GB2230270A - Thermoplastic aromatic polymers - Google Patents
Thermoplastic aromatic polymers Download PDFInfo
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- GB2230270A GB2230270A GB8908395A GB8908395A GB2230270A GB 2230270 A GB2230270 A GB 2230270A GB 8908395 A GB8908395 A GB 8908395A GB 8908395 A GB8908395 A GB 8908395A GB 2230270 A GB2230270 A GB 2230270A
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- formula
- phenylene
- dianhydride
- aromatic
- diamine
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
- C07C225/22—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/16—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C317/22—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/26—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C317/32—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C317/34—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring
- C07C317/36—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring with the nitrogen atoms of the amino groups bound to hydrogen atoms or to carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/70—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form
- C07C45/71—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form being hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Thermoplastic aromatic polymers comprising a repeat unit of formula -D-Z- wherein D is a divalent aromatic radical derived from diamines of formula I H2N Ph' X Ph Y Ar Y Ph X Ph' NH2 I in which Ar is a phenylene unit or a polyaromatic group containing at least two aromatic units which are either linked directly together or are linked by -CO-, -S-, -SO2-, -O-, -S-, -C(CH3)2 or other aliphatic groups; Ph is 1,4-phenylene; Ph' is 1,3 or 1,4-phenylene; X is -CO-, -SO- or -SO2-; and Y is -O- or -S- and Z is <IMAGE> in which Ar' is a tetravalent aromatic radical derived from a dianhydride or corresponding derivative thereof. Up to 50 mole % of the radicals D can be replaced by divalent organic radicals derived from other diamines. The polymers can be prepared by reacting a diamine of formula I with a dianhydride of formula <IMAGE> or a corresponding derivative thereof.
Description
Aromatic Polymers
This invention relates to aromatic polymers.
According to the present invention, a thermoplastic aromatic polymer comprises a repeat unit of formula wherein D is a divalent aromatic radical derived from amines of formula
I
H2N Ph' X Ph Y Ar Y Ph X Ph' NH2 wherein
Ar is a phenylene unit or a polyaromatic group containing at least two aromatic units which are either linked directly together or are linked by -CO-, -SO-, -S02-, -O-, -S-, -C(CH3)2 or other aliphatic group;
Ph is 1,4-phenylene;
Ph' is 1,3- or 1,4-phenylene;
X is -CO-, -SO- or SOZ-;; and
Y is -O- or -S
and Z is C l - N - C H 0 O H I II r I -N-C C-N o C \ / or N Ar' N HO. - or HO-C o-oa II II II o o O O wherein Ar' is a tetravalent aromatic radical derived from a dianhydride or corresponding derivative thereof; and wherein up to 50 mole X of the radicals D are optionally replaced by divalent organic radicals derived from other diamines.
Also according to the present invention, a process of forming a thermoplastic aromatic polymer as defined in the preceding paragraph comprises reacting a dianhydride of formula
or a corresponding derivative thereof, wherein Ar' is as hereinbefore defined, with at least one amine of formula I and, optionally, with up to 50 mole Z of at least one other amine.
Preferably, Ph' is 1,3 - phenylene.
By "directly linked together" we mean that the aromatic units are linked by a direct link between the rings as in biphenylene or terphenylene or are linked in a polynuclear aromatic system as in naphthalene. Examples of Ar groups include:
The Ar groups may be substituted, for example by C1 to C4 alkyl or perfluoroalkyl groups, aryl groups eg phenyl, halogen and nitro groups.
Examples of preferred diamines of formula I for such applications are: -
By "derivative" we mean a derivative of a tetracarboxylic acid which will condense with a diamine to form a polymer and, as is well understood in the art, such derivatives include the acid itself, diesters and acid chlorides.
Examples of preferred dianhydrides usable to form polymers of the invention are:pyromellitic dianhydride, benzophenone dianhydride, biphenyl dianhydride, diphenyl ether dianhydride, diphenyl sulphone dianhydride, bis (dicarboxyphenyl) hexafluoropropane dianhydride and 1,4,5,8naphthalene dianhydride.
The other diamines which can be used to the extent of replacing up to 50 mol Z of the diamines of formula I may be selected from any diamine, preferably an aromatic diamine, such as 4,4'diaminodiphenyl sulphone, 3,3 'diaminodiphenyl sulphone, 3,4'diaminodiphenyl sulphone, 4,4'diamino benzophenone, 3,3'diamino benzophenone, 3,4' diaminobenzophenone, 4,4 'diaminodiphenyl ether, 3,3 'diaminodiphenyl ether, 3,4'diaminodiphenyl ether, 3,3'diaminodiphenyl ether, 3,4' diaminodiphenyl ether, 3,3' diaminodiphenyl ether, 3,4 diaminodiphenyl ether, 4,4'diaminodiphenyl methane, m-phenylene diamine, p-phenylene diamine, o-phenylene diamine, 4,4'bis(4 amino phenoxy) diphenyl sulphone and 1,3 bis (3 amino phenoxy) benzene.
At least 50 mol Z, and preferably at least 60 mole Z, of the total diamine content used to form the polyimide should be a diamine of formula I. Other diamines may be present, and may be usefully employed when it is required to increase the glass transition temperature (Tg) of the polyimide produced. Increases in Tg may have adverse effects on processability. On the other hand chemical and environmental resistance may be improved and the ultimate choice of co-reactant amine, if any, will depend on the intended application.
Preferably, polymers of the invention are polyimides. However, the invention includes polymers which are polyamic acids, ie polyimide precursors, which, for example, find use as adhesives, varnishes, impregnation materials and the like. In such applications, the polyamic acid is applied to a component as a solution, the acid then being dehydrated to convert it into the corresponding polyimide.
Thus, according to another aspect of the present invention, an article comprises a polyimide formed by the in situ dehydration of a polyamic acid according to the first aspect of the invention.
The preferred polymers of the invention are essentially linear even when fully ring closed and the preferred polyimides are substantially free from residual reactive groups such as anhydride, acid, amide or amine end groups. By "essentially linear" is meant that although the polymer may be branched to a limited extent it must be essentially free from cross-links which would render it no longer melt processible at temperatures below the decomposition temperature of the polyimide.
By being "substantially free from residual reactive groups such as anhydride, acid, amide or amine end groups", a melt stable polymer will be obtained. Preferably, the number of functional end groups in the polyimide is less than 1.5 per 100 repeat units in the polyimide. The preferred process for making a polyimide according to the invention which is melt processible comprises reacting a slight excess of either the dianhydride or the diamine components and end-capping with a suitable monofunctional reagent. It is preferred than an excess of terminal amine groups are present in the initial reactants and that the terminal amine groups are end-capped, using, for example, phthalic anhydride or a phthalic acid ester so that the polyimide end groups are essentially all unsubstituted aromatic groups.
The condensation reaction between the dianhydride and the diamine is preferably carried out in a dipolar, aprotic solvent such as dimethylacetamide, N-methylpyrollidone, dimethylsulphoxide and dimethyl formamide. Mixtures of dipolar aprotic solvents may be used. Mixtures of solvents one of which is not a dipolar aprotic solvent may be used.
It is advantageous to complete the cyclisation reaction and to end cap the polymer whilst the polymer is in solution. Preferably a high boiling solvent is used to keep the polyimide in solution until the cyclisation reactions are completed at elevated temperature, in excess
o of 100 C.
In order to obtain products of the required melt stability it is generally necessary to use an excess of end-capping agent over that required for theoretical conversion of the calculated molar excess of functional end groups. When the reactants contain an excess of amine reactant the concentration of monofunctional end capping agent such as phthalic anhydride must be in excess of the calculated amine functionalities. It may be necessary to use as much as a 200Z molar excess of end-capping agent to obtain the required melt stability when the end-capping reaction is done under conditions where the cyclised polymer comes out of solution as it is formed or when cyclisation is performed in solution but at low temperature. When the polymer is kept in solution at elevated temperature during cyclisation much less end-capping agent can be used to obtain satisfactory melt stability.
Under these conditions a 50X molar excess gives excellent stability and as little as a 25Z molar excess can be used.
An advantage of the products of the present invention is that because the chemical reactions are virtually complete little or no provision needs to be made for removing evolved condensation by-products.
The reaction conditions can be controlled to produce polyimides over a wide range of molecular weight.
Preferred polyimides according to the invention exhibit advantageously low Tg and melt viscosity. Consequently, such preferred polyimides are thermoformable in the sense of being repeatedly formable when held at elevated temperature. Thus not only can shaped articles be 0 formed at processing temperatures of the order of 400 or less, but the material remains sufficiently thermoformable, that is the polymer remain sufficiently linear to be thermoformed in further high temperature thermoforming operations. This property is advantageous because it is possible to supply a fabricator with a composite in which the chemistry (evolution of volatiles) has been completed, rather than requiring the fabricator to deal with the problem of performing the chemistry and removing the volatiles and voids during fabrication of shaped parts.
The polyimides of the invention can be used to form films or fibres, particularly by melt extrusion of the polymer.
The polyimides of the invention may be reinforced with 2 to 70Z by weight fibrous materials, for example short or continuous fibres such as carbon, glass and organic or inorganic filaments such as a alumina fibres. Continuous fibres may be provided as unidirectional filaments or in woven form.
Stabilisers, fillers, pigments and other additivies including short fibre reinforcing materials (ie fibres of length less than 3 mm) may also be employed.
Thus, also according to the present invention, an article comprises a polyimide according to the first aspect of the invention.
The invention is illustrated by reference to the following
Examples.
ExamPle 1
The diamine of formula II was prepared as follows: 4-fluoro-3'-aminodiphenylsulphone (0.1 mol, 25.1 g) was charged into a 250 ml conical flask fitted with an N2 inlet, a PTFE coated magnetic stirrer, a thermometer and a condenser. Hydroquinone (0.05 mol, 5.5 g) and N-methylpyrrolidone (50 ml) were added to the flask. The contents of the flask were stirred whilst potassium carbonate (0.1 mol, 13.8g) was added, which caused an immediate yellow colouration. The temperature of the contents was raised to and held at 1000C for one hour and then raised to and held at 17O0C for three hours. The contents of the flask were allowed to cool then precipitated into 150 ml of rapidly stirred demineralised water. The crude product was recovered by filtration, washed twice with demineralised water and then recrystallised from aqueous dimethylacetamide.
Yellow crystals were recovered in 95Z yield which had a melting point of 156-1580C.
The product was identified by nuclear magnetic resonance (nmr) spectroscopy as being the diamine of formula II.
The prepared diamine of formula II was then condensed with pyromellitic dianhydride to form a polyimide as follows:
To a 3-necked round bottom flask fitted with N2 inlet, stainless steel mechanical stirrer and a drying tube was added 0.02 mol, 11.45g of the diamine of formula II prepared as described above together with 80ml of dimethylacetamide in which it dissolved. To this stirred solution was added pyromellitic dianhydride (0.02 mol, 4.36g) in a single portion, the stirring being continued for a further three hours at room temperature. This viscous solution was precipitated into water contained in a Waring Blendor to give a suspended powder which was recovered by filtration, and washed with three portions of demineralised water.The powder was then dried in a vacuum oven at 804C overnight and then heated to 2000C for seven hours under vacuum.
A sample of the polymer was compression moulded at 350 0C to give a clear yellow moulding which had an inherent viscosity of 0.36 (0.5Z solution in concentrated H2SO4) and a glass transition temperature of 2570C (DSC onset).
Example II
The diamine of formula III was prepared as follows:
The assembly used to prepare the diamine in Example I was charged with 4-fluoro-3'-aminobenzophenone (0.08 mol, 17.22g), 4,4' biphenol (0.04 mol, 7.45g), N-methyl pyrrolidone (40 ml) and potassium carbonate (0.08 mol, 11.06g). The mixture was stirred and the temperature was
o o raised to and held at 100 C for 1 hour and then raised and held at 170 C for 5 hours. The flask contents were cooled, and precipitated into 100 mls of demineralised water to give a yellow solid which was washed with demineralised water, filtered and dried to give 22.61 grams (91.7Z 0 yield) of crude product melting at 184-186 C.
The product was identified by nmr spectroscopy as being the diamine of formula III.
The prepared diamine of formula III was then condensed with pyromellitic dianhydride to form a polyimide as follows:
The assembly described in Example 1 for preparing the polymer was charged with 0.0125 mol, 7.21g of formula III prepared as described above together with 30 mls of dimethylacetamide in which it dissolved.
With stirring pyromellitic dianhydride (0.0125 mol, 2.73g) was added in a single portion and washed through with a further 10 ml of dimethylacetamide. Stirring was continued for three hours at room temperature before the polymer was isolated and converted to polyimide in a similar fashion to that described in Example 1.
o
A compression film moulded at 350 C was creasable, ie tough, and has a glass
o transition temperature of 258 C as measured by differential scanning calorimetry (DSC).
Example 3
The assembly and reagents for making the polymer as described in
Example 2 were used except that pyromellitic dianhydride was replaced by benzophenone dianhydride (0.0125 and 4.03g). The resulting polymer was
o compression moulded at 350 C to give a tough film which had a glass 0 transition temperature of 223 C by DSC.
Claims (2)
1. A thermoplastic aromatic polymer which comprises a repeat unit of formula
- D - Z wherein D is a divalent aromatic radical derived from amines of formula I
H2N Ph' X Ph Y Ar Y Ph X Ph' NH2 I in which
Ar is a phenylene unit or a polyaromatic group containing at least two aromatic units which are either linked directly together or are linked by -CO-, -SO-, -S02-, -O-, -S-, -C(CE3)2 or other aliphatic groups;
Ph is 1,4-phenylene;
Ph' is 1,3- or 1,4-phenylene;
X is -CO-, -SO- or -S02-; and
Y is -O- or -Sand Z is
in which Ar' is a tetravalent aromatic radical derived from a dianhydride or corresponding derivative thereof; and wherein up to 50 mole X of the radicals D are optionally replaced by divalent organic radicals derived from other diamines.
2. A process of forming a thermoplastic aromatic polymer as defined in claim 1 which comprises reacting a dianhydride of formula
or a corresponding derivative thereof, with at least one amine of formula I
H2N Ph' X Ph Y Ar Y Ph X Ph' NH2 I as defined in claim 1 and, optionally, with up to 50 mole Z of at least one other amine.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8908395A GB2230270A (en) | 1989-04-13 | 1989-04-13 | Thermoplastic aromatic polymers |
| EP19900303007 EP0392680A3 (en) | 1989-04-13 | 1990-03-20 | Aromatic compounds |
| JP9329090A JPH02292243A (en) | 1989-04-13 | 1990-04-10 | Aromatic compound and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8908395A GB2230270A (en) | 1989-04-13 | 1989-04-13 | Thermoplastic aromatic polymers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB8908395D0 GB8908395D0 (en) | 1989-06-01 |
| GB2230270A true GB2230270A (en) | 1990-10-17 |
Family
ID=10654993
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8908395A Withdrawn GB2230270A (en) | 1989-04-13 | 1989-04-13 | Thermoplastic aromatic polymers |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2230270A (en) |
-
1989
- 1989-04-13 GB GB8908395A patent/GB2230270A/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| GB8908395D0 (en) | 1989-06-01 |
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