USRE34563E - Heat-stable copolycondensate molding materials - Google Patents
Heat-stable copolycondensate molding materials Download PDFInfo
- Publication number
- USRE34563E USRE34563E US07/883,955 US88395592A USRE34563E US RE34563 E USRE34563 E US RE34563E US 88395592 A US88395592 A US 88395592A US RE34563 E USRE34563 E US RE34563E
- Authority
- US
- United States
- Prior art keywords
- mol
- sum
- copolycondensate
- heat
- stable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- 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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
- C08G75/23—Polyethersulfones
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
-
- 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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/05—Polymer mixtures characterised by other features containing polymer components which can react with one another
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0333—Organic insulating material consisting of one material containing S
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
Definitions
- the present invention relates to heat-stable copolycondensate molding materials which contain polyarylene sulfone and polyarylene ether sulfone units in random distribution and are obtainable by polycondensation of a mixture of
- R 7 , R 8 , R 9 and R 10 are each hydrogen, Cl or F or may have the same meanings as R 1 and R 2 , q and p are each 0 or 1 and r, s, t and u may each be an integer from 0 to 4, with the proviso that one or more of the components, C and E are present and the molar ratio of B to the sum of A+C is not greater than 1.
- the present invention furthermore relates to a process for the preparation of such copolycondensate molding materials and their use for the production of printed circuit boards and electrical plug connections, and to molding which are obtained from the novel copolycondensate molding materials as essential components.
- Polyethersulfones containing the general structural unit ##STR10## are characterized by very low water absorption and hence very good dimensional stability (of the moldings produced from them).
- the heat distortion resistance (which is frequently described in terms of the maximum temperature during continuous operation) is not sufficient for some applications, particularly in the case of printed circuit boards (also referred to as PCB's) produced from these materials.
- polyethersulfones containing the general structural unit ##STR11## possess better heat distortion resistance, but the water absorption is substantially higher. The consequence of this is that moldings produced from polyethersulfones tend to swell and become distorted, which is undesirable when used in the electrical industry and electronics (production of printed circuit boards).
- EP-A 113 112 also describes copolycondensates of a mixture of dihydroxy compounds, A, B and C and dihalogen compounds D.
- the molar ratio of B to A and C is always greater than 1, which has an adverse effect on the water absorption.
- copolycondensates have in general better properties than the polysulfones or polyethersulfones, the heat distortion resistance and the stress cracking resistance are still unsatisfactory. These copolycondensates can be used only to a very restricted extent for the production of printed circuit boards.
- novel heat-stable copolycondensates are obtainable by polycondensation of a mixture of aromatic dihydroxy compounds A, B and, if required, C with aromatic dihalogen compounds D and, if required, E, and it is essential for one or more of the compounds C and E to be present.
- the dihydroxy compound A is 2,2-di-(4-hydroxyphenyl) -propane, which is known as bisphenol A, and the dihydroxy compound B is 4,4'-dihydroxyphenyl sulfone, which is also referred to as bisphenol S.
- the dihydroxy compounds C are of the general formula ##STR12## (when n or p is .Iadd.not .Iaddend.0), R 1 and R 2 are each alkyl or alkoxy, each of 1 to 6 carbon atoms, R 3 and R 4 are each hydrogen, alkyl or alkoxy of 1 to 6 carbon atoms, aryl or halogen-substituted alkyl of 1 to 4 carbon atoms, m is 0 or 1, preferably 1, and n and p are each 0, 1, 2, 3, or 4.
- R 1 and R 2 are each preferably alkyl of 1 to 4 carbon atoms, eg. methyl, ethyl, isopropyl, n-propyl or n-, iso- or tert-butyl or corresponding alkoxy groups. Methyl and ethyl are particularly preferred.
- R 3 and R 4 are C 1 -C 4 -alkyl groups, as described for R 1 and R 2 , aryl or halogen-substituted alkyl, such as CF 3 and CCl 3 , to mention but two examples.
- n is 0 or 1, and is preferably 1 particularly when p is 0, ie. no substituents R 2 are present.
- n and p may each be 0, 1, 2, 3, or 4, preferably 0, 1, 2 or 3.
- the mixture of the dihydroxy compounds A, B and, where relevant, C contains from 2 to 98 mole % of A, from 2 to 98 mol % of B and from 0 to 96 mol % of C, the percentages in each case being based on the sum of A-C.
- Preferred mixtures are those which contain from 20 to 80, in particular from 25 to 70, mol % of A, from 20 to 80, in particular from 25 to 70, mol % of B and from 0 to 60, in particular from 5 to 60, mol % of C.
- Component C is present in the mixture whenever component E is not used.
- component E is not used.
- mol % based on the sum of compounds A to C, of dihydroxy compound C are used.
- the molar ratio of dihydroxy compound B to the sum of A and C is not more than 1. If this ratio is greater than 1, the water absorption is adversely affected and becomes too high. Products of this type are less suitable for the production of components in the electrical industry and electronics.
- Compounds D and E which are reacted with the mixture of compounds, A, B and, if required, C to give the novel heat-stable copolycondensate molding materials, are aromatic dihalogen compounds.
- Compound D is 4,4'-dichloro- or 4,4'-difluorodiphenyl sulfone or their C 1 -C 6 -alkyl-substituted or halogen-substituted derivatives, such as 3,3,5,5'-tetramethyl-4,4'-dichlorodiphenyl sulfone or the corresponding fluorine compound.
- the two halogen substituents may be identical or different.
- v and w can be 0, 1, 2, 3 or 4, and are preferably 0, 1 or 2.
- the compounds E are of the general formula ##STR28## or a chemical bond
- R 7 , R 8 , R 9 and R 10 are each hydrogen, Cl or F or may have the same meanings as R 1 and R 2
- q and p are each 0 or 1 and r
- s, t and u may each be an integer from 0 to 4.
- Z 2 is preferably a chemical bond, or --SO 2 --, and R 7 , R 8 , R 9 and R 10 are each preferably hydrogen, methyl, ethyl or Cl or F, r, s, t and u may each be 0, 1, 2, 3 or 4, preferably 0, 1 or 2.
- the amount of dihalogen compound D is from 1 to 100, preferably from 20 to 100, particularly preferably from 50 to 100, mol %, based on the sum of D and E.
- the dihalogen compounds E are present when no dihydroxy compound C is used.
- the amount of the dihalogen compound E is preferably from 5 to 50, particularly preferably from 10 to 40, mol %, based on the sum of D and E.
- novel copolycondensate molding materials can be mixed with other thermoplastics, for example polyesters, nylons, polyurethanes, polyolefins, polyvinyl chloride and polyoxymethylenes, in amounts of from 5 to 50, preferably from 20 to 50, % by weight, based on the molding materials.
- other thermoplastics for example polyesters, nylons, polyurethanes, polyolefins, polyvinyl chloride and polyoxymethylenes
- They may furthermore be modified with reinforcing fillers and, if required, transparent pigments and other assitants and additives.
- reinforcing fillers are asbestos, carbon and preferably glass fibers, the latter being used in the form of, for example, glass fabrics, mats, surface mats and/or preferably glass rovings or cut glass filaments of low-alkali E glasses having a diameter of from 5 to 200 ⁇ m, preferably from 8 to 15 ⁇ m, which, after being incorporated, have a mean length of from 0.05 to 1 mm, preferably from 0.1 to 0.5 mm.
- the molding materials reinforced with glass rovings or cut glass filaments contain from 10 to 60, preferably from 20 to 50, % by weight, based on the total weight, of the reinforcing material, while the impregnated-glass fabrics, mats and/or surface mats contain from 10 to 80, preferably from 30 to 60, % by weight, based on the total weight, of copolycondensates.
- suitable pigments are titanium dioxide, cadmium sulfide, zinc sulfide, barium sulfate and carbon black.
- suitable additives and assistants are dyes, lubricants, eg. graphite or molybdenum disulfide, abrasives, eg. carborundum, light stabilizers and stabilizers against hydrolysis.
- the pigments, additives and assistants are usually used in amounts of from 0.01 to 3% by weight, based on the weight of polycondensates.
- Wollastonite, calcium carbonate, glass spheres, quartz powder, silicon nitride and boron nitride or mixtures of these fillers may also be used.
- the polycondensation of the dihydroxy compounds A, B and, where relevant, C with the dihalogen compounds D and, where relevant, E can be carried out in principle by the processes which are known for the preparation of polysulfones or polyethersulfones and are described in the literature. A preferred process for the preparation of the novel copolycondensates is described below as a typical example.
- the mixture of the aromatic dihydroxy compounds A, B and, if required, C can be reacted with aromatic dihalogen compounds in a molar ratio of from 0.8:1 to 1.2:1, preferably from 0.9:1 to 1.1:1, in particular from 0.98:1 to 1.02:1, and particularly preferably with an equimolar amount of aromatic dihalogen compounds in the presence of from 1.0 to 2.0, preferably from 1.05 to 1.5, moles of an anhydrous alkali metal carbonate, in particular K 2 CO 3 , in an aprotic, polar solvent.
- Preferred aprotic polar solvents are N-substituted acid amides and lactams, N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone may be mentioned merely by way of example.
- an azeotrope former may be added to the solvent in order to remove the water of reaction.
- an azeotrope former may also advantageously be omitted.
- the amount of monomers is in general from 20 to 80, preferably from 30 to 70, in particular from 40 to 60% by weight, based on the total amount of the solvent.
- the major part of the water of reaction formed can be removed at from 100° to 200° C., preferably from 130° to 180° C. This can be effected, for example, by heating alone, by adding an azeotrope former or, preferably, by reducing the pressure.
- the condensation can then be continued at from 180° to 220° C. until the desired molecular weight or the desired degree of condensation is reached.
- the total reaction time is, as a rule, from 5 to 20, preferably from 7 to 15, hours and is of course dependent on the reaction conditions (temperature and pressure) and on the desired molecular weight of the product.
- the product can be reacted with an arylating or alkylating agent, eg. methyl chloride, in order to stabilize free terminal phenolate groups.
- an arylating or alkylating agent eg. methyl chloride
- This reaction is preferably carried out at from 50° to 200° C., preferably from 50° to 150° C.
- the suspended alkali metal halide obtained in the polycondensation can be separated off by means of a suitable separating apparatus, for example a clarifying filter or a centrifuge.
- the copolycondensate can be isolated from the solution by evaporation of the solvent or precipitation in a suitable nonsolvent.
- novel copolycondensation particularly products prepared by the process described above, generally have a reduced viscosity of from 0.35 to 2.0, preferably from 0.45 to 1.0, in particular from 0.45 to 0.85, measured as a 1% by weight solution in 1:1 phenol/o-dichlorobenzene at 25° C.
- the novel copolycondensate molding materials are distinguished by their balanced properties. They possess high heat distortion resistance and good stress cracking resistance coupled with low water absorption and very good processability.
- the molding materials according to the invention can be used for the production of moldings, film and fibers. Because of their good properties, they are particularly useful for the production of circuit boards and electrical plug connections.
- the reaction mixture was first heated for one hour at 180° C. under 300 mbar (30 kPa) with constant removal of the water of reaction and N-methylpyrrolidone by distillation, and was kept at this temperature for 3 hours. The reaction was then continued for 6 hours at 190° C.
- the polycondensation was terminated by adding methyl chloride at 150° C. and carrying out the reaction for 2 hours under pressure (0.5 bar).
- Example 1 The procedure described in Example 1 was followed, except that 25 mol % of bisphenol A and 75 mole % of 4,4'-dihydroxydiphenyl sulfone were used.
- Example 1 The procedure described in Example 1 was followed, except that a mixture of 75 mol % of bisphenol A and 25 mol % of 4,4'-dihydroxydiphenyl sulfone (DHDPS) was used.
- DHDPS 4,4'-dihydroxydiphenyl sulfone
- a 50:50 (mol %) mixture of a polysulfone and a polyethersulfone was used.
- Example 1 The procedure described in Example 1 was followed, except that the dihydroxy compounds and dihalogen compounds stated in the Table were used.
- Table 1 also shows the heat distortion resistance (Tg) and the water absorption after storage under standard conditions of temperature and humidity (23° C., 50% relative humidity) and after storage in H 2 O at 23° C., for 180 days in each case.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Polyesters Or Polycarbonates (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Copolycondensate molding materials are obtainable by polycondensation of
from 2 to 98 mol % of 2,2-di-(4'-hydroxyphenyl)-propane (A),
from 2 to 98 mole % of 4,4'-dihydroxydiphenyl sulfone (B) and
from 0 to 96 mole % of (C) ##STR1## where R1 and R2 are each H, C1 -C6 -alkyl or C1 -C6 -alkoxy, X is a chemical bond, --S--, --O--, --CO--, CR3 R4 (where R3 and R4 are different when n and p are each 0), or SO2 -- only when n or p is .Iadd.not .Iaddend.0), R3 and R4 are each H, C1 -C6 -alkyl, C1 -C6 -alkoxy, aryl or halogen-substituted alkyl of 1 to 4 carbon atoms, m is 0 or 1, and n and p are each 0, 1, 2, 3, or 4,
with from 1 to 100 mole % of (D) ##STR2## where R5 and R6 have the same meaning as R1 and R2, and v and w are each 0, 1, 2, 3 or 4, and from 0 to 99 mol % of (E) ##STR3## where R7 -R10 are each Cl or F or have the same meanings as R1 and R2, q is 0 or 1, r, s, t and n are each 0, 1, 2, 3 or 4, Z1 is --SO2 -- or --CO-- and Z2 is --O--, --S--, --SO2 --, --CO-- or a chemical bond,
with the proviso that one or more of the components C and E are present and the molar ratio of B to the sum of A and C is not greater than 1.
Description
The present invention relates to heat-stable copolycondensate molding materials which contain polyarylene sulfone and polyarylene ether sulfone units in random distribution and are obtainable by polycondensation of a mixture of
(A) from 2 to 98 mole %, based on the sum of (A)-(C), of ##STR4##
(B) from 2 to 98 mole %, based on the sum of (A)-(C), of ##STR5## and
(C) from 0 to 96 mol %, based on the sum of (A)-(C), of ##STR6## where X is a chemical bond or ##STR7## (only when n or p is .Iadd.not .Iaddend.0), R1 and R2 are each alkyl or alkoxy, each of 1 to 6 carbon atoms, R3 and R4 are each hydrogen, alkyl of 1 to 6 carbon atoms, aryl or halogen-substituted alkyl of 1 to 4 carbon atoms, m is 0 or 1 and n and p are 0, 1, 2, 3 or 4.
with
(D) from 1 to 100 mol %, based on the sum of (D) and (E), of ##STR8## where R5 and R6 are each hydrogen or have the same meanings as R1 and R2, and v and w are each 0, 1, 2, 3 or 4, and
(E) from 0 to 99 mole %, based on the sum of (D) and (E), of ##STR9## or a chemical bond, R7, R8, R9 and R10 are each hydrogen, Cl or F or may have the same meanings as R1 and R2, q and p are each 0 or 1 and r, s, t and u may each be an integer from 0 to 4, with the proviso that one or more of the components, C and E are present and the molar ratio of B to the sum of A+C is not greater than 1.
The present invention furthermore relates to a process for the preparation of such copolycondensate molding materials and their use for the production of printed circuit boards and electrical plug connections, and to molding which are obtained from the novel copolycondensate molding materials as essential components.
Polyethersulfones containing the general structural unit ##STR10## (frequently referred to, as below, simply as polysulfones) are characterized by very low water absorption and hence very good dimensional stability (of the moldings produced from them). However, the heat distortion resistance (which is frequently described in terms of the maximum temperature during continuous operation) is not sufficient for some applications, particularly in the case of printed circuit boards (also referred to as PCB's) produced from these materials.
Compared with polysulfones, polyethersulfones containing the general structural unit ##STR11## possess better heat distortion resistance, but the water absorption is substantially higher. The consequence of this is that moldings produced from polyethersulfones tend to swell and become distorted, which is undesirable when used in the electrical industry and electronics (production of printed circuit boards).
Mixtures of polysulfones and polyethersulfones exhibit a linear relationship between mixing ratio and water absorption, but the polysulfone component has an adverse effect on the heat distortion resistance. Moreover because of the incompatibility of the two components, moldings produced from such mixtures are not transparent, and this is a substantial disadvantage. U.S. Pat. No. 4,175,175, EP-A 113 112 and EP-A 135 130 describe copolycondensates which are obtainable by condensation of mixtures of 2,2-di-(4-hydroxyphenyl)propane (bisphenol A) and 4,4'-dihydroxyphenyl sulfone (bisphenol S) with 4,4'-dichlorodiphenyl sulfone (DCDCPS).
EP-A 113 112 also describes copolycondensates of a mixture of dihydroxy compounds, A, B and C and dihalogen compounds D. However, the molar ratio of B to A and C is always greater than 1, which has an adverse effect on the water absorption.
Although these copolycondensates have in general better properties than the polysulfones or polyethersulfones, the heat distortion resistance and the stress cracking resistance are still unsatisfactory. These copolycondensates can be used only to a very restricted extent for the production of printed circuit boards.
It is an object of the present invention to provide heat-stable polycondensates which have a balanced property spectrum, ie. sufficient heat distortion resistance coupled with low water absorption and high stress cracking resistance, and are suitable for the production of circuit boards, in particular printed circuit boards.
We have found that this object is achieved, according to the invention, by the heat-stable copolycondensate molding materials defined at the outset.
Preferred copolycondensates of this type are mentioned in the subclaims and in the detailed description below.
The novel heat-stable copolycondensates are obtainable by polycondensation of a mixture of aromatic dihydroxy compounds A, B and, if required, C with aromatic dihalogen compounds D and, if required, E, and it is essential for one or more of the compounds C and E to be present.
The dihydroxy compound A is 2,2-di-(4-hydroxyphenyl) -propane, which is known as bisphenol A, and the dihydroxy compound B is 4,4'-dihydroxyphenyl sulfone, which is also referred to as bisphenol S.
The dihydroxy compounds C are of the general formula ##STR12## (when n or p is .Iadd.not .Iaddend.0), R1 and R2 are each alkyl or alkoxy, each of 1 to 6 carbon atoms, R3 and R4 are each hydrogen, alkyl or alkoxy of 1 to 6 carbon atoms, aryl or halogen-substituted alkyl of 1 to 4 carbon atoms, m is 0 or 1, preferably 1, and n and p are each 0, 1, 2, 3, or 4.
R1 and R2 are each preferably alkyl of 1 to 4 carbon atoms, eg. methyl, ethyl, isopropyl, n-propyl or n-, iso- or tert-butyl or corresponding alkoxy groups. Methyl and ethyl are particularly preferred.
Preferred substituents R3 and R4 are C1 -C4 -alkyl groups, as described for R1 and R2, aryl or halogen-substituted alkyl, such as CF3 and CCl3, to mention but two examples.
m is 0 or 1, and is preferably 1 particularly when p is 0, ie. no substituents R2 are present.
n and p may each be 0, 1, 2, 3, or 4, preferably 0, 1, 2 or 3.
A few examples of preferred dihydroxy compounds are listed below.
__________________________________________________________________________ ##STR13## Di-(4-hydroxyphenyl)-methane ##STR14## 2,2-Di-(4-hydroxyphenyl)-ethane ##STR15## 1-Phenyl-1,1-di-(4-hydroxyphenyl)-metha ne ##STR16## Diphenyl-di-(4-hydroxyphenyl)-methane ##STR17## Tetramethylbisphenol A ##STR18## 4,4'-Dihydroxydiphenyl ether ##STR19## 4,4'-Dihydroxydiphenyl sulfide ##STR20## Dihydroxybenzophenone ##STR21## 1,4-Di-(4'-hydroxyphenylcarbonyl)-benze ne ##STR22## Tetramethylbisphenol S ##STR23## Hydroquinone ##STR24## 2,3,6-Trimethylhydroquinone ##STR25## 4,4'-Dihydroxydiphenyl ##STR26## 3,3',5,5'-tetramethyl-4,4'-dihydroxydip henyl ##STR27## Dihydroxybenzophenone __________________________________________________________________________ ether
The mixture of the dihydroxy compounds A, B and, where relevant, C contains from 2 to 98 mole % of A, from 2 to 98 mol % of B and from 0 to 96 mol % of C, the percentages in each case being based on the sum of A-C.
Preferred mixtures are those which contain from 20 to 80, in particular from 25 to 70, mol % of A, from 20 to 80, in particular from 25 to 70, mol % of B and from 0 to 60, in particular from 5 to 60, mol % of C.
Component C is present in the mixture whenever component E is not used. In this case, as a rule from 5 to 60, preferably from 10 to 40, mol %, based on the sum of compounds A to C, of dihydroxy compound C are used.
The molar ratio of dihydroxy compound B to the sum of A and C is not more than 1. If this ratio is greater than 1, the water absorption is adversely affected and becomes too high. Products of this type are less suitable for the production of components in the electrical industry and electronics.
Compounds D and E, which are reacted with the mixture of compounds, A, B and, if required, C to give the novel heat-stable copolycondensate molding materials, are aromatic dihalogen compounds. Compound D is 4,4'-dichloro- or 4,4'-difluorodiphenyl sulfone or their C1 -C6 -alkyl-substituted or halogen-substituted derivatives, such as 3,3,5,5'-tetramethyl-4,4'-dichlorodiphenyl sulfone or the corresponding fluorine compound. The two halogen substituents may be identical or different. v and w can be 0, 1, 2, 3 or 4, and are preferably 0, 1 or 2.
The compounds E are of the general formula ##STR28## or a chemical bond, R7, R8, R9 and R10 are each hydrogen, Cl or F or may have the same meanings as R1 and R2, q and p are each 0 or 1 and r, s, t and u may each be an integer from 0 to 4.
Z2 is preferably a chemical bond, or --SO2 --, and R7, R8, R9 and R10 are each preferably hydrogen, methyl, ethyl or Cl or F, r, s, t and u may each be 0, 1, 2, 3 or 4, preferably 0, 1 or 2.
Some preferred dihalogen compounds D and E are listed below merely as typical examples.
__________________________________________________________________________ Name of chlorine compound __________________________________________________________________________ ##STR29## 4,4'-Dichlorobenzophenone ##STR30## 1,4-Di-(4'-chlorophenylcarbonyl)-benz ene ##STR31## 1,10-Di-(4'-chlorophenylsulfonyl)-dip henyl ##STR32## 4,4'-Dichlorodiphenyl sulfone ##STR33## 3,3',5,5'-Tetramethyl-4,4'-dichlorodi phenyl sulfone ##STR34## 3-Chloro-4,4'-dichlorodiphenyl sulfone ##STR35## 3,3'-4,4'-Tetrachlorodiphenyl sulfone ##STR36## 1,3-Dimethyl-4,6-di-(4-chlorophenylsu lfonyl)benzene __________________________________________________________________________
The amount of dihalogen compound D is from 1 to 100, preferably from 20 to 100, particularly preferably from 50 to 100, mol %, based on the sum of D and E.
The dihalogen compounds E are present when no dihydroxy compound C is used. In this case, the amount of the dihalogen compound E is preferably from 5 to 50, particularly preferably from 10 to 40, mol %, based on the sum of D and E.
The novel copolycondensate molding materials can be mixed with other thermoplastics, for example polyesters, nylons, polyurethanes, polyolefins, polyvinyl chloride and polyoxymethylenes, in amounts of from 5 to 50, preferably from 20 to 50, % by weight, based on the molding materials.
They may furthermore be modified with reinforcing fillers and, if required, transparent pigments and other assitants and additives.
Examples of reinforcing fillers are asbestos, carbon and preferably glass fibers, the latter being used in the form of, for example, glass fabrics, mats, surface mats and/or preferably glass rovings or cut glass filaments of low-alkali E glasses having a diameter of from 5 to 200 μm, preferably from 8 to 15 μm, which, after being incorporated, have a mean length of from 0.05 to 1 mm, preferably from 0.1 to 0.5 mm. The molding materials reinforced with glass rovings or cut glass filaments contain from 10 to 60, preferably from 20 to 50, % by weight, based on the total weight, of the reinforcing material, while the impregnated-glass fabrics, mats and/or surface mats contain from 10 to 80, preferably from 30 to 60, % by weight, based on the total weight, of copolycondensates. Examples of suitable pigments are titanium dioxide, cadmium sulfide, zinc sulfide, barium sulfate and carbon black. Examples of other suitable additives and assistants are dyes, lubricants, eg. graphite or molybdenum disulfide, abrasives, eg. carborundum, light stabilizers and stabilizers against hydrolysis. The pigments, additives and assistants are usually used in amounts of from 0.01 to 3% by weight, based on the weight of polycondensates.
Wollastonite, calcium carbonate, glass spheres, quartz powder, silicon nitride and boron nitride or mixtures of these fillers may also be used.
The polycondensation of the dihydroxy compounds A, B and, where relevant, C with the dihalogen compounds D and, where relevant, E can be carried out in principle by the processes which are known for the preparation of polysulfones or polyethersulfones and are described in the literature. A preferred process for the preparation of the novel copolycondensates is described below as a typical example.
The mixture of the aromatic dihydroxy compounds A, B and, if required, C can be reacted with aromatic dihalogen compounds in a molar ratio of from 0.8:1 to 1.2:1, preferably from 0.9:1 to 1.1:1, in particular from 0.98:1 to 1.02:1, and particularly preferably with an equimolar amount of aromatic dihalogen compounds in the presence of from 1.0 to 2.0, preferably from 1.05 to 1.5, moles of an anhydrous alkali metal carbonate, in particular K2 CO3, in an aprotic, polar solvent.
Preferred aprotic polar solvents are N-substituted acid amides and lactams, N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone may be mentioned merely by way of example.
If desired, an azeotrope former may be added to the solvent in order to remove the water of reaction. Compounds of this type are described in the literature. However, an azeotrope former may also advantageously be omitted.
The amount of monomers is in general from 20 to 80, preferably from 30 to 70, in particular from 40 to 60% by weight, based on the total amount of the solvent.
The major part of the water of reaction formed can be removed at from 100° to 200° C., preferably from 130° to 180° C. This can be effected, for example, by heating alone, by adding an azeotrope former or, preferably, by reducing the pressure.
The condensation can then be continued at from 180° to 220° C. until the desired molecular weight or the desired degree of condensation is reached.
The total reaction time is, as a rule, from 5 to 20, preferably from 7 to 15, hours and is of course dependent on the reaction conditions (temperature and pressure) and on the desired molecular weight of the product.
After the polycondensation, the product can be reacted with an arylating or alkylating agent, eg. methyl chloride, in order to stabilize free terminal phenolate groups. This reaction is preferably carried out at from 50° to 200° C., preferably from 50° to 150° C.
The suspended alkali metal halide obtained in the polycondensation can be separated off by means of a suitable separating apparatus, for example a clarifying filter or a centrifuge.
The copolycondensate can be isolated from the solution by evaporation of the solvent or precipitation in a suitable nonsolvent.
The novel copolycondensation, particularly products prepared by the process described above, generally have a reduced viscosity of from 0.35 to 2.0, preferably from 0.45 to 1.0, in particular from 0.45 to 0.85, measured as a 1% by weight solution in 1:1 phenol/o-dichlorobenzene at 25° C.
The novel copolycondensate molding materials are distinguished by their balanced properties. They possess high heat distortion resistance and good stress cracking resistance coupled with low water absorption and very good processability.
The molding materials according to the invention can be used for the production of moldings, film and fibers. Because of their good properties, they are particularly useful for the production of circuit boards and electrical plug connections.
86 kg of N-methylpyrrolidone, 11.41 kg (50 moles) of bisphenol A, 12.51 kg (50 moles) of 4,4'-dihydroxydiphenyl sulfone and 28.72 kg of 4,4'-dichlorodiphenyl sulfone were dissolved under a nitrogen atmosphere in a 300 l vessel provided with a stirrer and a N2 connection, and 15.2 kg (150 moles) of anhydrous potassium carbonate were added.
The reaction mixture was first heated for one hour at 180° C. under 300 mbar (30 kPa) with constant removal of the water of reaction and N-methylpyrrolidone by distillation, and was kept at this temperature for 3 hours. The reaction was then continued for 6 hours at 190° C.
The polycondensation was terminated by adding methyl chloride at 150° C. and carrying out the reaction for 2 hours under pressure (0.5 bar).
After the addition of 125 kg of N-methylpyrrolidone, the inorganic components were filtered off and the polymer was isolated as a solid by precipitation in methanol. After drying at 100° C. under reduced pressure, the polymer was converted to granules.
The procedure described in Example 1 was followed, except that 25 mol % of bisphenol A and 75 mole % of 4,4'-dihydroxydiphenyl sulfone were used.
The procedure described in Example 1 was followed, except that a mixture of 75 mol % of bisphenol A and 25 mol % of 4,4'-dihydroxydiphenyl sulfone (DHDPS) was used.
A 50:50 (mol %) mixture of a polysulfone and a polyethersulfone was used.
The procedure described in Example 1 was followed, except that the dihydroxy compounds and dihalogen compounds stated in the Table were used.
The following abbreviations are used in the Table:
TABLE ______________________________________ Bis A Bisphenol A T-Bis A Tetramethylbisphenol A DHDPS 4,4'-dihydroxyphenyl sulfone DHDP 4,4'-dihydroxydiphenyl T-DHDP 3,3',5,5'-tetramethyl-4,4'-dihydroxydi- phenyl TMH 2,3-trimethylhydroquinone DCDPS 4,4'-dichlorodiphenyl sulfone DDP 1,10-di-(4'-chlorophenylsulfonyl)-diphenyl DDB 1,3-dimethyl-4,6-di-(4'-chlorophenyl- sulfonyl)-benzene. ______________________________________
Table 1 also shows the heat distortion resistance (Tg) and the water absorption after storage under standard conditions of temperature and humidity (23° C., 50% relative humidity) and after storage in H2 O at 23° C., for 180 days in each case.
TABLE __________________________________________________________________________ Water absorption Component A Component B Component C Component D Component E Standard Example (mol) (mol) (mol) (mol) (mol) Tg °C. conditions H.sub.2 O __________________________________________________________________________ 1V+ Bis A DHDPS -- DCDPS -- 210 0.14 1.05 (0.05) (0.05) (0.1) 2V+ Bis A DHDPS -- DCDPS -- 215 0.21 1.37 (0.025) (0.075) (0.1) 3V+ Bis A DHDPS -- DCDPS -- 197 0.11 0.78 (0.075) (0.025) (0.1) 4V*+ -- -- -- -- -- 189/224 0.18 1.15 5 Bis A DHDPS T-Bis A DCDPS -- 252 0.12 0.89 (0.025) (0.05) (0.025) (0.1) 6 Bis A DHDPS DHDP DCDPS -- 225 0.12 0.92 (0.025) (0.05) (0.025) (0.1) 7 Bis A DHDPS T-DHDP DCDPS -- 241 0.10 0.88 (0.025) (0.05) (0.025) (0.025) 8 Bis A DHDPS -- DCDPS DDP 225 0.16 1.09 (0.05) (0.05) (0.05) (0.05) 9 Bis A DHDPS -- DCDPS DDP 245 0.17 1.11 (0.05) (0.05) (0.075) (0.025) 10 Bis A DHDPS -- DCDPS DDB 225 0.13 0.99 (0.05) (0.05) (0.05) (0.05) 11 Bis A DHDPS TMH DCDPS -- 215 0.15 1.10 (0.0375) (0.05) (0.0125) (0.1) 12 Bis A DHDPS DHDP DCDPS 221 0.13 1.03 (0.025) (0.075) (0.05) (0.1) 13 Bis A DHDPS T-DHDP DCDPS 226 0.10 0.90 (0.055) (0.02) (0.025) (0.1) __________________________________________________________________________ *50:50 mixture of polysulfone and polyethersulfone +Examples 1 to 4 are Comparative Examples
Claims (7)
1. A heat-stable copolycondensate molding material which contains polyarylene sulfone and polyarylene ether sulfone units in random distribution and is obtainable by polycondensation of a mixture of
(A) from 2 to 98 mol %, based on the sum of (A)-(C), of ##STR37## (B) from 2 to 98 mol %, based on the sum of (A)-(C), ##STR38## and (C) from 0 to 96 mol %, based on the sum of (A)-(C), of ##STR39## where X is a chemical bond or ##STR40## ##STR41## (only when n or p is .Iadd.not .Iaddend.0), R1 and R2 are each alkyl or alkoxy, each of 1 to 6 carbon atoms, R3 and R4 are each hydrogen, alkyl of 1 to 6 carbons atoms, aryl or halogen-substituted alkyl of 1 to 4 carbon atoms, m is 0 or 1 and n and p are 0, 1, 2, 3 or 4, with
(D) from 1 to 100 mol %, based on the sum of (D) and (E), of ##STR42## where R5 and R6 are each hydrogen or have the same meanings as R1 and R2, Y is Cl or F, and v and w are each 0, 1, 2, 3 or 4, and
(E) from 0 to 99 mol %, based on the sum of (D) and (E), of ##STR43## or a chemical bond, R7, R8, R9 and R10 are each hydrogen, Cl or F or may have the same meanings as R1 and R2, q and p are each 0 or 1 and r, s, t and u may each be an integer from 0 to 4, with the proviso that one or more of the components C and E are present and the molar ratio of B to the sum of A+C is not greater than 1.
2. A heat-stable copolycondensate molding material as claimed in claim 1, which is obtainable by polycondensation of a mixture of
from 25 to 70 mol % of A,
from 25 to 70 mol % of B and
from 5 to 60 mol % of C,
the percentages in each case being based on the sum of A to C, with
from 1 to 100 mol % of D and
from 0 to 99 mol % of E,
the percentages in each case being based on the sum of D and E.
3. A heat-stable copolycondensation molding material as claimed in claim 1, which is obtainable by polycondensation of a mixture of
from 20 to 80 mol % of A
from 20 to 80 mol % of B and
from 0 to 60 mol % of C,
the percentages in each case being based on the sum of A to C, with
from 50 to 95 mol % of D and
from 5 to 50 mol % of E,
the percentages in each case being based on the sum of D and E.
4. A heat-stable copolycondensate molding material as claimed in claim 1, which is obtainable by polycondensation of a mixture of
from 25 to 70 mol % of A
from 25 to 70 mol % of B and
from 5 to 60 mol % of C,
the percentages in each case being based on the sum of A to C, with
from 50 to 95 mol % of D and
from 5 to 50 mol % of E,
the percentages in each case being based on the sum of D and E.
5. A molding which is obtainable from a heat-stable copolycondensate molding material as claimed in claim 1 as the central component.
6. A printed circuit board consisting of a heat-stable copolycondensate molding material as claimed in claim 1.
7. An electrical plug connection consisting of a heat-stable copolycondensate molding material as claimed in claim 1.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/883,955 USRE34563E (en) | 1986-04-30 | 1992-05-15 | Heat-stable copolycondensate molding materials |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19863614753 DE3614753A1 (en) | 1986-04-30 | 1986-04-30 | HIGH TEMPERATURE RESISTANT COPOLY CONDENSATE MOLDS |
DE3614753 | 1986-04-30 | ||
US07/036,446 US4925910A (en) | 1986-04-30 | 1987-04-09 | Heat-stable copolycondensate molding materials |
US07/883,955 USRE34563E (en) | 1986-04-30 | 1992-05-15 | Heat-stable copolycondensate molding materials |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US07/036,446 Reissue US4925910A (en) | 1986-04-30 | 1987-04-09 | Heat-stable copolycondensate molding materials |
Publications (1)
Publication Number | Publication Date |
---|---|
USRE34563E true USRE34563E (en) | 1994-03-15 |
Family
ID=6299942
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US07/036,446 Ceased US4925910A (en) | 1986-04-30 | 1987-04-09 | Heat-stable copolycondensate molding materials |
US07/242,161 Expired - Fee Related US4904754A (en) | 1986-04-30 | 1988-09-09 | Heat-stable copolycondensate molding materials |
US07/883,955 Expired - Lifetime USRE34563E (en) | 1986-04-30 | 1992-05-15 | Heat-stable copolycondensate molding materials |
Family Applications Before (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US07/036,446 Ceased US4925910A (en) | 1986-04-30 | 1987-04-09 | Heat-stable copolycondensate molding materials |
US07/242,161 Expired - Fee Related US4904754A (en) | 1986-04-30 | 1988-09-09 | Heat-stable copolycondensate molding materials |
Country Status (4)
Country | Link |
---|---|
US (3) | US4925910A (en) |
EP (1) | EP0243833A3 (en) |
JP (1) | JPS62288631A (en) |
DE (1) | DE3614753A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5569681A (en) * | 1994-05-19 | 1996-10-29 | Jsp Corporation | Flame-retardant foamed particles of polyolefin resin |
US20060115695A1 (en) * | 2002-12-26 | 2006-06-01 | Ube Industries, Ltd. | Bisphenol compound and aromatic polyaryl ether |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4536559A (en) * | 1983-06-17 | 1985-08-20 | The Boeing Company | Thermally stable polyimide polysulfone compositions for composite structures |
US4871475A (en) * | 1985-10-07 | 1989-10-03 | The Boeing Company | Polysulfone and polyethersulfone oligomers |
DE3840617A1 (en) * | 1988-07-23 | 1990-02-01 | Bayer Ag | METHOD FOR PRODUCING AROMATIC POLYETHERKETONES |
DE3825148A1 (en) * | 1988-07-23 | 1990-01-25 | Bayer Ag, 51373 Leverkusen | NEW AROMATIC POLYETHERSULPHONES, METHOD FOR THEIR PRODUCTION AND THEIR USE |
ES2094751T3 (en) * | 1989-03-17 | 1997-02-01 | Sumitomo Chemical Co | NEW POLYARYLENE ETERS. |
US5084548A (en) * | 1989-11-09 | 1992-01-28 | E. I. Du Pont De Nemours And Company | Fluorinated poly(ether sulfone) |
US5196604A (en) * | 1989-11-09 | 1993-03-23 | E. I. Du Pont De Nemours And Company | Fluorinated poly(ether sulfones) |
EP0447358A3 (en) * | 1990-03-12 | 1991-10-23 | Ciba-Geigy Ag | Soluble polyarylene ether sulfones |
CN106699688A (en) * | 2016-12-08 | 2017-05-24 | 斯芬克司药物研发(天津)股份有限公司 | Phenyl piperazidine thioether and preparation method thereof |
US20230090902A1 (en) | 2017-06-26 | 2023-03-23 | Basf Se | New membrane polymer and membranes |
CN110914336A (en) | 2017-07-20 | 2020-03-24 | 巴斯夫欧洲公司 | Sulfonated polyaryl ether sulfones and membranes thereof |
EP3655460A1 (en) | 2017-07-20 | 2020-05-27 | Basf Se | Hydrophilic copolymers and membranes |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4489181A (en) * | 1983-11-07 | 1984-12-18 | Fox Daniel W | Thermoplastic polycarbonate-polysulfone carbonate molding compositions |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4175175A (en) * | 1963-07-16 | 1979-11-20 | Union Carbide Corporation | Polyarylene polyethers |
DE2749645A1 (en) * | 1977-11-05 | 1979-05-10 | Basf Ag | PROCESS FOR MANUFACTURING POLYAETHERS |
CA1246295A (en) * | 1982-12-23 | 1988-12-06 | Robert A. Clendinning | Aromatic amorphous thermoplastic terpolymers |
US4703081A (en) * | 1986-04-08 | 1987-10-27 | Phillips Petroleum Company | Poly(arylene sulfide) resin ternary blends |
-
1986
- 1986-04-30 DE DE19863614753 patent/DE3614753A1/en not_active Withdrawn
-
1987
- 1987-04-09 US US07/036,446 patent/US4925910A/en not_active Ceased
- 1987-04-18 EP EP87105760A patent/EP0243833A3/en not_active Withdrawn
- 1987-04-27 JP JP62102169A patent/JPS62288631A/en active Pending
-
1988
- 1988-09-09 US US07/242,161 patent/US4904754A/en not_active Expired - Fee Related
-
1992
- 1992-05-15 US US07/883,955 patent/USRE34563E/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4489181A (en) * | 1983-11-07 | 1984-12-18 | Fox Daniel W | Thermoplastic polycarbonate-polysulfone carbonate molding compositions |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5569681A (en) * | 1994-05-19 | 1996-10-29 | Jsp Corporation | Flame-retardant foamed particles of polyolefin resin |
US20060115695A1 (en) * | 2002-12-26 | 2006-06-01 | Ube Industries, Ltd. | Bisphenol compound and aromatic polyaryl ether |
Also Published As
Publication number | Publication date |
---|---|
DE3614753A1 (en) | 1987-11-05 |
EP0243833A2 (en) | 1987-11-04 |
US4925910A (en) | 1990-05-15 |
US4904754A (en) | 1990-02-27 |
EP0243833A3 (en) | 1989-07-26 |
JPS62288631A (en) | 1987-12-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
USRE34563E (en) | Heat-stable copolycondensate molding materials | |
US5008364A (en) | Thermoplastic molding materials which are stable at high temperatures and have improved melt stability | |
US4762869A (en) | High temperature resistant molding materials | |
EP0107897B1 (en) | Polyamino-bis-imide resin | |
US4065437A (en) | Aromatic polyether-sulfones | |
US5212278A (en) | Polyarylene ethers | |
JPH024828A (en) | Polyaryl ether ketone improved in processability | |
US4755556A (en) | Thermoplastic composites comprising a polyaryl ether sulphone matrix resin | |
EP0480543B1 (en) | Thermosetting resin composition | |
JPH08198966A (en) | Production of polyarylene sulfide | |
US3594446A (en) | Heat-resistant,linear,aromatic copolymers and process for their production | |
CA1306575C (en) | Production of aromatic sulfide/ketone polymers | |
US4785072A (en) | Polyaryl ether sulphones | |
JPH05186585A (en) | Modified polyarylene ether block copolymer | |
US4551493A (en) | Transparent flame-retardant poly(arylether-arylsulfone) molding materials | |
US5126427A (en) | Soluble polyarylene ether sulfones | |
US5212264A (en) | Modified polyarylene ether sulfones | |
US4937309A (en) | Polymer useful for molding into a circuit board subtrate | |
DE4237768A1 (en) | New polyarylene ether derivs. with reduced viscosity - used to prepare moulded bodies, foils, fibres and membranes, as matrix resins, adhesives or coating agents or as polymer additives | |
US4814419A (en) | Polyarylether sulfones useful for molding into a circuit board substrate | |
US4973650A (en) | Polyarylsulfone derived from 1,4"-(bishalophenylsulfone)terphenyl | |
JPS63152633A (en) | High temperature stable polyether sulfone/polyether ketone block copolymer | |
US4816505A (en) | New polyarylethersulfone circuit board substrates | |
US4324881A (en) | Preparation of amide-containing polyethers | |
US4973653A (en) | Linear polyether resins |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
FP | Lapsed due to failure to pay maintenance fee |
Effective date: 19940515 |
|
FPAY | Fee payment |
Year of fee payment: 8 |