JPS62190253A - Polymer composition - Google Patents

Abstract

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

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to polymeric compositions, particularly polymeric acids containing polyaryl ether derivatives and fibrous reinforcements.

Among the polyarylether ethyl derivatives with good high temperature properties, polyarylethersulfone Koma 1 is generally amorphous, but only C2, has a glass transition temperature exceeding 200 °C, and has a polyaryletheryl -Thylketones are generally crystalline, but typically less than 200°C, e.g., 140°C to 165°C. Some 6-boaryl ether ketones have glass transition temperatures of about 200°C
However, typically they have melting points near or above about 400''C and therefore must be processed at temperatures close to that at which rapid degradation occurs.

For example, polyarylether derivative compositions containing fibrous reinforcement described in EPA 3119B have high flexural moduli and high heat distortion temperatures, but exhibit significant degradation at temperatures above the glass transition temperature. , many of those annoying polyester types? , compositions based thereon are heated well below 200°C, typically from 140°C to
- Degradation at 165°C7 We have found that polymer compositions based on a particular range of copolymers have improved retention of mechanical properties at temperatures above 200°C.

According to the invention, the polymer composition has a border j~units -Ph-S
O2 -Ph-yendo-3O2-yen1-1 and -Ar-n (where Ph is noeny, 1/n- and Ar is -4
is the aromatic group of j) via an ether bond from 25:75 to 60:4
Calculated based on the sum of components a), ruby a) and b) which contain at least -.50-.BO
% of component b) which is a fibrous reinforcing material (1
．． Symptoms include 5.

Ph is preferably paraphenylene. Ar is fennin or bifus, -21/n, etc.;
L is a poly-group, but preferably one in which an aromatic viscosity is bonded via a non-aromatic group, specifically, Ar is represented by the following formula: Runie Ar'
-Z- to r1- (Each Δr1 may be the same or different, and is a divalent aromatic hydrocarbon group, and Z-SOS07-5
o, -CO-, and divalent aliphatic hydrocarbon secondary groups).

Ar' is a thousand or a poly- group, preferably 1. <
is phenylene, especially paraphenylene.

In component a) the repeating unit is preferably Ph'-SO2-Ph'-Ph'-SO2-Ph'-
IA and Ph' SOx -Ph' I
IA (where Phl is para-phenylene).

The ether bond may be one that connects two units (2), two units (2), or a unit (2) and a unit (2).

In any particular polysulfone there may be a plurality of different units n satisfying the definition Ar, but preferably the units ■ are the same in any particular polymer; Mixtures may be used.

If component a) of the composition is a mixture of polysulfones, one of which contains only units 1 or IIA;
Preferably, the other one is composed of two types thereof containing both units, and the mixture should again contain units I and II in a relative molar ratio of 25:75 to 60:40, respectively. In this way, the mixture may contain, for example, 5
A polymer containing only units II in a 0% molar concentration and a polymer containing units I and (2) in a relative molar ratio of 50:50. If a mixture of polysulfones is used as component a), it contains only units II (preferably less than 20% by weight) of units I and
60:40 or each containing units I and n in a relative molar ratio I:II ranging from 25:75 to 60:40. It is either a mixture of molar ratios of polymers contained. The preferred range for any such system is 25:75 to 50:50.

Useful results have been obtained when component a) is a single polysulfone containing units IA and IIA in equimolar proportions.

The polysulfone or mixture has a reduced viscosity (R
V) is preferred. Particularly preferred polysulfones have an RV in the range of 0.2 to 1.0, especially 0.3 to 0.8.
has.

The fibrous reinforcement can be either organic or inorganic (e.g. poly-bara phenylene terephthalamide fibers, glass fibers or preferably carbon fibers) and typically has an average fiber length of several strands, especially less than 2cI11, e.g. about 6+nn+. are added as short or chopped fibers having a fiber content of 5 to 3.
5. Preferably contains at least 20% by weight of fibrous reinforcement. For structural applications, continuous fibrous materials,
For example, it is preferable to use glass or carbon in an amount of 30 to 70% by volume, more particularly 50 to 70% by volume.

The compositions of the present invention may also contain one or more other materials, such as organic and inorganic fillers such as polytetrafluoroethylene, graphite, boron nitride, mica, talc, and vermiculite, nucleating agents, and stabilizers such as phosphates. May be included. The sum of such materials and fibrous reinforcement should be such that the composition contains at least 20% by volume polysulfone or mixture.

The compositions of the present invention are made by mixing the polysulfone or mixture with the fibrous reinforcement and optionally other materials, such as by particle or melt blending.

Specifically, the dry powder or granular polysulfone or mixture can be mixed with the fibrous reinforcement and optionally other materials using techniques such as end-over-end blending or high speed mixers. The blend thus obtained is extruded into laces and cut into granules. These granules can be used to produce molded articles, for example by injection molding or extrusion.

Alternatively, the composition is made by passing the fibrous reinforcement as substantially continuous fibers of, for example, glass or carbon, in contact with a melt formed from polysulfone or a mixture. The composition in the form of filaments of fibrous reinforcement impregnated with polysulfones or mixtures may be used alone or together with other materials, such as the same or different polysulfones or mixtures. , a 1""c molded product is formed. , 2 technology is EP
-A 56703.102158 and 102159.

Yet another composition manufacturing technique consists of making a solution of the polysulfone or mixture and applying the fibrous reinforcement thereto. Examples of suitable solvents include dichloromethane, N,N-dimethylborumamide 1-, dimethyl sulfoxide, and 1-methyl-2-
The 6 fibrous reinforcement (5), which may include bilidone and the like, is stirred with the solution, separated and dried to remove the solvent.

The substantially continuous fibers are passed through a container containing the solution and then passed through a heated region -I! ' The solvent may be distilled off. This solution typically contains 1 to 20 g, preferably 2 to 10 g, of polysulfone per 1004 solution. This is not a particularly preferred technique because it is difficult to completely remove the solvent and the presence of the solvent may adversely affect the properties of the composition.

Furthermore, in one method, 1. 'Noilum-like polysulfone or mixture is used as a non-woven material with relatively short fibers.'
So I, woven fabric or material material VE 1. The material is laminated into a fibrous sleeve reinforcement material in the form of fibers. This Firno may be formed from a solution of: F-tosting 1, but preferably 1. The film is formed by, for example, stretching a film extruded from one Suroso I with rollers. Such fiber δ11
Lamination of the filler J to L is carried out under conditions of temperature and pressure, preferably at least 32 Or at a temperature of 340°C to 420°C and a pressure of at least 0.1, preferably at least IOMN/%. It is convenient to carry out the six-layer laminations carried out using at least one pair of heated laminations.

Although the polysulfones of component a) of the compositions of the invention can be prepared by electrophilic methods, it is convenient to prepare them by nucleophilic methods.

Nucleophilic methods for producing such polysulfones are described in particular in CA-N 1078234, 1153053,
1397260.

1558671, 1569602 plbi1586
972 and Canada special 3? It is described in each specification of No. f847963. , polysulfone 11 containing enthronement 1
and its manufacturing method are described in GB-A1397260 and Polymer, 1B (1977) 359-
It is described on pages 364 and 369-374.

Polysulfones are preferably prepared from polycondensation of at least one aryl dihalide and at least one bisphenol, or at least two different halophenols. This polycondensation leads to metal f, -f, ne, -
1. In particular, the dihalide is added by reaction with an alkali metal hydroxide, eg, an alkali metal hydroxide, and the reaction solution is then heated to a polycondensation temperature, typically at least 150°C. , -. This polycondensation is preferably carried out in the presence of an alkali metal carbon, an acid salt or a bicarbonate or a mixture thereof. It is also preferably carried out in the presence of a solvent such as diphenylsulfone or a substituted derivative thereof. The temperature is 150
℃-400℃ is convenient, the final temperature is 280℃-
= -320°C is preferred.

Polysulfones are compounds with the following general formula: 25:75
-60:2xl-Ph-so, -enhi-Pli-3o2-Pb- which is conveniently prepared by polycondensation in a molar ratio of ■:■ of 40
X7TIT and x3-Ar-χ4hf Circle 1 and AI- in the above formula have the same meanings as above, and x
l,x! =, x ″ and X' are each halogen or -011, and the ratio of ■ and ■ and X 1.
2. Is the nature of X 3 and X' halogen and -011 woody? The stoichiometric proportions are such that 6 X' and/or 2: If X4 is a halogen, then they are -5O-, -so.

- or 100- group to activate it to the or-I-- or preferably i to <H, ma-para positions. Preferred polysulfones are compounds 1 and 4,4'-
Bis(4-chlorophenylsulfonyl)biphenyl (A
) and compound (1) and i-te4,4'-dihi IS roxydiphenyl sulfone (B) or (3).

It is prepared using a mixture of 4+4'-dichlorosiphaer-sulfone <C>. Compounds (A), (B) and (C
) is 1:2:1 to 2:2:0. The substantially stoichiometric ratio 1 to '7 also includes a small excess of dihalide or bisphenol, for example about 5% mole, and it is particularly preferred to use an excess of dihalide.

Fibrous reinforcement filaments impregnated with polysulfone or mixtures, especially UP-A 56703.

102158 and 102159 by the application of heat and pressure, such as by compression molding or heated rollers, to a temperature conveniently at least 3 above the glass transition temperature of the polysulfone or mixture.
They can be laminated together at 20°C, typically about 400°C and particularly at a pressure of at least 0.1, preferably at least 5 MN/mf.

Compositions of the invention, particularly those obtained with substantially continuous fibrous reinforcement, may be formed into multilayer laminates. This may be anisotropic, where the fibers are oriented essentially parallel to each other, or conveniently, such that in each layer the fibers are in an almost quasi-isotropic laminate relative to the top or bottom fibers. is 45°, but perhaps e.g. 30” or 60°
Alternatively, it may be quasi-isotropic with an angle of 90° or an angle intermediate therebetween. Orientations intermediate between anisotropic and quasi-isotropic, and combination laminates are also provided. A suitable laminate contains at least 4 layers, preferably at least 8 layers. The number of layers will vary depending on the application of the laminate, such as the strength required, and laminates containing 32 or even more layers, such as several hundred layers, may be desirable.

In particularly preferred compositions, the polysulfone contains repeating units IA and IIA in substantially equimolar proportions and the fibrous reinforcement is substantially continuous carbon fiber. Moldings made therefrom, and in particular laminates, show at temperatures up to 240.degree. C. a deterioration in the flexural modulus of less than 30%, measured at 230.degree. Furthermore, although the polysulfone is amorphous, the composition has environmental resistance superior to that of many other amorphous polymers. That is, after 14 days of water exposure at 100 DEG C., such compositions exhibited less than 5% weight gain, substantially unaffected lateral flexural strength and short-beam shear strength.

Furthermore, after exposure to hydraulic fluids for 14 days at 70° C., similar compositions showed only slight weight loss (less than 0.2% by weight), short-beam shear strength virtually unaffected and 3.
It showed less than 0% decreased lateral flexural strength.

The present invention will now be illustrated in more detail with reference to Examples.

The fruit spot contains the above units IA and UA in substantially equimolar proportions bonded via an ether bond, and N.

0, determined at 25°C using a 1.0% by weight solution in a solution of 100- in N-dimethylformamide.
Polysulfone having a reduced viscosity of 37 was triblended with diphenylsulfone in a 1:1 weight ratio by inversion in a closed vessel.

25 continuous carbon fibers each containing about 12,000 individual filaments (Magnamite AS-4
.

Hercules, Praue, USA) tow was stretched over a series of stationary guide rods at a speed of 300 mm/min.
A strip of approximately 150 mm+ width with a tension of approximately 50 kg was obtained.

As the fibers were guided side by side, they were pulled onto a series of four 12.6 mm diameter fixed heated cylindrical rods maintained at 390°C. A powder mixture of polymer and diphenyl sulfone was fed into a nip formed between the carbon fiber strip and a first fixed cylindrical rod. This powder melts quickly, giving a pool of melt in the nip,
It impregnated the fiber strip that passed over the rod. This structure was further passed over and under a Miki heating bar without adding any further polymer mixture. Equipment was provided to extract the diphenylsulfone fumes generated.

The product obtained was 60% by weight (by weight) well wetted with polymer.
53% by volume) of carbon fiber. 1501 width and 0
．． It was a continuous tape with a thickness of 125 mm.

The sections cut from the mullioned sole tape were laminated by compression molding at a pressure of IOMN/mf at 400°C for 5 minutes, and then heated to about 80°C with air and then while still under pressure in the press. Cooling was performed using water, giving a cooling rate of approximately 15° C. per minute. Sixteen thick tapes were stacked to obtain a uniaxial array of approximately 2 mm thick carbon fiber laminates.

Figure 1 shows the results of a mechanical test at a typical temperature of C.

Table 1 ------- Super liquid) (a) Vertical flexibility is ASTM test method r) 790-8
By 0's technology? Measurement was performed using IJ 100ml 11 spans.

ND means not measured 7 (1)) Lateral bending i8 old (I is ^STM test method D79
0. -40ml/l with 80 technology! Measured using a span.

(c) 5BSS & Short-B-1, shear strength measured by the technique of STM test method D-2344-72 using a span-to-sample thickness ratio of 5:1. Ta.

−A boundary surface ↓− Samples of laminates exposed to hot water, others are hydraulic fluid (Sk
hydro1 grade L D 4, Mon5anto Ch
made by en+1cal) ζ, = exposed. The laminates before and after and their mechanical properties were measured. The results are not shown in Table 2L.

Table-----9-Next water + 0.47 100
95Skydrol -0,0973
100 Note) Both (1)) and (0) are as shown in the notes in Table 1.

(d) Water means 14-meter water at 100"C. 5kydrol means 14-meter hydraulic fluid (Skydro1 grade 1., D 4) at 70"C.
6(e) Crew changes are given as 1-/100th of the original weight. (- does not indicate weight increase l.- indicates heavy ball...loss.

(f) Retention rate is expressed as 100% of the original measured value and 1.

11 - Using the method of Example 1, a polysulfone with only units i1A, i.e. rVictrex J® pl
BS (polyarylether sulfone) aromatic polymer 5
200P grade (Imperial CliemCl
Manufactured by Indust, riesPLC, original viscosity 0.5
2) Forming a composition from 1.

The polymer to diphenyl sulfone ratio was cooled at a weight ratio of 1 to 1.

Ice some laminate samples made from it as described in Example 1? 5 kydro exposure 1 ~, other samples 5 kydro
The test results are shown in Table 3.

Margin below, table --- Freshwater + 0.58 93
94Skydrol →Q, 03
66 99 soup) (1)) and (c) are both 14 and 15 as shown in Table 1.

(d), (e) and (f) are the same as all 7 Tables 2A)
Yi,.

Comparison of the results shown in Tables 2 and 34 shows that the composition of Example 1 has better water and hydraulic pressure than that of the composition of Comparative Example. It can be seen that it shows resistance to L-form.

Is this specifically a polymer composition? 5. - Put it on? ) How about 2)
This is evident in the retention of lateral bending strength, a property that is also most sensitive to defects.

y-Example 1. The weight ratio of polymer to diphenyl sulfone was 1:2 and 1~&
The same method as in Example 1 was repeated in steps 1 to 1, except that the product contained 13% by volume (65% by volume) of carbon fiber.

The following margins are m It was made in one step. C, J, Fourie (C) at various temperatures.
, J., l1ooley) and S.

Turner's method (Mechan)
ical Testing Plastics, In5t
Itute of Mechanical Engine
eers.

June/July 1979, Automotive Eng.
Impact resistance testing was performed using a 12.7 mm diameter drop weight dart and a 75 mm square sample placed unclamped on a 5011++n support ring by an inier). The levels of energy absorbed in causing damage of standard area are shown in Table 4.

-556,019,2 235,921,2 XJ and Example 1 The preparation of the laminate described in Example 1 was repeated using different Ha-Sochi polymers and 68% w/w fiber. The products were tested in the same manner at various temperatures, but with the exception of transverse flexural modulus. An additional 40 layer anisotropic laminate panel was fabricated and the panel was machined with a 6mm wide cuboid groove on each side leaving a 1mm thick central plane area in the direction perpendicular to the fibers, then the panel was machined in the fiber direction. A characterized in that it comprises measuring compressive strength by applying a force to
Tested according to the method of STM D 695-85. The results are shown in Table 5.

Margin Table 5 Note: (a), (b), and (c) have the same meaning as in Table 1.

Margin below

Claims (1)

[Claims] 1. Repeating unit -Ph-SO_2-Ph-Ph-SO_2-Ph-
I and -Ar- II (where Ph is phenylene and Ar is a divalent aromatic group) through an ether bond in a relative molar ratio I:II in the range of 25:75 to 60:40. component a), which is at least one aromatic polysulfone, and component b), which is a fibrous reinforcement, in an amount of 5 to 80% by weight calculated based on the sum of components a) and b). Characterized polymer compositions. 2. Ar is a divalent mono- or poly-group or -Ar^
1-Z-Ar^1- group (where Ar^1 may be the same or different and is a divalent aromatic hydrocarbon group; and Z is -SO-, -SO_2-, -CO- and The composition according to claim 1, wherein the composition is selected from divalent aliphatic hydrocarbon groups. 3. Component a) is unit -Ph^1-SO_2-Ph^1-Ph^1-SO_2
The composition according to claim 2, containing -Ph^1 IA and -Ph^1-SO_2-Ph^1-IIA (provided that Ph^1 is paraphenylene). 4. Component a) is a single polysulfone or each has different units.
A mixture of polysulfones with II, or one of them as a unit
A mixture of two polysulfones, one containing only II and the other containing both units I and II, or at least one polymer containing units I and II from 25:75 to 60:4.
A composition according to any one of claims 1 to 3, which is a mixture containing a relative molar ratio I:II of 0. 5. A composition according to any one of claims 1 to 4, wherein the polysulfone or mixture has a reduced viscosity in the range of 0.05 to 2.0, preferably 0.2 to 1.0. 6. The composition according to any one of claims 1 to 5, wherein the ratio of the two units is in the range of 25:75 to 50:50. 7. Repeating unit -Ph^1-SO_2-Ph^1-Ph^1-SO_2
-Ph^1- and -Ph^1-SO_2-Ph^1-IIA in substantially equimolar amounts and a substantially continuous carbon fiber, claims 1 to 6
The composition according to any of paragraphs. 8. A laminate formed from the composition according to any one of claims 1 to 7. 9, a) Repeating unit -Ph-SO_2-Ph-Ph-SO_2-Ph-
I and -Ar- II (where Ph is phenylene and Ar is a divalent aromatic group) through an ether bond in a ratio of unit I: unit II in the range of 25:75 to 60:40. polysulfone or a mixture comprising in combination in a desired molar ratio; b) 5 to 80% by weight of fibrous reinforcement calculated based on the sum of a) and b); and at least one continuous fibrous reinforcement. A method for producing a composition, characterized in that mixing is carried out by contacting and passing through a melt formed from polysulfone or a mixture. 10. A method according to claim 9, characterized in that the composition in the form of impregnated fibers is laminated with other impregnated fibers of the composition by applying heat and pressure.