JPH04504546A - Molded objects from aromatic polyester - Google Patents

Abstract

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

Description

[Detailed description of the invention] Molded objects from aromatic polyester Technical field The present invention provides one or more phthalic acid halides produced from diphenols and phthalic acid halides. The present invention relates to a molded article made of aromatic polyester.

Current state of technology Moldings of this type are known, for example, from European Patent Specification Letters 64971 and 6497. No. 2, in the form of a film produced by casting from a polyester solution, It is publicly known. However, the polyester described in European Patent No. 64972 is 1,1 - based on bis(4-hydroxyphenyl)-1-phenylethane, This requires extrusion or injection molding as it requires high processing temperatures of 330-400℃. It is recognized that it is difficult to process by 9,9-bis(4-hydroxyphenyl)fluoro, known from Japanese Patent Application No. 64971. Ren-based polyesters generally have no melting range, with temperatures as high as about 400°C. It is known that thermal decomposition begins at a certain temperature.

Description of the invention The present invention, as opposed to a film, is a wide (can take any form, The object is to provide a molded article of the type described above.

Such a problem arises when measuring by DSC at a temperature in the range of 220 to 400℃. one or more glass transition points and higher than 4ON/mm”, preferably 6O Consisting of a sintered body with a tensile strength according to DIN 53455 higher than "N/mm" This problem can be solved by the molded article according to the present invention, which is characterized by the following. In this case The aromatic polyester used may have one or more formulas is advantageously based on a diphenol of (Both are hydrocarbon groups containing one aromatic or alicyclic ring.

Using starting materials of the same type and quality, the sintered body according to the invention can be made into a cast film. It has a high resistance to certain solvents such as carbon tetrachloride compared to It is recognized that These facts and those described in further detail herein Other facts indicate that the polyester forming the sintered body has some degree of crosslinking. It can be concluded that

In one preferred embodiment of the invention, the sintered body according to the invention is essentially 9.9-bi Based on (4-hydroxyphenyl)fluorene (composed of aromatic polyester) ing.

Another preferred embodiment of the sintered body according to the invention consists essentially of 1.1-polyester. It consists of

The invention furthermore relates to an advantageous method for producing the moldings according to the invention.

This method involves compressing powdered aromatic polyester under pressure, compressed powder The body is heated to a temperature higher than the glass transition temperature of the polyester used while maintaining its pressure. gradually heating the powder to a new temperature, thus compressing the powder and under pressure. holding at three temperatures for a predetermined holding time until a sintered body is formed; It is characterized by slowly cooling the sintered body obtained as described above. in this case Polyester in powder form is exposed to pressure higher than 3000 N/c+a2, preferably or a pressure higher than 500 ON/am", for example about 10,0 OON/cm" It is advantageous to compress under a pressure of .

According to a preferred embodiment of the method of the invention, the compressed polyester is slowly The heating is carried out at a heating rate in the range of 1.5 to 4.0°C/min and/or the sintered body is heated slowly. The cooling is carried out at a rate ranging from 0.5 to 2.5°C/min.

In another preferred embodiment of the method of the invention, the sintered body to be produced is pressurized. Using holding times ranging from 5 to 20 minutes per mm of average thickness measured in the direction .

In yet another preferred embodiment of the method of the invention, at least in part The sintered body is cooled under a pressure load that is significantly lower than the maximum pressure applied. cormorant.

A method for carrying out the invention Next, the present invention will be explained in detail according to examples.

The sintered bodies produced by these examples are described in European Patent Nos. 64972 and 6. Two aromatic polyesters, such as those described in No. 4971: 1. 1° 1-bis( 4-Hydroxyphenyl)-1-phenylethane and phthalic acid chloride (iso/te Aromatic polyester (hereinafter referred to as CPE) based on 2, 9. 9-bis(4-hydroxyphenyl)fluorene and chlorine phthalate Glass temperature of 325°C as measured by DSC based on An aromatic polyester (hereinafter referred to as FPE) that exhibits a transition temperature.

Starting materials for the production of sintered bodies have an intrinsic viscosity of 0.5 to 3.8 dl/g ( 500,000 (measured as described in the aforementioned European patent) Produced as a powder during synthesis with an average molecular weight MW of ~1,200,000 Use recycled polyester. 6 in the polyester powder produced during synthesis A sieve with a particle size of less than 00 μm, preferably between 50 and 400 μm Use fractions.

Such a powder fraction exhibits good sinterability due to its small particle size.

However, the exclusion of even the finest fractions poses a disadvantage to the pressing technique. This prevents the packing density from becoming too low, which could result in

Next, the production of a sintered body from CPE by the so-called pressure sintering method will be explained in detail. .

A heatable mold is used to produce a plate-shaped sintered body with dimensions of 200 x 220 x 4 mm. use After preheating the mold to 150℃, first pour zero into the cavity in the lower half of the mold. , a corresponding amount of vacuum-dried CPE powder with a packing density of 35 g/ctm”. The mold is closed by loading the lower mold half, which is pushed into the mold cavity. Jiru. Next, the mold was transferred to a press, and the CPE powder was compressed with a compression force of 500ON/cm. CPE at 250°C with a heating rate of approximately 1°C/min. heating to 270°C, which is higher than the glass transition point of Hold for 0 minutes. The mold was then cooled to 230℃ at a rate of ℃/min, and then the pressure was reduced. , only to ensure good thermal conductivity, about 20 N/c m2 to a low value, after which the mold is further cooled to 50°C before finishing. The rising sintered body is taken out from the mold. The sintered body thus obtained is ASTM D Glass transition temperature of 250 °C and 1,21 g/cm’ as measured according to 3418-82 It has a density of

Similarly, sintered bodies can also be produced from FPE powder. CPE sintered body The difference between manufacturing and FPE is that the latter has a glass transition temperature of 330°C (325°C). Processing is carried out at a holding temperature of That is true. The FPE sintered body produced in this way has a glass transition point of 325°C. and a density of 1.22 g/cm''.

Sintered bodies from CPE or FPE have an amber color and are free from alcohol, fats and oils, Resistant to grease.

As mentioned above, polyester becomes reticulated upon sintering.

Casting from CPE and FPE each having an average molecular weight MW=about 500.000 A film and a sintered body were manufactured. After remelting the film or sintered material, the film The sintered material also showed a molecular weight MW of 500.000, whereas the sintered material showed a molecular weight MW of 500.000. The molecular weight decreased to a value of MW=50,000. In terms of the reduced molecular weight of the sintered body , even though its resistance to solvents would also be expected to decrease as well. , unlike that, sintered bodies are more resistant to certain solvents than film materials. shows. For example, in a 90 hour immersion in carbon tetrachloride, the CPE In the case of aluminum, it absorbs about twice as much solvent as in the case of sintered material, and in FPE it is nine times as much. Become.

Next, an improved method for producing a sintered body will be described below. In this method, It cannot heat itself, but instead the obturator can be under pressure. Use the type shown below. Pour the mold after filling with polyester powder (CPE or FPE) The contents of the mold were then compressed to approximately 10°00 ON/cm” and pressed. After removing the mold from the mold, both mold halves still exert high pressure on the contents. The mold is closed under pressure so that it can be closed. The mold is then slowly placed in a heated oven. i.e. 270°C (for CPE) or 33°C at a heating rate of 2°C/min. Heating to 0 °C (for FPE) and 60 minutes for production of 4 mm thick sintered plates. Maintain this temperature for a long time. After that, stop heating the oven and let the mold cool. So After reaching a temperature 20°C lower than the respective glass transition points, the molds were removed from the oven. The sintered body is further cooled to 50° C., and then the finished sintered body is taken out.

In the production of sintered bodies, it is important to slowly heat and cool the mold. . The permissible heating and cooling rates are lower the greater the thickness of the sintered body to be produced. . The same applies to the holding time required for the highest mold temperature. oh As a rough standard, a holding time of approximately 15 minutes should be used for each mm of thickness of the sintered body. It is possible.

In the table below, the sintered body produced from CPE or FPE as described above ( Indicates some important quality.

1. Mechanical properties (room temperature, according to DIN standards) Properties Unit: CPE FPE Tensile strength N/mm287 72 Cutting elongation % 9.4 4.2 Elastic modulus (tensile) N/i++a22500 2800 Bending strength N/mm21 25 123 Elastic modulus (bending) N/Gate 22550 2780 Hardness Rockwell M 104 1 17 Shore D 88 91 Measured with a bottle-disk measuring machine according to DIN 31680. Surface roughness Ry=2μm Units using discs made from roller bearing steel: CPE, FPE Friction number 0.8 0.8 Wear coefficient Ql13/Nl 3.5・10-' 19.0・10-6 unit CP E FPE method Glass transition point ’C25032S Shape stability by DSC heat ℃217.5 307 TMA (Method A) Linear expansion coefficient K-' 75.10-' 70.10-' Tel^ Thermal conductivity 1 /mK　O,190,254, electrical properties (Illm) (關) dielectric constant (at IMHz) - Room temperature storage 3.68 4.55C48h/23℃15 0% Storage in water 3.03 4.13 D24h/23℃ dielectric loss (at IMHz) - Room temperature storage 18.7-10-' 16.4-10-' C48h/23℃150% Storage in water 23.2・10-317.5・1O-3D24h/23℃ Electrical resistance ohm - room temperature storage 3.252.10'43.971.10I5C 48/23℃150% Properties Unit CPE FPE Water absorption rate (Stored in water, 23℃, 24 hours) % 0.20 0.25 Oxygen index: CPE 33.5% FPE 40.0% Industrial applicability The above sintered body can generally be used as a semi-finished product, that is, a material for molded parts. , then the desired product can be manufactured from it by normal mechanical cutting. Ru.

Summary book Dibuenols, such as 1,1-bis(4-hydroxyphenynolyl-phenylene) ruethane or 9,9-bis(4-hydroxyphenyl)fluorene, and phthal Sintered bodies made of aromatic polyesters produced on the basis of acid halides are one or more glass transition points in the range of 400°C and greater than 4ON/mm” Large, preferably thicker than 6ON/mm' (indicating bow 1 tensile strength).

For the production of the above sintered body, 300ON/L was added to the polyester powder in a closed mold. cm", the mold is heated slowly and the glass is heated for a long time. The temperature is maintained above the transition point and then slowly cooled. Reduce pressure during cooling Shitsuru. Crosslinking of the polyester material occurs during the sintering process, increasing its resistance to solvents. sex increases. These sintered bodies are generally semi-finished products or preformed semi-finished parts. These parts can then be machined into desired products. I can do it.

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Claims (11)

[Claims] 1. Glass transition temperature in the range 220-400°C as measured by DSC and 4 DIN 5345 higher than 0 N/mm2, preferably higher than 60 N/mm2 essentially a diphenol, characterized in that it is a sintered body having a tensile strength of one or more aromatic polyesters made from alcohol and phthalic acid halides A molded body consisting of 2. Aromatic polyesters have one or more formulas ▲ mathematical formulas, chemical formulas, tables, etc. S▼ diphenols, and its tensile strength is higher than 70 N/mm2 The molded article according to item 1 above, characterized in that: 3. Essentially 9,9-bis(4-hydroxyphenyl) as diphenol Item 2 above, characterized in that it is made of an aromatic polyester based on fluorene. molded body. 4. Essentially 1,1-bis(4-hydroxyphenyl)-1-phenylethane based aromatic polyester and higher than 50N/mm2, especially 70N characterized by having a tensile strength according to DIN 53455 higher than /mm2 The molded article according to item 2 above. 5. Compress powdered aromatic polyester under pressure and maintain the pressure of the compressed powder Below, the polyester used is heated slowly to a temperature higher than its glass transition temperature. The powder thus compressed under pressure is then compressed to a predetermined length until a sintered body is formed. Maintain this temperature for the holding time and slowly cool the sintered body. A method for producing a molded article according to any of the above items 1 to 4, characterized in that: 6. Powdered polyester at higher than 3000N/cm2, especially 5000N/cm2 6. The method according to item 5, characterized in that the compression is carried out under a pressure higher than cm2. 7. Compressing powdered polyester under a pressure of approximately 10,000 N/cm2 The method according to item 6 above, characterized in that: 8. Slow heating of compressed polyester powder ranges from 1.5 to 4.0°C/min. 8. The method according to any of the above items 5 to 7, characterized in that the heating is carried out at a heating rate of . 9. Slow cooling of the sintered body may be carried out at a rate in the range 0.5-2.5°C/min. The method according to any of the above items 5 to 8, characterized in that: 10. The holding time is calculated based on the average specific thickness of 1 mm in the pressing direction of the sintered body to be manufactured. 10. The method according to any of the above items 5 to 9, wherein the heating time is in the range of 5 to 20 minutes. 11. The cooling of the sintered body is, at least in part, at a temperature significantly lower than the maximum pressure applied. 11. The method according to any of the above items 5 to 10, characterized in that the method is carried out under the effect of reduced pressure.