JP2006519911A - Method for reducing melt viscosity of aromatic sulfone polymer composition and method for producing aircraft component - Google Patents

Abstract

A method for reducing the melt viscosity of an aromatic sulfone polymer composition [composition (I)] comprising one or more aromatic sulfone polymers and optionally one or more other components, comprising: Using one or more fluorocarbon polymers containing repeating units derived from fluorinated monoolefins and one or more perfluoroalkyl vinyl ethers and optionally an additive [additive (A)] comprising one or more other components A method involving that. A method of manufacturing an aircraft component comprising an aromatic sulfone polymer composition comprising one or more aromatic sulfone polymers and optionally one or more other components, said method for reducing melt viscosity comprising said aromatic Applying to the aliphatic sulfone polymer composition.

Description

This application claims the priority of US Patent Application No. 60 / 452,960 filed on March 10, 2003 and US Patent Application No. 60 / 517,406 filed on November 6, 2003.
The present invention relates to a method for reducing the melt viscosity of an aromatic sulfone polymer composition. The present invention also relates to a method of manufacturing an aircraft component comprising an aromatic sulfone polymer composition, the method comprising applying to the aromatic sulfone polymer composition a method for reducing melt viscosity as described above.

In the last few years, the aircraft industry has used fire-resistant and ultra-tough materials to produce aircraft interior components such as wallboards, overhead storage lockers, cooking trays, seat backs, cabin bulkheads, and tubes. I needed it. The basic requirements that these materials must meet are best met by prior art aromatic sulfone polymer compositions. Aromatic sulfone polymers, in particular polybiphenyl ether sulfones, actually provide an attractive combination of properties, particularly high fire resistance and super toughness. However, existing aromatic sulfone polymer compositions are no longer fully satisfactory and far from satisfactory.
The problem is that current aviation industry trends have created a need for materials that also have very high fluidity. In the present invention, a substance having a high fluidity means a substance having a low melt viscosity. Highly flowable materials could form thin wall and thus lightweight aircraft interior components, among others.
In addition to the first problem, another possible problem is that the toughness must be kept at a very high level in some cases while seeking to increase the fluidity of the material. Perhaps another possible problem in addition to the first problem is that more refractory materials are sometimes required.
None of the sulfone polymer compositions supplied to this market, particularly the commercially available aromatic polybiphenyl ether sulfone polymer compositions, provide the desired fluidity. Thus, nonetheless, none of them provide the desired combination of very high fluidity, very high fire resistance and super toughness.

As detailed below, while substantial investigative efforts have already been made to develop methods for increasing the fire resistance of aromatic sulfone polymer compositions, Applicants We are not aware of the investigations conducted to develop a method to reduce viscosity.
US Pat. No. 5,204,400 discloses an aromatic sulfone polymer composition suitable for the manufacture of aircraft interior components comprising polybiphenyl ether sulfone, a fluorocarbon polymer such as polytetrafluoroethylene, and 2 parts by weight or more of anhydrous zinc borate. Is described. In this composition, the fluorocarbon polymer and anhydrous zinc borate act synergistically to increase the flame retardancy of the aromatic sulfone polymer composition (see especially column 21, lines 50-53).
US Pat. No. 5,916,958 describes an aromatic sulfone polymer composition suitable for the manufacture of aircraft interior components comprising a polybiphenyl ether sulfone, a fluorocarbon polymer such as polytetrafluoroethylene, and 3 parts by weight or more of titanium dioxide. Has been. In this alternative composition, the fluorocarbon polymer and titanium dioxide act synergistically to increase the flame retardancy of the aromatic sulfone polymer composition (see especially column 13, lines 13-17). .
Fire resistant (especially flame retardant) aromatic sulfone polymer compositions that have been found suitable for use in demanding applications such as aircraft interiors over the past few years are all very lightweight materials. Is no longer satisfactory because it does not exhibit a sufficiently low melt viscosity to produce Thus, nonetheless, none of them provide the desired combination of very high fluidity, very high fire resistance and super toughness.

  Therefore, there remains a strong need for a method for reducing the melt viscosity of an aromatic sulfone polymer composition. Advantageously, the method also increases the fire resistance of the aromatic sulfone polymer composition and retains the super toughness behavior.

The present invention relates to a melt viscosity of an aromatic sulfone polymer composition obtained by using an additive comprising a fluorocarbon polymer comprising repeating units derived from one or more perfluorinated monoolefins and one or more perfluoroalkyl vinyl ethers. Based on the amazing drop effect.
One aspect of the present invention is a method for reducing the melt viscosity of an aromatic sulfone polymer composition [composition (I)] comprising one or more aromatic sulfone polymers and optionally one or more other components. An additive comprising one or more fluorocarbon polymers comprising repeating units derived from one or more perfluorinated monoolefins and one or more perfluoroalkyl vinyl ethers, and optionally one or more other components (A)].
One embodiment of the present invention is:
-Providing a component of composition (I),
-Providing a component of additive (A); and-preparing an aromatic sulfone polymer composition [composition (II)] comprising the component of composition (I) and the component of additive (A). The process of
The melt viscosity of the composition (II) is lower than the melt viscosity of the composition (I).
In another embodiment of the invention, the viscosity of composition (II) measured at 380 ° C. under a shear rate of 498.6 sec ⁻¹ is less than 600 Pascal seconds.
In another embodiment of the present invention, the viscosity of composition (II) measured at 380 ° C. under a shear rate of 498.6 sec ⁻¹ is measured at the same temperature and the same shear rate ( It is less than 1/2 times the viscosity of I).
In another embodiment of the invention, composition (II) is super tough.
In another embodiment of the invention, the fire resistance of composition (II) is increased over that of composition (I).
In another embodiment of the present invention, the amount of heat released under fire conditions of the composition (II) is lower than that of the composition (I).

In another embodiment of the invention, the aromatic sulfone polymer comprises one or more polybiphenyl ether sulfones.
In another embodiment of the invention, more than 80% by weight of the aromatic sulfone polymer comprises polybiphenyl ether sulfone.
In another embodiment of the invention, the aromatic sulfone polymer further comprises more than 20% by weight of one or more bisphenol A polysulfones.
In another embodiment of the invention, the fluorocarbon polymer comprises repeating units derived from tetrafluoroethylene and perfluoromethyl vinyl ether.
In another embodiment of the invention, composition (II) comprises less than 10% by weight of fluorocarbon polymer, based on the total weight of composition (II).
In another embodiment of the invention, additive (A) further comprises a polymer selected from the group consisting of polyetherimide, polycarbonate, poly (aryl ether ketone), and liquid crystal polymer.
In another embodiment of the present invention, the composition (II) does not contain an inorganic flame retardant or contains less than 2 parts by mass of an inorganic flame retardant based on the mass of the aromatic sulfone polymer. Anhydrous zinc borate is an example of an inorganic flame retardant.
In another embodiment of the invention, the composition (II) does not contain titanium dioxide or contains less than 3 parts by weight of titanium dioxide relative to the weight of the aromatic sulfone polymer.
In another embodiment of the present invention, the composition (II) contains 3 parts by mass or more of titanium dioxide based on the mass of the aromatic sulfone polymer.

Another aspect of the invention produces an aircraft component comprising an aromatic sulfone polymer composition [Composition (I)] consisting of one or more aromatic sulfone polymers and optionally one or more other components. A method comprising applying the method for reducing melt viscosity described above to the aromatic sulfone polymer composition.
Another aspect of the present invention is for reducing the melt viscosity of an aromatic sulfone polymer composition [composition (I)] comprising one or more aromatic sulfone polymers and optionally one or more other components. An additive comprising one or more fluorocarbon polymers comprising repeating units derived from one or more perfluorinated monoolefins and one or more perfluoroalkyl vinyl ethers, and optionally one or more other components (A)].
Another aspect of the invention is a method of preparing an aromatic sulfone polymer composition that needs to reduce its melt viscosity, comprising:
Providing one or more aromatic sulfone polymers;
One or more comprising repeating units derived from one or more perfluorinated monoolefins and one or more perfluoroalkyl vinyl ethers in an amount effective to reduce the melt viscosity of the aromatic sulfone polymer composition Providing a component of an additive [additive (A)] comprising a fluorocarbon polymer and optionally one or more other components;
-Optionally providing one or more components other than the aromatic sulfone polymer and a component of the additive (A);
-Contacting the aromatic sulfone polymer, the component of additive (A) and, if present, one or more components other than the aromatic sulfone polymer and the component of additive (A), and advantageously The process of mixing,
It is a method including.

Another aspect of the present invention is:
An additive comprising one or more aromatic sulfone polymers and one or more fluorocarbon polymers comprising repeating units derived from one or more perfluorinated monoolefins and one or more perfluoroalkyl vinyl ethers. (A)]
Aromatic sulfone polymer composition [Composition (II)] containing an aromatic sulfone polymer whose melt viscosity is lower than the melt viscosity of the same composition [Composition (I)] without additive (A) It is a thing.
Another aspect of the present invention is an aircraft component comprising composition (II).
In one embodiment, the aircraft component is an overhead passenger service facility, window frame, air return grill, aircraft wallboard, aircraft overhead storage locker, aircraft cooking tray, aircraft seat back, aircraft cabin Selected from the group consisting of bulkheads and aircraft tubes.
Finally, an aspect of the invention is an aircraft that includes the aforementioned aircraft components.
Detailed Description of the Preferred Embodiment

The present invention relates to the use of certain types of additives that reduce the melt viscosity of aromatic sulfone polymer compositions. In one preferred aspect of the present invention, the use of additives increases fire resistance in addition to reducing melt viscosity. In another preferred aspect of the present invention, the use of additives provides super toughness behavior in addition to reducing melt viscosity. In a highly preferred aspect of the present invention, the use of additives provides reduced melt viscosity, increased fire resistance and super toughness behavior.
Criteria for determining these properties include, for example:
1. Melt viscosity Melt viscosity measurements can be performed using a Kayeness® LCR series capillary rheometer according to ASTM D3835. Since high shear rates are achieved during thin wall injection molding, high fluidity at high shear rates (about 100 sec- ¹ or more) is particularly important. Injection molding is a technique commonly used in the production of aromatic sulfone polymer compositions.
The viscosity of composition (II), measured at 380 ° C. under a shear rate of 3513.5 sec ⁻¹ , is advantageously less than 200 Pascal seconds, and preferably less than about 175 Pascal seconds.
The viscosity of composition (II) measured at 380 ° C. under a shear rate of 498.6 sec ⁻¹ is advantageously less than 600 Pascal seconds, preferably less than 450 Pascal seconds, very preferably Less than 300 Pascal seconds.
The viscosity of composition (II), measured at 380 ° C. under a shear rate of 23.2 sec ⁻¹ , is advantageously less than 800 Pascal seconds, preferably less than 700 Pascal seconds.

The viscosity of composition (II) measured at 380 ° C. under a shear rate of 3513.5 sec ⁻¹ is less than 9/10 times the viscosity of composition (I) measured at the same temperature under the same shear rate And is preferably less than 4/5 times the viscosity of the composition (I).
The viscosity of composition (II) measured at 380 ° C. under a shear rate of 498.6 sec ⁻¹ is less than 9/10 times the viscosity of composition (I) measured at the same temperature under the same shear rate Is preferably less than 4/5 times the viscosity of the composition (I), more preferably less than 3/5 times the viscosity of the composition (I), even more preferably the composition ( It is less than 1/2 times the viscosity of I).
The viscosity of composition (II) measured at 380 ° C. under a shear rate of 23.2 s ⁻¹ is less than 9/10 times the viscosity of composition (I) measured at the same temperature under the same shear rate Is preferably less than 4/5 times the viscosity of the composition (I), more preferably less than 7/10 times the viscosity of the composition (I).
2. Toughness Toughness can be measured by a notched Izod impact test according to ASTM D-256.
The notched Izod value of the composition (II) measured by the above test is advantageously a notched Izod value of 1/3 or more of the notched Izod value of the composition (I) measured under the same conditions. Preferably, it is a notched Izod value of 2/3 or more, and still more preferably a 4/5 notched Izod value.
Super toughness behavior or super toughness is manifested by notched Izod values, usually greater than 10 ft-lb / inch, and by ductile fracture mode in the notched Izod impact test according to ASTM D-256.
The composition (II) is advantageously super tough.

3. Fire resistance Fire resistance can be measured by criteria or a combination of criteria such as low heat dissipation, high self-extinguishing and low smoke generation, as described above.
The term “increased fire resistance” means that one or more of these criteria exhibit improved behavior.
The composition (II) advantageously has an increased fire resistance compared to the composition (I).
4. Heat dissipation amount The heat dissipation characteristic can be determined according to the procedure of Title 14, Part 25 of the Federal Regulations.
The composition (II) is advantageous in that the amount of heat released under fire conditions is lower than that of the composition (I).
Composition (II) advantageously satisfies the 65/65 1990 compliant amount in the standard for total heat dissipation and maximum heat dissipation for 2 minutes, preferably exhibits excellent heat dissipation performance and greatly exceeds the 1990 standard. The heat dissipation characteristics of the composition (II) were evaluated according to FAR 25.853 Amendment 25-83, Appendix F, Part IV. Would <5 kW / (min · m ²⁾ and 30～40KW / maximum heat release rate of the Ohio State University m ² (OSU) heat radiation performance level is fulfilled by 2 minutes.

5. The self-extinguishing property of the self-extinguishing composition was evaluated according to FAR 25.853 Amendment 25-83 (a) Appendix F, Part I, 9a0, 1, (I): 60 seconds.
An increase in self-extinguishability can correlate with a decrease in combustion length and / or combustion time.
The composition (II) advantageously has a self-extinguishing property which is higher than that of the composition (I).
6. Smoke generation Smoke generation can be measured by smoke density test according to FAR25.853 (a-1) / ASTM F814 / E662.
In the present invention, the reduction in smoke generation is one of the following characteristics measured by the above test: (i) smoke concentration, (ii) total toxic gas emissions, and (iii) carbon monoxide emissions. It means to show the above decline.
The smoke generation of the composition (II) under fire conditions is advantageously less than or equal to the smoke generation of the composition (I) under the same fire conditions.
The smoke concentration of composition (II) measured in 4 minutes according to FAR 25.853 (a-1) / ASTM F814 / E662 is advantageously 2 or less, preferably 1 or less.
The total toxic gas emission of composition (II), measured according to BSS 7239-ATS 1000 / ABD0031, is advantageously less than 200 ppm, preferably less than 20 ppm.
The carbon monoxide emissions measured according to BSS 7239-ATS 1000 / ABD0031 are advantageously less than 100 ppm, preferably less than 10 ppm.

Aromatic sulfone polymers Aromatic sulfone polymers are, inter alia, one or more aromatic dihalo compounds containing one or more —S (═O) ₂ — groups and two or more aromatic rings, and one or more aromatics. Any polymer may be used as long as it contains 50 mol% or more of repeating units (R1) formed by a polycondensation reaction between group diols.
The aromatic sulfone polymer preferably comprises 80 mol% or more, very preferably 95 mol% or more of repeating units (R1). More preferably, it consists of repeating units (R1).
Examples of aromatic dihalo compounds suitable for the present invention are, inter alia, dihalobenzene disulfone compounds of the general formula

（式中、Xはハロゲン、特にClであり、Qは式QH₂の分子から２個の置換可能な水素を除去することにより得られる２価の基であり、例えば以下のような基である。）

(Wherein X is a halogen, in particular Cl, and Q is a divalent group obtained by removing two substitutable hydrogens from the molecule of formula QH ₂ , for example the following groups: .)

（式中、Rは、メチレン、エチレン又はイソプロピレンのような６個以下の炭素原子の２価の脂肪族基である。）

(Wherein R is a divalent aliphatic group of up to 6 carbon atoms such as methylene, ethylene or isopropylene.)

Another suitable aromatic dihalo compound is 4,4′-dihalodiphenyl sulfone.
Aromatic dihalo compounds advantageously contain at most 4 —S (═O) ₂ — groups, preferably at most 2 —S (═O) ₂ — groups, more preferably Contains at most one —S (═O) ₂ — group.
The aromatic dihalo compound preferably comprises at most 6, more preferably at most 4 aromatic rings, even more preferably at most 2 aromatic rings.
The most preferred aromatic dihalo compound is 4,4′-dihalodiphenyl sulfone.
Any aromatic diol capable of polymerizing with an aromatic dihalo compound is suitable. Non-limiting examples of such aromatic diols are 4,4′-biphenol (ie, 4,4′-dihydroxybiphenyl), bisphenol A, 4,4′-dihydroxy-diphenylsulfone (also known as bisphenol S). Hydroquinone, and 4,4′-dihydroxy-diphenyl ether.
Advantageously, the aromatic diol does not contain functional groups other than -OH groups.
The aromatic diol advantageously contains at most two aromatic rings. It is preferably selected from 4,4′-biphenol, bisphenol A, 4,4′-dihydroxy-diphenyl sulfone and 4,4′-dihydroxy-diphenyl ether.
Non-limiting examples of aromatic sulfone polymers suitable for the present invention include polyethersulfones comprising the following repeating units:

Polyether ether sulfone composed of the following repeating units,

And copolymers of the above two repeating units, polybiphenyl ether sulfone and bisphenol A polysulfone.
The aromatic sulfone polymer contains 50 repeating units formed by a polycondensation reaction between one or more polybiphenyl ether sulfones, that is, one or more 4,4′-dihalodiphenyl sulfones and 4,4′-biphenol. It is advantageous to include a polymer containing at least mol%. The polybiphenyl ether sulfone preferably consists of repeating units formed by a polycondensation reaction between one or more 4,4′-dihalodiphenyl sulfones and 4,4′-biphenol, as shown by the following formula: .

In a preferred embodiment of the present invention, 80% by mass or more of the aromatic sulfone polymer is composed of polybiphenyl ether sulfone. In this embodiment, the aromatic sulfone polymer more preferably comprises polybiphenyl ether sulfone.
In another preferred embodiment of the present invention, the aromatic sulfone polymer contains, in addition to polybiphenyl ether sulfone, 10% by weight or more of one or more bisphenol A polysulfones, ie, one or more 4,4′-disulfones. It includes a polymer containing 50 mol% or more of repeating units formed by a polycondensation reaction between halodiphenylsulfone and bisphenol A. The bisphenol A polysulfone preferably consists of repeating units formed by a polycondensation reaction between one or more 4,4′-dihalodiphenyl sulfones and bisphenol A, as shown by the following formula:

In this embodiment, the aromatic sulfone polymer more preferably comprises more than 20% by weight of one or more bisphenol A polysulfones. Even more preferably, it comprises more than 20% by weight of one or more bisphenol A polysulfones and more than 70% by weight of polybiphenyl ether sulfones.
The composition (II) advantageously contains 65% by weight or more, preferably 75% by weight or more, more preferably 85% by weight or more of the aromatic sulfone polymer, based on the total weight of the composition.
Aromatic sulfone polymers are described in U.S. Pat.Nos. 3,634,355, 4,008,203, 4,108,837, and 4,175,175, all of which are known to those skilled in the art and all of which are incorporated herein by reference. Can be prepared by suitable methods such as those described.
The molecular weight of the aromatic sulfone polymer advantageously has a melt index of about 4 to about 28 g / 10 min measured using ASTM D-1238 at 380 ° C. under a load of 2.16 kg. The use of an aromatic sulfone polymer such as polybiphenyl ether sulfone having a melt index of less than 2 g / 10 min usually results in a material with poor melt secondary processability. On the other hand, the use of aromatic sulfone polymers such as polybiphenyl ether sulfones with a melt index greater than 28 g / 10 min can result in poor or unsatisfactory chemical resistance materials. For injection molding applications, the melt flow range will preferably be between 8 and 20 g / 10 min for optimum performance.
Examples of commercially available aromatic sulfone polymers useful in compositions according to the present invention include, among others, UDEL® bisphenol A polysulfone, RADEL® R polybiphenyl ether sulfone and RADEL® A sulfone polymer. included. These are available from Solvay Advanced Polymers, LLC.
Composition (II) may also have a slightly lower specific gravity.
The increase in fluidity can advantageously use composition (II) for thin-walled parts due to mass loss.

Fluorocarbon polymer A fluorocarbon polymer comprising repeating units derived from one or more perfluorinated monoolefins and one or more perfluoroalkyl vinyl ethers is advantageously used when used alone as additive (A). It decreases the melt viscosity of the sulfone polymer composition (I).
In certain embodiments of the invention, the fluorocarbon polymer has a substantially crystalline structure and a melting point greater than 120 ° C.
Suitable perfluorinated monoolefins include, among others, octafluorobutene, hexafluoropropylene and tetrafluoroethylene. The perfluorinated monoolefin preferably comprises tetrafluoroethylene. Most preferably, the perfluorinated monoolefin is tetrafluoroethylene.
In the present invention, “perfluoroalkyl vinyl ether” is perfluorinated (that is, all hydrogen atoms are substituted with fluorine atoms), and is derived from —O— (ether group) and —NH— (amino group). It is meant to indicate an ethylenically unsaturated compound containing one or more selected groups (G).
Examples of perfluoroalkyl vinyl ethers are suitable, inter alia, in the formula F perfluoromethylvinyl ether of ₂ C = CFOCF _3, wherein F ₂ C = CFOC ₂ perfluoroethyl vinyl ether F ₅ and formula _{F 2 C = CFOC 3 F 7} ( wherein, C ₃ F ₇ are included perfluoropropylvinylether, and perfluoro -N- methyl allylamine of the formula _{F 2 C = CF-CF 2} -NH-CF 3 of indicating either isopropyl or n- propyl group.).
Perfluoroalkyl vinyl ethers preferably contain one and only one group (G).
The group (G) is preferably an ether group.
The group (G) is preferably bound on the one hand with a vinyl or allyl group and on the other hand with a C ₂ -C ₂₀ hydrocarbyl group. The group (G) is very preferably bonded on one hand to a vinyl group and on the other hand to a C ₂ -C ₂₀ alkyl group.
The alkyl group of the perfluoroalkyl vinyl ether preferably contains no more than 6 carbon atoms, very preferably no more than 3 carbon atoms, and even more preferably 1 carbon atom.

Good results have been obtained when perfluoromethyl vinyl ether, perfluoroethyl vinyl ether or perfluoropropyl vinyl ether is used as the perfluoroalkyl vinyl ether. Excellent results were obtained when perfluoromethyl vinyl ether was used as the perfluoroalkyl vinyl ether.
Advantageously, more than 50%, preferably more than 90% by weight of the repeating units contained in the fluorocarbon polymer are derived from one or more perfluorinated monoolefins and one or more perfluoroalkyl vinyl ethers. Most preferably, the fluorocarbon polymer consists essentially of repeating units derived from one or more perfluorinated monoolefins and one or more perfluoroalkyl vinyl ethers. Even more preferably, the fluorocarbon polymer consists of repeating units derived from one or more perfluorinated monoolefins and one or more perfluoroalkyl vinyl ethers.
Very good results have been obtained when using a copolymer consisting of repeating units derived from tetrafluoroethylene on the one hand and perfluoromethyl vinyl ether, perfluoroethyl vinyl ether or any perfluoropropyl vinyl ether on the other hand as the fluorocarbon polymer. . Excellent results were obtained when a copolymer (MFA copolymer) consisting of repeating units derived from tetrafluoroethylene and perfluoromethyl vinyl ether was used as the fluorocarbon polymer. MFA copolymers are commercially available in particular as HYFLON® from SOLVAY SOLEXIS SpA.
Advantageously, the composition (II) comprises less than 20% by weight, preferably less than 10% by weight and more preferably less than 6% by weight of fluorocarbon polymer, based on the total weight of the composition (II).
Composition (II) comprises more than 0.1% by weight, preferably more than 0.5% by weight, more preferably more than 1% by weight of fluorocarbon polymer, relative to the total weight of composition (II). Is advantageous.
In certain embodiments, the composition (II) is 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18 and 19% by weight and all values and subranges between them Includes fluorocarbon polymers.
In certain embodiments of the present invention, composition (II) comprises a polybiphenyl ether sulfone polymer, 1 to 15% by weight MFA, and optionally 0 to 10%, based on the total weight of composition (II). Liquid crystal polymer (LCP).

The optional component additive (A) contained in the additive (A) is any component that reduces the melt viscosity of the composition (I) when used alone as the additive of the composition (I). In addition to the fluorocarbon polymer.
In a preferred embodiment of the invention, additive (A) consists of a fluorocarbon polymer.
In another preferred embodiment of the present invention, additive (A) further comprises a polymer (P) selected from the group consisting of polyetherimide, polycarbonate, poly (aryl ether ketone) and liquid crystal polymer.
The selection of the special components of the additive (A) other than the fluorocarbon polymer and their content will probably depend on the intended end use of the material.
For example, to extrude into a sheet having a thickness of less than about 0.32 cm (0.125 inches), a large amount of polybiphenyl ether sulfone and an additive containing poly (aryl ether ketone) in addition to the fluorocarbon polymer ( A composition comprising with A) may be preferred. In this case, a large amount of polybiphenyl ether sulfone is usually more than 70% by weight or more than about 75% by weight of polybiphenyl ether sulfone relative to the total weight of polybiphenyl ether sulfone and poly (aryl ether ketone). Means. For injection molding applications, less than 70 wt.% Or less than about 65 wt.% Polybiphenyl ether sulfone can be used. Such compositions containing more than 70% by weight of polybiphenyl ether sulfone may exhibit poor processing in many injection molding applications, but such content will provide good processing for extrusion applications. .

Poly (aryl ether ketone) is a kind of crystalline aromatic polymer which is in a general sense. These resins are readily available from a variety of commercial sources and their preparation is described, for example, in U.S. Pat. Nos. 3,441,538, 3,442,857, 3,516,966, 4,396,755, and 4,816,556 (these All of which are known, including the methods described in (which are all incorporated herein by reference). Commercially available resins include VICTREX® PEEK poly (aryl ether) ketones available from Victrex, LTD.
The polymer (P) is preferably a liquid crystal polymer (LCP). When present in additive (A), the liquid crystal polymer is 10, 20, 30, 40, 50, 70, 80 or 90% by weight, or their weight, based on the total weight of additive (A). Any other value between and the amount of the partial range. In this embodiment, the amount of liquid crystal polymer is preferably in the range of 1 to 6% by weight relative to the total weight of the composition.
The liquid crystal polymer is advantageously a fully aromatic polyester.
Fully aromatic polyesters are in particular commercially available as XYDAR® from SOLVAY ADVANCED POLYMERS LLC.

Optional component contained in composition (I) The optional component contained in composition (I) is a component that, when used alone as an additive for aromatic sulfone polymer, does not lower the melt viscosity of the aromatic sulfone polymer. Is advantageously selected from:
In a preferred embodiment of the invention, composition (I) consists of an aromatic sulfone polymer.
In another preferred embodiment of the invention, composition (I) comprises one or more components in addition to the aromatic sulfone polymer. The selection and content of special additional ingredients will likely depend on the intended end use of the material.
The presence of titanium dioxide would be expected to reduce the mechanical properties of the aromatic sulfone polymer. However, as the examples below show, aromatic sulfone polymers comprising titanium dioxide can be extremely tough. Thus, in one embodiment of the invention, composition (I) also includes titanium dioxide. In another embodiment of the invention, composition (I) is substantially free of titanium dioxide or optionally free of titanium dioxide. This means that the amount of titanium dioxide measured according to the procedure normally used in the field is an undetectable amount.
When present, titanium dioxide suitable for use in the present invention includes any commercially available TiO ₂ . The particle size of TiO ₂ is preferably about 2μ or less. This is because larger particle sizes adversely affect the physical properties of the polymer. Any available crystalline form of titanium dioxide can be used, but the rutile form is preferred due to its excellent pigment properties.
The total amount of TiO ₂ is preferably 11, 10, 9, 8, 7, 6, 5, 4, 3, to the total mass of the composition (I) in order to avoid compounding and processing difficulties. It will be less than about 12% by weight, including less than 2, and 1% by weight and all values and subranges between them. Certain embodiments of the present invention use about 1 to about 10 weight percent TiO ₂ because the materials have better processability. In certain other embodiments of the present invention, the amount of TiO ₂ in the polymer composition is about 7-10% by weight.

In certain embodiments of the invention, composition (I) is about 1 to 50 masses, including all values and subranges therebetween, relative to the total mass of composition (I). % Solid filler or reinforcing agent. In certain other embodiments of the present invention, the amount of solid filler or toughening agent is about 10-30% relative to the total weight of composition (I).
Fibers that can act as a reinforcing medium include, but are not limited to, glass fibers, graphitic carbon fibers, amorphous carbon fibers, synthetic polymer fibers, aluminum fibers, aluminum silicate fibers, and aluminum fibers, titanium fibers, magnesium. Metal oxides such as fiber, wollastonite, rock wool fiber, steel fiber, tungsten fiber are included. Typical fillers and other materials include glass, calcium silicate, silica, clay, talc, mica, and pigments such as carbon black, iron oxide, cadmium red, iron blue, and wollastonite, graphite, aluminum. Other additives such as trihydrate, sodium aluminum carbonate, barium ferrite and the like are included.
The composition (I) may further contain additional additives commonly used in the resin industry, such as heat stabilizers, UV stabilizers, and plasticizers.
The composition (II) can be prepared by a blending method usually used at the resin blending site. For example, the individual components, usually provided in the form of chips, pellets or powder, are physically mixed in a suitable apparatus such as a mechanical drum tumbler and then, if desired, physical to facilitate compounding. In order to remove water from the experimental mixture, it is optionally dried, preferably under reduced pressure or in a warm air oven. The composition of solid polymer particles, which can also contain reinforcing fillers, fiber pigments, additives, etc., can then be pelletized by, for example, forming by melt extrusion strands that can be solidified and then broken into chips or pellets. It is not necessary for all ingredients to be brought together in a single operation. For example, a composition containing a fluorocarbon may be first blended and then melt blended with the desired amount of TiO ₂ in subsequent operations.

Composition (II) can be further secondary processed by melt processing to form various relatively rigid shaped articles and molded articles including three-dimensional molded articles, fibers, films, tapes, etc. Or used to form sheets for coating applications.
Composition (II) can be used to produce a variety of products that are usually made with aromatic sulfone polymers. The method of secondary processing such products can be carried out according to known methods in the field of forming products using, for example, injection molding or extrusion. For example, the composition (II) can be used to produce aircraft components, particularly aircraft interior components.
Furthermore, composition (II) would be used where decreasing shear flow behavior, good toughness, and fire resistance (particularly flame retardancy) for thin wall parts are important. Such applications include, but are not limited to overhead passenger service equipment, window frames, air return grilles, wallboards, overhead storage lockers, cooking trays, seat backs, cabin bulkheads, and tubes. included. Furthermore, another embodiment of the present invention is an aircraft that includes one or more of these aircraft components.

The following examples show great expectations in the flowability of compositions comprising an aromatic sulfone-based polymer, i.e. RADEL® R-5000NT polybiphenyl ether sulfone, obtained by applying the method according to the invention. An improvement is shown.
All polymer resins in the example compositions were dried in a dehumidifying oven at 150 ° C. for about 16 hours. The composition was prepared by tumble blending all components of the aromatic sulfone polymer composition for about 30 minutes. The aromatic sulfone polymer composition was then subjected to about 11.3 kg / hr (25 lbs) at a screw speed of about 200 times / min using a 25 mm twin screw two-stage vented Berstorff extruder with an L / D ratio of 33: 1. / Hour). The aromatic sulfone polymer composition was extruded at a melting temperature of 350 ° C. The first vent was opened for air and the second vent was connected to a vacuum pump. The strand was then passed through a water tank to cool and pelletized.
Melt viscosity Melt viscosity measurements were performed using a Kayeness® capillary rheometer according to ASTM D3835. A sample of 20 g of aromatic sulfone polymer composition was dried at 160 ° C. for 2 hours before testing. Each sample was loaded into a barrel and melted. A motor driven crosshead equipped with a load transducer used a 2224N filling force to drive the piston into a heated steel cylinder held at a temperature of 380 ° C. Samples were loaded at a controlled rate into a 1.02 mm (0.040 inch) diameter, 20.32 mm (0.800 inch) die having an inlet angle of 120 °. The sample rate and force were used to calculate the viscosity of the aromatic sulfone polymer composition at each shear rate of 23.2 to 3513.5 sec ⁻¹ .

Properties other than melt viscosity
Mechanical Properties Mechanical properties were evaluated by molding standard ASTM specimens of 3.2 mm (0.125 inch) thickness for tensile properties and impact resistance. Tensile tests were performed according to ASTM D-638, and Izod impact tests were performed according to ASTM D256.
The heat dissipation properties of the heat dissipating aromatic sulfone polymer composition were evaluated according to FAR 25.853 Amendment 25-83, Appendix F, Part IV. Test specimens were prepared by injection molding 15.2 cm x 15.2 cm x 0.20 cm (6 "x 6" x 0.080 ") plaques from the composition in a Mitsubishi molding press. The sample was placed vertically and exposed to a plurality of pilot flames at the top and bottom of the sample fixture, at the same time the sample was exposed to a radiant heat flow rate of 3.5 W / cm ² and 2.4 m ² / min (85 feet was measured heat radiation during combustion ^{by 3} / min) exposed to air flow. inlet air to measure the temperature difference between the exhaust air.
The self-extinguishing properties of the vertical combustion flammability test compositions were evaluated according to FAR 25.853 Amendment 25-83 (a), Appendix F, Part I, 9a0, 1, (I): 60 seconds. Test specimens were prepared by injection molding 7.6 cm x 30.5 cm x 0.20 cm (3 "x 12" x 0.080 ") standard plaques from the composition in a Mitsubishi molding press. The flame was exposed to a burner located 1.9 cm (0.75 inch) from the bottom of the specimen, the flame was applied for 60 seconds, and then removed and measured as it was burning. The length burned at the end was measured.
Smoke density The smoke density test was performed according to FAR 25.853 (a-1) / ASTM F814 / E662. In this test, a 7.6 cm × 7.6 cm × 2 cm (3 ″ × 3 ″ × 0.80 ″) test piece was measured at 2.5 W / cm ^{2 in} a sealed US standard bureau smoke concentration chamber. Exposed to multiple burning small flames with a radiant heat source, smoke concentration was determined by the attenuation of the light intensity of the 2200K light source in the direction of raising the test chamber vertically. A microphotometer was used, and the optical density is a measure of the amount of smoke generated during combustion, which was recorded after 4 minutes of combustion.
The concentration test of toxic smoke was performed according to FAR25.853 (a-1) / ASTM F814 / E662. In this test, a 7.6 cm × 7.6 cm × 2 cm (3 ″ × 3 ″ × 0.80 ″) test piece was measured at 2.5 W / cm ^{2 in} a sealed US standard bureau smoke concentration chamber. Exposed to multiple burning small flames with radiant heat sources Toxicity measurements were performed in accordance with the Boeing Specification Support Standard BSS 7239, simultaneously with smoke concentration tests. Colorimetry and multiple gas detector Drager tubes were used to measure the concentration of six specific gases: hydrogen cyanide (HCN), carbon monoxide (CO), nitrogen oxides (NO + NO) ₂ ), sulfur dioxide (SO ₂ ), hydrogen fluoride (HF), and hydrogen chloride (HCl).

Melt viscosity results All the sulfone polymer compositions in the examples exhibit very low melt viscosities at any shear rate between 23.2 and 3513.5 sec- ¹ . The method according to the invention can reduce the melt viscosity of the control composition CE by about 20% or more, depending on the shear rate, about 60% or less and more. The compositions in the examples have a very low melt viscosity, especially at a shear rate of 498.6 sec ^-1 , 300 sec ^-1 or less.
Fire resistance results Tables 3-6 show that all compositions in the examples have very high levels of fire resistance that far exceed the requirements, in addition to very low melt viscosity (as shown in Table 2). Clarify showing sex. In this regard, it is at least comparable to the control composition CE, indicating that certain properties such as heat dissipation are better.

Mechanical properties results Table 7 shows that all compositions in the examples typically have “super toughness” or “super toughness behavior” (in addition to the very low melt viscosity (as shown in Table 2)). It is shown that it exhibits a very high level of toughness called notched Izod impact strength higher than 10 ft-lb / in and ductile fracture in Izod impact tests.

All documents, patents, applications, tests, standards, documents, printed materials, pamphlets, original texts, papers, etc. mentioned in this specification are incorporated herein by reference. Numerical limits or ranges are stated but endpoints are included. All values and subranges within numerical limits or ranges are also included as specified.
Obviously, many modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as described herein.

Claims (23)

  A method for reducing the melt viscosity of an aromatic sulfone polymer composition [composition (I)] comprising one or more aromatic sulfone polymers and optionally one or more other components, comprising: Using one or more fluorocarbon polymers containing repeating units derived from fluorinated monoolefins and one or more perfluoroalkyl vinyl ethers and optionally an additive [additive (A)] comprising one or more other components A method involving that. -Providing a component of composition (I),
-Providing a component of additive (A);-preparing an aromatic sulfone polymer composition [composition (II)] comprising the component of composition (I) and the component of additive (A) The process of
The method according to claim 1, wherein the melt viscosity of the composition (II) is lower than the melt viscosity of the composition (I). The method according to claim 2, wherein the viscosity of the composition (II) measured at 380 ° C under a shear rate of 498.6 sec ^-1 is less than 600 Pascal seconds. The viscosity of the composition (II) measured at 380 ° C. under a shear rate of 498.6 sec ⁻¹ is ½ times the viscosity of the composition (I) measured at the same temperature and the same shear rate. 4. A method according to claim 2 or 3 wherein   The method according to any one of claims 2 to 4, wherein the composition (II) is super tough.   The method according to any one of claims 2 to 5, wherein the fire resistance of the composition (II) is increased from that of the composition (I).   The method according to claim 6, wherein the amount of heat released under fire conditions of the composition (II) is lower than that of the composition (I).   The method according to claim 2, wherein the aromatic sulfone polymer comprises one or more polybiphenyl ether sulfones.   The method according to claim 8, wherein 80% by mass or more of the aromatic sulfone polymer comprises polybiphenyl ether sulfone.   The method of claim 8, wherein the aromatic sulfone polymer further comprises greater than 20% by weight of one or more bisphenol A polysulfones.   The method according to any one of claims 2 to 10, wherein the fluorocarbon polymer comprises repeating units derived from tetrafluoroethylene and perfluoromethyl vinyl ether.   The method according to any one of claims 2 to 11, wherein the composition (II) comprises less than 10% by mass of a fluorocarbon polymer based on the total mass of the composition (II).   The method according to any one of claims 2 to 12, wherein the additive (A) further comprises a polymer selected from the group consisting of polyetherimide, polycarbonate, poly (aryl ether ketone), and liquid crystal polymer.   The method according to any one of claims 2 to 13, wherein the composition (II) does not contain an inorganic flame retardant or contains less than 2 parts by mass of an inorganic flame retardant based on the mass of the aromatic sulfone polymer.   The method according to any one of claims 2 to 14, wherein the composition (II) does not contain titanium dioxide or contains less than 3 parts by mass of titanium dioxide with respect to the mass of the aromatic sulfone polymer.   The method according to any one of claims 2 to 14, wherein the composition (II) contains 3 parts by mass or more of titanium dioxide based on the mass of the aromatic sulfone polymer.   A method of manufacturing an aircraft component comprising an aromatic sulfone polymer composition [Composition (I)], comprising one or more aromatic sulfone polymers and optionally one or more other components, comprising: A method comprising applying a method according to any of claims 16 to 16 to the aromatic sulfone polymer composition.   One or more perfluorinated polymers for reducing the melt viscosity of an aromatic sulfone polymer composition [composition (I)] comprising one or more aromatic sulfone polymers and optionally one or more other components Use of one or more fluorocarbon polymers comprising repeating units derived from monoolefins and one or more perfluoroalkyl vinyl ethers and optionally an additive [additive (A)] comprising one or more other components. A method of preparing an aromatic sulfone polymer composition that needs to reduce its melt viscosity, comprising:
Providing one or more aromatic sulfone polymers;
One or more comprising repeating units derived from one or more perfluorinated monoolefins and one or more perfluoroalkyl vinyl ethers in an amount effective to reduce the melt viscosity of the aromatic sulfone polymer composition Providing a component of an additive [additive (A)] comprising a fluorocarbon polymer and optionally one or more other components;
-Optionally providing one or more components other than the aromatic sulfone polymer and a component of the additive (A);
-Contacting the aromatic sulfone polymer, the component of the additive (A) and, if present, one or more components other than the aromatic sulfone polymer and the component of the additive (A);
Including methods. An additive comprising one or more aromatic sulfone polymers, and one or more fluorocarbon polymers comprising repeating units derived from one or more perfluorinated monoolefins and one or more perfluoroalkyl vinyl ethers. (A)]
Aromatic sulfone polymer composition [Composition (II)] containing an aromatic sulfone polymer whose melt viscosity is lower than the melt viscosity of the same composition [Composition (I)] without additive (A) Composition.   21. An aircraft component comprising the aromatic sulfone polymer composition of claim 20.   Select from the group consisting of overhead passenger service equipment, window frames, air return grilles, aircraft wall plates, aircraft overhead storage lockers, aircraft cooking trays, aircraft seat backs, aircraft compartment bulkheads, and aircraft tubes The aircraft component of claim 21.   An aircraft comprising the aircraft component according to claim 21 or 22.