml CH3COOH, and finally added 1.0 ml of phase transfer catalyst Bu4NOH. The polymerization product was dissolved in CDC13, and the spectrum of 1H-NMR was measured at 25 ° C. Chemical positions of para-styrene copolymers containing hydroxyl functional groups The chemical shift of phenyl hydrogen (benzyi 丨 c pr〇t〇n, sps_c6H5-CI ^ -Br) in the starting material is located at 4.42ppm, and the intermediate product (Sps-C6H5- Ci ^ -〇COCH3) The chemical shift of its phenyl hydrogen is at 5.00 ppm; and the hydroxyl group-containing para-styrene copolymer (sPS-C6HrCH2-OH) obtained after hydrolysis is the chemical shift of its phenyl hydrogen It is located at 4.54ppm. The reaction equation and some experimental results are as follows: (Please read the precautions on the back before filling in this page) Order, 七 CHjH 廿 CH, 丨 妖 叫 -⑶ 士 6 Cli ,, CO〇W 娌Printed by the Ministry of Economic Affairs, China Bureau of Industrial and Consumer Cooperatives: Η2Β · CNS (210 × 297 mm) 41416 | 087110126 Patent Specification "Additional Amendments" (Revised Date: 89.9.7) V. Creation Instructions (14) Attachment Table 3. Reaction No. Bromination SPS-pMS (g) CH3COOH (ml) NaOH (g) Bu4NOH (ml) Rxn Time (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 1 LJC-031 0.5 4.0 4.06 1.0 21 Table 4. Product analysis results Reaction No hydroxyl 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 LJC-031 2.1 88 188 9.83 ^ in ^^^ 1 ^^^ 1 ^ i · — ^ In ^^^ 1 ^^ 1 (#Read the notes on the back and fill in this note) Example 18: Amination reaction of sPS-pMS Printed by the Central Labor Bureau of the Ministry of Economic Affairs l_lg Deodorized SPS and 40ml THF / Toluene (v / v = l / l) in a 250ml double-necked reaction flask. The upper end is equipped with a condenser tube, and the other opening is sealed with a serum stopper. Nitrogen was passed in, and the oil was heated and dissolved by stirring. The temperature of the oil bath is 80t. Heat it for about 0.5 hours to dissolve the polymer. Reduce the temperature of the oil bath to 60 ° C. Then slowly add 5ml of 0.1ml of diethanolamine (DEA) with a syringe. Isopropyl alcohol (IPA) and continuous mixing. Nitrogen was passed, and the oil bath was heated to 90 ° C (Reflux temperature). After 16 hours of reaction, the reaction solution was poured into about 200 ml of methanol to precipitate a polymerization product. The precipitated polymer product is 50% (v / v) __π mifm ___ This paper size is applicable to China National Standards (CNS) A4 specifications (210X297 cm) 3 4 Attachment I 42g I 087110126 Patent Specification "Additional amendments _____ — (Revision date: 89.9.7) V. Creation instructions (15) Wash the methanol solution 3 times, filter and collect the product, and dry it under vacuum at 70t for 16 hours. From the results of 1H-NMR analysis, it can be found that the chemical shift of the methylene group of the starting material SPS <: 6H5_CHrBr is 4.42 PPm, and the chemical shift of the product by 1H-NMR analysis shows that the chemical shift is 3'54 ppm 'as SPS-C6HrCHrN- (CH2CH2 〇H) 2 chemical shift, and 2 63 卯 claw shell sPS-C ^ -CTVN-tq ^ CHpH) 2 chemical shift. The reaction formula and experimental results are as follows: (Please complete the notes on the back of the product before filling out this I). Table 5. Conditions and results of the amination reaction Rxn. No SPS-pMS (g) I PA (ml) DEA (8) Rxn time (hr) Amine hydroxyl (%) Tg (° C) Tm (° C) ΔΗ (J / g) LJC-045 1.0 10 2.61 19 2.1 99 240 10.7 LJC -047 \ A 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 —_____ 18 (revised TF page $ ^ 浪 尤 1 逋 uses 0 standard in the garden (CNS) Α4 specifications {210X297 mm > "Creation Explanation" of the patent specification No. 087110126 of the Central Liangzhun Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, Inc. Supplementary amendments __. —_ (Date of revision: 89.9.7) V. Creative Instructions (16) Example 19: Etherification scale of sPS-pMS Take 3 g of brominated sPS and 50 ml of toluene in a 250 ml double-mouthed reaction bottle In the middle, the upper end is equipped with a condenser tube, and the other-the opening is sealed with a serum plug. Pass through the record, heat by oil bath and search for dissolution. The temperature of the oil bath is 100 ° C, the polymer is dissolved, and the oil bath The temperature was reduced to 6 (rc), and then a syringe was used to slowly add 20 ml of a methanol solution containing 0.5 g of potassium hydroxide and 0.3 g (: Η3 ((χΉ2αΐ2; > 3〇ΡΙ), and then add 5ml of Bu4NOH and continue stirring The oil bath was heated to 90 t (Reflux temperature). After 16 hours of reaction, the reaction solution was poured into about 200 ml of methanol to precipitate a polymerization product. The polymer products that were precipitated were then mixed at 50% (v / v) Washed with methanol aqueous solution 3 times, collected the product by filtration, and dried at 70 ° C (6 hours under vacuum). From the results of 1H-NMR analysis, it can be found that the chemical shift of the methylene group of the starting material spS_C6HrCHrBr is 4.42 ppm. After the analysis of the product after the etherification reaction, it is found that the chemical shift at 3.3 ppm is sPS-C6HrCH2. The chemical shift of -0- (CH2CH20) 3CH3 is the result of the removal of hydrogen bromide by the reaction of brominated SPS-pMS with CH3 (OCH2CH2) 3OH. Although the present invention has been disclosed above in a preferred embodiment, it is not It is used to limit the present invention. Any person skilled in the art can make changes and decorations without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention shall be determined by the scope of the attached patent application. . This paper is again free to use Chinese Standards (CNS) A4 (210X297 mm) ---- IΓ ---- II (Please read the note on the back before filling in this note) Order: Delete No. 26 Amendment of "Patent Application Fan Jr. Wai" of the Patent Specification (Date of amendment: 89.9.7) Attachment 4 «Printed by the Central Ministry of Economy and Trade Organization of China Industrial Cooperatives 6. Application for Patent Fan Garden 1. A functionalized alignment A styrene / p-alkylstyrene copolymer having the following Chemical formula: '/, R1, Α wherein R and R2 are independently selected from the group consisting of hydrogen, alkyl, primary and secondary haloalkyl, and X is a functional group selected from halogen-containing metal, oxygen In the group consisting of sulfur, stone, nitrogen, carbon, scale functional groups and mixtures thereof, a is 10 to 15000, b is 0 to 2000, and c is 1 to 2000. 2. The functionalized para-styrene / p-alkylstyrene copolymer 'as described in item 丨 of the patent application, wherein X is a halogen. 3. The functionalized para-benzyl ethylene / p-alkylphenyl ethyl fluorene copolymer 'described in item i of the scope of the patent application, where X is an alkali metal or an alkaline earth metal. 4. The functionalized para-stilbene / para-stilbene ethene compound as described in item 1 of the scope of the patent application, where X is selected from alkoxides, phenoxides, In the group of carbaxyiates. 20 (Revised page) (Please read the precautions before writing this page) 4T * t ;. J This paper ruler and GM Zhonggu 11 companies (CNS) A4 size (210x297 mm) Annex IV Ministry of Economy Revised “Scope of Patent Application” of the Patent Specification No. 10126 of the Sinopec Bureau of Shellfish Consumer Cooperatives (Revision Date: 89.9.7) β, Patent Application Range 5. Functionalization as described in item i of the patent application range P-phenylene / p-alkylstyrene copolymers, where X is selected from thiolates, thiophenolates, thioethers, and thiocarboxylates , Dithiocarboxylates, thioureas, dithiocarbamates, xanthates, and thiocyanates. 6. If applying for a patent The functionalized para-styrene / p-alkylstyrene copolymer described in Fanyuan Item 1 wherein X is selected from the group consisting of JM silanes and halosilanes. 7. The functionalized para-phenylethyl ethene / p-alkylstyrene copolymer described in item 1 of the scope of the patent application, wherein X is selected from malonates, cyanides, In the group consisting of CR and CR33, R3 is an organic group. 8. The functionalized para-styrene / p-alkylstyrene copolymer as described in item 1 of the scope of the patent application, wherein X is selected from amides, amines, and leaves ( carbazoles, phthalimides, ° ratio β (pyridines), maleimides, cyanates. 9. The functionalized para-p-ethylene / p-alkylstyrene copolymer as described in item 1 of the scope of the patent application, wherein X is a phosphine. 10. The functionalized para-styrene / p-alkylstyrene copolymer described in item 1 of the scope of the patent application, wherein R1 and R2 are independently selected from hydrogen, CN5 alkyl 'and < ^ _ 5 — The first and second iS alkyl groups. 21 (Revised page) This paper size is in Chinese National Standard (CNS) A4 (210〆297mm) ---- r— > —.-. Ί ---- r Pack-(please first Note on the back of the occasional reading, please fill in this page, and then fill in this page): Yes> Attachment 4 Revised "Scope of Patent Application" of Patent Specification No. 4342: ®_087110126 by the Central Rubbing Bureau of the Ministry of Economy (Date of revision: 89.9 .7) 6. Scope of Patent Application 11. The functionalized para-styrene / p-alkylstyrene copolymer described in item 1 of the scope of patent application, which is based on cyclopentadienyl metal compound (metallocene) Obtained in the presence of the catalyst. 12. The functionalized para-phenylene vinyl / p-alkylene styrene copolymer 'described in item 1 of the scope of the patent application, wherein the number average molecular weight of the polymer is at least. 22 (Revised page) This paper size is applicable to the Central Solid State Government (CNS) standard (210X297 mm) {Please read the notes on the back before filling in this card)