CA2079795A1 - Moulded aromatic-polyester article - Google Patents
Moulded aromatic-polyester articleInfo
- Publication number
- CA2079795A1 CA2079795A1 CA002079795A CA2079795A CA2079795A1 CA 2079795 A1 CA2079795 A1 CA 2079795A1 CA 002079795 A CA002079795 A CA 002079795A CA 2079795 A CA2079795 A CA 2079795A CA 2079795 A1 CA2079795 A1 CA 2079795A1
- Authority
- CA
- Canada
- Prior art keywords
- sintered
- article
- pressure
- powder
- larger
- 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.)
- Abandoned
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 19
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000003118 aryl group Chemical group 0.000 claims abstract description 16
- 230000009477 glass transition Effects 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- -1 phthalic-acid halides Chemical class 0.000 claims abstract description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 23
- 229950005499 carbon tetrachloride Drugs 0.000 claims description 8
- 229920001230 polyarylate Polymers 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 5
- YWFPGFJLYRKYJZ-UHFFFAOYSA-N 9,9-bis(4-hydroxyphenyl)fluorene Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YWFPGFJLYRKYJZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims description 2
- 230000001588 bifunctional effect Effects 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 238000010583 slow cooling Methods 0.000 claims description 2
- VOWWYDCFAISREI-UHFFFAOYSA-N Bisphenol AP Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=CC=C1 VOWWYDCFAISREI-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 239000002904 solvent Substances 0.000 abstract description 10
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 238000005520 cutting process Methods 0.000 abstract description 2
- SOFILIHJTWSLCM-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)fluoren-1-yl]phenol Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC3=CC=CC=C3C2=CC=C1 SOFILIHJTWSLCM-UHFFFAOYSA-N 0.000 abstract 1
- 239000011265 semifinished product Substances 0.000 abstract 1
- 238000005245 sintering Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/003—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/006—Pressing and sintering powders, granules or fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08J2367/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the hydroxy and the carboxyl groups directly linked to aromatic rings
Landscapes
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Engineering & Computer Science (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Polyesters Or Polycarbonates (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Materials For Medical Uses (AREA)
- Polishing Bodies And Polishing Tools (AREA)
Abstract
ABSTRACT
Translucent, pore-free sintered aromatic polyesters made from diphenols such as 1,1-bis(4-hydroxyphenyl)fluorene and phthalic-acid halides evince one or more glass transition points in the range of 220 to 400° C and a tensile strength larger than 40 N/mm2 but advantageously larger than 60 N/mm2. They also evince higher resistance to some solvents such as carbon tetrachloride when in the form of poured films as regards the same material. To manufacture the sintered article, the polyester powder is subjected in a closed mold to a pressure larger than 3,000 N/cm2, the mold meantime being slowly heated and then kept for an appreciable time above the glass transition point and there-upon being slowly cooled. As a rule the sintered articles are used as semi-finished products or as pre-formed component-blanks from which the desired end products are made by mechanical cutting.
Translucent, pore-free sintered aromatic polyesters made from diphenols such as 1,1-bis(4-hydroxyphenyl)fluorene and phthalic-acid halides evince one or more glass transition points in the range of 220 to 400° C and a tensile strength larger than 40 N/mm2 but advantageously larger than 60 N/mm2. They also evince higher resistance to some solvents such as carbon tetrachloride when in the form of poured films as regards the same material. To manufacture the sintered article, the polyester powder is subjected in a closed mold to a pressure larger than 3,000 N/cm2, the mold meantime being slowly heated and then kept for an appreciable time above the glass transition point and there-upon being slowly cooled. As a rule the sintered articles are used as semi-finished products or as pre-formed component-blanks from which the desired end products are made by mechanical cutting.
Description
2~7~79~
AROMAT~C-POLYESTER ARTICI E
Technical Field The invention concerns a molded body essentially consisting of one or several aromatic polyesters, namely polyarylates, which are manufactured from phthalic-s acid halides and diphenols of formula ~O~R~O~
where R is a bifunctional hydrocarbon residue containing at least one aromatic or cyclo-aliphatic ring. The invention moreover concerns an advantageous method for making such an article.
State of the Art Articles of thîs kind are known for instance from the European patents s 64,971 and 64,972, namely in the form of sheets made from a polyester solution by pouring. The polyester described in the European patent 64,972 is made from 1,1-bis(4-hydroxyphenyl)--phenylethane and it was found such can be processed only with difficulty because of the high required processing temperatures of 330 to 400~ C, whereas the polyester of the European patent 64,971 made from 9,9-bis(4-hydroxyphenyl)-fluorene lacks any melting range at all, instead already starting to thermally decompose at a raised temperature of about 400 C. The Russian publication PLASTICHESKIE MASSY, Nr.
7, 1976, p 56, "Physical properties of heat-resistant aromatic polymers", of which the English translation was published in INTERNATIONAL POLYMER SCIENCE AND
TECHNOLOGY, vol. 3, #11, 1976, compares the properties of polyarylate films with -2- 2~979~?
blocks made of the s~me material molded at high temperatures. It was found that as a rule the foils evince higher densities than blocks made of the same material but that the solubilities are the same in several common solvents. Now adequate solubility of such polyarylates in suitable solvents is the precondition for their being processed into ~llms s using pouring methods. On the other hand such solubility precludes many applications for polyarylates that demand substantial resistance to chernicals and solvents.
Discussion of the Invention The first object of the invention is to create an article of the initially citedkind which contrary to the case of the sheets shall be able to assume a substantially 0 arbitrary three-dimensional shape and which also shall evince higher solvent resistance than poured foils made from the same plastic.
This problem is solved by the molded article of the invention, which is characterized in that it consists of a translucent, substantially pore-free sintered body with one or more glass transition point(s) in the range of 220 to 400 C measured by the DSC
~s method, further evincing a DIN 53455 tensile strength larger than 40 N/rnm2, advanta-geously however larger than 60 N/rnm2, and where a test specimen about 1.0 mm thick shall absorb hydrocarbon chloride at rates less than 1.0 ~o, advantageously less than 0.8 % of the specirnen weight for a test duration of 24 h in a bath of carbon tetrachloride at 23~C.
Now it was discovered that with equal kind and quality of the raw material, the sintered articles of the invention evince higher resistance to some solvents such as carbon tetrachloride compared to poured sheets. On this and other grounds which shall be further discussed below, it may be concluded with fair probability that the polyester substance forrning the sintered article is crosslinked to some extent.
2 ~ 7 9 7 ~ Li In one advantageous implementation of the invention, the sintered article of the invention consists essentially of an aromatic polyester based on 9,9-bis(4-hydroxy-phenyl)-fluorene as diphenol. In another advantageous implementation of the sintered article of the invention, said article essentially consists of an aromatic polyester based son l,l-bis-(4-hydroxyphenyl)-1-phenylethane and evinces a DIN 53455 tensile strength larger than 50 N/mm2, in particular however larger than 70 N/mm2.
Moreover the invention concerns an advantageous method for making the article molded in the manner of the invention. This method is characterized in that the aromatic polyester(s) in powder forrn are compacted under pressure, in that the compact-0ed powder is slowly heated, while the pressure is maintained, to temperatures higher than the glass transition point(s) of the polyester(s) used, in that the powder material so compressed and pressurized is kept at those temperatures for a substantial dwell-time in order to form a sintered article and in that the article sintered in this manner shall be slowly cooled. The powder-form polyester(s) are compacted in this process at a pressure exceeding 3,000 N/cm2, preferably however in excess of 5,000 N/cm2, for instance about 10,000 N/cm2.
In advarltageous implementations of the method of the invention, the slow heating of the compressed polyester powder takes place at a rate of l.S to 4.0 C/min and/or the slow cooling of the sintered article takes place at a rate of O.S to 2.5 C/rnin.
20In another advantageous implementation of the method of the invention, the dwell-time is in the range of S - 20 min/mrn of the mean thickness determined in the direction of the applied pressure of the sintered article to be manufactured.
In a yet further advantageous implementation of the method of the inven-tion, the cooling of the sintered article is carried out at least in part while at a pressure WO 92/13698 PC~7/~0~
which is much reduced compared to the maximum applied pressure. In a last advanta-geous implementation of the method of the invention, the sintered article is cooled at leas~ in part at a pressure which is much reduced compared to the applied maximum pressure.
s Several Ways to Implement the Invention The invention is elucidated below in relation to Examples. Ihe sintered articles made according to these Examples consist of aromatic polyesters as described in the European patents 64,972 and 64,971, namely 1. Aromatic polyesters based on .0 1,1-bis(4-hydroxyphenyl)-1-phenylethaneandphthalic-acidchloride(iso-tere 50/50) vith a glass transition point of 250 C measured by DSC and hereafter called CPE, 2. Aromatic polyesters based on 9,9-bis-(4-hydroxyphenyl)fluorene and phthal-ic-acid chloride (iso/tere 5Q/50) with a glass transition point of 325~ C measured by DSC
and hereafter called FPE.
s The raw material for the manufacture of the sintered articles are the polyesters in synthetic powder form which evince a mean molecular weight MW of 50,000 to 1,200,000, corresponding to an inherent viscosity in the range of 0.5 to 3.8 dl/g (measured in the rnanner of the above cited European patents). The screen fractions of the synthetic polyester powder with particles sizes less than 600,u, advantageously between 50 and 400 ~, shall be used.
Because of low particle sizes, these powder fractions evince high sintering activity. However by discarding the finest fractions, the bulk density is prevented from being unduly small, an eventuality which would be disadvantageous for pressing.
5 ~ 7~ 7~
The manufacture of a CPE sintered article by means of a so-called com-pression sintering process is described in further detail herebelow.
A heated mold is used to make the sintered panel with dimensions 200 x 220 x 4 rnm. Upon preheating the mold to 150 C, the CPE powder already previously heated at 150 C for several hours in a vacuum oven is introduced in bulk form with a density of 0.35 g/cm3 and in a suitable amount into the molding space of the lower mold half and the mold is closed by depositing on it the upper mold half entering the molding space. The mold is then moved into a press and the CPE powder is compressed at apressure of 5,000 N/cm2, the mold being slowly heated, that is at a rate of about .0 2 C/min to a temperature of 270 C, that is, above the CPE powder glass transition point of 250 C, and said temperature of 270 C is maintained for about 60 min. Thereupon the mold is cooled at a rate of about 1 C/min to 230D C, the compression is reduced to a low value of about 20 N/cm2 with the essential purpose merely to allow good heat dissipation, and then the mold is cooled further to 50 C and the finished sintered article is removed from the mold. The sintered body so made evinces a glass transition point of 250 C as determined by ASTM D 3418-82 and a density of 1.21 g/cm3.
FPE-powder sintered articles may be manufactured in the same manner.
In contrast with the manufacture of CPE sintered articles, a dwell-temperature of 330 C
(higher than the glass transition point of 325O C) was used for FPE and the pressure relief during cooling took place at 290 C. The FPE sintered article so made evinces a glass transition point of 325 C and a density of 1.22 g/cm3.
The CPE or FPE sintered articles evince an amber color and are resistant to alcohols, oils and fats.
~ .
-6- 2~79~9~
As already mentioned initially, compared with poured, pore-free sheets, the sintered articles evince higher resistance to some solvents such as carbon tetrachloride.
A poured sheet and a sintered article were made each from CPE and FPE
with each a mean molecular weight of about 500,000. Following re-dissolution of the ssheet or sintered-article material, the sheet material retained a molecular weight of 500,000 whereas the sintered material molecular weight had dropped to 50,000. Contrary to expectation, which was that the lower molecular weight of the sintered article would entail lower resistance to solvents, the sintered article did evince higher resistance to certain solvents than did the sheet material.
.0Comparison test results are shown below that relate to absorption of carbon tetrachloride by test samples, namely CPE and FPE sintered articles and sheet specimens resp., made from the same aromatic polyesters.
The tests were carried out on square specimens abou~ 0.7 to 1.1 rnm thick and 24 x 24 rnm resp. A sheet specimen (F) and a sintered-article specimen (X) were kept at room temperature (23 C) immersed in beakers filled with carbon tetrachloride for 4 h and 24 h and, thereupon, after wiping dry the surface, they were weighed and measured.
The results are as follows:
- 7 - 2 ~ 9 ~
Polyester Specimen rhickness Weight Weigh~, % %increas2 % weight (mm)Oh, g 4h, g increase in weight increase in weight 24 h s CPE lX 0,930,59~1~0,59~.5 1,6a3 0,59634,718 lF ~,950,57790,~805 4,499 0,!S87817,131 CPE 2X 1,020, 7û600,7073 1,841 0,70965,099 2F 1,04~0,70S20,7091 5,530 0,717817,867 CPE 3X 0,-t490,S0590,5071 ~,3?2 0,508~~,93 3F 0,7430,51d40,~166 ~,27~ 0,52141~.tO~
F~?E ~X 0, 98Q, a8220, 883~ 1, 360 O, 8854'1, 62~
4~ O,9~g~,8022~,8072 6,233 0,820222,438 FPE 5X 1,0080,89290,E19~0 1,232 0,89714,~04 S~ 1,014,81B~0,8230 S,l;!9 0,842~29,:S11 As shown by the above Table, the absorption of solvent after 24 h exposure is a multiple for the sheet specimens than for the corresponding sinter-article specimens.
s On the other hand, in the light of the known Russian publica~ion, there could be no differences in solubility between the specimens of sheets and of blocks pressed at higher temperatures, as explicitly stated for polyarylate products. In retrospect, the explanation may be that those blocks investigated by and in accordance with the Russian publication might not have been pore-free. In fact applicant carried out measurements on sintered articles that were not translucent because of insufficient sintering and manifestly still contained pores and found values of carbon-tetrachloride absorption substantially higher than for the translucent, pore-free sintered articles made according to this invention.
An improved method for sintering is described below. A mold is used in that method which is not self-heating but on the other hand it can be locked under pressure. After being filled with the polyester powder (CPE or FPE), this mold is moved into a press wherein the compressed material is pressed by 10,000 N/mt and the mold is locked under pressure, as a result of which even after the mold has been removed from .
wo 92/13698 - 8 - PC~/gT71/ooog1 the press, the two mold halves continue exerting a high pressure on the compressed material. Thereupon the mold is slowly heated in an oven at a rate of 2~ C/min to 279 C
(for CPE) and to 330 C (for FPE~ and those temperatures are maintained for 60 min when making a sintered panel 4 mm thick~ Thereafter the oven heater is shut off and the mold is allowed to cool. After it reaches a temperature 20 C below the particular glass transition point, the mold is then further cooled outside the oven down to 50 C and then the finished sintered article is removed from it.
It is important in the manufachure of the sintered articles that the mold be slowly heated and cooled. The permissible heating and cooling rates will be the smaller, .0 the larger the thickness of the sintered article to be made. Similar considerations apply also to the maximum mold-temperahlre dwell-times to be observed. As a rule of thumb, the dwell time ought to be about 15 min/mm of thickness of sintered article.
Several essential properties of the CPE or FPE sintered articles manu-fachured in the above manner are listed in the Tables below.
PC~ /AT91/00091 WO 92113698 ,~ ~3 7 ~ 7 9 ~
1. Mechanical Properties (DIN, room temperature) Property Unlt CPE FPE
s Tensile strength N/mm2 87 72 Tear resistance h 9.4 4.2 Young's modulus (traction) N/mm2 2500 2800 Bending strength 125 123 Young's modulus (bending) ~ 2550 2780 .0 Hardness Rockwell M 104 117 Shore D 88 g1 2. Tribologlcal Properties Measured on pin-pane apparatus per DIN 31680 Pane is made from rolled bearing steei with a surFace roughness F~ = 2 microns Unlts CPE FPE
Coefficient of friction 0.8 0.8 Wear coefficient mrn3 /Nm 3.5 x 10 5 19.0 x 1 ~"
_ 3. Thermal Propertles Unlts CPE FPE Procedure 3s Glasstransition point C 250 325 DSC
Thermal dimensional stability (procedure A) C 217.5 307 TMA
Unear expansion coefficient ~' 75 x 10 5 70 x 10 5 TMA
Thermal conductivity W/mK 0.19 0.25 - 10- 2~7~7~
AROMAT~C-POLYESTER ARTICI E
Technical Field The invention concerns a molded body essentially consisting of one or several aromatic polyesters, namely polyarylates, which are manufactured from phthalic-s acid halides and diphenols of formula ~O~R~O~
where R is a bifunctional hydrocarbon residue containing at least one aromatic or cyclo-aliphatic ring. The invention moreover concerns an advantageous method for making such an article.
State of the Art Articles of thîs kind are known for instance from the European patents s 64,971 and 64,972, namely in the form of sheets made from a polyester solution by pouring. The polyester described in the European patent 64,972 is made from 1,1-bis(4-hydroxyphenyl)--phenylethane and it was found such can be processed only with difficulty because of the high required processing temperatures of 330 to 400~ C, whereas the polyester of the European patent 64,971 made from 9,9-bis(4-hydroxyphenyl)-fluorene lacks any melting range at all, instead already starting to thermally decompose at a raised temperature of about 400 C. The Russian publication PLASTICHESKIE MASSY, Nr.
7, 1976, p 56, "Physical properties of heat-resistant aromatic polymers", of which the English translation was published in INTERNATIONAL POLYMER SCIENCE AND
TECHNOLOGY, vol. 3, #11, 1976, compares the properties of polyarylate films with -2- 2~979~?
blocks made of the s~me material molded at high temperatures. It was found that as a rule the foils evince higher densities than blocks made of the same material but that the solubilities are the same in several common solvents. Now adequate solubility of such polyarylates in suitable solvents is the precondition for their being processed into ~llms s using pouring methods. On the other hand such solubility precludes many applications for polyarylates that demand substantial resistance to chernicals and solvents.
Discussion of the Invention The first object of the invention is to create an article of the initially citedkind which contrary to the case of the sheets shall be able to assume a substantially 0 arbitrary three-dimensional shape and which also shall evince higher solvent resistance than poured foils made from the same plastic.
This problem is solved by the molded article of the invention, which is characterized in that it consists of a translucent, substantially pore-free sintered body with one or more glass transition point(s) in the range of 220 to 400 C measured by the DSC
~s method, further evincing a DIN 53455 tensile strength larger than 40 N/rnm2, advanta-geously however larger than 60 N/rnm2, and where a test specimen about 1.0 mm thick shall absorb hydrocarbon chloride at rates less than 1.0 ~o, advantageously less than 0.8 % of the specirnen weight for a test duration of 24 h in a bath of carbon tetrachloride at 23~C.
Now it was discovered that with equal kind and quality of the raw material, the sintered articles of the invention evince higher resistance to some solvents such as carbon tetrachloride compared to poured sheets. On this and other grounds which shall be further discussed below, it may be concluded with fair probability that the polyester substance forrning the sintered article is crosslinked to some extent.
2 ~ 7 9 7 ~ Li In one advantageous implementation of the invention, the sintered article of the invention consists essentially of an aromatic polyester based on 9,9-bis(4-hydroxy-phenyl)-fluorene as diphenol. In another advantageous implementation of the sintered article of the invention, said article essentially consists of an aromatic polyester based son l,l-bis-(4-hydroxyphenyl)-1-phenylethane and evinces a DIN 53455 tensile strength larger than 50 N/mm2, in particular however larger than 70 N/mm2.
Moreover the invention concerns an advantageous method for making the article molded in the manner of the invention. This method is characterized in that the aromatic polyester(s) in powder forrn are compacted under pressure, in that the compact-0ed powder is slowly heated, while the pressure is maintained, to temperatures higher than the glass transition point(s) of the polyester(s) used, in that the powder material so compressed and pressurized is kept at those temperatures for a substantial dwell-time in order to form a sintered article and in that the article sintered in this manner shall be slowly cooled. The powder-form polyester(s) are compacted in this process at a pressure exceeding 3,000 N/cm2, preferably however in excess of 5,000 N/cm2, for instance about 10,000 N/cm2.
In advarltageous implementations of the method of the invention, the slow heating of the compressed polyester powder takes place at a rate of l.S to 4.0 C/min and/or the slow cooling of the sintered article takes place at a rate of O.S to 2.5 C/rnin.
20In another advantageous implementation of the method of the invention, the dwell-time is in the range of S - 20 min/mrn of the mean thickness determined in the direction of the applied pressure of the sintered article to be manufactured.
In a yet further advantageous implementation of the method of the inven-tion, the cooling of the sintered article is carried out at least in part while at a pressure WO 92/13698 PC~7/~0~
which is much reduced compared to the maximum applied pressure. In a last advanta-geous implementation of the method of the invention, the sintered article is cooled at leas~ in part at a pressure which is much reduced compared to the applied maximum pressure.
s Several Ways to Implement the Invention The invention is elucidated below in relation to Examples. Ihe sintered articles made according to these Examples consist of aromatic polyesters as described in the European patents 64,972 and 64,971, namely 1. Aromatic polyesters based on .0 1,1-bis(4-hydroxyphenyl)-1-phenylethaneandphthalic-acidchloride(iso-tere 50/50) vith a glass transition point of 250 C measured by DSC and hereafter called CPE, 2. Aromatic polyesters based on 9,9-bis-(4-hydroxyphenyl)fluorene and phthal-ic-acid chloride (iso/tere 5Q/50) with a glass transition point of 325~ C measured by DSC
and hereafter called FPE.
s The raw material for the manufacture of the sintered articles are the polyesters in synthetic powder form which evince a mean molecular weight MW of 50,000 to 1,200,000, corresponding to an inherent viscosity in the range of 0.5 to 3.8 dl/g (measured in the rnanner of the above cited European patents). The screen fractions of the synthetic polyester powder with particles sizes less than 600,u, advantageously between 50 and 400 ~, shall be used.
Because of low particle sizes, these powder fractions evince high sintering activity. However by discarding the finest fractions, the bulk density is prevented from being unduly small, an eventuality which would be disadvantageous for pressing.
5 ~ 7~ 7~
The manufacture of a CPE sintered article by means of a so-called com-pression sintering process is described in further detail herebelow.
A heated mold is used to make the sintered panel with dimensions 200 x 220 x 4 rnm. Upon preheating the mold to 150 C, the CPE powder already previously heated at 150 C for several hours in a vacuum oven is introduced in bulk form with a density of 0.35 g/cm3 and in a suitable amount into the molding space of the lower mold half and the mold is closed by depositing on it the upper mold half entering the molding space. The mold is then moved into a press and the CPE powder is compressed at apressure of 5,000 N/cm2, the mold being slowly heated, that is at a rate of about .0 2 C/min to a temperature of 270 C, that is, above the CPE powder glass transition point of 250 C, and said temperature of 270 C is maintained for about 60 min. Thereupon the mold is cooled at a rate of about 1 C/min to 230D C, the compression is reduced to a low value of about 20 N/cm2 with the essential purpose merely to allow good heat dissipation, and then the mold is cooled further to 50 C and the finished sintered article is removed from the mold. The sintered body so made evinces a glass transition point of 250 C as determined by ASTM D 3418-82 and a density of 1.21 g/cm3.
FPE-powder sintered articles may be manufactured in the same manner.
In contrast with the manufacture of CPE sintered articles, a dwell-temperature of 330 C
(higher than the glass transition point of 325O C) was used for FPE and the pressure relief during cooling took place at 290 C. The FPE sintered article so made evinces a glass transition point of 325 C and a density of 1.22 g/cm3.
The CPE or FPE sintered articles evince an amber color and are resistant to alcohols, oils and fats.
~ .
-6- 2~79~9~
As already mentioned initially, compared with poured, pore-free sheets, the sintered articles evince higher resistance to some solvents such as carbon tetrachloride.
A poured sheet and a sintered article were made each from CPE and FPE
with each a mean molecular weight of about 500,000. Following re-dissolution of the ssheet or sintered-article material, the sheet material retained a molecular weight of 500,000 whereas the sintered material molecular weight had dropped to 50,000. Contrary to expectation, which was that the lower molecular weight of the sintered article would entail lower resistance to solvents, the sintered article did evince higher resistance to certain solvents than did the sheet material.
.0Comparison test results are shown below that relate to absorption of carbon tetrachloride by test samples, namely CPE and FPE sintered articles and sheet specimens resp., made from the same aromatic polyesters.
The tests were carried out on square specimens abou~ 0.7 to 1.1 rnm thick and 24 x 24 rnm resp. A sheet specimen (F) and a sintered-article specimen (X) were kept at room temperature (23 C) immersed in beakers filled with carbon tetrachloride for 4 h and 24 h and, thereupon, after wiping dry the surface, they were weighed and measured.
The results are as follows:
- 7 - 2 ~ 9 ~
Polyester Specimen rhickness Weight Weigh~, % %increas2 % weight (mm)Oh, g 4h, g increase in weight increase in weight 24 h s CPE lX 0,930,59~1~0,59~.5 1,6a3 0,59634,718 lF ~,950,57790,~805 4,499 0,!S87817,131 CPE 2X 1,020, 7û600,7073 1,841 0,70965,099 2F 1,04~0,70S20,7091 5,530 0,717817,867 CPE 3X 0,-t490,S0590,5071 ~,3?2 0,508~~,93 3F 0,7430,51d40,~166 ~,27~ 0,52141~.tO~
F~?E ~X 0, 98Q, a8220, 883~ 1, 360 O, 8854'1, 62~
4~ O,9~g~,8022~,8072 6,233 0,820222,438 FPE 5X 1,0080,89290,E19~0 1,232 0,89714,~04 S~ 1,014,81B~0,8230 S,l;!9 0,842~29,:S11 As shown by the above Table, the absorption of solvent after 24 h exposure is a multiple for the sheet specimens than for the corresponding sinter-article specimens.
s On the other hand, in the light of the known Russian publica~ion, there could be no differences in solubility between the specimens of sheets and of blocks pressed at higher temperatures, as explicitly stated for polyarylate products. In retrospect, the explanation may be that those blocks investigated by and in accordance with the Russian publication might not have been pore-free. In fact applicant carried out measurements on sintered articles that were not translucent because of insufficient sintering and manifestly still contained pores and found values of carbon-tetrachloride absorption substantially higher than for the translucent, pore-free sintered articles made according to this invention.
An improved method for sintering is described below. A mold is used in that method which is not self-heating but on the other hand it can be locked under pressure. After being filled with the polyester powder (CPE or FPE), this mold is moved into a press wherein the compressed material is pressed by 10,000 N/mt and the mold is locked under pressure, as a result of which even after the mold has been removed from .
wo 92/13698 - 8 - PC~/gT71/ooog1 the press, the two mold halves continue exerting a high pressure on the compressed material. Thereupon the mold is slowly heated in an oven at a rate of 2~ C/min to 279 C
(for CPE) and to 330 C (for FPE~ and those temperatures are maintained for 60 min when making a sintered panel 4 mm thick~ Thereafter the oven heater is shut off and the mold is allowed to cool. After it reaches a temperature 20 C below the particular glass transition point, the mold is then further cooled outside the oven down to 50 C and then the finished sintered article is removed from it.
It is important in the manufachure of the sintered articles that the mold be slowly heated and cooled. The permissible heating and cooling rates will be the smaller, .0 the larger the thickness of the sintered article to be made. Similar considerations apply also to the maximum mold-temperahlre dwell-times to be observed. As a rule of thumb, the dwell time ought to be about 15 min/mm of thickness of sintered article.
Several essential properties of the CPE or FPE sintered articles manu-fachured in the above manner are listed in the Tables below.
PC~ /AT91/00091 WO 92113698 ,~ ~3 7 ~ 7 9 ~
1. Mechanical Properties (DIN, room temperature) Property Unlt CPE FPE
s Tensile strength N/mm2 87 72 Tear resistance h 9.4 4.2 Young's modulus (traction) N/mm2 2500 2800 Bending strength 125 123 Young's modulus (bending) ~ 2550 2780 .0 Hardness Rockwell M 104 117 Shore D 88 g1 2. Tribologlcal Properties Measured on pin-pane apparatus per DIN 31680 Pane is made from rolled bearing steei with a surFace roughness F~ = 2 microns Unlts CPE FPE
Coefficient of friction 0.8 0.8 Wear coefficient mrn3 /Nm 3.5 x 10 5 19.0 x 1 ~"
_ 3. Thermal Propertles Unlts CPE FPE Procedure 3s Glasstransition point C 250 325 DSC
Thermal dimensional stability (procedure A) C 217.5 307 TMA
Unear expansion coefficient ~' 75 x 10 5 70 x 10 5 TMA
Thermal conductivity W/mK 0.19 0.25 - 10- 2~7~7~
4. Electrlcal Propertles sPROPERTY UNIT P R E - CPE FPi-TREATMENT thickness thickness (mm) (mm) value value Dielectric ratio at 1 MHz Climate contr~ 3.68 4 55 C48h/23~ C/50~ 1 Storageinwater 3.03 4.13 D24h/23 C
Dissipation factorat 1 MHz Climate control 18.7x10-3 16.4x1~3 C48h/23 C/50%
Storage in water 23.2x1~3 17.!jx1tr3 D24h/23 C
2~ Voiume resistance ohm climate contrOI 3-25 2X1014 3.97 1x1O'5 C48/23 C/50%
-5. Hygroscopic Properties PROPERTY UNIT CPE FPE
Water absorption (storage in water, 23 C, 24h) % 0.20 0.25 6. Combustlble Propertles OXYGEN INDEX
CPE 33.5 %
FPE 40.0 %
~ . .
~s Industrial Applicability As a rule the described sintered articles serve as semi-finished goods or as preformed construction blanks ~om which the desired end products then can be finished by conventional cutting processing.
Dissipation factorat 1 MHz Climate control 18.7x10-3 16.4x1~3 C48h/23 C/50%
Storage in water 23.2x1~3 17.!jx1tr3 D24h/23 C
2~ Voiume resistance ohm climate contrOI 3-25 2X1014 3.97 1x1O'5 C48/23 C/50%
-5. Hygroscopic Properties PROPERTY UNIT CPE FPE
Water absorption (storage in water, 23 C, 24h) % 0.20 0.25 6. Combustlble Propertles OXYGEN INDEX
CPE 33.5 %
FPE 40.0 %
~ . .
~s Industrial Applicability As a rule the described sintered articles serve as semi-finished goods or as preformed construction blanks ~om which the desired end products then can be finished by conventional cutting processing.
Claims (10)
1. A molded article essentially consisting of one or several aro-matic polyesters, namely polyarylates, manufactured from phthalic-acid halides and diphenols of the formula where R is a bifunctional hydrocarbon residue containing at least one aromatic or cycloaliphatic ring, characterized in that said molded article consists of a translucent, substantially pore-free sintered body with one or several glass transition point(s) in the range of 220 to 400°C measured by the DSC procedure and a DIN 53455 tensile strength larger than 40 N/mm2, advantageously larger than 60 N/mm2, and, in the form of a test specimen about 1.0 mm thick, evinces a carbon-tetrachloride absorption less than 1.0 %, advantageously less than 0.8 % of the specimen weight for a treatment duration of 24 h in a 23° C bath of carbon tetrachloride.
2. Article defined in claim 1, characterized in that it essentially consists of an aromatic polyester based 9,9-bis-(4-hydroxyphenyl)fluorene as diphenol.
3. Article defined in claim 1, characterized in that it essentially consists of an aromatic polyester based on 1,1-bis-(4-hydroxyphenyl)-1-phenylethane and evinces a DIN 53455 tensile strength larger than 50 N/mm2, in particular larger than 70 N/rnm2.
4. A method for manufacturing a molded article defined in one of claims 1 through 3, characterized in that the aromatic polyester(s) in powder form are compacted under pressure, in that the com-pacted powder subjected to maintained pressure is slowly raised to temperatures higher than the glass transition point(s), in that the powder mass so compressed and kept under pressure is kept for a substantial dwell-time at these temperatures to form a sintered article, and in that the article so sintered is slowly cooled.
5. Method defined in claim 4, characterized in that the polyes-ter(s) in powder form are compacted under a pressure in excess of 3,000 N/mm2, in particular in excess of 5,000 N/mm2.
6. Method defined in claim 5, characterized in that the powder polyesters are compacted under a pressure of about 10,000 N/mm2.
7. Method defined in one of claims 4 through 6, characterized in that the slow heating of the compressed polyester powder takes place at a rate of 1.5 to 4.0° C/min.
8. Method defined in one of claims 4 through 7, characterized in that the slow cooling of the sintered article takes place at a rate of 0.5 to 2.5° C/min.
PCTtAT91/00091
PCTtAT91/00091
9. Method defined in one of claims 4 through 8, characterized in that the dwell-time is in the range of 5 to 20 min/mm of the mean thickness of the sintered article to be made as determined in the direction of the applied pressure.
10. Method defined in one of clamns 4 through 9, characterized in that the cooling of the sintered article takes place at least in part under a pressure much reduced in comparison with the applied maximum pressure.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ATPCT/AT91/00017 | 1991-02-04 | ||
| PCT/AT1991/000017 WO1991011312A1 (en) | 1990-02-02 | 1991-02-04 | Aromatic polyester moulded compacts |
| PCT/AT1991/000091 WO1992013698A1 (en) | 1991-02-04 | 1991-07-26 | Moulded aromatic-polyester article |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2079795A1 true CA2079795A1 (en) | 1992-08-05 |
Family
ID=3682980
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002079795A Abandoned CA2079795A1 (en) | 1991-02-04 | 1991-07-26 | Moulded aromatic-polyester article |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0527957B1 (en) |
| JP (1) | JPH05504920A (en) |
| AT (1) | ATE112710T1 (en) |
| CA (1) | CA2079795A1 (en) |
| DE (1) | DE59103239D1 (en) |
| WO (1) | WO1992013698A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103381640A (en) * | 2012-05-03 | 2013-11-06 | 上海市纺织科学研究院 | Preparation method for high temperature-resistant polysulfonamide sheet material |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6177645B2 (en) * | 2013-09-30 | 2017-08-09 | ユニチカ株式会社 | Prepreg and manufacturing method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3558550A (en) * | 1967-02-07 | 1971-01-26 | Montedison Spa | Sinterings of polytetrafluoroethylene loaded with titanium and the preparation thereof |
| BE789542A (en) * | 1971-10-01 | 1973-03-29 | Carborundum Co | PRODUCTION OF INFUSIBLE AND FORMABLE PARA-OXYBENZOYL POLYESTER |
| US4011293A (en) * | 1973-08-21 | 1977-03-08 | E. I. Du Pont De Nemours And Company | Toughened linear aromatic polymers |
| US3980749A (en) * | 1973-08-31 | 1976-09-14 | The Carborundum Company | Partially crosslinked linear aromatic polyesters |
| ATE33027T1 (en) * | 1981-05-07 | 1988-04-15 | Isovolta | HIGH MOLECULAR MOLECULAR AROMATIC POLYESTER, PROCESS FOR MANUFACTURE OF FILM FROM SUCH POLYESTER AND FOIL FROM SUCH POLYESTER, ELECTRICAL CONDUCTOR WITH INSULATION FROM SUCH POLYESTER AND METHOD FOR MANUFACTURE OF SUCH INSULATION. |
| CA2050310A1 (en) * | 1990-02-02 | 1991-08-03 | Peter Fialla | Aromatic polyester moulded compacts |
-
1991
- 1991-07-26 CA CA002079795A patent/CA2079795A1/en not_active Abandoned
- 1991-07-26 DE DE59103239T patent/DE59103239D1/en not_active Expired - Fee Related
- 1991-07-26 JP JP3512325A patent/JPH05504920A/en active Pending
- 1991-07-26 AT AT91913567T patent/ATE112710T1/en not_active IP Right Cessation
- 1991-07-26 WO PCT/AT1991/000091 patent/WO1992013698A1/en active IP Right Grant
- 1991-07-26 EP EP91913567A patent/EP0527957B1/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103381640A (en) * | 2012-05-03 | 2013-11-06 | 上海市纺织科学研究院 | Preparation method for high temperature-resistant polysulfonamide sheet material |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0527957A1 (en) | 1993-02-24 |
| WO1992013698A1 (en) | 1992-08-20 |
| JPH05504920A (en) | 1993-07-29 |
| EP0527957B1 (en) | 1994-10-12 |
| DE59103239D1 (en) | 1994-11-17 |
| ATE112710T1 (en) | 1994-10-15 |
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