CN1264896C - Method for continuous double-screw preparation of polysulfone amide spinning solution - Google Patents
Method for continuous double-screw preparation of polysulfone amide spinning solution Download PDFInfo
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- CN1264896C CN1264896C CNB200410084387XA CN200410084387A CN1264896C CN 1264896 C CN1264896 C CN 1264896C CN B200410084387X A CNB200410084387X A CN B200410084387XA CN 200410084387 A CN200410084387 A CN 200410084387A CN 1264896 C CN1264896 C CN 1264896C
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- screw
- spinning solution
- dds
- continuous double
- polymerization
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
Abstract
The present invention relates to a method for continuously preparing a polysulfonamide spinning solution, which is characterized in that 4'4-DDS and 3'3-DDS are dissolved in a DMAC polar solvent according to the mass percentage ratio of 10:90 to 90:10 and cooled in a cooler, then, reactants are added into a double-screw extruding machine as a main reactor through prepolymerization or not through prepolymerization to stay for 10 to 25 minutes, and an obtained polymer solution is directly used for spinning after hydrogen chloride containing polysulfonamide is extruded and neutralized with calcium hydroxide or calcium oxide. The application of the double-screw extruding machine in the present invention is favorable to the settlement of the problem of heat dissipation in the system to avoid the problem of nonuniform polymer molecular weights and is also favorable to the partial removal of the hydrogen chloride of small molecule byproducts in the polymerization system.
Description
Technical field
The present invention relates to a kind of method of continuous double-screw preparation of polysulfone amide spinning solution, relating to a kind of or rather is the method that main reactor prepares polysulfone amide spinning solution with the twin screw extruder.
Background is held art
Polysulfonamides has excellent thermotolerance and flame resistant, and excellent high temperature electrical insulation capability, is used for preparation anti-flame material of fire prevention and high use temperature insulating material, as fiber, and paper etc.
The method of existing preparation polysulfonamides is low temperature solution polymerization normally:
4 ' the 4-diaminodiphenylsulfone(DDS) (4 ' 4-DDS) and 3 ' the 3-diaminodiphenylsulfone(DDS) (3 ' 3-DDS) of certain proportioning are dissolved in the amide solvent, in lesser temps down and p-phthaloyl chloride (TPC) polymerization prepare polysulfonamides, hydrogenchloride as by product neutralizes in solution, comprises above-mentioned neutralization and the polymers soln that is dissolved in an alkali metal salt hydrochlorate in the polymerization system that generates can be directly used in spinning.The shortcoming of this method is to adopt discontinuous mode, and reaction heat is difficult for removing, and local superheating then easily causes the difference of molecular weight.And contain a large amount of salt in the reaction system, bring difficulty for the washing of the fiber of subsequent preparation, and residual salt can reduce the physical and mechanical properties and the electrical insulation capability of fiber greatly in the finished product fiber.
Summary of the invention
The object of the invention is to provide a kind of method of continuous double-screw preparation of polysulfone amide spinning solution, because adopting twin screw extruder is that main reactor is to realize the serialization of polysulfonamides cryogenic fluid polycondensation, be beneficial to the solution of the heat dissipation problem of reaction system, thereby avoided the inhomogenous problem of polymericular weight.And the method that part is removed the hydrogen chloride gas of small molecule by-product in the polymerization system in the method provided by the invention, thereby the consumption of minimizing neutralizing agent reduce the content of salt in the final system.Because the extruding between the screw rod helps hydrogen chloride gas and discharges from polymerization system, and got rid of by venting hole.
The present invention can also effectively improve the solid content of reaction system, enhances productivity.In the prior art, the very thickness because reaction later stage system becomes stirs difficulty, has limited the raising of solid content.
The present invention is a kind of method with twin screw extruder continuously preparing poly sulfonamide spinning solution, comprises following steps:
1) dissolving, 4 ' 4-DDS and 3 ' 3-DDS are dissolved in the polar organic solvent in proportion, and cooling.
2) pre-polymerization mixes the TPC (p-phthaloyl chloride) of solution in the step 1) and reaction ratio, generates and contains the prewired thing that by product is a hydrogenchloride.
3) polymerization, prewired thing joins in the twin screw extruder, extrudes the polysulfonamides that contains hydrogenchloride.Perhaps prepolymerization step 2) be optional step, the TPC of solution in the step 1) and reaction ratio can be joined in the twin screw extruder, extrude the polysulfonamides that contains hydrogenchloride.
4) neutralization, with the hydrogenchloride that generates in the polymerization procedure with in alkali metal hydroxide or the alkalimetal oxide and after, polymers soln can be directly used in spinning, the calcium chloride of generation is not only soluble in solvent system, and stable favourable to polymers soln.
Prepare in the method for polysulfonamides in the present invention, be preferably more than 1: 30 as the length-to-diameter ratio of the twin screw extruder of main reactor, diameter is greater than 25mm.
Prepare in the method for polysulfonamides in the present invention, 4 ' 4-DDS and the concentration of 3 ' 3-DDS in polymerization system are 0.3～0.7mol/1, and prepolymerized temperature is-20 ℃ to 20 ℃.
Prepare in the method for polysulfonamides in the present invention, the time that the polymerization procedure reactant stops in twin screw extruder is 10～25 minutes.The temperature that stops preferably is divided into three districts, and each distinguishes temperature and is respectively-5-5 ℃, 0-20 ℃, 10-100 ℃.
Prepare in the method for polysulfonamides in the present invention, polymer concentration is 12-20% in the polysulfone amide spinning solution that makes.
Prepare in the method for polysulfonamides in the present invention, comprising in the polysulfone amide spinning solution that it is characterized in that making with the polysulfonamides is the calcium chloride of benchmark 1-20wt%.
Prepare in the method for polysulfonamides in the present invention, it is characterized in that the reaction solvent system is N, N '-N,N-DIMETHYLACETAMIDE (DMAC), it is with 4 ' 4-diaminodiphenylsulfone(DDS) (4 ' 4-DDS) and 3 ' 3-diaminodiphenylsulfone(DDS) (3 ' 3-DDS), be dissolved in N in 10: 90 by mass percentage to 90: 10, in N '-dimethylacetamide solvent.
In method provided by the invention, carry out the prepolymerization of sulfobenzide (MPD) and p-phthaloyl chloride (TPC) earlier.MPD is dissolved in earlier in the polar organic solvent, and concentration is 0.3-0.7mol/l, preferably 0.4-0.6mol/l.The TPC of mole ratio such as adding then, the temperature of this moment is-20 ℃ to+20 ℃, is preferably-20 ℃ to+10 ℃.
Then, prepolymer after the filtration enters the twin screw extruder as main reactor, perhaps without prepolymerization step, the TPC of the molten state of 4 ' directly that cooled dissolving is good 4-DDS and the solution of 3 ' 3-DDS and reaction ratio joins in the twin screw extruder, the temperature in control twin screw main reactor three districts is preferably at-5-0 ℃, 0-10 ℃, 10-60 ℃.The self-cleaning type twin screw extruder that the present invention adopts is made up of two intermeshing screw rods, contains the reverse thread groove on the forward screw thread, so material reaches thorough mixing at short notice, thereby can improve the homogeneity of the molecular weight and the polycondensate of product.Screw slenderness ratio generally was controlled at 1: 40 to 1: 60 greater than 1: 30, the adjustable-speed joint.The residence time of material in twin screw extruder is 10-25 minute.This twin screw extruder in position is equipped with gas barrier, by vacuumizing the low-molecular material that continuous eliminating reaction produces, as water or hydrogenchloride etc.Because the existence of gas barrier not only can make the viscosity of product improve, and has reduced the hydrogen chloride content in the reflection system, thereby reduces the consumption of further neutralizing agent, and then reduced the saltiness of final spinning solution.
Owing to still contain the hydrogenchloride of part by the polymers soln of twin screw extruder, so select the neutralization of alkali metal hydroxide and alkalimetal oxide for use, the alkali metal hydroxide and the alkalimetal oxide that generate are dissolved in the reflection system, and stable favourable to spinning solution.The solid content of final spinning solution is 12-20wt%, and comprising with the polysulfonamides is the calcium chloride 1-20wt% of benchmark.The content of calcium hydroxide or calcium oxide is 1-20%, and optimum is 1-5%, and the logarithmic viscosity number of polysulfonamides is more than 1.4.
The logarithmic specific concentration viscosity of resin is to be solvent with the vitriol oil, is made into the solution of 0.5g/100ml, adopts dark type viscometer, in 30 ℃ of mensuration, is calculated as follows:
η
inh＝ln(t/t
0)/c
T in the formula
0Be the solvent elution time, t is the solution elution time, and c is a polymer solution concentration, and unit is g/100ml.
Description of drawings
Fig. 1 prepares the polysulfone amide spinning solution schema for continuous double-screw forcing machine provided by the invention.
Embodiment
The part and the percentage ratio that relate in the following example except that special instruction is arranged, are weight part.
Embodiment 1:
0.6 part of 4 ' 4-DDS of exsiccant and 0.4 part of 3 ' 3-DDS be dissolved among 8.5 parts the new distillatory exsiccant DMAC, add 0.823 part of particulate state purified TPC down at-5 ℃ and carry out pre-polymerization, entering diameter then is 35mm, length-to-diameter ratio is 60, rotating speed is the twin screw extruder of 100rpm, the temperature in control double-screw reactor three districts is at 0 ℃, and 10 ℃, 60 ℃.Extruded water white polymer in about 12 minutes, then with 0.226 part CaO neutralization.Finally obtain containing polymkeric substance 14.4%, η
InhBe 1.5, CaCl
2Content is 3.1% polysulfonamides solution, and the later solution that neutralizes can be directly used in spinning.
Comparative example 1: in having the tank reactor of agitator, 0.6 part of 4 ' 4-DDS of exsiccant and 0.4 part of 3 ' 3-DDS be dissolved among 9 parts the new distillatory exsiccant DMAC, add 0.823 part of particulate state purified TPC down at-5 ℃, the temperature of controlling reactor is at 60 ℃, afterreaction finished in one hour, obtain water white polymer, the subsequent neutralization, the amount of CaO are 0.226 part.Finally obtain containing polymkeric substance 13.8%, η
InhBe 1.38, CaCl
2Content is 4.1% spinning solution, and the later solution that neutralizes can be directly used in spinning.
Embodiment 2:
0.6 part of 4 ' 4-DDS of exsiccant and 0.4 part of 3 ' 3-DDS be dissolved among 8.5 parts the new distillatory exsiccant DMAC, it is 35mm that TPC delicate metering following at-5 ℃ and 0.823 part adds diameter, length-to-diameter ratio is 60, rotating speed is the twin screw extruder of 100rpm, the temperature in three districts of control double-screw reactor is at-5 ℃, 10 ℃, 60 ℃., extruded water white polymer in about 12 minutes, then with 0.226 part CaO neutralization.Finally obtain containing polymkeric substance 14.4%, η
InhBe 1.43, CaCl
2Content is 3.1% polysulfonamides solution, and the later solution that neutralizes can be directly used in spinning.
Embodiment 3
4 ' 4-DDS and 3 ' 3-DDS mass percent are 10: 90, are dissolved in N, in N '-N,N-DIMETHYLACETAMIDE polar organic solvent, obtain polymers soln and be directly used in spinning after pre-polymerization, polymerization, neutralization.Specifically referring to embodiment 1.
Embodiment 4
4 ' 4-DDS and 3 ' 3-DDS mass percent are 85: 15, are dissolved among the DMAC without pre-polymerization directly entering twin screw extruder as main reactor, and be concrete as embodiment 2.Obtain polymers soln after the neutralization, be directly used in spinning.
Claims (10)
1, a kind of continuous double-screw forcing machine prepares the method for polysulfone amide spinning solution, it is characterized in that may further comprise the steps:
(a) dissolving was dissolved in N in 10: 90 by mass percentage to 90: 10 with 4 ' 4-diaminodiphenylsulfone(DDS) and 3 ' 3-diaminodiphenylsulfone(DDS), in N '-dimethylacetamide solvent, and cooled off in water cooler;
(b) pre-polymerization is carried out pre-polymerization with solution in the step (a) and p-phthaloyl chloride, generates the prepolymer that contains byproduct hydrogen chloride;
(c) polymerization joins prepolymer in the twin screw extruder as main reactor, and the residence time is 10～25 minutes, and the temperature of stop is divided into 3 districts, and the temperature in each district is respectively-5～5 ℃, 0～20 ℃ and 10～100 ℃; Extrude the polysulfonamides that contains hydrogenchloride;
(d) neutralization the polysulfonamides that contains hydrogenchloride that step (c) is generated with in calcium hydroxide or the calcium oxide and after, the polymers soln of gained is directly used in spinning.
2, the method for preparing polysulfone amide spinning solution by the described continuous double-screw forcing machine of claim 1, it is characterized in that 4 ' 4-diaminodiphenylsulfone(DDS) and the concentration of 3 ' 3-diaminodiphenylsulfone(DDS) in polymerization system are 0.3～0.7mol/l, the pre-polymerization temperature is-20 ℃ to+20 ℃.
3, the method for preparing polysulfone amide spinning solution by claim 1 or 2 described continuous double-screw forcing machines, it is characterized in that 4 ' 4-diaminodiphenylsulfone(DDS) and the concentration of 3 ' 3-diaminodiphenylsulfone(DDS) in polymerization system are 0.4～0.6mol/l, the pre-polymerization temperature is-20 ℃ to 10 ℃.
4, the method for preparing polysulfone amide spinning solution by the described continuous double-screw forcing machine of claim 1, it is characterized in that the twin screw extruder as main reactor is a self-cleaning type, it is made up of two intermeshing screw rods, contain the reverse thread groove on the forward screw thread, screw slenderness ratio was greater than 1: 30, and diameter is greater than 25mm.
5, the method for preparing polysulfone amide spinning solution by claim 1 or 4 described continuous double-screw forcing machines is characterized in that screw slenderness ratio is 1: 40 to 1: 60; The temperature of three humidity provinces is respectively-5～0 ℃, 0～10 ℃ and 10～60 ℃.
6, prepare the method for polysulfone amide spinning solution by the described continuous double-screw forcing machine of claim 1, it is characterized in that solid content is 12-20wt% in the final spinning solution, comprising with the polysulfonamides is the calcium chloride 1-20wt% of benchmark.
7, a kind of continuous double-screw forcing machine is the method that main reactor prepares polysulfone amide spinning solution, it is characterized in that comprising following each step:
(a) dissolving was dissolved in N in 10: 90 by mass percentage to 90: 10 with 4 ' 4-diaminodiphenylsulfone(DDS) and 3 ' 3-diaminodiphenylsulfone(DDS), in N '-dimethylacetamide solvent, and cooled off in water cooler;
(b) polymerization with the solution of step (a) and etc. the p-phthaloyl chloride of mole ratio molten state directly join in the twin screw extruder as main reactor, the residence time is 10～25 minutes, the temperature that stops is divided into 3 districts, the temperature in each district is respectively-5～5 ℃, 0～20 ℃ and 10～100 ℃; Extrude the polysulfonamides that contains hydrogenchloride;
(c) neutralization the polysulfonamides that contains hydrogenchloride that step (b) is generated with in calcium hydroxide or the calcium oxide and after, the polymers soln of gained is directly used in spinning.
8, be the method that main reactor prepares polysulfone amide spinning solution by the described continuous double-screw forcing machine of claim 7, it is characterized in that the twin screw extruder as main reactor is a self-cleaning type, it is made up of two intermeshing screw rods, contain the reverse thread groove on the forward screw thread, screw slenderness ratio was greater than 1: 30, and diameter is greater than 25mm.
9, the method for preparing polysulfone amide spinning solution by claim 7 or 8 described continuous double-screw forcing machines is characterized in that screw slenderness ratio is 1: 40 to 1: 60; The temperature of three humidity provinces is respectively-5～0 ℃, 0～10 ℃ and 10～60 ℃.
10, prepare the method for polysulfone amide spinning solution by the described continuous double-screw forcing machine of claim 7, it is characterized in that solid content is 12-20wt% in the final spinning solution, comprising with the polysulfonamides is the calcium chloride 1-20wt% of benchmark.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200410084387XA CN1264896C (en) | 2004-11-19 | 2004-11-19 | Method for continuous double-screw preparation of polysulfone amide spinning solution |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200410084387XA CN1264896C (en) | 2004-11-19 | 2004-11-19 | Method for continuous double-screw preparation of polysulfone amide spinning solution |
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| CN1631941A CN1631941A (en) | 2005-06-29 |
| CN1264896C true CN1264896C (en) | 2006-07-19 |
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| CN101275308B (en) * | 2007-03-26 | 2010-06-02 | 上海特安纶纤维有限公司 | Preparation for all-metaposition aromatic polyamide fibre |
| US7700190B2 (en) | 2007-08-22 | 2010-04-20 | E.I. Du Pont De Nemours And Company | Flame resistant spun staple yarns made from blends of fibers derived from diamino diphenyl sulfone and textile fibers and fabrics and garments made therefrom and methods for making same |
| US8133827B2 (en) | 2007-08-22 | 2012-03-13 | E.I. Du Pont De Nemours And Company | Fibers comprising copolymers containing structures derived from 4,4 diamino diphenyl sulfone and a plurality of acid monomers and methods of making same |
| US7618707B2 (en) * | 2007-08-22 | 2009-11-17 | E.I. Du Pont De Nemours And Company | Flame resistant spun staple yarns made from blends of fibers derived from diamino diphenyl sulfone and modacrylic fibers and fabrics and garments made therefrom and methods for making same |
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| US8118975B2 (en) | 2007-12-21 | 2012-02-21 | E. I. Du Pont De Nemours And Company | Papers containing fibrids derived from diamino diphenyl sulfone |
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| CN106519220B (en) * | 2015-09-11 | 2020-08-07 | 中国科学院上海有机化学研究所 | Polysulfone aramid fiber, slurry to be spun and manufacturing method thereof |
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