CN109071937A

CN109071937A - The polymer composition of increase-volume

Info

Publication number: CN109071937A
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: 2018-12-21
Anticipated expiration: 2037-04-28
Also published as: WO2017186923A1; CN109071937B

Abstract

A kind of polymer composition includes poly- (to phenylene sulfide) (PPS), at least one poly- (aryl ether sulfone) (PAES) and at least one alkali carbonate.Preferably, the polymer composition is free or substantially free of solvent.A kind of method includes by poly- (to phenylene sulfide) (PPS), at least one poly- (aryl ether sulfone) (PAES) and at least one alkali carbonate melting mixing.

Description

The polymer composition of increase-volume

Related application

The U.S. Provisional Application No. 62/329,522 submitted this application claims on April 29th, 2016 and on September 8th, 2016 The priority of the European Patent Application No. 16187800.4 of submission, for all purposes by the whole of each of these applications Content is incorporated herein by quoting mode.

Technical field

The present invention relates to the high-performance comprising poly- (to phenylene sulfide) (PPS) and at least one poly- (aryl ether sulfone) (PAES) The polymer composition of increase-volume.

Background technique

Polymer can be blended to obtain the new compositions with desired characteristic；However, most polymer are It can be miscible with one another.When polymer can be miscible with one another, attempt to frequently result in the blending of these polymer into heterogeneous multiphase combination Object.Such composition can show several thermal transition temperatures (Tg, Tm), usually show the mechanical property gone on business, and by point Layer and/or aesthetic drawback.

In fact, the mechanical property and workability of specific blends depend on the compatibility degree of polymers compositions.It is main Polymers compositions is wanted to be commonly known as continuous phase or matrix, and minor polymer component is typically defined as dispersed phase.It is compatible Property degree can be characterized by the adhesion level between the size and matrix and dispersed phase of the dispersed phase in continuous phase.It is certain high Unmixing blend is spent due to high mould port expansion and can not be squeezed out in normal operation condition, and being therefore can not quotient Purchase.

Known PPS has extraordinary chemical resistance and low melt viscosity, and known PAES has excellent machinery special Property and good thermal stability.Therefore, it is intended that these polymer to be blended to the combination to realize their characteristic.However, PPS and The blend of PAES be not always it is very compatible, shown in some cases difference tensile properties, since there are these The big domain (domain) that object is polymerized alone in the blend of polymer and due to the poor adhesion between these phases.

Therefore, for the new blend of PPS and PAES with increased compatibility, there are demands.

Detailed description of the invention

Fig. 1 shows transmission electron microscope (TEM) figure of the composition of example 1 (Figure 1A) and comparison example 11 (Figure 1B) Picture.

Fig. 2 shows the TEM images of the composition of example 2 (Fig. 2A) and comparison example 12 (Fig. 2 B).

Fig. 3 shows the TEM image of the composition of example 3 (Fig. 3 A) and comparison example 13 (Fig. 3 B).

Fig. 4 shows the TEM image of the composition of example 4 (Fig. 4 A) and comparison example 14 (Fig. 4 B).

Fig. 5 shows the TEM image of the composition of example 5 (Fig. 5 A) and comparison example 6 (Fig. 5 B).

Fig. 6 shows the TEM image of the composition of example 7 (Fig. 6 A) and comparison example 8 (Fig. 6 B).

Fig. 7 shows the TEM image of the composition of example 9 (Fig. 7 A) and example 10 (Fig. 7 B).

Fig. 8 shows the TEM image of the composition of example 15 (Fig. 8 A) and comparison example 18 (Fig. 8 B).

Fig. 9 shows the TEM image of the composition of example 17 (Fig. 8 A) and comparison example 21 (Fig. 8 B).

Figure 10 shows the TEM image of the composition of comparison example 27.

Figure 11 shows the TEM image of the composition of comparison example 8.

Figure 12 shows the TEM image of the composition of comparison example 29.

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

Specific embodiment

Applicant unexpectedly it have been discovered that, it is possible to prepare have increased compatibility polymer be blended Object, the blend of polymer for example poly- (to phenylene sulfide) (PPS) and poly- (aryl ether sulfone) (PAES) including high miscibility.

Exemplary embodiment be directed to a kind of polymer composition, the polymer composition include PPS, at least one PAES, And at least one alkali carbonate of the about 0.05wt.% of the total weight based on polymer in the composition to about 2wt.%. Preferably, the weight ratio of PPS and at least one PAES is in the range of from 0.2 to 20.

In some embodiments, polymer composition is free or substantially free of solvent, that is to say, that the composition is not wrapped It containing solvent and include to be, for example, less than 1wt.%, be less than 0.5wt.% no more than 2wt.% (total weight based on the composition) Or one or more solvents less than the amount of 0.1wt.%.

In some embodiments, polymer composition is free or substantially free of polyetherimide (PEI), that is to say, that The composition does not include PEI and includes no more than 2wt.% (total weight based on the composition), is, for example, less than 1wt.%, small In the 0.5wt.% or PEI of the amount less than 0.1wt.%.

In some embodiments, polymer composition is free or substantially free of epoxides, that is to say, that the composition It not comprising epoxides and include to be, for example, less than 1wt.%, be less than no more than 2wt.% (total weight based on the composition) The epoxides of 0.5wt.% or the amount less than 0.1wt.%.

For the sake of clarity, run through the application:

Term " alkali carbonate " includes alkali carbonate and can derive in situ during processing at high temperature Any reagent of the alkali carbonate, such as alkali metal hydrogencarbonate.

Term " solvent " means that at least one of polymer in polymer composition at least partially dissolves wherein Liquid；

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

" essentially simultaneously " mean in 30 seconds；

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

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

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

" there is no mould port expansion " means the mould port expansion less than 5%；And

Term " halogen " includes fluorine, chlorine, bromine and iodine, unless otherwise noted.

Generally, PPS and PAES has range from 5,000g/mol to 150,000g/mol, preferably from 10,000g/mol To the weight average molecular weight of 100,000g/mol.

In this application:

Any explanation, even described in specific embodiment, be suitable for the other embodiments of present disclosure and It can be exchanged with other embodiments；

When by a kind of element or component be said to be including and/or selected from cited multiple elements or component inventory When middle, it should be understood that in the related embodiment taken explicitly into account here, the element or component can also be these individually The element enumerated or any one of component and be also selected from the element or component clearly enumerated by these Any two or more composed by group；Any element or component enumerated in element or the inventory of component can be from these It is saved in a inventory；And

Herein by endpoint logarithm range it is any enumerate including include in cited range it is all number with And the endpoint of the range and equivalent.

Poly- (to phenylene sulfide) (PPS)

As used in this, " poly- (to phenylene sulfide) (PPS) " indicates that at least 50mol% of its repetitive unit is tool There is the repetitive unit (R of formula (L)_PPS) any polymer:

In PPS preferably at least 60mol%, 70mol%, 80mol%, 90mol%, 95mol%, 99mol% and most Preferably all of repetitive unit is repetitive unit (R_PPS)。

PPS by Su Wei special type Polymer Co., Ltd of the U.S. (Solvay Specialty Polymers USA, LLC) with trade namePPS is manufactured and is sold.

PPS can be pickling or non-acid wash.In some embodiments, PPS is the PPS that acetic acid is washed.

Poly- (aryl ether sulfone) (PAES)

For the purposes of the present invention, " poly- (aryl ether sulfone) (PAES) " indicates that at least 50mol.% of its repetitive unit is that have Repetitive unit (the R of formula (K)_PAES) any polymer:

Wherein:

(i) each R, is same or different to each other, selected from halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, Amide, acid imide, alkali or alkaline earth metal sulfonate, alkyl sulfonic ester, alkali or alkaline earth metal phosphonate, alkyl phosphonic acid Ester, amine and quaternary ammonium；

(ii) each h, is same or different to each other, and is the integer of range from 0 to 4；And

(iii) T is selected from by a key, sulfuryl [- S (=O)_2-] and group-C (R_j)(R_kThe group of)-composition, wherein R_j And R_k, it is same or different to each other, is selected from hydrogen, halogen, alkyl, alkenyl, alkynyl, ether, thioether, carboxylic acid, ester, amide, acid imide, alkali Metal or alkaline earth metal sulfonate, alkyl sulfonic ester, alkali or alkaline earth metal phosphonate, phosphonate ester, amine and quaternary ammonium.R_j And R_kPreferably methyl group.

In PAES preferably at least 60mol%, 70mol%, 80mol%, 90mol%, 95mol%, 99mol% and most Preferably all of repetitive unit is repetitive unit (R_PAES)。

In a preferred embodiment, PAES is polyphenylsulfone (PPSU).As used in this, " polyphenylsulfone (PPSU) " Indicate its repetitive unit is any polymer with the repetitive unit of formula (K '-A) more than 50mol%:

In PPSU preferably at least 60mol%, 70mol%, 80mol%, 90mol%, 95mol%, 99mol% and most Preferably all of repetitive unit is the repetitive unit with formula (K '-A).

PPSU can be prepared by known method, and be notably from the limited duty of U.S.'s Su Wei special copolymer The conduct of Ren companyObtained by PPSU.

In some embodiments, PAES is polyether sulfone (PES).As used in this, " polyether sulfone (PES) " indicates that its is heavy At least 50mol% of multiple unit is any polymer with the repetitive unit of formula (K '-B):

In PES preferably at least 60mol%, 70mol%, 80mol%, 90mol%, 95mol%, 99mol% and most Preferably all of repetitive unit is the repetitive unit with formula (K '-B).

PES can be prepared by known method, and be notably from the limited duty of U.S.'s Su Wei special copolymer The conduct of Ren companyObtained by PESU.

In some embodiments, PAES is polysulfones (PSU).As used in this, " polysulfones (PSU) " it is single to indicate that it is repeated At least 50mol% of member is any polymer with the repetitive unit of formula (K '-C):

In PSU preferably at least 60mol%, 70mol%, 80mol%, 90mol%, 95mol%, 99mol% and most Preferably all of repetitive unit is the repetitive unit with formula (K '-C).

PSU can be prepared by known method, and be from the conduct of Su Wei special type Polymer Co., Ltd of the U.S.Obtained by PSU.

When PAES is to be selected from the group by PPSU, PES, PSU or combinations thereof, excellent result is obtained.

Alkali carbonate

Polymer composition includes the total weight based on the polymer in polymer composition, and range is from about 0.05wt.% To about 2wt.%, about 0.1wt.% to about 1.8wt.%, about 0.1wt.% to about 1.6wt.%, about 0.1wt.% to about 1.5wt.%, about 0.1wt.% are to about 1.3wt.%, about 0.1wt.% to about 1.0wt.%, about 0.1wt.% to about At least one alkali carbonate of the amount of 0.8wt.%, about 0.1wt.% to about 0.5wt.%.In some embodiments, alkali gold Belong to carbonate amount based on the total weight of the polymer in polymer composition from about 0.1wt.% to about 0.5wt.%, about In the range of 0.2wt.% to about 0.5wt.%, about 0.4wt.% to about 0.5wt.%.In some embodiments, alkali metal carbonic acid The amount of salt be the total weight based on the polymer in polymer composition be less than or equal to 1.0wt.%, 0.9wt.%, 0.8wt.%, 0.7wt.%, 0.6wt.%, 0.5wt.%, 0.4wt.%, 0.3wt.%, 0.2wt.%, 0.1wt.%.

Alkali carbonate can be selected from sodium carbonate, potassium carbonate, cesium carbonate and lithium carbonate.Potassium carbonate is preferred.It can To use the mixture of two or more alkali carbonates.

In some respects, partial size D50 (the middle several diameters or median of particle diameter distribution) from 2 microns to 1000 micron, it is excellent In the range of from 2 to 500 microns, most preferably from 3 to 200 microns of choosing.

Optional reactive polymer

PPS and at least one PAES can in the form of reactive (i.e. reactive polymer) or non-reacted shape Formula exists.

Under their reactive form, these polymer include at least 5, at least 10, at least 15, preferably at least 20, it is excellent Select the hydroxyl (- OH) or mercapto (- SH) end group of at least 50 every gram of microequivalents (μ eq/g).One of such reactive polymer Example is reactive polyether sulfone (rPES), is from the conduct of Su Wei special type Polymer Co., Ltd of the U.S.Obtained by PESU.

In some embodiments, polymer composition includes at least one reactivity in addition to PPS and at least one PAES Poly- (aryl ether sulfone) (rPAES).RPAES is preferably chosen from reactive polysulfones (rPSU), reactive polyether sulfone (rPES) and reactivity Polyphenylsulfone (rPPSU).

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

Under their non-reacted form, PPS and PAES include one or more non-reactive end groups.Non-reacted end Base is preferably-Cl ,-F or-O-CH₃.Preferably, non-reactive polymer includes at least 20, preferably more than 50 every gram of microequivalents The non-reactive end groups of (μ eq/g).

In some respects, polymer composition can be free or substantially free of rPAES.

PPS preferably exists in the form of its reactivity.As used herein abbreviation " PPS " includes reactive and non-reaction Property both poly- (to phenylene sulfide) (PPS).

Optional reinforcing filler

Largely selected reinforcing filler can be added in polymer composition.They are preferably chosen from threadiness and fill out Fill agent and particle filler.Fibrous reinforcing filler is considered to have the material of length, width and thickness herein, wherein putting down Equal length is significantly greater than both width and thicknesses.Preferably, such material at least 5 draw ratio (be defined as length with Average ratio in width and thickness between reckling).Preferably, the draw ratio of these reinforcing fibers is at least 10, more preferably Ground at least 20, still more preferably at least 50.Particle filler has at most 5, preferably up to 2 draw ratio.

Preferably, the reinforcing filler be selected from mineral filler, as talcum, mica, titanium dioxide, kaolin, calcium carbonate, Calcium silicates, magnesium carbonate；Glass fibre；Carbon fiber, boron carbide fibre；Wollastonite；Silicon carbide fibre；Boron fibre, graphene, carbon are received Mitron (CNT) and analog.

Reinforcing filler can in polymer composition with the total weight based on polymer composition be at least 5wt.%, The amount of preferably at least 10wt.%, more preferably at least 15wt.% exist.

Reinforcing filler is at most further preferably 60wt.%, more preferably up to the total weight based on polymer composition 50wt.%, the amount presence even more preferably from most 40wt.%.

Preferably, the amount of reinforcing filler polymer composition slave 0.1wt.% to 60wt.%, more preferably from 5wt.% to 50wt.%, even more preferably from the range of from 10wt.% to 40wt.%.According to some embodiments, combination of polymers Object is free of fibrous filler.Alternatively, polymer composition may be free of particle filler.In certain specific embodiments In, polymer composition is preferably free of reinforcing filler.

Additional optional compositions

In some respects, polymer composition is made of or substantially PPS, at least one PAES and alkali carbonate It is made from it；However, in other respects, polymer composition may include one or more additional additives.

Polymer composition can optionally further include other compositions, such as (such as dyestuff and/or pigment are such as colorant Titanium dioxide, zinc sulphide and zinc oxide), UV light stabilizing agent, heat stabilizer, antioxidant (such as organic phosphite and sub- phosphine Acid esters), acid scavenger, processing aid, nucleating agent, lubricant, fire retardant, smog inhibitor, antistatic agent, anti-caking agent and/ Or conductive additive (such as carbon black).

When there are one or more other compositions, their total weight of the total weight based on polymer composition is preferably small In 20wt.%, it is less than 10wt.%, less than 5wt.% and more preferably less than 2wt.%.

Unexpectedly, it has been found that having pKa < 7.5, organic and inorganic acid constituent preferably < 7 that can stablize the present invention Polymer composition melt viscosity.The non-limiting example of organic and inorganic component with pKa < 7.5 is dibastic sodium phosphate (NaH₂PO₄), sodium dihydrogen citrate, sodium bioxalate and hydrogen phthalate sodium.Preferably inorganic component such as has The NaH of pKa < 7₂PO₄.Excellent result: 2.5 < pKa < 7.5, preferably 3 is obtained with the organic and inorganic component with following pKa <pKa<7.Organic or inorganic acid constituents with pKa < 7.5 can be with the total weight based on the polymer in polymer composition In the range of from 0.05wt.% to 5wt.%, preferably from 0.1wt.% to 2wt.%, more preferably from 0.2wt.% to 1wt.% Amount exist.

Exemplary polymer blends

Preferred polymer composition has been shown in table 1.Every kind of polymer composition may include except those of listed Except other compositions.Every kind of preferred polymer composition further include range be from 0.05wt.% to the amount of about 2wt.% or The alkali carbonate (preferably potassium carbonate or sodium carbonate) of other amount as herein disclosed.Every kind of preferred combination of polymers Object optionally includes acid constituents 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 polymer composition, the concentration of each in PPS, PAES and rPAES is independently selected from polymer group Close the slave 0wt.%, preferably at least 1wt.%, 2wt.% of total weight of the polymer in object, 5wt.%, 10wt.%, 15wt.%, 20wt.%, 25wt.%, 30wt.%, 35wt.%, 40wt.%, 45wt.%, 50wt.%, 55wt.%, 60wt.%, 65wt.%, 70wt.%, 75wt.%, 80wt.%, 85wt.%, 90wt.%, 95wt.%, 98wt.%, 99wt.%.

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

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

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

In some embodiments, model of the weight ratio of the amount of PPS and at least one PAES from 0.5 to 5, preferably 1 to 3 In enclosing, and it is 0.15wt.% to 0.4wt.%, preferably that polymer composition, which includes the total weight based on polymer in composition, At least one alkali carbonate, preferably potassium carbonate or sodium carbonate of 0.2wt.% to 0.4wt.%.

In some embodiments, polymer composition includes:

i)PPS；

ii)PPSU；And

Iii the total weight) based on polymer in the composition, at least one alkali from about 0.05wt.% to about 2wt.% Metal carbonate,

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

The illustrative properties of polymer composition

Polymer composition of the invention may include the dispersed phase being dispersed in continuous phase or matrix.It is shown in Fig. 4 A The example of dispersed phase.

In some embodiments, the average surface area of each discrete particles is preferably less than or equal to about 4 μm², about 3 μm²、 About 2 μm², about 1 μm², about 0.5 μm², about 0.25 μm²。

In some embodiments, the maximum particle diameter of dispersed phase is≤3 μm, preferably≤2 μm ,≤1 μm ,≤0.8 μm ,≤0.6 μ M ,≤0.4 μm, most preferably≤0.1 μm.

In an alternative embodiment, blend polymer may include co-cable transmission, it is characterised in that when electric by transmission There are the continuous bands of polymers compositions when sub- microscopic method (TEM) is observed.In such embodiments, the mean breadth of these bands is excellent Choosing less than or equal to about 3 μm, more preferably less than or equal to about 2 μm, wherein the mean breadth be by take the 10 of bandwidth times with Machine measured value discards longest and shortest measured value and calculates the summation of remaining measured value divided by 8.

In some embodiments, polymer composition of the invention presents the basis within the scope of from 25 to 50ft-lbs The Dynatup of ASTM D3763 impacts gross energy.

Polymer composition can show corresponding to each at least two in at least two different polymer not Same glass transition temperature (Tg)；However, compared with the Tg of the identical polymer with not in polymer composition when, these Tg can be different (that is, displacement).In some embodiments, the difference (Δ Tg) in polymer composition between corresponding Tg be to Few 0.5 DEG C, preferably at least 1 DEG C, more preferably from 5 DEG C to 50 DEG C, even more preferably from 5 DEG C to 10 DEG C.

In certain specific embodiments, the combination of polymers when squeezing out polymer composition from extruder as melt Object without or there is no mould port expansion, and the temperature of the melt is in the range of from 300 DEG C to 430 DEG C.

The method for preparing polymer composition

In some embodiments, the present invention includes that one kind prepares polymer as described herein by item below melting mixing The method of composition: i) PPS, ii) at least one PAES and iii) total weight based on polymer in composition is about At least one alkali carbonate of 0.05wt.% to about 2wt.%.Preferably, the weight ratio of PPS and at least one PAES 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 can be independently reactivity or non-reacted.PPS is preferably Reactive polymer.PPS can be pickling or non-acid wash.

The component of mixture can in any order, the score of any amount or their total amounts be added or mix, and It can separately or concurrently mix.

The preparation of the polymer composition can be melted by any be suitable for preparing known to thermoplastic molding compoistions Melt mixed method to carry out.Polymer can be by being heated to above the melting temperature of semi-crystalline polymer with shape by such method Melt at polymer and/or the Tg higher than amorphous polymer are carried out.In some embodiments, processing temperature is from about In the range of 250 DEG C -450 DEG C, preferably from about 280 DEG C -420 DEG C.Preferably, processing temperature is than the highest in polymer composition The glass transition temperature (Tg) of Tg polymer big at least 15 DEG C, preferably at least 50 DEG C, preferably at least 100 DEG C, preferably at least 150 DEG C and/or it is at least 15 DEG C bigger than the melting temperature (Tm) of the highest Tm polymer in polymer composition.

In some aspects for the method for being used to prepare polymer composition, the component for forming the polymer composition is fed Into melting mixing device and in the apparatus melting mixing.Suitable melting mixing device is, for example, kneader, Banbury Mixing machine, single screw extrusion machine and double screw extruder.Preferably, using such extruder, which is equipped with for inciting somebody to action Desired component feed intake into extruder (feed intake into extruder throat or be dosed into melt) device.Preferably, the extrusion Equipped with one or more ports, these ports allow to be fed in melt at different machine barrels during extrusion process machine.

Component with mixture of powders or can be expected that the form of grain mixture (also known as dry blend) is fed or can be with simultaneously It feeds respectively.

In some embodiments, all polymer and alkali carbonate are added to the throat of extruder, preferably simultaneously Or it substantially simultaneously adds.In other respects, it a variety of can add one of polymer or together with alkali carbonate One or more other polymers are added in the melt at the extruder barrel to the throat of extruder, and then.Example Such as, PPS and rPAES, preferably rPES can be added to the throat of extruder together with alkali carbonate, and can be subsequent PAES is added at the downstream machine barrel of the extruder.When added, acid constituents can be added at the throat of extruder, or It is added in the melt at any machine barrel of the extruder.Preferably, acid constituents is added in the melt at the machine barrel of downstream, So that itself and melt contacts shortly before by melt extrusion.Preferably, in some being added to after alkali carbonate Carve addition acid constituents.

In the exemplary embodiment, multipass extrusion can be carried out.It, will be logical from for the first time in multipass extrusion The extrudate crossed is reintroduced back in extruder, preferably in throat, it is made to pass through the extruder for the second time.It is squeezed out in multipass In, it can be passed through two, three, four or more times, and appointing for machine production line can squeezed out in any What some place's addition polymer, alkali carbonate, acid constituents or other compositions.For example, can be by PPS and alkali metal carbonic acid Salt is added to the throat of extruder together, then can be added to this at least for being recycled to from the extrudate passed through for the first time In a kind of extruder of PAES, and can by acid constituents second by closing to an end when addition.Alternatively, it can incite somebody to action Recycling is carried out for passing through for the third time by the extrudate generated by second, is passing through period in third time, for example, can be It is extruded as that acid constituents and/or filler material being added in melt before final products.

In some respects, can be passed through at least twice, and carry out in being recycled into extruder it is primary or Repeatedly it is additional pass through before, component can be added to in extrudate and/or be added to the technique (example carried out to the extrudate Such as, mix) in.

Extruder can be operated with any suitable speed.Extruder speed and the temperature of extruder barrel can be constant Or variation.Preferably, one or more extruder screws with about 100rpm to about 900rpm, preferably from about 200 to about 500rpm is rotated；However, speed and temperature can be adjusted based on the specific polymer composition being blended.

" total residence time " means the total time that the component that longest stops is spent in an extruder, packet as used in this Include multipass (if any).Total residence time is preferably from about 15 seconds to about 4 minute, preferably from about 30 seconds to about 2 points In the range of clock.

Polymer composition described herein provides advantageously in the form of spherolite, can be used for note known in the art It penetrates in molding or extrusion process.

Exemplary embodiment is related to a kind of method, this method comprises:

(a1) PPS, at least one PAES and alkali carbonate are contacted to form the first original mixture；

(a2) it contacts PPS with alkali carbonate to form the second original mixture, and then makes this second initial Mixture is contacted at least one PAES mixture to form the second mixture；

(a3) it contacts at least one PAES with alkali carbonate to form third original mixture, and then makes The third original mixture is contacted with PPS to form third mixture；Or

(a4) it contacts PPS to form the 4th original mixture at least one PAES, and then makes at the beginning of the 4th Beginning mixture is contacted with alkali carbonate to form the 4th mixture；And

(b) optionally make the first original mixture, the second mixture, third mixture or the 4th mixture and such as this paper The acid constituents contact.

In an alternative embodiment, this method comprises:

(a1) make PPS, at least one PAES, rPAES and alkali carbonate contact to form the first initial mixing Object；

(a2) PPS, rPAES and alkali carbonate are contacted to form the second original mixture, and then makes this Second original mixture is contacted at least one PAES to form the second mixture.

(a3) at least one PAES, rPAES and alkali carbonate are contacted to form third original mixture, And contact the third original mixture with PPS to form third mixture；Or

(a4) PPS, at least one PAES and rPAES are contacted to form the 4th original mixture, and is then made 4th original mixture is contacted with alkali carbonate to form the 4th mixture；And

In some embodiments, this method comprises:

(a1) PPS, at least one PAES and alkali carbonate are contacted to form the first original mixture, and And contact first original mixture with rPAES to form the first mixture；

(a2) PPS and alkali carbonate are contacted to form the second original mixture, and then makes this second initial Mixture is contacted at least one PAES and rPAES to form the second mixture；

(a3) at least one PAES and alkali carbonate are contacted to form third original mixture, and is then made The third original mixture is contacted with PPS and rPAES to form third mixture；Or

(a4) it contacts PPS and at least one PAES to form the 4th original mixture, and then makes at the beginning of the 4th Beginning mixture is contacted with alkali carbonate and rPAES to form the 4th mixture；And

(b) optionally make the first mixture, the second mixture, third mixture or the 4th mixture and as described herein Acid constituents contact.

Formed article comprising polymer composition

Exemplary embodiment further includes the article comprising above-mentioned polymer composition.

The article can be used suitable melt-process method and be made from polymer composition.Particularly, they can lead to It crosses injection-molded, extrusion molded, roational molding or blown-moulding is made.

The polymer composition can be well suited to manufacture useful article in diversified final use.

The present invention will be described in more detail in following part by non-limiting example below.

If by the disclosure content of quoting any patent, patent application and publication that mode is incorporated herein with The application's illustrates mutually to conflict to may cause the unclear degree of term, then this explanation should be preferential.

Example

Example 1-10 and comparison example 11-14

The blend of example 1-10:PPSU and PPS (include K₂CO₃)

The blend of comparison example 11-14:PPSU and PPS are free of K₂CO₃

Material:

-PPSU R-5900NT comes from U.S. Su Wei special type Polymer Co., Ltd

-PPS QA200N comes from U.S. Su Wei special type Polymer Co., Ltd

-PPS QA250N comes from U.S. Su Wei special type Polymer Co., Ltd

-PPS QC160N comes from U.S. Su Wei special type Polymer Co., Ltd

-PPS QC220N comes from U.S. Su Wei special type Polymer Co., Ltd

-K₂CO₃, UNID EF-90

Mixture:

It usesZSK-26 co-rotating twin screw extruder (the L/D ratio with 48:1) is with 200- Blend is carried out mixture by 300rpm and 12-18kg/hr.Barrel temperatures set point is as follows: region 1 to 6 is 360 DEG C, and region 7 is arrived 12 be 340 DEG C, and is 360 DEG C at die orifice.

Measurement:

Melt viscosity is measured under 360 DEG C and 400 1/ seconds according to ASTM D5630.

The form of blend is had checked, by transmission electron microscopy (TEM) to find out the maximum gauge of dispersion phase region.

As a result:

Blend composition and measured value are shown in table 2 below.Blend is shown in the TEM image of Fig. 1-7 Form.

Example 1,2,3 and 4 and comparison example 11,12,13 and 14 are respectively compared and (see also Fig. 1-4), unexpectedly Ground discovery, adds 0.4wt%K₂CO₃The compatibility of the blend of PPSU and PPS is significantly improved, such as by much smaller dispersed phase Domain sizes (≤0.5 μm, compared to >=2 μm) and blend (are wherein added to K₂CO₃) increased melt viscosity proved. Example 1 and 2 is shown compared with comparison example 11 and 12, and using the blend rich in PPSU, (PPSU is as continuous phase and PPS conduct Dispersed phase) realize improved compatibility；And example 3 and 4 is shown compared with comparison example 13 and 14, with being total to rich in PPS Mixed object (PPS is as continuous phase and PPSU is as dispersed phase) also achieves improved compatibility.

Example 5 to 10 (Fig. 5-7) illustrates to change PPS:PPSU ratio and K₂CO₃Amount effect.

Example 15-18 and comparison example 19-22

Example 15-18:PPSU, PPS and K₂CO₃Blend, wherein PPS is washed with acetic acid.

Comparison example 19-22:PPSU, PPS and K₂CO₃Blend, wherein PPS unused acetic acid washing.

Material:

-PPSU R-5900NT comes from U.S. Su Wei special type Polymer Co., Ltd

-PPS QA250N comes from U.S. Su Wei special type Polymer Co., Ltd；Acetic acid washing

-PPS QC220N comes from U.S. Su Wei special type Polymer Co., Ltd；Calcium acetate washing

-PPS PR34 comes from U.S. Su Wei special type Polymer Co., Ltd；Water washing

-K₂CO₃UNID EF-90

Mixture and measurement

The mixed blend as in example 1.

Measurement as carried out melt viscosity and form in example 1.

As a result:

Blend composition and measured value are shown in following table 3.

Example 15,16 and 17 (is seen also into Fig. 8 and 9) compared with comparison example 18,19,20 and 21, it can be seen that use The PPS polymer washed with acetic acid unexpectedly improves the compatibility of the blend of PPSU and PPS, such as by using What the smaller dispersed phase domain sizes of the blend of the PPS polymer contacted with acetic acid were proved.In each case, using use The maximum dispersion phase domain sizes of water or the blend of the PPS polymer of calcium acetate washing are unexpectedly greater than use and are washed with acetic acid The maximum dispersion phase domain sizes of the blend for the PPS polymer washed.

Example 22-26

The blend of comparison example 22:PPS/PES.

Example 23-27:PPS/PES/K₂CO₃Blend.

Composition is described in table 4.

Material:

-PESU 3300ULT comes from U.S. Su Wei special type Polymer Co., Ltd

-PPS QA200N comes from U.S. Su Wei special type Polymer Co., Ltd

-K₂CO₃LH-90 comes from Howard industrial group (Howard Industries, Inc).

Mixture:

Use the 26mm diameter of L/D ratio with 48:1The intermeshing of ZSK-26 rotating Vortex part Double screw extruder make the composition of table 4 be subjected to melting mixture.Barrel section 2 to 12 and die orifice are heated to following set Set point temperature:

2-6:360 DEG C of machine barrel

7-12:350 DEG C of machine barrel

Die orifice: 360 DEG C

In each case, use gravity-feeder with the percent of pass of range 30-40lb/hr in machine resin and additive It is fed at cylinder section 1 and at barrel section 5.The extruder is operated with the screw speed of about 200RPM.With about 27 inches of mercury Vacuum level applies vacuum at machine barrel area 10.Single hole die orifice is used for all compounds, and the molten polymer that will leave die orifice Stock cools down in the sink, and then cuts in pelletizer.

Injection molding:

Polymer composition is carried out injection-molded thick for (0.125 inch) of 3.2mm of testing mechanical characteristic to produce ASTM stretch and bending sample and 4 × 4 × 0.125 inch of substrate.Use the following approximate temperature on machine barrel and mold Condition stretches ASTM sample to I type and the progress of 4 × 4 × 0.125 inch of substrate is injection-molded:

Back zone: 680 °F

Middle area: 680 °F

Proparea: 700 °F

Nozzle: 700 °F

Mold: 285 °F

Measurement:

It is used for using the ASTM test sample (4 × 4 × 0.125 inch of substrate) of 0.125 injection-molded inch The mechanical properties of all preparations is tested in Dynatup shock-testing (D-3763: high speed breakdown multi-axial Impact).

Continue 24 hours by the way that curved rod to be exposed to methyl ethyl ketone under variable stresses and evaluates chemical resistance (resistance to ring Border stress cracking resistance).Increase when being exposed to methyl ethyl ketone in the case where material does not show any rupture or micro-crack Between.

As a result:

Tensile properties after high speed breakdown multi-axial Impact (Dynatup impact) data and heat ageing are reported in table 4:

Table 4

N.D.* can not test no K₂CO₃Blend because according to the above method material can not be produced.It squeezes out The excessive expansion of blend and the melt strength of difference make it impossible to generate spherolite in the process, these spherolites be later used to stretch and It is bent the injection-molded of sample.

K₂CO₃Introducing unexpectedly enhance PPS and PES blend impact characteristics and resisting environmental stress and cracking Property.

Comparison example 27,28 and 29 and example 30

Comparison example 27: 50/50 part of blend PPS/PES, continue the residence time of 5min.

Comparison example 28: 45/45/10 part of blend PPS/PES/rPES, continue the residence time of 5min.

Comparison example 29: 45/45/10/2 part of blend PPS/PES/rPES/ZnO, continue the residence time of 3min.

Example 30: blend PPS/PES/rPES/K₂CO₃45/45/10/0.5 part continues the residence time of 3min.

Material:

- PPS reference product T 4G comes from Dainippon Ink Chemicals (DIC Corporation)

-PESU 3600P comes from U.S. Su Wei special type Polymer Co., Ltd.

Reactive poly- (ether sulfone) (rPES): according to known methods from 4,4 '-dichloros two in the sulfolane as solvent The rPES that benzene sulfone, bisphenol S (excess), potassium carbonate (excess) synthesize.The end group titration of rPES polymer gives:

The concentration of ο hydroxyl end groups [- OH]=219 μ eq/g

The concentration of ο potassium phenate end group [- OK]=60 μ eq/g

The concentration of ο chlorine end group [- Cl]=7 μ eq/g

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

Potassium carbonate K₂CO₃UNID EF-80

Zinc oxide ZnO

Mixture:

Be heated to 380 DEG C and equipped with allow control the residence time recirculation circuit DSMDouble spiral shells Mixed blend in bar (100rpm) extruder.It is extruded into before strand in material (7g in total) by it while introducing and mix Certain time (residence time).

Measurement:

Torque needed for measuring rotary extrusion machine screw rod during blending.Torque is related to the viscosity of melt blended material, more Big power shows bigger viscosity.

The level of mould port expansion is observed in the exit of extruder and is classified as follows: -- very big mould port expansion ,-one A little mould port expansions ,+limited mould port expansion, ++ there is no mould port expansion.

Thermal characteristic, i.e. melting temperature and crystallization temperature are measured by DSC.

The form of blend is analyzed, by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) to give The maximum gauge of dispersed phase out.

As a result:

Blend composition and measured value are shown in following table 5.The form of blend is shown in Fig. 9-12.

Table 5

It is unmixing that PPS and PES, which is shown in FIG. 10, obviously.As shown in fig. 11, rPES is (hydroxy-end capped PES introducing) does not make polymer increase-volume significantly, and observed very big mould port expansion.In addition, such as showing in Figure 12 Out, further also without result in the form of PPS and PES blend significant changes occur for addition alkali ZnO, and still observe Some mould port expansions.

Unexpectedly, however, when by other alkali K₂CO₃When being added in PPS, PES and rPES polymer composition, The good increase-volume that observed PPS and PES, as shown by the dispersed phase (Figure 13) by example 30.In addition, example 30 is poly- Polymer composition also unexpectedly shows no mould port expansion, this is for example with being advantageous in standard-sized extrusion stock 's.

Claims

1. a kind of polymer composition, includes:

I) poly- (to phenylene sulfide) (PPS)；

Ii) at least one poly- (aryl ether sulfone) (PAES)；And

Iii the total weight) based on polymer in the composition, at least one alkali metal carbon of about 0.05wt.% to about 2wt.% Hydrochlorate,

Wherein, the weight ratio of poly- (to phenylene sulfide) (PPS) and at least one poly- (aryl ether sulfone) (PAES) from 0.2 to In the range of 20.

2. polymer composition as described in claim 1, wherein the polymer composition do not include one or more solvents or Person includes one or more solvents of the amount no more than 2wt.% (total weight based on the composition).

3. polymer composition as claimed in claim 1 or 2, wherein poly- (aryl ether sulfone) (PAES) is selected from by polysulfones (PSU), the group of polyether sulfone (PES) and polyphenylsulfone (PPSU) composition.

4. polymer composition as claimed in any one of claims 1-3, wherein at least one alkali carbonate includes Sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate or combinations thereof, preferably potassium carbonate.

5. such as polymer composition of any of claims 1-4, wherein at least one alkali carbonate is base The carbonic acid of amount of the total weight of polymer in the range of from about 0.1wt.% to about 0.5wt.% in the polymer composition Potassium.

6. polymer composition according to any one of claims 1 to 5, in which:

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

The polymer composition include based in the composition the total weight 0.15wt.% to 0.4wt.% of polymer this extremely A kind of few alkali carbonate, preferably potassium carbonate.

7. such as polymer composition of any of claims 1-6, wherein poly- (to phenylene sulfide) (PPS) is Poly- (to phenylene sulfide) (PPS) through pickling.

8. the acid constituents with pKa≤7.5 is further included such as polymer composition of any of claims 1-7, It is preferred that inorganic acid constituent, more preferable NaH₂PO₄。

9. such as polymer composition of any of claims 1-8, wherein

I) at least one poly- (aryl ether sulfone) (PAES) is reactive poly- (aryl ether sulfone) (rPAES), or

Ii) polymer composition further includes at least one reactive poly- (aryl ether sulfone) (rPAES),

Wherein, the reactivity poly- (aryl ether sulfone) (rPAES) includes-OH end group, and the concentration of the end group is poly- greater than 5 μ eq/g reactivity (aryl ether sulfone) (rPAES).

10. polymer composition as claimed in any one of claims 1-9 wherein, wherein the polymer composition includes:

Dispersed phase, the surface area of each discrete particles are≤about 4 μm², or

Co-cable transmission, wherein the mean breadth of the band of single polymers is less than or equal to about 2 μm, wherein the mean breadth is By taking 10 arbitrary measures of the bandwidth, longest and shortest measured value are discarded, and by the summation of remaining measured value It is calculated divided by 8.

11. the polymer composition as described in any one of claims 1 to 10, wherein the polymer composition is free of or base Without polyetherimide (PEI) or free or substantially free of epoxides in sheet, preferably free or substantially free of polyethers Both acid imide (PEI) and epoxides.

12. a kind of method for preparing polymer composition, this method includes melting mixing:

I) poly- (to phenylene sulfide) (PPS)；

Ii) at least one poly- (aryl ether sulfone) (PAES)；And

Wherein:

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

The polymer composition is preferably free of solvent substantially free of solvent.

13. method as claimed in claim 12, wherein this method comprises:

(a1) make poly- (to phenylene sulfide) (PPS), at least one poly- (aryl ether sulfone) (PAES) and the alkali metal carbonic acid Salt is contacted to form the first original mixture；

(a2) poly- (to phenylene sulfide) (PPS) is contacted with the alkali carbonate to form the second original mixture, and And contact second original mixture to form the second mixture at least one poly- (aryl ether sulfone) (PAES)；

(a3) at least one poly- (aryl ether sulfone) (PAES) is contacted with the alkali carbonate to form third original mixture, And contact the third original mixture to form third mixture with poly- (to phenylene sulfide) (PPS)；Or

(a4) poly- (to phenylene sulfide) (PPS) is contacted to be formed at the beginning of the 4th at least one poly- (aryl ether sulfone) (PAES) Beginning mixture, and contact the 4th original mixture with the alkali carbonate to form the 4th mixture；And

(b) optionally make first original mixture, second mixture, the third mixture or the 4th mixture and tool There is the acid constituents of pKa≤7.5 to contact.

14. polymer composition made of a kind of method as described in any one of claim 12 and 13.

15. a kind of formed article includes the polymer composition as described in any one of claim 1 to 11 and 14.