Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
  • C08G75/20—Polysulfones
  • C08G75/23—Polyethersulfones
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
  • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
  • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
  • C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
  • C08G65/4056—(I) or (II) containing sulfur

Definitions

• the present invention relates to a process of preparing block copolymers and the block copolymers prepared therefrom.
• the present invention relates to a process of preparing block 5 copolymers comprising of at least two types of homoblocks belonging to the family of polysulfones, more particularly selected from PSSD, PSU, PSS, PPSU, PSSB, PES, TPES, PESK and TMPSS, and to the block copolymer prepared therefrom.
• the present invention relates to di- and tri-blocks as well as
• PSU Polysulfones
• PPSU Polysulfones
• PES Polysulfones
• Polysulfones are readily processible using common plastics processing techniques such as injection molding, compression molding, blow molding and extrusion. This makes them very versatile and useful plastics, having a myriad of applications in electronics, the electrical industry, medicine, general engineering, food
• PSU Glass Transition Temperature
• PES has a Tg of 225°C
• PPSU has a Tg of 222°C.
• PSU has an overall lower thermal resistance in terms of its dimensional stability compared to PPSU and especially PES, which has the highest thermal resistance.
• PES also has a higher tensile strength (> 90 MPa) compared to PSU and PPSU (both 70-75 MPa).
• PPSU has an outstanding impact resistance, like Polycarbonate (PC) and its Izod notched impact strength is 670-700 J/m. Both PES and PSU have lower Izod notched impact strengths of only 50-55 J/m.
• PC Polycarbonate
• PES and PSU have lower Izod notched impact strengths of only 50-55 J/m.
• articles made from PPSU can withstand > 1000 sterilization cycles without crazing, while PSU based articles withstand about 80 cycles and PES based articles withstand only about 100 cycles.
• PSU on the other hand, has the lightest color and can be more readily processed, while PPSU is darker and more difficult to process than either PSU or PES.
• PSU properties such as easy processibility and light color properties
• PPSU properties such as high temperature and impact resistance
• Incorporating a proportion of PSU into PPSU may also bring down the overall cost.
• the physical blending of PPSU and PSU is one way of accomplishing this, it destroys one of the most important properties of the two homopolymers, namely their transparency.
• physical blend of PES and PSU is not only opaque but also not processible to give blends of desirable properties, as they are very incompatible polymers. In any case, these combinations only show Tg ⁇ 225C.
• Tg Polyaryl ether sulfone (TMPES) is prepared by using 3,3',5,5'-tertamethyl-4'4'-dihydroxydiphenyl sulfone and 4,4'dichlorodiphenyl sulfone as monomers,
• Tg Polyaryl sulfones having biphenyl units like 4,4'- di-(4-chlorophenyl-sulfonyl)-biphenyl and 4,4'-di-(4-hydroxyphenyl-sulfonyl)-biphenyl are mentioned in
• TMPSS -C 6 H 4 -SO 2 -C 6 H 4 -C 6 H 4 -SO 2 -C 6 H 4 -O-C 8 H 8 -SO 2 -C 8 H 8 -
• the polysulfones are prepared using one or more aromatic Dihalo compounds like Dichlorodiphenyl sulfone (DCDPS), Dichloro benzophenone (DCB) or Dichlorodiphenyl disulfonylbiphenyl (CSB) and their respective mono, di tri or tetra methyl or alkyl derivatives and one or more of aromatic di-hydroxy monomer like Bisphenol A, Dihydroxy diphenylsulfone (DHDPS), Biphenol, Dihydroxydiphenyl disulfonylbiphenyl (HSB), Dihydroxy diphenyl ether, Dihydroxy diphenyl methane, ⁇ Bis-(3,5-dimethyl-4-hydroxyphenyl)sulfone ⁇ their respective mono, di, tri or tetra substituted Methyl derivatives, etc.
• DCDPS Dichlorodiphenyl sulfone
• DCB Dichloro benzophenone
• CSB Dichlorodiphenyl disul
• the di-hydroxy compound used is Biphenol (HO-C 6 H 4- C 6 H 4- OH), for PES, it is DHDPS, for PSU, it is Bisphenol A (HO-C 6 H 4 -C(CH 3 ) 2 -C6H4-OH), and for TPES, it is TMDHDPS (HO-C 6 H 2 (CH 3 ) 2 -SO 2 -C 6 H 2 (CH 3 ) 2 -OH), while DCDPS is used as a second monomer for all these Polysulfones.
• Biphenol HO-C 6 H 4- C 6 H 4- OH
• DHDPS for PSU, it is Bisphenol A (HO-C 6 H 4 -C(CH 3 ) 2 -C6H4-OH), and for TPES, it is TMDHDPS (HO-C 6 H 2 (CH 3 ) 2 -SO 2 -C 6 H 2 (CH 3 ) 2 -OH), while DCDPS is used as a second monomer for all these Polysulf
• the di-hydroxy compound used is DHDPS
• HO-C 6 H 4- SO 2- C 6 H 4 -OH and for PSSB, it is Biphenol (HO-C 6 H 4 -C 6 H 4 -OH), for TMPSS, it is TMDHDPS (HO-C 6 H 2 (CH 3 ) 2 -SO 2 -C 6 H 2 (CH 3 ) 2 -OH), for PSS, it is HSB (OH- C 6 H 4 -SO 2 -C 6 H 4 -C 6 H 4 -SO 2 -C 6 H 4 -OH); while CSB (Cl- C 6 H 4- SO 2- C 6 H 4 -C 6 H 4 -SO 2 -C 6 H 4 -Cl) is used as a second monomer.
• PESK can be made by using DCB (Dichlorobenzophenone) and DHDPS. Similarity other homopolymers can be made by reacting DCB with other Dihydroxy compound like DHDPS, Biphenol, TMDHDPS and HSB.
• the homoblocks prepared above can be reacted with other homoblock like PSS, PSSD, PPSU, PES, PSU, TPES, PSSB and TMPSS, etc.
• PAS polymer known as "PAS” manufactured by Amoco
• PAS PAS
• DHDPS digital high-semiconductor
• the third monomer is added at the start of the manufacturing process and so gets polymerized in a random sequence in the polymer chain.
• the homoblock produced was subsequently reacted with a tetracarboxylic acid, such as benzophenonetetracarboxylic dianhydride, and another diamine, such as 4,4'- diaminodiphenylmethane, to make a block copolymer of PSU-PI.
• a tetracarboxylic acid such as benzophenonetetracarboxylic dianhydride
• another diamine such as 4,4'- diaminodiphenylmethane
• Gerhard and coworkers (US Patent 3,647,751) have prepared Polyarylether sulfones using dihalo-diphenyl-disulphonearyls and of alkali metal bis- phenolates.
• Toluene or monochlorobenzene (MCB) is added to facilitate dehydration.
• the temperature of the mixture is then slowly increased to from 140 0 C to 230 0 C depending on the solvent utilized, whereupon the alkaline carbonate reacts with the phenol to give a salt and liberate water.
• the water gets distilled off, which is facilitated by toluene or MCB, if present.
• reaction mixture after water removal is then heated to a temperature in the range of 170 0 C to 250 0 C, depending on the solvent, alkali and the dihydroxy monomer used, until the desired viscosity or molecular weight is attained. Thereafter, the growing chains are optionally end-capped with MeCl and the reaction mass is filtered to remove salt and then polymer chains are precipitated in water or MeOH, further treated to remove the residual solvent, and dried. Alternately, solvent may be flashed off and reaction mass may be passed through a devolatizing extruder directly to remove residual solvent and for polymer granulation.
• Each homoblock should have two identical end groups i.e. -OH or -CNO. iii) The two homoblocks should be mixed in exact stoichiometric proportions to give high molecular weights block copolymers.
• the present invention discloses a process of preparing block copolymers using two or more different polysulfones homoblocks while the strict requirement of each homoblock having exactly similar end groups is avoided. Similarly, the exact stoichiometry for two or more homoblocks can be avoided for high molecular weight block polymer formation.
• the present invention relates to a process of preparing block copolymers, comprising of at least two types of homoblocks, selected from either 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 of PPSU, PES or PSU, wherein each of the said homoblock has an identical or different molecular weight of at least 1000 and has at least 5 % of the overall weight and wherein the block copolymer has a molecular weight of at least 2000, the process steps comprising of : (a) preparing each of the aforesaid homoblocks by heating at least one aromatic diol/dihydroxy compound with at least one aromatic dihalo compound, one of which contains at least one sulfone group, in the presence of at least one alkali optionally in at least one solvent and further optionally in the presence of an azeotropic agent,
• the present invention also relates to the block copolymers prepared using the aforesaid process and block copolymers comprising of at least two types of homoblocks, selected from either 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 of PPSU, PES or PSU, that are linked together either directly or by a linking group to form block copolymer chains, wherein each of the homoblock has an identical or different molecular weight of at least 1000 and has at least 5 % of overall weight and wherein the block copolymer has a molecular weight of at least 2000.
• novel block copolymers are prepared using a technique whereby lower molecular weight homoblocks are first separately prepared and then mixed in different proportions and reacted further to give high molecular weight block copolymers. It becomes possible, using this technique, to ensure the formation of the block structures, as well as their sequences and the block molecular weights. Besides segmented multi-blocks copolymers, even high molecular weight di-blocks or tri- blocks as well as multi-blocks with known block molecular weights are feasible using this method. Block copolymers thus prepared find usage as novel polysulfone plastics, and also as compatibilizers. DESCRIPTION OF THE INVENTION
• two possible chain end structures exist on a polymeric chain of a homoblock of a polysulfone. These end groups are -Cl, emanating from a dihalo (DCDPS, CSB, DCB, etc) moiety and -OH emanating from the Phenolic monomer. A mixture of the both end groups is also possible for a given homoblock polymeric chain.
• Polysulfones usually have some -Cl and some -OH end groups.
• concentration of each is decided by two important factors : firstly the initial molar ratio of dihalo compound like DCDPS, DCB or CSB etc to dihydroxy Phenolic monomer used and secondly the molecular weight of the polymer that is allowed to build up, if the mole ratio is not strictly 1:1.
• the ratio of the two monomers is a very important factor because, in order to build a very high molecular weight, the ratio must be kept closer to 1:1 on a molar basis.
• no monomer should be present in a concentration of more than approximately 1-2 mole % higher than the other monomer.
• the mole ratio generally remains within the range 1.02: 1.00 to 1.00: 1.02 to get high molecular weights.
• An increase in the concentration of any one monomer to a value outside of this range generally results in a disturbance in stoichiometry to such a substantial extent that the molecular weight of the copolymer does not get built up enough and most polymeric properties suffer, as they do not reach optimum values.
• a stringent stoichiometry is surprisingly not necessary since high molecular weight build up is not required.
• a monomer ratio as high as 1.15:1.00 has been employed successfully in the present invention.
• the monomer ratio range, in homoblock has thus been increased from 1.02:1.00 to 1.15:1.00, without sacrificing the ultimate molecular weights of the block copolymer.
• the present invention relates to novel polysulfone block copolymer structures and the novel process by which their preparation takes place.
• this invention relates to the preparation of new types of block copolymers made using PES, PPSU, PSSD, PSSB, PSS, TPES, PSU, TMPSS and PESK, or similar polysulfone homoblocks and the methods of their preparation.
• the block copolymers may be made using at least two types of different polysulfones and may be made using more than two types of polysulfones.
• the process of the present invention involves the preparation of novel block copolymers of the polysulfone family using solution polymerization techniques.
• block copolymers are prepared using lower molecular weight, oligomeric homoblocks of, for example, Polyphenylene Sulfone (PPSU), PES, PSSB, PSSD, TPES, PSS, TMPSS, PSU and PESK.
• PPSU Polyphenylene Sulfone
• PSSB Polyphenylene Sulfone
• PSSD Polyphenylene Sulfone
• TPES TPES
• PSS TMPSS
• PSU PESK
• the present invention relates to a block copolymer having a high deflection temperature and high glass transition temperature.
• the block copolymer retains useful mechanical and physical properties at elevated temperatures (> 220 C) and in harsh chemical environments.
• the block copolymer disclosed in the prior art had lower heat deflection temperatures and therefore could be used only for applications requiring continuous use temperatures below 180 C and could not be used in high temperature application such as lamp housings, aerospace composites and other articles that exposed to thermal and mechanical stress.
• a major novel and unexpected aspect of the process of the present invention is that it can do away with the stringent requirements that the given homoblock should have only one type of two end groups as well as the stoichiometry between homoblocks used must be 1:1.
• the process of the present invention makes it possible to prepare high molecular weight block copolymers without having identical end groups on each homoblock as well as without the stoichiometry being closely controlled.
• the present invention therefore greatly simplifies the formation of block copolymers.
• greater combinations of composition range of block copolymers can be readily made using same homoblocks by this invention as compare to the earlier methods of segmented block copolymer preparations.
• using homoblocks with identical end groups and having them in exact stoichiometric proportions does not harm the process in any way, but these are no longer preconditions for the build up of high molecular weight block copolymers.
• the novel block copolymers are made by first using initially separately prepared lower molecular weight homoblocks with reactive chain end groups.
• homoblock it is meant that each block has either a PES or PSSB or TPES or PSSD or PPSU or TMPSS or PSS, PSU or PESK or some such polysulfone structure and different homoblocks have structures differing from each other.
• the two homoblocks are separately prepared and are arranged to have two end groups which in turn are either the same or different. It is important to realize as taught by this invention that there should be, nevertheless, a near stoichiometric balance of the two differing end groups, in this case say -Cl and -OH. What is important is that both end groups are allowed to be present on both the homoblocks.
• the different ways of preparing homoblocks are as follows :
• the first set of homoblocks is prepared with predominantly halogen end groups, such as -F, -Cl, -Br and -I.
• the second set of homoblocks is prepared with predominantly the second type of end group, which is capable of reacting with a halogen end group, such as -OH (which may be present as the salts -OK, -ONa, or -OLi). This is done by taking large mole access of dihalo monomer as compared to dihydroxy monomer in the first case and reversing the ratio in the second.
• the block copolymer obtained has blocks of PSSD & PSSB having similar molecular weights as that of the starting homoblocks.
• the present invention thus makes it possible for the molecular weights of homoblocks to be nearly same as their molecular weights as block in part of the chains. It is also possible to prepare, according to this invention, block copolymers where the homoblock of PSSD has halogen end groups and the PSSB homoblock has phenolic -OH end groups, as well as the reverse where PSSD has the hydroxy end groups and PSSB has halogen end groups.
• the end groups may be interchangeable for a given homoblock.
• each homoblocks has non-identical end groups (-Cl and -OH for example)
• both homoblocks to have both end groups and still being used for making high molecular weight block copolymers. This can be done by taking both monomers in near equal mole ratio. In such cases, the end groups will be halogen and hydroxy, irrespective of molecular weights of homoblocks.
• the block copolymers formed may have blocks having in-chain molecular weights, which are similar or higher than the homoblocks' molecular weights.
• the aforesaid method of preparation of homoblocks is true and same for all the homoblocks, viz. PSSD, PSU, PPSU, PSSB, PES, TPES, PSS, PESK or TMPSS, etc.
• This invention also teaches that besides random homoblock sequence in the block copolymer thus prepared, one can also make di- and tri-block copolymers by adjusting the molecular weights of the homoblocks and the stoichiometry of the two homoblocks reacted to form the block copolymers.
• the invention therefore teaches preparation of di-block, tri-block as well as segmented block copolymers where the homoblocks may alternate or be present in random sequence.
• this invention makes it possible to build high molecular weight copolymers having essentially alternate homoblock structures in the chains. In such block copolymers all the blocks will have similar molecular weights to those of the two initial homoblocks. If the molecular weights of the homoblocks are kept high, then one can build di- and tri-block copolymers of relatively high molecular weights.
• z degree of block copolymerization
• z degree of block copolymerization
• special tri-block copolymers can also be prepared by using judicious control of the molecular weight, stoichiometry and end groups of the homoblocks.
• the novel aspect of this invention is the recognition that by varying the stoichiometry of the basic monomers that are used for the preparation of homoblocks, particularly when they are of lower molecular weights, one can make these homoblocks with predominantly known end groups.
• one monomer say, CSB in an excess of, say, 3 mole % over DHDPS i.e. a molar stoichiometry of >1.03: 1.00, one obtains PSSD with essentially only -Cl as end groups.
• the aforesaid method of preparation of homoblocks is true and same for all the homoblocks, viz. PSSD, PSU, PPSU, PSSB, PES, TPES, PSS, PESK or TMPSS.
• One important aspect of this invention is deliberate use of higher ratios of the two monomers for the preparation of homoblocks to give essentially one type of end groups.
• the ratio may be 1.03 - 1.15:1.00, that is having 3 to 15 mole % higher quantity of one monomer over the second monomer.
• Another important aspect of this invention is that the homoblocks can also be conveniently prepared using near equal stoichiometry of the two base monomers, keeping the molecular weights of the homob locks as desired and, by mixing, preparing high molecular weight block copolymers of the desired composition.
• the important aspect of this invention is therefore the preparation of lower molecular weight homoblocks with known end groups and their mixing in the right proportions to yield random block copolymers of higher molecular weights.
• a further novel and important aspect of this invention is the preparation of di- and tri-block copolymers.
• These di- and tri-block copolymers are also materials of a novel composition.
• homoblocks can be prepared with different molecular weights with essentially known end groups.
• Polysulfones of sufficiently high molecular weight or inherent viscosity, (Inhv.) are required to give optimum mechanical and other polymer properties, one can build that range of molecular weight homoblocks.
• PSSD of a number average molecular weight (Mn) say of 50000 with -Cl end groups and PSSB of say similar molecular weight with -OK end groups when mixed and reacted in a proportion of 1 : 1 on a molar basis will give almost double the molecular weight, giving a di-block.
• Mn number average molecular weight
• PSSB number average molecular weight with -OK end groups
• di-blocks are allowed to react further to give still higher molecular weight, we get a tri- and tetra-block and so on.
• di-blocks of the structure — [PSSB-PSSD ⁇ will further react to give tri-blocks of the structure -[--]- [-PSSB- PSSD-PSSB ⁇ and - [-PSSD-PSSB-PSSD ⁇ and which, on further reaction, will yield tetra-blocks and higher multi-blocks.
• this invention makes it possible to prepare di-block and tri-block and multi-block copolymers of PSSB and PSSD.
• the aforesaid method of preparation of homoblocks is true and same for all the homoblocks, viz. PSSD, PSU, PPSU, PSSB, PES, TPES, PSS, PESK or TMPSS.
• This invention further makes it possible to prepare a tri block using three different types of homoblocks as follows. First a di block is prepared using two homoblocks, where two end groups present on one homoblock are same and similarly second homoblock has two similar end groups on its chains but different than the first one. This di-block is reacted with third homoblock with two end groups similar to either first or second homoblock to give tri-blocks.
• the block polymers thus produced may be checked for GPC molecular weight, Inhv., DSC, Tg, MFI, etc. for quality control.
• the block copolymers may be used as powder for compounding and subsequently for granulation or may be added as a compatibilizer to the already separately manufactured high molecular weight homologue polysulfones.
• the present invention seeks to achieve the following :
• the invention preferably uses Sulfolane, NMP, DMAc, DMSO, DMSO2, Diphenyl sulfone or any other aprotic organic solvent for the preparation of low molecular weight homoblocks and the high molecular weight block copolymers thereof.
• MCB or Toluene or any other non-reacting solvent is used as a diluent and dehydrating agent for the salt formation, dehydration and polymerization steps.
• the process uses the above mentioned solvent in the temperature range of 120 0 C to 250 0 C and with alkali such as NaOH, KOH, NaHCO 3 ,
• KHCO 3 Na 2 CO 3 or K 2 CO 3 either by themselves or in a combination of these or any other such suitable alkaline substances.
• a process of producing novel homoblocks and multi-block copolymers using an aprotic organic solvent or solvents in the temperature range of 120°C-250°C and then end capping with MeCl or any suitable end capping agent.
• the process includes the preferred steps of filtration of the salt and precipitation of the block copolymer from the reaction mixture in a non-solvent like H 2 O or MeOH or a mixture of the two, and then giving further water/or MeOH treatments to reduce the residual solvent content of the powder and subsequently drying the polymeric powder.
• EXAMPLE 1 TPSS : A block-copolymer of 50:50 PSSD:PSSB
• Part 1 The preparation of the PSSD homoblock.
• PSSD is made by using DHDPS and CSB as monomers.
• a 4 -necked, 3 -litre glass flask was equipped with an overhead stirrer attached to a stainless steel paddle through its center neck. Through one of its side necks, a Cloisonne adapter was attached. The other neck of the Cloisonne adapter was attached to a Dean-Stark trap and a water-cooled condenser.
• a thermocouple thermometer was inserted through another of the side necks. A nitrogen gas inlet was inserted through the other side neck. The flask was placed in an oil bath, which was connected to a temperature controller.
• the toluene acts as an azeotropic solvent.
• the temperature of the reactants was slowly increased to 220 0 C over 5 hours and the stirring speed was set to 400 rpm.
• the water formed due to the reaction of Na2CO3 with DHDPS was distilled over as an azeotrope with toluene and collected in the Dean-Stark trap.
• the toluene was then returned to the reaction mixture once it had been separated from the water. Once the water had been completely removed, toluene addition back to the reaction vessel was stopped. The toluene was then removed completely 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 0 C and when the viscosity started to increase the stirring speed was raised to 500 rpm. At the required Mn of 17,000, MW of about 20,000 and MWD 1.19, the reaction was stopped by reducing temperature to ⁇ 130C.
• the relatively high molar ratio of CSB to DHDPS gave PSSD of a relatively low molecular weight and with predominantly end groups of -Ph-Cl Part 2 : The preparation of the PSSB homoblock.
• PSSB is made by using Biphenol and CSB as monomer Sulfolane (4410 gms, 3500 ml/mole) and toluene (1000 ml/mole) were placed in the flask, through which nitrogen gas was bubbled continuously, and heated to 45°C.
• 4,4' Bis [(4-Chlorophenyl) Sulfonyl] Biphenyl (CSB) (503 gms) and Biphenol (188 gms) were added to the flask and Biphenol : CSB being in a molar ratio of 1.01 : 1.00, and the reaction mixture was stirred for 30 minutes.
• Anhydrous sodium carbonate (123 gms) was added.
• the toluene acts as an azeotropic solvent.
• the temperature of the reactants was slowly increased to 220 0 C over 5 hours and the stirring speed was set to 400 rpm.
• the water formed due to the reaction was distilled over as an azeotrope with toluene and collected in the Dean-Stark trap.
• the toluene was then returned to the reaction mixture once it had been separated from the water. Once the water had been completely removed, toluene addition back to the reaction vessel was stopped.
• the toluene was then removed completely from the reaction mixture as the temperature of the reactants increased.
• the desired temperature was reached after 4 hours.
• the reaction temperature was then maintained at 220 0 C and when the viscosity started to increase the stirring speed was raised to 500 rpm.
• reaction mass was quickly cooled to stop further polymerization.
• the relatively high molar ratio of Biphenol to CSB gave PSSB of a relatively low molecular weight and with predominantly end groups of -Ph-OH.
• Part 3 The preparation of the block copolymer.
• the reaction mixtures of Part 1 and Part 2 were mixed in equal proportions by weight and the block polymerization was conducted at 220 0 C. After the required MW was achieved, as shown by GPC, the reaction mixture was quenched with Sulfolane (504 gms, 400 ml/mole) and its temperature reduced to 210 0 C. Methyl Chloride gas was then bubbled through the reaction mixture for 3 hrs to ensure complete end capping. The reaction mixture was then diluted with Sulfolane (400 ml/mole) for a second time. The polymer solution was filtered through a 15 micron filter in a pressure filter funnel using 2 kg/cm 2 pressure of nitrogen to remove salts.
• the block copolymer was finally recovered by slowly adding the salt-free polymer solution to de-ionized water (13 ml/gm of polymer) under high-speed agitation. The precipitated polymer was then recovered by filtration. The precipitated polymer was ground and refiuxed three times with de-ionized water at 90 0 C to completely remove all salts and Sulfolane. The precipitated polymer was then filtered and dried in an oven at 140 0 C until the moisture content as determined by Karl Fischer titration was ⁇ 0.5 %.
• the block copolymer powder was then mixed with 0.25 % heat stabilizer and granulated using a twin screw extruder.
• the Tg and the specific gravity of PSSD are 259°C and 1.29 respectively, while those of high molecular weight PSSB itself are 270 0 C and 1.320.
• the transparent granules of block copolymer (TPSS) showed a DSC Tg of 266°C and a specific gravity of 1.31. The transparency of the granules, the single GPC peak, the intermediate
• Part 1 The preparation of the PSSD homoblock : PSSD is made by using DHDPS and CSB as monomer An experimental set up similar to that described in Example 1 was used. Sulfolane (1687 gms, 1500 ml/mole) and toluene (700 ml/mole) were placed in the flask, through which nitrogen gas was bubbled continuously, and heated to 45°C.
• the rest of the procedure is the same as that described in Part 1 of Example 1.
• the homoblock obtained had GPC molecular weights of Mn 17,000, an Mw of23,000 and an MWD of 1.36.
• PSSB The preparation of the PSSB homoblock.
• PSSB is made by using Biphenol and CSB as monomer.
• Sulfolane (437 gms, 3500 ml/mole) and toluene (1000 ml/mole) were placed in the flask, through which nitrogen gas was bubbled continuously, and heated to 45°C.
• the rest of the procedure is the same as that described in Part 2 of Example 1.
• the homoblock obtained had GPC molecular weights of Mn 10,000, an Mw of 12,000 and an MWD of 1.20.
• Part 3 The preparation of the block copolymer.
• the reaction mixtures of Part 1(9 parts) and Part 2 (1 parts) were mixed together and the block polymerization was conducted at 220 0 C. After the required MW was achieved, as shown by GPC, the reaction mixture was quenched with Sulfolane (504 gms, 400 ml/mole) and its temperature reduced to 210 0 C. Methyl Chloride gas was then bubbled through the reaction mixture for 3 hrs to ensure complete end capping. The reaction mixture was then diluted with Sulfolane (400 ml/mole) for a second time. The polymer solution was filtered through a 15 micron filter in a pressure filter funnel using 2 kg/cm 2 of nitrogen to remove any salts.
• the block copolymer was finally recovered by slowly adding the salt-free polymer solution to de-ionized water (13 ml/gm of polymer) under high-speed agitation. The precipitated polymer was then recovered by filtration. The precipitated polymer was ground and refiuxed three times with de-ionized water at 90 0 C to completely remove all salts and Sulfolane. The precipitated polymer was then filtered and dried in an oven at 140 0 C until the moisture content as determined by Karl Fischer titration was ⁇ 0.5 %.
• the block copolymer produced had a significantly higher molecular weight than the two homoblocks used as monomer units, indicating the preparation of a block copolymer.
• the block copolymer powder was then mixed with 0.25 % heat stabilizer and granulated using a twin screw extruder.
• the Tg and the specific gravity of PSSD are 260 0 C and 1.29 respectively, while those of PSSB are 270 0 C and 1.330.
• the transparent granules of block copolymer showed a DSC Tg of 266°C and a specific gravity of 1.34.
• Part 1 The preparation of the PSSD homoblock PSSD is made by using DHDPS and CSB as monomer
• the rest of the procedure is the same as that described in Part 1 of Example 1.
• the homoblock obtained had GPC molecular weights of Mn 20,000, an Mw of 22,000 and an MWD of 1.10.
• Part 2 The preparation of the PSS homoblock.
• PSS is made by using HSB and CSB as monomer
• the rest of the procedure is the same as that described in Part 2 of Example 1.
• the homoblock obtained had GPC molecular weights of Mn 29,000, an Mw of 38,000 and an MWD of 1.31.
• Part 3 The preparation of the block copolymer.
• the reaction mixtures of Part 1 and Part 2 were mixed in equal proportions by weight and the block polymerization was conducted at 230 0 C. After the required MW was achieved, as shown by GPC, the reaction mixture was quenched with Sulfolane (504 gms, 400 ml/mole) and its temperature reduced to 210 0 C. Methyl Chloride gas was then bubbled through the reaction mixture for 3 hrs to ensure complete end capping. The reaction mixture was then diluted with Sulfolane (400 ml/mole) for a second time. The polymer solution was filtered through a 15 micron filter in a pressure filter funnel using 2 kg/cm 2 of nitrogen to remove any salts.
• the block copolymer was finally recovered by slowly adding the salt-free polymer solution to de-ionized water (13 ml/gm of polymer) under high-speed agitation. The precipitated polymer was then recovered by filtration. The precipitated polymer was ground and refluxed three times with de-ionized water at 90 0 C to completely remove all salts and Sulfolane. The precipitated polymer was then filtered and dried in an oven at 140 0 C until the moisture content as determined by Karl Fischer titration was ⁇ 0.5 %. GPC analysis of the block copolymer showed an Mn of 89,000, an Mw of 122,000 and an MWD of 1.37 based on the polystyrene standards.
• the copolymer produced had a significantly higher molecular weight than the two homoblocks used as monomer units, indicating the preparation of a block copolymer.
• the block copolymer powder was then mixed with 0.25 % heat stabilizer and granulated using a twin screw extruder.
• the Tg and the specific gravity of PSSD are 259°C and 1.29 respectively, while those of PSS are 270 0 C and 1.32.
• the transparent granules of block copolymer (DPSS) showed a DSC Tg of 267°C and a specific gravity of 1.31.
• Part - 1 The preparation of the PES homoblock
• the toluene acts as an azeotropic solvent.
• the temperature of the reactants was slowly increased to 236°C over 6 hrs and the stirring speed was set to 400 rpm.
• the water formed due to the reaction OfNa 2 CO 3 with DHDPS was distilled over as an azeotrope with toluene and collected in the Dean-stark trap.
• the toluene was then returned to the reaction mixture once it had been separated from the water. Once the water had been completely removed, toluene addition back to the reaction vessel was stopped.
• the toluene was then removed completely from the reaction mixture as the temperature of the reactants increased.
• the desired temperature was reached after 6 hours.
• the reaction temperature was then maintained at
• the temperature of the reactants was slowly increased to 236°C over 6 hrs and the stirring speed was set to 400 rpm.
• the water formed due to the reaction of N a 2CC>3 with TMDHDPS was distilled over as an azeotrope with toluene and collected in the Dean-stark trap.
• the toluene was then returned to the reaction mixture once the water had been completely removed, toluene addition back to the reaction vessel was stopped.
• the toluene was then removed completely from the reaction mixture as the temperature of the reactants increased.
• the desired temperature was reached after 6 hrs. Once the water had been completely removed the reaction temperature was then maintained at 236°C and when the viscosity started to increase the stirring speed was raised to 500 rpm.
• the reaction mixtures of Part 1 and Part 2 were mixed in equal proportions by weight and the block polymerization was conducted at 236°C. After the required MW was achieved, as shown by GPC, the reaction mixture was quenched with Sulfolane (250 gms, 200 ml/mole) and its temperature reduced to 220 0 C. Methyl Chloride gas was then bubbled through the reaction mixture for 3 hrs to ensure complete end capping. The reaction mixture was then diluted with Sulfolane (200 ml/mole) for a second time. The polymer solution was filtered through a 15 micron filter in a pressure filter funnel using 2 kg/cm 2 of nitrogen to remove any salts.
• Sulfolane 250 gms, 200 ml/mole
• Methyl Chloride gas was then bubbled through the reaction mixture for 3 hrs to ensure complete end capping.
• the reaction mixture was then diluted with Sulfolane (200 ml/mole) for a second time.
• the block copolymer was finally recovered by slowly adding the salt-free polymer solution to de-ionized water (13 ml/gm of polymer) under high-speed agitation. The precipitated polymer was then recovered by filtration. The precipitated polymer was ground and refluxed three times with de-ionized water at 90 0 C to completely remove all salts and Sulfolane. The precipitated polymer was then filtered and dried in an oven at 140 0 C until the moisture content as determined by Karl Fischer titration was ⁇ 0.5 %.
• the block copolymer produced had a significantly higher molecular weight than the two homoblocks used as monomer units, indicating the preparation of a block copolymer.
• the block copolymer powder was then mixed with 0.25 % heat stabilizer and granulated using a twin screw extruder.
• the Tg and the specific gravity of PES are 225°C and 1.37 respectively, whilst those of TPES are 271 0 C and 1.33.
• the transparent granules of block copolymer showed a DSC Tg of 267°C and a specific gravity of 132.
• Part - 1 The preparation of the PES homoblock
• Example 2 An experimental set up similar to that described in Example 1 was used. Sulfolane (480 gms, 1000 ml/m), and toluene ( 344 gms, 1000 ml/mole) were placed in the flask , through which nitrogen gas was bubbled continuously, and heated to 40 0 C. Dihydroxy diphenylsulfone (DHDPS) (100.5 gms) ,4,4 ' Dichlorodiphenyl sulfone (DCDPS) (114.8 gms) were added to the flask. The DCDPS and DHDPS being in a molar ratio of 1.00:1.005 and the reactants were stirred for 30 minutes. Anhydrous sodium carbonate (50 gms) was added. A nitrogen atmosphere was maintained in the flask by purging. The toluene acts as an azeotropic solvent.
• DHDPS Dihydroxy diphenylsulfone
• DCDPS Dichlorodiphenyl sulf
• the rest of the procedure is the same as that described in Part 2 of Example 4.
• the homoblock obtained had GPC molecular weights of Mn 20,000, an Mw of 22,000 and an MWD of 1.10.
• Part 3 The preparation of the block copolymer.
• the reaction mixtures of Part 1 and Part 2 were mixed in equal proportions by weight and the block polymerization was conducted at 236°C. After the required MW was achieved, as shown by GPC, the reaction mixture was quenched with Sulfolane (250 gms, 200 ml/mole) and its temperature reduced to 220 0 C. Methyl Chloride gas was then bubbled through the reaction mixture for 3 hrs to ensure complete end capping. The reaction mixture was then diluted with Sulfolane (200 ml/mole) for a second time. The polymer solution was filtered through a 15 micron filter in a pressure filter funnel using 2 kg/cm 2 of nitrogen to remove any salts.
• Sulfolane 250 gms, 200 ml/mole
• Methyl Chloride gas was then bubbled through the reaction mixture for 3 hrs to ensure complete end capping.
• the reaction mixture was then diluted with Sulfolane (200 ml/mole) for a second time.
• the block copolymer was finally recovered by slowly adding the salt-free polymer solution to de-ionized water (13 ml/gm of polymer) under high-speed agitation. The precipitated polymer was then recovered by filtration. The precipitated polymer was ground and refiuxed three times with de-ionized water at 90 0 C to completely remove all salts and
• the precipitated polymer was then filtered and dried in an oven at 140 0 C until the moisture content as determined by Karl Fischer titration was ⁇ 0.5 %.
• the block copolymer produced had a significantly higher molecular weight than the two homoblocks used as monomer units, indicating the preparation of a block copolymer.
• the block copolymer powder was then mixed with 0.25 % heat stabilizer and granulated using a twin screw extruder.
• the Tg and the specific gravity of PES are 225°C and 1.37 respectively, whilst those of TPES are 271 0 C and 1.33.
• the transparent granules of block copolymer showed a DSC Tg of 258°C and a specific gravity of 132.
• TMPES A block -copolymer of 60:40 PES:TPES
• Part - 1 The preparation of the PES homoblock
• Example 4 The homoblock obtained had a GPC molecular weight of Mn 25,000, an Mw of 28,000 and an MWD of 1.12.
• Part -2 The preparation of the TPES homoblock
• the rest of the procedure is the same as that described in Part 2 of Example 4.
• the homoblock obtained had a GPC molecular weight of Mn 18,000, an Mw of 20,000 and an MWD of 1.10.
• Part 3 The preparation of the block copolymer.
• the reaction mixtures of Part 1 and Part 2 were mixed in equal proportions by weight and the block polymerization was conducted at 236°C. After the required MW was achieved, as shown by GPC, the reaction mixture was quenched with Sulfolane (250 gms, 200 ml/mole) and its temperature reduced to 220 0 C. Methyl Chloride gas was then bubbled through the reaction mixture for 3 hrs to ensure complete end capping. The reaction mixture was then diluted with Sulfolane (200 ml/mole) for a second time. The polymer solution was filtered through a 15 micron filter in a pressure filter funnel using 2 kg/cm 2 of nitrogen to remove any salts.
• the block copolymer was finally recovered by slowly adding the salt-free polymer solution to de-ionized water (13 ml/gm of polymer) under high-speed agitation. The precipitated polymer was then recovered by filtration. The precipitated polymer was ground and refiuxed three times with de-ionized water at 90 0 C to completely remove all salts and Sulfolane. The precipitated polymer was then filtered and dried in an oven at 140 0 C until the moisture content as determined by Karl Fischer titration was ⁇ 0.5 %. GPC analysis of the block copolymer showed an Mn of 85,700, an Mw of
• the copolymer produced had a significantly higher molecular weight than the two homoblocks used as monomer units, indicating the preparation of a block copolymer.
• the block copolymer powder was then mixed with 0.25 % heat stabilizer and granulated using a twin screw extruder.
• the Tg and the specific gravity of PES are 225°C and 1.37 respectively, whilst those of TPES are 271°C and 1.33.
• the transparent granules of block copolymer showed a DSC Tg of 247°C and a specific gravity of 1.32.
• Part 1 The preparation of the PSSD homoblock
• PSSD is made by using DHDPS and CSB as monomers.
• TMPSS is made by using TMDHDPS and CSB as monomer
• the rest of the procedure is the same as that described in Part 2 of Example 1.
• the homoblock obtained had GPC molecular weights of Mn 29,000, an Mw of 38,000 and an MWD of 1.31.
• Part 3 The preparation of the block copolymer.
• the reaction mixtures of Part 1 and Part 2 were mixed in equal proportions by weight and the block polymerization was conducted at 230 0 C. After the required MW was achieved, as shown by GPC, the reaction mixture was quenched with Sulfolane (504 gms, 400 ml/mole) and its temperature reduced to 210 0 C. Methyl Chloride gas was then bubbled through the reaction mixture for 3 hrs to ensure complete end capping. The reaction mixture was then diluted with Sulfolane (400 ml/mole) for a second time. The polymer solution was filtered through a 15 micron filter in a pressure filter funnel using 2 kg/cm 2 of nitrogen to remove any salts.
• the block copolymer was finally recovered by slowly adding the salt-free polymer solution to de-ionized water (13 ml/gm of polymer) under high-speed agitation. The precipitated polymer was then recovered by filtration. The precipitated polymer was ground and refluxed three times with de-ionized water at 90 0 C to completely remove all salts and
• the precipitated polymer was then filtered and dried in an oven at 140 0 C until the moisture content as determined by Karl Fischer titration was ⁇ 0.5 %.
• the block copolymer produced had a significantly higher molecular weight than the two homoblocks used as monomer units, indicating the preparation of a block copolymer.
• the block copolymer powder was then mixed with 0.25 % heat stabilizer and granulated using a twin screw extruder.
• the Tg and the specific gravity of PSSD are 259°C and 1.29 respectively, while those of TMPSS are 268°C and 1.31.
• the transparent granules of block copolymer (TMDPSS) showed a DSC Tg of 264°C and a specific gravity of 1.31.
• TMBPSS TMPSS
• Part 1 The preparation of the PSSB homoblock :
• PSSB is made by using Biphenol and CSB as monomer
• Example 1 The homoblock obtained had GPC molecular weights of Mn 19,000, an Mw of 23,000 and an MWD of 1.21.
• Part 2 The preparation of the TMPSS homoblock.
• TMPSS is made by using TMDHDPS and CSB as monomer Sulfolane (4410 gms, 3500 ml/mole) and toluene (1000 ml/mole) were placed in the flask, through which nitrogen gas was bubbled continuously, and heated to 45°C.
• 4,4' Bis [(4-Chlorophenyl) Sulfonyl] Biphenyl (CSB) (503 gms) and Tetramehtyl dihydroxydiphenyl Sulfone (309 gms TMDHDPS) were added to the flask and TMDHDPS : CSB being in a molar ratio of 1.01 : 1.00, and the reaction mixture was stirred for 30 minutes.
• Anhydrous sodium carbonate (123 gms) was added.
• the toluene acts as an azeotropic solvent.
• the rest of the procedure is the same as that described in Part 2 of Example 1.
• the homoblock obtained had GPC molecular weights of Mn 23,000, an Mw of 26,000 and an MWD of 1.11.
• Part 3 The preparation of the block copolymer.
• the reaction mixtures of Part 1 and Part 2 were mixed in equal proportions by weight and the block polymerization was conducted at 230 0 C. After the required MW was achieved, as shown by GPC, the reaction mixture was quenched with Sulfolane(504 gms, 400 ml/mole) and its temperature reduced to 210 0 C. Methyl Chloride gas was then bubbled through the reaction mixture for 3 hrs to ensure complete end capping. The reaction mixture was then diluted with Sulfolane (400 ml/mole) for a second time. The polymer solution was filtered through a 15 micron filter in a pressure filter funnel using 2 kg/cm 2 of nitrogen to remove any salts.
• the block copolymer was finally recovered by slowly adding the salt-free polymer solution to de-ionized water (13 ml/gm of polymer) under high-speed agitation. The precipitated polymer was then recovered by filtration. The precipitated polymer was ground and refluxed three times with de-ionized water at 90 0 C to completely remove all salts and Sulfolane. The precipitated polymer was then filtered and dried in an oven at 140 0 C until the moisture content as determined by Karl Fischer titration was ⁇ 0.5 %.
• the block copolymer powder was then mixed with 0.25 % heat stabilizer and granulated using a twin screw extruder.
• the Tg and the specific gravity of PSSB are 270 0 C and 1.33 respectively, while those of TMPSS are 268°C and 1.31.
• Part 1 The preparation of the PPSU homoblock : PPSU is made by using Biphenol and DCDPS as monomer An experimental set up similar to that described in Example 1 was used. Sulfolane (4410 gms, 3500 ml/mole) and toluene (1000 ml/mole) were placed in the flask, through which nitrogen gas was bubbled continuously, and heated to 45°C. 4,4' Dichloro diphenylsulfone (DCDPS) (298 gms) and Biphenol (186 gms) were added to the flask and DCDPS : DHDPS being in a molar ratio of 1.04: 1.00 and the reaction mixture was stirred for 30 minutes. Anhydrous sodium carbonate (123 gms) was added. A nitrogen atmosphere was maintained in the flask by purging. The toluene acts as an azeotropic solvent.
• DCDPS 4,4' Dichloro diphenylsulfone
• the rest of the procedure is the same as that described in Part 1 of Example 1.
• the homoblock obtained had GPC molecular weights of Mn 23,000, an Mw of 29,000 and an MWD of 1.26.
• Part 2 The preparation of the TMPSS homoblock.
• TMPSS is made by using TMDHDPS and CSB as monomer Sulfolane (4410 gms, 3500 ml/mole) and toluene (1000 ml/mole) were placed in the flask, through which nitrogen gas was bubbled continuously, and heated to 45°C.
• 4,4' Bis [(4-Chlorophenyl) Sulfonyl] Biphenyl (CSB) (503 gms) and Tetramehtyl dihydroxydiphenyl Sulfone (309 gms TMDHDPS) were added to the flask and TMDHDPS : CSB being in a molar ratio of 1.01 : 1.00, and the reaction mixture was stirred for 30 minutes.
• Anhydrous sodium carbonate (123 gms) was added.
• the toluene acts as an azeotropic solvent.
• the rest of the procedure is the same as that described in Part 2 of Example 1.
• the homoblock obtained had GPC molecular weights of Mn 25,000, an Mw of 35,000 and an MWD of 1.40.
• Part 3 The preparation of the block copolymer.
• the reaction mixtures of Part 1 and Part 2 were mixed in equal proportions by weight and the block polymerization was conducted at 230 0 C. After the required MW was achieved, as shown by GPC, the reaction mixture was quenched with Sulfolane (504 gms, 400 ml/mole) and its temperature reduced to 210 0 C. Methyl Chloride gas was then bubbled through the reaction mixture for 3 hrs to ensure complete end capping. The reaction mixture was then diluted with Sulfolane (400 ml/mole) for a second time. The polymer solution was filtered through a 15 micron filter in a pressure filter funnel using 2 kg/cm 2 of nitrogen to remove any salts.
• the block copolymer was finally recovered by slowly adding the salt-free polymer solution to de-ionized water (13 ml/gm of polymer) under high-speed agitation. The precipitated polymer was then recovered by filtration. The precipitated polymer was ground and refiuxed three times with de-ionized water at 90 0 C to completely remove all salts and Sulfolane. The precipitated polymer was then filtered and dried in an oven at 140 0 C until the moisture content as determined by Karl Fischer titration was ⁇ 0.5 %.
• the block copolymer produced had a significantly higher molecular weight than the two homoblocks used as monomer units, indicating the preparation of a block copolymer.
• the block copolymer powder was then mixed with 0.25 % heat stabilizer and granulated using a twin screw extruder.
• the Tg and the specific gravity of PPSU are 220 0 C and 1.29 respectively, while those of TMPSS are 268°C and 1.31.
• Part 1 The preparation of the PES homoblock
• Example 1 The homoblock obtained had GPC molecular weights of Mn 25,000, an Mw of 29,000 and an MWD of 1.16.
• TMPSS The preparation of the TMPSS homoblock.
• TMPSS is made by using TMDHDPS and CSB as monomer Sulfolane (4410 gms, 3500 ml/mole) and toluene (1000 ml/mole) were placed in the flask, through which nitrogen gas was bubbled continuously, and heated to 45°C.
• Part 3 The preparation of the block copolymer.
• the reaction mixtures of Part 1 and Part 2 were mixed in equal proportions by weight and the block polymerization was conducted at 230 0 C. After the required MW was achieved, as shown by GPC, the reaction mixture was quenched with Sulfolane (504 gms, 400 ml/mole) and its temperature reduced to 210 0 C. Methyl Chloride gas was then bubbled through the reaction mixture for 3 hrs to ensure complete end capping. The reaction mixture was then diluted with Sulfolane (400 ml/mole) for a second time. The polymer solution was filtered through a 15 micron filter in a pressure filter funnel using 2 kg/cm 2 of nitrogen to remove any salts.
• the block copolymer was finally recovered by slowly adding the salt-free polymer solution to de-ionized water (13 ml/gm of polymer) under high-speed agitation. The precipitated polymer was then recovered by filtration. The precipitated polymer was ground and refiuxed three times with de-ionized water at 90 0 C to completely remove all salts and Sulfolane. The precipitated polymer was then filtered and dried in an oven at 140 0 C until the moisture content as determined by Karl Fischer titration was ⁇ 0.5 %. GPC analysis of the block copolymer showed an Mn of 85,000, an Mw of 115,000 and an MWD of 1.35 based on the polystyrene standards.
• the copolymer produced had a significantly higher molecular weight than the two homoblocks used as monomer units, indicating the preparation of a block copolymer.
• the block copolymer powder was then mixed with 0.25 % heat stabilizer and granulated using a twin screw extruder.
• the Tg and the specific gravity of PES are 225°C and 1.29 respectively, while those of TMPSS are 268°C and 1.31.
• the transparent granules of block copolymer showed (TMDPES) a DSC Tg of 255°C and a specific gravity of 1.30.
• Part 1 The preparation of the PSSB homoblock
• PSSB is made by using Biphenol and CSB as monomer An experimental set up similar to that described in Example 1 was used.
• the rest of the procedure is the same as that described in Part 1 of Example 1.
• the homoblock obtained had GPC molecular weights of Mn 19,000, an Mw of23,000 and an MWD of 1.21.
• Part 2 The preparation of the PESK homoblock.
• PESK is made by using DCB and DHDPS as monomer
• the rest of the procedure is the same as that described in Part 2 of Example 1.
• the homoblock obtained had GPC molecular weights of Mn 25,000, an Mw of 35,000 and an MWD of 1.40.
• Part 3 The preparation of the block copolymer.
• the reaction mixtures of Part 1 and Part 2 were mixed in equal proportions by weight and the block polymerization was conducted at 230 0 C. After the required MW was achieved, as shown by GPC, the reaction mixture was quenched with Sulfolane (504 gms, 400 ml/mole) and its temperature reduced to 210 0 C. Methyl Chloride gas was then bubbled through the reaction mixture for 3 hrs to ensure complete end capping. The reaction mixture was then diluted with Sulfolane (400 ml/mole) for a second time. The polymer solution was filtered through a 15 micron filter in a pressure filter funnel using 2 kg/cm 2 of nitrogen to remove any salts.
• the block copolymer was finally recovered by slowly adding the salt-free polymer solution to de-ionized water (13 ml/gm of polymer) under high-speed agitation. The precipitated polymer was then recovered by filtration. The precipitated polymer was ground and refiuxed three times with de-ionized water at 90 0 C to completely remove all salts and
• the precipitated polymer was then filtered and dried in an oven at 140 0 C until the moisture content as determined by Karl Fischer titration was ⁇ 0.5 %.
• the block copolymer produced had a significantly higher molecular weight than the two homoblocks used as monomer units, indicating the preparation of a block copolymer.
• the block copolymer powder was then mixed with 0.25 % heat stabilizer and granulated using a twin screw extruder.
• the Tg and the specific gravity of PSSB are 270 0 C and 1.33 respectively, while those of PESK are
• TMDPSU A block -copolymer of 50:50 PSU:TMPSS
• Part 1 The preparation of the PSU homoblock PSU is made by using Bisphenol A and DCDPS as monomer An experimental set up similar to that described in Example 1 was used. Sulfolane (4410 gms, 3500 ml/mole) and toluene (1000 ml/mole) were placed in the flask, through which nitrogen gas was bubbled continuously, and heated to 45°C. 4,4' Dichloro diphenylsulfone (DCDPS) (298 gms) and Bisphenol A (250 gms) were added to the flask and DCDPS : Bisphenol A being in a molar ratio of 1.04: 1.00 and the reaction mixture was stirred for 30 minutes. Anhydrous Potassium Carbonate (154 gms) was added. A nitrogen atmosphere was maintained in the flask by purging. The toluene acts as an azeotropic solvent.
• Sulfolane 4410 gms, 3500 ml/mole
• Part 2 The preparation of the TMPSS homoblock.
• TMPSS is made by using TMDHDPS and CSB as monomer Sulfolane (4410 gms, 3500 ml/mole) and toluene (1000 ml/mole) were placed in the flask, through which nitrogen gas was bubbled continuously, and heated to 45°C.
• 4,4' Bis [(4-Chlorophenyl) Sulfonyl] Biphenyl (CSB) (503 gms) and Tetramehtyl dihydroxydiphenyl SuIf one (309 gms TMDHDPS) were added to the flask and TMDHDPS : CSB being in a molar ratio of 1.01:1.00, and the reaction mixture was stirred for 30 minutes.
• Anhydrous sodium carbonate (123 gms) was added.
• the toluene acts as an azeotropic solvent.
• the reaction mixtures of Part 1 and Part 2 were mixed in equal proportions by weight and the block polymerization was conducted at 220 0 C. After the required MW was achieved, as shown by GPC, the reaction mixture was quenched with Sulfolane (504 gms, 400 ml/mole) and its temperature reduced to 200 0 C. Methyl Chloride gas was then bubbled through the reaction mixture for 3 hrs to ensure complete end capping. The reaction mixture was then diluted with Sulfolane (400 ml/mole) for a second time. The polymer solution was filtered through a 15 micron filter in a pressure filter funnel using 2 kg/cm 2 of nitrogen to remove any salts.
• the block copolymer was finally recovered by slowly adding the salt-free polymer solution to de-ionized water (13 ml/gm of polymer) under high-speed agitation. The precipitated polymer was then recovered by filtration. The precipitated polymer was ground and refiuxed three times with de-ionized water at 90 0 C to completely remove all salts and Sulfolane. The precipitated polymer was then filtered and dried in an oven at 140 0 C until the moisture content as determined by Karl Fischer titration was ⁇ 0.5 %.
• the block copolymer produced had a significantly higher molecular weight than the two homoblocks used as monomer units, indicating the preparation of a block copolymer.
• the block copolymer powder was then mixed with 0.25 % heat stabilizer and granulated using a twin screw extruder.
• the Tg and the specific gravity of PSU are 190 0 C and 1.29 respectively, while those of TMPSS are 268°C and 1.31.
• the transparent granules of block copolymer showed
• Various homoblocks can be prepared using one or more dichloro compounds and one or more dihydroxy compounds, some of which are listed below :
• AROMATIC DIHALO COMPOUNDS :
• Dichloro diphenyl sulfone (DCDPS), 4,4' Bis (4 - chlorophenyl sulfonyl) biphenyl (CSB), Dichloro Benzophenone, Dichloro diphenyl ether, Dichloro biphenyl, Dichloro diphenyl methylene, Di Methyl dichloro diphenyl sulfone, tetra methyl dichloro diphenyl sulfone, dihalodiphenyl biphenyl, dihalo diphenoxy biphenyl, dihalo diphenyl biphenyl diether (disulfone or diketo) (C1-C6H4-C6H4-X-C6H4-C6H4-X-C6H4-C6H4-CL), C1-C6H4-X-C6H4-C6H4-Y-C6H4-C6H4-C1-,
• Y -O-, -SO2-, -CO-, -CH2-, and -Cl implies any halogen.

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