TW397849B - Liquid crystalline poly(ester-imides) - Google Patents

Description

A7 B7 V. Description of the Invention (1) This application is US Patent Application No. 08/24, filed on May 17, 994, 288 and titled Liquid Crystal Poly (Ester-Amidine), partly connected Mine application 0 The invention of backside heat-resistant% crystalline polymers can be used for many purposes, especially as a resin for manufacturing < electronic connections and mechanical parts such as automotive parts. Although many such polymer compositions are known, novel compositions with desirable properties and low yields are continuously sought. U.S. Patent Nos. 4,727,1.29 and 4,728,714 and Japanese Patent 4-66259 describe a polymer containing only aromatic repeating units, some of which are derived from trimellitic anhydride and tertiary butylquinone. The present invention relates to a new orientated thermotropic liquid crystal poly (ester-fluorenimine) containing repeating units and other monomers derived from a third butyl hydrogen roller and styramic anhydride on the first floor. These polymers can be used as molding Resin, and when used in combination with polytetrafluoroethylene can be used for abrasion resistance. Summary of the Invention The present invention relates to a liquid crystal which is basically composed of a repeating unit of the following formula (please read the precautions on the back before filling this page).

This paper size applies to China National Standard (CNS) A4 specification (2 丨 0X297 mm) _4 A7 B7 V. Description of the invention (2) M Central Government Standards Bureau, Ministry of Economic Affairs, Consumer Cooperative Printing

(Please read the precautions on the back before filling this page) The size of the paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) A7 B7 V. Description of the invention (3) Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ¾ .. where the amount of (1) + (1) constitutes 10 to about 30 moles of the repeating unit,! K; the amount of (M) + (IV) + (V) constitutes 0 to of the repeating unit About 70 mol *; Υ is p-phenylene or R is chlorine, phenyl or an alkyl group containing 1 to 4 carbon atoms; and Z is -〇 (〇) —, -_s_ | -0 (^ -V The liquid crystal polymers disclosed herein are derived from substituted hydrogen hydrazones, polytrimellitic anhydride (TMA), and other monopoly (ester-trimethylene). Units (I) and (I) contain TMA as fluorene-containing Part of the imino dicarboxylic acid monomer, the ammonium group will react with the hydrogen substituted hydrogen hydrazone. Those skilled in the art will understand that in all the single charge 1 shown in the above formula, the "R" The radical can be in all positions of the stupid ring to which it is connected (relative to the rest of the repeating unit). The second floor acid of formula (I) can be prepared by the reaction of TMA with p-amino stearic acid, and the formula ( 1) Dijunic acid can be obtained from 2 Moore TMA is made by reacting with suitable diamines, for example, with 4,4, -oxydibenzylamine and p-phenylenediamine. Except for the repeat rare units (V) derived from p-phenylbenzoic acid (PHBA) In addition, all other repeating units contain an ester linkage to a suitable dicarboxylic acid having a substituted hydrogen wax. In the repeating units (M) and (IV), the dicarboxylic acids are parabendicarboxylic acid and 2, 6-Qinic acid. In some preferred polymers, the repeating unit (I) or U) is a repeating unit of 105; in other preferred polymers, there is only one unit u), ( Please read the notes on the back before filling this page) The size of the paper is applicable to the Chinese national standard (CNS) A4 (210X29 · 7 mm) _6 A7 __._ B7 V. Description of the invention (4) Central Ministry of Economic Affairs Printed by the male consumer co-operative of the Bureau (IV) or (V), and (I) ,; (I) or (I) + (I) the director (as the case may be) of Ju Fei. · · Compound of about 50 to 100 Dear Ears. In the preferred polymer, γ is and preferably Z is -0-. In the preferred polymer, the repeating units (I) and (I) constitute a repeating unit of 100 «In other preferred polymers, R is methyl Or a third butyl group, more preferably a third butyl group. -. The poly (ester-fluorenimine) of the present invention can be prepared by a method well known in the art, such as a suitable dicarboxylic acid, which can be polymerized by substituting hydrogen and P 及 Β A (if present) to form a polymerization reaction mixture. . The hydroxyl groups of substituted hydrogen hydrazone and PHBA, when added to the polymerization reaction mixture, can be formed in situ by reaction with stoichiometric lower alkylcarboxylic anhydrides such as acetic anhydride. After the acetate is formed, the temperature is increased to condense the monomers into polymers and to distill off low-carbon carboxylic acid by-products such as acetic acid. Usually at the end of the polymerization, a vacuum M is applied to give the final polymer the desired molecular weight or viscosity. The final temperature is generally about 3001C to about 360 °. A catalyst such as potassium acetate M may be added to accelerate the polymerization reaction. The polymers of the present invention can be mixed with materials conventionally known as polymers, such as pigments, colorants' antioxidants, flame retarders, lubricants, toughening agents and fillers, including glass, minerals such as clay and talc ), Carbon fiber, and carbon fiber. In addition * the polymers of the invention can be mixed with other polymers. Those skilled in the art will appreciate that the conventional additives listed briefly above are merely illustrative and do not explicitly describe every material that can be mixed with the polymers of the present invention. (Please read the precautions on the back before filling this page) The size of the paper used in this edition applies to the Chinese National Standard (CNS) Α4 specification (2 丨 0X297 mm) A7 ______B7 V. Description of the invention (5) Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs The printed polymer of the present invention can be used as a molding resin for electronic connections, automotive parts, and other applications. It usually has a high glass transition temperature and is particularly blendable with tetrafluoroethylene polymers for parts requiring good abrasion properties such as friction. When the polymer of the present invention is blended with a tetrafluoroethylene polymer, the tetrafluoroethylene polymer is a polymer in which about 902 or more repeating units are derived from tetrafluoroethylene, ie, having a CF2CF2- structure. It is preferred that any other comonomer in the tetrafluoroethylene polymer is a perfluorinated one. A particularly preferred tetrafluoroethylene polymer is a homopolymer of tetrafluoroethylene (ie, polytetrafluoroethylene (PTFE)). Tetrafluoroethylene polymers are commercially available in various grades K. Tetrafluoroethylene polymers can be in the form of fine powder, granules or fibers. If a dimensional shape is used, it is preferred that the fiber length is small, preferably 0.4 mm or less, and that the fiber is less than 10 denier / single. If the tetrafluoroethylene polymer is PTFE, various grades can be used, such as granules or powder * K powder is preferred. Manufacturers of PTFE have special grades, which are recommended for use in blends where wear resistance is particularly important, and these grades are particularly suitable for blending with the liquid crystal polymer of the present invention. The blend with the tetrafluoroethylene polymer preferably contains about 3 to about 50 weights X, more preferably about 10 to about 40 weights S :, and most preferably about 20 to about 35 weights ^: of the tetrafluoroethylene polymer. , Which is based on the total weight of M poly (ester-fluorene) and tetrafluoroethylene polymer. In the example of the window example, the following abbreviations are used: ”AA” -Acetic anhydride (read the precautions on the back before filling this page) The size of the paper is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) _8 ΑΊ Β7 V. Description of the invention (6 DSC "-differential scanning card meter HM" -heat of fusion, J / g 2,6-fT-2,6-naphthalenedicarboxylic acid T "-p-dibenzoic acid Tg "-glass transfer Temperature TπΓ'-Melting point. TBHQ "-Third butylhydroquinone TMB " -Dicarboxylic acid having the following structure

co2h TMO "-a dicarboxylic acid having the following structure.

(Please read the precautions on the back before filling this page) Order the printed window of the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. Example 1 -TMR ^ Preparation of 200 g of stearic anhydride and 145 g of p-aminobenzyl formate_ and 1 Liter of Ν, Ν-dimethylformamide (" DMF ") was added to a 2 liter four-necked round-bottomed flask. A condenser tube, a mechanical stirrer and a thermometer were attached to the flask, and the paper cover was heated by electricity and the paper was heated. Standards are applicable to Chinese National Standards (CNS) A4 specifications (210 × 7 mm) _9_ A7 B7 V. Description of invention (7) The contents of the stirrer flask printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, the contents are stirred and heated for 4.5 hours 'Then let the solution cool to room temperature, then add 1 liter of methanol under stirring, followed by ore stirring for 5 minutes, use a magnetic funnel to pass through the resulting precipitate for the solid and liquid mixture, and wash the solid Ml with formic acid. Then, 2 liters Distilled water was boiled in a 4 liter beaker and the washed solid was added under stirring, followed by stirring for 5 minutes. The resulting mixture was filtered using a magnetic funnel and the solid was washed with 1 liter of methanol. The solid product was poured into a vacuum oven with nitrogen flowing at about 170T. Dry for about 18 hours at C. Preparation of g 酴 剜 2-TMM 299 g of trimellitic anhydride is dissolved in a four-necked round bottom flask containing 500 ml of DMF, which is equipped with a calcium sulfate dry tower, mechanical stirrer, thermometer The reflux condenser and the funnel were added one by one. The acid anhydride solution was heated to 50 scoops, and 350 ml of DMF solution containing 4-aminobenzyl ether (150 g) was added dropwise to the acid anhydride solution through the addition funnel over one hour. Subsequently, the resulting solution was added. Heat to reflux for 3 hours, and then cool to room temperature. Add 1 liter of formazan to the anti-content and recover the product by depressurization. Stir the recovered yellow solid in 2 liters of boiling water for several minutes. Ml liter of formic acid was washed, and the solid product was dried in a vacuum oven under nitrogen blowing at about 100 * 0 for about 24 hours. The DSC Tη of the product was 3801; and no unreacted anhydride or partially reacted amidine was detected-醯. When Dangli 1-7 prepared all the polymers of 贲 Examples 1-7 by the same basic steps. The polymerization components listed in Table 1 were added to a resin kettle equipped with a stirrer and the liquid metal bath was used under nitrogen. Medium heating, the bath is heated to reflux at about 170¾, and the reflux is performed for 1 hour, Later, when the temperature of the golden bath gradually increased to about 31 ° t during about 2.5 hours: the acetic acid was distilled off; the temperature slowly rose to about 350t: to 360t, and (Please read the precautions on the back before filling (This page), ιτ This paper size applies to Chinese National Standards (CNS) A4 specifications (210X297 mm) A7 ___B7 V. Description of invention (8) Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economy Slowly reduce pressure within 1 to 2 hours Until it reaches about 133-1330 bar. The pressure is reduced but the golden bath is maintained at 350 t: to 360 t :. The temperature is maintained at a low pressure until the required viscosity is reached (measured by the current draw of the stirrer motor), which takes 4 hours. . Subsequently, the stirring was stopped and the polymer was removed from the resin kettle. The polymer was cooled and subjected to DSC analysis. The ingredients and polymer properties used to make the polymers of each example are shown in Table 1 ° In all examples, Tg and Tm are measured by DSC at a heating rate of 25 t: / min. The reported Tg and Tm polymers are the first The value of the secondary heating. The midpoint of M transfer was taken as the maximum of Tg and the melting endotherm of M was taken as Tib. Example 8 The apparatus used to make the polymer containing this methyl hydrogen roll was the same as in Example 1-7. After the acetic acid was refluxed for 40 minutes *, it began to output. When the temperature reached about 190t :, the reaction mixture became lumpy and stopped stirring. The temperature of the bath was set at 330 10. At this time, the reaction mixture was melted and stirring was started again. The temperature rose to 340t: the output of acetic acid was started again, and the completion under vacuum was at 340 ° C, and the vacuum was applied as described in Example 1-7. The ingredients used to make the polymer are shown in Table 1 along with the polymer properties. Clover Example 9-10 In Example 9-10, a blend of poly (ester-fluorenimine) and polytetrafluoroethylene was prepared and tested for abrasion resistance. In Example 9, the poly (ester-etherimine) of Example 1 was used, and in Example 10, the poly (ester-imide) of Examples 4 and 5 were used together (the two are the same). The polytetrafluoroethylene used in Examples 9 and 10 is a Teflon® fine powder with an average particle size of 20 microns and is recommended for lubrication and abrasion purposes (please read the precautions on the back before filling this page). Standards are applicable to China National Standard (CNS) A4 specifications (210X deduction 7 mm).-V. Description of invention (8) A7 B7 Printed by the Pike Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Μ P 1 5 0 0 PTFE (purchased from E. I. du Ρ de nt de N e ιη 〇ursand Company), hereinafter referred to as MP 1 500. The LCP-PTFE blends of Examples 9 and 10 were prepared as follows. Dry and granulated LCP is blended with MP 1500 to obtain a blend containing 70 weight LCP and 30 weight X MP 1500. This blend is at 1 ^ 1'1161'-? '; (* 16〗 € | 6 ^ 1'.28mm twin-screw extruder (equipped with standard mixing screw, vacuum receiver connected to the mixing zone and 4.8mm diameter ring die) are melt-mixed. The temperature of the barrel and die is set at an appropriate temperature ( That is higher than the Tg and Tm of LCP in the blend, the spiral is 150 rpn, and the blend is extruded at a rate of μ 5.8 kg / hour. The blend is pelletized, dried, and then the barrel temperature is set higher than The Tg and Tm of the LCP in the blend were injection molded on a 170 g injection molding machine with a mold temperature set at 100.0. The blend was molded into a 3.2 mm thick flex bar per ASTM D790. Abrasion For the test, the self-deflecting rod was cut into 6.35 mm square (3.2 mm thick) "pins", and the three pins were set on a 3.18 cm outer diameter circular support at intervals of '120 °. The original longitudinal axis of the flexing rod Set the ring tangentially to 2.38 cm average diameter. Pin M pressure P axial load pressure 3.18 cm outer diameter and 1.59 cm inner diameter steel washer (by the American Iron and Steel Association) Made from 1018 carbon mesh and has a coarseness of 0.40 mm (AA). The scrubber rotates at a V rate (measured at the average diameter of the scrubber (2.38 cm)). The temperature of the scrubber is measured and this temperature is regarded as LCP-PTFE The temperature of the surface of the blend is summarized in the following table 2. The higher the pressure (P) and / or the rate (V), the more stringent the test and the better the abrasion. Κ is the volume abrasion rate in addition to M PV and the reporting unit It is (cm 2 / kg) X10S. The lower the K value, the better the abrasion resistance of the blend (please read the precautions on the back before filling this page),?! This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 (Mm) A7 B7 5. The invention description (10) is good, and Table 2 also shows the scrubber temperature (W. temperature) KC indicates that the blends of Examples 9 and 10 both show excellent abrasion resistance. (Please first Read the notes on the back and fill in this page) Order the paper printed by the Central Consumers Bureau of the Ministry of Economic Affairs, Consumer Cooperatives. The paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) Knowing 5 Ugly Businessmen's 100 ppmfNlg® ^ Banknote Cutoff. ^^^^ ι ^^ δΗ4330θϊΓΓ-. 'f L; sJ ^ ris De painting by% m2009t! 童 {b. Hoofs's ^ sd''ffinsM ^ aisa. ff 2_i§ci-a ^ # ^ srs®. A7 B7 ¾ wa 4cr ¾ 6. 7 8 238.3 342.1 ^ 6.9 263.6 22.6 348.9 477.5 442-6 ¥ »

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TBHQ

47U 352.7 253.1 50 18 50 .Mw% Τω 478.0 686.00 6S6.8 454.6 346.0 50 § 18 50 30 135.1 144.9 50 50 M.%

TMO (Please read the notes on the back before filling this page) Thank you for ordering% 179.4 318 · 5 50 30 M'w% 2,62: mi

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PHBA 226 217 189 201 203 187 211 162 3200 336 § 3150. 31¾ 232 364 331 2.4 Production 1 1.0 20 2.8 1.2 Production 6 1.6 This paper size applies to China National Standard (CNS) A4 specifications · (210X297 mm) -14-

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o-sH 391840 at B7 V. Description of the invention (l2) Yiyi 2 «P (MPa) V (Μ / Μίη) κ, W. Temperature / (° α · / 9 2.76 53.3 16.4. 167 2.76 61.0 1276 196 10 2.76 53.3 27.6 166 2.76 > 61.0 18.9 146 (Please read the notes on the back before filling out this page)-^ · Ordering printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs This paper size applies the Chinese National Standard (CNS) A4 specification (210X297) %) _15_

Claims (1)

Patent No. 84105416 by You 庵 v * Manuscript Series Patent Amendment and April) Positive charge repair 4th E April 185. # Patent application scope 397840 Birch liquid crystal polymer, which is mainly composed of one or two repeating units (I) 0 0 II -C 0 R And (Π) Ο η R -0- and optionally one or more of the following repeating units (ΠΙ) I ------ 1T / 31¾ (please read the note on the back first and then fill out this page) Central Ministry of Economic Affairs Ministry of Economic Affairs r fee cooperative print R This paper size applies to Chinese National Standards (CNS > A4 specifications (210X2 ^ mm pen 84105416, patent request please 庵 v * text by the patent circle revised version and April) Positive charge repair 4th E April 185. # Patent application scope 397840 Birch liquid crystal polymer, which is mainly composed of one or two repeating units (I) 0 0 II -C 0 R And (Π) Ο η R -0- and optionally one or more of the following repeating units (ΠΙ) I ------ 1T / 31¾ (please read the note on the back first and then fill out this page) Central Ministry of Economic Affairs Ministry of Economic Affairs r fee cooperative print R This paper size applies to Chinese national standards (CNS > A4 specifications (210X2 ^ mm 3S7840 A8 B8 C8 D8 VI. Patent application scope 0V) And (V) 0 I! -C where (ΐ > + (1) is 30-100 moles of repeating unit 3 !; (18) + (IV + (V) is 0 to 70 moles of repeating unit S;; Υ is p-phenylene or R is third butyl; and Z is —〇——, —C (O)-S. (Please read the notes on the back before filling this page) Liang Jun Bureau Shellfisher Consumer Cooperative Printing Co., Ltd. 2. -C (CH3) 2—or—so2 The liquid crystal polymer according to item 1 of the scope of patent application, wherein 100 χχ of the repeating unit is (1 > and (1 ) Or 100 mol 5K of the repeating unit is ([> or (I) 根 root application patent _ item 2 of the liquid crystal polymer, which includes ([> or (1 [>. This paper The standard is applicable to the country's national ratio (CNS) A4 specification (210 × 297 mm) A8 397849 cl D8 6. Application for patent scope 4. The liquid crystal polymer according to item 1 of the patent scope, which includes (I), (IV ) Or (V). 5. The liquid crystal polymer according to item 3 of the patent application scope, wherein (I) or (I) is 50 to 100 moles of the repeating unit 3: 6. According to the application Liquid crystal of item 3 of patent scope Compound, wherein (I) or (E) is at least 50 mole% of the repeating unit. 7. The liquid crystal polymer according to item 1 of the patent application scope, wherein the repeating unit is mainly composed of (I) or ί I) and (If) and (IV) or 8. It is composed of the liquid crystal polymer of the first patent scope, where Y is 9. According to the liquid crystal polymer of the fourth patent scope, where Y is i 0. The liquid crystal polymer of the sixth scope of the patent application scope of Genbo, among which Y is printed by the Ministry of Economic Affairs, the Ministry of Economic Affairs and Consumer Cooperatives < please read the precautions on the back before filling in this page) _0 ~ (^) — Π. The liquid crystal polymer of item 丨 of the patent scope is a blend of polytetrafluoroethylene. The paper size is applicable to China National Standard (CNS) A4 (210X297 mm) A8 B8 C8 D8 397849 Patent application scope 12. Liquid crystal polymer according to item 11 of the patent application scope, wherein the polytetrafluoroethylene is 10 to 50 weight of the total weight of the blend of the liquid crystal polymer and the polytetrafluoroethylene 1¾. (Please read the notes on the back before filling out this page) Printed by Consumer Cooperatives This paper is sized for China National Standard (CNS) A4 (210 × 297 mm)