TW420697B - Novel prescription of copolyesters - Google Patents

Novel prescription of copolyesters Download PDF

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TW420697B
TW420697B TW88106608A TW88106608A TW420697B TW 420697 B TW420697 B TW 420697B TW 88106608 A TW88106608 A TW 88106608A TW 88106608 A TW88106608 A TW 88106608A TW 420697 B TW420697 B TW 420697B
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Taiwan
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acid
terephthalic acid
sum
isophthalic acid
patent application
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TW88106608A
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Chinese (zh)
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Wu-Bin You
Meng-Sung Jeng
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You Wu Bin
Jeng Meng Sung
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Abstract

The traditional synthesis of high shrinkage copolyesters made of isophthalic acid, terephthalic acid and ethylene glycol. The traditional high shrinkage copolyesters were unstable, when they were spun, drawn, textured, woven and dyed. However, the novel composition of copolyesters are used 9,9'-bis[4(2-hydroxyethoxy) phenyl] fluorene, and/or isophthalic acid, terephthalic acid and ethylene glycol as raw materials. It can be improved the unstable shrinkage that be caused by process or storage.

Description

Λ7 420697 五、發明説明(1 ) 一般傳統合成高收縮性共聚酯是以間苯二甲酸 (Isophthalic acid)、對苯二曱酸(Terephthalic acid)、乙二 醇(Ethylene glycol)為原料。所合成之高收縮性共聚酯, 經由紡絲、併絲、延伸、假撚、織布、染整等加工過程時, 會出現收縮性不穩定的現象。本發明共聚酯新穎配方是以 9,9’-雙[4_ (2-羥基乙氧基)苯基]苟{9,9’-bis[4(2-hydroxyethoxy) phenyl] fluorene}和/或間苯二甲酸、對苯二 曱酸和乙二醇為原料合成高收縮性共聚酯,可改善上述加 工或儲存時所造成收縮率不穩定現象。 從專利文獻整理得一般合成高收縮共聚醋之原料有如 下;(1)以間苯二甲酸、對苯二曱酸和乙二醇為原料合成 高收縮性共聚酯之專利說明有日本公開特許52-25118號, 經濟部中央標準局員工消費合作社印製 2-139409 號,2-104722 號,53-139823 號,53-2210 號,59-112026 號,8-35120 號,3-260116 號,3-90616 號,4-257333 號 ’ 5-302210 號 ’ 59-112025 號,3-161519 號 ^ 3-174016 號, 4-57920號’ 9-268434號等公開說明書及美國專利4046739 號等s但有收縮性不穩定的缺點。(2)以2,2,-雙-[4-(2-經 基乙氧基)苯基]丙烷’對笨二甲酸及乙二醇為原料合成高收 縮性共聚酯之日本公開特許為8-74127號,55-57013號,9- 78356 號,62-223322 號 ’ 8-113825 號,60-35450 號,55-57013 號,61-13009號,8-144144號,8-109520號等公開說明書, 及美國專利4110315號與4042^65號專利說明書。(3)以4, t il a ( cns ) A^m ΙΊϊόΤ^^]-~~--- 經濟部中央標隼局貝工消費合作社印裝 420697 ; A7 ______; _B7 五、發明説明(2 ) 4’·雙-[4 - β - (2-經基乙氧棊)-二苯基石風,對苯二甲酸及乙 二醇為原料合成高縮性共聚之美國專利說明書為4115363 及 4547563 號。 本發明主要是以環氧樹脂之單體原料之9,9,-雙[4- 〇經 基乙氧基)苯基]芴為共單體與對苯二甲酸、乙二醇,和/或 間苯二甲酸為原料’合成高收縮性纖維材料。 本發明合成高收縮共聚酯纖維材料,在130 °C下收縮率 低於15% ’而在170-180 °C的溫度收縮率大於25%。不像 傳統南收縮性共聚醋纖維(以間苯二甲酸為共單體)在 C的收縮率大於30%,會造成加工或平常储存時就會有收 縮性的現象,致使收縮率不穩定。 本發明製程所用觸媒可以為銻系化合物(如三氧化二 錄、醋酸錄等等),錫系化合物[如二丁基亞錫(dibutyltin oxide)、二丁基二月桂錫(dibutyl dilauryl tin)等等],欽 化合物[如四丁基欽(tetrabutyi titanate)、四異丙基欽 (tetraisoprojpyl titanate)等等]為聚合觸媒,也可以和醋 酸納、醋酸鉀、醋酸艤、醋酸鈣、醋酸猛、醋酸鈷、醋酸 辞、醋酸船等等合用。 本發明製程可以使用安定劑,如三甲基磷酸6旨 (trimethyl phosphate ),三笨基磷酸酯(triphenyl phosphate)、鱗酸、IrganoxlOlO 等等。 茲舉數個實施例說明如下,所舉實施例僅係對本發明 » 方法作概括性例示,並無限制f發明範圍之意,就此先作 本紙張尺度適用中國國家標準(CMS > A4規格(210X297公釐) "~ ~ — (請先閲讀背面之注意事項再填寫本頁) 4-衣.Λ7 420697 V. Description of the invention (1) General traditional synthetic high-shrinkage copolyester is made from isophthalic acid, terephthalic acid, and ethylene glycol (Ethylene glycol) as raw materials. The as-synthesized high-shrinkage copolyester undergoes inconsistency in shrinkage during processing such as spinning, parallel spinning, drawing, false twisting, weaving, dyeing and finishing. The novel copolyester formulation of the present invention is based on 9,9'-bis [4_ (2-hydroxyethoxy) phenyl] go {9,9'-bis [4 (2-hydroxyethoxy) phenyl] fluorene} and / or Isophthalic acid, terephthalic acid, and ethylene glycol are used as raw materials to synthesize a high shrinkage copolyester, which can improve the instability of shrinkage caused by the above processing or storage. The raw materials for the general synthesis of high-shrinkage copolymerized vinegar which are sorted out from the patent literature are as follows; (1) The patent description of the synthesis of high-shrinkage copolyester using isophthalic acid, terephthalic acid, and ethylene glycol as raw materials is published in Japan No. 52-25118, Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs printed No. 2-139409, No. 2-104722, No. 53-139823, No. 53-2210, No. 59-112026, No. 8-35120, and No. 3-260116, 3-90616, 4-257333 '5-302210' 59-112025, 3-161519 ^ 3-174016, 4-57920 '9-268434, etc. and U.S. Patent No. 4046739 etc. There is a disadvantage of unstable shrinkage. (2) The Japanese public license for synthesizing high-shrinkage copolyester using 2,2, -bis- [4- (2-alkylethoxy) phenyl] propane 'p-phenylenedicarboxylic acid and ethylene glycol as raw materials 8-74127, 55-57013, 9- 78356, 62-223322 '8-113825, 60-35450, 55-57013, 61-13009, 8-144144, 8-109520, etc. Published Specification, and US Patent Nos. 4,110,315 and 4042 ^ 65. (3) printed with 4, t il a (cns) A ^ m Ι ^ όΤ ^^-~~ --- Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 420697; A7 ______; _B7 V. Description of the Invention (2) US patent specifications for 4 '· bis- [4-β-(2-Ethylethoxyfluorene) -diphenyl stone wind, terephthalic acid and ethylene glycol as raw materials for high-shrinkage copolymerization are 4115363 and 4475563. The present invention mainly uses 9,9, -bis [4-o-alkylethoxy) phenyl] fluorene as a comonomer as the monomer raw material of epoxy resin, and terephthalic acid, ethylene glycol, and / or Isophthalic acid is a raw material of synthetic high shrinkable fiber material. The synthetic high-shrinkage copolyester fiber material of the present invention has a shrinkage of less than 15% at 130 ° C and a shrinkage of more than 25% at a temperature of 170-180 ° C. Unlike the traditional South shrinkable copolymerized vinegar fiber (with isophthalic acid as a co-monomer), the shrinkage of C is greater than 30%, which will cause shrinkage during processing or ordinary storage, resulting in unstable shrinkage. The catalyst used in the process of the present invention may be an antimony-based compound (such as dioxin, acetic acid, etc.), and a tin-based compound [such as dibutyltin oxide, dibutyl dilauryl tin) Etc.], Chin compounds [such as tetrabutyi titanate, tetraisoprojpyl titanate, etc.] are polymerization catalysts, and can also be combined with sodium acetate, potassium acetate, osmium acetate, calcium acetate, acetic acid It can be used together with cobalt, cobalt acetate, acetate, and acetate boat. The process of the present invention can use stabilizers, such as trimethyl phosphate, triphenyl phosphate, triphenyl phosphate, IrganoxlOlO, and the like. A few examples are described below. The examples are merely general illustrations of the method of the present invention, and are not intended to limit the scope of the invention. In this regard, the Chinese paper standard (CMS > A4 specifications ( 210X297 mm) " ~ ~ — (Please read the precautions on the back before filling this page) 4-clothing.

1T 經濟部中央標準局貝工消費合作社印製 420697 ' A7 ------ -- B7 五、發明説明(3 ) 聲明。 實施何1.(高收蝻共聚酯合成) 將反應物(對苯二甲酸和乙二醇,莫耳比為1/14)放入 反應槽内,開始昇溫及擾拌,當反應槽内溫昇至附 近’再加入9,9’_雙[4* (2羥基乙氧基>苯基]努和/或間苯二 甲酸和/或乙;醇及觸媒,反應1·5小哮後,.便開始抽真空, 其真空度母隔6分鐘往下調cmjjg ,直到真空度達% cmHg (76 cmHg為高真空度,〇 cmHg為1大氣壓)時,開 始使用馬力較大之馬逹抽高真空,此時反應槽内溫度约 C附近’維持正常合成聚對笨二甲酸二乙酿之反應溫度至 授拌扭力上昇至某一定值後,使用氮氣破真空,加壓下料, 所得樣品分析如下表(表1)。本合成使用觸煤為三氧化二 錄/醋酸鍾/醋酸鋅/錯酸納(SOOppju/ 2〇〇ppm/ 200ppm/ 200PPm),其中雙酸與雙醇之莫耳比為1/14,其雙醇不足 部份則用乙二醇補足。 %ν.黏度測試方法 以四氯乙娱*/苯紛重量比40/60為溶劑,其中配製樣品濃 度為 0.5g/cH ' 0.33g/dl、0.213g/dl 和 〇.i25g/d卜於 30 °C下, 使爾Cannon-lSO型黏度管測樣品溶液流過黏度管時間,經 過辞算及作圖求得I.V。值。 疼 ^#-----\ -i- I (請先閲讀背面之注意事項再填寫本頁) (CNS ) A4規格(2I0X 297公釐) 42 0697 A7 B7 五、發明説明(4 表1丨合成希收縮共聚輯之組成及結果 編號 配方铤成(莫耳比) ι·ν· 01 TPA/IPA(90/10) 0.64 02 TPA/IPAyBEPF(90/l 0/5) 0.65 03 TPA/BEPF(l〇Q/l〇) 0.64 04 TPA/IPA/BP(90/10/6) 0.65 *雙酸與雙醇的莫耳比為1/1.5 **備註:TPA :對苯二甲酸 IPA:間苯二甲酸 BP : 2,2、雙-[4-(2-經基乙氧基)苯基]丙烷 郎1>1?:9,9’-雙[4-(2-羥基乙氧基)笨基]芴 (諸先閱讀背面之注意寧項再镇寫本頁〕 rk -計. 經濟部中央標準扃負工消費合作社印製 實施例2 將上述合成共聚酯(編號01-04)在250x24的押出機上, 於275-290 °C下熔融押出紡絲,其捲取速度為, 纺得75丹尼/24根的絲後’於120 °C延伸,其延伸倍率為 3.5倍,所紡得纖維於13〇。〇及170 °C測其收縮測其收縮 率及收縮率穩定性評估。 M30 °C下收縮率測試 纖維在0.1克/丹尼荷重下,其原長為,在130 下, 受熱30分鐘後,測其長度為L广在13〇它下之收縮率為: _____ 5 私紙浪尺度適用中國國家標準(CNS ) A4規格(210X297公釐> —Μ^---il·__ 420697 經濟部中央標隼局負工消费合作社印裝 A7 五、發明説明(5 ) — ' 收縮率 MLo-Ii/L^xioo% *170 °C下收縮率測試 纖維在0.1克/丹尼荷重下,其原長為4,在17〇 t下受熱 15分鐘後,測其長度為A。 則170 ΐ下收縮率為: 收縮率 KVA /4 ) X 1〇〇% *收縮率穩定性評估 將上述纖維織成襪營後,立刻測其收縮率及放著一個 月後,再測其收縮率,若二者收縮率差5%以内則打◎, 若差超過5%則打〇 (諳先Μ讀背面之注意事項再填寫本頁)1T Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 420697 'A7 -------B7 5. Statement of Invention (3) Statement. What to do 1. (Synthesis of high-yield copolyester) Put the reactants (terephthalic acid and ethylene glycol, with a molar ratio of 1/14) into the reaction tank, start heating and stir. When the reaction tank The temperature rises to the vicinity ', and then add 9,9'_bis [4 * (2hydroxyethoxy > phenyl] nu) and / or isophthalic acid and / or ethyl alcohol and catalyst, reaction 1.5 hours After wheezing, vacuuming was started, and the vacuum degree was adjusted down by cmjjg every 6 minutes until the vacuum reached% cmHg (76 cmHg is high vacuum, 0 cmHg is 1 atmosphere), and a horsepower horse with a high horsepower was used. Evacuate high vacuum, at this time, the temperature in the reaction tank is about C. The reaction temperature of the normal synthetic poly-p-dibenzoic acid diethyl alcohol is maintained until the mixing torque rises to a certain value, and the vacuum is broken by nitrogen and the material is cut off under pressure. The sample analysis is shown in the following table (Table 1). This synthesis uses coal oxides as trioxide / bell acetate / zinc acetate / sodium bisulfate (SOOppju / 200ppm / 200ppm / 200PPm). The ear ratio is 1/14, and the insufficient part of the bis-ol is supplemented with ethylene glycol.% Ν. The viscosity test method is based on the weight ratio of tetrachloroethene * / benzene to 40/60 as the solvent. The sample concentration was 0.5g / cH '0.33g / dl, 0.213g / dl and 0.125g / d at 30 ° C. The Cannon-lSO type viscosity tube was used to measure the time for the sample solution to flow through the viscosity tube. And drawing to get IV. Value. Pain ^ # ----- \ -i- I (Please read the precautions on the back before filling in this page) (CNS) A4 specification (2I0X 297 mm) 42 0697 A7 B7 V. Description of the invention (4 Table 1 丨 Composition and results of synthetic shrinkage copolymerization and numbering formula (mole ratio) ι · ν · 01 TPA / IPA (90/10) 0.64 02 TPA / IPAyBEPF (90 / l 0 / 5) 0.65 03 TPA / BEPF (lQ / l〇) 0.64 04 TPA / IPA / BP (90/10/6) 0.65 * Molar ratio of diacid to diol is 1 / 1.5 ** Remarks: TPA : Terephthalic acid IPA: isophthalic acid BP: 2,2, bis- [4- (2-Ethylethoxy) phenyl] propane lang 1 > 1?: 9,9'-bis [4- (2-Hydroxyethoxy) benzyl] 芴 (Please read the note on the reverse side and write this page again) rk-gauge. Central Standard of the Ministry of Economic Affairs 扃 Consumer Cooperative Cooperative Printed Example 2 Copolymerization of the above synthesis The ester (No. 01-04) was melt-extruded on a 250x24 extruder at 275-290 ° C, and its winding speed was After 5 denier / 24 filaments' was stretched at 120 ° C, the stretching ratio was 3.5 times, and the fiber was spun at 130. 〇 and 170 ° C measured its shrinkage and its shrinkage rate and shrinkage rate stability assessment. The shrinkage test fiber at M30 ° C under 0.1g / Denny load, its original length is, at 130 ° C, after heating for 30 minutes, the length is measured as L, and the shrinkage ratio under 13 ° is: _____ 5 Pri Paper wave scale is applicable to China National Standard (CNS) A4 specification (210X297 mm > —Μ ^ --- il · __ 420697 Printed A7 by the Consumers ’Cooperative of the Central Standardization Bureau of the Ministry of Economic Affairs 5. Description of the invention (5) — ' Shrinkage MLo-Ii / L ^ xioo% * The shrinkage test fiber at 170 ° C has a original length of 4 under a load of 0.1 g / Danny, and its length is A after 15 minutes of heating at 170 ° C. Then the shrinkage rate at 170 ° C: shrinkage rate KVA / 4) X 100% * Stability assessment of shrinkage rate After weaving the above-mentioned fibers into socks, measure the shrinkage rate immediately and leave it for one month to measure the shrinkage. Rate, if the difference between the two shrinkage rates is within 5%, then ◎, if the difference is more than 5%, then hit 〇 (谙 read the precautions on the back before filling in this page)

編號 130 °C收縮率 (%) 170 °C收縮率 (%) 收縮穩定 性 01 43 f ------- 45 〇 02 13 35 ◎ 03 7 29 ◎ 04 11 ------ 33 ◎ 本紙浪尺度逋用中國国家標华(CMS > Α4规格公釐)No. 130 ° C Shrinkage (%) 170 ° C Shrinkage (%) Shrinkage stability 01 43 f ------- 45 〇02 13 35 ◎ 03 7 29 ◎ 04 11 ------ 33 ◎ This paper uses Chinese National Standard (CMS > Α4mm)

Claims (1)

42 ABCD本告^171 9 6 ο42 ABCD This Report ^ 171 9 6 ο 六、申請專利範園 1·一種合成高收縮性共聚酯之新潁組成配方,其由 ⑴9,9’-雙-[4-(2_經基乙氧基)苯基]苟,其用量為1 至20莫耳百分比(以間苯二甲酸和對苯二甲酸 的莫耳數和為100%),和 (2) 間苯二甲酸,其用量為1至25莫耳百分比(以 間苯二甲酸和對苯二甲酸的莫耳數和為100%),和 (3) 對苯二甲酸,其用量為75至99莫耳百分比(以 間苯二甲酸和對苯二甲酸的莫耳數和為100%),和 乙二醇(9,9,-雙-f4-(2-羥基乙氧基)苯基]芴和乙二醇 的莫耳數和與間苯二甲酸和對苯二甲酸的莫耳敦和 比為1.2至1.7)所舍成。 2. 如申請專利範圍第1項之組成配方 ,其申請專利範中 9,9’-雙-[4-(2_經基乙氧基)苯基]芴之用量為2至15莫耳百 分比(以間苯二甲酸和對苯二甲酸的莫耳數和為100%)。 3. 如申請專利範圍第1項之組成配方 ,其申請專利範圍 中間苯二甲酸用量為1至15莫耳百分比(以間苯二甲酸 和對苯二甲酸的莫耳數和為100%)。 (請先聞讀背面之注意事頃再填寫本頁) 本紙張尺度適用中國國家標準(CNS ) A4規格(210 X 297公釐) 42 ABCD本告^171 9 6 ο6. Application for a patent Fan Yuan 1. A new compound of high-shrinkage copolyester, which is composed of 99,9'-bis- [4- (2- (Ethylethoxy) phenyl)] and its dosage 1 to 20 mol% (based on the sum of the number of mols of isophthalic acid and terephthalic acid), and (2) isophthalic acid in an amount of 1 to 25 mol% (based on m-benzene Molar sum of dicarboxylic acid and terephthalic acid is 100%), and (3) terephthalic acid is used in a percentage of 75 to 99 moles (in terms of moles of isophthalic acid and terephthalic acid) The sum is 100%), and the molar numbers of ethylene glycol (9,9, -bis-f4- (2-hydroxyethoxy) phenyl) fluorene and ethylene glycol and isophthalic acid and terephthalic acid The molar ratio of formate is 1.2 to 1.7). 2. If the composition formula of item 1 of the scope of patent application, the amount of 9,9'-bis- [4- (2_ylethoxy) phenyl] fluorene used in the patent application range is 2 to 15 mole percent (The sum of the molar numbers of isophthalic acid and terephthalic acid is 100%). 3. If the composition formula of item 1 of the scope of patent application, the scope of patent application of the scope of patent application is 1 to 15 mol percentage of intermediate phthalic acid (the sum of the molar numbers of isophthalic acid and terephthalic acid is 100%). (Please read the notes on the reverse side before filling out this page) This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 42 ABCD This Notice ^ 171 9 6 ο 六、申請專利範園 1·一種合成高收縮性共聚酯之新潁組成配方,其由 ⑴9,9’-雙-[4-(2_經基乙氧基)苯基]苟,其用量為1 至20莫耳百分比(以間苯二甲酸和對苯二甲酸 的莫耳數和為100%),和 (2) 間苯二甲酸,其用量為1至25莫耳百分比(以 間苯二甲酸和對苯二甲酸的莫耳數和為100%),和 (3) 對苯二甲酸,其用量為75至99莫耳百分比(以 間苯二甲酸和對苯二甲酸的莫耳數和為100%),和 乙二醇(9,9,-雙-f4-(2-羥基乙氧基)苯基]芴和乙二醇 的莫耳數和與間苯二甲酸和對苯二甲酸的莫耳敦和 比為1.2至1.7)所舍成。 2. 如申請專利範圍第1項之組成配方 ,其申請專利範中 9,9’-雙-[4-(2_經基乙氧基)苯基]芴之用量為2至15莫耳百 分比(以間苯二甲酸和對苯二甲酸的莫耳數和為100%)。 3. 如申請專利範圍第1項之組成配方 ,其申請專利範圍 中間苯二甲酸用量為1至15莫耳百分比(以間苯二甲酸 和對苯二甲酸的莫耳數和為100%)。 (請先聞讀背面之注意事頃再填寫本頁) 本紙張尺度適用中國國家標準(CNS ) A4規格(210 X 297公釐)6. Application for a patent Fan Yuan 1. A new compound of high-shrinkage copolyester, which is composed of 99,9'-bis- [4- (2- (Ethylethoxy) phenyl)] and its dosage 1 to 20 mol% (based on the sum of the number of mols of isophthalic acid and terephthalic acid), and (2) isophthalic acid in an amount of 1 to 25 mol% (based on m-benzene Molar sum of dicarboxylic acid and terephthalic acid is 100%), and (3) terephthalic acid is used in a percentage of 75 to 99 moles (in terms of moles of isophthalic acid and terephthalic acid) The sum is 100%), and the molar numbers of ethylene glycol (9,9, -bis-f4- (2-hydroxyethoxy) phenyl) fluorene and ethylene glycol and isophthalic acid and terephthalic acid The molar ratio of formate is 1.2 to 1.7). 2. If the composition formula of item 1 of the scope of patent application, the amount of 9,9'-bis- [4- (2_ylethoxy) phenyl] fluorene used in the patent application range is 2 to 15 mole percent (The sum of the molar numbers of isophthalic acid and terephthalic acid is 100%). 3. If the composition formula of item 1 of the scope of patent application, the scope of patent application of the scope of patent application is 1 to 15 mol percentage of intermediate phthalic acid (the sum of the molar numbers of isophthalic acid and terephthalic acid is 100%). (Please read the notes on the back before filling out this page) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm)
TW88106608A 1999-04-23 1999-04-23 Novel prescription of copolyesters TW420697B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112574400A (en) * 2021-02-26 2021-03-30 中国科学院宁波材料技术与工程研究所 High glass transition temperature and high transparency polyester, polyester product, preparation method and application thereof
CN112592467A (en) * 2021-02-26 2021-04-02 中国科学院宁波材料技术与工程研究所 High glass transition temperature low melting point polyester, polyester product, and preparation method and application thereof
CN112592471A (en) * 2021-02-26 2021-04-02 中国科学院宁波材料技术与工程研究所 High-heat-resistance high-toughness polyester, polyester product, preparation method and application thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112574400A (en) * 2021-02-26 2021-03-30 中国科学院宁波材料技术与工程研究所 High glass transition temperature and high transparency polyester, polyester product, preparation method and application thereof
CN112592467A (en) * 2021-02-26 2021-04-02 中国科学院宁波材料技术与工程研究所 High glass transition temperature low melting point polyester, polyester product, and preparation method and application thereof
CN112592471A (en) * 2021-02-26 2021-04-02 中国科学院宁波材料技术与工程研究所 High-heat-resistance high-toughness polyester, polyester product, preparation method and application thereof
CN112592467B (en) * 2021-02-26 2021-04-30 中国科学院宁波材料技术与工程研究所 High glass transition temperature low melting point polyester, polyester product, and preparation method and application thereof
CN112592471B (en) * 2021-02-26 2021-05-07 中国科学院宁波材料技术与工程研究所 High-heat-resistance high-toughness polyester, polyester product, preparation method and application thereof

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