經濟部中央榣準局β工消t合作社印製 Λ 6 ΙΪ6 五、發明説明（1 ) 本發明俗有關一種含有長鏈脂族二酸酯單位的熱向性 液晶共聚酯，其為（1) 4,4'-二羥基聯苯，（2)碩數目為 6-12的脂族二酸，及（3)碩數目為13-20的艮鏈脂族二酸的 共聚合體。此種共聚酯具有熱向性液晶性質，並具有優異 的韌性，可作為熱塑性塑膠。 [先前之技藝] 4，4 '二經基聯苯（4,4'-dihydroxybiphenyl)與碳數 目為6-12的脂族二酸（aliphatic diacid)的均聚合體可形 成液晶相[A.Blumstein, K.M.Sivaramakrishnau , R.B. Blumstein and S.B.Clough, Polymer, 23， 47 (1982)及 J.Arsar , H.Toriumi, J.Watanabe, W.R.Kr i gbaum, A. Cifferi and J.Preston, J.Po1ym.Si.Po1ym.Phys. Ed., 21，Π19(19δ3)]。此種液晶均聚酯具有明潁的液晶特性 ，但其結晶度很商（ΔΗηι約為10cal/g)，待性非常脆，無 法作為優良的熱塑性塑膠材料。欲使其具有較佳的韌性， 有必要降低其結晶度。而引入一長鏈的柔曲性脂族二酸作 為共單體，除可降低其結晶度外，尚可提供足夠的柔曲性 ，而使得液晶共聚酯具有慶異的鄣性。 [本發明的詳細説明] 本發明為一種含有長鏈脂族二酸酯單位的熱向性液晶 共聚酯。此種共聚酯為（1)4,4’-二羥基聯苯（4,4’-dihydroxybiphenyl)，（2)— 碳數目為6-12脂族二酸（alphatic diacid)，及（3)-·磺數目為1320的長鏈脂族二酸的共聚 合體，具有匮異的韌性，可作為熱塑性塑膠。 (請先閱誚背而之注意事項#填寫本頁) 裝< 線· 本紙張尺度边用中B困家標毕（CNS)TM規格（210x29·/公；40 81.6. 10,0005*： (!|) 經濟部中央標準局兵工消费合作社印製 Λ 6 B6 五、發明説明（2 ) 4,4’-二羥基聯苯與碩數目為6-12的脂族二酸之均聚 酯已知為熱向性液晶聚合體。然而，其待性非常脆，無法 作為良好的熱塑性塑膠。欲使其具有實用價值，有必要提 高其鄴性。此種液晶聚酯非常脆的主要原因之一為其結晶 度高（熔化熱約為10cal/g)。 提高很脆的聚合體靱性的一種方法為添加柔曲性的可 塑劑，然而由4,4’-二羥基聯苯與癸二酸（sebacic acid) 與D0P(鄰苯二甲酸二辛醋；dioctyl phthalate)的混合效 果來看，D0P幾乎無法將其可塑化。在约250¾下D0P無法 與此均聚酯互溶。因此，此種液晶均聚酯不容易以可塑劑 來提高韌性。提高脆性聚合體的另一種方法為添加耐衝擊 改質劑，4,4’-二羥基聯苯與癸二酸的均聚酯與PBT (聚 對苯二甲酸丁二酯）熔融混合，發現所得仍為一很脆的混 合物。同樣的，此液晶聚酯與一柔曲性聚酯聚己二酸丁二 酯的摻合物亦很脆。再者，此液晶聚酯與EPPM(乙烯-丙烯 -二烯共聚合體）橡膠的摻合物的待性亦很脆。此液晶均聚 酯與這些改質劑間的相容性不佳，是造成摻合物韌性無法 提高的主要原因。 共聚合是降低聚合體結晶度的最有效方法之一，因此 本發明乃利用共聚合法將一柔曲性高的長鏈脂族二酸（磺 數目為13-20)引入原來是很脆的液晶聚酯中，而得具有優 異勒性的液晶共聚酯。長鏈脂族二酸共單體的引入可將均 聚酯原約為lOcal/g的熔化熱大幅降低，可使液晶共聚酯 的熔化熱降至l-3cal/g,熔化熱最大可降低約1〇倍。而柔 本紙張尺度遑用中國國家樣準(CNS)甲4規格(210X297公;jf) (請先閲讀背面之注意事項再填寫本頁) t 象 ^05065 Λ 6 Π 6 五、發明説明（3) 曲性長鏈脂族二酸的引入大幅度提高了®性。在某些組成 範圍，液晶共聚酯的耐衝擊強度可達均聚酯的10倍以上。 此外，共聚合對於液晶共聚酯的液晶性質的影響亦很有趣 。以4,4’-二羥基聯苯，癸二酸及1,20-二十烷二酸的共聚 酯為例，共聚合大幅降低了熔化溫度（Tm)(結晶相轉變為 液晶相的溫度）及其熔化熱，但對於等方化溫度Ti (液晶相 轉變為液相的溫度，isotropization temperature)的影 鎏則有所不同。共聚酯的Ti大致上介於兩均聚酯的Ti之間 ，約略符合混合物定律（r u 1 e 〇 f m i X t u r e)。此外，共聚醋 的等方化熱（heat of isotropization)約在 10-13cal/g 之 間，與均聚酯接近，此表示共聚合不太會影響液晶程度 (liquid crystalline order)。由於共聚合大幅降低了共 聚酯的結晶度，而長鏈脂族二酸酯單位又提供了足夠的柔 曲性，使得液晶共聚酯具有優異的韌性。 經沭部中央櫺準局貝工消"合作社印製 (請先閲讀背而之注意事項洱埸寫本頁) 本發明為-種含有艮鍵脂族二酸單位的熱向性液晶共 聚酯，其組成單位為（1)4,4’-二羥基聯苯，（2)碩數目為 6-12的脂族二酸及（3)碩數目為13 .20的長鏈脂族二酸，其 中脂族二酸可為 1,6-己二酸，1,7-庚二酸，1,8-辛二酸 ,1,9-壬二酸，1，10-癸二酸，1,11-十一烷二酸，1,12 -十二烷二酸等；長鏈脂族二酸可為I 13 .十三烷二酸， 1,14 ·十四烷二酸，1,15-十五烷二酸，1，16 -十六烷二酸 ,1,17-十七烷二酸，1，18·十八烷二酸，1，19 -十九烷二 酸，1,20-二十烷二酸等。4,4^.二羥基聯苯與脂族二酸及 長鏈脂族二酸在高溫下直接酯化聚合所得的共聚@分·子- 本紙張尺度边用中a租家揉毕（CNS)lM規格(210x297公龙） 81. 6. 10,000¾ (11) 0506α 經濟部中央標準局员工消费合作社印製 Α6 Β6 五、發明説明（4) 下直接酯化聚合所得的共聚酯的分子量很低，僅是寡聚合 體，而且顔色不佳（棕黑色）。因此，本發明的共聚酯並不 適合以高溫直接酯化法來製造。基於此，將酚基加以醋酸. 酯化，再進行熔融聚縮合可得高分子量的共聚酯，此種方 法如 Tasi等人[H.B.Tsai, C.Lee, N.S.Chang, M.S.Chen, and S.J.Chang, J.Appl. Polym.Sci., 40, 1499 (1990)] 所述的合成對羥基苯甲酸共聚合體的方法。如此，本發明 中4,4'-二羥基聯苯與酯酸酐或其他酸酐先行反應而得 4,4’-二羥基聯苯二醋酸酯或4,4’-二羥基聯苯的二丙酸酯 ，二丁酸酯等。這些酯化的4,4’-二羥基聯苯可容易的與 脂族二酸及長鍵脂族二酸在高溫下熔融聚縮合，並在後段 抽真空提高分子量而得高分子量的液晶共聚酯。由於熔融 聚縮後段必須抽真空將副産物如醋酸蒸出，故所用的酯化 4,4’-二羥基聯的酸的碩數目不宜太高，因而，所用的酯化 的4,4'-二羥基聯苯單體可為4,4’-二羥基聯苯二醋酸酯， 4,4’-二羥基聯苯二丙酸酯，4,4-二羥基聯苯二丁酸酯， 4,4’-二羥基聯苯二戊酸酯，4,4’-二羥基聯苯二己酸酯等 ，而以前三者為較佳。在熔融聚縮合時可以不使用酯交換 觸媒，亦可使用一些酯交換觸媒如四丁基鈦酸酯（tetrabutyl orthotitanate),可加速聚合反應。 由上所述，本發明偽有關一種新型含有長鍵脂族二酸 酯單位的熱向性液晶共聚酯，具有優異的韌性，可怍為熱 塑性塑膠。調整其組成，並可得不同液晶範圍的共聚酯。 [實施例] 本紙張尺度边用中國Β家標準(CNS)甲4規格(210x297公;¢) (請先閲讀背面之注意事項再填窝本頁) t 良 Λ 6 Η 6 五、發明説明（5 ) (請先閲讀背面之注意事項再場寫本頁) Η以下列實施例更詳細説明本發明，但本發明並不受 此實施例之限制。 共聚酯的本性粘度是在301：下，以酚/四氯乙烷（重量 比為60 : 40)為溶劑，以Ubblohde粘度計測得。共聚酯的 液晶性質則以DSC輔以偏光顯微鏡觀察分析之。共聚酯加 熱至等方化溫度以上，熱壓成片狀，再切割成試片，利用 ASTM D-256的方法測其耐衝擊強度。 比較例1. 在1升的反應器内加入0.5莫耳（135克）的4,4’-二羥基 聯苯二酸酯，及0.5莫耳（101克）的1,10-癸二酸，通氮氣下 將反應物加熱至24010,反應副産物（醋酸）會從凝管蒸出。 反應約2.1,時後，大部份醋酸蒸出後，逐漸抽真空至0.5mra Hg,並將反應物加熱至28013,抽真空時間約1.5小時。所 得均聚酯的本性粘度為〇.61dL/g。由DSC分析知其具有兩 個轉變吸熱峰，分別為熔化溫度Tm(212t：)及等方化溫度 Τί(283υ),在偏光頴徹鏡下，Tm〜Ti之間具有熔融雙折 光性，可確定其在Tin 5： Ti間為液晶相。另外，所得均聚 酯非常脆，測得的耐衝擊強度為〇.6Kg.cro/cm。 經濟部中央標準局貝工消#合作社印製 比較例2. 如同比較例1所使用的方法，但以1,20-二十烷二酸取 代1,10-癸二酸，且在後段抽真空時反應溫度加熱至260°C ，最後得到4,4 二羥基聯苯與1,20-二十烷二酸的均聚酯。 其本性粘度為〇.39dl/g, Τη»及Ti分別為172t：及1951C,此 本紙張尺度边用中《 8家榣準(CNS)甲4規格(210X297公龙) i- 〇506d A 6 Η 6 五、發明説明（6 ) 經濟部中央標準局A工消費合作社印製 均聚酯亦相當脆，耐衝撃強度為0.8kg/·〇ιη/(：ιη,其他相 關數據列於於表1中。. 實施例1 如同比較例1所甩的方法，但以0.25莫耳1,10-癸二 酸及0.25莫耳1,20-二+烷二酸取代0.5莫耳1,10-癸二酸 ，後段反應溫度為260Ό，而得4,4’-二羥基聯苯，1,10-癸二酸及1，20-二十烷二酸的共聚酯。其本性粘度為0.70 dl/g, Tm及Ti分別為100及206°C。此共聚酯的特性很韌， 耐衝擊強度為11kg/· cm/cro,其他相關數據列於表1中。 與兩比較例相比，此共聚酯的熔化熱為1.5cal/g，遠較兩 均聚酯（約lOcal/g)為小，而其耐衝擊強度則較兩均聚酯 為高。 實施例2-9 如同比較例1所用的方法，以不同單體組成的1,10-癸 二酸及1,20-二十烷二酸取代1,10-癸二酸，後段反應溫 度為260t,而製得不同組成的共聚酯。各實施例的組成， 本性粘度，液晶性質以芨耐衝擊強度如表1所示。由表1可 知，共聚酯有較高的勒性，而基於二酸單體，1,20-二十 烷二酸含量為20至60莫耳百分比時，共聚酯有更優異的韌 性。 實施例10 如同比較例1所用的方法，以0.25某耳1,8 -辛二酸及 0.25莫耳1,20-二十烷二酸取代0.5某耳no-癸二酸，後 (請先閲讀背面之注意事項再瑱寫本頁) 裝· 訂· -線. 本紙張尺度边用中8 B家標準(CNS)肀4規格(210X297公龙) 咖㈣ A6 B6 五、發明説明ί 7 ) 段反應溫度為260°C,而得4,4’-二羥基聯苯，1,8-辛二酸 及1,20-二十烷二酸的共聚酯。其本性粘度為0.5Sdl/g,Printed Λ 6 ΙΪ6 by β 工 消 t Cooperative of the Central Bureau of Economic Affairs of the Ministry of Economy V. Description of the invention (1) The present invention relates to a thermotropic liquid crystal copolyester containing a long-chain aliphatic diester unit, which is (1 ) 4,4'-dihydroxybiphenyl, (2) an aliphatic diacid with a number of 6-12, and (3) a copolymer of a 13-20 aliphatic number of aliphatic diacids. This kind of copolyester has the properties of thermotropic liquid crystal, and has excellent toughness, can be used as a thermoplastic plastic. [Prior art] The homopolymer of 4,4'-dihydroxybiphenyl (4,4'-dihydroxybiphenyl) and aliphatic diacid with 6-12 carbon atoms can form a liquid crystal phase [A. Blumstein , KMSivaramakrishnau, RB Blumstein and SBClough, Polymer, 23, 47 (1982) and J. Arsar, H. Toriumi, J. Watanabe, WRKr i gbaum, A. Cifferi and J. Preston, J. Po1ym.Si. Po1ym. Phys. Ed., 21, Π19 (19δ3)]. This kind of liquid crystal homopolyester has the liquid crystal properties of Mingying, but its crystallinity is very commercial (ΔΗηι about 10cal / g), and its waiting property is very brittle, so it cannot be used as an excellent thermoplastic plastic material. To make it have better toughness, it is necessary to reduce its crystallinity. Introducing a long-chain flexible aliphatic diacid as a comonomer, in addition to reducing its crystallinity, can still provide sufficient flexibility, and makes the liquid crystal copolyester with a remarkable singularity. [Detailed description of the present invention] The present invention is a thermotropic liquid crystal copolyester containing a long-chain aliphatic diacid unit. This type of copolyester is (1) 4,4'-dihydroxybiphenyl (4,4'-dihydroxybiphenyl), (2) —the carbon number is 6-12 aliphatic diacid, and (3) -· The copolymer of long chain aliphatic diacid with 1320 sulfonate has poor toughness and can be used as thermoplastic plastic. (Please read the notes before filling in #fill this page) Install &Line; This paper scale is used in the B-side home standard (CNS) TM specification (210x29 · / male; 40 81.6. 10,0005 *: (! |) Printed by the Ordnance Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Λ 6 B6 V. Description of the invention (2) 4,4'-dihydroxybiphenyl and the homopolyester of 6-12 aliphatic diacids It is known as a thermotropic liquid crystal polymer. However, its hospitality is very brittle and cannot be used as a good thermoplastic. To make it practical, it is necessary to improve its Ye. The main reason for this liquid crystal polyester is very brittle One is its high crystallinity (the heat of fusion is about 10 cal / g). One way to improve the properties of very brittle polymers is to add flexible plasticizers. However, 4,4'-dihydroxybiphenyl and sebacic acid (Sebacic acid) and DOP (dioctyl phthalate) mixed effect, DOP can hardly be plasticized. At about 250¾ DOP can not be miscible with this polyester. Therefore, this liquid crystal Homopolyester is not easy to improve toughness with plasticizers. Another way to improve brittle polymers is to add impact resistance The quality agent, homopolyester of 4,4'-dihydroxybiphenyl and sebacic acid, and PBT (polybutylene terephthalate) were melt-mixed and found to be a very brittle mixture. Similarly, this liquid crystal The blend of polyester and a flexible polyester polybutylene adipate is also very brittle. Furthermore, the blend of liquid crystal polyester and EPPM (ethylene-propylene-diene copolymer) rubber It is also very brittle. The poor compatibility between this liquid crystal homopolyester and these modifiers is the main reason why the toughness of the blend cannot be improved. Copolymerization is one of the most effective methods to reduce the crystallinity of the polymer. Therefore, the present invention uses a copolymerization method to introduce a long-chain aliphatic diacid with a high flexibility (the number of sulfonic acids is 13-20) into the liquid crystal polyester which is originally very brittle, and a liquid crystal copolyester with excellent flexibility is obtained. The introduction of long-chain aliphatic diacid comonomer can greatly reduce the heat of fusion of the original homopolyester of about 10 cal / g, and can reduce the heat of fusion of the liquid crystal copolyester to l-3 cal / g, the maximum heat of fusion Reduce it by about 10 times. The size of the flexo paper is not in accordance with the Chinese National Standard (CNS) Grade 4 (210X297 g; jf) (please read the back (Notes are required to fill out this page) t Elephant ^ 05065 Λ 6 Π 6 V. Description of the invention (3) The introduction of the flexible long-chain aliphatic diacid greatly improves the properties. In some composition ranges, the liquid crystal copolyester The impact strength can be more than 10 times of the average polyester. In addition, the effect of copolymerization on the liquid crystal properties of the liquid crystal copolyester is also very interesting. 4,4'-dihydroxybiphenyl, sebacic acid and 1,20- As an example of the copolyester of eicosanedioic acid, the copolymerization greatly reduces the melting temperature (Tm) (the temperature at which the crystal phase changes to the liquid crystal phase) and its heat of fusion, but for the isotropic temperature Ti (the liquid crystal phase changes to the liquid Phase temperature, isotropization temperature) is different. The Ti of the copolyester is roughly between the Ti of the two homopolyesters, which roughly conforms to the law of the mixture (r u 1 e 〇 f m i X t u r e). In addition, the heat of isotropization of the copolymerized vinegar is about 10-13 cal / g, which is close to that of the homopolyester, which means that the copolymerization will not affect the liquid crystal order (liquid crystalline order). Since the copolymerization greatly reduces the crystallinity of the copolyester, the long-chain aliphatic diacid unit provides sufficient flexibility, making the liquid crystal copolyester excellent in toughness. Printed by Beigong Consumer Co., Ltd. of the Central Bureau of the Ministry of Economic Affairs (please read the precautions first and write this page). This invention is a thermotropic liquid crystal copolymer containing a unit of aliphatic diacid units. Ester, its composition unit is (1) 4,4'-dihydroxybiphenyl, (2) aliphatic diacid with a number of 6-12 and (3) long-chain aliphatic diacid with a number of 13.20 , Where the aliphatic diacid can be 1,6-adipic acid, 1,7-pimelic acid, 1,8-suberic acid, 1,9-azelaic acid, 1,10-sebacic acid, 1, 11-undecanedioic acid, 1,12-dodecanedioic acid, etc .; the long-chain aliphatic diacid may be I 13. tridecanedioic acid, 1,14 · tetradecanedioic acid, 1,15- Pentadecanedioic acid, 1,16-hexadecanedioic acid, 1,17-heptadecanodioic acid, 1,18 · octadecanedioic acid, 1,19-nonadecanodioic acid, 1,20- Eicosanedioic acid and so on. 4,4 ^. Copolymerization of dihydroxybiphenyl with aliphatic diacids and long-chain aliphatic diacids directly esterified and polymerized at high temperature @ 分 · 子-This paper is scaled with a renter (CNS) lM specifications (210x297 male dragons) 81. 6. 10,000¾ (11) 0506α Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Α6 Β6 V. Description of the invention (4) The molecular weight of the copolyester obtained by direct esterification polymerization is very low , Only oligomers, and the color is not good (brown black). Therefore, the copolyester of the present invention is not suitable for production by direct high-temperature esterification. Based on this, the phenol group is esterified with acetic acid, and then subjected to melt polycondensation to obtain a high molecular weight copolyester, such as Tasi et al. [HBTsai, C. Lee, NSChang, MSChen, and SJChang , J. Appl. Polym. Sci., 40, 1499 (1990)] described in the synthesis of p-hydroxybenzoic acid copolymer. In this way, in the present invention, 4,4'-dihydroxybiphenyl reacts with ester anhydride or other acid anhydride to obtain 4,4'-dihydroxybiphenyl diacetate or 4,4'-dihydroxybiphenyl dipropionate Ester, dibutyrate, etc. These esterified 4,4'-dihydroxybiphenyl can be easily melt-condensed with aliphatic diacids and long-bond aliphatic diacids at high temperature, and vacuumized in the later stage to increase molecular weight to obtain high molecular weight liquid crystal copolymerization ester. Since the rear stage of the melt polycondensation must be evacuated to evaporate by-products such as acetic acid, the number of esterified 4,4'-dihydroxy-linked acids should not be too high. Therefore, the esterified 4,4'-bis The hydroxybiphenyl monomer can be 4,4'-dihydroxybiphenyldiacetate, 4,4'-dihydroxybiphenyldipropionate, 4,4-dihydroxybiphenyldibutyrate, 4,4 '-Dihydroxybiphenyl divalerate, 4,4'-dihydroxybiphenyl dihexanoate, etc., the former three are preferred. In the melt polycondensation, the transesterification catalyst may not be used, and some transesterification catalysts such as tetrabutyl orthotitanate may be used to accelerate the polymerization reaction. As mentioned above, the present invention is pseudo-related to a new type of thermotropic liquid crystal copolyester containing long bond aliphatic diacid units, which has excellent toughness and can be used as a thermoplastic plastic. Adjust its composition and obtain copolyesters with different liquid crystal ranges. [Embodiment] This paper uses Chinese Beta Standard (CNS) Grade 4 specifications (210x297 g; ¢) (please read the precautions on the back before filling the nest page) t Liang Λ 6 Η 6 5. Description of the invention ( 5) (Please read the precautions on the back before writing this page) Η The following examples illustrate the present invention in more detail, but the present invention is not limited by this example. The intrinsic viscosity of the copolyester is measured at 301: using phenol / tetrachloroethane (60:40 by weight) as the solvent and Ubblohde viscometer. The liquid crystal properties of the copolyester are analyzed by DSC with a polarizing microscope. The copolyester is heated to above the equalization temperature, hot pressed into a sheet, and then cut into test pieces, and its impact strength is measured by the method of ASTM D-256. Comparative Example 1. In a 1 liter reactor, 0.5 mol (135 g) of 4,4′-dihydroxybiphenyl dicarboxylate and 0.5 mol (101 g) of 1,10-sebacic acid were added, Heat the reactant to 24010 under nitrogen, and the reaction by-product (acetic acid) will be distilled from the condenser. After about 2.1 hours of reaction, after most of the acetic acid was distilled off, the vacuum was gradually evacuated to 0.5 mra Hg, and the reaction was heated to 28013, and the vacuum time was about 1.5 hours. The intrinsic viscosity of the obtained homopolyester was 0.61 dL / g. It is known from DSC analysis that it has two transition endothermic peaks, namely melting temperature Tm (212t :) and isotropic temperature Τί (283υ). Under the polarizing mirror, Tm ~ Ti has melting birefringence, which can be It is determined that it is a liquid crystal phase between Tin 5: Ti. In addition, the resulting homopolyester was very brittle, and the measured impact strength was 0.6 Kg.cro / cm. Comparative Example 2. Printed by the Ministry of Economic Affairs, Central Standard Bureau, Beigongxiao #Cooperative. The method used in Comparative Example 1, except that 1,10-sebacic acid was replaced with 1,20-eicosanedioic acid, and a vacuum was drawn in the latter stage. When the reaction temperature is heated to 260 ° C, the homopolyester of 4,4 dihydroxybiphenyl and 1,20-eicosanedioic acid is finally obtained. Its intrinsic viscosity is 0.39 dl / g, Τη »and Ti are 172t: and 1951C, respectively. This paper scale is used in the" 8 home standard (CNS) A 4 specifications (210X297 male dragon) i- 〇506d A 6 Η 6. V. Description of invention (6) The average polyester printed by A Industrial and Consumer Cooperative of Central Bureau of Standards of the Ministry of Economic Affairs is also quite brittle, and the impact strength is 0.8kg / · 〇ιη / (: ιη, other relevant data are listed in Table 1. Middle .. Example 1 The same method as in Comparative Example 1, except that 0.5 mol 1,10-decane was replaced with 0.25 mol 1,10-decanedioic acid and 0.25 mol 1,20-di + alkanedioic acid Acid, the reaction temperature in the latter stage is 260Ό, and a copolyester of 4,4'-dihydroxybiphenyl, 1,10-sebacic acid and 1,20-eicosanedioic acid is obtained. Its intrinsic viscosity is 0.70 dl / g , Tm and Ti are 100 and 206 ° C. The characteristics of this copolyester are very tough, the impact strength is 11kg / · cm / cro, other relevant data are listed in Table 1. Compared with the two comparative examples, this total The heat of fusion of polyester is 1.5 cal / g, which is much smaller than that of two homopolyesters (about 10 cal / g), and its impact resistance is higher than that of two homopolyesters. Examples 2-9 are used as in Comparative Example 1. Method of 1,10-sebacic acid and 1,2 composed of different monomers 0-Eicosanedioic acid is substituted for 1,10-sebacic acid, and the reaction temperature in the latter stage is 260t, and copolyesters with different compositions are prepared. The composition, intrinsic viscosity, and liquid crystal properties of each example are based on the impact resistance of Pyrene as shown in the table. 1. It can be seen from Table 1 that the copolyester has higher sterility, and based on the diacid monomer, when the 1,20-eicosanedioic acid content is 20 to 60 mole percent, the copolyester has more Excellent toughness. Example 10 As in the method used in Comparative Example 1, 0.25 of 1,8-octanedioic acid and 0.25 mol of 1,20-eicosanedioic acid were substituted for 0.5 of no-sebacic acid. (Please read the precautions on the back before writing this page) Binding · Order ·-Line. This paper uses 8 B home standard (CNS) 4 specifications (210X297 male dragon). A6 B6 5. Description of the invention ί 7) The reaction temperature is 260 ° C, and the copolyester of 4,4'-dihydroxybiphenyl, 1,8-suberic acid and 1,20-eicosanedioic acid is obtained. Its intrinsic viscosity is 0.5Sdl / g,
Tm及Ti分別102t：及212°C。其熔化熱為1.4cal/g,靦衝擊 強度為7.4kg 亦有匮異的韌性。 表1.共聚酯的組成，本性粘度，液晶性質及酎衝擊強度。 組成a 本性粘度 Tin AHmb Ti ΔΗί° 耐衝擊強度 (dL/g) (°C) (cal/g) (° 0 (Cal/g) (kg/ · cra/cm) (請先閏讀背面之注意事項再填寫本百) 實施例1 1:0.5:0,5 0.70 100 1.5 206 11.4 11 實施例2 1:0.9:0.1 0.89 172. 4.6 264 10.4 1.8 實施例3 1:0,8:0.2 0.72 140 1.9 250 12.2 8.1 實施例4 1:0.7:0.3 0.80 110 1.6 230 11.3 7.5 實施例5 1:0.6:0.4 0.77 94 1.0 220 11.5 10 實施例6 1:0.4:0.6 0,54 112 2.7 203 12.1 8.2 實施例7 1:0.3:0.7 0.26 129 3.1 220 12.9 3.1 實施例8 1:0.2:0.8 0.14 152 6.3 202 12.1 1.2 實施例9 1:0.1:0.9 0.37 170 9.1 197 11.0 0.7 實施例10 1:0.5:0.5 0.58 102 1.4 212 12.1 7.4 比較例1 1:0:0 0.61 212 9.6 283 13.2 0.6 比較例2 1:0:1 0.39 172 11.2 195 9.6 0.8 -裝· •打· •線. 經濟部中央櫺準局貝工消费合作社印製 a. 除實施例10所用的脂族二酸為1.8-辛二酸外，其餘實施例 所用的脂族二酸為1,10-癸二酸。組成奠耳比為4,4 二羥 基聯苯：脂族二酸：1,20-二十烷二酸。 b. 熔化熱 c. 等方化熱 本紙張尺度適用中國國家標準（CNS)甲4規格(210x297公釐)Tm and Ti are respectively 102t: and 212 ° C. Its heat of fusion is 1.4 cal / g, and its impact strength is 7.4 kg. Table 1. Copolyester composition, intrinsic viscosity, liquid crystal properties, and impact strength. Composition a Intrinsic viscosity Tin AHmb Ti ΔΗί ° Impact resistance (dL / g) (° C) (cal / g) (° 0 (Cal / g) (kg / · cra / cm) (please read the note on the back first Please fill in the matter 100) Example 1 1: 0.5: 0,5 0.70 100 1.5 206 11.4 11 Example 2 1: 0.9: 0.1 0.89 172. 4.6 264 10.4 1.8 Example 3 1: 0,8: 0.2 0.72 140 1.9 250 12.2 8.1 Example 4 1: 0.7: 0.3 0.80 110 1.6 230 11.3 7.5 Example 5 1: 0.6: 0.4 0.77 94 1.0 220 11.5 10 Example 6 1: 0.4: 0.6 0,54 112 2.7 203 12.1 8.2 Example 7 1: 0.3: 0.7 0.26 129 3.1 220 12.9 3.1 Example 8 1: 0.2: 0.8 0.14 152 6.3 202 12.1 1.2 Example 9 1: 0.1: 0.9 0.37 170 9.1 197 11.0 0.7 Example 10 1: 0.5: 0.5 0.58 102 1.4 212 12.1 7.4 Comparative Example 1 1: 0: 0 0.61 212 9.6 283 13.2 0.6 Comparative Example 2 1: 0: 1 0.39 172 11.2 195 9.6 0.8 -installed Printing a. Except that the aliphatic diacid used in Example 10 is 1.8-suberic acid, the aliphatic diacid used in the remaining examples is 1,10-sebacic acid. The composition molar ratio is 4,4 dihydroxy Biphenyl: Aliphatic diacid: 1,20-Eicosanedioic acid.b . The heat of fusion c. The heat of equalization This paper scale is applicable to the Chinese National Standard (CNS) A4 specifications (210x297 mm)