JPH01124A - Method for improving melt stability of polymers - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing poly(arylene sulfide ketones). In another aspect, the invention relates to a method of making poly(arylene sulfide sulfone)s. The invention also relates to fibers and other articles that are products made from these polymers.

Poly(arylene sulfitogetones) and poly(arylene sulfide sulfones) have potential commercial interest in films, fibers, molded articles and composite products due to their high melting points and heat resistance in thermoplastic engineering. It's plastic.

General processes for the production of poly(arylene sulfide ketones) and poly(arylene sulfide sulfones) are already known. Poly(arylene sulfide ketones) can be made by reacting a polyoctoday aromatic getone, such as 4,4''-dichlorobenzophenone, with an alkali metal sulfide in a polar organic solvent. Poly(arylene sulfide sulfone) ) can be made, for example, by reacting a polyoctoday aromatic sulfone, such as bis(p-chlorophenyl) sulfone, with an alkali metal sulfide in a polar organic solvent.

However, the major drawback of the poly(arylene sulfide ketones) and poly(arylene sulfide sulfone) compounds produced in this way is that they have relatively low melt stability.

Furthermore, the polymer quality is poor in that the cured or processed polymer is black, brittle, shows signs of outgassing, and appears to have carbonaceous grain.

It would be most desirable to make melt stable poly(arylene sulfitegetones) and poly(arylene sulfide sulfones) with good polymer quality that can be processed and cured. Melt stable poly(arylene sulfide ketones) and poly(arylene sulfide sulfone)s will provide improved processability, color, grain, flexibility and tenacity. In addition, melt-stable poly(arylene sulfide ketones) and poly(arylene sulfide sulfones) can be cured slowly or under controlled conditions to increase the molecular weight without compromising the quality of the polymer. It must be able to be cured.

It is an object of our invention to provide a method for preparing melt-stable poly(arylene sulfide ketones) and poly(arylene sulfide sulfones). It is a further object of our invention to provide a method for preparing poly(arylene sulfide ketones) and poly(arylene sulfide sulfones) with good polymer quality.

It is a further object of our invention to prepare poly(arylene sulfide ketones) and poly(arylene sulfide sulfones) of good polymer properties with stable melt flow.

Melt-stable poly(arylene sulfitogetones) and poly(arylene sulfide sulfones) can be prepared by contacting specific polymers, either poly(arylene sulfide ketones) or poly(arylene sulfide sulfones), with calcium cations (Ca""). ) was found to be prepared. The poly(arylene sulfide ketones) or poly(arylene sulfide sulfones) made therefrom were not contacted with calcium cations.
arylene sulfide sulfone) exhibits stable melt flow and favorable polymer properties.

According to the invention, poly(arylene sulfide ketone)
Melt stable poly(arylene sulfide ketones) or poly(arylene sulfide sulfones) are prepared by contacting either poly(arylene sulfide sulfones) or poly(arylene sulfide sulfones) with calcium cations (C84+). Any method by which calcium cations and polymers are contacted, e.g.
It is considered that even products that are melt-mixed with (o) are within the scope of the present invention.

Mixtures or copolymers of poly(arylene sulfitogetones) and/or poly(arylene sulfide sulfones) are also considered to be within the scope of this invention. However, a homopolymer is more preferred.

In the present invention, poly(arylene sulfide ketone>
(PASK) or poly(arylene sulfide sulfone) (PASS) is preferably treated with water-soluble calcium cations (Ca"+), such as calcium salts,
It is more preferred if the calcium cation is used as a salt such as calcium halide or calcium carboxylate; more preferred salts of calcium include calcium chloride, calcium fluoride, calcium bromide/calcium iodide, calcium acetate, etc.; Any two or a mixture of two or more of these are included. The most preferred calcium salts in view of their effectiveness and practicality are calcium chloride and calcium acetate.

In the present invention, the calcium treatment step is preferably carried out in a two-step process. Prior to contacting the polymer with water-soluble calcium cations, it is preferred to contact the polymer with a diluting effective amount of an aqueous solution of an alkali metal salt or an alkali metal base, such as an alkali metal hydroxide. Alkali metal hydroxides are preferred and include sodium hydroxide (NaOH), lithium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide.

In view of its effectiveness and practicality, the most preferred alkali metal base is sodium hydroxide.

Currently, the most preferred method is to wash the polymer with an aqueous solution of sodium hydroxide followed by washing the polymer with an aqueous solution of calcium acetate.

In the present invention, it is likewise preferred to cure the calcium-treated polymer. Polymers treated according to the invention are melt stable and can be cured over a reasonable period of time.

The cured polymers in this invention have higher molecular weights when compared to uncured polymers. These cured calcium-treated polymers are more suitable than uncured calcium-treated polymers for certain products such as injection molding compounds and films. However, care must be taken not to cure the polymer excessively. This is because an excessively hardened polymer cannot be processed.

According to the invention, the molecular weight of a polymer is indicated by its internal viscosity. A high internal viscosity indicates that the polymer has a high molecular weight.The internal viscosity is
In the case of poly(arylene sulfide ketone), 30
Determined according to ASTM D2857 in concentrated sulfuric acid at 0.degree. C. and in the case of poly(arylene sulfide sulfone) in N-methyl-2-pyrrolidone at 30.degree.

Preferred high molecular weight poly(arylene sulfide ketones) of the invention generally have an internal viscosity of at least about 0.3, preferably at least about 0.4, and most preferably from 0.5 to 1 deciliter per gram (d1/g). That would be expected. Preferred high molecular weight poly(arylene sulfide sulfones) generally have a molecular weight of at least 0.25.
Preferably it would be expected to have an internal viscosity of at least 0.35- and most preferably 0.4-0.8 deciliters/gram.

The polymers of the present invention are preferably cured after the calcium treatment, the curing being carried out at elevated temperature for a suitable curing time. The polymer can be cured as a solid material below its melting point or as a polymer eluate above its melting point. Typically, the temperatures used are from about 150°C to 500°C, and the curing times range from about 5 minutes to 72 hours, more preferably from about 250°C to 400°C for about 1
It ranges from 5 minutes to 24 hours. The rate of cure is temperature dependent, with higher temperatures increasing the rate of cure.

The polymers of the present invention can be cured under low pressure or high pressure. However, the polymer is preferably cured in an oxidizing atmosphere such as air at near atmospheric pressure. Curing the polymer according to the present invention can also increase the arsenal stability of the polymer.

Curing the polymer during calcium treatment is also possible, but less preferred. This type of hardening is
It can be carried out at elevated temperatures with the presence of calcium cations and oxygen.

In the present invention, the calcium-treated polymer can be subjected to a second treatment using hydrogen peroxide or other known chemical treatment agents such as sodium hypochlorite. This second treatment is generally performed before curing but after the calcium treatment.

The melt stability of the polymer prepared according to the present invention is A
Evaluate by noting the change in melt flow rate of each polymer after being held at elevated temperature in the barrel of a melt index measurement device for a period ranging from about 5 minutes to about 30 minutes according to the STM D1238 test method. Can be done. The temperature is 371°C for poly(arylene sulfide ketone) and 343°C for poly(arylene sulfide sulfone).

Measurements of melt flow at any given time are determined by extruding the molten polymer through an orifice in the barrel using a 5 kg driving weight. The time required to extrude a predetermined volume of polymer through the orifice is recorded and the weight of the cooled extrudate is measured. Melt flow is calculated as grams of polymer extruded per 10 minutes of flow. If little or no change occurs in the polymer melt flow during a holding period of 5 to 30 minutes, then it is clear that a stable melt flow product is being tested. - It can be seen that the reduction in melt flow occurred due to the longer time required to extrude the predetermined amount of polymer into the membrane from the barrel. However, in some instances, an increase in melt flow occurs as indicated by a decrease in the time required for a predetermined amount of polymer to be extruded through the barrel. For purposes of this invention, a polymer is optionally considered unacceptable if there is a change in extrusion velocity of the polymer over a 5 to 10 minute period of melt flow of more than about ±50'%. Ru.

Melt-stable polymers are either jelly (arylene sulfide ketone) or poly (arylene sulfide sulfone) polymers that are treated with a sufficient amount of calcium at a temperature, pressure, and time sufficient to improve the melt stability of the polymer. prepared by contacting with cations. - Within the membrane the polymer is contacted with calcium cations at a temperature of about 50°C to 350°C. Preferably the polymer has calcium cations and a temperature of 100°C to 200"C1 pressure 1
5-1 500 psia and a time of about 172 minutes to 3 hours.

The amount of calcium cations added to contact the polymer can vary depending on the desired quality of the final treated volisée. - Inside the membrane there is no calcium salt solution
．． 0.001% by weight up to the solubility limit of the particular salt used.

Preferably, the calcium salt solution ranges from 0.1 to % Sfi.

The time that the polymer is contacted with calcium cations varies over a wide range and depends in part on the temperature and the nature of the polymer. - In the membrane will be in the range of about 30 seconds to 3 hours, preferably 1 minute to 1 hour. The pressure should be sufficient to maintain the liquid phase, which is about 0 to 1,50
It can vary in the range of 0 psia. Iterative processing can be used if desired, and the process can be carried out in several stages if desired.

Heating and contacting with calcium cations can be accomplished using conventional equipment. A convenient way to carry out the process is to contact the polymer and calcium cations in a closed tank with a stirrer. Contacting can be performed using a single container or multiple containers. Separation of the polymer from the contacted reaction product can be accomplished by any suitable method, including reducing the pressure to atmospheric pressure, filtration, or similar means. The polymer is then dried for other applications where it is desired.

Mie'U Genkyuya I-PASK can be prepared by contacting a polyhaloaromatic ketone and a sulfur source under polymerization conditions. r'
One preferred method for preparing ASK is to contact a reaction mixture of polyhalobenzophenone, alkali metal sulfide and water in effective proportions with each other under polymerization conditions in a polar organic medium.

Examples of polyhalobenzophenones are: 4.4"-dichlorobenzophenone, 4,4°-difluorobenzophenone, 4,4°-dibromobenzophenone, 4.4
°-Short benzophenone, 2.4°-dichlorobenzophenone.

2.4.4°-Trichlorobenzophenone etc. and mixtures thereof. When preparing PASK, in this method,
Dihalobenzophenones of the following formula are more preferably used.

(wherein X is selected from the group consisting of chlorine, bromine, fluorine, and iodine.) For reasons of effectiveness and commercial availability, the currently preferred dihalobenzophenone is 4,4'-dichlorobenzophenone.

A further preferred method of preparing PASK is to prepare a dihalobenzophenone, such as 4.4°-dichlorobenzophenone, from an alkali gold sulfide, such as sodium bisulfide, and an alkali metal hydroxide, such as sodium bisulfide. The alkali metal sulfide and water are reacted in a polar organic solvent of an organic amide such as N-methyl-2-pyrrolidone to form a repeating unit of phenylene sulfide ketone represented by the following formula.

During the required polymerization time, additional amounts of 4-chlorobenzophenone or 4,4'-dichlorobenzophenone can optionally be added for the purpose of adding to the end of the polymer near its end point.

-N PASS can be prepared by contacting a polyhaloaromatic sulfone and a sulfur source under polymerization conditions. P
One preferred method for the preparation of ASS is to contact a reaction mixture containing an effective proportion of polyhaloaromatic sulfone, alkali metal sulfide, and water in a polar organic medium under polymerization conditions.

When preparing PASS, our method uses polyhaloaromatic sulfones. Preferably our method uses dihaloaromatic sulfones. More preferably, our method uses a dihaloaromatic sulfone of the formula:

(wherein each X is selected from the group consisting of fluorine, chlorine, bromine, and iodine, and Z is a divalent group selected from the group consisting of the following groups: (wherein n is 0 or 1; A is selected from the group consisting of oxygen, sulfur, sulfonyl, and CR2; each R is selected from the group consisting of hydrogen, alkyl groups having from 1 to about 4 carbon atoms, and the sum of all carbon atoms of the R groups in the molecule is from O to about 12. Preferably each n is 0.)) Bis(p-halophenyl)sulfone is a presently preferred reactant in the process of the invention and is represented by the formula below.

(wherein each
The total number of carbon atoms in each molecule ranges from 12 to about 24. ) Examples of some dihaloaromatic sulfones that can be used in the process of the invention are bis(p-fluorophenyl)sulfone, bis(p-chlorophenyl)sulfone, bis(p-fluorophenyl)sulfone, bis(p-chlorophenyl)sulfone, bis(p-chlorophenyl)sulfone,
-bromophenyl) sulfone, bis(p-iodophenyl) sulfone, p-chlorophenyl, p-bromophenyl sulfone, p-iodophenyl-3-methyl-4-fluorophenyl sulfone.

Bis(2-methyl-4-chlorophenyl)sulfone.

Bis(2,5-diethyl-4-bromophenyl)sulfone, bis(3-isopropyl-4-iodophenyl)sulfone, bis(2,5-dipropyl-4-chlorophenyl)sulfone, bis(2-butyl-4- fluorophenyl) sulfone, bis(2,3,5,6-tetramethyl-
4-chlorophenyl) sulfone.

2-isobutyl-4-chlorophenyl-1,3-butyl-4-bromophenylsulfone, 1,4-bis(p-chlorophenylsulfonyl)benzene, 1-methyl-2,
4-bis(p-fluorophenylsulfonyl)benzene, 2,6-bis(p-bromophenylsulfonyl)naphthalene, 7-ethyl-1,5-bis(p-iodophenylsulfonyl)naphthalene.

4.4-'Bis(p-chlorophenylsulfonyl)biphenyl, bis[p-(p-bromophenylsulfonyl)phenyl]ether, bis[p-(ρ-chlorophenylsulfonyl)phenyl]sulfide, bis[p-(
p-chlorophenylsulfonyl) phenylsulfone, bis[p-(p-bromophenylsulfonyl)phenylcomethane, 5,5-bis[3-ethyl-4-(p-chlorophenylsulfonyl)phenyl]nonane, etc., and mixtures thereof. be.

A currently preferred dihaloaromatic sulfone, based on its effectiveness and commercial availability, is bis(p-chlorophenyl) sulfone.

A more preferred method of PASS preparation is to prepare a dihaloaromatic sulfone, such as bis(p-chlorophenyl)sulfone.
An alkali metal sulfide prepared from an alkali metal hydrosulfide such as sodium hydrosulfide and an alkali metal hydroxide such as sodium hydroxide and water;
- An organic amide such as pyrrolidone (NMP) is reacted in a polar organic solvent to form a repeating unit of phenylene sulfide sulfone represented by the following formula.

PASK　　　PASS　　　　”.

Alkali metal sulfides can be prepared from the reaction products of alkali metal hydrosulfides and alkali metal hydroxides in aqueous solution. The molar ratio of alkali metal hydrosulfide and alkali metal hydroxide may vary slightly, but especially in PASK.
It is more preferred to have a slight excess of alkali metal bisulfide by about 0.5 to about 2 mole percent compared to alkali metal hydroxide when preparing - is about 1=1, preferably about 0.95 to 1.05
, more preferably in the range of about 1:1 to 1.01:l, and most preferably 1.005:1. The alkali metal bisulfides used in the present invention include lithium bisulfide, sodium bisulfide, , potassium bisulfide, rubidium bisulfide, cesium bisulfide and mixtures thereof.

In terms of its effectiveness and ease of use, the preferred alkali metal hydrosulfide is sodium hydrosulfide (NaSH).In terms of its effectiveness and ease of use, the preferred alkali metal hydroxide is sodium hydroxide (NaOH). be.

Solvents useful in preparing the polymers of our invention are polar organic solvents. Such polar organic solvents include amides and sulfones.

Polar organic solvents used in the preparation of polymers in this invention must be substantially liquid under the reaction temperatures and pressures used; they may be cyclic or acyclic; It can have 1 to about 18 carbon atoms.

Specific examples of such polar organic solvents include 1,3-dimethyl-2-imidazolidinone, formamide, acetamide, hexamethylphosphoamide, tetramethylurea,
N, N'-ethylene-2-pyrrolidone, N-methyl-
2-pyrrolidone (NMP), 2-pyrrolidone, ε-caprolactam, N-ethylcaprolactam, sulfolane,
Included are N,N'-dimethylacetamide, diphenylsulfone, and mixtures thereof. A preferred polar organic solvent is NMP because of its effectiveness and commercial applicability.

Particularly when preparing PASK, a molar excess (stoichiometric excess) of the alkali metal hydrosulfide is present in the reaction mixture.
Preferably, water is present.

Although the ratio of molar excess water to hydrosulfide may vary slightly, - the molar ratio in the membrane is from about 3.5:1 to 7:1, preferably from about 11:1 to 6=1, and more. Preferably about 4.7
:1 to 5.7:1. When preparing PASS, the molar ratio of water to hydrosulfide is approximately 2:1 to 12.
: It is preferable to set it in the range of 1.

The examples presented are intended to be helpful in further understanding the invention.

The specific materials, species, and conditions employed are intended to more particularly illustrate the invention and are not intended to limit the reasonable scope of the invention.

This example describes the preparation of poly(phenylene sulfitogetone) (PASK) as a control experiment. A 2 gallon stainless steel reaction kettle equipped with an anchor stirrer and nitrogen gas inlet was charged with the following:

・2.01 mol sodium bisulfide solution (1 in solution
Contains 91.8 grams of Na5H) - 2.00 moles of sodium hydroxide
OH80g, Mallinckrodt, In
c.

SL, Louis, Mo. product), 2.00 moles of 4.4-"dichlorobenzophenone (DCBP502 grams, product of Ihara Chemical Industry Co., Ltd.), 24.84 moles of N-methyl-2-pyrrolidone (NM
P2400zf, BASF product) 6 moles of deionized water (108 tj water, 3 sealed reactors, 1100 psi N
The kettle was flushed several times with two gases and then degassed to remove the air in the kettle while the reaction kettle mixture was stirred at room temperature.

The reaction kettle mixture was then heated to a temperature of about 250°C and held at this temperature for about 4 hours. The pressure inside the pot is approximately 180psi
After reaching Fi, the reaction vessel was cooled to about 200°C. Approximately 0.025 mol of 4,4'-dichlorobenzophenone was introduced with an end-capping group (en
Do not charge the reactor for the purpose of dcap).

The system was heated to 250° C. for an additional hour and then cooled to room temperature overnight. After filtration, it was washed once with deionized cold water and three times with deionized hot water, and dried in a forced convection air oven at -'qllo° C. for about 6 hours. PP5K prepared from this hand condyle showed acceptable melt stability, however outgassing of the polymer melt was evident and the polymer extrudates were black and brittle. The polymer also took on a black, carbonaceous appearance.

This example uses PP prepared in the same manner as in Example ①.
5K was contacted (washed) with a NaOH aqueous solution and then a CaCL aqueous solution to obtain a PPS with good melt stability.
This is a concrete explanation of the preparation of K.

The crude product taken out from the reaction vessel was washed with hot water (tap water/distilled water/ionized water) and filtered. The washing step is typically repeated five times to remove residual by-products and solvents. The wet polymer was charged back into the 2 gallon reactor with a 1% NaOH solution (3000 z1 of solution per 500 grams of polymer). Apply pressure to the reaction vessel,
Flushed several times (3 times) with 00psi N2 gas 9
The reaction mixture was heated to about 125°C and immediately cooled.

The polymer was then filtered and rinsed once with distilled water, after which the polymer t! The mixture was returned to the reaction vessel together with 3,000 zl of -5% calcium chloride (CaCf2) aqueous solution.

The reaction mixture was pressurized with 100 psi N2 gas and heated several times (
Flashed 3 times. The reaction mixture was then heated to 185°C for 3
Heated for 0 minutes and cooled. The reaction mixture was then rinsed once with distilled water and dried in a forced convection air oven at about 100 DEG to about 110 DEG C. for about 18 hours. The melt stability and physical properties of PP5K are summarized in Table I.

Table 1 7- releases CaCl2 or Na011 gas; extruded product is black and brittle.

without washing.

#2 No end cap, poly 247 168
1027- is Na011 then CaCL No gas release; extruded product gray and washed with melt. It becomes less brittle over time in the indexer.

#3 4=ritltl benzophenone 376
668 580 with end cap, poly gas release; extrusion is black and brittle.

mer is CaCl2 or No washing with Na011.

#4 4-ri I7+7 Benzofeno 163
95 End eV tube at 32mm, no gas release; extruded product is gray and melt boiler +7? - is Na08th index? - Over time, the brittleness disappears by cleaning with CnC1z.

Note: (a) Melt indexer - 371°C (b) Flow My/10 min Results in Table I - PP5K polymer washed with sodium hydroxide and calcium cations shows no outgassing (no bubbles or voids) and extrusion The product is gray, indicating that as time passes in the melt indexer, it becomes less brittle and becomes more tenacious. Compared to that, N
PP5K that was not cleaned with aOH and CaC1z showed outgassing, the extrudate was black and brittle, and the polymer had a black carbonaceous appearance.From the results in Table 1, PP5K was
When aOH and CaC12 are contacted sequentially, NaOH
Compared to PP5K that was not contacted with CaCl2, P
It is clear that this would improve the melt stability and polymer quality of P5K.

From the above results, it is clear that processing PP5K poses some unique problems. As shown by the above data, PP5K treated or cleaned according to the present invention is dramatically improved in quality; the melt stability of PP5K treated according to the present invention is improved to the extent that it can be injection molded.

This example describes the preparation of poly(phenylene sulfide sulfone) (PPSS) as a control experiment. A 2 gallon stainless steel reactor equipped with an anchor stirrer and nitrogen gas inlet was charged with the following:

2.01 molar sodium bisulfide solution (190.5 grams of a 59.15 weight percent aqueous solution of NaSH)
2.11 moles of sodium acetate (172.9 grams as Na Ac, N1acet Corp, Nia
Gara Falls.

N, Y, product) - 2.01 mol of bis(p-chlorophenyl)sulfone (557. as bis(p-chlorophenyl)sulfone).
1 gram, Union Carbide product), 16.5 moles of NMP (1600zz, BASF product), 6 moles of deionized water (108 il of water). Seal the reaction vessel and add 1100 p.
The air inside the kettle was removed by flushing with siN2 gas several times and then venting, while the mixture in the reaction kettle was stirred at room temperature.

While stirring the reaction kettle mixture at 400 rpm,
The mixture was heated to a temperature of 0.degree. C. and maintained at this temperature for approximately 2 hours. The pressure within the kettle reached approximately 100 psig.

The reaction kettle mixture was then heated to 200°C and held at this temperature for 1 hour. The pressure within the kettle reached 1105 psi. The reaction vessel was then cooled to room temperature overnight. The product was a smooth cloudy purple solid that was filtered, triturated in a Waring Blender®, washed once with cold water, and dried in a forced convection air oven for approximately 110 min. It was dried at ℃ for about 18 hours. The ppss prepared by this procedure showed acceptable melt stability, but outgassing from the polymer melt was evident and the polymer extrudates were dark and brittle.

Fire village! This example is a pps manufactured in the same manner as in Example ①.
This illustrates that ppss of good quality and melt stability was prepared by contacting (washing) S with an aqueous solution of NaOH and then an aqueous solution of calcium chloride or calcium acetate.

ppss was prepared in the same manner as in Example 2, with the following minor modifications.

・2.00 Molar sodium bisulfide solution (NaSH 5
187.52 grams of aqueous solution with a concentration of 9.15% by weight)・2
．． 02 mol of sodium acetate (N aA c , 165
．． 7 grams, N1acet Corp,, of N
iagara falls.

N, Y, product) 2.02 moles of bis(p-talolophenyl) sulfone 580.02 grams, Union Carbide product) 2
．． 02 moles of sodium carbonate (214,1 grams) 1
6.166 moles of NMP (1562z/, BASF product) - 6 moles of deionized water (water 108zf) The reaction kettle mixture was heated with continued stirring and slowly raised to a temperature of about 200°C over about 2172 hours. . The kettle pressure at this time reached 180 psig. This temperature was maintained for approximately 4 hours. The reaction vessel was then rapidly cooled to approximately room temperature.

The crude product from the reaction kettle was ground in a Waring blender, washed once with deionized cold water and three times with deionized hot water, and filtered. The washing step is to remove residual salt by-products and solvents. The water-containing polymer was returned to the reaction vessel together with a 1% by weight NaOH aqueous solution (500 grams of polymer and 3,000 grams of aqueous solution).The reaction vessel was pressurized with 1100 psi N2 gas and The reaction kettle mixture was then heated to about 120°C and immediately cooled.The polymer was then filtered off and rinsed three times with distilled water at room temperature.The wet polymer was 5% by weight.
The reaction mixture was returned to the reaction vessel together with 3000 z1 of calcium chloride (CaCf2) or calcium acetate solution, was pressurized with 1100 psi N2 gas, and was heated several times (
3 times). The reaction mixture was then heated to 185°C for approximately 30 minutes. The reaction mixture was cooled, filtered, washed three times with distilled water, and heated to approximately 100 °C in a forced convection air oven.
It was dried at about 110° C. for about 18 hours.

The melt stability and physical properties of ppss are summarized in Table H.

(Note) (a) Melt indexer temperature 343℃ (b)
Flow rate expressed in 2710 minutes (c) Test is 88.
Finished in 29 seconds, polymer quality was poor and showed outgassing.

(d) The washed polymer has a very light amber color;
Only very slight outgassing was observed during melt flow rate measurements.

(e) Measurement of the flow velocity of the melt flow was completed within the first 30 seconds after the flow started.

The results in Table H show that the ppss washed with sodium hydroxide and calcium chloride showed no outgassing and the extrudates were amber in color and became less brittle and tougher with time in the melt indexer. It is shown that. In comparison, ppss that was not washed with NaOH and CaCL
showed outgassing, the extrudates were black and brittle, and the polymer had a black carbonaceous appearance. As is clear from the results in Table ■, ppss is mixed with NaOH and CaC1z.
Contacting with NaOH and CaC would clearly improve the melt stability and polymer quality of ppss compared to no contact with NaOH and CaC9 From the above results, processing of ppss poses some unique problems. It is obvious to do so. As shown by the data above, the quality of the ppss is dramatically improved when the ppss is processed according to the present invention. The melt stability of ppss treated according to the invention is improved to the extent that it can be injection molded.

11! This example illustrates that curing the polymers of the present invention increases the molecular weight of the polymer while improving polymer quality.

The molecular weight of the polymer of Example 1 above and Run #4 of Table I was measured at various points during curing. The results are shown in the table below■
Shown below.

Sac-"L During melt-"> Internal viscosity [(c) 0.58 0.64 0.67 0.7
5 Note) (a) Melt indexer temperature 700'F (3
71℃) (b) Flow rate g/10 minutes (c) dl/y Deciliters/grams above table■
The results show good curing. The polymer cured as described above showed good mechanical properties and good film forming ability. The results show that improved polymer properties are obtained by curing PP5K in contact with NaOH and CaCl2.

(4 other people)

Claims (27)

[Claims] (1) A method for improving the melt stability of poly(arylene sulfide ketone) or poly(arylene sulfide sulfone) comprising treating the polymer with calcium cations. (2) Polymer and calcium cation at a temperature of about 100°C to 200°C, about 15 to 1500 ps
2. The method of claim 1, comprising contacting for about 1/2 minute to 3 hours under a pressure of ia. (3) The method according to claim 1 or 2, wherein the calcium cation is derived from a calcium salt. (4) The method according to claim 3, wherein the calcium salt is calcium carboxylate. (5) The method according to claim 4, wherein the calcium carboxylate is calcium acetate. (6) The method according to claim 3, wherein the calcium salt is a calcium halide. (7) The method according to claim 6, wherein the calcium halide is calcium chloride. (8) The method according to any one of claims 1 to 7, wherein the polymer is a poly(arylene sulfide ketone) represented by a repeating unit of the following structural formula. ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (9) The poly(arylene sulfide ketone) is
phenylene sulfide ketone). (10) The method according to any one of claims 1 to 7, wherein the polymer is a poly(arylene sulfide sulfone) represented by a repeating unit of the following structural formula. ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (11) The method according to claim 10, wherein the poly(arylene sulfide sulfone) is poly(phenylene sulfide sulfone). (12) Claims 1 to 9 in which the poly(arylene sulfide ketone) to be contacted is obtained by contacting a polyhaloaromatic ketone and an alkali metal sulfide under polymerization conditions in a polar organic solvent. The method described in any of the above. (13) Water is also present in the polar organic solvent, and the amount thereof is about 3.5:1 to 7 in a molar ratio of water to alkali metal sulfide.
The method according to claim 12 in the scope of: 1. (14) The method according to claim 12 or 13, wherein the polyhaloaromatic ketone is dihalobenzophenone and the polar organic solvent is an organic amide. (15) The dihalobenzophenone consists of 4,4'-dichlorobenzophenone, and the organic amide is N-methyl-
15. The method of claim 14 comprising 2-pyrrolidone. (16) Claims 1 to 7 in which the poly(arylene sulfide sulfone) to be contacted is obtained by contacting a polyhaloaromatic sulfone and an alkali metal sulfide under polymerization conditions in a polar organic solvent. , 10th
12. The method according to any one of paragraphs 1 and 11. (17) Water is also present in the polar solvent, and the amount thereof is in a molar ratio of water to the alkali metal sulfide of about 2:1 to about 12
The method according to claim 16 in the scope of: 1. (18) The method according to claim 16 or 17, wherein the polyhaloaromatic sulfone comprises a dihaloaromatic sulfone, and the polar organic solvent comprises an organic amide. (19) The method according to claim 18, wherein the dihaloaromatic sulfone comprises bis(p-chlorophenyl)sulfone and the organic amide comprises N-methyl-2-pyrrolidone. (20) An alkali metal sulfide is prepared from an alkali metal hydrosulfide and an alkali metal hydroxide, and the molar ratio of the alkali metal hydrosulfide to the alkali metal hydroxide is about 0.95:
1 to 1.05:1, and the molar ratio of monomer to alkali metal hydrosulfide is about 0.95:1 to 1.05:1.
20. A method according to any one of claims 12 to 19 in scope 1. (21) The method according to claim 20, wherein the molar ratio of sodium bisulfide to sodium hydroxide is about 1.005:1. (22) The resulting poly(arylene sulfide ketone) or poly(arylene sulfide sulfone) is diluted with an alkali metal base prior to contacting the poly(arylene sulfide ketone) or poly(arylene sulfide sulfone) with a cation. 22. A method according to any one of claims 12 to 21, comprising treatment with an aqueous solution. (23) The method according to claim 22, wherein the alkali metal base is an alkali metal hydroxide. (24) The method according to claim 23, wherein the alkali metal hydroxide is sodium hydroxide. (25) The method according to any one of claims 1 to 24, wherein the polymer is cured after being contacted with the calcium cation. (26) Solvent-stable poly(arylene sulfide ketones) or poly(arylene sulfide sulfones) containing calcium cations. (27) A fiber of the polymer according to claim 26.