[19] State Intellectual Property Office of People’s Republic of China
`
`[51]Int. Cl7.
`C08G 75/20
`B29C 47/38
`D01F 6/76
`
`
`[12] Specification of Invention Patent Application
`[21] Application number: 200410084387.X
`[43] Publication date: June 29th, 2005
`[11] Publication number: CN 1631941A
`[74] Patent Agency: Shanghai Zhixin
`Patent Agency Inc. Ltd.
`Attorney: PAN Zhensu
`
`
`
`
`
`
`Claims: 2 Pages
`Specifications: 5 Pages
`Accompanying figures : 1 Page
`
`[22] Application date: November 19th 2004
`[21] Application number: 200410084387.X
`[71] Applicant(s): Shanghai Research Institute
`of Synthetic Fiber
`Address: No. 988, Pingliang Road, Shanghai
`200082
`Joint Applicant: Donghua University
`[72] Inventors: CHEN Lei, LIU Zhaofeng,
`HU Zuming, YOU Xiulan,
`WANG Haifeng, WANG
`Xiaofeng, NI Ruqing
`
`
`[54] Invention Title
`Method for continuous preparation of polysulfone amide spinning solution with a twin-
`screw extruder
`[57] Abstract
`The present invention relates to a method for continuous preparation of polysulfone amide
`spinning solution, wherein 4’4-DDS and 3’ 3-DDS by mass ratio 10:90 ~ 90:10 are dissolved
`in DMAC polar solvent, cooled down in a cooler, then the reactants, pre-polymerized or not,
`are loaded into a twin-screw extruder which functions as main reactor and remained for 10 ~
`25 minutes. Polysulfone amide containing hydrogen chloride is extruded, and neutralized with
`calcium hydroxide or calcium oxide. The obtained polymer solution can be directly applied
`for spinning. The use of the twin-screw extruder in the present invention is beneficial for
`solving heat dissipation problem of the system, avoiding the inhomogeneity of the polymer
`molecular weight, as well as helpful to partially remove hydrogen chloride gas, the low
`molecular weight byproduct from the polymerization system.
`
`
`
`BASF SE Ex. 1009, pg. 1
`
`

`

`
`
`BASF SE Ex. 1009, pg. 2
`
`

`

`200410084387.X Claims Page 1 of 2
`
`
`1. A method for continuous preparation of polysulfone amide spinning solution
`with a twin-screw extruder, wherein it compromises following steps:
`
`(a) Dissolution: 4’ 4-diaminodiphenylsulfone and 3’ 3-diaminodiphenylsulfone
`by mass ratio of 10:90 ~ 90:10 are dissolved in N, N’-dimethylacetamide
`solvent, and cooled down in a cooler;
`
`(b) Pre-polymerization: the solution in step (a) and paraphthaloyl chloride are
`pre-polymerized, generating a prepolymer product containing hydrogen
`chloride byproduct;
`
`(c) Polymerization: the prepolymer is loaded into a twin-screw extruder, which
`is used as a main reactor, retained for 10 ~ 25 minutes and the temperature is
`divided into three zones with temperature at -5 to 5 oC, 0 to 20 oC and 10 to
`100 oC, respectively. The polysulfone amide containing hydrogen chloride is
`extruded.
`
`the polysulfone amide containing hydrogen chloride
`(d) Neutralization:
`generated in step (c) is neutralized with calcium hydroxide or calcium oxide,
`and the obtained polymer solution can be directly applied for spinning.
`
`2. Said method for continuous preparation of polysulfone amide spinning
`solution with a twin-screw extruder according to Claim 1, wherein the
`concentration of 4’ 4-diaminodiphenylsulfone and 3’ 3-diaminodiphenylsulfone
`in the polymerization system is 0.3 ~ 0.7 mol/L, and the pre-polymerization
`temperature is -20 to 20 oC.
`
`3. Said method for continuous preparation of polysulfone amide spinning
`solution with a twin-screw extruder according to Claim 1 or 2, wherein the
`
`BASF SE Ex. 1009, pg. 3
`
`

`

`concentration of 4’ 4-diaminodiphenylsulfone and 3’ 3-diaminodiphenylsulfone
`in the polymerization system is 0.4 ~ 0.6 mol/L, and the pre-polymerization
`temperature is -20 to 10 oC.
`
`4. Said method for continuous preparation of polysulfone amide spinning
`solution with a twin-screw extruder according to Claim 1, wherein the twin-
`screw extruder as a main reactor is self-cleaning, comprised of two intermeshed
`screws, the right-hand thread has a left-hand thread groove, the length-diameter
`ratio of the screw is higher than 1 : 30 and the diameter is greater than 25 mm.
`
`5. Said method for continuous preparation of polysulfone amide spinning
`solution with a twin-screw extruder according to Claim 1 or 4, wherein the
`length-diameter ratio of the screw is 1:40 to 1:60; the temperature of three
`temperature zones is -5 to 0 oC, 0 to 10 oC and 10 to 60 oC, respectively.
`
`6. Said method for continuous preparation of polysulfone amide spinning
`solution with a twin-screw extruder according to Claim 1, wherein the solid
`content is 12 ~ 20% by weight in the final spinning solution and it contains
`calcium chloride at 1 ~ 20 % by weight according to polysulfone amide.
`
`7. A method for continuous preparation of polysulfone amide spinning solution
`with a twin-screw extruder as main reactor, wherein it compromises following
`steps:
`
`(a) Dissolution: 4’ 4-diaminodiphenylsulfone and 3’ 3-diaminodiphenylsulfone
`by mass ratio of 10:90 ~ 90:10 are dissolved in N, N’-dimethylacetamide
`solvent, and cooled down in a cooler;
`
`(b) Polymerization: the solution in step (a) and molten paraphthaloyl chloride of
`equal mole are loaded into a twin-screw extruder, which is used as main
`reactor, retained for 10 ~ 25 minutes and the temperature is divided into three
`zones with temperature at -5 to 5 oC, 0 to 20 oC and 10 to 100 oC,
`
`BASF SE Ex. 1009, pg. 4
`
`

`

`respectively. The polysulfone amide containing hydrogen chloride was
`extruded.
`
`the polysulfone amide containing hydrogen chloride
`(c) Neutralization:
`generated in step (b) is neutralized with calcium hydroxide or calcium oxide,
`and the obtained polymer solution can be directly applied for spinning.
`
`8. Said method for continuous preparation of polysulfone amide spinning
`solution with a twin-screw extruder as main reactor according to Claim 7,
`wherein the twin-screw extruder as main reactor is self-cleaning, comprised of
`two intermeshed screws, the right-hand thread has a left-hand thread groove, the
`length-diameter ratio of the screw is higher than 1:30 and the diameter is greater
`than 25 mm.
`
`9. Said method for continuous preparation of polysulfone amide spinning
`solution with a twin-screw extruder according to Claim 7 or 8, wherein the
`length-diameter ratio of the screw is 1:40 to 1:60; the temperature of three
`temperature zones is -5 to 0 oC, 0 to 10 oC and 10 to 60 oC, respectively.
`
`10. Said method for continuous preparation of polysulfone amide spinning
`solution with a twin-screw extruder according to Claim 7, wherein the solid
`content is 12 ~ 20% by weight in the final spinning solution, and it contains
`calcium chloride at 1 ~ 20 % by weight according to polysulfone amide.
`
`BASF SE Ex. 1009, pg. 5
`
`

`

`Specifications
`
`
`Method for continuous preparation of polysulfone amide spinning
`solution with a twin-screw extruder
`
`Technical Field
`The present invention involves a method for continuous preparation of
`polysulfone amide spinning solution with a twin-screw extruder, more especially
`speaking, it involves a method for continuous preparation of polysulfone amide
`spinning solution with a twin-screw extruder as main reactor.
`
`Technical Background
`
`Polysulfone amide has excellent heat resistance, flame resistance, and
`outstanding high temperature resistance and electrical insulation properties,
`which is used for preparing flame resistant material and insulating material at
`high application temperature, such as fiber, paper, etc.
`The currently available method for preparing polysulfone amide is generally low
`temperature solution polymerization.
`A certain proportion of 4’ 4-diaminodiphenylsulfone (4’ 4-DDS) and 3’ 3-
`diaminodiphenylsulfone (3’ 3-DDS) were dissolved in an amide solution, and
`polymerized with paraphthaloyl chloride (TPC) at a low temperature to prepare
`polysulfone amide. The byproduct hydrogen chloride was neutralized in solution.
`The polymer solution containing the hydrochloride salt of alkali metal, which
`was generated via above-mentioned neutralization and solved
`in
`the
`polymerization system, can be directly used for spinning. The disadvantage of
`the method is that it used a discontinuous manner, the reaction heat is difficult to
`be removed, local overheating easily results in diversity of molecular weight.
`Moreover, the reaction system contains a great amount of salt, which makes it
`difficult to subsequently water-wash the fiber produced, and residual salt in final
`
`BASF SE Ex. 1009, pg. 6
`
`

`

`fiber product will significantly decrease the physical and mechanical properties,
`electrical insulation property of the fibers.
`
`Contents of the Invention
`The objective of the present invention is to provide a method for continuous
`preparation of polysulfone amide spinning solution with a twin-screw extruder.
`Because the twin-screw extruder was used as main reactor to realize continuous
`low-temperature solution condensation polymerization of polysulfone amide,
`which is beneficial for solving heat dissipation problem in the reaction system,
`and thus avoid the inhomogeneity problem of polymer molecular weight.
`Moreover, the method provided by the present invention partially remove
`hydrogen chloride gas,
`the
`low molecular weight byproduct
`in
`the
`polymerization system, thereby decreases the usage of neutralizer, decreases the
`amount of salts in the final system. Because of extruding among screws,
`hydrogen chloride gas is apt to be released from the polymerization system and
`eliminated through exhaust vent.
`The present invention has also effectively increased the solid content of the
`reaction system, which enhances the production efficiency. In the currently
`available technologies, because the system becomes very thick in the late phase,
`it is hard to stir and limits the increase of solid content.
`The present invention discloses a method for continuous preparation of
`polysulfone amide spinning solution with a twin-screw extruder, wherein it
`compromises following steps:
`
`1) Dissolution: 4’ 4-diaminodiphenylsulfone and 3’ 3-diaminodiphenylsulfone
`according to a ratio are dissolved in polar solvent, and cooled down;
`
`2) Pre-polymerization: the solution in step 1) and TPC (paraphthaloyl chloride)
`are mixed by a reaction ratio, generating prepolymerization product including
`byproduct hydrogen chloride;
`
`BASF SE Ex. 1009, pg. 7
`
`

`

`3) Polymerization: the prepolymer is loaded into a twin-screw extruder and
`polysulfone amide containing hydrogen chloride is extruded. Alternatively,
`the pre-polymerization step 2) is optional, wherein the solution in step 1) and
`TPC are loaded into the twin-screw extruder and then polysulfone amide
`containing hydrogen chloride is extruded.
`
`4) Neutralization: hydrogen chloride generated in the polymerization step is
`neutralized with hydroxide or oxide of alkali metals, and the polymer
`solution can be directly applied for spinning. The generated calcium chloride
`can be dissolved in the solvent system, and is also favorable for the stability
`of the polymer solution.
`
`In the method of the present invention for preparing polysulfone amide, the
`length-diameter ratio of the twin-screw extruder as main reactor is preferably
`greater than 1:30 and the diameter is greater than 25 mm.
`
`In the method of the present invention for preparing polysulfone amide, the
`concentration of 4’4-DDS and 3’3-DDS in the polymerization system is 0.3 ~
`0.7 mol/L, and the pre-polymerization temperature is -20 to 20 oC.
`
`In the method of the present invention for preparing polysulfone amide, the
`retention time of the reactants in the polymerization step in the twin-screw
`extruder is 10 ~ 25 minutes. The retention temperature is preferably divided into
`three zones, with each temperature is -5 to 5 oC, 0 to 20 oC and 10 to 100 oC,
`respectively.
`
`In the method of the present invention for preparing polysulfone amide, the
`concentration of the polymer in the produced polysulfone amide spinning
`solution is 12 ~ 20%.
`
`BASF SE Ex. 1009, pg. 8
`
`

`

`In the method of the present invention for preparing polysulfone amide, wherein
`the obtained polysulfone amide spinning solution contains calcium chloride at 1
`~ 20 % by weight according to polysulfone amide.
`
`In the present method for preparing polysulfone amide, wherein the reaction
`solvent
`system
`is
`N,
`N’-dimethylacetamide
`(DMAC).
`4’4-
`diaminodiphenylsulfone (4’4-DDS) and 3’3-diaminodiphenylsulfone (3’3-DDS)
`by mass ratio of 10:90 ~ 90:10 are dissolved in N, N’-dimethylacetamide
`solvent.
`
`In the method provided by the present invention, the pre-polymerization
`between diphenyl sulfone (MPD) and paraphthaloyl chloride (TPC) is firstly
`conducted. MPD is first solved in polar organic solvent. The concentration is 0.3
`~ 0.7 mol/L, preferentially 0.4 ~ 0.6 mol/L. Then TPC of equal mole is added,
`wherein the temperature is -20 to 20 oC, preferentially -20 to 10 oC.
`
`Then, the pre-polymerization system after filtration is loaded into a twin-screw
`extruder as main reactor, or without pre-polymerization step, the solved 4’4-
`DDS and 3’3-DDS solution after cooling is loaded together with molten TPC at
`reaction ratio into the twin-screw extruder. The three zones of the twin-screw
`extruder main reactor are controlled preferentially at -5 to 0 oC, 0 to 10 oC and
`10 to 60 oC, respectively. The self-cleaning twin-screw extruder in the present
`invention is comprised of two intermeshed screws, the right-hand thread has a
`left-hand thread groove. Therefore, the material can be completely mixed in
`rather short time, leading to higher molecular weight of the product and
`homogeneity of the condensed polymer. The length-diameter ratio of the screw
`is higher than 1:30, usually 1:40 to 1:60. The speed of the screw is controllable.
`The retention time of the material in the twin-screw extruder is 10 ~ 25 minutes.
`The twin-screw extruder is facilitated with exhaust vent at proper position,
`therefrom the low molecule product produced from the reaction is continuously
`removed via vacuum, such as water and hydrogen chloride. The presence of
`
`BASF SE Ex. 1009, pg. 9
`
`

`

`exhaust vent results not only in the enhancement of the viscosity of the product,
`but also in the decrease of the hydrogen chloride in the reaction system, which
`decreases the usage of further neutralizer and decreases the salt content of the
`final spinning solution.
`
`Since partial hydrogen chloride remains in the polymer solution out of the twin-
`screw extruder, it is neutralized with hydroxide or oxide of alkali metals. The
`generated hydroxide or oxide of alkali metals is dissolved in the reaction system,
`favorable for the stability of the spinning solution. The final spinning solution
`contains solid content of 12 ~ 20% by weight, and calcium chloride 1-20% by
`weight according to polysulfone amide. The content of calcium hydroxide or
`calcium oxide is 1 ~ 20%, preferentially 1 ~ 5%. The logarithmic viscosity
`number of the polysulfone amide is above 1.4.
`
`The logarithmic viscosity number of the resin prepared as solution of 0.5 g/100
`ml with concentrated sulfuric acid as solvent is determined with Ubbelohde
`viscometer at 30 oC, and calculated according to the following equation:
`
`
`Wherein, t0 is the flow-through time of solvent, t is the flow-through time of
`solution, c is the concentration of the polymer solution with unit of g/100ml.
`
`
`Illustration of accompanying figures
`
`Figure 1 is a schematic figure of the continuous preparation of polysulfone
`amide spinning solution with a twin-screw extruder.
`
`Implementation
`
`The portions or percentage involved in the following implementation examples
`are all by weight, unless specifically noted.
`
`BASF SE Ex. 1009, pg. 10
`
`

`

`Implementation example 1:
`
`0.6 portion of dried 4’4-DDS and 0.4 portion of dried 3’3-DDS was dissolved
`into 8.5 portions of dried DMAC freshly distilled. 0.823 portion of granular
`refined TPC was loaded therein for pre-polymerization at -5 oC. The mixture
`was loaded into a twin-screw extruder with a diameter of 35 mm, length to
`diameter of 60 and rotation speed of 100 rpm. The three zones of the twin-scree
`extruder reactor were 0 oC, 10 oC and 60 oC, respectively. After about 12
`minutes, colorless transparent polymer was extruded, and neutralized with 0.226
`portion of CaO. Finally, polysulfone amide solution was obtained with polymer
`of 14.4%, ηinh of 1.5, CaCl2 content of 3.1%. The solution can be directly used
`for spinning after neutralization.
`
`Comparison example 1:
`
`0.6 portion of dried 4’4-DDS and 0.4 portion of dried 3’3-DDS was dissolved
`into 9 portions of freshly-distilled dried DMAC in a tank reactor with stirrer.
`0.823 portion of granular refined TPC was loaded therein at -5 oC. The
`temperature of the reactor was controlled at 60 oC. After 1 hour, the reaction was
`complete, obtaining colorless transparent polymer. Then, it was neutralized with
`0.226 portion of CaO. Finally, spinning solution was obtained with polymer of
`13.8%, ηinh of 1.38, CaCl2 content of 4.1%. The solution can be directly used for
`spinning after neutralization.
`
`Implementation example 2:
`
`0.6 portion of dried 4’4-DDS and 0.4 portion of dried 3’3-DDS was dissolved
`into 8.5 portions of dried DMAC freshly distilled. 0.823 portion of TPC was
`carefully weighted and loaded into a twin-screw extruder with a diameter of 35
`mm, length to diameter of 60 and rotation speed of 100 rpm. The three zones of
`the twin-scree extruder reactor were controlled at -5 oC, 10 oC and 60 oC,
`
`BASF SE Ex. 1009, pg. 11
`
`

`

`respectively. After about 12 minutes, colorless transparent polymer was
`extruded, and neutralized with 0.226 portion of CaO. Finally, polysulfone amide
`solution was obtained with polymer of 14.4%, ηinh of 1.43, CaCl2 content of
`3.1%. The solution can be directly used for spinning after neutralization.
`
`Implementation example 3
`
`4’4-DDS and 3’3-DDS was dissolved by weight ratio 10:90 into N,N’-
`dimethylacetamide
`polar
`organic
`solvent. After
`pre-polymerization,
`polymerization and neutralization, polymer solution was obtained to be used for
`spinning directly. Concretely, please refer to the implementation example 1.
`
`Implementation example 4
`
`4’4-DDS and 3’3-DDS was dissolved by weight ratio 85:15 into DMAC. The
`solution was directly loaded into a twin-screw extruder as main reactor without
`pre-polymerization. Concretely, please refer to the implementation example 2.
`After neutralization, polymer solution was obtained and directly used for
`spinning.
`
`
`
`
`BASF SE Ex. 1009, pg. 12
`
`

`

`Accompanying figure
`______________________________________________________
`
`
`
`
`
`
`Figure 1
`
`***************************************************************************
`End
`
`
`
`
`
`
`
`BASF SE Ex. 1009, pg. 13
`
`

`

`AE TRANSLATION OFFICE
`Owner: DR. WENLIANG YANG
`
`scientist and court sworn translator
`
`Osterholzweg 34, D—381 10 Braunschweig. Germany
`Tell: 0049—05307-495008 od. 0049-01708785630
`Fax: 0049—5307-495009
`
`F-mail: dr.wenliang.yang@t~onlinede
`
`
`CERTIFICATION
`
`This is to certify that the following is, to the best of our knowledge and belief, a
`
`true and accurate translation into ENGLISH of the attached document(_s) relating
`
`to:
`
`Chinese Patent No. CN1631941A, written in Chinese.
`
`I hereby declare that all statements made herein of my own knowledge are true and
`
`that all statements made on information and belief are believed to be true; and
`
`further that these statements were made with the knowledge that willful false
`
`statements and the like so made are punishable by fine or imprisonment, or both,
`
`under Section 1001 ofTitle 18 ofthe United States Code and that such willful false
`
`statements may jeopardize the results of these proceedings.
`
`I declare under penalty of perjury under the laws of the United States of America
`
`that the foregoing is true and accurate.
`
`AE TRANSLATION OFFICE
`
`Dr. Wenliang Yang
`
`09/08/201
`
`
`
`BASF SE EX. 1009, pg. 14
`
`BASF SE Ex. 1009, pg. 14
`
`

`

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`BASF SE Ex. 1009, pg. 15
`
`

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`BASF SE EX. 1009, pg. 17
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`BASF SE Ex. 1009, pg. 17
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`BASF SE EX. 1009, pg. 18
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`BASF SE Ex. 1009, pg. 18
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`BASF SE EX. 1009, pg. 19
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`BASF SE Ex. 1009, pg. 19
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`BASF SE EX. 1009, pg. 20
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`BASF SE Ex. 1009, pg. 20
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`BASF SE EX. 1009, pg. 21
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`BASF SE Ex. 1009, pg. 21
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`BASF SE EX. 1009, pg. 22
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`BASF SE Ex. 1009, pg. 22
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`BASF SE EX. 1009, pg. 23
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`BASF SE Ex. 1009, pg. 23
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