JPS6372755A - Compatible blend of amide and/or imide-containing polymer and polyarylate - Google Patents

Abstract

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

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application] The present invention relates to a compatible blend of an amide- and/or imide-containing polymer and a polyarylate or arylate-carbonate copolymer, and Find ways to improve solubility. The blends are useful in the production of extruded sheets, high temperature connectors, aircraft and mass transit vehicle interiors, injection molded and extruded profiles, and thermoformable articles.

Aromatic polycarbomides, meaning polyamides, polyimides, and poly(amide-imides), are considered a class of polymers. Typically, these well-known aromatic polymers are high melt, high glass transition temperature resins that exhibit excellent mechanical properties and thermal resistance, and very good chemical resistance. A major drawback of these goods is the fact that they are often extremely difficult to process. For example, polyamides which can be described as self-condensation products of p-aminobenzoic acid include sulfuric acid (almost anhydrous or oleum (=flaming sulfuric acid)), chlorosulfonic acid, fluorosulfonic acid or lithium chloride and phosphorous compounds, e.g. It is always spun from solution using a strong solvent such as in combination with N,N-dimethyldimethylphosphineamide. Spinning can also be accomplished using nitrogen-containing solvents such as, for example, N,N,N''Nl-tetramethylurea, optionally in combination with inorganic salts.

Better solubility can be obtained using aromatic polyamides that are not entirely loosely bonded. High molecular weight polyamides prepared by reacting isophthaloyl chloride with phenylenediamine are soluble in chloroform. However, these polyamides are also very difficult to melt process.

Polyamides having softening oxygen bridges in their molecules, such as those based on 2,2-bis(4-(4-aminophenoxy)phenylpropane and iso- and/or terephthaloyl chloride), They are said to have improved melt processability. These resins exhibit good thermal stability, good electrical and mechanical properties, and can be molded into useful shapes even if moldability is still poor. Ease of processing can be improved by plasticizing these polyamides, for example with various phthalimides, siloxanes. 52
Improvements can also be made by blending with poly(arylether sulfones) or polyarylates, as described in No. 347.

Aromatic polyamides are also well known, eg, by Classic E, Kirk Osmer, Encyclopedia of Chemical Technology, 3rd edition, tan, 70.
It is described on pages 4-719.

Polyimides in general, and aromatic polyimides in particular, have excellent heat resistance, but are difficult to process. The same is generally true for aromatic poly(amide-imides).

Therefore, according to B. E., K. E. et al. (cited above), "totally aromatic polyimide molding powders must be made by sintering at high temperatures and pressures"; injection molding and extrusion are generally not possible. , J.M.
Atoushi-9, polyimides, K, L, Mitsushiru,
The editors, 1984, published by Brenham Press, New York, state on page 1024:

"Polyimides, made by the chemical reaction of aromatic dianhydrides and aromatic diamines, were the first of the aromatic thermally stable polymers introduced in the mid-1950s. Polyimides have a linear structure. However, it did not behave as a thermoplastic.

The polymer backbone consists of a rigid, inherently stable aromatic phenylene and polyimide endowed with imide rings, which have excellent thermal oxidation properties and at the same time due to their high, sometimes moderate melting points. It is extremely difficult to process. According to Tee, B., Gannett, et al. in U.S. Pat. This is a typical polyimide of the group polyimide. Alberino et al., U.S. Patent 3,708.45
8, polyimides with repeating units of the formula "possess very useful structural strength properties, but their relatively poor flow in molds makes it difficult to mold them by compression at high temperatures. It is difficult to

These patentees also claim that 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride and 2,4
-or 2.8-) Polyimides containing a proportion of the reaction product with luenediamine (or corresponding diisocyanates) in the polymer backbone are also disclosed. This copolymer is stated to have better flowability in the mold, even in criteria where difficult molding procedures such as "sintering or hot working" are used.

Therefore, aromatic imide-based polymers are generally not easy to melt process them other than perhaps by compression molding.

The processability of some of these imide-based materials is that they can be melt-processed more easily by blending them with other resins or making them more easily thermoformable and injection moldable. For example, Robeline et al. in U.S. Pat. No. 4,293,670 disclose blends of polyaryl ether resins and polyetherimide resins that have excellent mechanical compatibility and good impact strength and resistance to cracking due to environmental stresses. ing. J.E., filed September 29, 1983, assigned to the present applicant.
Harris et al., U.S. Patent Application No. 537,042, filed June 29, 1984, filed June 29, 1984, assigned to Assignee XI, describes blends of selected polyaryl ketones and polyetherimides. Harris et al., US Pat. No. 626,105, describes blends of poly(amide-imides) and poly(aryletherketones). Additionally, US Pat. No. 4,258,155 describes blends of poly(amide-imide) and poly(etherimide).

Although polyarylates have been known in the technical literature since 1957, they have only recently become widely available from commercial sources. Polyarylates are polyesters derived from dihydric phenols and at least one aromatic dicarboxylic acid, such as polyarylates based on bisphenol A and mixtures of phthalic and isophthalic acids.
rate. The processability and properties of polyarylate are
L, M.

“Engineering Thermoplastics: Blobatties and Applications” by H. Maresca, M. Robeson, edited by J.M. Morgolis, 2.
55, Marcel Detzker, Inc., New York, 1985.

Arylate copolymers containing carbonate linkages in addition to aromatic ester groups are also known. Phosgene or other carbonate generating species are used in their preparation along with diacids and bisphenols.

Blends of polyarylates and other polymers are disclosed in U.S. Pat.
, 231 , 922.4, 246.38L 4,25
It is the subject of several patents, including No. 9.458 and No. 3,946.091. U.S. Pat.
Blends of polyarylates and poly(etherimides) are disclosed, including blends of polyarylates and certain polyetherimides.

The compatibility of polymer blends confers certain advantages; for example, such blends tend to be transparent, have a single glass transition temperature, and exhibit other properties of a single material; By varying the relative proportions, the mechanical properties can be tailored to meet the needs of a particular application without losing the transparency and other desirable properties typically typical of single-phase materials.

Despite considerable research in the field of miscibility of polymer blends, this technique is expected to be unattainable. According to authorities: (a) "It is well known that compatible polymer blends are rare." Wamp and Cooper, Journal
of Po1yIIler 5science, Po
Lymer Plastics Edition, 2
Volume 1, page 11, (+983).

(b) "Compatibility in polymer-polymer blends is currently the subject of wide theoretical as well as practical interest. Over the past decade or so, many polymers known to be compatible The number of blends has increased considerably.

Furthermore, many systems have been found which exhibit upper and lower critical melting temperatures, ie, are completely compatible only within a limited temperature range. Modern thermodynamic theory has so far had limited success in predicting compatibility behavior in detail. These limitations have given rise to a degree of pessimism about the possibility of developing any theory that can accommodate the true complexity that nature has endowed in polymer-polymer interactions. did.

Cumber, Bendler and Bob, Macromolec
ulars 1983. vol. 16, p. 753.

(C) "The majority of two-phase blends in the form of polymer pairs, after mixing, can be inferred to have a low entropy of wetting for very large molecules. These blends are generally opaque, distinct They are generally characterized by thermal transitions and poor mechanical properties; however, with special care in the preparation of two-phase blends, composites with better mechanical properties can be produced. plays a major role in the polymer industry, in some cases dominating a larger market than either of the pure components. , Academic Press, New York, NY, 7 pages.

(d) ``It is well known that incompatibility is the norm during the mixing of thermoplastic polymers and that compatibility and even partial compatibility are exceptional. Since the thermoplastic one coalescence of is incompatible with the thermoplastic one coalescence of the pond,
The discovery of homogeneous mixtures of partially compatible mixtures of two or more thermoplastic polymers is indeed inherently unpredictable with any degree of certainty. P.J.Flory, Pr1ciples of Polyme
r Chemistry, Cornell University Press, 1953, Chapter 13, Page 555.

Johns, U.S. Pat. No. 4,371,672 (e) ``The study of polymer blends has become more important in recent years, and the resulting research efforts have led to the discovery of numerous compatible polymer combinations. is an outlier among ternary polymer mixtures, which normally tend to form phase-separated systems.While much of the work has been qualitative in nature, molecular weight and blend preparation conditions variables have often been overlooked. Criteria for establishing compatibility also vary and cannot all be accepted at all times for a particular system. Saeki, Colai, and Matsukueun, Polymer.
1983. Vol. 25, January, p. 60.

Such compatible blends are uncommon.

The criteria for determining whether two polymers are compatible are now well established. Olabisi et al., P.

IyIer-Polymer Miscibility
% 1979, published by Academic Press, New York, New York, p. 120), ``The most common method for establishing compatibility of partial phase mixing in or in polymer-polymer blends. A commonly used method is through measurement of the glass transition temperature (or transition) of the blend relative to the glass transition temperature of the unblended components. It will exhibit a single glass transition temperature between the Tg of each component, such that the transition temperature is sharp as well as the temperature.If the compatibility is borderline, the width of the transition temperature will be If the compatibility is limited, two separate transition temperatures will occur between the glass transition temperatures of each component, a phase rich in component 1 and a phase rich in component 2. When a strong specific interaction occurs, T
The fundamental limit to the usefulness of measuring glass transition temperatures to establish polymer-to-polymer compatibility is that g has a maximum value as a number of concentrations that are equal or similar. This is the case when performing a blend composed of components having a Tg (a difference of 20°C), and here it is not possible to divide the two Tg using the techniques discussed above.
” W, J, Matsuf Knight, etc., Polymer Blend
s, D, R.

Ball, and S., Newman II, 1978, Academic Press, New York, NY, 18.
On page 8 it is stated as follows:

"Perhaps the least obscure criterion for polymer compatibility is the detection of a single glass transition temperature whose temperature is between those corresponding to the two component polymers." Text omitted from this article From the author, compatibility is miscibility-1
ie, implying single-phase behavior. See, for example, the discussion in Chapter 1 in the same study by R. Ball.

As a particular example of how difficult it is to predict polymer compatibility preferences, U.S. Patent 4,258.155
Take an example from Example 8, which demonstrates that poly(amide-imide) and polyetherimide are compatible with mono-T8 in the blend. However, European patent application 016354
The closely related poly(amide-
(imide) copolymers are not compatible with the above-mentioned polyetherimides even though they contain 50 mole % of the same amide-imide repeating units.

In this regard, U.S. Pat. It describes a blend of suspended U-type resins. Although composites with improved formability properties are obtained, the patent does not state that a truly compatible alloy has been discovered, even though a significantly larger number of systems were tested.

Compatible blend compositions of polyarylates and amide- and/or imide-containing polymers would represent a useful advance in resin technology.

[Means to solve the problem]

Polyarylates containing carbonate linkages and their copolymers form compatible blends with selected amide- and/or imide-containing polymers. The compositions of the present invention exhibit a single phase in the amorphous state. tend to form and are therefore compatible systems. Such blends are generally transparent, particularly when injection molded, and exhibit considerably improved processability compared to amide- and/or imide-containing polymers, as well as glass transition temperatures and, therefore, their The ultimate use temperature of the blends is significantly higher than the polyarylate or arylate-carbonate copolymers used to form the blends. The compositions of the present invention also exhibit improved environmental stress cracking resistance as well as better Demonstrates melt processability.

The amide and/or imide-containing polymers useful in the practice of this invention are more fully described as a class by the term aromatic "polycarbomides." This term refers to polyimides, polyamides and poly(amide-imides)
This includes the neck.

More particularly, these polymers are polycarboxylic acids or derivatives thereof having the formula Ar(COOH)n, where n is 2.3 or 4, and having the formula H2N-A rl-N Ht It is characterized as a polycondensation product of aromatic polyamines or their appropriate derivatives or precursors. Ar and Ar1 groups are independently carbocyclic groups, such as mononuclear aromatic groups such as phenylene, naphthalene, etc., and divalent, trivalent and tetravalent polynuclear aromatic groups, in which a plurality of aromatic nuclei The bridging part of the value,
For example, it is selected from aromatic groups selected from the group consisting of those linked by ether, thioether, alkylidene, carbonyl, sulfone, and the like.

Typical polycarboxylic acids have a single aromatic nucleus, such as various isomeric forms of phthalic acid, trimellitic acid,
and ◎-×-◎, (wherein X is the same or different divalent bridging moiety, from -〇・, -5-1-802, C heat ~ C3 alkylidene, -C〇-, etc. di-, tri-, and tetra-functional polynuclear aromatic carboxyl compounds represented by (selected).

One group of the aromatic polyamine component of polycarbomide is preferably ether, thioether, alkylidene,
Preferably, such diamines are polynuclear aromatic groups consisting of a plurality of aromatic carbocyclic nuclei interconnected by divalent bridging groups such as carbonyl, sulfone, etc., where X is (with the meaning defined in ) is included.

Preferred polycarbomides are imide- and/or amide-containing polymers containing repeating units selected from the group represented by the following structural formula.

and (Ar and ^"1 independently (3-502-◎ , >0-◎ , 00-◎ , Hs (D-0-CH502-(D-0-◎ , C)Is
an aromatic group selected from the group consisting of CH3 and mixtures thereof).

The amide and/or imide containing polymers can be homopolymers, random copolymers, and block copolymers. The amide- and/or imide-containing polymer may be based on more than 1 diamine or polycarboxylic acid, with minor amounts of up to 20 mol % of other diamines or polycarboxylic acids, which do not substantially affect compatibility. It should be recognized that this can be included.

In accordance with the teachings of the present invention, in order to form a compatible blend with the polyarylate, the aromatic polycarbomide repeat unit contains at least one alkylidene-linked polynuclear aromatic group, preferably an arylene (
Ar1) portion is formed. The weight fraction of alkylidene units present in the polycarbomide influences its compatibility with the polyarylate, and the minimum level of alkylidene units required for compatibility is determined by the amount of amide and imide groups linking the aromatic components of the polycarbomide. Depends on relative quantities.

Generally, for the blends of this invention, the minimum level of alkylidene (expressed as isopropylidene) linkages necessary for compatibility is determined by the following relationship:

Isopropylidene unit ≧ 8-3 (imide) weight% (
(minimum) where (imide) is the fraction of imide groups present in the polycarbomide, ie (imide)+(amide)=1. The preferred minimum content of isopropylidene bonds is as follows.

Isopropylidene Units ≧ 12-2 (Imide) Weight % (Minimum) Polycarbomides useful in the practice of this invention are therefore prepared from polynuclear aromatic diamines or polyaromatic polycarboxylic acids, preferably divalent isoalkylidenes. It contains a sufficient amount of units derived from isobripylidene linking units or moieties that provide the necessary level of isoalkylidene units for compatibility.

Polycarbomides useful in the practice of this invention are prepared by any method well known in the art.

For example, aromatic polyamides can be produced by solution methods. That is, the acid chlorides and diamines may be dissolved in a suitable solvent such as N-methylpyrrolidone, N, By reaction in N,N',N'-tetramethylurea, N,N-dimethylacetamide, N-methylcaprolactam, hexamethylphosphoramide, chloroborum, methylene chloride, and the like. Polyamides can also be produced via the interfacial route and by reaction of diisocyanates with diacids. Polyamides have a temperature range of about 1 from the ambient temperature.
It can be prepared by reacting an organic diamine with a tetracarboxylic acid dianhydride at a temperature in the range of 75°C. Alternatively, the tetracarboxylic acid dianhydride can be reacted with a diisocyanate instead of the diamine. Reaction of the isocyanate with the anhydride group produces a seven-membered cyclic intermediate, which simultaneously collapses to form the imide and generate carbon dioxide.

A similar reaction is performed with poly(amide-imide), except that tricarboxylic acid monoanhydride or its derivatives are used instead of tetracarboxylic acid dianhydride.
used in the production of Poly(amide-imide) can also be produced via the routes shown in the following reaction formulas (1) to (2). The chemistry of these routes is
imide) and polyimide as described above. It should be noted that the terms dicarboxylic acid, tricarboxylic acid monoanhydride and diamine are meant to include derivatives of appropriate reactivity required for polymerization. Dicarboxylic acids thus also include the corresponding diacid chlorides, and diamines also include the corresponding di-N-acylated derivatives. These latter materials have been shown to be very useful in the production of poly(amide-imides). Kesuke, Polymer Preprints,
See Vol. 25, No. 2, p. 12 (1984).

I: Tetracarboxylic acid dianhydride + dicarboxylic acid + diamine → poly(amide-imide) ■: Tricarboxylic acid monoanhydride + dicarboxylic acid + diamine → poly(amide-imide) ■: Tricarboxylic acid monoanhydride + tetracarboxylic acid Dianhydride + diamine → poly(amide-imide) ■: Tricarboxylic acid monoanhydride + tetracarboxylic acid dianhydride + dicarboxylic acid + diamine → poly(amide-imide) Reaction formula! The useful substance in ~■ is Ar as defined above.
(COOH)n and H2NA "INH2.

Furthermore, small amounts of other polycarboxylic acid and/or diamine components, such as ararifatic, ciflorarifatic, alifatic components, of up to 20 mol X, preferably 10 mol χ, and most preferably not exceeding 5 mol 2 Others can be used.

Isoalkylidene, preferably isopropylidene, bridge-containing monomers are commercially available and can be made by known methods. In a general sense, the starting materials for preparing these monomers are typically aromatic nuclei doubly substituted with isoalkenyl groups, such as 1,4-diisopropenylbenzene. Acid-catalyzed condensation of such compounds with aniline leads to the desired diamino monomer, whereas Friedel-Crafts reaction with alkyl-substituted aromatic hydrocarbons, such as xylene, followed by oxidation and dehydration leads to isoalkylidenes or isobripylidenes. Produces dianhydrides containing bridges. The sequential process can be used to produce tricarboxylic acid monoanhydrides as well as dicarboxylic acids having isoalkylidene or isopropylidene groups in the molecule.

Polyaryl ethers suitable for use in the present invention are polymers and copolymers derived from dihydric phenol and at least one aromatic dicarboxylic acid, in which a portion of the dicarboxylic acid component is carbonyl halide or carbonate ester. Or polyarylates, including arylate-carbonate copolymers replaced by carbonate precursors such as bisphenol dihaloformates, have a polyarylate content of about 0.
4 to greater than about 1.0, preferably about 0.6 to 0.8 dl
/g of chloroform (0.5 g/100 ml of chloroform) or other suitable solvents at 25°C.

Particularly preferably, the dihydric phenol has the formula
1 is a divalent saturated or unsaturated aliphatic hydrocarbon group, especially 1-
An alkylene or alkylidene group having 6 carbon atoms, or a cycloalkylidene or cycloalkylene group having up to 9 carbon atoms, o, so2 or S. Dihydric phenols can be used independently or in combination. Bisphenol A is the most preferred bisphenol.

Aromatic dicarboxylic acids that can be used to form the polyarylates used in the practice of this invention include terephthalic acid, isophthalic acid, any sulfthalene dicarboxylic acids and mixtures thereof, and mixtures of these carboxylic acids. Included are alkyl-substituted congeners in which the alkyl group contains 1 to 4 carbon atoms, as well as those containing other inert substituents, such as halides, alkyl or aryl ethers. Hydroxybenzoic acid can also be used. Preferably a mixture of isophthalic acid and terephthalic acid is used. The ratio in the mixture (of isophthalic acid to terephthalic acid) is from o:too to about +00:0, preferably about 75:2.
S ~ about 50:50. Also included are about 0.5 to about 20% aliphatic diacids containing 2 to 10 carbon atoms, such as adipic acid, sebacic acid, and the like.

Polyarylates useful in the practice of this invention are well known and commercially available. The polyarylate may also be prepared by any of the well-known prior art polyester forming reactions, such as the reaction of a diaryl ester of an aromatic dicarboxylic acid with a dihydric phenol, or the diester derivative of a dihydric phenol of an aromatic diacid. It can be produced by reaction with

A+'')-late-carbonate copolymers and methods for their preparation are described, for example, in U.S. Pat. No. 3,169,121, which is incorporated herein by reference.

Such copolyesters containing repeating unit carbonate groups, carboxylate groups and aromatic carboxylic acid groups in the linear polymer chain are readily available commercially or are present as essential components. It can be produced by reacting a divalent carboxylic acid, a difunctional phenol, and a carbonate precursor. Methods for making these copolyesters are well known. Generally, bisphenol or its ester-forming derivative is condensed with a diacid or its ester-forming derivative and then with a carbonate precursor. Typical carbonate precursors are carbonyl halides, carbonate esters or bisphenol dihaloformes. Obviously mixtures of bisphenols and mixtures of diacids can also be used. The preferred poly(aryl carbonates) can contain up to 65 mole percent carbonate linkages, but for most purposes the arylate-
Carbonate copolymers will contain less than 50% carbonate linkages.

Blends of the present invention are about 2% to about 98%, preferably about 20%
~About 80! % polyarylate and correspondingly about 98-2, preferably about 80-20% by weight polycarbomide.

Blends of the present invention may further contain mineral fillings including chalk, calcite or other carbonates or dolomites, mica, talc, wallostenite; silicon dioxide and similar silicates; glass spheres; glass powder; aluminum; viscosity; quartz; It can be further compounded with additional materials such as agents and reinforcing fibers such as glass fibers, carbon fibers, etc. The blend also contains dyes, pigments and similar additives such as carbon black and titanium dioxide, heat stabilizers, UV stabilizers, plasticizers,
Flame retardants and the like can be included as is commonly practiced in the resin art. The blends of the present invention may optionally contain additional suspended organic associates such as poly(aryletherketones), polysulfones, polysulfones, etc. (ether sulfones), poly(aryl sulfones), poly(aryl ether sulfone!m), liquid crystalline aromatic polyesters;
Poly(etherimides), polycarbonate-based polyesters, such as poly(ethylene terephthalate),
May include aliphatic and aliphatic-aromatic polyamides (eg, nylon-6,6), fluorocarbon polymers, and the like.

The blends of the invention can be formed into any desired shape, i.e.
It can be fabricated into coatings, films, or fibers.

〔Example〕

The practice of the invention will be better understood in consideration of the following examples, which are offered as specific illustrations of the practice of the invention.

The following names used in the examples have the following meanings:

Yijiang'jiang' - A polymer having a repeating unit of the following formula, in which 25
It has an intrinsic viscosity of 0.48 dl/g measured at °C (0.2 g/100+sl solution). This polymer contained 13.3% by weight of isopropylidene units and the ratio of amide to imide groups was O:l. See Control E for construction details.

A polymer having a repeating unit of the following formula.

This polymer is not soluble in NMP, 6.0% by weight
of isopropylidene units. The ratio of amide to imide groups was 0:1.

Imide (2) was produced by the following method. To a 5001 round bottom flask equipped with a thermometer and mechanical stirrer was added 0.050 moles of diamine and 100 g of dimethylacetamide. The solution was stirred and cooled to 10-15°C in a water bath. 16.11 in dimethylacetamide of IO,Og
Following the addition of g (0,050 mol) of benzophenone tetracarboxylic acid dianhydride, the amber solution was stirred for 3 hours at 20-23<0>C. The solution was then diluted with 2001 dimethylacetamide. Imidization is 11.8
The next day, the contents of the flask were condensed in deionized water and diluted with acetone. Bicycle rinsed and dried in vacuo at 80°C to constant weight.

U process 1: Polymerization having a repeating unit of the following formula.

This polymer contains 16.81% by weight of isopropylidene units, with a ratio of amide to imide groups of 0.5:0.
It was 5.

Imide (2) was produced by the following method. A 0.05 molar amount of aromatic diamine was placed in a 5001 round bottom flask containing 120 g of N,N-dimethylacetamide (DMAC). After dissolving, the solution was cooled to 0°C and 0.0
5 moles of anhydrous trimellilite acid chloride were added.

The solution was brought to room temperature with stirring, at which point 0.15 mole of pyridine was added. The yellow solution was stirred for 2 hours and then treated with 1203 DMAC, an additional 0.15M pyridine, and 0.30M acetic anhydride.

The solution was heated at 90-100°C for 1 hour. The resulting solution or semisolid was coagulated in 2 liters of methanol.

The resulting fluff was collected and reslurried in 2 liters of fresh methanol. After collecting this fluff by filtration, the polymer was placed in a vacuum oven for 9
It was dried at 0°C for 16 hours. The intrinsic viscosity of the polymer is NMP
It was 0.84 dl/g measured at 25°C.

Earthwork ■: A polymer having a repeating unit of the following formula, with an intrinsic viscosity of 0.50 d measured at 25°C in NMP
It has 178. This polymer contained 5.1% by weight of isopropylidene units, and the ratio of amide groups to imide groups was 0.5:0.5.

Ue... A lamp υ having a repeating unit of the following formula, with an intrinsic viscosity of 0.5 measured at 25°C in NMP
It has 9 old/g. This polymer contained 3.6% by weight of isopropylidene units and the ratio of amide groups to imide groups was 0.5:0.5.

Earthworks J: A polymer having a repeating unit of the following formula, with an intrinsic viscosity of 0.
49 dl/g. This polymer contained 14% by weight of isopropylidene groups and the ratio of amide groups to imide groups was 0:1.

1e] * *e A random copolymer having a repeating unit of the following formula, and having an intrinsic viscosity of 0.66 at 25°C in chloroform.
dl/g. This polymer contained 15.211% by weight of isopropylidene groups, and the ratio of amide groups to imide groups was 0.25:0.75.

Uヱ''...A polymer having a repeating unit of the following formula, and has an intrinsic viscosity of 1.15 dlag at 25°C in NMP. This monomer contains 6.3% by weight of isopropylidene groups, with a ratio of amide groups to imide groups of 0:1.
Met.

1-- was obtained as Ardel Dloo from Union Carbide Corporation and had the following structure.

Hs where the ratio of para to meta bonds in the diacid residue is 50
It was 150.

Heat was made by polycondensing bisphenol A diacetate with isophthalic acid in the presence of diphenyl ether as a processing aid. This procedure is described in US Pat.
, 294,956. This polymer has the following structural formula: H3 where all bonds in the diacid residues are meta. This polyarylate had an intrinsic viscosity of 0.6 dl/g, measured at 25 DEG C. in a 60/40 phenol/tetrachloroethane mixture.

1-- was obtained from Celanese Polymer Company as Durel DKXOO3 and had the following structure.

Here, the ratio of para to meta bonds in the diacid residue is 25
/75.

Har +-+ + -Bo, - is Lefsan (Le
xan) 3250 from General Electric Company and had the following structure.

In the formula, the ratio of para to meta bond in the diacid residue is 73/
It was 27.

1, l 1-Le-71,- is Refsan (L
exan) 4501 from General Electric Company and had the following structure.

In the formula, the ratio of para to meta bond in the diacid residue is 30/
It was T.O.

No.1 1--Ha,- was obtained from General Electric Company as Lexan 4701 and had the following structure.

In the formula, the ratio of para to meta bonds in the diacid residue is 83/
It was 17.

Chang 1-11, - is Lexan lot
obtained from General Electric Company as
It had the following structure.

H3 vs ¥! A Imide I was compression molded in a 4×4×0.20 inch cavity mold at about 380° C. in a South Bend hydraulic press. The sample was cooled while in the press by passing water through the cooling channels in the hot platen.

Cooling from 380°C to room temperature took about 10 minutes. l/8
Inch strips were sheared from the molded product.

The strips were tested for 1 g secant modulus, tensile strength and elongation at break U$ according to ASTM-638, and pendulum impact strength according to procedures similar to ASTM D-638.

Pendulum impact strength was measured as follows. A cylindrical pendulum with a diameter of 0.83 inches and a weight of 1.562 bond is used.The striking body is a cylinder with a diameter of 0.3 inches attached almost to the top of the pendulum, and a length of 4 inches. , width 0.12
A 5 inch and approximately 1 to 30 mil thick film sample is clamped between the jaws of the tester with the jaws 1 inch apart, and a 0.125 inch wide piece of film is attached vertically to the sample. 13 Raise the pendulum to a certain height to add a foot bond. The position of the pendulum at the height of zero recovery, i.e. the maximum point of the upward swing, when the finger is released and the cylindrical striking piece breaks the sample striking film with its flat end and passes over the measured height. The impact strength, expressed in footbonds per cubic inch, is obtained by dividing the energy loss of the pendulum by the volume of the sample. The results are shown in Table 1.

The glass transition temperature of the molded blacks (plaques) was measured in two ways. Polymer-Bolimamermitsibilité, (P.) by Olabisi et al.

lymer-polys+er Miscibilit
y), academic press
The modulus-resilience method described in ESS), NY, page 126 was used to determine 1 g of as-formed black at a heating range of 1.6°C/min. Control A Tg was also DuPont 109 with dual DSC sample cell.
Determined by placing it in a zero thermal analyzer.
The Tg (or Tg's) is determined by methods well known in the polymer science art by heating to 100 for 7 minutes. The results are shown in Table ■.

Evaluation of the processability of a melt of a polymer or polymer blend is obtained as follows. For the modulus-resilience measurements used to determine <Tg as described above, a 178 inch wide, 0.02-inch thick thick strip with a 2 inch gauge length is clamped between the shows of an Instron mechanical tester.

The oven was surrounded by a glass tube to allow observation while the sample was heated at 1.6° C./min, which allowed the determination of modulus-temperature and resilience-temperature curves. The temperature at which the sample begins to sag without supporting its own weight in a vertical position is called the flow temperature; for a given resin, the flow temperature is a good approximation of the temperature required to melt process it by extrusion or injection molding. That's what I found out. Polymers that are extremely viscous or have poor melt stability due to thermal crosslinking generally do not measure anything up to the temperature limit of 400°C on an Instron oven and are said to have no flow temperature. Flow temperatures for Control A are given in Table 1.

Control B imide ■ was heated at about 380°C in a South Bend hydraulic press
Compression molding was performed in a x4x0.02 inch cavity mold. The sample was cooled while in the press by passing water through the cooling channels in the hot platen. The molded black was tested as a control and the results are shown in Tables 1 and 2.

Control C imide ■ at about 380°C in a South Bend hydraulic press.
Compression molding was performed in a x4x0.02 inch cavity mold. The sample was cooled while in the press by passing water through the cooling channels in the hot platen. The molded blacks were tested for mechanical properties and Tg as in Control A. The results are shown in Tables 1 and 2.

Control D Ali-Rate ■ in a South Bend hydraulic press at approximately 380%
Compression molded in a 4X4X 0.02 inch cavity mold at <0>C. The sample was cooled while in the press by passing water through the cooling channels in the hot platen. The molded blacks were tested as in Control A and the results are shown in Tables 1 and 0.

Control E 875 g of N-methyl-pyrrolidone and 52,37 g (0,15225 mol) of bis(aniline P) CH3C113 were added to a 3-vertical round bottom flask.

After the diamine is dissolved, benzophenone-3,3',4
゜4'-Tetracarboxylic acid direduct hydrate (BTDA)48.
3 g (0.15 mol) were charged with vigorous stirring, 0.66 g (0.0045 mol) of phthalic anhydride, 0.15 mol of para-toluenesulfonic acid and chlorobenzene 3758 were then charged, the mixture was stirred at room temperature for 30 minutes. , then brought to reflux (+50-160°C) for 2 hours.
) heated. The solution was refluxed for 4 hours, allowed to cool, filtered and the filtrate was treated with N-methylpyrrolidone (NMP) 125
Diluted with 0+*I. Coagulation in methanol is imide I
This produced a polyimide named . This was first air dried and then dried in a vacuum oven at 100°C for about 16 hours. The intrinsic viscosity of this material was determined at 250°C by NMP (0,
0.48dl/ when measured in 2g/1001 solution)
It was there.

The pale yellow powder obtained above was compression molded in a 4 x 4 x 0.02 inch cavity mold at about 370°C in a South Bend hydraulic press. The sample was cooled by passing water through the cooling channel inside the heating plate. The moldings were tested for mechanical properties and Tg as in Control A.

Furthermore, the melt flow index of the resin is determined by ASTM DI.
Determined at 375°C in a similar manner to 238. See the results
Shown in Table and Table ■.

Example 1 136 parts by weight of the imide of Control A and 164 parts by weight of the arylate were melt compounded in a Brabender Plasticorder mixer at about 380°C. The blend was then blended 4X4X0.02 in a South Bend hydraulic press at about 380°C. Compression molded in an inch cavity mold. Cooling the compound in a heat U? Water was passed through channel A and cooled in the press. The molded formulation was tested as in Control A and the results were compared to the first
It is shown in Table and Table 0.

Example 2 Control B imide II 501i parts and arylate 15
0 parts by weight were melt blended in a Brabender Plasticorder mixer at about 380°C. The blend was then compression molded in a 4 x 4 x 0.02 inch casting mold at about 380°C in a South Bend hydraulic press. The formulation was cooled while in the compressor by passing water through the cooling channels in the v+at. The molded formulations were tested as in Control A and the results are shown in Tables 1 and 0.

Example 3 50 parts by weight of the imide m of Control C and 150 parts by weight of the arylate were melt compounded in a Brabender Plasticorder mixer at about 380<0>C.The blend was then blended 4X4X0.02 in a South Bend hydraulic press at about 380<0>C. Compression molded in an inch cavity mold. The formulation was cooled while in the press by passing water through cooling channels in the hot platen. The molded formulations were tested for mechanical properties and Tg as in Control A and the results are shown in Tables 1 and 0.

Furthermore, the melt flow index of the formulation was adjusted to 375°C.
and 43.25 psi using a procedure similar to ASTM D123B. This formulation had no melt flow after 10 minutes of preheating, compared to no melt flow for the imide polymer ■.
．． It had a melt flow of 2 grams/10 minutes.

After 30 minutes of preheating, the flow of the compound was 0.9 grams halo.

Controls F, G and H Arylates III and ■ were compression molded in a 4 x 4 x 0.02 inch cavity mold at approximately 350°C in a South Bend hydraulic press. The resin was cooled while in the press by passing water through cooling channels in the hot platen. The moldings were tested for Ia properties and Tg as in Control E. The results are shown in Tables ■ and Table ■.

Examples 4, 5 and 6 150 parts by weight of polyimide of Control E (made as detailed above) was mixed at 350° C. in an alavender plasticoder mixer at 7 Lee rates 1, II or 5.
0 parts by weight. The formulations were compression molded in a 4 x 4 x 0.02 inch cavity mold at approximately 350°C in a South Pent hydraulic press. The formulation was cooled in the press by passing water through the cooling tgya in the hot platen. The moldings were tested for mechanical properties and Tg as in Control E. The results are shown in Tables M and II.

As shown by the data in Table 1, polyarylates are compatible with imide I regardless of the para/meta (tele/iso) ratio in the diacid residues. Imido! The Tg of polyarylate increases when polyarylate is added, while imide! When added to, melt flow is improved and therefore processability is improved.

Control 1. J and poly(arylate-carbonate)1. tl and Um in a South Bend hydraulic press at approximately 350°C 4X4X0.0
Compression molded in a 2 inch cavity mold. Water was passed through the cooling channel in the hot platen to cool the resin in the press. The moldings were tested for mechanical properties and Tg as in Control E. The results are shown in Tables 7 and 4.

In contrast, polycarbonate I was heated in a South Bend hydraulic press at approximately 3
Compression molded to 4 x 4 x 0.02 inch black at 50°C. The resin was cooled while in the press by passing water through cooling channels in the hot platen. The molded articles were tested for mechanical properties and Tg as in Control E. The results are shown in Tables 7 and 4.

Example? , 8.9 and 10 vs. 50 parts by weight of Imide I (see detailed preparation above) or Control C imide and parts by weight of poly(arylate-carbonate) ■, ■ or mso at about 350"C. Mixed in a Brabender Plasticorder mixer. The formulation was mixed in a 4X4X0 at about 350°C in a South Bend hydraulic press.
．． Compression molded in a 0.02 inch cavity mold. The formulation was cooled while in the press by passing water through cooling channels in the hot platen. The moldings were tested as in Control E for mechanical properties, Tg and melt flow index. The results are shown in Tables 7 and 4.
Melt flow data at 442.5 psi are: MFI0 = 0.86 d3/min, MF30/min for Example 7.
MF10=0.97; -FlO=0 for Example 8
．． 35dg/min, MF30/MFIO=1.64. Met.

Example 11 A formulation containing 111 parts of Polycarbonate 1501 and 50 parts by weight of Control C imide was made in a Brabender Plasticorder mixer at about 350°C. The formulations were compression molded in a 4 x 4 x 0.02 inch cavity mold at about 350°C in a South Bend hydraulic press.

The formulation was cooled while in the press by passing water through cooling channels in the hot platen. The moldings were tested as in Control E for mechanical properties, Tg and melt flow properties. The results are shown in Tables 7 and 4, and the melt flow data is MF10=1. OOdg/min.

MF30/MF10=25.2.

From the above results, the following is proven.

l) Blends of selected amide- and/or imide-containing polymers, i.e. polycarbomides, with polyarylates:
They are compatible as indicated by a single Tg with a value intermediate between the Tg's of these components. .

2) For compatible formulations, the Tg of the formulation is significantly greater than the Tg of the polyarylate.

3) The formulation has significantly improved processability compared to the polycarbomide component.

4) Polycarbomids such as polyimides, poly(amide-imides) and polyamides having a minimum isopropylidene content defined by the following formula, i.e. isopropylidene units f [amount χ (min) ≧ 8-3 (imide)
[where (imide) is the proportion of imide groups in the polymer] is compatible with the polyarylate. An example illustrating the validity of the above relationship is given in Table 1, which shows the phase behavior of blends of equal parts by weight of polyarylate I and various imide-containing polymers.

Compatibility was determined by the presence of a unique Tg and the clarity of the formulation.

5) Blends of polycarbomide and co-arylate-carbonate exhibit reduced compatibility, as suggested by the existence of two Tg values for most of the formulations summarized in Table 4. It seems to have. However, blends with less than 50 moles of carbonate groups are compatible. Compositions comprised of arylate-carbonate copolymers having carbonate groups greater than 5 o moles 2 exhibit improved processability, although less compatibility, properties that are beneficial for many applications.

Accordingly, the present invention provides a compatible composition comprising a polyarylate and an aromatic polycarbomide, the polycarbomide being a polycondensate of units derived from a particular aromatic polycarboxylic acid and a particular aromatic polyamine. be. The polycarbomide further comprises at least 51jlX isoalkylidene, preferably isopropylidene, as a divalent group linking the aryl nuclei of the polynuclear aromatic group to form either or both of the aromatic polyamine and aromatic polycarboxylic acid components of the polycarbomide. It is described as including parts. The compatibility of the polycarbomide with the polyarylate component depends on the isopropylidene content of the polycarbomide in relation to the imide and amine group content of the polycarbomide, and the minimum level of isopropylidene content required for compatibility is based on the imide group content. As the proportion decreases, the polycarbomide may further contain small amounts, usually up to 20 moles, of repeating units based on polycarboxylic acids and diamines, which are usually incompatible with the polyarylate. For example, pyromellitimide. Polyimides based on polyamides are generally crystalline, have high melting points and are
Not compatible with rate.

The compositions of the present invention can contain two pyromellitimides without losing the compatibility conferred by the isoalkylene-containing repeat unit.
Polycarbomids containing up to 0 mole 2 may be included.

This invention also describes a method of improving the compatibility of polycarbomides with polyarylates by incorporating polycarboxylic acids or polyamines containing isopropylidene moieties into the polycarbomide component. Furthermore, variations and modifications of the teachings herein are possible, as will be apparent to those skilled in the polymer arts.

It will be understood, however, that the scope of the invention, as illustrated by the non-limiting examples set forth in the specification, is defined by the appended claims.

Table 1 Hon0 Li (Imide) / San〇su1 Li-L- at 23℃
) Mechanical properties of the compound 11 secant line Tensile Yield modulus Strength Elongation'M ML
fi LLI! JI C1 Sochi〕 CIU■
(JIA Imide I 100
299 14.5
+0.51 Imide I 36
209 10.5 8.571
1-L-) 1 64 0? Cool rate 1100 227
9.5 8. OB imide-n
100 30+ 14
．． 4 11.02 Imide [50--
-7 Lee rate I 50 C imide m 100 289
14.3 10.43 Imide m
50 251 12.0
9.87 Lee 1-11 50 break to 0nd, Flora offshore in 70° example! IJ Ill (,n
(IJA Imide I 100
11.0 66 cum
Imide I 36 8.8
82 -717-Rate I 6
4 07 Lee 1-t 1 100 17.0
140 290B Imide
n 100 20. Ogo
= Shi2 Imide-1150--330 1 Li-L-)1 50 C imide-m 100 13.0
97 None 3 Imido-m
50 15.0 68
3707 Relay annotation 0 to, inf 0. = ft-1b/i in destruction
See example Control A in the main text for the n3 unit concretion type impact strength test method.

Table ■Glass transition temperature A of Imide 0 Riimito 7 bottles @ 1J7 Ritoto blend 1100265263,4
1 imide)-limer 1 36 21
0 One 0s7 Q-L・To I
640 pieces 0s 7 relays 11100
190 192B Imide Hon0 Rimmer II 100 225
225.52 Imide n
50 205 -
7 leetoto l 50 C imide m too 2
70 2723 Imido-m
50 220
2237 Leet I
50 Table ■ 1% Secant Line Tensile Yield Modulus Lath Strength Elongation 1% 01 [l Jusha D ■And D ■E Imide I 100 272 1
4.4 None F 7 Lee &-) 1 1
00 227 9.5
8.0G? +1-L・)II 100
219 9.1 8
．． OH71J-L-)m 100 1
98 9.2 9.34
Imide I 50 253
+1.8 10.37 Lee rate I
50 5 Imide 1 50 254
Chapter 12.2 Shi? Lee rate II
50 6 Imide I 50 250
12.4 9.8717-Rate m 50 Break to 0nd.

Elongation In 70゜ Wide uL Wataru L1L1〕 (1〕 E Imide 1100 10
13F 7 Lee L-) 1 too
17 140G
7 Lee [・) IIloo 11
+45H7 Lee L-tm 100
32 1454
Imide I 50 II
687 ri b-t s
.

5 Imide I 50 10
25? Leased n
50 6 Imi)'' I 50 10
40 - 9"2" - Notes: See notes to Table 1.

Table ■Diacid -1L℃ 80U/Down 11UX 011"D Up--Shijiyu limb Mengho"g West E Imide I 100
240 240
F? Two 1-t 1 100 50150
190 194G 1 ritoto ■ 100 0/100
180 180H Ari-&-)m
100 25/75 185
+784 imido-150501
502152057+7-L-to 1 50 5 Imide-1500/100 2+
0 2001 Lee-L-) 11 50 6 Imide-15025/75 21
0 10? Ali-b-1m s
.

Men 2 1 JL standing ε imido I 100
None F 7S・Rate I 100 C7 Relay) n 100 ■ ? Lee rate m 100 4 Imide-15019,81,4? REET 1-LET
1 50 5 Imide I 50 26
．． 6 0.777ri-toto ■ 5
0 6 Imide I 50 7.
1 0.21-1ヱuni'' = 2 Comments: 442.5psi after preheating at 375℃ for 10 minutes
, dg/min. Table 7 11 secant line Tensile yield modulus] Las strength Elongation f2!
Book 0su (7 riere) too 213
B, 5 8.7h book))
! ni book 0su (7Q-L-to 100 197
8.7 10. Ohs book゛todo)■ L book0thul book”ne・)I 100 24
2 9.5 6.27 Imide I
50 273 1
1.7 8.8 Control + 50 8 Imide I 50 253
12.0 No control K
50 11 imide-m 50 25
4 +0.0 7.3 Control L
50 rupture to 0nd.

Elongation Inf 1゜ff! l lIi! UUil (z)
1 0su (1 Lee-L-) +00
12 262 cal references) ■ 6 books (7 bows) 100 2
4 282 liter book nate)■ L 0 liter book nate 1100 136
2237 Imide-1501262 Control + 50 8 Imide I 50 8
．． 3 38 control 50 +1 imide III 50 8
．． 2 35th Annotation: See the annotation in Table 1.

Table 4 7 reels, l - Nishipi Ω defeat! flJ LLjLX1! JJ View ■11
”Anus 1 0su (71J-rate 100B
7ha 3 180 180 force book nate) ■ J book 0su (71) - rate 100 40/6
0 - 180 power book-nate) ■ ni book' Q (7-year tote book rate) m 100 34/6B
+80 179L 0th full book I 100 0/+00 145
+457 Imide I
5087/13 215
198 Control 150 8 Imido-San〇Limer-15034/66 17
5 One control K 50
2059 Imido m 50B?
/+3 − 188 control 1
50 10 imide-m 50 40/6
0 175 control J 50 2+
511 imide book 0 rimmer 1 50 0/10
0 150 -1 aNote: 717-11. #1 Rulph, = Molar ratio of 7-lead tote bonded to Cal book-net;

Table 1? Compatible (50150) blends of leerate I and various negative Jh0-nomites in !flχ
3f! If 辷L knee (-LL 2 and base including 2 companies m1 2) phase "blind" student! Imide-113,315 present 2 Imide II 6.0
1 5 Yes Li3 Imido-m
16.8 0.5 6.5
Yes12 Imide mV 5.1
0.5 6.5 None13 Imide V 3.6 0.5 6
．． 5 None14 Imide-Vl
14.0 1 5
Yes Li15 Imido ■ 15.2 0.
75 5.75 Yes me 1゜

Claims (1)

[Claims] 1. (a) polyarylate, and (b) the following formulas ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ mathematical formulas, chemical formulas,
There are tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [Ar and Ar^1 in the formula are ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, and ▲ Mathematical formulas , chemical formulas, tables, etc. ▼ {X in the formula is a chemical bond, O, S, SO, SO_2, CO
and C_1-C_3 alkylidene}. 2. The blend according to claim 1, wherein the polycarbonomide contains more than 5% by weight of isopropylidene moieties. 3. The polycarbonomide contains an isopropylidene moiety, and the weight percent of the isopropylidene moiety is (8-3(
Claim 1 in which the amount of imide)) is greater than or equal to {(imide) is a portion of the imide group of the polycarbonomide}
Blends as described in Section. 4. The blend according to claim 1, wherein the polyarylate is a polyarylate/carbonate copolymer. 5. The blend according to claim 1, wherein the polycarbonomide contains a repeating unit of the following formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ 6. The blend according to claim 1, wherein the polycarbonomide contains a repeating unit of the following formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ 7. Units derived from polyarylates, polycarboxylic acids selected from trimellitic acid and Ar(CO_2H)_4, and diamines with the formula H_2NAr^1NH_2 {Ar and Ar^ 1 has ▲mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼A fragrance selected from the group consisting of a polycarbonamide containing a group group}, and a compatible blend comprising: 8. The polycarbonomide contains an isopropylidene moiety,
The weight percent of the isopropylidene moiety is greater than or equal to the amount of (8-3(imide)), and (imide)
8. A blend according to claim 7, wherein is part of the imide group of said polycarponomide. 9. Diamine H_2NAr^1NH is selected from the group consisting of ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Claim 7 Blends as described in Section. 10. The blend according to claim 7, wherein the polyarylate is an arylate-carbonate copolymer.