CN100345889C - Polysulfone and polyethersulfone copolymer preparation method - Google Patents
Polysulfone and polyethersulfone copolymer preparation method Download PDFInfo
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- CN100345889C CN100345889C CNB2005100172598A CN200510017259A CN100345889C CN 100345889 C CN100345889 C CN 100345889C CN B2005100172598 A CNB2005100172598 A CN B2005100172598A CN 200510017259 A CN200510017259 A CN 200510017259A CN 100345889 C CN100345889 C CN 100345889C
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Abstract
The present invention belongs to the field of macromolecular materials, which particularly relates to a method for preparing series copolymer of polysulfone and polyethersulfone in a set of production equipment by using a ternary polymerization technology. The present invention uses a method for preparing terpolymer with different glass transition temperature by simultaneously reacting three monomers of dichlor, bisphenol-S and bisphenol-A in organic solvent. The glass transition temperature Tg of the prepared terpolymer varies from 190DEG C to 225DEG C. The terpolymer has the same or different performance with polysulfone and polyethersulfone. In addition, through regulating the excessive amount or insufficient amount of dichlor of the ternary comonomer, the present invention can prepare two products whose terminal groups are respectively chlorine terminal groups or hydroxyl terminal groups, and the two products have different usages. The present invention has the characteristics that the preparation technology is simple, and different requirements of markets for resin products can be satisfied.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of method of utilizing the terpolymer technology in a cover production unit, to prepare serial polysulfones and polyethersulfone copolymer.
Background technology
Polysulfones is two kinds of different special engineering plastics with polyethersulfone, have many corresponding patents both at home and abroad about its technology of preparing, but these patents all is homopolymer patent separately.Be monomer promptly, obtain polysulfones by the following formula reaction, that is: with two chlorine and bisphenol-A
And be monomer with two chlorine and bis-phenol-S, obtain polyethersulfone by the following formula reaction, that is:
Study in the process of polyethersulfone at us, can be in a cover production unit if method for ternary polymerization is adopted in discovery, only, can not only obtain the performance resin suitable, and can obtain the performance many kind multipolymer different with both with both by the ratio allotment of three component monomers.
Summary of the invention
The purpose of this invention is to provide a kind of method, it is in ternary copolymerization system, ratio allotment by the two chlorine of three kinds of components, bisphenol-A, bis-phenol-S, thereby prepare and polysulfones and the suitable resin of polyethersulfone performance (Tg), can also further prepare polysulfones and the polyethersulfone copolymer product of performance (Tg) between polysulfones and polyethersulfone.
When the consumption of two chlorine when being excessive, obtain the polysulfones and the polyethersulfone copolymer resin of chlorine end group, when the consumption of two chlorine during, obtain the polysulfones and the polyethersulfone copolymer resin of terminal hydroxy group for the amount of owing.
The polysulfones of chlorine end group of the present invention and polyethersulfone copolymer resin reaction formula are as follows:
X is adjustable arbitrarily between 0.01～0.99 in the formula.
The preparation method of the polysulfones of chlorine end group and polyethersulfone copolymer resin, the steps include: in the ternary copolymerization system reaction unit, add organic solvent (dimethyl sulfone, tetramethylene sulfone or sulfobenzide), add two chlorine then in turn, bis-phenol-S, and bisphenol-A, the molar weight of two chlorine is with respect to bis-phenol-S and bisphenol-A integral molar quantity excessive 1%, bis-phenol-S accounts for 0.01～0.99 of bis-phenol integral molar quantity, solid content in the solvent is (two chlorine, the quality of bis-phenol-S and bisphenol-A and/pair chlorine, bis-phenol-S, the quality of bisphenol-A and organic solvent and) 25～40%, adding with the organic solvent mass ratio is to stir behind 10～20% the dimethylbenzene again, heating, it all being dissolved and add concentration expressed in percentage by weight when treating that temperature rises to 80 ℃～90 ℃ is 30～35% alkaline solution, be heated to the system azeotropic, continue again to reflux 10～60 minutes, after the clarification of upper strata dimethylbenzene layer, begin to steam dimethylbenzene, when continuing intensification degree to 200～250 ℃ again, maintenance constant temperature stopped reaction after 6～10 hours, with the polymerization mucus cooling that obtains, pulverize, add water boil, till removing chlorion, powder after will making with extra care is again dried in baking oven, promptly obtains the polysulfones and the polyethersulfone copolymer resin of chlorine end group of the present invention.
The preparation method of terminal hydroxy group polysulfones and polyethersulfone copolymer, the steps include: in the ternary copolymerization system reaction unit, add organic solvent, add two chlorine then in turn, bis-phenol-S and bisphenol-A, the molar weight of two chlorine is with respect to bis-phenol-S and the bisphenol-A integral molar quantity amount of owing 1%, bis-phenol-S accounts for 0.01～0.99 of bis-phenol integral molar quantity, solid content in the solvent is 25～40%, adding with the organic solvent mass ratio is to stir behind 10～20% the dimethylbenzene again, heating, it all being dissolved and add concentration expressed in percentage by weight when treating that temperature rises to 80 ℃～90 ℃ is 30～35% alkaline solution, be heated to the system azeotropic, continue again to reflux 10～60 minutes, begin to steam dimethylbenzene, when continue rising 6 temperature to 200～250 ℃ again, keep constant temperature stopped reaction after 6～10 hours, with the polymerization mucus cooling that obtains, pulverize, add water boil, till removing chlorion, the powder after will making with extra care is again dried in baking oven, promptly obtains terminal hydroxy group polysulfones of the present invention and polyethersulfone terpolymer resin.
Two chlorine are 4,4 '-dichloro diphenyl sulfone; Bis-phenol-S is 4,4 '-dihydroxy diphenylsulphone; Bisphenol-A is 2,2 '-two (4-hydroxyphenyl propane).
Description of drawings
The ratio of components of Fig. 1: bis-phenol-S and bisphenol-A is to the influence curve of multipolymer Tg;
As shown in Figure 1, wherein X-coordinate is the shared ratio of bis-phenol-S in the batching, when x＜3%, the Tg and the polysulfones of the multipolymer that obtains are suitable, that is: Tg=190 ℃ (seeing embodiment 1 for details), and when x＞97%, the Tg and the polyethersulfone of the multipolymer that obtains are suitable, that is: Tg=225 ℃ (seeing embodiment 6 for details).And when x is between 3～97%, then can obtain the terpolymer (seeing embodiment 2～5 and accompanying drawing for details) of the different Tg of Tg between, thereby finished this patent.
Embodiment
Embodiment 1:
In three mouthfuls of reaction flasks that thermometer, logical nitrogen tube, condensation water trap, agitator are housed, add 540.00g dimethyl sulfone (also can adopt tetramethylene sulfone, sulfobenzide etc.) earlier, add the two chlorine of 145.02g (0.505mol, excessive 1%) then in turn
And 1.25g (0.005mol) bis-phenol-S
113.00g (0.495mol) bisphenol-A
Adding 54g dimethylbenzene (solvent 10%) back again stirs, heating (reaction flask is put into the respective electrical hot jacket), it is all dissolved and add the alkaline solution (concentration of alkaline solution is advisable) that contains 40.0g NaOH when treating that temperature is heated to 80 ℃ between 30～35% concentration expressed in percentage by weights, system begins azeotropic when continuing more than the heat temperature raising to 100 ℃ again, there are water and dimethylbenzene to be condensed in the water trap, the upper strata refluxing xylene, lower layer of water is constantly emitted, when treating that water is recycled near theoretical amount (be in the alkaline solution the summation of moisture and NaOH and bis-phenol-S and bisphenol-A water generation reaction), upper strata dimethylbenzene begins clear, continue again to reflux 20 minutes, begin from system, to steam dimethylbenzene then, this moment, system was also risen by the indirect heating temperature thereupon, when temperature reaches 220 ℃, keep constant temperature, the beginning polymerization system viscosity constantly increases, and continues stopped reaction after 6 hours, cools off pouring in the enamel tray under the polymerization mucus high temperature.After treating abundant cooled and solidified, broken with pulverizer with pigment, and filter.The gained powder is added 1000ml water in there-necked flask, stir and boil 1 hour, and filter.Boil so repeatedly 7～8 times, until using AgNO
3Solution checks that muddiness does not take place filtrate, show that chloride ion content is qualified till.
With the 130 ℃ of oven dry 12 hours in baking oven of the powder after refining, make moisture content be lower than 0.5% and promptly obtain the copolymer resin of the chlorine end group of x=0.99 as the formula (3).Measure with DSC, its second-order transition temperature is Tg=190 ℃, and (PSU) is identical with polysulfones.
Embodiment 2:
Change the ratio of components of embodiment 1, still get the 540g dimethyl sulfone, add the two chlorine of 145.02g (0.505mol, excessive 1) then in turn, 25.0g (0.1mol) bis-phenol-S, 91.32g (0.4mol) bisphenol-A.Thereafter dimethylbenzene and the add-on of NaOH and add conditionally complete with embodiment 1, and finish reaction and carry out identical refinement treatment by same reaction conditions.Obtain shown in (3) formula the chlorine end group resin of x=0.8.The polymkeric substance that obtains records polymkeric substance with the same terms:
Tg＝196℃
Embodiment 3:
Change the ratio of components of embodiment 1, add the refining tetramethylene sulfone of 540g earlier, add the two chlorine of 145.02g (0.505mol) then in turn, 50.05g (0.2mol) bis-phenol-S, 68.49g (0.3mol) bisphenol-A, embodiment 1 reaction, refining, dry is pressed in later reinforced and reaction control fully, obtains shown in (3) formula the chlorine end group multipolymer of x=0.6.
With recording polymkeric substance with embodiment 1 same procedure and condition:
Tg＝202℃
Embodiment 4:
Change the ratio of components of embodiment 1 again, tetramethylene sulfone is constant with two chlorine dosages, add 75.05g (0.3mol) bis-phenol-S then, 45.66g (0.2mol) bisphenol-A, later reinforced and reaction control fully by embodiment 1 react, make with extra care, dry, obtain structure shown in (3) formula, the chlorine end group multipolymer of x=0.4.
Record polymkeric substance with the method identical and condition with embodiment 1:
Tg＝209℃
Embodiment 5:
Change the ratio of components of embodiment 1, tetramethylene sulfone and two chlorine dosage are constant, add 100.11g (0.4mol) bis-phenol-S then, 22.83g (0.1mol) bisphenol-A, later reinforced and reaction control fully by embodiment 1 react, make with extra care, dry, obtain structure shown in (3) formula, the chlorine end group multipolymer of x=0.2.Record polymkeric substance with the method identical and condition with embodiment 1:
Tg＝217℃
Embodiment 6:
Change the ratio of components of embodiment 1, tetramethylene sulfone is constant with two chlorine dosages, add 123.88g (0.495mol) bis-phenol-S then, 1.14g (0.005mol) bisphenol-A, later reinforced and reaction control fully by embodiment 1 react, make with extra care, dry, obtain structure shown in (3) formula, the chlorine end group multipolymer of x=0.1.Record polymkeric substance with the method identical and condition with embodiment 1:
Tg＝225℃
Its performance and polyethersulfone (PES) are suitable.
Embodiment 7:
Change the ratio of components of embodiment 6, with wherein two chlorine charging capacitys 145.02g (0.505mol by embodiment 1, excessive 1%) changes into 142.15g (0.495mol, the amount of owing 1%), other feeding quantity and reaction, refining, dry fully identical with embodiment 6, then obtain the terminal hydroxy group resin different with embodiment 1～6, its reaction formula and structure are shown in (4) formula.
Measure with identical DSC, its:
Tg＝225℃
Result by the foregoing description 1～7 adopts this patent as can be known, the control of the ratio of components when can not only be on same production line feeding intake in only by production process just can prepare the terpolymer resin of second-order transition temperature from any new texture of 190 ℃～250 ℃ of scopes by ratio of components according to the different demands in market.
Claims (5)
1, the preparation method of chlorine end group polysulfones and polyethersulfone copolymer, the steps include: in the ternary copolymerization system reaction unit, add organic solvent, add 4 in turn then, 4 '-dichloro diphenyl sulfone, 4,4 '-dihydroxy diphenylsulphone and 2,2 '-two (4-hydroxyphenyl propane), 4, the molar weight of 4 '-dichloro diphenyl sulfone is with respect to 4,4 '-dihydroxy diphenylsulphone and 2,2 '-two (4-hydroxyphenyl propane) integral molar quantity excessive 1%, 4,4 '-dihydroxy diphenylsulphone accounts for 0.01～0.99 of bis-phenol integral molar quantity, solid content in the solvent is 25～40%, adding with the organic solvent mass ratio is to stir behind 10～20% the dimethylbenzene again, heating, it all being dissolved and add concentration expressed in percentage by weight when treating that temperature rises to 80 ℃～90 ℃ is 30～35% alkaline solution, be heated to the system azeotropic, continue again to reflux 10～60 minutes, begin to steam dimethylbenzene, when continuing intensification degree to 200～250 ℃ again, maintenance constant temperature stopped reaction after 6～10 hours is with the polymerization mucus cooling that obtains, pulverize, add water boil, till removing chlorion, powder after will making with extra care is again dried in baking oven, promptly obtains chlorine end group polysulfones of the present invention and polyethersulfone terpolymer resin.
2, the preparation method of chlorine end group polysulfones as claimed in claim 1 and polyethersulfone copolymer is characterized in that: organic solvent is any in dimethyl sulfone, tetramethylene sulfone, the sulfobenzide.
3, the preparation method of chlorine end group polysulfones as claimed in claim 1 or 2 and polyethersulfone copolymer is characterized in that: the regulation and control by three kinds of monomeric ratio of components obtain any chlorine end group polysulfones and the polyethersulfone terpolymer between Tg=190 ℃ to Tg=225 ℃.
4, the preparation method of terminal hydroxy group polysulfones and polyethersulfone copolymer, the steps include: in the ternary copolymerization system reaction unit, add organic solvent, add 4 in turn then, 4 '-dichloro diphenyl sulfone, 4,4 '-dihydroxy diphenylsulphone and 2,2 '-two (4-hydroxyphenyl propane), 4, the molar weight of 4 '-dichloro diphenyl sulfone is with respect to 4,4 '-dihydroxy diphenylsulphone and 2,2 '-two (4-hydroxyphenyl propane) the integral molar quantity amount of owing 1%, 4,4 '-dihydroxy diphenylsulphone accounts for 0.01～0.99 of bis-phenol integral molar quantity, solid content in the solvent is 25～40%, adding with the organic solvent mass ratio is to stir behind 10～20% the dimethylbenzene again, heating, it all being dissolved and add concentration expressed in percentage by weight when treating that temperature rises to 80 ℃～90 ℃ is 30～35% alkaline solution, be heated to the system azeotropic, continue again to reflux 10～60 minutes, begin to steam dimethylbenzene, when continuing intensification degree to 200～250 ℃ again, maintenance constant temperature stopped reaction after 6～10 hours is with the polymerization mucus cooling that obtains, pulverize, add water boil, till removing chlorion, powder after will making with extra care is again dried in baking oven, promptly obtains terminal hydroxy group polysulfones of the present invention and polyethersulfone terpolymer resin.
5, the preparation method of terminal hydroxy group polysulfones as claimed in claim 4 and polyethersulfone copolymer is characterized in that: the regulation and control by three kinds of monomeric ratio of components obtain any terminal hydroxy group polysulfones and the polyethersulfone terpolymer between Tg=190 ℃ to Tg=225 ℃.
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| CN101704951B (en) | 2009-10-27 | 2012-01-25 | 金发科技股份有限公司 | Method for preparing terpolymer of poly-diphenyl sulphone ether and polyether sulfone |
| CN104277221A (en) * | 2014-10-08 | 2015-01-14 | 江苏林泉汽车装饰件有限公司 | Interfacial polycondensation method for preparing polyethersulfone |
| CN105504263B (en) * | 2015-12-30 | 2018-07-27 | 金发科技股份有限公司 | A kind of composition of sulfone polymer and the preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1066450A (en) * | 1992-04-10 | 1992-11-25 | 吉林大学 | Aromatic polyether-ether ketone-the contain preparation of biphenyl polyether sulfone tactic block copolymer |
| CN1145374A (en) * | 1996-01-11 | 1997-03-19 | 吉林大学 | Synthesis of polyether etheralone resin containing diphenyl structure |
| US6228970B1 (en) * | 1998-09-25 | 2001-05-08 | Bp Amoco Corporation | Poly (biphenyl ether sulfone) |
| JP2004263154A (en) * | 2003-01-10 | 2004-09-24 | Sumitomo Chem Co Ltd | Poly (biphenyl ether sulfone) and its manufacturing method |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1066450A (en) * | 1992-04-10 | 1992-11-25 | 吉林大学 | Aromatic polyether-ether ketone-the contain preparation of biphenyl polyether sulfone tactic block copolymer |
| CN1145374A (en) * | 1996-01-11 | 1997-03-19 | 吉林大学 | Synthesis of polyether etheralone resin containing diphenyl structure |
| US6228970B1 (en) * | 1998-09-25 | 2001-05-08 | Bp Amoco Corporation | Poly (biphenyl ether sulfone) |
| JP2004263154A (en) * | 2003-01-10 | 2004-09-24 | Sumitomo Chem Co Ltd | Poly (biphenyl ether sulfone) and its manufacturing method |
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