CN109071937B

CN109071937B - Compatibilized polymer composition

Info

Publication number: CN109071937B
Application number: CN201780026584.1A
Authority: CN
Inventors: S.乔尔; M.蒙塔兹; C.布舍曼; W.E.萨特奇
Original assignee: Solvay Specialty Polymers USA LLC
Current assignee: Solvay Specialty Polymers USA LLC
Priority date: 2016-04-29
Filing date: 2017-04-28
Publication date: 2022-09-06
Anticipated expiration: 2037-04-28
Also published as: CN109071937A; WO2017186923A1

Abstract

A polymer composition comprises poly (p-phenylene sulfide) (PPS), at least one poly (aryl ether sulfone) (PAES), and at least one alkali metal carbonate. Preferably, the polymer composition is free or substantially free of solvent. One method includes melt mixing poly (p-phenylene sulfide) (PPS), at least one poly (aryl ether sulfone) (PAES), and at least one alkali metal carbonate.

Description

Compatibilized polymer composition

RELATED APPLICATIONS

This application claims priority from U.S. provisional application No. 62/329,522 filed on day 29, 2016 and european patent application No. 16187800.4 filed on day 8, 9, 2016, each of which is incorporated by reference in its entirety for all purposes.

Technical Field

The present invention relates to high performance compatibilized polymer compositions comprising poly (p-phenylene sulfide) (PPS) and at least one poly (aryl ether sulfone) (PAES).

Background

The polymers may be blended to obtain new compositions having desired properties; however, most polymers are miscible with each other. When the polymers are miscible with each other, attempts to blend these polymers often result in heterogeneous multiphase compositions. Such compositions may exhibit several thermal transition temperatures (Tg, Tm), often exhibit poor mechanical properties, and suffer from delamination and/or aesthetic defects.

In fact, the mechanical properties and ease of processing of a particular blend depend on the degree of compatibility of the polymer components. The major polymeric component is generally referred to as the continuous phase or matrix, while the minor polymeric component is typically defined as the dispersed phase. The degree of compatibility can be characterized by the size of the dispersed phase in the continuous phase and the level of adhesion between the matrix and the dispersed phase. Certain highly immiscible blends are not possible to extrude under normal operating conditions due to high die swell and are therefore not commercially available.

PPS is known to have very good chemical resistance and low melt viscosity, and PAES is known to have excellent mechanical properties and good thermal stability. It is therefore desirable to blend these polymers to achieve a combination of their properties. However, blends of PPS and PAES are not always very compatible, exhibiting poor tensile properties in some cases, due to the presence of large domains (domains) of the individual polymers in the blend of these polymers and due to poor adhesion between these phases.

Therefore, there is a need for new blends of PPS and PAES with increased compatibility.

Drawings

Fig. 1 shows Transmission Electron Microscope (TEM) images of the compositions of example 1 (fig. 1A) and comparative example 11 (fig. 1B).

Fig. 2 shows TEM images of the compositions of example 2 (fig. 2A) and comparative example 12 (fig. 2B).

Fig. 3 shows TEM images of the compositions of example 3 (fig. 3A) and comparative example 13 (fig. 3B).

Fig. 4 shows TEM images of the compositions of example 4 (fig. 4A) and comparative example 14 (fig. 4B).

Fig. 5 shows TEM images of the compositions of example 5 (fig. 5A) and comparative example 6 (fig. 5B).

Fig. 6 shows TEM images of the compositions of example 7 (fig. 6A) and comparative example 8 (fig. 6B).

Fig. 7 shows TEM images of the compositions of example 9 (fig. 7A) and example 10 (fig. 7B).

Fig. 8 shows TEM images of the compositions of example 15 (fig. 8A) and comparative example 18 (fig. 8B).

Fig. 9 shows TEM images of the compositions of example 17 (fig. 8A) and comparative example 21 (fig. 8B).

Fig. 10 shows a TEM image of the composition of comparative example 27.

Fig. 11 shows a TEM image of the composition of comparative example 8.

Fig. 12 shows a TEM image of the composition of comparative example 29.

Figure 13 shows a TEM image of the composition of example 30.

Detailed Description

Applicants have now unexpectedly found that it is possible to prepare polymer blends with increased compatibility, including blends of highly miscible polymers such as poly (p-phenylene sulfide) (PPS) with poly (aryl ether sulfone) (PAES).

Exemplary embodiments are directed to a polymer composition comprising PPS, at least one PAES, and about 0.05 wt.% to about 2 wt.% of at least one alkali metal carbonate, based on the total weight of polymers in the composition. Preferably, the weight ratio of PPS to the at least one PAES is in the range of from 0.2 to 20.

In some embodiments, the polymer composition is free or substantially free of solvent, that is, the composition contains no solvent and contains one or more solvents in an amount of no more than 2 wt.% (based on the total weight of the composition), for example, less than 1 wt.%, less than 0.5 wt.%, or less than 0.1 wt.%.

In some embodiments, the polymeric composition is free or substantially free of Polyetherimide (PEI), that is, the composition does not include PEI and comprises PEI in an amount of no more than 2 wt.% (based on the total weight of the composition), e.g., less than 1 wt.%, less than 0.5 wt.%, or less than 0.1 wt.%.

In some embodiments, the polymer composition is free or substantially free of epoxide, that is, the composition does not contain epoxide and contains epoxide in an amount of no more than 2 wt.% (based on the total weight of the composition), for example, less than 1 wt.%, less than 0.5 wt.%, or less than 0.1 wt.%.

For clarity, throughout this application:

the term "alkali metal carbonate" includes alkali metal carbonates as well as any agent that can derivatise the alkali metal carbonate in situ during processing at elevated temperatures, such as alkali metal bicarbonates.

The term "solvent" means a liquid in which at least one of the polymers in the polymer composition will be at least partially dissolved;

"substantially free of solvent" means less than 2 wt.% solvent, e.g., less than 1 wt.%, less than 0.5 wt.%, or less than 0.1 wt.% (based on the total weight of the composition);

"substantially simultaneously" means within 30 seconds;

"substantially free of Polyetherimide (PEI)" means less than 2 wt.% of Polyetherimide (PEI), for example less than 1 wt.%, less than 0.5 wt.%, or less than 0.1 wt.% (based on the total weight of the composition);

by "substantially free of epoxide" is meant less than 2 wt.% epoxide, for example less than 1 wt.%, less than 0.5 wt.%, or less than 0.1 wt.% (based on the total weight of the composition);

"substantially free of rPAES" means less than 2 wt.% rPAES, based on the total weight of polymers in the polymer composition;

"substantially no die swell" means less than 5% die swell; and is

The term "halogen" includes fluorine, chlorine, bromine and iodine unless otherwise indicated.

In general, PPS and PAES have a weight average molecular weight ranging from 5,000g/mol to 150,000g/mol, preferably from 10,000g/mol to 100,000 g/mol.

In the present application:

any description, even if described with respect to a specific embodiment, applies to and is interchangeable with other embodiments of the present disclosure;

-when an element or component is said to be comprised in and/or selected from a list of enumerated elements or components, it is understood that in the relevant embodiments explicitly contemplated herein, the element or component may also be any one of the individual enumerated elements or components and may also be selected from the group consisting of any two or more of the explicitly enumerated elements or components; any element or component listed in a list of elements or components may be omitted from this list; and is

Any recitation herein of numerical ranges by endpoints includes all numbers subsumed within that range and the endpoints of that range and equivalent amounts.

Poly (p-phenylene sulfide) (PPS)

As used herein, "poly (p-phenylene sulfide) (PPS)" means that at least 50 mol% of its repeating units are repeating units (R) having formula (L) _PPS ) Any polymer of (a):

it is preferred that at least 60 mol%, 70 mol%, 80 mol%, 90 mol%, 95 mol%, 99 mol% and most preferably all of the repeating units in the PPS are repeating units (R) _PPS )。

PPS is available from Solvay Specialty Polymers USA (LLC)

PPS is manufactured and sold.

PPS may be acid washed or non-acid washed. In some embodiments, the PPS is ethyl acetate washed PPS.

Poly (aryl ether sulfone) (PAES)

For the purposes of the present invention, "poly (aryl ether sulfone) (PAES)" means that at least 50 mol.% of its recurring units are recurring units (R) of formula (K) _PAES ) Any polymer of (a):

wherein:

(i) each R, equal to or different from each other, is selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium;

(ii) each h, equal to or different from each other, is an integer ranging from 0 to 4; and is provided with

(iii) T is selected from a bond, sulfone [ -S (═ O) _2- -]And the group-C (R) _j )(R _k ) -wherein R is _j And R _k Identical or different from each other, selected from hydrogen, halogen, alkyl, alkenyl, alkynyl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium. R _j And R _k Methyl groups are preferred.

Preferably at least 60 mol%, 70 mol%, 80 mol%, 90 mol%, 95 mol%, 99 mol% and most preferably all of the recurring units in the PAES are recurring units (R) _PAES )。

In a preferred embodiment, the PAES is polyphenylsulfone (PPSU). As used herein, "polyphenylsulfone (PPSU)" means any polymer whose more than 50 mol% of its repeating units are repeating units having the formula (K' -a):

preferably at least 60 mol%, 70 mol%, 80 mol%, 90 mol%, 95 mol%, 99 mol% and most preferably all of the recurring units in the PPSU are recurring units of formula (K' -a).

PPSU can be prepared by known methods and is notably available from Soviet polymers, Inc. in the United states

PPSU is available.

In some embodiments, the PAES is Polyethersulfone (PES). As used herein, "Polyethersulfone (PES)" means any polymer of which at least 50 mol% of its repeating units are repeating units having the formula (K' -B):

preferably at least 60 mol%, 70 mol%, 80 mol%, 90 mol%, 95 mol%, 99 mol% and most preferably all of the recurring units in the PES are recurring units of the formula (K' -B).

PES can be prepared by known methods and is notably available from Suweite polymers, Inc. of U.S.A

Available to PESU.

In some embodiments, the PAES is Polysulfone (PSU). As used herein, "Polysulfone (PSU)" means any polymer whose at least 50 mol% of its repeating units are repeating units having the formula (K' -C):

preferably at least 60 mol%, 70 mol%, 80 mol%, 90 mol%, 95 mol%, 99 mol% and most preferably all of the recurring units in the PSU are recurring units of the formula (K' -C).

PSU can be prepared by known methods and is available from Suweites Polymer, Inc. of USA as

PSU is available.

Excellent results are obtained when PAES is selected from the group consisting of PPSU, PES, PSU, or a combination thereof.

Alkali metal carbonate

The polymer composition includes at least one alkali metal carbonate in an amount ranging from about 0.05 wt.% to about 2 wt.%, about 0.1 wt.% to about 1.8 wt.%, about 0.1 wt.% to about 1.6 wt.%, about 0.1 wt.% to about 1.5 wt.%, about 0.1 wt.% to about 1.3 wt.%, about 0.1 wt.% to about 1.0 wt.%, about 0.1 wt.% to about 0.8 wt.%, about 0.1 wt.% to about 0.5 wt.%, based on the total weight of the polymers in the polymer composition. In some embodiments, the amount of alkali metal carbonate ranges from about 0.1 wt.% to about 0.5 wt.%, about 0.2 wt.% to about 0.5 wt.%, about 0.4 wt.% to about 0.5 wt.%, based on the total weight of the polymers in the polymer composition. In some embodiments, the amount of alkali metal carbonate is less than or equal to 1.0 wt.%, 0.9 wt.%, 0.8 wt.%, 0.7 wt.%, 0.6 wt.%, 0.5 wt.%, 0.4 wt.%, 0.3 wt.%, 0.2 wt.%, 0.1 wt.% based on the total weight of the polymers in the polymer composition.

The alkali metal carbonate may be selected from sodium carbonate, potassium carbonate, cesium carbonate and lithium carbonate. Potassium carbonate is preferred. Mixtures of two or more alkali metal carbonates may be used.

In some aspects, the particle size D50 (median diameter or median value of the particle size distribution) is in the range from 2 microns to 1000 microns, preferably from 2 to 500 microns, most preferably from 3 to 200 microns.

Optionally reactive polymers

The PPS and the at least one PAES may be present in a reactive form (i.e., a reactive polymer) or a non-reactive form.

In their reactive form, these polymers comprise at least 5, at least 10, at least 15, preferably at least 20, preferably at least 50, microequivalents per gram (. mu. eq/g) of hydroxyl (-OH) or thiol (-SH) end groups. One example of such a reactive polymer is reactive polyethersulfone (rPES) available from suwiter polymers llc of the united states as

Available to PESU.

In some embodiments, the polymer composition comprises at least one reactive poly (aryl ether sulfone) (rPAES) in addition to PPS and at least one PAES. The rPAES is preferably selected from reactive polysulfone (rPSU), reactive polyethersulfone (rPES) and reactive polyphenylsulfone (rPPSU).

Preferably, the total amount of rPAES in the polymer composition is in the range of from 0 to 60 wt.%, 1 to 50 wt.%, 5 to 30 wt.%, 5 to 25 wt.%, 5 to 20 wt.%, 5 to 15 wt.%, most preferably about 10 wt.%, based on the total weight of polymers in the polymer composition.

In their non-reactive form, PPS and PAES include one or more non-reactive end groups. The non-reactive end group is preferably-Cl, -F, or-O-CH ₃ . Preferably, the non-reactive polymer comprises at least 20, preferably more than 50, micro-equivalents per gram (μ eq/g) of non-reactive end groups.

In some aspects, the polymer composition may be free or substantially free of rPAES.

PPS is preferably present in its reactive form. The abbreviation "PPS" as used herein includes both reactive and non-reactive poly (p-phenylene sulfide) (PPS).

Optional reinforcing fillers

A large amount of the selected reinforcing filler may be added to the polymer composition. They are preferably selected from fibrous fillers and particulate fillers. Fibrous reinforcing fillers are considered herein to be materials having a length, a width, and a thickness, wherein the average length is substantially greater than both the width and the thickness. Preferably, such materials have an aspect ratio (defined as the average ratio between length and the smallest of width and thickness) of at least 5. Preferably, the aspect ratio of the reinforcing fibers is at least 10, more preferably at least 20, still more preferably at least 50. The particulate filler has an aspect ratio of at most 5, preferably at most 2.

Preferably, the reinforcing filler is selected from mineral fillers such as talc, mica, titanium dioxide, kaolin, calcium carbonate, calcium silicate, magnesium carbonate; glass fibers; carbon fibers, boron carbide fibers; wollastonite; silicon carbide fibers; boron fibers, graphene, Carbon Nanotubes (CNTs), and the like.

The reinforcing filler may be present in the polymer composition in an amount of at least 5 wt.%, preferably at least 10 wt.%, more preferably at least 15 wt.%, based on the total weight of the polymer composition.

The reinforcing filler is also preferably present in an amount of up to 60 wt.%, more preferably up to 50 wt.%, still more preferably up to 40 wt.%, based on the total weight of the polymer composition.

Preferably, the amount of reinforcing filler is in the range of from 0.1 to 60 wt.%, more preferably from 5 to 50 wt.%, still more preferably from 10 to 40 wt.% of the polymer composition. According to some embodiments, the polymer composition is free of fibrous fillers. Alternatively, the polymer composition may be free of particulate filler. In certain specific embodiments, the polymer composition is preferably free of reinforcing fillers.

Additional optional ingredients

In some aspects, the polymer composition consists of or consists essentially of PPS, the at least one PAES, and an alkali metal carbonate; however, in other aspects, the polymer composition may include one or more additional additives.

The polymer composition may further optionally include other ingredients, such as colorants (e.g., dyes and/or pigments such as titanium dioxide, zinc sulfide, and zinc oxide), ultraviolet light stabilizers, heat stabilizers, antioxidants (e.g., organic phosphites and phosphonites), acid scavengers, processing aids, nucleating agents, lubricants, flame retardants, smoke inhibitors, antistatic agents, antiblock agents, and/or conductive additives (e.g., carbon black).

When one or more other ingredients are present, their total weight is preferably less than 20 wt.%, less than 10 wt.%, less than 5 wt.% and most preferably less than 2 wt.%, based on the total weight of the polymer composition.

It has been unexpectedly found that has a pKa<7.5, preferably<The organic and inorganic acid components of 7 are capable of stabilizing the melt viscosity of the polymer compositions of the present invention. Having a pKa<7.5 non-limiting example of organic and inorganic Components is sodium hydrogen phosphate (NaH) ₂ PO ₄ ) Monosodium citrate, sodium hydrogen oxalate, and sodium hydrogen phthalate. Preference is given to inorganic components, such as, for example, having a pKa<NaH of 7 ₂ PO ₄ . Excellent results were obtained with organic and inorganic components having pKa as follows: 2.5<pKa<7.5, preferably 3<pKa<7. Having a pKa<The organic or inorganic acid component of 7.5 may be present in an amount ranging from 0.05 wt.% to 5 wt.%, preferably from 0.1 wt.% to 2 wt.%, more preferably from 0.2 wt.% to 1 wt.%, based on the total weight of the polymers in the polymer composition.

Exemplary Polymer blends

Preferred polymer compositions are shown in table 1. Each polymer composition may include other ingredients in addition to those listed. Each preferred polymer composition also includes an alkali metal carbonate (preferably potassium carbonate or sodium carbonate) in an amount ranging from 0.05 wt.% to about 2 wt.%, or in an additional amount as disclosed herein. Each preferred polymer composition may optionally include an acid component as described herein.

TABLE 1

Polymer composition	Polymer (A)	Polymer (B)	Polymer (C)
				1	PPS	PSU	--
2	PPS	PES	--
				3	PPS	PPSU	--
7	PPS	rPSU	--
				8	PPS	rPES	--
9	PPS	rPPSU	--
				10	PPS	PSU	rPSU
11	PPS	PES	rPES
				12	PPS	PPSU	rPPSU

In the polymer composition, the concentration of each of the PPS, PAES, and rPAES is independently selected from 0 wt.%, preferably at least 1 wt.%, 2 wt.%, 5 wt.%, 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.%, 50 wt.%, 55 wt.%, 60 wt.%, 65 wt.%, 70 wt.%, 75 wt.%, 80 wt.%, 85 wt.%, 90 wt.%, 95 wt.%, 98 wt.%, 99 wt.% of the total weight of the polymers in the polymer composition.

In some embodiments, the polymer composition comprises about 85 wt.%, preferably about 75 wt.%, more preferably about 65 wt.%, and most preferably about 50 wt.% PPS or PAES and about 15 wt.%, preferably about 25 wt.%, more preferably about 35 wt.%, most preferably about 50 wt.% of the other of the PPS or PAES, respectively, based on the total weight of the polymers in the polymer composition.

In some aspects, the polymer composition comprises (i) from 15 to 85 wt.%, preferably 25 to 75 wt.%, 30 to 70 wt.%, 40 to 60 wt.%, 45 to 55 wt.%, most preferably about 45% wt.% PPS, (ii) from 85 to 15 wt.%, preferably 75 to 25 wt.%, 70 to 30 wt.%, 60 to 40 wt.%, 55 to 45 wt.%, most preferably about 45 wt.% PAES, and (iii) from 1 to 20 wt.%, preferably about 10 wt.% rPAES, based on the total weight of the polymers in the polymer composition.

Preferably, the weight ratio of PPS to the at least one PAES is in the range of from 0.2 to 20, 0.3 to 15, 0.4 to 10, 0.5 to 5, and most preferably 1 to 3.

In some embodiments, the weight ratio of PPS to the amount of the at least one PAES is in the range of from 0.5 to 5, preferably 1 to 3, and the polymer composition comprises 0.15 wt.% to 0.4 wt.%, preferably 0.2 wt.% to 0.4 wt.%, of the at least one alkali metal carbonate, preferably potassium carbonate or sodium carbonate, based on the total weight of polymers in the composition.

In some embodiments, the polymer composition comprises:

i)PPS；

ii) a PPSU; and

iii) from about 0.05 wt.% to about 2 wt.% of at least one alkali metal carbonate, based on the total weight of polymers in the composition,

wherein the weight ratio of PPS/PPSU is in the range from 0.2 to 20.

Exemplary Properties of the Polymer composition

The polymer composition of the present invention may comprise a dispersed phase dispersed in a continuous phase or matrix. An example of a dispersed phase is shown in fig. 4A.

In some embodiments, the average surface area of each dispersed particle is preferably less than or equal to about 4 μm ² About 3 μm ² About 2 μm ² About 1 μm ² About 0.5 μm ² About 0.25 μm ² 。

In some embodiments, the maximum particle size of the dispersed phase is 3 μm or less, preferably 2 μm or less, 1 μm or less, 0.8 μm or less, 0.6 μm or less, 0.4 μm or less, and most preferably 0.1 μm or less.

In an alternative embodiment, the polymer blend may include a co-continuous phase characterized by the presence of a continuous band of polymer components when viewed by Transmission Electron Microscopy (TEM). In such embodiments, the average width of the bands is preferably less than or equal to about 3 μm, more preferably less than or equal to about 2 μm, where the average width is calculated by taking 10 random measurements of the band width, discarding the longest and shortest measurements, and dividing the sum of the remaining measurements by 8.

In some embodiments, the polymer compositions of the present disclosure exhibit a Dynatup impact total energy according to ASTM D3763 in the range of from 25 to 50 ft-lbs.

The polymer composition can exhibit at least two different glass transition temperatures (Tg) corresponding to each of the at least two different polymers; however, these tgs may be different (i.e., shifted) compared to the Tg of the same polymer when not in the polymer composition. In some embodiments, the difference between the corresponding tgs in the polymer composition (Δ Tg) is at least 0.5 ℃, preferably at least 1 ℃, more preferably from 5 ℃ to 50 ℃, even more preferably from 5 ℃ to 10 ℃.

In certain embodiments, the polymer composition has no or substantially no die swell when extruded from the extruder as a melt, and the temperature of the melt is in the range from 300 ℃ to 430 ℃.

Process for preparing polymer compositions

In some embodiments, the present invention includes a method of making a polymer composition described herein by melt mixing: i) PPS, ii) at least one PAES, and iii) about 0.05 wt.% to about 2 wt.% of at least one alkali metal carbonate, based on the total weight of the polymers in the composition. Preferably, the weight ratio of PPS to the at least one PAES is in the range of from 0.2 to 20, preferably 0.3 to 15, 0.4 to 10, 0.5 to 5, and most preferably 1 to 3. Preferably, the polymer composition is free or substantially free of solvent. PPS and PAES may be independently reactive or non-reactive. PPS is preferably a reactive polymer. PPS may be acid washed or not.

The components of the mixture can be added or mixed in any order, in any amount, or as a fraction of their total amount, and can be mixed separately or simultaneously.

The preparation of the polymer composition may be carried out by any known melt mixing process suitable for preparing thermoplastic molding compositions. Such a process may be carried out by heating the polymer above the melting temperature of the semi-crystalline polymer to form a melt of the polymer and/or above the Tg of the amorphous polymer. In some embodiments, the processing temperature is in the range of from about 250 ℃ to 450 ℃, preferably from about 280 ℃ to 420 ℃. Preferably, the processing temperature is at least 15 ℃, preferably at least 50 ℃, preferably at least 100 ℃, preferably at least 150 ℃ greater than the glass transition temperature (Tg) of the highest Tg polymer in the polymer composition and/or at least 15 ℃ greater than the melting temperature (Tm) of the highest Tm polymer in the polymer composition.

In some aspects of the method for preparing a polymer composition, the components that form the polymer composition are fed to and melt mixed in a melt mixing device. Suitable melt mixing devices are, for example, kneaders, Banbury mixers, single-screw extruders and twin-screw extruders. Preferably, an extruder is used which is equipped with means for feeding the desired components into the extruder (either into the throat of the extruder or into the melt). Preferably, the extruder is equipped with one or more ports that allow feeding into the melt at different barrels during the extrusion process.

The components may be fed simultaneously or may be fed separately in the form of a powder mixture or a mixture of pellets (also referred to as a dry blend).

In some embodiments, all of the polymer and alkali metal carbonate are added to the throat of the extruder, preferably at the same time or substantially at the same time. In other aspects, one or more of the polymers may be added to the throat of an extruder along with an alkali metal carbonate, and then one or more other polymers are added to the melt at the extruder barrel. For example, PPS and rPAES, preferably rPES, may be added to the throat of an extruder along with an alkali metal carbonate, and PAES may be subsequently added at a downstream barrel of the extruder. When added, the acid component may be added at the throat of the extruder, or to the melt at any barrel of the extruder. Preferably, the acid component is added to the melt at the downstream barrel such that it contacts the melt shortly before extruding the melt. Preferably, the acid component is added at some point after the alkali metal carbonate is added.

In an exemplary embodiment, multiple passes of extrusion may be performed. In multi-pass extrusion, the extrudate from the first pass is reintroduced into the extruder, preferably at the throat, for a second pass through the extruder. In multi-pass extrusion, two, three, four or more passes may be made, and the polymer, alkali metal carbonate, acid component, or other ingredient may be added at any point in the extruder line in any one pass. For example, PPS may be added to the throat of the extruder along with the alkali metal carbonate, and then the extrudate from the first pass may be recycled to the extruder to which the at least one PAES is added, and the acid component may be added towards the end of the second pass. Alternatively, the extrudate resulting from the second pass may be recycled for a third pass during which, for example, the acid component and/or filler material may be added to the melt prior to extrusion into the final product.

In some aspects, at least two passes may be made, and components may be added to the extrudate and/or to the process (e.g., mixing) performed on the extrudate before it is recycled to the extruder for one or more additional passes.

The extruder may be operated at any suitable speed. The extruder speed and the temperature of the extruder barrel may be constant or variable. Preferably, the one or more extruder screws are rotated at about 100rpm to about 900rpm, preferably from about 200 to about 500 rpm; however, the speed and temperature may be adjusted based on the particular polymer composition being blended.

As used herein, "total residence time" means the total time spent in the extruder by the longest-residing component, including multiple passes, if any. The total residence time preferably ranges from about 15 seconds to about 4 minutes, preferably from about 30 seconds to about 2 minutes.

The polymer compositions described herein are advantageously provided in the form of pellets, which can be used in injection molding or extrusion processes known in the art.

An exemplary embodiment relates to a method comprising:

(a1) contacting PPS, the at least one PAES, and an alkali metal carbonate to form a first initial mixture;

(a2) contacting PPS with an alkali metal carbonate to form a second initial mixture, and subsequently contacting the second initial mixture with the at least one PAES mixture to form a second mixture;

(a3) contacting the at least one PAES with an alkali metal carbonate to form a third initial mixture, and subsequently contacting the third initial mixture with PPS to form a third mixture; or

(a4) Contacting PPS with the at least one PAES to form a fourth initial mixture, and subsequently contacting the fourth initial mixture with an alkali metal carbonate to form a fourth mixture; and is provided with

(b) Optionally contacting the first initial mixture, the second mixture, the third mixture, or the fourth mixture with an acid component as described herein.

In an alternative embodiment, the method comprises:

(a1) contacting PPS, the at least one PAES, rPAES, and alkali metal carbonate to form a first initial mixture;

(a2) contacting PPS, rPAES, and an alkali metal carbonate to form a second initial mixture, and subsequently contacting the second initial mixture with the at least one PAES to form a second mixture.

(a3) Contacting the at least one PAES, rPAES, and alkali metal carbonate to form a third initial mixture, and then contacting the third initial mixture with PPS to form a third mixture; or

(a4) Contacting PPS, the at least one PAES, and rPAES to form a fourth initial mixture, and then contacting the fourth initial mixture with an alkali metal carbonate to form a fourth mixture; and is provided with

In some embodiments, the method comprises:

(a1) contacting PPS, the at least one PAES, and an alkali metal carbonate to form a first initial mixture, and subsequently contacting the first initial mixture with rPAES to form a first mixture;

(a2) contacting PPS and an alkali metal carbonate to form a second initial mixture, and subsequently contacting the second initial mixture with the at least one PAES and rPAES to form a second mixture;

(a3) contacting the at least one PAES and an alkali metal carbonate to form a third initial mixture, and subsequently contacting the third initial mixture with PPS and rPAES to form a third mixture; or

(a4) Contacting PPS and the at least one PAES to form a fourth initial mixture, and subsequently contacting the fourth initial mixture with an alkali metal carbonate and rPAES to form a fourth mixture; and is provided with

(b) Optionally contacting the first mixture, the second mixture, the third mixture, or the fourth mixture with an acid component as described herein.

Shaped article comprising a polymer composition

Exemplary embodiments also include articles comprising the polymer compositions described above.

The article may be made from the polymer composition using a suitable melt-processing method. In particular, they can be made by injection molding, extrusion molding, rotational molding, or blow molding.

The polymer composition may be well suited for making articles useful in a wide variety of end uses.

The invention will be explained in more detail below by way of non-limiting examples in the following sections.

If the disclosure of any patent, patent application, and publication incorporated by reference in this application conflicts with the description of the present application to the extent that terminology may become unclear, the description shall take precedence.

Examples of the invention

Examples 1 to 10 and comparative examples 11 to 14

Examples 1 to 10: blend of PPSU and PPS (containing K) ₂ CO ₃ )

Comparative examples 11 to 14: blend of PPSU with PPS without K ₂ CO ₃

Materials:

-

PPSU R-5900NT from Suweiter Polymer, Inc. of USA

-

PPS QA200N, from Suweiter polymers, Inc. of America

-

PPS QA250N, from Suweiter polymers, Inc. of America

-

PPS QC160N, available from Suweiter polymers, Inc. of U.S.A

-

PPS QC220N, available from Suweiter polymers, Inc. of U.S.A

-K ₂ CO ₃ ，UNID EF-90

Mixing:

use of

The blend was compounded on a ZSK-26 co-rotating twin screw extruder (with an L/D ratio of 48: 1) at 200-300rpm and 12-18 kg/hr. Barrel temperature set points were as follows: zones 1 to 6 are 360 deg.c, zones 7 to 12 are 340 deg.c, and 360 deg.c at the die.

Measurement:

melt viscosity was measured according to ASTM D5630 at 360 ℃ and 4001/sec.

The morphology of the blend was examined by Transmission Electron Microscopy (TEM) to find the maximum diameter of the dispersed phase domains.

As a result:

the blend compositions and measurements are shown in table 2 below. The morphology of the blends is shown in the TEM images of fig. 1-7.

Comparing examples 1, 2, 3, and 4 with comparative examples 11, 12, 13, and 14, respectively (see also FIGS. 1-4), it was unexpectedly found that the addition of 0.4 wt% K ₂ CO ₃ The compatibility of the blend of PPSU and PPS is significantly improved, such as by much smaller dispersed phase domain size (< 0.5 μm, compared to ≥ 2 μm) and blends (to which K has been added) ₂ CO ₃ ) As evidenced by the increased melt viscosity of (a). Comparison of examples 1 and 2 with comparative examples 11 and 12 shows that improved compatibility is achieved with PPSU-rich blends (PPSU as continuous phase and PPS as dispersed phase); while a comparison of examples 3 and 4 with comparative examples 13 and 14 shows that improved compatibility is also achieved with PPS-rich blends (PPS as the continuous phase and PPSU as the dispersed phase).

Examples 5 to 10 (FIGS. 5-7) illustrate varying the PPS to PPSU ratio and K ₂ CO ₃ The effect of the amount of (c).

Examples 15 to 17 and comparative examples 18 to 21

Examples 15 to 17: PPSU, PPS and K ₂ CO ₃ Wherein the PPS is washed with acetic acid.

Comparative examples 18 to 21: PPSU, PPS and K ₂ CO ₃ Wherein the PPS is not washed with acetic acid. Materials:

-

PPSU R-5900NT from Suweiter Polymer, Inc. of USA

-

PPS QA250N, from suweiter polymers llc, usa; washing with acetic acid

-

PPS QC220N, from suweiter polymers llc, usa; washed with calcium acetate

-

PPS PR34, available from suweite polymers llc, usa; water-washed

-K ₂ CO ₃ UNID EF-90

Compounding and measurement

The blend was compounded as in example 1.

Melt viscosity and morphology measurements were performed as in example 1.

As a result:

the blend compositions and measurements are shown in table 3 below.

Comparing examples 15, 16, and 17 with comparative examples 18, 19, 20, and 21 (see also fig. 8 and 9), it can be seen that the use of a PPS polymer washed with acetic acid unexpectedly improves the compatibility of the PPSU with the blend of PPS, as evidenced by the smaller dispersed phase domain size of the blend of PPS polymer that has been contacted with acetic acid. In each case, the maximum dispersed phase domain size of the blends using PPS polymers washed with water or calcium acetate is unexpectedly greater than the maximum dispersed phase domain size of the blends using PPS polymers washed with acetic acid.

Examples 22 to 26

Comparative example 22: a blend of PPS/PES.

Examples 23 to 27: PPS/PES/K ₂ CO ₃ The blend of (1).

The compositions are described in table 4.

Materials:

-

PESU 3300ULT from SUWISTE POLYMER GmbH, USA

-

PPS QA200N, from Suweiter polymers, Inc. of America

-K ₂ CO ₃ LH-90 from Howard Industries, Inc.

Mixing:

using a 26mm diameter with an L/D ratio of 48:1

The compositions of Table 4 were subjected to melt compounding by a ZSK-26 co-rotating partially intermeshing twin screw extruder. Barrel sections 2 through 12 and the die are heated to the following setpoint temperatures:

barrels 2-6: 360 deg.C

Barrels 7-12: 350 deg.C

Die opening: 360 deg.C

In each case, the resin and additives were fed at barrel section 1 and barrel section 5 using a gravimetric feeder at a throughput rate in the range of 30-40 lb/hr. The extruder was operated at a screw speed of about 200 RPM. Vacuum was applied at barrel zone 10 with a vacuum level of about 27 inches of mercury. A single orifice die was used for all compounds and the molten polymer strand exiting the die was cooled in a water tank and then cut in a pelletizer.

Injection molding:

the polymer composition was injection molded to produce 3.2mm (0.125 inch) thick ASTM tensile and flexural samples and 4 x 0.125 inch plaques for mechanical property testing. Type I tensile ASTM samples and 4 x 0.125 inch plaques were injection molded using the following approximate temperature conditions on the barrel and mold:

a rear area: 680 DEG F

An intermediate zone: 680 DEG F

Front zone: 700 DEG F

A nozzle: 700 DEG F

A mould: 285 DEG F

Measurement:

mechanical properties of all formulations were tested using injection molded 0.125 inch thick ASTM test specimens (4X 0.125 inch plaques) for Dynatup impact testing (D-3763: high speed puncture multiaxial impact).

Chemical resistance (environmental stress crack resistance) was evaluated by exposing the bent rods to methyl ethyl ketone under variable stress for 24 hours. The time of exposure to methyl ethyl ketone is increased without the material exhibiting any cracking or microcracking.

As a result:

high speed breakdown multiaxial impact (Dynatup impact) data and tensile properties after thermal aging are reported in table 4:

TABLE 4

N.d. impossible test without K ₂ CO ₃ Because it is not possible to produce the material according to the above-mentioned method. Excessive expansion of the blend during extrusion and poor melt strength make it impossible to produce pellets which are later used for injection molding of tensile and flexural samples.

K ₂ CO ₃ The incorporation of (a) unexpectedly enhances the impact properties and environmental stress crack resistance of blends of PPS and PES.

Comparative examples 27, 28 and 29 and example 30

Comparative example 27: 50/50 parts of blend PPS/PES, with a residence time of 5 min.

Comparative example 28: 45/45/10 parts of the blend PPS/PES/rPES, with a residence time of 5 min.

Comparative example 29: 45/45/10/2 parts of blend PPS/PES/rPES/ZnO, for a residence time of 3 min.

Example 30: blend PPS/PES/rPES/K ₂ CO ₃ 45/45/10/0.5 part, for a residence time of 3 min.

Materials:

PPS reference T4G from DIC Corporation (DIC Corporation)

-

PESU 3600P from suweiter polymers llc, usa.

-reactive poly (ether sulfone) (rPES): rPES synthesized according to known methods from 4, 4' -dichlorodiphenyl sulfone, bisphenol S (excess), potassium carbonate (excess) in sulfolane as solvent. End group titration of rPES polymer gives:

concentration of o hydroxy end group [ -OH ] -, 219 μ eq/g

Concentration of potassium phenoxide end group [ -OK ] & gt, 60 μ eq/g

Concentration of omicron chloride end group [ -Cl ] & gt, 7 μ eq/g

-number average molecular weight (Mn) — 2,000,000/([ -OH ] + [ -OK ] + [ -Cl ]) 7,000g/mol

-Potassium carbonate K ₂ CO ₃ UNID EF-80

-zinc oxide ZnO

Mixing:

DSM heated to 380 ℃ and equipped with a recirculation loop allowing control of residence time

The blend was compounded in a twin screw (100rpm) extruder. The material (7 g total) was introduced and mixed simultaneously for a certain time (residence time) before being extruded into a strand.

And (3) measurement:

the torque required to rotate the extruder screw was measured during blending. Torque is related to the viscosity of the molten blend, with greater force indicating greater viscosity.

The level of die swell at the exit of the extruder was observed and classified as follows: very large die swell, some die swell, + limited die swell, + no die swell.

The thermal properties, i.e. melting temperature and crystallization temperature, were determined by DSC.

The morphology of the blends was analyzed by Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) to give the maximum diameter of the dispersed phase.

As a result:

the blend compositions and measurements are shown in table 5 below. The morphology of the blends is shown in fig. 9-12.

TABLE 5

	C27	C28	C29	E30
					PPS (in)	50	45	45	45
PES (parts)	50	45	45	45
					rPES (parts)	-	10	10	10
ZnO (copies)	-	-	2	-
					K ₂ CO ₃ (share)	-	-	-	0.5
Residence time (min)	5	5	3	3

Initial force (N)	900	753	665	1,680
					Final force (N)	1010	850	730	2,178

					Die orifice expansion	--	--	-	++

					Tc(℃)	239	236	236	224
Tm(℃)	281	280	283	279

In fig. 10 it is shown that PPS and PES are clearly immiscible. As shown in fig. 11, the introduction of rPES (hydroxyl terminated PES) did not significantly compatibilize the polymer, and very large die swell was observed. Furthermore, as shown in fig. 12, further addition of the base ZnO also did not result in significant changes in the morphology of the PPS and PES blend, and some die swell was still observed.

However, unexpectedly, when additional base K is added ₂ CO ₃ When added to PPS, PES, and rPES polymer compositions, good compatibilization of PPS and PES was observed, as shown by the dispersed phase of example 30 (fig. 13). In addition, the polymer composition of example 30 also unexpectedly exhibited no die swell, which is advantageous in extruded strands having, for example, a standard size.

If the disclosure of any patent, patent application, and publication incorporated by reference herein conflicts with the description of the present application to the extent that terminology may become unclear, the description shall take precedence.

Claims

1. A polymer composition comprising:

i) poly (p-phenylene sulfide) (PPS);

ii) at least one poly (aryl ether sulfone) (PAES); and

iii) 0.05 to 2 wt.%, based on the total weight of polymers in the composition, of at least one alkali metal carbonate,

wherein the weight ratio of the poly (p-phenylene sulfide) (PPS) to the at least one poly (aryl ether sulfone) (PAES) is in the range of from 0.2 to 20,

wherein the poly (p-phenylene sulfide) (PPS) is an acid-washed poly (p-phenylene sulfide) (PPS),

wherein the poly (p-phenylene sulfide) (PPS) is in a reactive form and comprises at least 5 micro equivalents per gram (mu eq/g) of hydroxyl (-OH) end groups, and

the at least one alkali metal carbonate comprises sodium carbonate, potassium carbonate, or a combination thereof.

2. The polymer composition of claim 1, wherein the polymer composition does not comprise one or more solvents or comprises one or more solvents in an amount of not more than 2 wt.%, based on the total weight of the composition.

3. The polymer composition of claim 1 or 2, wherein the poly (aryl ether sulfone) (PAES) is selected from the group consisting of Polysulfone (PSU), Polyethersulfone (PES), and polyphenylsulfone (PPSU);

wherein Polysulfone (PSU) represents any polymer wherein at least 50 mol% of the recurring units are recurring units of the formula (K' -C):

polyethersulfone (PES) represents any polymer in which at least 50 mol% of the recurring units are recurring units having the formula (K' -B):

and

polyphenylsulfone (PPSU) represents any polymer in which more than 50 mol% of the recurring units are recurring units of formula (K' -a):

4. the polymer composition of claim 1 or 2, wherein the at least one alkali metal carbonate comprises potassium carbonate.

5. The polymer composition of claim 1 or 2, wherein the at least one alkali metal carbonate is potassium carbonate in an amount ranging from 0.1 to 0.5 wt.%, based on the total weight of polymers in the polymer composition.

6. The polymer composition of claim 1 or 2, wherein:

-the weight ratio of the poly (p-phenylene sulfide) (PPS) to the at least one poly (aryl ether sulfone) (PAES) is in the range of from 0.5 to 5, and

-the polymer composition comprises 0.15 to 0.4 wt.% of the at least one alkali metal carbonate, based on the total weight of polymers in the composition.

7. The polymer composition of claim 6, wherein the at least one alkali metal carbonate is potassium carbonate.

8. The polymer composition of claim 1 or 2, wherein the poly (p-phenylene sulfide) (PPS) is in reactive form and comprises at least 10 microequivalents per gram (μ eq/g) of hydroxyl (-OH) end groups.

9. The polymer composition of claim 1 or 2, further comprising an acid component having a pKa ≦ 7.5.

10. The polymer composition of claim 1 or 2, further comprising an inorganic acid component.

11. The polymer composition of claim 1 or 2, further comprising NaH ₂ PO ₄ 。

12. The polymer composition of claim 3, wherein the polymer composition comprises a combination of:

poly (p-phenylene sulfide) (PPS) and Polysulfone (PSU);

poly (p-phenylene sulfide) (PPS) and Polyethersulfone (PES);

poly (p-phenylene sulfide) (PPS) and polyphenylsulfone (PPSU);

poly (p-phenylene sulfide) (PPS) and reactive polysulfone (rPSU);

poly (p-phenylene sulfide) (PPS) and reactive polyethersulfone (rPES);

poly (p-phenylene sulfide) (PPS) and reactive polyphenylsulfone (rPPSU);

poly (p-phenylene sulfide) (PPS), Polysulfone (PSU), and reactive polysulfone (rPSU);

poly (p-phenylene sulfide) (PPS), Polyethersulfone (PES), and reactive polyethersulfone (rPES);

poly (p-phenylene sulfide) (PPS), polyphenylsulfone (PPSU), and reactive polyphenylsulfone (rPPSU).

13. The polymer composition according to claim 1 or 2, wherein,

i) the at least one poly (aryl ether sulfone) (PAES) is a reactive poly (aryl ether sulfone) (rPAES), or

ii) the polymer composition further comprises at least one reactive poly (aryl ether sulfone) (rPAES),

wherein the reactive poly (aryl ether sulfone) (rPAES) comprises-OH end groups at a concentration of greater than 5 μ eq/g reactive poly (aryl ether sulfone) (rPAES).

14. The polymer composition of claim 1 or 2, wherein the polymer composition comprises:

a dispersed phase having a surface area of 4 μm or less per dispersed particle ² Or is or

-a co-continuous phase, wherein the average width of the tapes of a single polymer is less than or equal to 2 μm, wherein the average width is calculated by taking 10 random measurements of the tape width, discarding the longest and shortest measurements, and dividing the sum of the remaining measurements by 8.

15. The polymer composition of claim 1 or 2, wherein the polymer composition is free or substantially free of Polyetherimide (PEI) or free or substantially free of epoxide.

16. The polymer composition of claim 1 or 2, wherein the polymer composition is free or substantially free of both Polyetherimide (PEI) and epoxide.

17. The polymer composition of claim 1 or 2, wherein the poly (p-phenylene sulfide) (PPS) is an acetic acid washed poly (p-phenylene sulfide) (PPS).

18. A method of making a polymer composition, the method comprising melt mixing:

i) poly (p-phenylene sulfide) (PPS);

ii) at least one poly (aryl ether sulfone) (PAES); and

wherein:

-the weight ratio of the poly (p-phenylene sulfide) (PPS) to the at least one poly (aryl ether sulfone) (PAES) is in the range of from 0.2 to 20,

-the poly (p-phenylene sulfide) (PPS) is an acid-washed poly (p-phenylene sulfide) (PPS),

-the poly (p-phenylene sulfide) (PPS) is in reactive form and comprises at least 5 micro equivalents per gram (μ eq/g) of hydroxyl (-OH) end groups,

the polymer composition is substantially free of solvent, and

-the at least one alkali metal carbonate comprises sodium carbonate, potassium carbonate, or a combination thereof.

19. The method of claim 18, wherein the polymer composition is solvent free.

20. The method of claim 18, wherein the method comprises:

(a1) contacting the poly (p-phenylene sulfide) (PPS), the at least one poly (aryl ether sulfone) (PAES), and the alkali metal carbonate to form a first initial mixture;

(a2) contacting the poly (p-phenylene sulfide) (PPS) with the alkali metal carbonate to form a second initial mixture, and subsequently contacting the second initial mixture with the at least one poly (aryl ether sulfone) (PAES) to form a second mixture;

(a3) contacting the at least one poly (aryl ether sulfone) (PAES) with the alkali metal carbonate to form a third initial mixture, and subsequently contacting the third initial mixture with the poly (p-phenylene sulfide) (PPS) to form a third mixture; or

(a4) Contacting the poly (p-phenylene sulfide) (PPS) with the at least one poly (aryl ether sulfone) (PAES) to form a fourth initial mixture, and subsequently contacting the fourth initial mixture with the alkali metal carbonate to form a fourth mixture; and is

(b) Optionally contacting the first initial mixture, the second mixture, the third mixture, or the fourth mixture with an acid component having a pKa ≦ 7.5.

21. The method of claim 18, wherein the poly (p-phenylene sulfide) (PPS) is an acetic acid washed poly (p-phenylene sulfide) (PPS).

22. A shaped article comprising the polymer composition of any of claims 1 to 17.