WO1994016017A1 - Polymer composition - Google Patents

Polymer composition Download PDF

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Publication number
WO1994016017A1
WO1994016017A1 PCT/NL1994/000008 NL9400008W WO9416017A1 WO 1994016017 A1 WO1994016017 A1 WO 1994016017A1 NL 9400008 W NL9400008 W NL 9400008W WO 9416017 A1 WO9416017 A1 WO 9416017A1
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Prior art keywords
polymer composition
units
polyimide
composition according
mol
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Application number
PCT/NL1994/000008
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French (fr)
Inventor
Cornelis Eme Koning
Lilian Marie Jeanne Teuwen
Original Assignee
Dsm N.V.
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Publication date
Application filed by Dsm N.V. filed Critical Dsm N.V.
Priority to AU58674/94A priority Critical patent/AU5867494A/en
Publication of WO1994016017A1 publication Critical patent/WO1994016017A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the invention relates to a polymer composition containing a polyimide (A) which comprises 3,3 ',4,4'- benzophenonetetracarboxylic dianhydride units and units of an aliphatic diamine or diisocyanate.
  • A polyimide
  • the polyimides which are described therein are essentially composed of units of 3,3 ',4,4 '-benzo- phenonetetracarboxylic dianhydride and units of a primary aliphatic diamine containing 3-12 carbon atoms. The good properties of these polymers are extensively discussed in
  • a disadvantage of the known polyimides is that the glass transition temperature is relatively low. As a result, these polyimides are less suitable for use in applications at high temperatures.
  • the object of the invention is to provide a polymer composition which does not have the abovementioned disadvantages.
  • the polymer composition according to the invention has the characteristic that it contains also a polyimide (B) which comprises units of a bifunctional
  • the glass transition temperature of the polymer composition is relatively high, as a result of which it is suitable for use in applications at high temperatures.
  • Another advantage of the polymer composition according to the invention is that it has surprisingly only one glass • 35 transition temperature, which indicates a homogeneously P mixed polymer composition.
  • the polymer composition according to the invention can be thermoplastically processed very well.
  • Polyimide (A) in the polymer composition according to the invention comprises 3,3 ',4,4 '- benzophenonetetracarboxylic dianhydride units and units of an aliphatic diamine or diisocyanate.
  • a minor amount of the 3,3 ',4, '-benzophenonetetracarboxylic dianhydride units is replaced by one or more other bifunctional carboxylic anhydrides.
  • bifunctional carboxylic anhydrides suitable for this purpose are pyromellitic dianhydride, 4,4 '-oxydiphthalic anhydride, 3,3 ',4,4 '-biphenyltetracarboxylic dianhydride, 2,3,3 ' , '-biphenyltetracarboxylic dianhydride, 3 ,3 ',4,4 '-diphenylsulphonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 1,4-bis(3,4-dicarboxybenzoyl)benzene dianhydride, 1,3-bis(3,4-dicarboxybenzoyl)benzene dianhydride, bis(3,4-dicardicar
  • the bifunctional carboxylic anhydride units in polyimide (A) are composed of at least 80 mol% of 3,3 ',4, '-benzophenonetetracarboxylic dianhydride. More preferably, this percentage is at least 90 mol%. The greatest preference is for a polyimide which contains at least 95 mol% of 3,3 ',4,4 '-benzophenonetetra- carboxylic dianhydride units as bifunctional carboxylic anhydride.
  • the units of the aliphatic diamine or diiso ⁇ cyanate in polyimide (A) are, for example, chosen from the group comprising ethylenediamine, trimethylene-diamine, tetramethylenediamine, hexamethylenediamine, pentamethyl- enediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 2,11-diaminododecane, 1,2-bis(3-aminopropoxy)ethane and 4, -dimethylhepta- methylenediamine, and the corresponding diisocyanate compounds.
  • the diisocyanate compounds can, for example, be obtained by allowing the diamine to react with phosgene.
  • a mixture of various diamines and/or diisocyanate compounds is used.
  • an aliphatic diamine or an aliphatic diisocyanate is preferably used which contains 2-9 carbon atoms per molecule. More preferably, it contains 3-6 carbon atoms per molecule.
  • an aliphatic diamine or an aliphatic diisocyanate containing four carbon atoms per molecule is most preferably used.
  • At least 50 mol% of the units of the aliphatic diamine or diisocyanate in polyimide (A) contain four carbon atoms. More preferably, this percentage is at least 75 mol%. Most preferably, this percentage is at least 95 mol%.
  • Polyimide (B) in the polymer composition according to the invention comprises units of a bifunctional carboxylic anhydride according to formula (I), where R is chosen from the group comprising -C(O)-, -, -0-, -S- and -S0 2 -, and units of an aromatic diamine or diisocyanate.
  • R is chosen from the group comprising -C(O)-, -, -0-, -S- and -S0 2 -, and units of an aromatic diamine or diisocyanate.
  • bifunctional carboxylic anhydride units which are chosen from the group comprising, 3,3 ',4,4'- benzophenonetetracarboxylic dianhydride, 3,3 ',4,4'- biphenyltetracarboxylic dianhydride or 2,3,3 ',4'- biphenyltetracarboxylic dianhydride, 4,4 '-oxydiphthalic anhydride, bis(3,4-dicarboxyphenyl) thioether dianhydride and 3,3 ' ,4, '-diphenylsulphonetetracarboxylic dianhydride, a minor amount may optionally be replaced by one or more other bifunctional carboxylic anhydrides much less resembling 3,3 ',4,4 '-benzophenonetetracarboxylic dianhydride in terms of dimensions.
  • bifunctional carboxylic anhydrides suitable for this purpose are pyromellitic dianhydride, 3,3 ',4,4'- diphenylpropane-2,2-tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 1,4-bis(3,4-dicarboxybenzoyl)benzene dianhydride, 1,3-bis(3,4-dicarboxybenzoyl)benzene dianhydride,
  • At least 80 mol% of the bifunctional carboxylic anhydride units in polyimide (B) are composed of units of a bifunctional carboxylic anhydride in accordance with formula (1). More preferably, this percentage is at least 90 mol%. Still more preferably, this percentage is at least 95 mol%.
  • the greatest preference is for a polyimide (B) which contains at least 80 mol of 3,3 ',4,4 '-benzophenonetetracarboxylic dianhydride units as bifunctional carboxylic anhydride units.
  • the units of the aromatic diamine or diisocyanate in polyimide (B) are, for example, chosen from the group comprising benzidine, m-phenylenediamine, p-phenylenediamine, 4,4 '-diaminodiphenylmethane, 2,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenyl ether, 2,4 '-diaminodiphenyl ether, 4,4 '-diaminobenzophenone, 4,4 '-diaminodiphenylsulphone, 3,3 '-diamino- diphenylsulphone, 4,4 '-oxydianiline, 1,l-(4,4 '-diamino ⁇ diphenyl)ethane, 2,2-(4,4 '-diaminodiphenyl)propane, 4-methyl-l,3-phenylenediamine and 4,4 '-bis(
  • a mixture of various diamines and/or diisocyanate compounds is used.
  • a mixture of 4,4 '-diaminodiphenylmethane and 4-methyl-l,3-phenylenediamine, or the corresponding diisocyanates is used.
  • the desired weight ratio between polyimide (A) and polyimide (B) is dependent on the desired mechanical and thermal properties of the polymer composition according to the invention and can be chosen within wide limits. This weight ratio is generally between 1:99 and 99:1, preferably between 25:75 and 75:25.
  • the synthesis of polyimides is generally known and is, for example, described in Mat.Res.Soc.Symp.Proc. , 154, (1989), pages 149-160, or in US-A-3,759,913.
  • the polymer composition according to the invention is produced in the standard way.
  • both polyimides are mixed with one another either in solution or in the melt in a standard, generally known mixing device.
  • the polymer composition according to the inven ⁇ tion can be processed thermoplastically in any known way. Apparatus suitable for this purpose is, for example, a single- or twin-screw extruder, a static mixer, an injection moulding machine, a press or a mixing roller.
  • the polymer composition according to the invention can be processed thermoplastically very well. As a result, this polymer is extremely suitable for producing all kinds of objects. In this connection, fibres, films, matrix material for composites and the most diverse moulding compounds, which are injection-moulded, come to mind.
  • thermoplastic polymers it is well possible to add other thermoplastic polymers to the polymer composition according to the invention.
  • miscibility promotors can also be added.
  • the polymer composition according to the invention is extremely suitable for blending with other thermoplastic polymers which have a processing temperature comparable to the processing temperature of this polymer composition.
  • examples of such polymers are polycarbonates, nylon 6, nylon 6.6, nylon 4.6, nylon 6.9, nylon 11, nylon 12, nylon 6.T, polyarylates, polyethersulphones, polyphenylene oxide, polyethylene terephthalate, styrene/maleimide copolymers, and polybutylene terephthalate.
  • Other suitable polymers are, for example, ethylene/propylene rubbers (EP rubbers) and ethylene/propylene/diene rubbers (EPDM).
  • additives can be added to the polymer composition according to the invention.
  • standard additives are carbon, stabilizers, antioxidants, lubricants, fillers, colorants, pigments, flame retarders, impact-strength promoters, reinforcing fibres and conductive fibres.
  • the additives may, optionally, be added before or during the processing step. The invention is explained further by reference to the examples below, without being restricted thereto.
  • a solution was also prepared of 15.5 grams of polyimide P84 (supplied by Lenzing AG) in 150 ml of NMP at a temperature of 160°C.
  • a platelet was pressed from the powder obtained in this way at a temperature of 320°C (1 min, 0 tonne; 5 min, 1 tonne; 2 min, 5 tonnes; 5 min, 5 tonnes; and cooling to 240°C at 50 tonnes).
  • the glass transition temperature of the pressed platelet was then determined with the aid of dynamic mechanical investigation as 230°C.
  • DAB/P84 blend was 20 °C (DSC measurement, 2nd heating curve, 20°C/min). From this blend test plates were injection moulded.
  • the Vicat softening point was determined according to ASTM D1525.
  • the modulus of elasticity, the elongation at break and the tensile strength at break were determined according to ASTM D638.
  • Vicat softening point 182°C.
  • Modulus of elasticity 3867 MPa.
  • DAB tetramethylenediamine
  • NMP N-methylpyrrolidine
  • 0.0323 mol (10.42 grams) of 3,3 ',4,4 '-benzophenonetetra ⁇ carboxylic dianhydride (BDTA) and 1.32 mmol (195.6 mgrams) of phthalic anhydride (as chain stopper) were then added at room temperature by means of a solids funnel.
  • the funnel was rinsed out with 50 ml of NMP.
  • the solution finally obtained was stirred overnight at a temperature of 40°C. Reaction water was removed by means of a Dean Stark unit.
  • a solution was also prepared of a polyimide on the basis of 0.033 mol (6.61 grams) of 4,4 '-oxydianiline (ODA), 0.0323 mol (10.42 grams) of
  • Both polymers were mixed with one another in solution in a 44:56 (BTDA-DAB : BTDA-ODA) weight ratio at a temperature of 160°C and then directly precipitated in methanol.
  • the reaction product was filtered and dried at a temperature of 60°C under reduced pressure.
  • a platelet was pressed from the powder obtained in this way at a temperature of 320°C (1 min, 0 tonne; 5 min, 1 tonne; 2 min, 5 tonnes; 5 min, 5 tonnes; and cooling to 240°C at 50 tonnes).
  • the glass transition temperature of the pressed platelet was then determined with the aid of a DSC measurement (2nd heating curve, 20°C/min) as 220°C.
  • a mixture was prepared (46 parts by weight BTDA-ODA and 54 parts by weight BTDA-DAB) of the two solutions obtained according to Example III.
  • the glass transition temperature was determined analogously to Example II: 207°C.
  • DAB 1,4-diaminobutane
  • NMP N-methylpyrrolidone
  • a platelet was pressed from the powder obtained in this way at a temperature of 320°C (1 min, 0 tonne; 5 min, 1 tonne; 2 min, 5 tonnes; 5 min, 5 tonnes; and cooling to 240°C at 50 tonnes).
  • the glass transition temperature was determined with the aid of a DSC measurement (2nd heating curve, 20°C/min) as 175°C.
  • P 84 polyimide composed of BTDA units and an
  • DAP trimethylenediamine
  • DAH hexamethylenediamine
  • DAN nonamethylenediamine
  • polyimide BTDA-DAB 1.5 grams of polyimide BTDA-DAB and 1.5 grams of polyimide composed of bisphenol-A-bisether-4-phthalic dianhydride and 1,3-phenylenediamine (Ultem 1000, supplied by General Electric) were dissolved in 50 ml of m-cresol at a temperature of 80°C. The clear solution was then directly precipitated in methanol. The glass transition temperature of the polymer composition obtained was then determined with the aid of a DSC measurement (2nd heating curve, 20°C/min). The polymer composition was found to have two glass transition temperatures, viz. 171°C and 209°C.
  • the polymer composition according to the invention has only one glass transition temperature, which indicates a homogeneously mixed polymer composition.
  • the glass transition temperature of the polymer composition is also relatively high, as a result of which it is suitable for use in applications at high temperatures.
  • the polymer composition can be processed thermoplastically very well and a high modulus of shear G' is obtained.

Abstract

The invention relates to a polymer composition containing a polyimide (A) which comprises 3,3',4,4'-benzophenonetetracarboxylic dianhydride units and units of an aliphatic diamine or diisocyanate. The polymer composition according to the invention has the characteristic that it contains also a polyimide (B) which is essentially composed of units of a bifunctional carboxylic anhydride in accordance with formula (I), where R is chosen from the group comprising -C(O)-, -, -O-, -S- and -SO2-, and units of an aromatic diamine or diisocyanate. The glass transition temperature of the polymer composition is relatively high, as a result of which it is suitable for use in applications at high temperatures. It has been found that the polymer composition according to the invention has only one glass transition temperature, which indicates a homogeneously mixed polymer composition. In addition, the polymer composition can be processed thermoplastically very well.

Description

POLYMER COMPOSITION
5 The invention relates to a polymer composition containing a polyimide (A) which comprises 3,3 ',4,4'- benzophenonetetracarboxylic dianhydride units and units of an aliphatic diamine or diisocyanate.
Such a polymer composition is described in
10 US-3,759,913. The polyimides which are described therein are essentially composed of units of 3,3 ',4,4 '-benzo- phenonetetracarboxylic dianhydride and units of a primary aliphatic diamine containing 3-12 carbon atoms. The good properties of these polymers are extensively discussed in
15 the abovementioned patent publication.
A disadvantage of the known polyimides is that the glass transition temperature is relatively low. As a result, these polyimides are less suitable for use in applications at high temperatures.
20 The object of the invention is to provide a polymer composition which does not have the abovementioned disadvantages. The polymer composition according to the invention has the characteristic that it contains also a polyimide (B) which comprises units of a bifunctional
25 carboxylic anhydride in accordance with the formula (I), where R is chosen from the group comprising -C(O)-, -, -0-, -S- and -S02-, and units of an aromatic diamine or diisocyanate. Reference is made to the formula sheet for formula (1) .
30 The glass transition temperature of the polymer composition is relatively high, as a result of which it is suitable for use in applications at high temperatures. Another advantage of the polymer composition according to the invention is that it has surprisingly only one glass • 35 transition temperature, which indicates a homogeneously P mixed polymer composition. As a further advantage the polymer composition according to the invention can be thermoplastically processed very well. Polyimide (A) in the polymer composition according to the invention comprises 3,3 ',4,4 '- benzophenonetetracarboxylic dianhydride units and units of an aliphatic diamine or diisocyanate. Optionally, a minor amount of the 3,3 ',4, '-benzophenonetetracarboxylic dianhydride units is replaced by one or more other bifunctional carboxylic anhydrides. Examples of bifunctional carboxylic anhydrides suitable for this purpose are pyromellitic dianhydride, 4,4 '-oxydiphthalic anhydride, 3,3 ',4,4 '-biphenyltetracarboxylic dianhydride, 2,3,3 ' , '-biphenyltetracarboxylic dianhydride, 3 ,3 ',4,4 '-diphenylsulphonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 1,4-bis(3,4-dicarboxybenzoyl)benzene dianhydride, 1,3-bis(3,4-dicarboxybenzoyl)benzene dianhydride, bis(3,4-dicarboxyphenyl)thioether dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, and bisphenol-A-bisether-4-phthalic dianhydride. Preferably, the bifunctional carboxylic anhydride units in polyimide (A) are composed of at least 80 mol% of 3,3 ',4, '-benzophenonetetracarboxylic dianhydride. More preferably, this percentage is at least 90 mol%. The greatest preference is for a polyimide which contains at least 95 mol% of 3,3 ',4,4 '-benzophenonetetra- carboxylic dianhydride units as bifunctional carboxylic anhydride.
The units of the aliphatic diamine or diiso¬ cyanate in polyimide (A) are, for example, chosen from the group comprising ethylenediamine, trimethylene-diamine, tetramethylenediamine, hexamethylenediamine, pentamethyl- enediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 2,11-diaminododecane, 1,2-bis(3-aminopropoxy)ethane and 4, -dimethylhepta- methylenediamine, and the corresponding diisocyanate compounds. The diisocyanate compounds can, for example, be obtained by allowing the diamine to react with phosgene. Optionally, a mixture of various diamines and/or diisocyanate compounds is used. In view of the optimum thermoplastic processibility, an aliphatic diamine or an aliphatic diisocyanate is preferably used which contains 2-9 carbon atoms per molecule. More preferably, it contains 3-6 carbon atoms per molecule. In view of the favourable combination of thermoplastic processibility and high melting point, an aliphatic diamine or an aliphatic diisocyanate containing four carbon atoms per molecule is most preferably used.
Preferably, at least 50 mol% of the units of the aliphatic diamine or diisocyanate in polyimide (A) contain four carbon atoms. More preferably, this percentage is at least 75 mol%. Most preferably, this percentage is at least 95 mol%.
Polyimide (B) in the polymer composition according to the invention comprises units of a bifunctional carboxylic anhydride according to formula (I), where R is chosen from the group comprising -C(O)-, -, -0-, -S- and -S02-, and units of an aromatic diamine or diisocyanate. Reference is made to the formula sheet for formula (1).
Optionally, a mixture of various bifunctional carboxylic acids is used.
Of the bifunctional carboxylic anhydride units which are chosen from the group comprising, 3,3 ',4,4'- benzophenonetetracarboxylic dianhydride, 3,3 ',4,4'- biphenyltetracarboxylic dianhydride or 2,3,3 ',4'- biphenyltetracarboxylic dianhydride, 4,4 '-oxydiphthalic anhydride, bis(3,4-dicarboxyphenyl) thioether dianhydride and 3,3 ' ,4, '-diphenylsulphonetetracarboxylic dianhydride, a minor amount may optionally be replaced by one or more other bifunctional carboxylic anhydrides much less resembling 3,3 ',4,4 '-benzophenonetetracarboxylic dianhydride in terms of dimensions. Examples of bifunctional carboxylic anhydrides suitable for this purpose are pyromellitic dianhydride, 3,3 ',4,4'- diphenylpropane-2,2-tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 1,4-bis(3,4-dicarboxybenzoyl)benzene dianhydride, 1,3-bis(3,4-dicarboxybenzoyl)benzene dianhydride,
2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, and bisphenol-A-bisether-4-phthalic dianhydride.
Preferably, at least 80 mol% of the bifunctional carboxylic anhydride units in polyimide (B) are composed of units of a bifunctional carboxylic anhydride in accordance with formula (1). More preferably, this percentage is at least 90 mol%. Still more preferably, this percentage is at least 95 mol%. The greatest preference is for a polyimide (B) which contains at least 80 mol of 3,3 ',4,4 '-benzophenonetetracarboxylic dianhydride units as bifunctional carboxylic anhydride units.
The units of the aromatic diamine or diisocyanate in polyimide (B) are, for example, chosen from the group comprising benzidine, m-phenylenediamine, p-phenylenediamine, 4,4 '-diaminodiphenylmethane, 2,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenyl ether, 2,4 '-diaminodiphenyl ether, 4,4 '-diaminobenzophenone, 4,4 '-diaminodiphenylsulphone, 3,3 '-diamino- diphenylsulphone, 4,4 '-oxydianiline, 1,l-(4,4 '-diamino¬ diphenyl)ethane, 2,2-(4,4 '-diaminodiphenyl)propane, 4-methyl-l,3-phenylenediamine and 4,4 '-bis(4-amino- phenoxy)diphenylsulphone, and the diisocyanate compounds corresponding thereto. Optionally, a mixture of various diamines and/or diisocyanate compounds is used. Preferably, a mixture of 4,4 '-diaminodiphenylmethane and 4-methyl-l,3-phenylenediamine, or the corresponding diisocyanates is used. The desired weight ratio between polyimide (A) and polyimide (B) is dependent on the desired mechanical and thermal properties of the polymer composition according to the invention and can be chosen within wide limits. This weight ratio is generally between 1:99 and 99:1, preferably between 25:75 and 75:25.
The synthesis of polyimides is generally known and is, for example, described in Mat.Res.Soc.Symp.Proc. , 154, (1989), pages 149-160, or in US-A-3,759,913. The polymer composition according to the invention is produced in the standard way. For this purpose, both polyimides are mixed with one another either in solution or in the melt in a standard, generally known mixing device. The polymer composition according to the inven¬ tion can be processed thermoplastically in any known way. Apparatus suitable for this purpose is, for example, a single- or twin-screw extruder, a static mixer, an injection moulding machine, a press or a mixing roller. The polymer composition according to the invention can be processed thermoplastically very well. As a result, this polymer is extremely suitable for producing all kinds of objects. In this connection, fibres, films, matrix material for composites and the most diverse moulding compounds, which are injection-moulded, come to mind.
It is well possible to add other thermoplastic polymers to the polymer composition according to the invention. Optionally, miscibility promotors can also be added. The polymer composition according to the invention is extremely suitable for blending with other thermoplastic polymers which have a processing temperature comparable to the processing temperature of this polymer composition. Examples of such polymers are polycarbonates, nylon 6, nylon 6.6, nylon 4.6, nylon 6.9, nylon 11, nylon 12, nylon 6.T, polyarylates, polyethersulphones, polyphenylene oxide, polyethylene terephthalate, styrene/maleimide copolymers, and polybutylene terephthalate. Other suitable polymers are, for example, ethylene/propylene rubbers (EP rubbers) and ethylene/propylene/diene rubbers (EPDM).
Optionally, additives can be added to the polymer composition according to the invention. Examples of standard additives are carbon, stabilizers, antioxidants, lubricants, fillers, colorants, pigments, flame retarders, impact-strength promoters, reinforcing fibres and conductive fibres. The additives may, optionally, be added before or during the processing step. The invention is explained further by reference to the examples below, without being restricted thereto.
Examples and comparative experiments
Example I
0.033 mol (2.91 gram) of 1,4-diaminobutane (DAB, tetramethylenediamine) was dissolved in 100 ml of N-methylpyrrolidone (NMP) under an N2 atmosphere. 0.0323 mol (10.42 gram) of 3,3 ' ,4,4 '-benzophenonetetra- carboxylic dianhydride (BDTA) and 1.32 mmol (195.6 mgram) of phthalic anhydride (as chain stopper) was then added at room temperature by means of a solids funnel. The funnel was rinsed out with 50 ml of NMP. The solution finally obtained was stirred overnight at a temperature of 40°C. 20 ml of m/p-xylene were then added, after which the solution was heated to reflux temperature (T=160°C) for 4 hours. The reaction water was removed from the solution by means of a Dean Stark unit.
A solution was also prepared of 15.5 grams of polyimide P84 (supplied by Lenzing AG) in 150 ml of NMP at a temperature of 160°C.
Both solutions were mixed at a temperature of 160°C and then directly precipitated in methanol. The reaction product was filtered and dried at a temperature of 60°C under reduced pressure.
A platelet was pressed from the powder obtained in this way at a temperature of 320°C (1 min, 0 tonne; 5 min, 1 tonne; 2 min, 5 tonnes; 5 min, 5 tonnes; and cooling to 240°C at 50 tonnes). The glass transition temperature of the pressed platelet was then determined with the aid of dynamic mechanical investigation as 230°C.
Also, the modulus of shear G' of the pressed platelet was determined at 23°C with the aid of a torsion damping experiment: G'=1450 N/mm2.
Example II
3 . 5 mol ( 308 g ) diaminobutane ( DAB ) was dissolved in 15 . 7 1 NMP under an N2-atmosphere . 3 . 6 mol (1150 g) 3,3 ',4, '-benzophenonetetracarboxylic dianhydride (BDTA) was then added at room temperature. The obtained solution was stirred overnight at a temperature of 40°C. The polyamid acid was formed. 572 g P84 (see under Examples V-VII) was dissolved in 4 1 NMP at 120°C. This solution of P84 in NMP was added to the polyamid acid- solution by means of a funnel. The funnel was rinsed out with 1.5 1 of NMP. 1 1 of m/p-xylene was then added, after which the solution was heated to reflux temperature (T= 160°C) for 2 hours. The reaction water was removed from the solution by means of a Dean Stark unit. The solution was then directly precipitated in methanol. The reaction- product was centrifuged, washed with methanol and dried at 100°C. The glass transition temperature of the BDTA-
DAB/P84 blend was 20 °C (DSC measurement, 2nd heating curve, 20°C/min). From this blend test plates were injection moulded.
The Vicat softening point was determined according to ASTM D1525.
The modulus of elasticity, the elongation at break and the tensile strength at break were determined according to ASTM D638.
Vicat softening point : 182°C. Modulus of elasticity : 3867 MPa.
Elongation at break : 1.6 %. Tensile strength at break: 58.6 MPa.
Example III 0.033 mol (2.91 grams) of 1,4-diaminobutane
(DAB, tetramethylenediamine) was dissolved in 100 ml of N-methylpyrrolidine (NMP) under an N2 atmosphere. 0.0323 mol (10.42 grams) of 3,3 ',4,4 '-benzophenonetetra¬ carboxylic dianhydride (BDTA) and 1.32 mmol (195.6 mgrams) of phthalic anhydride (as chain stopper) were then added at room temperature by means of a solids funnel. The funnel was rinsed out with 50 ml of NMP. The solution finally obtained was stirred overnight at a temperature of 40°C. Reaction water was removed by means of a Dean Stark unit.
20 ml of m/p-xylene was then added, after which the solution was heated to reflux temperature (T=160°C) for 4 hours.
A solution was also prepared of a polyimide on the basis of 0.033 mol (6.61 grams) of 4,4 '-oxydianiline (ODA), 0.0323 mol (10.42 grams) of
3,3 ',4,4 '-benzophenonetetracarboxylic dianhydride (BDTA) and 1.32 mmol (195.6 mgrams) of phthalic anhydride (as chain stopper) in 150 ml of NMP.
Both polymers were mixed with one another in solution in a 44:56 (BTDA-DAB : BTDA-ODA) weight ratio at a temperature of 160°C and then directly precipitated in methanol. The reaction product was filtered and dried at a temperature of 60°C under reduced pressure.
A platelet was pressed from the powder obtained in this way at a temperature of 320°C (1 min, 0 tonne; 5 min, 1 tonne; 2 min, 5 tonnes; 5 min, 5 tonnes; and cooling to 240°C at 50 tonnes). The glass transition temperature of the pressed platelet was then determined with the aid of a DSC measurement (2nd heating curve, 20°C/min) as 220°C.
Example IV
A mixture was prepared (46 parts by weight BTDA-ODA and 54 parts by weight BTDA-DAB) of the two solutions obtained according to Example III. The glass transition temperature was determined analogously to Example II: 207°C.
Comparative experiment A
0.033 mol (2.91 grams) of 1,4-diaminobutane (DAB, tetramethylenediamine) was dissolved in 100 ml of N-methylpyrrolidone (NMP) under an N2 atmosphere.
0.0323 mol (10.42 grams) of 3,3 ',4,4 '-benzophenonetetra¬ carboxylic dianhydride (BTDA) and 1.32 mmol (195.6 mgrams) of phthalic anhydride (as chain stopper) were then added at room temperature by means of a solids funnel. The funnel was rinsed out with 50 ml of NMP. The solution finally obtained was stirred overnight at a temperature of 40°C.
20 ml of m/p-xylene were then added, after which the solution was heated to reflux temperature (T=160°C) for 4 hours and then directly precipitated in methanol. The reaction product was filtered and dried at a temperature of 60°C under reduced pressure.
A platelet was pressed from the powder obtained in this way at a temperature of 320°C (1 min, 0 tonne; 5 min, 1 tonne; 2 min, 5 tonnes; 5 min, 5 tonnes; and cooling to 240°C at 50 tonnes).
Finally, the glass transition temperature was determined with the aid of a DSC measurement (2nd heating curve, 20°C/min) as 175°C.
Examples V-VII
1.5 grams of polyimide A and 1.5 grams of poly- imide B were dissolved in 50 ml of m-cresol at a tempera¬ ture of 80°C. The clear solution was then directly precipitated in methanol. The glass transition temperature of the polymer composition obtained was then determined with the aid of a DSC measurement (2nd heating curve, 20°C/min). The various polyimides A and B, and also the glass transition temperature Tg are reported in Table 1.
TABLE 1
Ex. Polyimide A polyimide B Tc
V P 84 BTDA-DAP 248°C
VI P 84 BTDA-DAH 195°C
VII P 84 BTDA-DAN 185°C where
P 84 = polyimide composed of BTDA units and an
80/20 mol/mol mixture of
4, '-diisocyanatodiphenylmethane and 4-methyl- 1,3-phenylene diisocyanate (Tg = 315°C)
DAP = trimethylenediamine DAH = hexamethylenediamine DAN = nonamethylenediamine
Comparative experiment B
1.5 grams of polyimide BTDA-DAB and 1.5 grams of polyimide composed of bisphenol-A-bisether-4-phthalic dianhydride and 1,3-phenylenediamine (Ultem 1000, supplied by General Electric) were dissolved in 50 ml of m-cresol at a temperature of 80°C. The clear solution was then directly precipitated in methanol. The glass transition temperature of the polymer composition obtained was then determined with the aid of a DSC measurement (2nd heating curve, 20°C/min). The polymer composition was found to have two glass transition temperatures, viz. 171°C and 209°C.
Comparative experiment C
1.5 grams of P 84 and 1.5 grams of polyimide composed of tetramethylenediamine and bisphenol-A- bisether-4-phthalic dianhydride were dissolved in 50 ml of m-cresol at a temperature of 80°C. The clear solution was then directly precipitated in methanol. The glass transition temperature of the polymer composition obtained was then determined with the aid of a DSC measurement (2nd heating curve, 20°C/min). The polymer composition was found to have two glass transition temperatures, viz. 150°C and 315°C.
From the examples, it is evident that the polymer composition according to the invention has only one glass transition temperature, which indicates a homogeneously mixed polymer composition. The glass transition temperature of the polymer composition is also relatively high, as a result of which it is suitable for use in applications at high temperatures. In addition, the polymer composition can be processed thermoplastically very well and a high modulus of shear G' is obtained.

Claims

C L I S
1. Polymer composition containing a polyimide (A) which comprises 3,3 ',4,4 '-benzophenonetetracarboxylic dianhydride units and units of an aliphatic diamine or diisocyanate, characterized in that the polymer composition also contains a polyimide (B) which comprises units of a bifunctional carboxylic anhydride in accordance with formula (1), where R is chosen from the group comprising -C(O)-, -, -0-, -S- and -S02-, and units of an aromatic diamine or diisocyanate.
2. Polymer composition according to Claim 1, charac- terized in that at least 80 mol% of the bifunctional carboxylic anhydride units in polyimide (B) are composed of units of a bifunctional carboxylic anhydride in accordance with formula (1).
3. Polymer composition according to one of Claims 1-2, characterized in that at least 80 mol% of the bifunctional carboxylic anhydride units in polyimide (B) are composed of 3,3 ',4,4 '-benzophenonetetra¬ carboxylic dianhydride units.
4. Polymer composition according to one of Claims 1-3, characterized in that the aromatic diamine or diiso¬ cyanate in polyimide (B) is a mixture of 4,4'- diaminodiphenylmethane and 4-methyl-l,3-phenylene- diamine or the corresponding diisocyanates.
5. Polymer composition according to one of Claims 1-4, characterized in that the
3,3 ',4,4 '-benzophenonetetracarboxylic dianhydride units in polyimide (A) form at least 80 mol% of the total amount of bifunctional carboxylic anhydride units.
6. Polymer composition according to one of Claims 1-5, characterized in that the units of the aliphatic diamine or diisocyanate in polyimide (A) contain 2-9 carbon atoms per molecule.
7. Polymer composition according to one of Claims 1-6, characterized in that at least 50 mol% of the units of the aliphatic diamine or diisocyanate in polyimide (A) contain four carbon atoms per molecule.
8. Polymer composition according to one of Claims 1-7, characterized in that the weight ratio between poly¬ imide (A) and polyimide (B) is between 1:99 and 99:1.
9. Moulding compound, film or fibre entirely or partly produced from the polymer composition according to one of Claims 1-8.
PCT/NL1994/000008 1993-01-14 1994-01-12 Polymer composition WO1994016017A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4225686A (en) * 1979-07-19 1980-09-30 The Upjohn Company Blends of copolyimides with copolyamideimides
US5110879A (en) * 1990-04-24 1992-05-05 Hoechst Celanese Corp. Miscible blends of polyimide polymers and process for forming the same
EP0522649A1 (en) * 1991-07-11 1993-01-13 Dsm N.V. Polyimide

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4225686A (en) * 1979-07-19 1980-09-30 The Upjohn Company Blends of copolyimides with copolyamideimides
US5110879A (en) * 1990-04-24 1992-05-05 Hoechst Celanese Corp. Miscible blends of polyimide polymers and process for forming the same
EP0522649A1 (en) * 1991-07-11 1993-01-13 Dsm N.V. Polyimide

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