JPS6042457A - Bridgeable and crystalline polyaryl ether and composite material - 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 BACKGROUND OF THE INVENTION The present invention relates to tough, solvent-resistant materials derived from polyaryl ethers and fiber-reinforced composites made from these materials.

In the polymer matrix [graphite in two, aromatic polyamide fiber,
BACKGROUND OF THE INVENTION Composite materials made of continuous fiber reinforcement such as and glass are useful structural materials because they have high specific strength and modulus compared to metals. Such composite feathers can be used, for example, in the production of load-bearing structures in automobiles and aircraft.

Most graphite-reinforced composites, epoxy resin systems are used as the base material. These resins are often brittle, so
The composite material made from C2 delaminates upon impact.

To improve the impact properties of fiber-reinforced composites, C2,2,2 = ductile materials such as polyaryl ethers derived from his(4-hydroxyphenyl)furopane (i.e. bisphenol A) and dichlorodiphenyl sulfone are used. Thermoplastics were used as matrix resins. Although this resin provides a composite material with good toughness, it is attacked by many common organic static agents such as chlorinated hydrocarbons, ketones and N,N-dimethylacetamide. Due to the lack of solvent resistance, the range of applications in which composite materials based on this resin can be used is limited.

Recently, attempts have been made to improve the solvent resistance of polyaryl ethers derived from bisphenol A and dichlorodiphenyl sulfone. The polymers were modified when heated (two chain extension reactions and a crosslinking reaction) by attaching the two end groups used at 6°C. Suitable end groups include maleimide, natimide and ethynyl. Maleimide-terminated polyaryl ethers are described in U.S. Pat. No. 3,839,287 (1);
H.

Shepard et al., Reinforced Plastic Tech/Combo Zyte Institute 36th Annunciation, 1981
February 16th to 20th, session 17-B.

Pages 1 to 5 (one is described, and the ethynyl-terminated polyaryl ether is
Journal of Polymer Science, Polymer Chemistry Edition, Volume 20, 1982, fl! 3131
All of these polyaryl ethers are prepared with bisphenol A as the aromatic diphenol. However, none of these resin systems has a high degree of solvent resistance.

]
) a crystallization accelerating plasticizer; (b) a fiber-reinforced composite produced by adding (If) to (1) as a base material resin;

The compositions of the present invention are of formula I derived from bisphenol A.
The fiber-reinforced composite materials of the present invention exhibit improved solvent resistance and environmental stress cracking resistance compared to compositions containing polyaryl ethers of carbon or graphite fibers, aromatic polyamide fibers, glass fibers, Polyethers having formula I containing fiber reinforcing agents selected from or boronic fibers include 4,4'-dihalodiphenylsulfone and aromatic ethers which are hydroxyl or 4,4'-biphenol as main It has a skeleton derived from diphenol. The preferred dino-rodiphenyl sulfone is 4.4-
Dichlorodiphenyl sulfone and the preferred dienol is hydroquinone. Diphenols up to 25% on a molar basis are converted into bisphenol A1 methylhuman tetraquinone,
Chlorohydroquinone, bis(4-hydrogy7pheni#)
melamine, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl) sulfone, resorcinol or U.S. Pat. No. 4,306°094 C
Up to 40 moles of the dihalodiphenylsulfone can be substituted with oligomeric hydroxyl-terminated polyaryl ethers such as those described in 4,4-difluorobenzophenone or 4,4'-dichlorobenzophenone. 7:C2,6 like 4-dihalobenzophenone or 2,6-dichlorobenzonitrile
- Can be replaced by other monomers C2, including dihalobenzonitrile.

The terminal group in formula I (2) is selected from: ■0 ocu2-cmiCI . Each of the above, when heated (two-chain extension reaction and crosslinking reaction occurs), the method for producing polyarylether of formula I is X (Niseki i do.

Reel ethers are prepared by: (1) in a dipolar aprotic solvent, in the presence of a base, about 1
Preparing a hydroxyl-terminated polyarylether by condensation of a molar excess of an aromatic diphenol with dichlorotetradiphenylnurphone at 00°C to about 220°C. Suitable process conditions are described in U.S. Patent No. 4,108,8.
No. 37 and No. 4,200,728, as well as British Patent No. 1,492,366. Substituted penzoylchloride (esterifying the di-terminal hydroxyl group). Either m-ethynylbenzoyl chloride or p-ethynylbenzoyl chloride can be used. Triethylamine is a suitable acid acceptor. Solvent binders include N-methylpyrrolidinone, tetrahtomifuran, methylene chloride or mixtures thereof.

A general procedure for the synthesis of polyaryl ethers is given in Journal of Polymer Science Polymer Chemistry Edition, Volume 20, 1982, Nos. 3131-31.
Page 46 - Doubled.

When X is: 1, the polyaryl ether of the formula ■ is (1
) Amine-terminated polyaryl ether from C2 by condensation of an aminophenol, a chamfered diphenyl sulfone, and an aromatic diphenol in the presence of a base in a dipolar aprotic solvent (at elevated temperature); (1) Adding maleic anhydride or nathoic anhydride, i.e., 5-norbornene-2,3-dicarboxylic anhydride, to a terminal amine group (2) to form diamic acid, then (Iil) heating≦2 or by method C2, which involves the addition of a dehydrating agent such as acetic anhydride (imidization of the amic acid group).

This method is Method A. The conditions from steps (1) to (Ill) are shown in the above-mentioned US Pat. No. 3,839,287 C; or alternatively (; step (+)) as described in U.S. Pat.
, No. 366, using the process conditions described in each specification.

The steps in Method As; are outlined in Diagram 112 using p-aminophenol, human tetraquinone, and acid anhydride. Molar ratio of phenol, J-
IJtl [do. The amount of Dino 10 diphenyl sulfone used is 0 activated norogenide per mole of hydroxyl group.
．． The amount is such that from 95 to 1.05-T-nyl is present. Either m-aminophenol or p-aminophenol can be used. When O can do.

The method involves: (1) forming a hydroxyl-containing imide from an aminophenol and either maleic anhydride or nathoic anhydride; (1) in the presence of a base (a dipolar non-tetratonic solvent During,
At a temperature of about 100°C to about 180°C, diphenyl sulfone, aromatic diphenol and
to condense the products from ? include. The conditions for this step ζ2 are similar to condition C2 for the formation of the amine-terminated polyaryl ether in Step 4(1)s- of Method A.

Method B is illustrated in Figure 11 using p-aminophenol, hydroquinone, and sodium chloride anhydride.

As described in publication C2 by Knoephardt et al.

When X is HO (2) the polyary-ether of formula I is (1)
Condensation of aminophenol, diphenylsulfone and aromatic diphenol in the presence of a base in a dipolar aprotic solution at a temperature of 100 to 210°C (2); more amino-terminated polyaryl producing an ether, then (B) amidating the di-, m- or p-ethynylbenzoyl chloride (the di-terminal amine group) in the presence of an acid acceptor at a temperature of -20°C to 50°C; Inclusion method (can be included in two ways)

When X is HO (2), the preferred solvent for the preparation of the polyaryl ether of formula I is N-methylpyrrolidinone, since N-methylpyrrolidinone is used in both step (1) and step (It) (1). These are the ones who can do it.

When X is, the polyarylether of formula I is 70 to
It can be produced by condensing an aromatic diphenol, dihalodiphenylsulfone and hietenylphenol in a dipolar aprotic solvent at 200 DEG C. in the presence of a base.

Synthesis of m-ethynylphenol is disclosed in U.S. Patent No. 4,108.
．． No. 926 [2] is described.

When X is 0CH2-C=CH (2 is the polyarylether of formula Preferably, propargyl chloride is added after the hydroxyl-terminated polyarylether has been formed from the dihalodiphenylsulfone and the excess aromatic diphenol.

In the composition (2), upon heating, the crystallization-promoting plasticizer promotes crystallinity in the backbone C2 of the polyarylether of formula I.

The crystallization-promoting plasticizer (2) is of two types; the first type is one that does not react with the polyarylether of formula I and has solubility with the polyarylether (glass transition temperature of 30°C, low volatility). The second type, which is characterized by a boiling point of Temperature and >200
°C boiling point (characterized by two. Examples of the first type are triaryl phosphate esters, terphenyl, hydrogenated terphenyl, coataphenyl, water-fated coater 7
E2 (in the formula, n = 2 to 15), 4,4'-dichlorodiphenylsulfone, 4,4'-dichlorobenzophenone,
Other substituted diphenyl sulfones or benzophenones, substituted diphenyl ethers and mixtures thereof. A preferred plasticizer of the second type is 4
, 4'-bis(3-ethynylphenoxy)diphenylsulfone, triallyl cyanurate, and sialyl phthalate, triallyl trimellitate, bisphenol A
biscyanate, diaminodiphenylmethane, 1-amino-3-ethynylbenzene, 1-hydroxy-3-ethynylbenzene, 2.2-bis(3-ethynyl-phenoxy-4-phenyl)propane, sivinyl acyhate,
Includes divinyl ether of 1,4-butanediol, N-phenylmaleimide, bismaleimide of 4,4-diaminodiphenylmethane, N-vinyl-2-biH lidinone, and mixtures thereof.

The crystalline and crosslinkable compositions of the present invention (i.e. (+) and (It) plus a plasticizer) are manufactured by Banbury (Bu
Early crosslinking can be prepared by mixing the components at a temperature of about 100°C to about 350°C in conventional polymer compounding equipment such as mixers or extruders. In order to minimize (=short mixing time and low mixing temperature is preferable)

When blending an ethynyl-terminated polyaryl ether, an inert gas atmosphere is preferred.

Another method for combining polyarylethers of formula I and crystallization promoters is to combine them with liquids such as N-methylpyrrolidinone, N,N-dimethylacetamide, methylene chloride, tetrahydrofuran, sulporan or mixtures thereof. Medium C2 is to dissolve or disperse. The liquid can be removed by evaporating the mixture or by pouring liquid C which dissolves the carrier but does not dissolve either the polyaryl)ether of formula I or the crystallization promoter. For many mixtures in N-methylpyrrolidinone or N,N-dimethylacetamide, precipitation in water is sufficient. □The solid mixture of polyarylether of formula I and the promoter is then recovered by filtration C2, dried and cured.

A composition having improved solvent resistance is prepared by heating a mixture of a polyarylether of formula (1) and a crystallization promoter at a temperature of about 100° C. to about 350° C. The time and temperature depend on the desired level of solvent resistance. Preferred temperatures are above the glass transition temperature of the mixture and below the melting point of the pure polyarylether of formula I.

The fiber reinforced composite material of the present invention is manufactured using techniques well known in the art. For example, thin films of mixtures of polyarylethers of formula I and crystallization promoters can be prepared and inserted between braids of fiber reinforcement in the form of woven fabrics or unidirectional tapes. This mass can be heated in a heated press (2) to produce a laminate. Alternatively, the polyarylether of formula I and the crystallization accelerator and the fibers may be thoroughly mixed (2). Composites can be made from prepregs, which are prepared by drawing the fibers through a heated bath containing a polyarylether of formula I, a crystallization promoter, and a solvent, and then It can also be produced by evaporating the solvent.

Other methods include, for example, U.S. Pat. No. 4,292.
No. 105, a slurry containing a polyarylether of formula I and a crystallization promoter is mixed with a reinforcing material (
=Includes coating, heating, and compression molding. Pre-impregnated reinforcement and C2 laminate sheets can be made using a C2 heated calender four-wheel as described, for example, in U.S. Pat. No. 3,849,174 by Danji.

The number average molecular weight of the polyaryl ether of formula l is approximately 2,0
00 to about 3000. Preferably about 2,500 to about 2
5.000, most preferably about 5.000 to about 20,
It is 000. The polyether polyol of formula l is 380
It is a solid that melts or softens at temperatures below ℃.

The compositions of the invention (with added polyarylate C crystallization promoter of formula I) can be used with (or without) reinforcements. In the absence of reinforcements, , the composition contains up to 50% by weight of crystallization promoter.

In the reinforced composition, the weight of the polyarylate ether of Formula I is from about 10 to about 90% by weight, the amount of crystallization promoter is from 0.5 to about 25% by weight, and The compositions can be extruded, compression molded, and injection molded.

The compositions can also be used as films, paints, adhesives and sealants. Their composition is carbon black, talc, and mica.

and can be combined with particulate photonic agents such as calcium carbonate. Chopped fibers and continuous filaments can also be used.

Suitable reinforcing materials have a melting point or decomposition point of 200°C or higher;
and alumina, titania, silicon carbide, silicon boride,
polybenzothiazole and one or more of the above two reinforcing agents.

Crosslinking can be carried out with the aid of free radical initiators or radiation. Suitable polymerization initiators include dicumyl peroxide, di-t-butyl peroxide, 1.1.2.2-
It includes buto-2arylethane, 1.1.1.2.2°-pentaarylethane, and the like.

EXAMPLES The following Example C describes the implementation of the invention in more detail, but these examples are not intended to limit the scope of the invention in any aspect.

Example 1 1 ton four-loaf flask C equipped with mechanical stirrer, thermometer, addition funnel, nitrogen purge line, Dean-Stark trap and condenser; dichlorodiphenylsulfone 12912r, hydroquinone 48.45f, p-
Aminophenol 2.21t1 Potassium carbonate 80.85
F, chlorotetrabenzene 137- and sulfolane 368- were charged. The mixture was kept at room temperature (25° C.) and purged with nitrogen for 30 minutes with stirring.

From the compound chlorotetrabenzene and lumibenzene-water 4
While distilling the boiling mixture, the mixture was heated to 2210° C. and 180° C. of benzene was added.
The temperature was then maintained at 210° C. for 2 hours. The reaction mixture now containing the Akun-terminated polyarylether was
Cool to 70°C and add 3.94 f of sodium acid anhydride. After 2 hours at a temperature of 160-170°C F: 1; Pour the mixture into a pan lined with 2 foils and allow to cool. Once the reaction product has solidified, break it and place it in a blender ( The insoluble matter was collected by filtration and washed with 2 t of deionized water.
) with deionized water (washed twice. 2t of the undissolved matter
The slurry was made into a slurry in methanol and then dried under reduced pressure. The isolated yield of product was 145t.

According to infrared analysis C2, the product was at 25°C (N-
It was shown to be a natimide-terminated polyarylether with a reduced viscosity of 0.50 measured at a concentration of 0.2 t/dt in metherpyrrolidinone.

Control Example A The following materials were added to two reaction flasks: 43.9 f of phenoxynabiimide, 35.3 f of bisphenol, 110.07 f of dioxydiphenyl sulfone, 55.6 f of potassium carbonate, and 760 f of a mixture of dimethylacetamide and toluene. −.

The contents were heated at 140°C for 72 hours.

Reaction product line N-methylpyrrolisi at 25°C /
Example 2 Preparation of Molded Plaques and Solvent Tests Molded articles of the material of Example 1 were When cured at 250 DEG C. for several hours, there was no effect at all when immersed in either methylene chloride or dimethylacetamide, while parts molded from the material of Comparative Example A had the same effect. When cured under conditions 1 and 2, swelled in these solvents (extreme C; 2).

This result shows that hydroquinone I as the diphenol in the polyaryl ether backbone: the composition of the present invention has improved solvent resistance compared to bisphenol A-based Control A.

However, further improvements, particularly improvements in environmental stress cracking resistance, are desirable, and means for achieving this are shown in Examples 3 and 4 below.

Solvent resistance of natimide-terminated polymer A B Sample Curing conditions Solvent influence control example A 250°C (= 2 hours) Thick swelling Example 1, influence.

Product of No shadow 0 A: 4' molded at 4000 psi, 275°C
X 4'X IX cut from 1 lac of 10 mil, 2f
M strip.

B: The solvent was methylene chloride unless special C was used.

C:N,N-dimethane/acetamide Control Example B The material from Example 1 above was heated to 310° C. (two times), then compression molded into a 4'X4X20 mil slurry (two times,
The mixture was allowed to react at 50° C. for 2 hours. Then, an annealing process was performed at 200° C. for 2 hours.

The resulting material was tested for environmental stress cracking resistance against acetone and methyl ethyl ketone C.

When subjected to a stress of 1000 Pato (2), the time to failure was 2 seconds for methyl ether ketone C2 and 3 seconds for acetamide.

Modulus-temperature data were obtained for the material described in this example which was molded and heated at 250°C for 2Vj but without annealing at 200°C.

The modulus-temperature data indicated an amorphous product with no crystalline modulus plateau. The measured secant modulus values at 200°C and 225C and 1250°C are 200 pat and 46 ps, respectively.
It was 8 pat. Calorific value data is DuPont 99
0 heat analysis Iron placed under N2 calculation atmosphere 210℃/fk
(obtained by heating at 400°C) (2). No evidence for crystallinity range was obtained.

Example 3 Product of Example 1 and Crystallization Accelerator The material from Example 1 above (8,5f) was slurried in an acetone solution C2 containing 1.52 kg of triphenyl phosphate. After liquefying the acetone, the material was heated at 310°C.
Heat the mixture and compression mold it into a 4X4X20 mil slurry.
Further, the reaction was carried out at 250C for 2 hours.
The annealing process was carried out at 00°C for 12 hours. The resulting material was tested for environmental stress cracking resistance against acetone and methyl ether ketone.
When subjected to a stress of 0.00 pat (2 hours), the time required for C2 to break is 0.08 hours at a stress of methyl ether ketone (2 hours,
It was 0.12 hours at acetate/(2).

Modulus-temperature data were obtained for two materials C described in this example (2), which were molded and heated at 250° C. for 2 hours but annealed at 200° C.

Modulus-temperature data showed a semi-crystalline product with a distinct crystalline modulus profile. measured 20
+0″c, 225°C and 25·01: (1% secant modulus at 2 is 8.650 psi, respectively.

7+870 P81 and 4,970 psi. The crystal melting point measured from the modulus-temperature data is 2
The temperature was 80°C. The calorific value data is DuPont 990 thermal analyzer ff! (obtained from C2 by heating at 10 C/min under N2 atmosphere at C2 and 400 C32. Crystallization was present. The crystal melting point was 272 C and the heat of fusion
．． It was 5 calories/f.

Example 4 The material from Example 1 above (FLOf) was combined with triphenyl phosphate 2. After liquefaction of O acetone slurried from an acetone solution containing OfC2, the material was heated at 310°C.
(Heated, compression molded into a 4' x 4' x 20 mil plaque, reacted at 250°C for 2 hours, then annealed at 200°C for 2 hours. The resulting material was tested for environmental stress cracking resistance against acetone and methyl ether ketone.10
When subjected to a stress C of 00 psi, the time required for methyl ether ketone to break is 2.13 hours,
(It took 1.20 hours at 250'C, but the molding was heated for 2 hours at 200°C.
Modulus-temperature data were obtained for the materials of this example (C) without annealing at 200c. , 225°C, and 250°C 1 m, * The secant modulus of 1 inch measured at 9.340 psi, ax 00 p, respectively.
si, and 6,000 psi.

The crystal melting point determined from the Modulus-Onta data is 28
The temperature was 5°C. The calorific data was measured at 10°C/min≦2 in a DuPont 990 thermal analyzer C2 under an N2 atmosphere at 400°C.
There was a degree of crystallinity obtained by heating at C2°C (2°C). The crystalline melting point was 283°C and the heat of fusion was 7.5 kJ-/f.

The results of Examples 3 and 4 show that plasticization of the polymer of Example 1 ≦
Second, it is shown that the environmental stress cracking resistance is improved.

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Claims (1)

[Scope of Claims] 1. A crystalline and Crosslinkable resin mixture. 2. The solubility of the crystallization-promoting plasticizer in polyaryl ether C, the glass transition temperature of about 30° C. or less, and the glass transition temperature of about 30° C.
The mixture according to claim 1, characterized by a boiling point of 0° C. or higher. 3. The crystallization-promoting plasticizer does not react with the polyarylether described in claim 1, and is not a triarylphos7ate ester, terephenyl, hydrogenated terephenyl, coataphenyl, hydrogenated coataphenyl, polyester. (phenylene oxide), tetralobenzophenone, substituted diphenyl sulfone, benzophenone, cytzenyl ether, or mixtures thereof; A mixture according to claim 1 characterized by a glass transition temperature of about 70°C or less and a boiling point C of about 200°C or more, wherein the crystallization-promoting plasticizer is 4,4′-bis(3-ethynylphenoxy)diphenylsulfone, triallyl cyanurate, diallyl phthalate, triallyl trimellitate, biscyanate of bisphenol A, which reacts with the polyaryl ether described in
Diaminodiphenylmethane, 1-amino-3-ethynylbenzene, 1-hydroxy-3-ethynylbenzene, 2
．． 2-bis(3-ethynyl-phenoxy-4-phenyl)propane, divinyl adipate), 1,4-butanediol nosyhinyl ether, N-phenyl-maleimide,
4. A mixture according to claim 4, which is selected from bismaleimide of 4'-diaminodiphenylmethane, N-vinyl-2-virolidino, and mixtures thereof. 6. A mixture according to claim 1 containing up to 50% by weight of a crystallization-promoting plasticizer. 7. (a) % of the resin mixture according to claim 1, and (b) carbon fiber or graphite fiber, aromatic polyamide fiber,
A reinforcing material selected from one or more of glass fibers, boron fibers, alumina, titania, silicon carbide, silicon boride, and polybenzothiazole. 8. Resin mixture (about 1 boaryaryl ether in 2
8. The composition of claim 7, wherein the composition is present in an amount of from 0 to about 90% by weight. 9. The composition of claim 7, wherein the crystallization promoting plasticizer in the resin mixture is present in an amount C2 of 0.5 to about 25% by weight. 10. The composition of claim 7 in which the reinforcing material is present in an amount of from about 5 to about 85 t% by weight. 11. (a) the crosslinked resin of claim 1. (b) carbon fiber or graphite fiber, aromatic polyamide fiber,
A composite material comprising a reinforcing material selected from one or more of glass fibers, boron fibers, alumina, titania, silicon carbide, silicon boride, and polybenzothiazole.