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CN-121975093-A - Hydrogenated polycycloolefin material for optical lens and preparation method thereof

CN121975093ACN 121975093 ACN121975093 ACN 121975093ACN-121975093-A

Abstract

The invention relates to the technical field of optical materials, in particular to a hydrogenated polycycloolefin material for an optical lens and a preparation method thereof. The structural general formula is shown in formula I: Wherein ,R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 is selected from at least one of hydrogen, a linear alkyl group of substituted or unsubstituted C 1 -C 20 , a branched alkyl group of substituted or unsubstituted C 1 -C 20 , a cycloalkyl group of substituted or unsubstituted C 3 -C 20 , an aryl group of substituted or unsubstituted C 6 -C 30 , a heteroaryl group of substituted or unsubstituted C 3 -C 20 , a halogen, or an ester group, and the ratio of x, y, z is (5-85): 5-85, and n is an integer of 1-10000. The hydrogenated polycycloolefin material has Tg of more than or equal to 200 ℃, light transmittance of more than or equal to 89% in a wavelength range of 400-800nm, refractive index of more than or equal to 1.57, and excellent mechanical property.

Inventors

  • ZHONG NING
  • ZHANG HENGCHEN
  • WANG ZHONGYAO
  • LI SHITAO
  • Xi Houhua

Assignees

  • 广东特聚新材料科技有限公司

Dates

Publication Date
20260505
Application Date
20260206

Claims (10)

  1. 1. A hydrogenated polycycloolefin material for an optical lens is characterized in that the structural general formula is shown in formula I: A formula I; wherein ,R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 is selected from at least one of hydrogen, a linear alkyl group of substituted or unsubstituted C 1 -C 20 , a branched alkyl group of substituted or unsubstituted C 1 -C 20 , a cycloalkyl group of substituted or unsubstituted C 3 -C 20 , an aryl group of substituted or unsubstituted C 6 -C 30 , a heteroaryl group of substituted or unsubstituted C 3 -C 20 , a halogen, or an ester group, the ratio of x, y, z being (5-85): 5-85, n being an integer of 1-10000.
  2. 2. The hydrogenated polycycloolefin material according to claim 1, wherein the hydrogenated polycycloolefin material has a Tg of not less than 200 ℃, a light transmittance of not less than 89% in a wavelength range of 400 to 800nm and a refractive index of not less than 1.57.
  3. 3. The hydrogenated polycycloolefin material according to claim 1, wherein the hydrogenated polycycloolefin material has a Tg of 200-250 ℃, a light transmittance of 89-93% in a wavelength range of 400-800nm, and a refractive index of 1.57-1.65.
  4. 4. The hydrogenated polycycloolefin material according to claim 1 or 3, wherein the raw materials for preparing the hydrogenated polycycloolefin material comprise reaction monomers, wherein the reaction monomers comprise a first monomer shown in a formula II, a second monomer shown in a formula III and a third monomer shown in a formula IV. A formula II; III; IV。
  5. 5. The hydrogenated polycycloolefin material according to claim 4, wherein the first monomer is prepared by Diels-Alder reaction of norbornadiene and anthracene derivative having R 1 、R 2 、R 3 、R 4 substituent, the second monomer is prepared by Diels-Alder reaction of norbornene and olefin having R 5 、R 6 、R 7 、R 8 substituent, the reaction temperature is 190-300 ℃, and the third monomer is prepared by Diels-Alder reaction of dicyclopentadiene and indene having R 9 、R 10 substituent, the reaction temperature is 160-250 ℃.
  6. 6. The hydrogenated polycycloolefin material according to claim 5, wherein the raw materials for preparing the hydrogenated polycycloolefin material further comprise a solvent, a metathesis polymerization catalyst, hydrogen, a terminator and a hydrogenation catalyst.
  7. 7. The hydrogenated polycycloolefin material according to claim 6, further comprising a polymerization inhibitor, a cocatalyst, a ligand and a polymerization molecular weight regulator.
  8. 8. A process for preparing hydrogenated polycycloolefin material as defined in claim 6, comprising the steps of ring-opening metathesis polymerization of the first monomer, the second monomer and the third monomer in the presence of a solvent and a metathesis polymerization catalyst under anhydrous and anaerobic conditions, terminating the reaction by adding a terminating agent after the completion of the reaction, and post-treating to obtain a cycloolefin polymer, mixing the cycloolefin polymer with a hydrogenation catalyst, carrying out hydrogenation under hydrogen atmosphere, and post-treating to obtain the hydrogenated polycycloolefin material.
  9. 9. The process for preparing hydrogenated polycycloolefin according to claim 8, wherein the molar ratio of cycloolefin polymer to hydrogenation catalyst is 1 (5X 10 -5 -5×10 -2 ).
  10. 10. The process for preparing a hydrogenated polycycloolefin material according to claim 8, wherein the hydrogenation reaction temperature is 60 to 300℃and the pressure is 1 to 10MPa.

Description

Hydrogenated polycycloolefin material for optical lens and preparation method thereof Technical Field The invention relates to the technical field of optical materials, in particular to a hydrogenated polycycloolefin material for an optical lens and a preparation method thereof. Background Polycycloolefins have become core materials in high-end fields such as optical lenses, display devices, and optoelectronic devices by virtue of excellent characteristics such as low birefringence, high light transmittance, low hygroscopicity, good thermal stability, and the like. However, the glass transition temperature (Tg) of the conventional polycycloolefin is generally limited to 130-150 ℃, so that the severe requirement of high-temperature application scenes such as a vehicle-mounted imaging system and a laser projection device on the heat resistance of the material is difficult to meet, and the further expansion of the high-end optical field is restricted. To solve this technical bottleneck, various modification attempts have been made in the industry. For example, the Tg of the chinese patent application CN1871291a is improved by blending modification, but the optical transparency is generally reduced, the thermal stability of the chinese patent CN100390217C is improved by constructing a crosslinked structure, which leads to excessive viscosity of the polymer, easy occurrence of polymerized gel, and difficulty in stable preparation of qualified products, and the Tg of the chinese patent application CN107216444a is improved by introducing a large group branched chain, which leads to excessive rigidity of the material, insufficient elongation at break, and limited mechanical processing property. The Chinese patent application CN117756986A discloses a cycloolefin copolymer prepared by ring-opening metathesis polymerization, wherein Tg reaches 139.58 ℃, elongation at break is 73.66%, young modulus is 1534MPa, although thermal stability is improved to a certain extent, tg is still lower than the standard of more than 180 ℃ required by high-temperature application, the thermal stability is easily affected in the hydrogenation post-treatment process, and meanwhile, the comprehensive balance performance of refractive index and light transmittance does not reach the application requirement of a high-end optical lens, and the uniformity of high heat resistance, high light transmittance and excellent processing performance cannot be achieved. Therefore, the development of the hydrogenated polycycloolefin material with remarkably improved Tg, excellent optical performance and stable preparation process becomes a key for breaking through the current technical bottleneck and pushing polycycloolefin to be widely applied to the field of high-end optical lenses, and has important technical value and market significance. Disclosure of Invention The first aspect of the invention provides a hydrogenated polycycloolefin material for an optical lens, and the structural general formula of the hydrogenated polycycloolefin material is shown as formula I: Wherein ,R1、R2、R3、R4、R5、R6、R7、R8、R9、R10 is selected from at least one of hydrogen, a linear alkyl group of substituted or unsubstituted C 1-C20, a branched alkyl group of substituted or unsubstituted C 1-C20, a cycloalkyl group of substituted or unsubstituted C 3-C20, an aryl group of substituted or unsubstituted C 6-C30, a heteroaryl group of substituted or unsubstituted C 3-C20, a halogen, or an ester group, and the ratio of x, y, z is (5-85): 5-85, and n is an integer of 1-10000. The research of the application discovers that a polymer system with regular and compact molecular chains and synergistic interaction is constructed through three monomer ternary polymerization structure designs and side group regulation and control, thereby realizing the synergistic unification of high Tg, high light transmittance, high refractive index, good mechanical properties and processability essentially, and the core mechanism is as follows: all three monomers are prepared by Diels-Alder reaction based on a cycloolefin skeleton, cycloolefin has optical basis of low birefringence and low hygroscopicity, molecular chains form an interweaved ordered network structure by ring-opening metathesis polymerization during ternary polymerization, space steric hindrance among chain segments is obviously increased, molecular chain movement is effectively limited, meanwhile, the rigidity of the molecular chains is further enhanced after hydrogenation reaction is saturated with double bonds, compared with a binary copolymerization system, the ternary structure can avoid chain segment arrangement defects, degradation is not easy to occur in the hydrogenation process, so that Tg is stably raised to be more than 200 ℃, and pain points with lower Tg of conventional polycycloolefins are solved; the uniform stacking of molecular chains and the thermodynamic compatibility of a ternary system avoid the common phase separati