TW200724571A - A process for preparing homoblock co-polysulfones and polysulfones prepared therefrom - Google Patents

Description

200724571 (1) Description of the Invention [Technical Field of the Invention] The present invention relates to a method for preparing a block copolymer and a block copolymer of the same. In particular, the invention relates to a process for the preparation of at least two homopolymers belonging to the group of polyterpenes, in particular f, PSU, PSS, PPSU, PSSB, PES, TPES φ TMPSS and related to their preparation. Block copolymer. Further, the present invention relates to di- and tri-blocks and random polymers and processes for their preparation. These homoblocks may have different molecular weights or may have amounts when compared to their molecular weight present in the embedding. These block copolymers exhibit a single glass transition temperature (transparency and can be easily added for molding, extrusion, and also as a high molecular weight compatibilizer using conventional plastic processing techniques. [Prior Art] Poly Maple The polymer family is well known in the art, and there are three types of polyfluorene (PSU), polyether oxime (PES) and polyphenylene phenyl ruthenium (PSU, PPSU, PES) which are good, usually at 3 50. It is a transparent, light amber amorphous plastic with a non-degradable processing temperature from °C to 4 〇〇 °C. It has excellent electrical properties and good chemical and fire resistance. The block is: selected from the same molecular Tg in PSSD, PESK and multi-block copolymers, and works well. It can promote the phase of the direct product, the high temperature resistance or discoloration of the wind (PPSU). This machine can be easily processed using general processing techniques such as injection molding, compression molding, blow molding and extrusion. This makes it a highly versatile and easy-to-use plastic with numerous applications in the electronics, electrical, medical, general engineering, food processing and other industries. The Poly PSU was discovered in Union Carbide (US Patent No. 4,1 08,8 3 7 ,1 97 8 ) in the early 1960s. Since then, it has been actively improving the quality of PSU, and for many years, it has continued to seek to improve color, thermal stability, molecular weight and reduce residual monomers and solvents. Although PSU, PES and PPSU have many similarities in color, electrical properties, chemical resistance, fire resistance, etc., there are also important differences. The most important difference is the glass transition temperature (Tg). The PSU has 189. (: Tg, PES has 225 t: Tg, and PPSU has 222. (: Tg. Therefore 'PSU compared with PPSU, especially compared with PES with the highest heat resistance, has its shape stability The overall lower heat resistance. In addition, PES also has a higher tensile strength (> 90 MPa) than PSU and PPSU (both 70 to 75 MPa). On the other hand, PPSU has the same polycarbonate. (PC) Excellent impact resistance, its Izod notched impact strength is 670 to 700 J/m. Both PES and PSU have a lower Izod notch resistance of only 50 to 5 5 J/m. Impact strength. Similarly, it is known in the art that articles made from PPSU can withstand > 1 000 sterilization cycles without cracking, but objects with PSU-based objects are subjected to about 80 cycles and PES-based objects are only It takes about 100 cycles. On the other hand, PSU has the lightest color and can be processed relatively easily, while ppsu is darker and more difficult to process than PSU or PES. 200724571 (3) Therefore, PSU properties (such as ease of processing and Light color properties) Combination with PPSU properties such as high temperature resistance and impact resistance. The incorporation of U into the PPSU also reduces the overall cost. Although the physical blending of PPSU and PSU is one way to achieve this, it destroys one of the most important properties of the two homopolymers, namely their transparency. The physical blend of PES and PSU is not only opaque, nor can it be processed to produce a blend of desirable properties because it is a highly incompatible polymer. B In either case, these compositions only show Tg<lt; 225 °c. Higher Tg polyaryl ether oxime (TMPES) uses 3,3',5,5'-tetramethyl-4,4'-dihydroxydiphenyl fluorene and 4,4' one-two Chlorodiphenylphosphonium is prepared as a monomer. U.S. Patent No. 5,008,3,64, the disclosure of other biphenyl units such as 4,4'-di(4-chlorophenylmonosulfonyl)-biphenyl and 4 , 4'-1-2 (4-hydroxyphenyl-sulfonyl)-biphenyl polyaryl fluorene, which has stability at high temperatures. Other compositions are also expected because they have a higher than 2 2 0 ° The Tg of C (Tg of PESB) is further improved by the incorporation of such compositions, and by incorporating PES, PSU or PPSU into its chain structure This high temperature resistant polymer is made easier to process. Some of the unit chain structure of the polyfluorene family is shown as follows: PPSU : --c6h4- so2- c6h4- o- c6h4- C6H4- ο--PSU : --c6h4- so2 - c6h4- o- c6h4- C(CH3)2- 〇-- PES : - - C 6 H 4 -SO 2 -C 6 H 4 - O -C 6 H 4 - S 0 2 - C 6 H 4 - 0 -- PSSD : --c6h4- so2- c6h4- c6h4- S〇2- c6h4~ o- 200724571 (4) C6H4 — S〇2 — C6H4 — PSSB : --C6H4- S〇2- C6H4- C6H4- S02- Ab 4 ～〇C6H4 — C6H4 — TPES : --C6H4 — S〇2~ C6H4 — 〇 — C sas ~~ S〇2 — p ^sH8 PSS : —c6H4 — so2- c6h4 — c6H4 — so2— c6h4~0- PESK : __c6h4- co2 — c.h4- o- c6h4- so2 ~ pu Z ^ 6 H 4 —

O — TMPSS : ,, c6h4— so2- C6H4— c6h4— so2n o —C^H^— S〇2--CgH8~ 〇-Polyfluorene uses one or more aromatic dihalogen compounds such as dichloro 2 _飒 (DCDPS), dichlorodiphenyl ketone (DCB) or dichlorodiphenyl-sulfonylbiphenyl (CSB) and its individual mono-, di-, tri- or tetra-methyl or its derivatives and one or A variety of aromatic dihydroxy monomers such as bisphenol A, bis-base II • guanidine (DHDPS), biphenol, dihydroxydiphenyldisulfonylbiphenyl (HSB), dihydroxydiphenyl ether, two Hydroxydiphenylmethane, {bis~(3,5-dimethyl-4-hydroxyphenyl)anthracene}, which are prepared by a single, two, ~~~~ tetrasubstituted methyl derivative. In the case of PPSU, the dihydroxy compound used is biphenyl (HO-C6H4-C6H4-OH), PES is DHDPS, and PSU is bis-A (HO-C6H4_C(CH3)2-C6H4-OH), and TPES is TMDHDPS (HO-C6H2(CH3)2-S02-C6H2(CH3)2-OH), and DCDPS is used as the second monomer of all such polyfluorenes. -8- 200724571

In the case of PSSD, the dihydroxy compound used is DHDPS (h〇-c6h4-so2-c6h4-〇h), and PSSB is biphenol (HO-C6H4-C6H4-OH), and TMSPS is TMDHDPS (H0). -C6H2(CH3)2_S02-C6H2(CH3)2-0H), PSS is HSB (oh-c6h4-so2-c6h4-c6h4-so2-c6h4-oh); and CSB (Cl-C6H4-S〇2-C6H4) is used. -C6H4_S02-C6H4-Cl) as the second monomer. PESK can be obtained by using DCB (dichlorodiphenyl ketone) and DHDPS φ. Similarly, other homopolymers can be prepared by reacting DCB with other dihydroxy compounds such as DHDPS, biphenol, TMDHDPS and HSB. The homoblocks prepared above can be reacted with other homoblocks such as PSS, PSSD, PPSU, PES, PSU, TPES, PSSB and TMPSS. The use of more than one dihydroxy monomer is also known. For example, a polymer called "PAS" manufactured by Amoco includes a small amount of hydroquinone outside of DCDPS and DHDPS. The third single system is added at the beginning of the process and is therefore polymerized in the polymer chain in a random sequence. φ Other random copolymers in the prior art display can also add a larger amount

The third monomer. Thus, GB Patent 4,331,79 8 (1 982) and US Patent 5,326,834 (1994) teach the preparation of terpolymers using 80 to 40 mole % DHDPS and corresponding 20 to 60 mole % biphenol. Close to the DCD of the Mox%. Since both patents teach that the polymerization begins with the monomer itself, it is known that the distribution of DHDPS and biphenol in the final copolymer is random. Therefore, take a random sequence such as... ABAABBBAABAAABBABABBAAABB--, where A and B appear in a random sequence and the amount of change occurs as A and B or DHDPS and 200724571 (6) phenol (DCDPS part will appear in AB, The initial concentration of AB & BB groups, not shown here). Similarly, European Patent No. 0,331,492 teaches the synthesis of random terpolymers of DCDPS and DHDPS/biphenol or bisphenol A/biphenol. Similarly, a random trimer (rather than a block copolymer) is produced from the three monomers starting from the cumulative molecular weight, wherein the sequence of A & B in the chain is random and unpredictable. The prior art has shown that block copolymers in which only one block is polyfluorene have been prepared. Hedtmann - Rein and Heinz (US Patent 5,036, 146-1991) teach the preparation of block copolymers of PSU and polyimine (PI). In this case, the homoblock of the polyfluorene of the amine terminal is first prepared. This is prepared using DCDPS, biguanide A and p-aminophenol to produce a homoblock having a molecular weight in the range of from 1 500 to 20,000. The resulting homoblock is then reacted with a tetracarboxylic acid (such as diphenyl ketone tetracarboxylic dianhydride) and another diamine (such as 4,4'-diaminodiphenylmethane) to produce PSu- Block copolymer of PI. The copolymer was prepared at 350 ° C in the molten phase.

McGrath and colleagues (Polymer preprints, 25, 14, 1 984) have prepared PSU-poly terephthalate copolymers. This is done using a mixture of DCDPS (〇· 141 mol) and hydroquinone with biphenol (each 〇·〇 75 mol) to produce a homoblock in solution, after which the homoblock is paired using solution or interfacial techniques. Reaction of phthalocyanine chloride with biphenol to produce a block copolymer

McGrath φ \ (Polymer Preprints, 26, 275, 1 98 5 ) further describes the use of an ethyl thiol end capping PSU with p-acetoxybenzoic acid or biphenol diacetate / terephthalic acid to produce a PSU / Polyether Embedding - 200724571 (7) Preparation of a segment copolymer, the latter being highly crystalline or even a liquid crystal polymer. The synthesis of the block copolymer is carried out in the presence of a melt or in the presence of diphenylphosphonium at 200 to 300 °C. The preparation of block copolymers is shown by the fact that the product is insoluble in common organic solvents.

Maresca et al. have prepared polyaryl ethers having an improved glass transition temperature containing at least 20% by weight of bis(3,5-dimethyl-4-hydroxyphenyl)anthracene. _ Wang and colleagues (Polymer International, 50(2), 249 200 1 have synthesized novel random and block copolymers composed of benzalamine and perfluoroisopropylidene-polyarylether.

Gerhard and coworkers (U.S. Patent 3,647,751) have used the dihalo-diphenyl-diindenyl and alkali metal bisphenolates to prepare polyaryl ether oximes.

McGrath and colleagues (Polymer Preprints, 26, 277, 1 9 8 5) also developed block copolymers of PSU and PEEK, which use hydroxyl terminated oligo P SU homoblocks and difluorodiphenyl ketone itself or Add hydrogen, hydrazine and/or biphenol, as appropriate. The first method does not produce a block copolymer, but instead produces a PSU block linked by difluorodiphenyl ketone. However, the second method has the potential to simultaneously produce both random and block structures in the PSU and PEEK copolymers. Although the foregoing studies have prepared PSU block copolymers, it has been found that most of the combinations of hydroxyl terminated PSUs with other monomers produce block copolymers upon polymerization. In such a process, the polymerized monomer is highly susceptible to a greatly variable block size such that certain PSU blocks are only joined by a single monomer unit having a molecular weight of only 300 or less (of course <1〇〇〇). Therefore, -11 - 200724571 (8) The molecular weight of the second block is not a PSU oligomer, and is ideally > 1000 square. Therefore, depending on the concentration, the second homoblock is preferably no more than a single or two monomer units. This can be avoided by separately preparing the two homoblocks and reacting them to produce a block copolymer.

Noshay and colleagues (J. Polymer Sci. A-1, 3147, 1971) have prepared block copolymers of amine terminal dimethyl methoxy oxane and hydroxyl terminal psu. The hydroxyl terminated PSU was prepared using slightly more bromine A (0.495 moles) than DCDPS (0.45 moles). This -ON a group is subsequently converted to an -OH group using oxalic acid and the product precipitates. The dried PSU powder was reacted with separately prepared amine terminal polyoxane in diethyl ether at 60 °C. It can be noted that since P S U is plastic and polyoxyalkylene is elastic, the composition produces a block copolymer having properties similar to thermoplastic elastomers. However, it is surprising that neither the described method nor the synthesis performed can form a thermoplastic block copolymer using two ruthenium blocks. The general method for preparing such polyfluorenes consists of the following processes: an aprotic organic solvent selected from cyclobutyl, N-methylpyrrolidone (NMP) or dimethyl hydrazine (DMS0) (usually on a base) Distillation) was placed in the reactor. DCDPS or any similar dihalo-based monomer (such as dichlorodiphenyldisulfonylbiphenyl (CSB), dichlorodiphenyl ketone, etc.) and a second dihydroxy monomer (biphenol, DHDPS, TMDHDS or HSB, etc.) are typically added to the reactor together with sodium carbonate or potassium carbonate at a molar ratio of 1.00: 1.00. Add toluene or monochlorobenzene (MCB) to promote dehydration. The temperature of the mixture is then gradually increased to 14 ° C to 230 ° C (depending on the solvent used). At this time, the test carbonate reacts with the phenol to produce a salt -12- 200724571 Ο) and releases water. The water is distilled off, which is increased by toluene or MCB (if present). The reaction mixture after removal of water is then heated to a temperature in the range of 170 ° C to 250 ° C (depending on the solvent, base and dihydroxy monomer used) until the desired viscosity or molecular weight is achieved. Thereafter, the chain of growth is optionally capped with MeCl, and the reaction mass is filtered to remove the salt, after which the precipitate chain is precipitated in water or MeOH, further treated to remove residual solvent φ and dried. Alternatively, the solvent may be flashed off and the reaction mass may be passed directly through a devolatilizer extruder to remove residual solvent and granulate the polymer. Addition of more than one hydroxy monomer to the foregoing produces a terpolymer in which a chain of three (but not two) monomer units is randomly incorporated. It is desirable to develop a block copolymer formation process in which two plastics, both of which are homoblocks based on ruthenium, are joined to form a single chain in the form of a block copolymer. As mentioned above, the block copolymers of different poly-Maple are unknown in the technical field. Generally, as is known in the art, the successful formation of block copolymers from the homoblocks must meet three requirements: i) the two The blocks should have terminal groups that react with each other, namely -OH & -CNO. Ii) Each homoblock should have two identical terminal groups, namely -OH or -CNO. i i i ) The two homoblocks should be mixed at the correct stoichiometric ratio to produce a local molecular weight block copolymer. The present invention discloses a process for preparing a block copolymer using two or more different poly-sand blocks, while avoiding the stringent requirements of each homoblock having substantially the same terminal group. Similarly, the need for proper stoichiometry of two or more homoblocks can be eliminated when forming high molecular weight block polymers. SUMMARY OF THE INVENTION The present invention is directed to a method of preparing a block copolymer comprising at least two homoblocks selected from the group consisting of PSSD, PSSB, TPES, PSS, TMPSS or PESK Or selected from at least one of PSSD, PSSB, TPES, PSS, TMPSS or PESK and at least one PPSU, PES or PSU, wherein the homoblocks each have at least 1 000 of the same or different molecular weight and have a total weight of at least 5%, Wherein the block copolymer has a molecular weight of at least 2000, the method step comprising: (a) by the presence of at least one base, optionally in at least one solvent, and optionally in the presence of an entraining agent, Heating at least one aromatic diol/dihydroxy compound and at least one aromatic dihalogen compound (one of which contains at least one maple group) to prepare the aforementioned various homoblocks, (b) the aforementioned homoblocks together! 3 〇 to 2 5 0. (wherein the temperature is optionally reacted in at least one solvent, and optionally the end of the block copolymer is subsequently capped, (c) the block copolymer is recovered. The invention also relates to the inlay prepared using the aforementioned method. a segment copolymer and a block copolymer comprising at least two homoblocks selected from the group consisting of p SSD, PSSB, TPES, PSS, TMPSS or pESK or selected from at least one of -14-200724571 (11) PSSD, PSSB, TPES, PSS, TMPSS or PESK and at least one PPSU, PES or PSU, directly bonded or bonded by a bonding group to form a ~block copolymer chain, wherein the homoblocks each have at least 1 000 identical Or, differing molecular weight and having a total weight of at least 5% and wherein the block copolymer has a molecular weight of at least 2000. These novel block copolymers are prepared by separately preparing a lower molecular weight homoblock. The technique of mixing and further reacting in different proportions to produce a polymer p-block copolymer. Using this technique, the formation of the block structure and its sequence and block molecular weight can be determined. In addition to the segmented multi-block compound, very High molecular weight diblock or triblock and multiblock having a known block molecular weight can be obtained by this method. The prepared block copolymer can be used as a novel polyfluorene plastic or as a compatibilizer. DESCRIPTION OF THE INVENTION In general, there are two possible chain end structures on the polymer chain of the homoblock of polyfluorene. These terminal groups are -C1 from the dihalo group (DCDPS, CSB, DCB, etc.) And a phenol monomer - a specific homoblock polymer chain may also have a mixture of both terminal groups. In the case of block copolymers, based on prior art predictions, one of the homoblocks should have only two - The C1 terminal group/chain and the second homoblock should have only two -ΟΗ terminal groups/chains. Mixing at the correct stoichiometric ratio and allowing it to react will result in a high molecular weight block copolymer. Since both homoblocks may have a -C1 or -oh mixed end group, the present invention shows that each of the homoblocks as described above may also have two identical end-15-200724571 (12) groups and Two uniform blocks must be mixed in the correct stoichiometric ratio The polyfluorene usually has a certain -C1 and some -OH end groups. The concentration of each is determined by two important factors: firstly a dihalogen compound such as DCDPS, DCB or CSB, etc. The initial molar ratio of the hydroxyphenol monomer, and secondly if the molar ratio is not exactly 1:1, the molecular weight of the polymer that can be constructed. The ratio of the two monomers is a very important factor, because the extremely high molecular weight is to be constructed, the ratio is The ohmmeter must be kept close to 1:1. Typically, the concentration of one monomer should not be about 1 to 2 moles higher than the other. Therefore, the molar ratio is usually maintained at 1.02: 1.00 to 1.00: 1.02. Inside to get a high molecular weight. Increasing the concentration of any of the monomers above this range generally results in stoichiometric disturbances to the extent that sufficient molecular weight of the copolymer cannot be constructed, and most of the polymer properties are impaired because they do not achieve optimum enthalpy. However, this harsh stoichiometry is unexpectedly not necessary when preparing oligomeric homoblocks because there is no need to construct high molecular weights. Thus, in terms of homoblock production, the present invention has successfully employed monomer ratios of up to 1.15: 1.00. The range of monomer ratios in the homoblock is thus increased from 1.02: 1.00 to 1.15: 1.00 without sacrificing the final molecular weight of the block copolymer. The present invention relates to novel poly-Maple block copolymer structures and novel methods of making the same. The invention relates in particular to the preparation of novel types of block copolymers which are prepared using PES, PPSU, PSSD, PSSB, PSS, TPES, PSU, TMPSS and PESK and similar polybenzazole blocks, and About its preparation method. The block copolymers can be made using at least two different polyfluorenes and can be made using more than two polyfluorenes. The process of the present invention comprises the use of solution polymerization techniques for the preparation of the novel polyblock-16-200724571 (13) family block copolymer. These block copolymers are prepared using relatively block (e.g., polyphenylene sulfide (PPSU), PES, - TPES, PSS, TPSSS, PSU, and PESK) - an important aspect of the present invention is related to the present invention. High glass transition temperature block copolymer. The embedded (> 22 0 °C) and rigorous chemical environments maintain pharmaceutically acceptable properties. The block copolymers disclosed in the prior art have a temperature of § and therefore can only be used for applications requiring continuous use, and cannot be used in high temperature applications such as luminaire materials and other articles exposed to thermal and mechanical stress. The main novel and unexpected aspect of the process of the invention is to give a homoblock having only a stoichiometric requirement of a 1:1 stoichiometry between one of the two terminal groups. High molecular weight block copolymers can be prepared, each embedding end groups and not strictly controlled stoichiometry. Due to the formation of oxime block copolymers. Moreover, the present invention makes it easier to use a block copolymer composition having a relatively large composition range as compared with the earlier preparation method. Of course, the homoblocks of the terminal groups are made and have the correct stoichiometry, but these conditions are no longer the construction of high molecular weight inlays. This method also allows for proper control of the terminal polymers, wherein the two are embedded. The segments have various molecular weights and have a wide range of compositions, and this point is discussed earlier in the low molecular weight oligomerization PSSB, PSSD, ί ° species with high flexural temperature copolymers at lower temperatures. The shell and space composites having a heat deflection of less than 180 ° C are not obeying the uniform block used, and the method of the present invention does not have the substantially simple segmented block copolymer of the present invention. The block is prepared by using a premise group having the same final ratio and never injuring the copolymer to prepare a block copolymer copolymer. Other types of blocks may be difficult or even in the -17-200724571 (14) polymer. It is impossible to achieve. Novel block copolymers are prepared by first using lower molecular weight homoblocks of the original individually prepared functional end chain groups. The term "all-in-segment." means that each block has PES or PSSB or TPES or PSSD or PPSU or TMPSS or PSS, PSU or PESK or some of such poly-Maple structures, and different homoblocks have structures different from each other. . The two homoblocks are individually prepared and arranged to have two sequential or distinct terminal groups. The heavy P point is the two-phase hetero-end group (in this case -C1 and -OH) to achieve the teachings of the present invention, and of course should be close to the stoichiometric equilibrium. It is important that both end groups are present on both homoblocks. The different ways of preparing the homoblocks are as follows: The first group of homoblocks is prepared to have predominantly halogen terminal groups such as -F, -Cl, -Br and -I. The second group of homoblocks is prepared to have predominantly a second terminal group which is reactive with a halogen terminal group such as -OH (which may be present in the form of a salt - OK, -ONa or -OLi). This is done in the first case by using a dihalogen monomer that is a large molar excess compared to the dihydroxy monomer, and in the second case it is swapped. Generally, when a lower molecular weight homoblock having mainly the first terminal group is reacted with another homoblock having mainly the second terminal group, a block copolymer having a high molecular weight is obtained. Thus, for example, a low molecular weight PSSB homoblock having predominantly an -OH end group reacts with a low molecular weight PSSD homoblock having predominantly a -C1 terminal group to produce [PSSD-PSSB]z in the block copolymer sequence or A novel block copolymer of {[PSSB...PSSD]z}. When a homoblock has predominantly identical terminal groups (eg, -C1) and reacts with a second homoblock having predominantly a second -18-200724571 (15) terminal group (eg, -OH), The resulting block copolymer has a PSSD & PSSB embedded segment with a molecular weight like the starting homoblock. The present invention thus makes it possible to make the molecular weight of the homoblock almost the same as the block which becomes a part of the chain. It is also possible according to the invention to prepare a block copolymer in which the homoblock of the PSSD has a halogen end group and the PSSB homoblock has a phenol-oh end group, and conversely wherein the PSSD has a hydroxyl end group and the PSSB has a halogen. a block copolymer of a terminal group. As shown in the present invention, the terminal groups of a particular homoblock can be exchanged with each other. When each homoblock has a different terminal group (e.g., -C1 and -OH), it is important to have a relatively identical stoichiometry in both homoblocks. When one or two high molecular weight homoblocks are produced, it is important that the two terminal groups remain as dissimilar as possible as in the two-block and three-block preparation. However, the present invention allows both homoblocks to have both terminal groups and still be used to make high molecular weight block copolymers. This can be achieved by using two monomers that are close to the same • Moerby. In this case, the terminal groups are halogen and hydroxyl groups, regardless of the molecular weight of the homoblock. Thus, using the foregoing examples, PSSD and PSSB homoblocks having both -C1 and -OH end groups can be prepared which are reacted together to form a block copolymer having the desired molecular weight. In this case, the block copolymer formed may contain a block having a chain molecular weight similar to or higher than the homoblock molecular weight. The foregoing method for preparing the homoblocks can be equally applied to all homoblocks, ie, PSSD, PSU, PPSU, PSSB, PES, TPES, PSS, PESK or TMPSS, etc. -19-200724571 (16) The present invention also teaches that in addition to the preparation In addition to the random average block sequence in the monoblock copolymer, it is also possible to produce a di- and - by adjusting the molecular weight of the homoblock and reacting to form the stoichiometry of the two homoblocks of the block copolymer. Block copolymer. The present invention thus teaches the preparation of di-block, tri-block and segmented block copolymers wherein the homoblocks are alternating or present in a random sequence. If the homoblock molecular weight is kept low enough and the terminal groups are carefully controlled, then the present invention can construct a high molecular weight copolymer having substantially alternating homoblock structures in the chain. In the block copolymers, all of the blocks have the same molecular weight as the two starting homoblocks. If the homoblock molecular weight is kept high, a di- and tri-block copolymer having a relatively high molecular weight can be constructed. Another important aspect of the foregoing invention is that the degree of block copolymerization z can vary from as low as 1 (di-block) to as much as 1 Torr or higher of alternating or random multi-block copolymers. Another important aspect of the present invention is the ability to prepare specific tri-block copolymers by properly controlling the molecular weight, stoichiometry, and terminal groups of the intercalated segments. The novel aspect of the present invention is to recognize the stoichiometry of the basic monomer used to prepare the homoblock, especially when the homoblock has a lower molecular weight, such that the homoblocks have predominantly known ends Group. Thus, a single monomer, i.e., about 3 moles of CSB in excess of DHDPS, i.e., molar stoichiometry > 1.0 3 : 1 · 0 0 , was used to obtain a PSSD having substantially only a -C 1 terminal group. This results in a substantially complete reaction of all -OH groups present on the DHDPS due to the higher concentration of CSB, thus limiting the molecular weight increase, while -20 - 200724571 (17) provides only the -c 1 terminus in the homoblock pss D Group. Similarly, when a homoblock is prepared using C S B , a high concentration of biphenol is used to obtain terminal groups (which are in the form of Na or K salts) which are substantially all -OH. A PSSB having substantially these phenolic groups does not react with itself to produce a higher molecular weight PSSB. Similarly, a PSSD having a -C1 terminal group is also unable to react with itself to produce a higher molecular weight PSSD. In these cases, the molecular weight does not increase further, indicating that the chain with other terminal groups is used up. However, when a PSSD homoblock having substantially a -C1 terminal group is substantially block-mixed with a PSSB substantially completely having an -OK end group, further polymerization occurs to form a PSSB-PSSD block. This reaction is further carried out to form a random block copolymer having a structure of the [PSSB-PSSD]z type, wherein the z system is greater than or equal to i, depending on the molecular weight of the homoblock and the stoichiometry and molecular weight of the structure. The foregoing method of preparing the homoblocks is equally applicable to all homoblocks, i.e., PSSD, PSU, PPSU, PSSB, PES, T P E S, P S S, P E S K or TMPSS. An important aspect of the present invention is the systematic use of a higher ratio of two monomers to produce a homoblock, resulting in a substantially class of terminal groups. The ratio may be from 1.03 to 1.15: 1.00, i.e., one monomer is from 3 to 15 mol% higher than the second monomer. Another important aspect of the present invention is that the homoblock can also be prepared by mixing and preparing a high molecular weight block copolymer having a desired composition, while maintaining a desired uniform block molecular weight, using nearly equal stoichiometry. The basic monomers are suitably prepared. -21 - 200724571 (18) An important aspect of the present invention is therefore to prepare lower molecular weight homoblocks having known terminal groups and to mix them at the correct ratio to produce random block copolymers having higher molecular weights. Things. Another novel and important aspect of the invention is the preparation of di- and tri-block copolymers. These di- and tri-block excipients are also materials of novel composition. For this formulation, it has again been confirmed that homoblocks having different molecular weights and having substantially known terminal groups can be prepared. In general, it is known that controlling the molecular weight of the homoblock and the block copolymer can sufficiently control the number of homoblocks present in the block copolymer, and the reaction can be stopped in the di- or triblock stage. Polymers with sufficient high molecular weight or specific viscosity (Inhv.) are required to produce optimum mechanical and other polymer properties, and we can construct a homoblock molecular weight range. Therefore, when the PSSD having a number average molecular weight (Μη) of about 50,000 and having a -C1 terminal group and PS SB having about the same molecular weight and having a -ΟΚ terminal group are mixed and reacted at a molar ratio of 1:1, the molecular weight is almost Multiply, producing a two-block. The molecular weight can be controlled using gel permeation chromatography (GPC). If the di-block is further reacted to produce a higher molecular weight, a tri- and tetra-block is obtained. Therefore, having the structure...[PSSB-PSSD] bis-block further reacts to produce a tri-block having the structure -[--]-[-PSSB-PSSD-PSSB] and --[-PSSD-PSSB-PSSD] Further reaction produces a tetra-block and a higher order poly-block. Thus, by controlling molecular weight, stoichiometry, and terminal groups, the present invention can prepare diblock- and tri-block and multi-block copolymers of PSSB and PSSD. The foregoing method for preparing the homoblocks is equally applicable to all homoblocks, i.e., -22-200724571 (19) PSSD, PSU, PPSU, PSSB, PES, TPES, PSS, PESK or TMPSS. The present invention can also be used to prepare three blocks using the following three different types of homoblocks. The diblock is first prepared using two homoblocks, wherein the two terminal groups present on a single homoblock are identical, and the same as the 'second homoblock' has two identical but different from the first End group. This di-block reacts with three homoblocks having two terminal groups identical to the first or second homoblock to produce a tri-block. The GPC molecular weight, specific viscosity, D S C, T g, M FI, etc. of the block polymer produced can be detected for quality control. The block copolymers can be formulated in powder form for subsequent granulation or can be added as a compatibilizing agent to the individually prepared high molecular weight homologues. The present invention seeks to achieve the following: Novel block copolymers having two or more different polyaryl maple block contents of controlled di-block, tri-block and multi-block structures. • Preparation of high molecular weight block copolymers using such polyaryl ruthenium blocks having low molecular weight and controlled chain end groups. • Preparation of high molecular weight di-block and tri-block copolymers using homoblocks with lower molecular weight and reactive chain ends. • Preparation of two homoblocks, each of which essentially has only a halogen or hydroxyl end group, thus producing a multi-block copolymer when reacted between the two, the block molecular weight being the same as the initial homoblock molecular weight. • Preparation of a block copolymer of a dimeric aryl group wherein the ratio of -23-200724571 (20) of the two homoblocks is in the range of 95:5 to 5:95. • A block copolymer of two or more polyarylfluorene homoblocks is prepared which is transparent and exhibits a single intermediate Tg. • Prepare block copolymers that are thermally stable and processable at temperatures ranging from 350 ° C to 400 ° C using conventional injection molding, extrusion or other acceptable plastic processing methods. • A method for preparing a polyaryl maple homoblock having a known molecular weight and a controlled end group. • A method of preparing a low molecular weight controlled chain terminal homoblock and another method of preparing a high molecular weight block copolymer having a structure in a di/tri/multi-block chain are provided. According to the present invention, there is provided a process for preparing a low molecular weight, controlled chain terminal homoblock, and the use of such homoblocks to prepare a di-, tri-, and poly-block copolymer having a high molecular weight. Preferably, the invention utilizes cyclobutyl hydrazine, NMP, DMAc, DMSO, DMS 02, diphenyl hydrazine or any other aprotic organic solution to produce low molecular weight homoblocks and high molecular weight block copolymers thereof. Preferably, MCB or toluene or any other non-reactive solvent is used as the diluent and dehydrating agent for the salt formation, dehydration and polymerization steps. The method is preferably carried out at a temperature of from 120 ° C to 25 (using the aforementioned solvent in the temperature range of TC) using a base such as NaOH, KOH, NaHC03, KHC03,

Na2C03 or K2C03 itself or a combination of these or any other such suitable base material. According to the present invention, there is provided a process for the manufacture of a novel homoblock and multi-block co--24-200724571 (21) polymer which is used in an aprotic organic solvent or solvent at a temperature ranging from 120 ° C to 25 ° C. The end capping is then carried out using MeCl or any suitable end capping-capping agent. The method comprises the following preferred steps: filtering the salt, and precipitating the block copolymer from the reaction mixture in a non-solvent such as H20 or MeOH or a mixture of the two, followed by further water/MeOH treatment to reduce the powder. The solvent content is residual, after which the polymer powder is dried. φ The invention will now be described with reference to the following examples. It is to be understood that the specific embodiments of the invention are not to be construed as limiting. EXAMPLES Example: Example 1: TPSS: 50: 50PSSD: Block copolymer of PSSB This TPSS (PSSD-PSSB) block copolymer was prepared using the following three-part method. Part 1: Preparation of PSSD homoblocks PSSD was prepared using DHDPS and CSB as monomers. A 4-neck 3 liter glass flask with an overhead stirrer connected to a stainless steel paddle that runs through the center of the heart. Connect the CloisonnS connector via one side neck. The other neck of the Cloisonn6 connector is connected to the Dean-Stark soda valve and the water-cooling condenser. Insert the thermocouple thermometer through the other side of the neck. The other side neck is inserted into the nitrogen inlet. The flask was placed in an oil bath which was attached to a temperature controller. -25- 200724571 (22) Put cyclopentanthene (4410 g, 3500 ml/mole) and toluene (1000 ml/mole) into the flask' and draw with nitrogen bubbles and heat to 45 °C. 4,4' bis[(4-chlorophenyl)sulfonyl]biphenyl (CSB) (523 g) and 4,4' dihydroxydiphenyl hydrazine (DHDPS) (250 g) were added to the flask. CSB: DHDPS is 1·〇4: 1.00 mol ratio, and the reaction mixture is stirred for 30 minutes. Anhydrous sodium carbonate (123 g) was added. Wash in a flask to maintain a nitrogen atmosphere. Toluene is used as an azeotropic solvent. The temperature of the reactants was gradually increased to 220 ° C in 5 hours, and the stirring speed was set at 400 rpm. The water system formed by the reaction of Na2C03 with DHDPS was distilled off in the form of azeotrope with toluene and collected in a Dean-Stark soda valve. The toluene is returned to the reaction mixture once it is separated from the water. Once the water is completely removed, the addition of toluene to the reactor is stopped. Toluene was then completely removed from the reaction mixture as the temperature of the reactants increased. The desired temperature was reached after 5 hours. The reaction temperature was then maintained at 220 ° C and the agitation speed was increased to 500 rpm as the viscosity began to increase. At the desired Μ 17,000, Mw of about 20,000 and MWD I 1.19, the reaction was stopped by lowering the temperature to < 130 °c. The relatively high molar ratio of CSB to DHDPS produces a PSSD having a relatively low molecular weight and predominantly having a -Ph-Cl end group. Part 2: Preparation of PSSB homoblocks PS SB is prepared using biphenol and CSB as monomers. Cyclopentane (4410 g, 3500 ml/mole) and toluene (1 ml/mol) were placed in a flask, and nitrogen bubbles were continuously passed through and heated to 45 °C. Add 4,4' bis[(4-chlorophenyl)sulfonyl]biphenyl (CSB) (503 g-26-200724571 (23)) and biphenol (1 8 8 g) to the flask, biphenol : CSB was 1.01 : 1_00 molar ratio, and the reaction mixture was stirred for 30 minutes. Anhydrous sodium carbonate (1 23 g) was added. Toluene is used as an azeotropic solvent. The temperature of the reactant was gradually increased to 220 ° C in 5 hours, and the stirring speed was set at 400 rpm. The water formed by the reaction was distilled off in the form of an azeotrope with toluene and collected in a Dean-Stark soda valve. The toluene is returned to the reaction mixture once it is separated from the water. Once the water is completely removed, the addition of toluene to the reactor P is stopped. Toluene was then completely removed from the reaction mixture as the temperature of the reactants increased. The desired temperature was reached after 4 hours. After that, the reaction temperature was maintained at 220 ° C. When the viscosity began to increase, the stirring speed was increased to 500 rpm. At the desired Mn 29,000, Mw of about 38,000 and MWD 1.31, the reaction mass was rapidly cooled to stop further polymerization. The relatively high molar ratio of biphenol to CSB produces a PSSB having a relatively low molecular weight and predominantly having a -Ph-OH end group. Part 3: Preparation of block copolymer The reaction mixture of the first part and the second part was mixed at an equal weight ratio, and block polymerization was carried out at 220 °C. After the desired MW (as indicated by GPC) was reached, the reaction mixture was quenched with cyclohexane (504 g, 400 mL/m) and the temperature was reduced to 210 °C. Methyl chloride gas was then bubbled through the reaction mixture over a period of 3 hours to determine completion of the end cap. The reaction mixture was then diluted a second time with cyclobutyl hydrazine (400 ml/mole). The polymer solution was filtered through a 15 micron filter using a 2 kg/cm 2 nitrogen pressure in a filter press funnel to remove salts. Finally, the block copolymer was recovered by slowly adding a polymer solution containing no salt of -27-200724571 (24) in deionized water (13 ml/g polymer) under high-speed stirring. The precipitated polymer is then recovered by filtration. The precipitated polymer was honed and refluxed three times with deionized water at 90 °C to completely remove all salts and butyl sulphate. The precipitated polymer was then filtered and dried in an oven at 1400 °C until the water content determined by Karl Fischer titration < 0.5%. GPC analysis of the block copolymer based on polystyrene standards showed a Μη of 88,000, a Mw of 121,000 and an MWD of 1.37. Therefore, the copolymer produced has a molecular weight far higher than the two homoblocks as monomer units, indicating the preparation of the block copolymer. The block copolymer powder was then mixed with 0.25% thermal stabilizer and granulated using a twin screw extruder. The Tg and specific gravity of PSSD are 25 9 ° C and 1.29, while the high molecular weight PSSB itself is 27 (TC and 1.3 20 . The transparent particles of block copolymer (TPSS ) show DSC Tg of 266 ° C and specific gravity of 1.31. The particle transparency of the product, the single GPC peak, the intermediate Tg and the specific gravity clearly indicate that the block copolymer of PSSD and PSSB has indeed been formed and the product is not only a blend of the two homopolymers PSSD and PP SB. The detailed properties are listed in the table. 1. Detailed chemical reaction is shown in (Figure I) Example 2: TPSS: 90: 10 PSSD: PSSB block copolymer The TPSS (PSSD: PSSB) block copolymer was prepared using the following three methods: Part 1: PSSD Preparation of Blocks -28- 200724571 (25) PSSD was prepared using DHDPS and CSB as monomers. The experimental configuration as described in Example 1 was used. Ring oxime (1687 g, 1500 ml/mole) and Toluene (700 ml/mole) was placed in a flask, continuously bubbled with nitrogen, and heated to 45 ° C. 4,4' bis[(4-chlorophenyl)sulfonyl]biphenyl (CSB) (461克) and 4,4' dihydroxydiphenyl hydrazine (DHDPS) (225 g) were added to the flask, CSB: DHDPS was 1.02 : 1.0 0 molar ratio, the reaction mixture was stirred for 30 minutes. Anhydrous sodium carbonate (1 1 2 · 5 g) was added, and the mixture was purged with air to maintain a nitrogen atmosphere. Toluene was used as an azeotropic solvent. The remaining method was the same as in Example 1. The homoblock obtained has the same GPC molecular weight 1η 17,000, Mw 23,000 and MWD 1 · 36. Part 2: Preparation of PS SB homoblocks PSSB is prepared using biphenol and CSB as monomers. • Place Cyclosporin (437 g, 3500 ml/mole) and toluene (1000 ml/mole) in a flask with continuous nitrogen bubbles and heat to 45 ° C. 4, 4, double [(4) Monochlorophenyl)sulfonyl]biphenyl (CSB) (50.8 g) and biphenol (18.6 g) were added to the flask, biphenol: CSB was 1·〇1: 1.00 mol ratio, and the reaction mixture was stirred 30 Anhydrous sodium carbonate (1 2 · 5 g) was added. The remaining methods were the same as those described in Example 2, Part 2. The resulting homoblock had a GPC molecular weight of 10,000 10,000, Mw 12,000 and MWD 1.20. 29 - 200724571 ( 26) Part 3: Preparation of block copolymers Mix the first part (9 parts) and the second part (1 part) The mixture should be subjected to block polymerization at 22 (TC). After reaching the desired MW (as indicated by GPC), the reaction mixture was quenched with cyclohexane (504 g, 400 ml/mol) and the temperature was lowered to 210 °C. . Methyl chloride gas was then bubbled through the reaction mixture over a period of 3 hours to determine completion of the end cap. The reaction mixture was then diluted a second time with cyclobutyl hydrazine (400 ml/mole). The polymer solution was filtered through a 15 micron filter using a 2 kg/cm 2 nitrogen pressure in a filter press funnel to remove salts. Finally, the block copolymer was recovered by slowly adding a salt-free polymer solution to deionized water (13 ml/g polymer) under high-speed stirring. The precipitated polymer is then recovered by filtration. The precipitated polymer was honed and refluxed three times with deionized water at 90 °C to completely remove all salts and Cyclopentane. The precipitated polymer was then filtered and dried in a 140 ° C oven until the water content determined by Karl Fischer titration < 0.5%. GPC analysis of the block copolymer based on polystyrene standards showed a Μη of 90,000, a Mw of 131,000 and a M WD of 1.37. Therefore, the copolymer produced has a molecular weight far higher than the two homoblocks as monomer units, indicating the preparation of the block copolymer. The block copolymer powder was then mixed with 0.25% thermal stabilizer and granulated using a twin screw extruder. The Tg and specific gravity of PSSD are 260 °C and 1.29, while those of PSSB are 270 °C and 1.330. The transparent particles of the block copolymer showed a DSC Tg of 266 ° C and a specific gravity of 1.34. Particle transparency of the product, single GPC peak, intermediate T g and specific gravity -30- 200724571 (27) TPSS ) The detail shows that the block copolymer of PSSD and PSSB has indeed been formed (and the product is not only the two homopolymer PSSD) And the blend of PPSB. The mass is listed in Table 1. Example 3: DPSS: 50: 50 PSSD: Block copolymerization of PSS: The block was prepared using the following three-part method to prepare DPSS (PSSD-PSS) polymer.

Part 1: Preparation of PSSD homoblocks PSSD was prepared using DHDPS and CSB as monomers. The experimental setup as described in Example 1 was used. Ring guanidine (4410 g, 3 500 ml/mole) and a halo: liter/mole were placed in a flask, and nitrogen bubbles were continuously passed through and heated. 4,4' bis[(4-chlorophenyl)sulfonyl]biphenyl (CSB) ( ) and 4,4' dihydroxydiphenyl hydrazine (DHDPS) (250 g) in a bottle, CSB: The DHDPS system was 1·04: 1·〇〇 molar ratio, and the anti-object was stirred for 30 minutes. Anhydrous sodium carbonate (1 23 g) was added. The nitrogen atmosphere was maintained in the flask. Toluene is used as an azeotropic solvent. The remaining methods are the same as those described in the first part of Example 1. The homoblock has a GPC molecular weight Μ 20,000, Mw 22,000 1.10. Part 2: Preparation of PSS homoblocks PSS is prepared using HSB and CSB as monomers.

(1000 ? 4 5 °c 523 g added to the burner should be mixed with the gas obtained in the obtained MWD -31 - 200724571 (28) ring butyl sulfonate (44 10 g, 3500 ml / mol) and toluene ((7) (10) ml / mol Put into the flask and continue to heat with nitrogen bubbles to 45 ° C. 4,4, bis[(4-chlorophenyl)sulfonyl]biphenyl (CSB) (503 g) and 4,4' Bis[(4-hydroxyphenyl)sulfonyl]biphenol (HSB) (471 g) was added to the flask, HSB: CSB was 1 〇1: 1.00 molar ratio, and the reaction mixture was stirred for 30 minutes. Anhydrous sodium carbonate (1 2 3 g) was added. Toluene was used as the azeotropic solvent. The rest of the procedure was the same as described in Part 2 of Example 1. The resulting homoblock had a GPC molecular weight of 29 29,000, Mw 38,000 and MWD 1.31. Part 3: Preparation of block copolymer The reaction mixture of Part 1 and Part 2 is mixed at an equal weight ratio, and block polymerization is carried out at 23 ° C. After reaching the desired MW (as indicated by GPC), the reaction is carried out. The mixture was quenched with cyclobutyl hydrazine (504 g, 400 ml/mol) and the temperature was lowered to 210 ° C. The methyl chloride gas was then bubbled through the reaction mixture over 3 hours. To complete the completion of the end-cap. The reaction mixture was then diluted a second time with cyclobutyl hydrazine (400 mL/mol). The polymer solution was filtered through a 15 μm filter using a 2 kg/cm 2 nitrogen pressure in a filter press funnel. The salt was removed. Finally, the block copolymer was recovered by slowly adding a salt-free polymer solution to deionized water (13 ml/g polymer) under high-speed stirring. The precipitated polymer was honed and refluxed three times with deionized water at 90 ° C to completely remove all salts and cyclohexane. The precipitated polymer was then filtered and applied at -32-200724571 (29) 140°. Drying in a C furnace until the water content determined by Karl Fischer titration < 0.5%. • The GPC analysis of the block copolymer based on polystyrene standards showed Μη. It was 89,000, Mw was 122,000 and the MWD was 1.37. The resulting copolymer has a molecular weight much higher than the two homoblocks as monomer units, indicating the preparation of the block copolymer. The block copolymer powder is then mixed with 0.25% heat stabilizer and granulated using a twin screw extruder. PS g T g The specific gravity is 259 ° C and 1.29, while the PSS is 270 ° C and 1.32. The transparent particles of the block copolymer (DPSS) show a DSC Tg of 267 ° C and a specific gravity of 1.31. Particle transparency, a single GP C peak, intermediate T g and specific gravity clearly indicate that block copolymers of PSSD and PSS have indeed been formed and the product is not only a blend of two homopolymers PSSD and PPS. The detailed properties are listed in Table 1. The detailed chemical reaction is shown in (Figure II). Example 4: TMPES: 25: 75 PES: Block copolymer of TPES • This TMPES (PES-TPES) block copolymer was prepared using the following three-step process. Part 1· Preparation of PES homoblock The same experimental configuration as that described in Example 1 was used.

Ring guanidine (300 g, 1 〇〇〇 ml/mole) and toluene (looo cc/mole) were placed in a flask, and nitrogen bubbles were continuously passed through and heated to 40 liters. Dihydroxydiphenyl hydrazine (DHDPS) (62.8 g), 4,4, dichloro-based guanidine (DCDPS) (71.75 g) was added to the flask, DCDPS-33-200724571 (30) and DHDPS were 1.00: 1·〇〇5 molar ratio, the reaction was stirred for 30 minutes. Anhydrous sodium carbonate (3 2 · 2 g) was added. Wash in a flask to maintain a nitrogen atmosphere. Toluene is used as an azeotropic solvent. The temperature of the reactant was gradually increased to 23 6 ° C over 6 hours, and the stirring speed was set at 4 rpm. The water system formed by the reaction of Na2C03 with DHDPS was distilled off as an azeotrope with toluene and collected in a Dean-Stark soda valve. The toluene is returned to the reaction mixture once it is separated from the water. Once the water is completely removed, the addition of toluene to the reactor is stopped. The toluene is then completely removed from the reaction mixture as the temperature of the reactants increases. The desired temperature was reached after 6 hours. The reaction temperature was then maintained at 23 6 ° C. When the viscosity began to increase, the stirring speed was increased to 500 rpm. The reaction mixture was cooled to approximately 200 ° C at the desired Μ 19,300, Mw of approximately 22,000 and MWD 1.14. The relative phase molar ratio of DHDPS to DCDPS produces a PES having a relatively low molecular weight and having predominantly a -Ph-OH end group. Part 2: Preparation of TPES homoblocks Cyclobutane (900 g, 1000 ml/mole) and toluene (64 5 g, 1000 ml/mole) were placed in a flask with continuous nitrogen bubbles. Heat to 4CTC. Tetramethyl phenol phenolphthalein (TMDHDPS) (229.5 g) and 4,4'-dichlorodiphenyl hydrazine (DCDPS) (221.7 g) were added to the flask, and the DCDPS and TMDHDPS systems were 1.03: 1.00 m The reaction mixture was stirred for 30 minutes. Anhydrous sodium carbonate Na2C03 (96.7 g) was added. The temperature of the reactant was gradually increased to 23 6 ° C over 6 hours, and the stirring speed was set at 400 rpm. The water system formed by the reaction of Na2C03 with TMDHDPS -34- 200724571 (31) was distilled off as an azeotrope with toluene and collected in a Dean_Stai*k steam trap. The toluene is returned to the reaction mixture once it is separated from the water. Once the water is completely removed, the addition of toluene to the reactor is stopped. Toluene was then completely removed from the reaction mixture as the temperature of the reactants increased. The desired temperature is reached after 6 hours. Thereafter, the reaction temperature was maintained at 2 3 6 ° C, and when the viscosity began to increase, the stirring speed was increased to 500 rpm. At the desired Μ1 8,200, Mw of about 20, and MWD 1.10, DCDPS produces a relatively low molecular weight TMPES with a relatively low molecular weight and predominantly a -Ph-Cl end group for TMDHDPS. Part 3: Preparation of block copolymer The reaction mixture of the first part and the second part was mixed at an equal weight ratio, and block polymerization was carried out at 23 6 °C. After reaching the desired MW (as indicated by GPC), the reaction mixture was quenched with cyclohexane (250 g, 200 mL / m) and the temperature was reduced to 220 °C. Methyl chloride gas was then bubbled through the reaction mixture over a period of 3 hours to determine completion of the end cap. The reaction mixture was then diluted a second time with cyclobutyl hydrazine (200 ml/mole). The polymer solution was filtered through a 15 micron filter using a 2 kg/cm 2 nitrogen pressure in a filter press funnel to remove salts. Finally, the block copolymer was recovered by slowly adding a salt-free polymer solution to deionized water (13 ml/g of polymer) under high-speed stirring. The precipitated polymer is then recovered by filtration. The precipitated polymer was honed and refluxed three times with deionized water at 90 °C to completely remove all salts and cyclopentane. The precipitated polymer was then filtered and dried in an oven at 140 ° C until the water content determined by Karl Fischer titration -35 - 200724571 (32) < 0.5%. GPC analysis of the block copolymer based on polystyrene standards showed a η of 79,800, a Mw of 115,000 and an MWD of 1.44. Therefore, the copolymer produced has a molecular weight far higher than the two homoblocks as monomer units, indicating the preparation of the block copolymer. The block copolymer powder was then mixed with 0.25% thermal stabilizer and granulated using a twin screw extruder. The Tg and specific gravity of PES are 225 °C and 1.37, while those of TPES are 271 °C and 1.33. The transparent particles of the block copolymer showed a DSC Tg of 267 ° C and a specific gravity of 1.32. The particle transparency of the product, the single GP C peak, the intermediate Tg and the specific gravity clearly indicate that the block copolymer (TMPES) of PES and TPES has indeed been formed and the product is not only a blend of the two homopolymers PES and TPES. The detailed properties are listed in Table 3. The detailed chemical reaction is shown in (Fig. 111). Example 5: TMPES: 40: 60 PES: Block copolymer of TPES The TMPES (PES-TPES) block copolymer was prepared using the following three-step process. Part 1: Preparation of PES homoblock The same experimental configuration as described in Example 1 was used. Cyclopentane (480 g, 1000 ml/mole) and toluene (344 g, 1000 ml/mole) were placed in a flask, and nitrogen bubbles were continuously passed through and heated to 40 °C. Dihydroxydiphenyl hydrazine (DHDPS) (100.5 g), 4,4'-dichlorodiphenyl maple (DCDPS) (114.8 g) was added to the flask, and the DCDPS and DHDPS systems were 1.00: 1.005 molar ratio. Reactant -36- 200724571 (33) Stir for 30 minutes. Add anhydrous sodium carbonate (5 g). Wash in a flask to maintain a nitrogen atmosphere. Toluene is used as an azeotropic solvent. The remaining methods are as described in Part 1 of Example 4. The resulting homoblock has a GPC molecular weight Μη 23,000, Mw 26, 〇〇〇 and MWD 1.11 Part 2: Preparation of TPES homoblock Φ Ring oxime (720 g, 1 〇〇〇 ml/mole) and toluene (516 g, 1 000 ml/mole) was placed in a flask, continuously bubbled with nitrogen, and heated to 40 ° C. Tetramethyl phenol phenolphthalein (TMDHDPS) (183.6 g) and 4,4'-dichlorodiphenyl hydrazine (DCDPS) (177.4 g) were added to the flask, and the DCDPS and TMDHDPS systems were 1.03: 1.00 mol ratio. The reaction mixture was stirred for 30 minutes. Anhydrous sodium carbonate Na2C03 (75 g) was added. The rest of the procedure was as described in Part 2 of Example 4. The resulting intercalated segments have GPC molecular weights 20,000 20,000, Mw 22,000 and MWD 1 _ 1 〇 Part 3: Preparation of block copolymers The reaction mixtures of Part 1 and Part 2 are mixed at equal weight ratios, at 23 6 Block polymerization was carried out at °C. After reaching the desired MW (as indicated by GPC), the reaction mixture was quenched with cyclobutyl hydrazine (250 g, 200 mL/m) and the temperature was reduced to 22 °C. Methyl chloride gas was then bubbled through the reaction mixture over a period of 3 hours to determine completion of the end cap. Reaction Mix -37- 200724571 (34) The compound was then diluted a second time with cyclohexane (200 ml/mole). The polymer solution was filtered through a 15 micron filter using a 2 kg/cm 2 nitrogen pressure in a filter press funnel to remove salts. Finally, the block copolymer was recovered by slowly adding a salt-free polymer solution to deionized water (13 ml/g polymer) under high-speed stirring. The precipitated polymer is then recovered by filtration. The precipitated polymer was honed and refluxed three times with deionized water at 90 °C to completely remove all salts and cyclopentane. The precipitated polymer was then dried and dried in a 140 ° C oven until the water content determined by Karl Fischer titration < 0.5%. GPC analysis of the block copolymer based on polystyrene standards showed a Μη of 80,900, a Mw of 119,000 and an MWD of 1.47. Therefore, the copolymer produced has a molecular weight far higher than the two homoblocks as monomer units, indicating the preparation of the block copolymer. The block copolymer powder was then mixed with 0.25% thermal stabilizer and granulated using a twin screw extruder. The Tg and specific gravity of PES are 225 °C and 1.37, while those of TPES are 271 °C and 1.33. The transparent particles of the block copolymer showed a DSC Tg of 2 5 8 ° C and a specific gravity of 1.32. The particle (TMPES) transparency of the product, the single GPC peak, the intermediate Tg and the specific gravity clearly indicate that the block copolymer of PES and TPES has indeed been formed and the product is not only a blend of the two homopolymers PES and TPES. The details are listed in Table 3. The detailed chemical reaction is shown in (Fig. III). Example 6: TMPES: 60: 40 PES: Block copolymer of TPES The PES-TMPES block copolymer was prepared using the following three-step process -38- 200724571 (35) Part 1: Preparation of PES homoblocks The embodiment of the first embodiment is consistent with the fe configuration. Cyclopentane (720 g, 1000 ml/mole) and toluene (516 g, 1000 ml/mole) were placed in a flask, and nitrogen bubbles were continuously passed through and heated to 40. (: Dihydroxydiphenyl hydrazine (DHDPS) (150.7 g), 4,4, dichlorodiphenyl hydrazine (DCDPS) (172.2 g) was added to the flask, and the DCDPS and DHDPS systems were 1.00: 1.005 The ear was stirred for 30 minutes than the 'reactant. Anhydrous sodium carbonate (75 g) was added and the mixture was purged with air to maintain a nitrogen atmosphere. Toluene was used as an azeotrope. The rest of the procedure was as described in Part 1 of Example 4. The resulting homoblock has GPC molecular weight Μη 25,000, Mw 28,000 and MWD 1.12 Part 2: Preparation of TPES homoblocks • Ring guanidine (480 g, 1000 ml/mole) and toluene (3 44 g, 1 000) Placed in a flask with nitrogen bubbles continuously, heated to 40 ° C. Tetramethyl phenol phenol (TMDHDPS) (122.4 g) and 4,4'-dichlorodiphenyl hydrazine (DCDPS) (118.24 g) was added to the flask, DCDPS and TMDHDPS were 1.03:1·〇〇 molar ratio, and the reaction mixture was stirred for 30 minutes. Anhydrous sodium carbonate Na2C03 (50 g) was added. The rest of the method was as in Example 4 Partially obtained. The resulting homoblock has GPC molecular weight Μη 1 8,000, Mw 20, 〇〇〇 and MWD 1.10 -39 - 200724571 (36) Part 3: Preparation of block copolymers The reaction mixtures of Part 1 and Part 2 are mixed at equal weight ratios and block polymerization is carried out at 2 3 ° C. to achieve the desired MW (As indicated by GP C), the reaction mixture was quenched with cyclobutyl hydrazine (250 g, 200 ml/mol) and the temperature was lowered to 22 (TC). The methyl chloride gas was then bubbled through the reaction mixture over 3 The hour was determined to complete the end capping. The reaction mixture was then diluted a second time with cyclobutyl hydrazine (200 ml/mol). The polymer solution was used in a filter press funnel using a 2 kg/cm2 nitrogen pressure through a 15 micron filter. Filtration to remove salts. Finally, the block copolymer was recovered by slowly adding a salt-free polymer solution to deionized water (13 ml/g polymer) under high-speed stirring. The polymer was precipitated and honed and refluxed three times with deionized water at 90 ° C to completely remove all salts and cyclobutyl hydrazine. The precipitated polymer was then filtered and dried in a 140 ° C oven. Until the water content determined by Karl Fischer titration < 0.5% The GPC analysis of the block copolymer based on polystyrene standards showed a Μη of 85,700, a Mw of 126,000 and an MWD of 1.47. Therefore, the copolymer produced had a molecular weight much higher than the two homoblocks as monomer units, A block copolymer was prepared. The block copolymer powder was then mixed with 0.25% thermal stabilizer and granulated using a twin screw extruder. The T g and specific gravity of P E S are 225 ° C and 1.37, while those of TPES are 27 1 ° C and 1.33. The transparent particles of the block copolymer showed a DSC Tg of 247 ° C and a specific gravity of 1.32 -40-

200724571 (37). The particle of the product (TMPES) transparency, the single GPC wave Tg and the specific gravity clearly indicate that PES and TPES have indeed been formed and the product is not only a blend of the two homopolymers P E S and TP E S as shown in Table 2. The detailed chemical reaction is shown in (Fig. ΠΙ). Example 7: TMDPSS: 50: 50 PSSD: TMPSS

This PSSD - TMPSS was prepared using the following three methods. Part 1: Preparation of PSSD homoblocks PSSD was prepared using DHDPS and CSB as monomers using the experimental configuration as described in Example 1. Dingfeng (4410 g, 3500 ml/mole) and a 3 ml/mole were placed in a flask, and nitrogen bubbles were continuously passed through and heated. Will be 4,4' bis[(4-chlorophenyl)sulfonyl]biphenyl (CSB) and 4,4' dihydroxydiphenyl fluorene (DHDPS) (250 g)% bottle, CSB: DHDPS The ratio was 1.04: 1.00 molar ratio, and the material was stirred for 30 minutes. Anhydrous sodium carbonate (123 g) was added. _ Maintain a nitrogen atmosphere in the flask. Toluene is used as an azeotropic solvent. The rest of the procedure was the same as described in the first part of Example 1. The homoblock had a GPC molecular weight of 8,000 18,000 and Mw of 22,000 1.22. Intermediate segment copolymerization detailed segment copolymerization copolymerization

£ (1000 to 45〇C: 523 g ^ added to the burn: should be mixed with ί gas and obtained from MWD -41 - 200724571 (38) Part 2: Preparation of TMPSS homoblocks TPSPS uses TMDHDPS and CSB as single The system was prepared. Put the cyclohexane (4410 g, 3500 ml/mole) and toluene (1000 ml/mole) into the flask, continuously pass nitrogen bubbles, and heat to 45 ° C. 4, 4, Bis[(4-chlorophenyl)sulfonyl]biphenyl (CSB) (503 g) and tetramethyldihydroxydiphenyl maple (3 09 g TMDHDPS) were added to the flask, TMDHDPS: CSB was 1.01: 1. The molar ratio of the mixture was stirred for 30 minutes, anhydrous sodium carbonate (123 g) was added, and toluene was used as the azeotropic solvent. The remaining methods were the same as those described in the second part of Example 1. The resulting homoblock has GPC molecular weight Μ 29,000, Mw 3 8,000 and MWD 1.31. Part 3: Preparation of block copolymer The reaction mixture of the first part and the second part was mixed at an equal weight ratio, and block polymerization was carried out at 23 ° C. After the desired MW (as indicated by GPC), the reaction mixture was quenched with cyclobutyl hydrazine (504 g, 400 ml/mole) at temperature. The temperature was lowered to 210 ° C. Methyl chloride gas was then bubbled through the reaction mixture over 3 hours to confirm completion of the end cap. The reaction mixture was then diluted a second time with cyclobutyl hydrazine (400 mL / mol). The solution was filtered through a 15 μm filter using a 2 kg/cm 2 nitrogen pressure in a filter press funnel to remove salt. Finally, a salt-free polymer solution was slowly added to the deionized water by high-speed stirring. The block copolymer was recovered in 3 ml/g of polymer. The precipitated polymer was recovered by filtration. The polymer of Precipitate-42-200724571 (39) was honed and refluxed three times with deionized water at 90 °C. 'To completely remove all salts and ring mills. The precipitated polymer was then filtered and dried in a 140 ° C oven until the water content determined by Karl Fischer titration was < 0.5%. Block copolymer based polystyrene The GPC analysis of the standard showed a Μη of 8 5,000, a Mw of 1 20,000 and an MWD of 1.41. Therefore, the copolymer produced had a molecular weight much higher than the two homoblocks as monomer units. Block copolymer powder It was then mixed with 0.25% heat stabilizer and granulated using a twin-screw extruder. The Tg and specific gravity of PSSD were 259 °C and 1.29, respectively, while those of TMSSS were 268 1: and 1.31. Block copolymer (TMDPSS) The transparent particles showed a DSC Tg of 264t: and a specific gravity of 1.31. The particle transparency of the product, the single GP C peak, the intermediate Tg and the specific gravity clearly indicate that the block copolymer of PSSD and TMPSS has indeed been formed and the product is not only a blend of the two homopolymers PSSD and TMPPS. The detailed properties are listed in Table 1. The detailed chemical reaction is shown in (Figure IV). Example 8: TMBPSS: 50: 50 PSSB: Block copolymer of TMPSS The TMBPSS (PSSB: TMPSS) block copolymer was prepared using the following three-part process. Part 1 · Preparation of PSSB Blocks PS SB was prepared using biphenol and CSB as monomers. The experimental configuration as described in Example 1 was used. Cyclopentane (4410 g, 3500 ml/mole) and toluene (1〇〇〇-43-200724571 (40) ml/mole) were placed in a flask, and nitrogen bubbles were continuously passed through and heated to 45 liters. Add 4,4' bis[(4-chlorophenyl)sulfonyl]biphenyl (CSB) (523 g) and biphenol ([86 g) to the flask, CSB: DHDPS is 1·〇4 : 1·〇〇莫耳比, the reaction mixture was stirred for 3 minutes. Anhydrous sodium carbonate (1 23 g) was added. Wash in a flask to maintain a nitrogen atmosphere. Toluene is used as an azeotropic solvent. The remaining methods are the same as those described in the first part of Example 1. The resulting homoblock had a GPC molecular weight of 19η 19,000, Mw of 23,000 and MWD 1.21. Part 2: Preparation of TMPSS homoblocks TMPSS was prepared using TMDHDPS and CSB as monomers. Cyclopentane (4410 g, 3500 ml/mole) and toluene (1 ml/mol) were placed in a flask, and nitrogen bubbles were continuously passed through and heated to 45 °C. Add 4,4' bis[(4-chlorophenyl)sulfonyl]biphenyl (CSB) (503 g) and tetramethyldihydroxydiphenyl hydrazine (3 09 g TMDHDPS) to the flask, TMDHDPS: The CSB was 1.01: 1.00 molar ratio and the reaction mixture was stirred for 30 minutes. Anhydrous sodium carbonate (123 g) was added. Toluene is used as an azeotropic solvent. The remaining methods are the same as those described in the second part of Example 1. The resulting homoblock had a GPC molecular weight of 3,000 23,000, Mw of 26,000 and MWD 1.11. Part 3 · Preparation of block copolymer -44- 200724571 (41) The reaction mixture of the first part and the second part was mixed at an equal weight ratio, and block polymerization was carried out at 230 °C. After the desired M W (as indicated by GP C) was reached, the reaction mixture was quenched with cyclohexane (504 g, 400 mL / m) and the temperature was reduced to 210 °C. Methyl chloride gas was then bubbled through the reaction mixture over a period of 3 hours to determine completion of the end cap. The reaction mixture was then diluted a second time with cyclobutyl hydrazine (400 ml/mole). The polymer solution was filtered through a 15 micron filter using a 2 kg/cm 2 nitrogen pressure in a filter press funnel to remove salts. Finally, the block copolymer was recovered by slowly adding a salt-free polymer solution to deionized water (13 ml/g polymer) under high-speed stirring. The precipitated polymer is then recovered by filtration. The precipitated polymer was honed and refluxed three times with deionized water at 90 °C to completely remove all salts and cyclopentane. The precipitated polymer was then filtered and dried in a 140 ° C oven until the water content determined by Karl Fischer titration < 0.5%. GPC analysis of the block copolymer based on polystyrene standards showed a Μη of 88,000, a Mw of 124,000 and an MWD of 1.40. Therefore, the copolymer produced has a molecular weight ' much higher than that of the two homoblocks as a monomer unit. The block copolymer powder was then mixed with 0.25% thermal stabilizer and granulated using a twin screw extruder. The Tg and specific gravity of PS SB are 270 ° C and 1.33, while those of TMSSS are 268 ° C and 1.31. The transparent particles of the block copolymer (TMBPSS) showed a DSC Tg of 268 ° C and a specific gravity of 1.32. The particle transparency of the product, the single GP C peak, the intermediate Tg and the specific gravity clearly indicate that the block copolymer of PSSB and TMPSS has indeed been formed and the product is not only a blend of the two homopolymers PSSB and TMPPS. -45- 200724571 (42) The detailed properties are listed in Table 1. The detailed chemical reaction is shown in (Figure V). Example 9: TMDPPSU: 50: 50 PPSU: Block copolymer of TMPSS The PPSU-TMPSS block copolymer was prepared using the following three-part method. Part 1: Preparation of PPSU homoblocks PPSU is based on biphenol and DCDPS. Made from monomers. The experimental configuration as described in Example 1 was used. Cyclopentane (44 10 g, 3500 ml/mole) and toluene (1000 ml/mole) were placed in a flask, and nitrogen bubbles were continuously passed through and heated to 45 °C. 4,4'-Dichlorodiphenyl hydrazine (DCDPS) (298 g) and biphenol (186 g) were added to the flask, and the DCDPS: DHDPS system was 1.04: 1.00 mol ratio, and the reaction mixture was stirred for 30 minutes. Anhydrous sodium carbonate (1 23 g) was added. Wash in a flask to maintain a nitrogen atmosphere. Toluene is used as a boiling solvent. The remaining methods are the same as those described in the first part of Example 1. The resulting homoblock had a GPC molecular weight of Mn 23,000, Mw 29, and MWD 1.26. Part 2: Preparation of TMPSS homoblocks TMPSS was prepared using TMDHDPS and CSB as monomers. Cyclopentane (4410 g, 3500 ml/mole) and toluene (1〇00 -46-200724571 (43) ml/mole) were placed in a flask, and nitrogen bubbles were continuously passed through and heated to 45. Oh. Add 4,4, bis[(4-chlorophenyl)sulfonyl]biphenyl (CSB) (5 03 g) and tetramethyldihydroxydiphenyl hydrazine (3 09 g TMDHDPS) to the flask, TMDHDPS : CSB is 1.01: 1.00 molar ratio, and the reaction mixture is stirred for 3 minutes. Anhydrous sodium carbonate (1 23 g) was added. Toluene is used as an azeotropic solvent. The remaining methods are the same as those described in the second part of Example 1. The resulting homoblock has a GPC molecular weight of 5,000 25,000, Mw of 35,000 and MWD 1.40. Part 3: Preparation of block copolymers The reaction mixture of Part 1 and Part 2 is mixed at equal weight ratios and block polymerization is carried out at 23 (TC). After reaching the desired MW (as indicated by GPC), the reaction is carried out. The mixture was quenched with cyclobutyl hydrazine (504 g, 400 mL / m) and the temperature was reduced to 210 ° C. The methyl chloride gas was then bubbled through the reaction mixture over 3 hours to complete the end closure. The reaction mixture was then diluted a second time with cyclobutyl hydrazine (400 ml/mol). The polymer solution was filtered through a 15 micron filter using a 2 kg/cm 2 nitrogen pressure in a filter press funnel to remove salts. The block copolymer was recovered by slowly adding a salt-free polymer solution to deionized water (13 ml/g polymer) under high-speed stirring, and then the precipitated polymer was recovered by filtration. Honing and refluxing with deionized water three times at 90 ° C to completely remove all salts and cyclobutyl hydrazine. The precipitated polymer was then filtered and dried in a 1 40 C oven until it was titrated by Karl Fischer. Water weight -47- 200724571 (44) < 0.5%. The GPC analysis of the segment copolymer based on polystyrene standards showed a Μη of 82,000, a Mw of 115,000 and an MWD of 1.40. Therefore, the copolymer produced had a molecular weight much higher than the two homoblocks as monomer units, indicating preparation. The block copolymer. The block copolymer powder was then mixed with a 0.25% thermal stabilizer and granulated using a twin-screw extruder. The Tg and specific gravity of the PPSU were 220 ° C and 1.29, respectively, while the TMSSS was 268 1: And 1.31. The transparent particles of the block copolymer (TMDPPSU) showed a DSC Tg of 240 ° C and a specific gravity of 1.30. The particle transparency of the product, the single GPC peak, the intermediate Tg and the specific gravity clearly indicate that the blocks of PPSU and TMPSS have indeed been formed. The copolymer and the product are not only a blend of the two homopolymers PPSU and TMPPS. The detailed properties are listed in Table 1. The detailed chemical reaction is shown in (Figure VI). Example 1 〇·· TMDPES · _ 50 : 50 PES : TMPSS The block copolymer was prepared using the following three-step process: Part 1 of the PES-TMPSS block copolymer: Preparation of the PES homoblock The PES system was prepared using DHDPS and DCDPS as monomers. The experiment as described in Example 1 was used. Configuration. Cyclobutane (4410 g, 3 500 ml/mole) and toluene (1 〇〇 () ml/mole) were placed in a flask, continuously passed through a nitrogen bubble, and heated to 45 χ: 4, 4' one two Chlorodiphenyl maple (DCDPS) (298 g) and 4,4,~ dihydroxydiphenyl hydrazine (DHDPS) (250 g) were added to the flask, -48- 200724571 (45) DCDPS ·· DHDPS is 1 · 〇4 : 1 · 0 0 molar ratio, the reaction mixture was stirred for 30 minutes. Anhydrous sodium carbonate (1 2 3 g) was added. Wash in a flask to maintain a nitrogen atmosphere. Toluene is used as an azeotropic solvent. The remaining methods are the same as those described in the first part of Example 1. The resulting homoblock had a GPC molecular weight of 5,000 25,000, Mw 29,000 and MWD 1.16. Part 2: Preparation of TMPSS homoblocks TMPSS was prepared using TMDHDPS and CSB as monomers. Cyclopentane (4410 g, 3500 ml/mole) and toluene (1000 ml/mole) were placed in a flask, and nitrogen bubbles were continuously passed through and heated to 45 °C. Add 4,4' bis[(4-chlorophenyl)sulfonyl]biphenyl (CSB) (503 g) and tetramethyldihydroxydiphenyl hydrazine (3 09 g TMDHDPS) to the flask, TMDHDPS: The CSB was 1.01: 1.00 molar ratio and the reaction mixture was stirred for 30 minutes. Anhydrous sodium carbonate (1 23 g) was added. Toluene is used as an azeotropic solvent. The remaining methods are the same as those described in the second part of Example 1. The resulting homoblock had a GPC molecular weight of 5,000 25,000, Mw of 35,000 and MWD 1.40. Part 3: Preparation of block copolymers The reaction mixture of Part 1 and Part 2 is mixed at equal weight ratios and block polymerization is carried out at 23 (TC). After reaching the desired MW (as indicated by GPC), the reaction is carried out. The mixture was quenched with cyclobutyl hydrazine (504 g, 400 ml/mol-49-200724571 (46)) and the temperature was lowered to 210 ° C. The methyl chloride gas was then bubbled through the reaction mixture over 3 hours to determine The end cap was completed. The reaction mixture was then diluted a second time with cyclobutyl hydrazine (400 mL/mol). The polymer solution was filtered through a 15 micron filter using a 2 kg/cm 2 nitrogen pressure in a filter press funnel. Salt. Finally, the block copolymer was recovered by slowly adding a salt-free polymer solution to deionized water (13 ml/g polymer) under high-speed stirring, and then the precipitated polymer was recovered by filtration. The polymer was honed and refluxed three times with deionized water at 90 ° C to completely remove all salts and cyclobutyl hydrazine. The precipitated polymer was then filtered and dried in a 140 ° C oven until Karl Fischer titration Determined water content < 0.5%. Block GPC analysis of the copolymer based on polystyrene standards showed Μη of 85,000, Mw of 115,000 and M WD of 1.35. Therefore, the copolymer produced had a molecular weight much higher than the two homoblocks as monomer units, indicating preparation The block copolymer. The block copolymer powder was then mixed with 0.25% thermal stabilizer and granulated using a twin-screw extruder. The Tg and specific gravity of the PES were 225 t: and 1.29, while the TMSSS was 26 8 °. C and 1.31. The transparent particles of the block copolymer (TMDPES) showed a DSC Tg of 2 5 5 ° C and a specific gravity of 1.30. The particle transparency of the product, the single GPC peak, the intermediate Tg and the specific gravity clearly indicate that PES and TMPSS have indeed been formed. The block copolymer and the product are not only a blend of two homopolymers PES and TMPPS. The detailed properties are listed in Table 1. The detailed chemical reaction is shown in (Figure VII). Example 11: BPSK: 50: 50 PSSB: PESK Block copolymer-50-200724571 (47) The PSSB-PESK block copolymer was prepared using the following three-part method. Part 1: Preparation of PSSB homoblocks PSSB was prepared using biphenol and CSB as monomers. Use as described in Example 1. The configuration was carried out. Put the ring guanidine (4410 g, 3500 ml/mole) and toluene (1 〇〇〇 ml/mole) into the flask, continuously pass nitrogen bubbles, and heat to 45 ° C. 4, 4 'bis[(4-chlorophenyl)sulfonyl]biphenyl (CSB) (523 g) and biphenol (1 86 g) were added to the flask, CSB: DHDPS was 1.04: 1.00 mol ratio, reaction The mixture was stirred for 30 minutes. Anhydrous sodium carbonate (1 2 3 g) was added. Wash in a flask to maintain a nitrogen atmosphere. Toluene is used as an azeotropic solvent. The remaining methods are the same as those described in the first part of Example 1. The resulting homoblock had GPC·molecular weight 19η 19,000, Mw 23,000 and MWD 1.21. Part 2: Preparation of PESK homoblocks PESK is produced using DCB and DHDPS as monomers. Cyclopentane (4410 g, 3500 ml/mole) and toluene (1 ml/mol) were placed in a flask, and nitrogen bubbles were continuously passed through and heated to 45 °C. Add 4,4'-dichlorodiphenyldiphenyl ketone (DCB) (251 g) and 4,4'-dihydroxydiphenyl hydrazine (DHDPS) (25 3 g) to the flask, DHDPS: The DCB system was 1.01 : 1 · 〇〇 molar ratio, and the reaction mixture -51 - 200724571 (48) was stirred for 30 minutes. Anhydrous sodium carbonate (123 g) was added. Toluene was used as the azeotropic solvent. The remaining methods are the same as those described in the second part of Example 1. The resulting homoblock had a GPC molecular weight of 5,000 25,000, Mw of 35,000 and MWD 1.40. Part 3: Preparation of block copolymer φ The reaction mixture of the first part and the second part was mixed at an equal weight ratio, and block polymerization was carried out at 230 °C. After reaching the desired M W (as indicated by GP C), the reaction mixture was quenched with cyclohexane (5,04 g, 400 ml/m) and the temperature was reduced to 210 °C. Methyl chloride gas was then bubbled through the reaction mixture over a period of 3 hours to determine completion of the end cap. The reaction mixture was then diluted a second time with cyclobutyl hydrazine (400 ml/mole). The polymer solution was filtered through a 15 micron filter using a 2 kg/cm 2 nitrogen pressure in a filter press funnel to remove salts. Finally, the block copolymer was recovered by slowly adding a non-salted polymer solution to deionized water (13 ml/g polymer) under high-speed stirring. The precipitated polymer is then recovered by filtration. The precipitated polymer was honed and refluxed three times with deionized water at 90 °C to completely remove all salts and cyclopentane. The precipitated polymer was then filtered and dried in a 140 ° C oven until the water content determined by Karl Fischer titration < 〇·5% 〇 block copolymer based on polystyrene standards by GPC analysis showed Μη 88,000, The Mw is 124,000 and the MWD is 1.40. Therefore, the copolymer produced has a molecular weight much higher than that of the two homoblocks as a monomer unit, and -52-200724571 (49) represents the preparation of a block copolymer. The block copolymer powder was then mixed with 0.25% thermal stabilizer and granulated using a twin screw extruder. The Tg and specific gravity of PS SB are 270 °C and 1.33, while those of P E S K are 185 °C and 1.2 8. The transparent particles of the block copolymer (BPSK) showed a DSC Tg of 23 5 ° C and a specific gravity of 1 · 3 2 . The particle transparency of the product, the single G P C peak, the intermediate T g and the specific gravity clearly indicate that the block copolymer of PS SB and PESK has indeed been formed and the product is not only a blend of the two homopolymers PS SB and TESK. The details are listed in Table 1. The detailed chemical reaction is shown in (Figure VIII). Example 12: TMDPSU: 50: 50 PSU: Block copolymer of TMPSS The PSU-TMPSS block copolymer was prepared using the following three-part method. Part 1: Preparation of PSU homoblocks # PSU using bisphenol A and DCDPS Made as a monomer. The experimental configuration as described in Example 1 was used. Cyclopentane (4410 g, 3500 ml/mole) and toluene (1000 ml/mole) were placed in a flask, continuously bubbled with nitrogen, and heated to 45 °C. 4,4'~Dichlorodiphenyl hydrazine (DCDPS) (298 g) and bisphenol A (250 g) were added to the flask, DCDPS: bisphenol A was 1·〇4: 1.00 mol ratio, reaction The mixture was stirred for 30 minutes. Anhydrous sodium carbonate (I54 g) was added. Wash in a flask to maintain a nitrogen atmosphere. Toluene is used as a boiling solvent. -53- 200724571 (50) The remaining methods are the same as those described in the first part of the first embodiment. The resulting homoblock has a GPC molecular weight Μ 20,000, MW 25,000 and MWD 1.25. Part 2: Preparation of TMPSS homoblocks TMPSS was prepared using TMDHDPS and CSB as monomers. Cyclopentane (44 10 g, 3500 ml / mol) and toluene (1 ml / mol) were placed in a flask, and nitrogen bubbles were continuously passed through and heated to 45 t:. Add 4,4, bis[(4-chlorophenyl)sulfonyl]biphenyl (CSB) (503 g) and tetramethyldihydroxydiphenyl hydrazine (3 09 g of TMDHDPS) to the flask. TMDHDPS: CSB is 1·〇1: 1.00 molar ratio, and the reaction mixture is stirred for 30 minutes. Anhydrous sodium carbonate (123 g) was added. Toluene is used as an azeotropic solvent. The remaining methods are the same as those described in the second part of Example 1. The resulting homoblock had a GPC molecular weight of 5,000 25,000, Mw of 35,000 and MWD 1.40. Part 3: Preparation of block copolymer The reaction mixture of the first part and the second part was mixed at an equal weight ratio, and block polymerization was carried out at 2200 °C. After reaching the desired M W (as indicated by G P C), the reaction mixture was quenched with cyclohexane (504 g, 400 mL / m) and the temperature was reduced to 200 °C. Methyl chloride gas was then bubbled through the reaction mixture over a period of 3 hours to determine completion of the end cap. The reaction mixture was then diluted a second time with cyclobutyl hydrazine (4 mL/mole). Polymer -54- 200724571 (51) The solution was filtered through a 15 μm filter using a 2 kg/cm 2 nitrogen pressure in a filter press funnel to remove salts. Finally, the block copolymer was recovered by slowly adding a salt-free polymer solution to deionized water (13 ml/g of polymer) under high-speed stirring. The precipitated polymer is then recovered by filtration. The precipitated polymer was honed and refluxed three times with deionized water at 90 °C to completely remove all salts and cyclopentane. The precipitated polymer was then filtered and dried in a 140 ° C oven until the water content determined by Karl Fischer titration < 0.5%. GPC analysis of the block copolymer based on polystyrene standards showed a Μη of 80,000, a Μη of 115,000 and a M WD of 1.44. Therefore, the copolymer produced has a molecular weight far higher than the two homoblocks as monomer units, indicating the preparation of the block copolymer. The block copolymer powder was then mixed with 0.25% thermal stabilizer and granulated using a twin screw extruder. The Tg and specific gravity of the PSU are 190 ° C and 1.29, while the TMSSS is 268 ° C and 1.31. The transparent particles of the block copolymer (TMDPSU) showed a DSC Tg of 23 0 ° C and a specific gravity of 1.30. The particle transparency of the product, the single GPC peak, the intermediate Tg and the specific gravity clearly indicate that the block copolymer of PES and TMPSS has indeed been formed and the product is not only a blend of the two homopolymers PSU and TMPPS. The detailed properties are listed in Table 1. The detailed chemical reaction is shown in (Figure IX). Various homoblocks are prepared using one or more dichloro compounds and one or more dihydroxy compounds, some of which are listed below: Aromatic dihalogen compounds: Dichlorodiphenyl milling (DCDPS), 4,4'-double ( 4-chlorophenylsulfonyl)biphenyl (CSB), dichlorodiphenyl ketone, dichlorodiphenyl ether, -55- 200724571 (52) dichlorobiphenyl, dichlorodiphenylmethylene , dimethyldichlorodiphenyl hydrazine, tetramethyldichlorodiphenyl fluorene, dihalodiphenylbiphenyl, dihalodiphenoxybiphenyl, dihalodiphenylbiphenyl diether (二飒 or 二_) (ci-c6h4-c6h4-x-c6h4-c6h4-x-c6h4-c6h4-cl),

C1-C6H4-X-C6H4-C6H4-Y-C6H4-C6H4-C1-, C1-C6H4-X-C6H4-C6H4-Y-C6H4-C1-, C1-C6H4-C6H4-X-C6H4-Y-C6H4- C6H4-C1-, C1-C6H4-C6H4-X-C6H4-Y-C6H4-C1, where X=-Ο-, -so2-, -CO-, -ch2- or any two C1-C6H4-C6H4-X -C6H4-C6H4-Y-C6H4-C6H4-CL where X = -so2-, -CO-, -ch2- and Y two:-0 -, -S Ο 2 - ' -CO-, -CH2-, and - Cl is a composition representing any halogen; Aromatic dihydroxy compounds: dihydroxydiphenyl maple (DHDPS), bisphenol A, biphenol, hydroquinone, dimethyl dihydroxy diphenyl hydrazine, tetramethyl dihydroxy diphenyl hydrazine, tetramethyl bis Phenol A, tetramethylbiphenol, dihydroxydiphenyl ketone, bis(hydroxyphenylsulfonyl)biphenyl, bis(hydroxyphenyl ketone)biphenyl, bis(hydroxyphenoxy)biphenyl, HO- C6H4X-C6H4-C6H4-Y-C6H4-OH wherein X & Y = -0-, -S02-, -CO-, -ch2 - and the phenyl or biphenyl ring may have one or two methyl substitutions, HO -C6H4-X-C6H4-Y-C6H4-OH, with or without methyl substitution. -56-

Claims (1)

200724571 (1) X. Patent Application No. 1 - A method for preparing a block copolymer comprising 'at least two homoblocks selected from the group consisting of PSSD, PSSB, TPES, · pss, TMPSS or PESK or selected from at least one of PSSD, PSSB, TPES > PSS > TMPSS or PESK and at least one PPSU, PES or PSU 'where the homoblocks each have an identical or different molecular weight of at least 1 Å and Having at least 5% by weight, wherein the block copolymer has a molecular weight of at least φ 2000, the method step comprising: (a) by the presence of at least one base and optionally in at least one solvent and optionally Heating at least one aromatic diol/dihydroxy compound and at least one aromatic dihalogen compound (one of which contains at least one boron group) in the presence of an entraining agent to prepare the aforementioned various homoblocks, (b) The blocks are together at a temperature between 1 and 3 (TC to 2 5 (between TC and optionally in at least one solvent, and optionally the end of the block copolymer is then capped, and # ( c ) Recycling the block 2. The method of claim 1, wherein the block copolymer is recovered by washing the reaction material to remove salts and bases and optionally solvents. The method of claim 1, wherein the block copolymer prepared in at least one solvent is precipitated by the salt and the block copolymer is precipitated in water or MeOH or a mixture of water and MeOH and further filtered and washed. The block copolymer is dried and recovered from the solvent. 4. The method of claim 1, wherein the block copolymer prepared in at least one solvent of -57-200724571 (2) is filtered by the salt and The solvent was distilled off and recovered. 5. The method of claim 1, wherein the aromatic dihalogen compound is selected from the group consisting of dichlorodiphenyl maple (DCDPS) and 4,4'-double (4-chlorophenylsulfonyl). Benzene (CSB), dichlorodiyl ketone, dichlorodiphenyl ether, dichlorobiphenyl, dichlorodiphenylmethylene, dimethyldichlorodiphenyl maple, tetramethyldichlorodiphenyl Base, dihalodiphenylbiphenyl, dihalodiphenoxybiphenyl, dihalodiphenylbiphenyl diether (dioxa or diketone) (C1-C6H4-C6H4-X-C6H4- C6H4-X-C6H4-C6H4-CL), C1-C6H4-X-C6H4-C6H4-Y-C6H4-C6H4-C1-, C1-C6H4-X-C6H4-C6H4-Y-C6H4-C1-, C1-C6H4 -C6H4-X-C6H4-Y-C6H4-C6H4-C1-, C1-C6H4-C6H4-X-C6H4-Y-C6H4-C1, where X = -0- ' -S〇2- ' -CO- ' - CH〗· or any two of C1-C6H4-C6H4-X-C6H4-C6H4-Y-C6H4-C6H4-CL where x ==-0 -, -S 0 2 - 5 -CO-, -ch2- and Y: =-0 -, -S 0 2 - '-CO-, -CH2-, and -Cl represents any halogen; 6. The method of claim 1, wherein the aromatic diol/dihydroxy compound is selected from the group consisting of dihydroxydiphenyl hydrazine (DHDPS), bisphenol A, biphenol, hydroquinone, dimethyl dihydroxyl Diphenyl maple, tetramethyldihydroxydiphenyl hydrazine (TMDHDPS), tetramethyl bisphenol A, tetramethylbiphenol-58- 200724571 (3), mono-phenyl hydrazine, bis(phenylphenyl) Mineral enzyme) biphenyl (HSB), bis(hydroxyphenylketone)biphenyl, bis(hydroxyphenoxy)biphenyl, HO-C6H4X-C6H4-C6H4-Y-C6H4-OH wherein X & Y di- 〇-, ···-S02-,-CO-,-CH2- and the phenyl or biphenyl ring may have one or two methyl-substituted, HO-C6H4-X-C6H4-Y-C6H4-OH, with or Does not have a methyl substitution. Φ 7. The method of claim 1, wherein the aromatic diol or the aromatic monohalogen compound is in an amount of more than or equal to 15 mol% more than the other. 8. The method of claim 1, wherein the homoblocks each have at least 10% of the total weight of the block copolymer. 9. The method of claim 1, wherein the homoblocks each have at least 25% of the total weight of the block copolymer. 10. The method of claim 1, wherein the homoblock each has at least 40% of the total weight of the block copolymer. 11. The method of claim 1, wherein the solvent is dimethylacetamide (DMA c), dimethyl hydrazine (DMSO), cyclobutyl hydrazine, N-methyl pyrrolidone, two Phenylhydrazine, dimethylhydrazine or a mixture thereof. The method of claim 1, wherein the base is a metal hydroxide or a mixture of two or more metal hydroxides. The method of claim 12, wherein the metal hydroxide is N a Ο Η, Κ Η or a mixture thereof. 14. The method of claim 1, wherein the base is a mixture of gold-59-200724571 (4) carbonate or two or more metal carbonates. The method of claim 14, wherein the metal carbonate is Na2C03, K2C03 or a mixture thereof. The method of claim 1, wherein the base is a mixture of a metal hydroxide and a metal carbonate. 17. The method of claim 1, wherein the method step (a) or (b) or both steps are carried out at a temperature between 160 ° C and 250 ° C. 18. The method of claim 1, wherein the entrainer is toluene. The method of claim 1, wherein the entrainer is monochlorobenzene. 20. The method of claim 1, wherein the end capping is performed using MeCl. 2 1 - A method of preparing a t-stacked copolymer substantially as described in the examples of the specification. 22. A block copolymer comprising at least two homoblocks selected from the group consisting of PSSD, PSSB, TPES, PSS, TMPSS or PESK or at least one PSSD, PSSB, TPES, PSS, TMPSS or PESK And at least one PPSU, PES or PSU, the homoblocks being bonded directly or by a bonding group to form a block copolymer chain, wherein the homoblocks each have at least 1,000 identical or different Molecular weight and having a total weight of at least 5% and wherein the block copolymer has a molecular weight of at least 2000. 2 3 · The block copolymer of claim 2, wherein the -60-200724571 (5) homoblock each has a molecular weight of from 2,000 to 10,000. 24. The block copolymer of claim 22, wherein the homoblocks each have a molecular weight of from 15,000 to 50,000. 25. The block copolymer of claim 22, wherein the block copolymer has a molecular weight of from 5,000 to 150,000. 26. The block copolymer of claim 22, wherein the block copolymer has a molecular weight of from 30,000 to 150,000. Φ 2 7. The block copolymer of claim 22, wherein the homoblocks each have at least 1% by weight of the total weight. 28. The block copolymer of claim 22, wherein the homoblocks each have at least 25 % of the total weight. 2. The block copolymer of claim 22, wherein the homoblocks each have at least 40% of the total weight. 30. The block copolymer of claim 22, wherein the bonding group is formed by reacting a diol or a glycol salt with a dihalide. #3 1 . The block copolymer of claim 30, wherein the diol or glycol salt is selected from the group consisting of aromatic dihydroxy compounds. 3. The block copolymer of claim 30, wherein the dihalide is an aryl dichloride. The block copolymer of claim 22, wherein the homoblock is prepared using at least one aromatic diol/dihydroxy compound and at least one aromatic dihalogen compound, one of which contains At least one of the bases of the invention, wherein the block copolymer of claim 33, wherein the -61 - 200724571 (6) aromatic dihalogen compound is selected from the group consisting of dichlorodiphenyl hydrazine (DCDPS), 4,4' a pair of (4-chlorophenylsulfonyl)biphenyl (CSB), dichlorodiphenyl ketone, dichlorodiphenyl ether, dichlorobiphenyl, dichlorodiphenylmethylene, Dimethyldichlorodiphenyl hydrazine, tetramethyldichlorodiphenyl fluorene, dihalodiphenylbiphenyl, dihalodiphenoxybiphenyl, dihalodiphenylbiphenyl diether ( Di- or diketone) (C1-C6H4-C6H4-X-C6H4-C6H4-X-C6H4-C6H4-CL), , C1-C6H4-X-C6H4-C6H4-Y-C6H4-C6H4-C1-, C1_C6H4- X-C6H4-C6H4-Y-C6H4-C1-, C1-C6H4-C6H4-X-C6H4-Y-C6H4-C6H4-C1-, C1-C6H4-C6H4-X-C6H4-Y-C6H4-C1, where χ = -Ο-,-S02-,-CO-,-CH2- or any two of ci-c6h4-c6h4-x-c6h4-c6h4-y-c6h4-c6h4-cl where X = -S ◦ 2 - '-CO-, -ch2- Y 2 :-0 -, -S 0 2 -5 -CO-, -ch2 and -Cl represents any halogen; 3. The block copolymer of claim 3, wherein the aromatic diol/dihydroxy compound is selected from the group consisting of dihydroxydiphenyl hydrazine (DHDPS), bisphenol a, biphenol, hydroquinone, Dimethyldihydroxydiphenylphosphonium, tetramethyldihydroxydiphenyl Maple (TMDHDPS), tetramethylbisphenol A, tetramethylbiphenol, dihydroxydiphenyl ketone, bis(hydroxyphenylsulfonate) Biphenyl (HSB), bis(hydroxyphenylketone)biphenyl, bis(hydroxyphenoxy)-62-200724571 (7) benzene, HO-C6H4X-C6H4-C6H4-Y-C6H4-OH where X & Y =-ο-, -so2-, -CO-, -CH2- and the phenyl or biphenyl ring may have one or two methyl substitutions, HO-C6H4-X-C6H4-Y-C6H4-OH, With or without methyl substitution. 3 6. A block copolymer substantially as described with reference to the specification examples. -63- 200724571 VII. Designated representative map: (1) The representative representative of the case is: None (2), the representative symbol of the representative figure is a simple description: None 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none