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CN-121991329-A - High-transparency thermoplastic polyester elastomer and preparation method thereof

CN121991329ACN 121991329 ACN121991329 ACN 121991329ACN-121991329-A

Abstract

The invention relates to a high-transparency thermoplastic polyester elastomer and a preparation method thereof, wherein the method comprises the following steps: mixing raw material monomers and a catalyst, wherein the raw material monomers comprise diacid monomers and diol monomers, the diacid monomers comprise cyclic diacid or esterified matters thereof, the diol monomers comprise aliphatic diol, cyclic diol and polyether diol, the esterification reaction is carried out under the atmosphere of protective gas to obtain an oligomer, the oligomer is subjected to pre-polycondensation, and the final polycondensation is carried out under the vacuum condition to obtain the high-transparency thermoplastic polyester elastomer. Compared with the prior art, the high-transparency thermoplastic polyester elastomer prepared by the invention has good light transmittance and controllable mechanical property and light transmittance.

Inventors

  • WANG YAXIONG
  • XI ZHENHAO
  • SUN SHUANGYI
  • JIANG JIE
  • XIA YONGLIANG
  • ZHAO LING
  • ZHANG RUNYU

Assignees

  • 中石油(上海)新材料研究院有限公司
  • 中国石油天然气股份有限公司
  • 华东理工大学

Dates

Publication Date
20260508
Application Date
20241104

Claims (10)

  1. 1. A highly transparent thermoplastic polyester elastomer characterized in that the chemical structural formula of the units of the elastomer is as follows: Wherein a, b and c are all integers which are not zero, a (a+b) is 0.1-0.95, c (a+b+c) is 0.05-0.8, R 1 is alkyl with 2-18 carbon atoms, R 2 is alicyclic, aromatic ring or furan ring, the aromatic ring is one or more selected from benzene ring, biphenyl ring and naphthalene ring, R 3 is polyether or polyester, and R 4 is aliphatic saturated ring.
  2. 2. A process for the preparation of a highly transparent thermoplastic polyester elastomer as claimed in claim 1, comprising the steps of: Mixing raw material monomers and a catalyst, wherein the raw material monomers comprise diacid monomers and diol monomers, the diacid monomers comprise cyclic diacid or esterified matters thereof, the diol monomers comprise aliphatic diol, cyclic diol and polyether diol, the esterification reaction is carried out under the atmosphere of protective gas to obtain an oligomer, the oligomer is subjected to pre-polycondensation, and the final polycondensation is carried out under the vacuum condition to obtain the high-transparency thermoplastic polyester elastomer.
  3. 3. The method for producing a highly transparent thermoplastic polyester elastomer according to claim 2, wherein the cyclic dibasic acid or an ester thereof is one or more selected from terephthalic acid, dimethyl terephthalate, isophthalic acid, dimethyl isophthalate, phthalic acid, dimethyl phthalate, 1, 4-cyclohexanedicarboxylic acid, and dimethyl 1, 4-cyclohexanedicarboxylate.
  4. 4. The method for producing a highly transparent thermoplastic polyester elastomer according to claim 2, wherein the aliphatic diol is one or more selected from the group consisting of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 2-methyl-1, 3-propanediol, and neopentyl glycol.
  5. 5. The method for producing a highly transparent thermoplastic polyester elastomer according to claim 2, wherein the cyclic diol is one or more selected from the group consisting of 1, 4-cyclohexanedimethanol, 2, 4-tetramethyl-1, 3-cyclobutanediol and isosorbide.
  6. 6. The method for preparing a highly transparent thermoplastic polyester elastomer according to claim 2, wherein the polyether glycol is one or more selected from polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol, and the number average molecular weight of the polyether glycol is 200-2000.
  7. 7. The method for preparing a highly transparent thermoplastic polyester elastomer according to claim 2, wherein the molar ratio of the dibasic acid monomer to the dihydric alcohol monomer is 1 (1.05-3).
  8. 8. The method for preparing the high-transparency thermoplastic polyester elastomer according to claim 2, wherein the catalyst is one or more catalysts with 1-12 carbon atoms selected from an organic aluminum compound, an organic tin compound and a titanate.
  9. 9. The method for producing a highly transparent thermoplastic polyester elastomer according to claim 2, wherein the molar ratio of the catalyst to the raw material monomer is (0.0002 to 0.005): 1.
  10. 10. The method for preparing a highly transparent thermoplastic polyester elastomer according to claim 2, wherein the esterification reaction is carried out at a temperature of 150-280 ℃, a rotational speed of 100-300 r/min, a time of 0.5-4 hours, The temperature of the pre-polycondensation is 180-280 ℃, the pressure is 3-10 kPa, the time is 0.5-2 hours, The temperature of the final polycondensation is 180-280 ℃, the vacuum degree is 50-300 Pa, and the time is 1-8 hours.

Description

High-transparency thermoplastic polyester elastomer and preparation method thereof Technical Field The invention belongs to the technical field of high polymer materials, and relates to a high-transparency thermoplastic polyester elastomer and a preparation method thereof. Background Elastomer refers broadly to a material that recovers its large deformation after removal of an external force, and rubber is the earliest used by humans and is also the most widely used elastomer. Due to the thermosetting nature of the rubber itself, it results in a short plate that is processed once and difficult to regenerate. Since the first Polyurethane (PU) was prepared by Bayer in the 40 th century, it was found that thermoplastic elastomers (TPE) have been rapidly developed because of their convenience in processing multiple times, and their ability to be used in place of rubber in multiple applications. Thermoplastic polyester elastomers (TPEEs) are generally a class of polyether ester copolymers with hard segments of high crystallinity, high melting polyester blocks and soft segments of amorphous polyethers having a relatively low glass transition temperature, also known as polyester thermoplastic elastomers or polyester rubbers. The amorphous polyether phase imparts resilience to the material and the hard segment of the polyester partially crystallizes to form crystalline domains which act as physical crosslinking points. TPEE has the elasticity of rubber and the strength of engineering plastic, soft segment gives it elasticity, making it resemble rubber, and hard segment gives it processability, making it resemble plastic. Compared with rubber, it has better processing property and longer service life, and compared with engineering plastics, it has the same high strength, better flexibility and dynamic mechanical property. TPEE has the characteristics of high strength, high elasticity, oil resistance, acid and alkali resistance, high temperature resistance, radiation resistance, excellent dynamic mechanical property and the like, and has a wide use temperature range of-50-180 ℃ and a hardness range of 25-80D. The purpose of the initial research and development of TPEE was to prepare highly elastic fibers for the textile industry. But TPEE is now an irreplaceable high-performance novel elastomer material and is widely applied to the fields of automobiles, electronics, electrics, railways and the like. But TPEE materials exhibit opacity due to the higher degree of microphase separation between the hard segment polyester and the soft segment polyether and the higher crystallinity of the hard segment, hampering their field of application. Therefore, proper monomer polymerization is selected to form soft and hard segments, which is an effective way for improving the transparency of the polyester elastomer, widening the application and realizing high-value utilization. The transparent polyester elastomer has excellent mechanical property and special optical property of the traditional polyester elastomer, and can be used as bulletproof glass interlayers, transparent protective products, automobile parts and the like. It is important to develop a TPEE with high transparency. Patent CN117304656a discloses a high-transparency thermoplastic polyester elastomer and a preparation method thereof, specifically, the method comprises the steps of mixing TPEE, plasticizer, nucleating agent, antioxidant, lubricant and other auxiliary agents, and processing the mixture through a twin-screw extruder to obtain the high-transparency thermoplastic polyester elastomer. The obtained transparent TPEE has excellent mechanical properties, but the material is a semitransparent product, the light transmittance is only 15.8 percent, and the product with higher transparency is not prepared from the aspect of mechanism regulation. Patent CN113429749A discloses a high-transparency low-melt-index thermoplastic polyester elastomer and a preparation method thereof, and specifically comprises the steps of mixing TPEE, an anti-reflection agent, a nucleating agent and an antioxidant, and performing twin-screw extrusion processing to obtain a high-transparency polyester material. The obtained material has low melt index and good light transmittance, but has poor mechanical property, and the crystal lattice size is changed only by adding an anti-reflection agent, so that the material is macroscopically transparent, and TPEE with different mechanical properties and light transmittance is not prepared from the in-situ polymerization point of view. Patent CN117343502a discloses a transparent toughened PET material and a preparation method thereof, specifically, the method comprises mixing polyethylene terephthalate (PET), polyethylene glycol-1, 4-cyclohexanedimethanol terephthalate (PCTG) and an antioxidant, preparing the transparent toughened PET material by twin-screw extrusion, wherein the preparation of modified PCTG is described in detail, mixing terephtha