CN112980162B

CN112980162B - Montmorillonite modified PET high-temperature-resistant optical polyester material and preparation method thereof

Info

Publication number: CN112980162B
Application number: CN202110294837.1A
Authority: CN
Inventors: 陈福德; 马寒冰
Original assignee: Southwest University of Science and Technology
Current assignee: Southwest University of Science and Technology
Priority date: 2021-03-19
Filing date: 2021-03-19
Publication date: 2022-04-15
Anticipated expiration: 2041-03-19
Also published as: CN112980162A

Abstract

The invention relates to a montmorillonite modified PET high-temperature resistant optical polyester material and a preparation method thereof, which is characterized in that the montmorillonite modified PET high-temperature resistant optical polyester material is prepared by blending organic montmorillonite and PET and melting and extruding, wherein the organic montmorillonite is obtained by modifying sodium-based montmorillonite by 2-epoxy ethylene methyl triphenyl phosphorus chloride. The modification method comprises the following steps: firstly, surface modification is carried out on montmorillonite by using 2-epoxy ethylene methyl triphenyl phosphonium chloride. And secondly, blending the modified montmorillonite and PET, and then carrying out melt extrusion, granulation and drying to obtain the PET high-temperature-resistant optical polyester film material. The invention has the advantages that: 2-ethylene oxide methyl triphenyl phosphorus chloride loaded by the montmorillonite can react with carboxyl and hydroxyl at two ends of a PET chain segment, so that the compatibility of the organic montmorillonite and the PET is improved, the light transmittance, the mechanical property, the gas barrier property and the heat resistance of the PET are improved, and the haze of the PET is reduced. The preparation process is simple, green and environment-friendly, and can be widely used in the field of optical polyester materials.

Description

Montmorillonite modified PET high-temperature-resistant optical polyester material and preparation method thereof

Technical Field

The invention relates to a montmorillonite-modified PET high-temperature-resistant optical polyester material and a preparation method thereof, belonging to the field of high polymer materials.

Background

Optical films are an important class of optical elements that are widely used in modern optics, optoelectronics, optical engineering, and other related scientific and technical fields. Play an irreplaceable role in the transmission, modulation, division and synthesis of spectrum and energy and conversion of light with other energy states.

In recent years, rapid development of a new-generation information industry represented by flexible electronics, flexible display, and the like has made urgent application demands for optical film materials. Polymer optical film materials, including polyethylene terephthalate (PET), polyethylene naphthalate (PEN), Triacetylcellulose (TAC), polyvinyl alcohol (PVA), Polycarbonate (PC), and the like, have been widely used in the information industry such as electronics and displays because of their excellent optical transparency, good mechanical properties, easy availability of raw materials, and low cost.

Compared with other optical films, the PET polyester film has the advantages of high light transmission, low haze, good stiffness, ultraviolet resistance, good processability, sufficient raw materials and the like, and can well meet the output requirement of the current electronic industry. However, with the continuous development of the electronic and display technology towards high speed, high integration, high density and ultra-thin, the PET polyester optical film material has increasingly high requirements on heat resistance, mechanical properties, water and oxygen resistance and the like. At present, the heat resistance of the common PET polyester optical film material is still insufficient, for example, the glass transition temperature Tg of PET is only 78 ℃, the mechanical strength is only 60MPa, and the water vapor transmission capacity is only 10 g/(m)²24h), it is urgent to improve the overall properties of the polyester optical film material, such as heat resistance, mechanical properties, and gas barrier properties.

At present, methods for improving the heat resistance, mechanical properties, gas barrier property and the like of PET polyester optical film materials can be mainly divided into copolymerization modification methods and blending modification methods.

The copolymerization modification method is a method for improving the performance of PET by adding a chemical modifier to carry out chemical copolymerization with PET and introducing a special functional group into PET molecules. The blending modification method is a method for uniformly dispersing a modifier material in PET (polyethylene terephthalate) by adding the modifier and mixing the modifier with the PET material so as to improve the performance of the PET. At present, a copolymerization modification method at home and abroad is mainly used for improving certain performance of PET by introducing flexible or rigid groups. For example: chinese patent CN105482088A discloses that by mixing polybutylene terephthalate and polyethylene glycol, a polybutylene terephthalate and polyethylene glycol block copolymer is obtained, the mechanical strength of PBT is improved, and the comprehensive properties such as resilience, use temperature range and the like are increased; the Chinese patent CN109553759A takes terephthalic acid or derivatives thereof and ethylene glycol as raw materials, and sodium benzoate ethylene glycol solution is added in the esterification process for copolymerization to prepare the modified PET polyester material. The crystallization rate of the obtained modified polyester is more than 3.5 times of that of the conventional polyester, and the melting crystallization peak temperature is higher than 208 ℃; CN108948332A introduces cis-2, 2, 4, 4-tetramethyl-1, 3-cyclobutanediol monomer in PET chain as third party monomer to prepare PET copolymer containing non-planar ring, and the glass transition temperature of the obtained copolymer can be raised to 90 ℃ at most; chen Xu et al copolymerized and modified PET with biphenyl dicarboxylic acid, the glass transition temperature of the obtained polymer alloy is increased with the addition of biphenyl dicarboxylic acid, and can be increased by 15 ℃ at most compared with the glass transition temperature of pure PET polymer alloy.

The blending modification method at home and abroad mainly adds organic and inorganic particles to blend with PET to improve the performance of PET. The method can be divided into organic blending modification and inorganic blending modification according to the types of the added particles. The organic blending modification is a blending system obtained by blending more than two organic polymers with different characteristics by a specific method, so that the advantages of the two polymers are simultaneously embodied in the alloy. Such as: the Chinese patent CN111363338A prepares a polymer alloy with the bending strength as high as 86.51MPa by blending PC and PET, and can completely replace the traditional aluminum-wood-plastic alloy. Inorganic blending modification is generally a method of doping inorganic particles into a polymer system to improve some property of the polymer. Such as: in the Chinese patent CN 104327465A, the thermal stability of the PET material is improved by adding calcium carbonate nano particles into the PET; US10808098B2 prepares nanocomposites by adding graphene and blending with PET; CN107778796A is added with targeting modified nano silicon nitride and is blended with PET to prepare the PET composite material with excellent temperature resistance; CN106751543A through modifying montmorillonite with catalyst and surfactant, and then blending with PET, the composite material has good gas barrier property, transparency, processability and mechanical property, and inorganic particles in the transparent composite material do not generate agglomeration and have good dispersibility.

The blending modification method and the copolymerization modification method can improve the heat resistance, the mechanical property and the like of the PET as shown in the domestic and foreign documents. In contrast, the copolymerization modification method has complex preparation process, difficult adjustment of process flow and high cost, and is not beneficial to popularization and application of PET. The blending modification method has the advantages of simple manufacturing process, low cost, contribution to recycling of the PET polyester film and the like, and is more favorable for large-scale application of the PET material. In the modifier used by the existing blending modification method, montmorillonite has the advantages of good heat resistance, high mechanical property, no color pollution and the like, and is more favorable for preparing an optical PET film material with good comprehensive properties such as optical property, mechanical property, barrier property, heat resistance and the like.

Montmorillonite is an inorganic material, surface modification is required to be carried out in advance when the montmorillonite is applied to PET, and organic surface modification of montmorillonite is also the key for improving the performance of the PET optical polyester film material. At present, the surface modifier commonly used for montmorillonite mainly comprises anion, cation and non-ion. Among them, the nonionic type is mainly polyether type, polyoxyethylene type, alkanolamide type. Such as: poriferous stage and the like use polyether amine as a modifier to carry out surface organic modification on montmorillonite to prepare modified montmorillonite with the interlayer spacing of 1.9 nmd; tung et al uses nonylphenol polyoxyethylene ether as hydrophobic modifier, and adopts ball-milling method to modify sodium-base montmorillonite so as to obtain the invented organic montmorillonite. The anions are mainly sulfonates, sulfates and carboxylates, such as: CN105733315A intercalates montmorillonite with carboxymethyl cellulose sodium as anion modifier to obtain modified montmorillonite. The prepared modified montmorillonite not only has catalytic performance, but also has the capability of improving the thermal stability and the flame retardant performance of the polymer; CN109021250A adopts anionic modifier organic amine sulfonate to organically modify montmorillonite. Organic amine sulfonate in the obtained modified montmorillonite enters into montmorillonite layers, so that the interlayer spacing of the montmorillonite is effectively opened, and the compatibility of the montmorillonite and organic matters is improved; li Yingyong et al successfully modify the surface of montmorillonite with sodium dodecylsulfate to obtain organic montmorillonite which can be uniformly dispersed in styrene and has significantly increased lipophilicity. The cationic surface modifier mainly comprises amine salt type, quaternary ammonium salt type, quaternary phosphate salt type and the like. The amine salt type cationic surface modifier mainly comprises higher aliphatic amines such as primary amine salt, secondary amine salt and tertiary amine salt generated by the neutralization reaction of aliphatic amine and acid. Such as: CN102583419A primary amine salts with different chain lengths such as dodecyl primary amine, tetradecyl primary amine and octadecyl primary amine, and tertiary amine salts with different chain lengths such as dodecyl dimethyl tertiary amine, tetradecyl dimethyl tertiary amine and octadecyl dimethyl tertiary amine are used for carrying out organic modification on montmorillonite to prepare the organic modified montmorillonite with the interlayer spacing up to 3.02nm, and the modification effect is obvious. CN 106495175A uses quaternary ammonium salts with different chain lengths to organically modify montmorillonite, and the organic quaternary ammonium salts react with cations in the montmorillonite to perform ion exchange with cations between montmorillonite layers to organically modify the montmorillonite; the quaternary ammonium salt is also called quaternary ammonium salt, is a compound generated by replacing four hydrogen atoms in ammonium ions with alkyl, and is often used as a cationic surfactant to carry out surface organic modification on montmorillonite. Such as: yangyuxiang et al use cetyl trimethyl ammonium bromide to modify sodium montmorillonite organically to obtain an organic montmorillonite which has positive charges on the surface and can adsorb and enrich pigment molecules with negative charges in water. The quaternary phosphonium salt is a high-temperature resistant cationic surfactant and is commonly used for surface modification of inorganic powder. Such as: souza et al exchange different quaternary phosphonium salts between layers of sodium-based montmorillonite by ion exchange to obtain modified montmorillonite, wherein the thermal decomposition starting temperature of organic matters in the modified montmorillonite is 30 ℃ higher than that of quaternary ammonium salt modified montmorillonite.

Compared with anionic and nonionic surface modifiers, cations in the cationic surface modifier can exchange ions with metal ions among montmorillonite layers, the cation surface modifier has stronger capacity of entering montmorillonite layers, can improve the interlayer spacing and the organophilic property of the montmorillonite, and is beneficial to the dispersion of the modified montmorillonite in a PET matrix. In the cationic surface modifier, compared with amine salt, quaternary ammonium salt and the like, the quaternary phosphonium salt has the advantages of high thermal decomposition temperature, yellowing resistance and the like, and is more favorable for the application of the modified montmorillonite in the PET optical polyester material. At present, the types of quaternary phosphonium salts used for modifying montmorillonite are mainly alkyl quaternary phosphonium salts and aryl quaternary phosphonium salts.

The alkyl quaternary phosphonium salt refers to a quaternary phosphonium salt in which organic groups are aliphatic groups and is generally obtained by reacting alkyl phosphonium and halogenated hydrocarbon, and at present, the quaternary phosphonium salts used for modifying polyesters such as PET and the like mainly comprise dodecyl trimethyl phosphonium chloride, tetradecyl trihexyl phosphonium chloride, tetrabutyl phosphonium and butyl triphenyl phosphonium bromide. Such as: liuyufang et al use dodecyl trimethyl phosphorus chloride to organically modify the surface of sodium montmorillonite, and the interlayer spacing of the organic montmorillonite is 2.193 nm. The aryl quaternary phosphonium salt is a quaternary phosphonium salt which contains aromatic groups such as benzene rings and is generally obtained by reacting triphenyl phosphonium with halogenated hydrocarbon. Such as: zhou Kunhao et al organically modified montmorillonite with hexadecyl triphenyl phosphonium salt and tetradecyl triphenyl phosphonium salt, respectively. The interlayer spacing of the hexadecyl triphenyl phosphonium salt modified organic montmorillonite reaches 3.93nm, and the interlayer spacing of the tetradecyl triphenyl phosphonium salt modified organic montmorillonite reaches 3.87 nm; in contrast, the aryl quaternary phosphonium salts have high heat resistance and good yellowing resistance. However, the aryl quaternary phosphonium salt used in the current montmorillonite modification research is not only high in cost, but also does not have a functional group capable of generating a crosslinking reaction with a PET matrix, and the modified organic montmorillonite is easy to cause the problems of interface incompatibility, PET degradation and the like when being used for a PET optical polyester material, and can not meet the requirements of the PET optical polyester material on optical performance, heat resistance, tensile strength, barrier property and the like.

In order to overcome the defects, the patent provides a PET high-temperature resistant optical polyester material modified by montmorillonite and a preparation method thereof.

Disclosure of Invention

The purpose of the invention is: aiming at the defects of the prior PET high-temperature resistant optical polyester material and the preparation method thereof, provides a PET high-temperature resistant optical polyester material modified by montmorillonite and the preparation method thereof. The method firstly utilizes a low-cost method to synthesize the epoxy-containing aryl quaternary phosphonium salt 2-oxiranylmethyl triphenyl phosphonium chloride, and the modified montmorillonite is used for modifying the montmorillonite, and the PET optical polyester material modified by blending the modified montmorillonite has the advantages of high light transmittance, low haze, high heat resistance, high tensile strength, high barrier property and the like.

The principle of the invention is as follows: firstly, replacing expensive epoxy iodopropane with cheap epoxy chloropropane to react with triphenyl phosphorus to generate aryl quaternary phosphonium salt 2-epoxy ethylene methyl triphenyl phosphonium chloride containing epoxy group, wherein the epoxy aryl quaternary phosphonium salt is a cationic surfactant and can perform ion exchange with metal ions between montmorillonite layers to perform organic intercalation modification on montmorillonite. The surface of the lamella of the prepared organic montmorillonite contains a large amount of epoxy functional groups, and the organic montmorillonite can generate crosslinking reaction with a PET matrix to play a role of a crosslinking agent. And melting and blending the organic montmorillonite and the PET polyester material to prepare the PET high-temperature-resistant optical polyester film material. Because the epoxy group aryl quaternary phosphonium salt loaded on the organic montmorillonite can chemically react with the carboxyl and the hydroxyl at the two ends of the PET molecular chain, the compatibility of the organic montmorillonite and the PET is increased, the light transmittance of the PET material is increased, the haze of the PET material is reduced, and the heat resistance, the mechanical property and the gas barrier property of the PET can be improved.

The content of the invention is as follows: a montmorillonite modified PET high temperature resistant optical polyester material is characterized in that the material is prepared by blending organic montmorillonite and polyester and melt extrusion, and the dosage of each raw material is as follows: 0.5-2.5 wt% of organic montmorillonite and 97.5-99.5 wt% of PET polyester. The organic montmorillonite is obtained by modifying sodium montmorillonite with 2-epoxy ethylene methyl triphenyl phosphonium chloride, and the polyester is polyethylene glycol terephthalate.

The second content of the invention is: a PET high-temperature resistant optical polyester material modified by montmorillonite. The method is characterized by comprising the following steps.

(1) Synthesis of 2-oxiranylmethyl triphenyl phosphonium chloride: firstly, adding 10g of triphenyl phosphine, 0-0.4g of catalyst sodium iodide and 10-30mL of epoxy chloropropane into a reaction kettle, and stirring at normal temperature until the triphenyl phosphine, the catalyst sodium iodide and the epoxy chloropropane are completely dissolved; then reacting for 6-10h at room temperature-100 ℃ under the protection of nitrogen; then carrying out reduced pressure distillation to remove unreacted epichlorohydrin to obtain a yellow reaction product, purifying with ethyl acetate, filtering, and drying to prepare 2-oxiranylmethyl triphenyl phosphorus chloride;

(2) preparing organic montmorillonite: 45g of sodium montmorillonite is added into a beaker filled with 800mL of distilled water, and the stirring is continued for 30min until the montmorillonite is uniformly dispersed. And (3) carrying out ultrasonic dispersion on the beaker filled with the suspension for 30min, standing for 5-10min after the ultrasonic dispersion is finished, and removing the sediment at the bottom. And (2) adding 10-20g of 2-oxiranylmethyl triphenyl phosphorus chloride prepared in the step (1), performing ultrasonic dispersion for 30min, stirring and reacting for 4-8 h at the temperature of room temperature-90 ℃, performing suction filtration, and washing for 4-5 times by using distilled water. Drying the product at 100 ℃, crushing the dried product, and sieving the crushed product with a 200-mesh sieve to prepare the organic modified montmorillonite;

(3) the preparation of the montmorillonite modified PET high temperature resistant optical polyester material comprises the following steps: and (3) blending 0.5-2.5 wt% of the organic montmorillonite prepared in the step (2) and 97.5-99.5 wt% of PET polyester by using a high-speed mixer, and then carrying out melt extrusion, granulation and drying by using a double-screw extruder to obtain the PET high-temperature-resistant optical polyester material.

THE ADVANTAGES OF THE PRESENT INVENTION

The organic modifier widely used by montmorillonite at present is quaternary ammonium salt cation modifier, which has poor heat resistance and the decomposition initial temperature is not more than 200 ℃. The initial decomposition temperature of the novel quaternary phosphonium salt synthesized by the method is close to 300 ℃ and is 100 ℃ higher than that of the quaternary ammonium salt. The heat resistance of the organic montmorillonite prepared by the method is obviously improved, and the color, mechanics, heat resistance and other properties of PET cannot be influenced by thermal decomposition of a modifier in the preparation process of the PET high-temperature-resistant optical polyester material.

The epoxy group aryl quaternary phosphonium salt synthesized by the invention has an epoxy functional group capable of reacting with a PET polyester matrix, and the organic montmorillonite loaded epoxy group aryl quaternary phosphonium salt obtained by modification of the epoxy group aryl quaternary phosphonium salt can chemically react with carboxyl and hydroxyl at two ends of a PET molecular chain, so that the compatibility of the organic montmorillonite and PET is increased, the light transmittance of the PET material is increased, the haze of the PET material is reduced, and the heat resistance, the mechanical property and the gas barrier property of the PET can be improved. Meanwhile, compared with other synthesis modes of epoxy group aryl quaternary phosphonium salt, the raw materials used in the invention have low price and wide sources, and are beneficial to popularization and utilization of the epoxy group aryl quaternary phosphonium salt and application of modified montmorillonite in PET high-temperature-resistant optical polyester material.

DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION

The present invention is further illustrated by the following specific examples, which are provided only for the purpose of facilitating understanding of the present invention, and are not to be construed as further limiting the scope of the present invention.

To illustrate the effects of the examples, the PET high temperature resistant optical polyester film material prepared in the examples was melt-extruded by a single screw extruder and cast into a sheet to obtain a PET high temperature resistant optical polyester sheet, and the PET high temperature resistant optical polyester sheet was stretched 6.25 times at a speed of 5mm/s at 125 ℃ by a biaxial stretcher to obtain a PET high temperature resistant optical polyester film. The synthesis yield of the epoxy aryl quaternary phosphonium salt is expressed as the actual yield of the epoxy aryl quaternary phosphonium salt divided by the theoretical yield. Modification effect of montmorillonite as₀₀₁The interlayer spacing of the surface is expressed, and the result is that the 2 theta angle obtained by testing the modified montmorillonite by an X-ray diffractometer is calculated by a Bragg equation. The tensile strength Rm of the PET high-temperature resistant optical polyester film is determined according to GB 1040.3-2006, and the sample is a standard dumbbell type sample; the gas barrier property of the PET high-temperature resistant optical polyester film is determined according to GB/T1038-2000. The optical properties of the PET high-temperature resistant optical polyester film are as follows: the transmittance a (%) and haze H (%) and the color difference value B, etc. were measured using a PET film transmittance haze meter. And testing the glass transition temperature Tg (DEG C) and the initial decomposition temperature Ts (DEG C) of the PET high-temperature resistant optical polyester film by using a comprehensive thermal analyzer DSC.

Specific example 1:

firstly, adding 10g of triphenyl phosphine and 10mL of epoxy chloropropane into a reaction kettle, and stirring at normal temperature until the triphenyl phosphine and the epoxy chloropropane are completely dissolved; then reacting for 6 hours at room temperature under the protection of nitrogen; then, decompressing and distilling to remove unreacted epoxy chloropropane to obtain a yellow reaction product, purifying by using ethyl acetate, filtering and drying to prepare the 2-epoxy ethyl methyl triphenyl phosphorus chloride.

Specific example 2

Firstly, adding 10g of triphenyl phosphine and 10mL of epoxy chloropropane into a reaction kettle, and stirring at normal temperature until the triphenyl phosphine and the epoxy chloropropane are completely dissolved; then reacting for 6h at 60 ℃ under the protection of nitrogen; then, decompressing and distilling to remove unreacted epoxy chloropropane to obtain a yellow reaction product, purifying by using ethyl acetate, filtering and drying to prepare the 2-epoxy ethyl methyl triphenyl phosphorus chloride.

Specific example 3

Firstly, adding 10g of triphenyl phosphine and 10mL of epoxy chloropropane into a reaction kettle, and stirring at normal temperature until the triphenyl phosphine and the epoxy chloropropane are completely dissolved; then reacting for 6h at 80 ℃ under the protection of nitrogen; then, decompressing and distilling to remove unreacted epoxy chloropropane to obtain a yellow reaction product, purifying by using ethyl acetate, filtering and drying to prepare the 2-epoxy ethyl methyl triphenyl phosphorus chloride.

Specific example 4

Firstly, adding 10g of triphenyl phosphine and 10mL of epoxy chloropropane into a reaction kettle, and stirring at normal temperature until the triphenyl phosphine and the epoxy chloropropane are completely dissolved; then reacting for 6h at 100 ℃ under the protection of nitrogen; then, decompressing and distilling to remove unreacted epoxy chloropropane to obtain a yellow reaction product, purifying by using ethyl acetate, filtering and drying to prepare the 2-epoxy ethyl methyl triphenyl phosphorus chloride.

TABLE 1 Effect of reaction temperature on Synthesis yield of epoxy aryl quaternary phosphonium salts

It can be concluded from the analysis of examples 1-4 that the synthesis temperature has a large influence on the synthesis yield of the epoxy aryl quaternary phosphonium salt. When the reaction temperature is 60 ℃ at room temperature, the synthesis yield of the epoxy radical aryl quaternary phosphonium salt with too low temperature is less than 2.5 percent. When the reaction temperature is 100 ℃, the reaction temperature is too high, so that epoxy chloropropane is greatly volatilized in the synthesis process, and the synthesis yield of the epoxy aryl quaternary phosphonium salt is low. As can be seen from Table 1, the optimal reaction temperature is 80 ℃, and the reaction rate is ensured, and meanwhile, the large-scale volatilization of the epichlorohydrin is not caused. Therefore, the present patent uses 80 ℃ as the reaction temperature of the synthesis reaction.

Detailed description of the preferred embodiment 5

Firstly, adding 10g of triphenyl phosphine and 10mL of epoxy chloropropane into a reaction kettle, and stirring at normal temperature until the triphenyl phosphine and the epoxy chloropropane are completely dissolved; then reacting for 8 hours at 80 ℃ under the protection of nitrogen; then, decompressing and distilling to remove unreacted epoxy chloropropane to obtain a yellow reaction product, purifying by using ethyl acetate, filtering and drying to prepare the 2-epoxy ethyl methyl triphenyl phosphorus chloride.

Specific example 6

Firstly, adding 10g of triphenyl phosphine and 10mL of epoxy chloropropane into a reaction kettle, and stirring at normal temperature until the triphenyl phosphine and the epoxy chloropropane are completely dissolved; then reacting for 10 hours at 80 ℃ under the protection of nitrogen; then, decompressing and distilling to remove unreacted epoxy chloropropane to obtain a yellow reaction product, purifying by using ethyl acetate, filtering and drying to prepare the 2-epoxy ethyl methyl triphenyl phosphorus chloride.

TABLE 2 Effect of reaction time on Synthesis yield of epoxy aryl quaternary phosphonium salts

As can be seen from the analysis of specific examples 3 and 5-6, the reaction time has a large influence on the synthesis yield of the epoxy aryl quaternary phosphonium salt. When the reaction time is short, the reaction is not terminated, a large amount of triphenylphosphine is not reacted, and the synthesis yield of the epoxy triphenyl phosphine is low. When the reaction time is 10 hours, the yield of the epoxy triphenyl phosphorus chloride is not obviously improved, so the reaction time is preferably 8 hours.

Base body example 7

Firstly, adding 10g of triphenyl phosphine and 20mL of epoxy chloropropane into a reaction kettle, and stirring at normal temperature until the triphenyl phosphine and the epoxy chloropropane are completely dissolved; then reacting for 8 hours at 80 ℃ under the protection of nitrogen; then carrying out reduced pressure distillation to remove unreacted epichlorohydrin to obtain a yellow reaction product, purifying with ethyl acetate, filtering, and drying to prepare 2-oxiranylmethyl triphenyl phosphorus chloride;

specific example 8

Firstly, adding 10g of triphenyl phosphine and 30mL of epoxy chloropropane into a reaction kettle, and stirring at normal temperature until the triphenyl phosphine and the epoxy chloropropane are completely dissolved; then reacting for 8 hours at 80 ℃ under the protection of nitrogen; then carrying out reduced pressure distillation to remove unreacted epichlorohydrin to obtain a yellow reaction product, purifying with ethyl acetate, filtering, and drying to prepare 2-oxiranylmethyl triphenyl phosphorus chloride;

TABLE 3 influence of epichlorohydrin content on the yield of synthesis of epoxy aryl quaternary phosphonium salts

As can be seen from the analysis of specific examples 2 and 4-5, the content of epichlorohydrin has a great influence on the synthesis yield of epoxy triphenyl phosphonium bromide. The epichlorohydrin is used as a raw material and also used as a solvent, when the content of the epichlorohydrin is too low, the yield obtained by the incomplete reaction of the triphenylphosphine is far lower than the theoretical yield, when the content of the epichlorohydrin is excessive, the subsequent treatment is not facilitated, the waste of the raw material is serious, and the synthetic yield is not obviously influenced. Therefore, the epoxy chloropropane is used in an amount of 20mL in the synthesis of the epoxy aryl quaternary phosphonium salt disclosed by the invention.

Specific example 9

Firstly, adding 10g of triphenyl phosphine, 0.2g of catalyst sodium iodide and 20mL of epoxy chloropropane into a reaction kettle, and stirring at normal temperature until the triphenyl phosphine, the catalyst sodium iodide and the epoxy chloropropane are completely dissolved; then reacting for 8 hours at 80 ℃ under the protection of nitrogen; then, decompressing and distilling to remove unreacted epoxy chloropropane to obtain a yellow reaction product, purifying by using ethyl acetate, filtering and drying to prepare the 2-epoxy ethyl methyl triphenyl phosphorus chloride.

Detailed description of example 10

Firstly, adding 10g of triphenyl phosphine, 0.4g of catalyst sodium iodide and 20mL of epoxy chloropropane into a reaction kettle, and stirring at normal temperature until the triphenyl phosphine, the catalyst sodium iodide and the epoxy chloropropane are completely dissolved; then reacting for 8 hours at 80 ℃ under the protection of nitrogen; then, decompressing and distilling to remove unreacted epoxy chloropropane to obtain a yellow reaction product, purifying by using ethyl acetate, filtering and drying to prepare the 2-epoxy ethyl methyl triphenyl phosphorus chloride.

TABLE 4 influence of catalyst content on the yield of synthesis of epoxy aryl quaternary phosphonium salts

It can be seen from the analysis of specific examples 3 and 6 to 7 that the content of the catalyst has a large influence on the yield of the epoxy aryl quaternary phosphonium salt. The lowest synthesis yield of the epoxy aryl quaternary phosphonium salt is only 19.7 percent when no catalyst is added, the synthesis yield of the epoxy aryl quaternary phosphonium salt is improved to 52.3 percent when 0.2g of the catalyst is added, and the synthesis yield of the epoxy aryl quaternary phosphonium salt is not obviously improved when 0.4g of the catalyst is added. This is because the catalyst can lower the activation energy of the reaction to lower the reaction conditions so that the reaction can proceed smoothly while accelerating the reaction rate. However, the catalytic effect of the catalyst under certain synthesis conditions is not improved continuously with the increase of the addition amount, and the subsequent purification treatment of the product is more complicated with more catalysts. From Table 1, it is clear that the addition of 0.2g of catalyst gives the best overall effect.

Specific example 11

(1) 45g of sodium montmorillonite is added into a beaker filled with 800mL of distilled water, and the stirring is continued for 30min until the montmorillonite is uniformly dispersed. And (3) carrying out ultrasonic dispersion on the beaker filled with the suspension for 30min, standing for 5-10min after the ultrasonic dispersion is finished, and removing the sediment at the bottom. Then adding 10g of self-made 2-oxiranylmethyl triphenyl phosphonium chloride, carrying out ultrasonic dispersion for 30min, stirring and reacting for 4h at room temperature, carrying out suction filtration, and washing for 4-5 times by using distilled water. Drying the product at 100 ℃, crushing the dried product, and sieving the crushed product with a 200-mesh sieve to prepare the organic modified montmorillonite;

(2) and (2) blending 20g of the organic modified montmorillonite prepared in the step (1) with 1980g of PET polyester by using a high-speed mixer, and then carrying out melt extrusion, granulation and drying by using a double-screw extruder to obtain the PET high-temperature-resistant optical polyester film material. The prepared PET high-temperature resistant optical polyester film material is subjected to melt extrusion and tape casting by a single-screw extruder to prepare a PET high-temperature resistant optical polyester sheet, and the PET high-temperature resistant optical polyester sheet is stretched by 6.25 times at the speed of 5mm/s by a biaxial stretcher at the temperature of 125 ℃ to prepare the PET high-temperature resistant optical polyester film. Specific properties are shown in Table 5.

Detailed description of example 12

(1) 45g of sodium montmorillonite is added into a beaker filled with 800mL of distilled water, and the stirring is continued for 30min until the montmorillonite is uniformly dispersed. And (3) carrying out ultrasonic dispersion on the beaker filled with the suspension for 30min, standing for 5-10min after the ultrasonic dispersion is finished, and removing the sediment at the bottom. Then adding 10g of self-made 2-oxiranylmethyl triphenyl phosphonium chloride, carrying out ultrasonic dispersion for 30min, stirring and reacting for 4h at the temperature of 60 ℃, carrying out suction filtration, and washing for 4-5 times by using distilled water. Drying the product at 100 ℃, crushing the dried product, and sieving the crushed product with a 200-mesh sieve to prepare the organic modified montmorillonite;

(2) and (2) blending 20g of the organic montmorillonite prepared in the step (1) with 1980g of PET polyester by using a high-speed mixer, and then carrying out melt extrusion, granulation and drying by using a double-screw extruder to obtain the PET high-temperature-resistant optical polyester film material. The prepared PET high-temperature resistant optical polyester film material is subjected to melt extrusion and tape casting by a single-screw extruder to prepare a PET high-temperature resistant optical polyester sheet, and the PET high-temperature resistant optical polyester sheet is stretched by 6.25 times at the speed of 5mm/s by a biaxial stretcher at the temperature of 125 ℃ to prepare the PET high-temperature resistant optical polyester film. Specific properties are shown in Table 5.

Specific example 13

(1) 45g of sodium montmorillonite is added into a beaker filled with 800mL of distilled water, and the stirring is continued for 30min until the montmorillonite is uniformly dispersed. And (3) carrying out ultrasonic dispersion on the beaker filled with the suspension for 30min, standing for 5-10min after the ultrasonic dispersion is finished, and removing the sediment at the bottom. Then adding 10g of self-made 2-oxiranylmethyl triphenyl phosphonium chloride, carrying out ultrasonic dispersion for 30min, stirring and reacting for 4h at the temperature of 70 ℃, carrying out suction filtration, and washing for 4-5 times by using distilled water. Drying the product at 100 ℃, crushing the dried product, and sieving the crushed product with a 200-mesh sieve to prepare the organic modified montmorillonite;

EXAMPLES example 14

(1) 45g of sodium montmorillonite is added into a beaker filled with 800mL of distilled water, and the stirring is continued for 30min until the montmorillonite is uniformly dispersed. And (3) carrying out ultrasonic dispersion on the beaker filled with the suspension for 30min, standing for 5-10min after the ultrasonic dispersion is finished, and removing the sediment at the bottom. Then adding 10g of self-made 2-oxiranylmethyl triphenyl phosphonium chloride, carrying out ultrasonic dispersion for 30min, stirring and reacting for 4h at the temperature of 80 ℃, carrying out suction filtration, and washing for 4-5 times by using distilled water. Drying the product at 100 ℃, crushing the dried product, and sieving the crushed product with a 200-mesh sieve to prepare the organic modified montmorillonite;

Specific example 15

(1) 45g of sodium montmorillonite is added into a beaker filled with 800mL of distilled water, and the stirring is continued for 30min until the montmorillonite is uniformly dispersed. And (3) carrying out ultrasonic dispersion on the beaker filled with the suspension for 30min, standing for 5-10min after the ultrasonic dispersion is finished, and removing the sediment at the bottom. Then adding 10g of self-made 2-oxiranylmethyl triphenyl phosphonium chloride, carrying out ultrasonic dispersion for 30min, stirring and reacting for 4h at the temperature of 90 ℃, carrying out suction filtration, and washing for 4-5 times by using distilled water. Drying the product at 100 ℃, crushing the dried product, and sieving the crushed product with a 200-mesh sieve to prepare the organic modified montmorillonite;

TABLE 5 Effect of modification temperature on various Properties of high temperature resistant polyester materials

Specific examples 11 to 15 reflect the influence of different modification temperatures on the performance of the PET high-temperature resistant optical polyester material, and when the modification temperature is 60 ℃, the modification temperature is relatively low, and the performance of the PET high-temperature resistant optical polyester material obtained by the poor montmorillonite modification effect is poor. When the modification temperature is 80 ℃, the modification temperature is proper, the exchange rate of the modifier between montmorillonite layers is high, so that the modification effect of montmorillonite is remarkable, and the performance of the PET high-temperature-resistant optical polyester material obtained by organic montmorillonite with good temperature resistance is good. When the modification temperature is 90 ℃, the modification temperature is higher, the separation speed of the modifier from the montmorillonite layers is too high, so that the modification effect of the montmorillonite is not obviously changed, and the performance of the obtained PET high-temperature resistant optical polyester material is not obviously improved.

EXAMPLE 16

(1) 45g of sodium montmorillonite is added into a beaker filled with 800mL of distilled water, and the stirring is continued for 30min until the montmorillonite is uniformly dispersed. And (3) carrying out ultrasonic dispersion on the beaker filled with the suspension for 30min, standing for 5-10min after the ultrasonic dispersion is finished, and removing the sediment at the bottom. Then adding 10g of self-made 2-oxiranylmethyl triphenyl phosphonium chloride, carrying out ultrasonic dispersion for 30min, stirring and reacting for 6h at the temperature of 80 ℃, carrying out suction filtration, and washing for 4-5 times by using distilled water. Drying the product at 100 ℃, crushing the dried product, and sieving the crushed product with a 200-mesh sieve to prepare the organic modified montmorillonite;

(2) and (2) blending 20g of the organic montmorillonite prepared in the step (1) with 1980g of PET polyester by using a high-speed mixer, and then carrying out melt extrusion, granulation and drying by using a double-screw extruder to obtain the PET high-temperature-resistant optical polyester film material. The prepared PET high-temperature resistant optical polyester film material is subjected to melt extrusion and tape casting by a single-screw extruder to prepare a PET high-temperature resistant optical polyester sheet, and the PET high-temperature resistant optical polyester sheet is stretched by 6.25 times at the speed of 5mm/s by a biaxial stretcher at the temperature of 125 ℃ to prepare the PET high-temperature resistant optical polyester film. Specific properties are shown in Table 6.

Specific example 17

(1) 45g of sodium montmorillonite is added into a beaker filled with 800mL of distilled water, and the stirring is continued for 30min until the montmorillonite is uniformly dispersed. And (3) carrying out ultrasonic dispersion on the beaker filled with the suspension for 30min, standing for 5-10min after the ultrasonic dispersion is finished, and removing the sediment at the bottom. Then adding 10g of self-made 2-oxiranylmethyl triphenyl phosphonium chloride, carrying out ultrasonic dispersion for 30min, stirring and reacting for 8h at the temperature of 80 ℃, carrying out suction filtration, and washing for 4-5 times by using distilled water. Drying the product at 100 ℃, crushing the dried product, and sieving the crushed product with a 200-mesh sieve to prepare the organic modified montmorillonite;

TABLE 6 influence of modification time on the Properties of the high temperature polyester materials

Specific examples 14, 16 and 17 reflect the influence of different modification times on the performance of the high temperature resistant polyester material, and when the modification temperature is 4 hours, the modification time is relatively low, and the performance of the PET high temperature resistant optical polyester material obtained by poor montmorillonite modification effect is poor. When the modification temperature is 6 hours, the modification time is appropriate, the modifier is fully exchanged among the montmorillonite layers, so that the modification effect of the montmorillonite is remarkable, and the performance of the PET high-temperature-resistant optical polyester material obtained by the organic montmorillonite with good temperature resistance is good. When the modification time is 8 hours, the modification time is longer, the exchange time of the modifier between the montmorillonite layers is too long, and a large amount of modifier in the montmorillonite layers escapes, so that the modification effect of the montmorillonite is not obviously improved, and the performance of the obtained PET high-temperature-resistant optical polyester material is not obviously improved.

Detailed description of example 18

(1) 45g of sodium montmorillonite is added into a beaker filled with 800mL of distilled water, and the stirring is continued for 30min until the montmorillonite is uniformly dispersed. And (3) carrying out ultrasonic dispersion on the beaker filled with the suspension for 30min, standing for 5-10min after the ultrasonic dispersion is finished, and removing the sediment at the bottom. Then adding 5g of self-made 2-oxiranylmethyl triphenyl phosphonium chloride, carrying out ultrasonic dispersion for 30min, stirring and reacting for 6h at the temperature of 80 ℃, carrying out suction filtration, and washing for 4-5 times by using distilled water. Drying the product at 100 ℃, crushing the dried product, and sieving the crushed product with a 200-mesh sieve to prepare the organic modified montmorillonite;

(2) and (2) blending 20g of the organic montmorillonite prepared in the step (1) with 1980g of PET polyester by using a high-speed mixer, and then carrying out melt extrusion, granulation and drying by using a double-screw extruder to obtain the PET high-temperature-resistant optical polyester film material. The prepared PET high-temperature resistant optical polyester film material is subjected to melt extrusion and tape casting by a single-screw extruder to prepare a PET high-temperature resistant optical polyester sheet, and the PET high-temperature resistant optical polyester sheet is stretched by 6.25 times at the speed of 5mm/s by a biaxial stretcher at the temperature of 125 ℃ to prepare the PET high-temperature resistant optical polyester film. Specific properties are shown in Table 7.

Specific example 19

(1) 45g of sodium montmorillonite is added into a beaker filled with 800mL of distilled water, and the stirring is continued for 30min until the montmorillonite is uniformly dispersed. And (3) carrying out ultrasonic dispersion on the beaker filled with the suspension for 30min, standing for 5-10min after the ultrasonic dispersion is finished, and removing the sediment at the bottom. Then adding 15g of self-made 2-oxiranylmethyl triphenyl phosphonium chloride, carrying out ultrasonic dispersion for 30min, stirring and reacting for 6h at the temperature of 80 ℃, carrying out suction filtration, and washing for 4-5 times by using distilled water. Drying the product at 100 ℃, crushing the dried product, and sieving the crushed product with a 200-mesh sieve to prepare the organic modified montmorillonite;

Detailed description of example 20

(1) 45g of sodium montmorillonite is added into a beaker filled with 800mL of distilled water, and the stirring is continued for 30min until the montmorillonite is uniformly dispersed. And (3) carrying out ultrasonic dispersion on the beaker filled with the suspension for 30min, standing for 5-10min after the ultrasonic dispersion is finished, and removing the sediment at the bottom. Then adding 20g of self-made 2-oxiranylmethyl triphenyl phosphonium chloride, carrying out ultrasonic dispersion for 30min, stirring and reacting for 6h at the temperature of 80 ℃, carrying out suction filtration, and washing for 4-5 times by using distilled water. Drying the product at 100 ℃, crushing the dried product, and sieving the crushed product with a 200-mesh sieve to prepare the organic modified montmorillonite;

TABLE 7 influence of modifier content on the Properties of the high temperature resistant polyester materials

Specific examples 16 and 18-20 reflect the influence of different modifier contents on the performance of the high temperature resistant polyester material, and when the modifier content is 10g, the modifier content is relatively low, and the performance of the high temperature resistant polyester material obtained by poor montmorillonite modification effect is poor. When the content of the modifier is 20g (1.0 wt%), the content of the modifier is too much, and the excessive modifier is adsorbed on the surface of the montmorillonite, so that the heat resistance of the montmorillonite is reduced, and the performance of the obtained high-temperature resistant polyester material is poor. When the content of the modifier is 15g, the content of the modifier is suitable for montmorillonite, the modification effect is good, the surplus modifier adsorbed on the surface of the montmorillonite is less, and the tensile property, the barrier property and the temperature resistance of the PET polyester optical film material obtained by the organic montmorillonite with good temperature resistance are the best.

Detailed description of example 21

(2) and (2) blending 10g of the organic montmorillonite prepared in the step (1) with 1990g of PET polyester by using a high-speed mixer, and then carrying out melt extrusion, granulation and drying by using a double-screw extruder to obtain the PET high-temperature-resistant optical polyester film material. The prepared PET high-temperature resistant optical polyester film material is subjected to melt extrusion and tape casting by a single-screw extruder to prepare a PET high-temperature resistant optical polyester sheet, and the PET high-temperature resistant optical polyester sheet is stretched by 6.25 times at the speed of 5mm/s by a biaxial stretcher at the temperature of 125 ℃ to prepare the PET high-temperature resistant optical polyester film. Specific properties are shown in Table 8.

Detailed description of the preferred embodiment 22

(2) and (2) blending 30g of the organic montmorillonite prepared in the step (1) with 1970g of PET polyester by using a high-speed mixer, and then carrying out melt extrusion, granulation and drying by using a double-screw extruder to obtain the PET high-temperature-resistant optical polyester film material. The prepared PET high-temperature resistant optical polyester film material is subjected to melt extrusion and tape casting by a single-screw extruder to prepare a PET high-temperature resistant optical polyester sheet, and the PET high-temperature resistant optical polyester sheet is stretched by 6.25 times at the speed of 5mm/s by a biaxial stretcher at the temperature of 125 ℃ to prepare the PET high-temperature resistant optical polyester film. Specific properties are shown in Table 8.

Specific example 23

(2) and (2) blending 40g of the organic montmorillonite prepared in the step (1) with 1960g of PET polyester by using a high-speed mixer, and then carrying out melt extrusion, granulation and drying by using a double-screw extruder to obtain the PET high-temperature-resistant optical polyester film material. The prepared PET high-temperature resistant optical polyester film material is subjected to melt extrusion and tape casting by a single-screw extruder to prepare a PET high-temperature resistant optical polyester sheet, and the PET high-temperature resistant optical polyester sheet is stretched by 6.25 times at the speed of 5mm/s by a biaxial stretcher at the temperature of 125 ℃ to prepare the PET high-temperature resistant optical polyester film. Specific properties are shown in Table 8.

Detailed description of example 24

(2) and (2) blending 50g of the organic montmorillonite prepared in the step (1) with 1950g of PET polyester by using a high-speed mixer, and then carrying out melt extrusion, granulation and drying by using a double-screw extruder to obtain the PET high-temperature resistant optical polyester film material. The prepared PET high-temperature resistant optical polyester film material is subjected to melt extrusion and tape casting by a single-screw extruder to prepare a PET high-temperature resistant optical polyester sheet, and the PET high-temperature resistant optical polyester sheet is stretched by 6.25 times at the speed of 5mm/s by a biaxial stretcher at the temperature of 125 ℃ to prepare the PET high-temperature resistant optical polyester film. Specific properties are shown in Table 8.

TABLE 8 influence of the content of organic montmorillonite on the properties of the high temperature resistant polyester materials

Specific examples 19 and 21-24 reflect the influence of different contents of organic montmorillonite on the performance of the high temperature resistant polyester material, and the performance of the PET optical polyester material is improved to different degrees with the increase of the content of the organic montmorillonite. However, when the content of montmorillonite is too high, the organic montmorillonite can agglomerate, so that the optical performance, tensile property and heat resistance of the PET high-temperature resistant optical polyester material are reduced. As can be seen from the above table, the combination of properties is best for the specific example 21.

In order to illustrate the advantages of the present invention, the present invention will be illustrated herein by way of comparative examples.

Comparative example 1

Melting and extruding 1980g of PET polyester by using a double-screw extruder, granulating and drying to obtain the PET high-temperature-resistant optical polyester film material. The prepared PET high-temperature resistant optical polyester film material is subjected to melt extrusion and tape casting by a single-screw extruder to prepare a PET high-temperature resistant optical polyester sheet, and the PET high-temperature resistant optical polyester sheet is stretched by 6.25 times at the speed of 5mm/s by a biaxial stretcher at the temperature of 125 ℃ to prepare the PET high-temperature resistant optical polyester film. Specific properties are shown in Table 9.

Comparative example 2

Blending 20g of unmodified montmorillonite with 1980g of PET polyester by using a high-speed mixer, and then carrying out melt extrusion, granulation and drying by using a double-screw extruder to obtain the PET high-temperature-resistant optical polyester film material. The prepared PET high-temperature resistant optical polyester film material is subjected to melt extrusion and tape casting by a single-screw extruder to prepare a PET high-temperature resistant optical polyester sheet, and the PET high-temperature resistant optical polyester sheet is stretched by 6.25 times at the speed of 5mm/s by a biaxial stretcher at the temperature of 125 ℃ to prepare the PET high-temperature resistant optical polyester film. Specific properties are shown in Table 9.

Comparative example 3

(1) 45g of sodium montmorillonite is added into a beaker filled with 800mL of distilled water, and the stirring is continued for 30min until the montmorillonite is uniformly dispersed. And (3) carrying out ultrasonic dispersion on the beaker filled with the suspension for 30min, standing for 5-10min after the ultrasonic dispersion is finished, and removing the sediment at the bottom. Then adding 15g of 5-carboxyl amyl triphenyl phosphonium bromide, carrying out ultrasonic dispersion for 30min, stirring and reacting for 6h at the temperature of 80 ℃, carrying out suction filtration, and washing for 4-5 times by using distilled water. Drying the product at 100 ℃, crushing the dried product, and sieving the crushed product with a 200-mesh sieve to prepare the organic modified montmorillonite;

(2) and (2) blending 20g of the organic montmorillonite prepared in the step (1) with 1980g of PET polyester by using a high-speed mixer, and then carrying out melt extrusion, granulation and drying by using a double-screw extruder to obtain the PET high-temperature-resistant optical polyester film material. The prepared PET high-temperature resistant optical polyester film material is subjected to melt extrusion and tape casting by a single-screw extruder to prepare a PET high-temperature resistant optical polyester sheet, and the PET high-temperature resistant optical polyester sheet is stretched by 6.25 times at the speed of 5mm/s by a biaxial stretcher at the temperature of 125 ℃ to prepare the PET high-temperature resistant optical polyester film. Specific properties are shown in Table 9.

Comparative example 4

(1) 45g of sodium montmorillonite is added into a beaker filled with 800mL of distilled water, and the stirring is continued for 30min until the montmorillonite is uniformly dispersed. And (3) carrying out ultrasonic dispersion on the beaker filled with the suspension for 30min, standing for 5-10min after the ultrasonic dispersion is finished, and removing the sediment at the bottom. Then adding 15g of n-butyl triphenyl phosphonium bromide, carrying out ultrasonic dispersion for 30min, stirring and reacting for 6h at the temperature of 80 ℃, carrying out suction filtration, and washing for 4-5 times by using distilled water. Drying the product at 100 ℃, crushing the dried product, and sieving the crushed product with a 200-mesh sieve to prepare the organic modified montmorillonite;

Comparative example 5

(1) 45g of sodium montmorillonite is added into a beaker filled with 800mL of distilled water, and the stirring is continued for 30min until the montmorillonite is uniformly dispersed. And (3) carrying out ultrasonic dispersion on the beaker filled with the suspension for 30min, standing for 5-10min after the ultrasonic dispersion is finished, and removing the sediment at the bottom. Then adding 15g of 2-hydroxyethyl triphenyl phosphonium chloride, carrying out ultrasonic dispersion for 30min, stirring and reacting for 6h at the temperature of 80 ℃, carrying out suction filtration, and washing for 4-5 times by using distilled water. Drying the product at 100 ℃, crushing the dried product, and sieving the crushed product with a 200-mesh sieve to prepare the organic modified montmorillonite;

Comparative example 6

(1) 45g of sodium montmorillonite is added into a beaker filled with 800mL of distilled water, and the stirring is continued for 30min until the montmorillonite is uniformly dispersed. And (3) carrying out ultrasonic dispersion on the beaker filled with the suspension for 30min, standing for 5-10min after the ultrasonic dispersion is finished, and removing the sediment at the bottom. Then adding 15g of allyl triphenyl phosphonium bromide, carrying out ultrasonic dispersion for 30min, stirring and reacting for 6h at the temperature of 80 ℃, carrying out suction filtration, and washing for 4-5 times by using distilled water. Drying the product at 100 ℃, crushing the dried product, and sieving the crushed product with a 200-mesh sieve to prepare the organic modified montmorillonite;

(2) and (2) blending 20g of the organic montmorillonite prepared in the step (1) with 1980g of PET polyester by using a high-speed mixer, and then carrying out melt extrusion, granulation and drying by using a double-screw extruder to obtain the PET high-temperature-resistant optical polyester film material.

TABLE 9 influence of modifier types on the Properties of the high temperature resistant polyester Material

Specific example 21 and comparative examples 3 to 6 reflect the influence of quaternary phosphate containing different functional groups on the optical property, barrier property, mechanical property and thermal stability of PET optical polyester film material, and the specific properties are shown in the table. The epoxy group and the carboxyl group can generate ring-opening reaction with the PET matrix, so that the PET molecules are grafted to the montmorillonite layer, and the crosslinking degree of the PET matrix is improved. Butyl triphenyl phosphonium bromide and allyl triphenyl phosphonium bromide which do not contain reactive groups can not react with matrix molecules, and the PET optical polyester film material prepared from the butyl triphenyl phosphonium bromide and the allyl triphenyl phosphonium bromide respectively has lower performance in all aspects than the former two. The 2-hydroxyethyl triphenyl phosphonium chloride containing hydroxyl contains hydroxyl and is alkaline, which can cause the degradation of PET matrix and the reduction of various performances of the obtained PET composite material in different degrees. Because the epoxy group can react with both hydroxyl and carboxyl in the PET matrix, and the carboxyl can only react with the hydroxyl, the PET optical polyester film material prepared by the epoxy group has the best performance.

Comparative example 7

(1) 45g of sodium montmorillonite is added into a beaker filled with 800mL of distilled water, and the stirring is continued for 30min until the montmorillonite is uniformly dispersed. And (3) carrying out ultrasonic dispersion on the beaker filled with the suspension for 30min, standing for 5-10min after the ultrasonic dispersion is finished, and removing the sediment at the bottom. Then adding 15g of hexadecyl trimethyl ammonium bromide, carrying out ultrasonic dispersion for 30min, stirring and reacting for 6h at the temperature of 80 ℃, carrying out suction filtration, and washing for 4-5 times by using distilled water. Drying the product at 100 ℃, crushing the dried product, and sieving the crushed product with a 200-mesh sieve to prepare the organic modified montmorillonite;

(2) and (2) blending 20g of the organic montmorillonite prepared in the step (1) with 1980g of PET polyester by using a high-speed mixer, and then carrying out melt extrusion, granulation and drying by using a double-screw extruder to obtain the PET high-temperature-resistant optical polyester film material. The prepared PET high-temperature resistant optical polyester film material is subjected to melt extrusion and tape casting by a single-screw extruder to prepare a PET high-temperature resistant optical polyester sheet, and the PET high-temperature resistant optical polyester sheet is stretched by 6.25 times at the speed of 5mm/s by a biaxial stretcher at the temperature of 125 ℃ to prepare the PET high-temperature resistant optical polyester film. Specific properties are shown in Table 10.

Comparative example 8

(1) 45g of sodium montmorillonite is added into a beaker filled with 800mL of distilled water, and the stirring is continued for 30min until the montmorillonite is uniformly dispersed. And (3) carrying out ultrasonic dispersion on the beaker filled with the suspension for 30min, standing for 5-10min after the ultrasonic dispersion is finished, and removing the sediment at the bottom. Then adding 15g of dioctadecyl dimethyl ammonium bromide, carrying out ultrasonic dispersion for 30min, stirring and reacting for 6h at the temperature of 80 ℃, carrying out suction filtration, and washing with distilled water for 4-5 times. Drying the product at 100 ℃, crushing the dried product, and sieving the crushed product with a 200-mesh sieve to prepare the organic modified montmorillonite;

Comparative example 9

(1) 45g of sodium montmorillonite is added into a beaker filled with 800mL of distilled water, and the stirring is continued for 30min until the montmorillonite is uniformly dispersed. And (3) carrying out ultrasonic dispersion on the beaker filled with the suspension for 30min, standing for 5-10min after the ultrasonic dispersion is finished, and removing the sediment at the bottom. Then adding 15g of hexadecyl trimethyl imidazole, carrying out ultrasonic dispersion for 30min, stirring and reacting for 6h at the temperature of 80 ℃, carrying out suction filtration, and washing for 4-5 times by using distilled water. Drying the product at 100 ℃, crushing the dried product, and sieving the crushed product with a 200-mesh sieve to prepare the organic modified montmorillonite;

Comparative example 10

(1) 45g of sodium montmorillonite is added into a beaker filled with 800mL of distilled water, and the stirring is continued for 30min until the montmorillonite is uniformly dispersed. And (3) carrying out ultrasonic dispersion on the beaker filled with the suspension for 30min, standing for 5-10min after the ultrasonic dispersion is finished, and removing the sediment at the bottom. Then adding 15g of polyetheramine, carrying out ultrasonic dispersion for 30min, stirring and reacting for 6h at the temperature of 80 ℃, carrying out suction filtration, and washing with distilled water for 4-5 times. Drying the product at 100 ℃, crushing the dried product, and sieving the crushed product with a 200-mesh sieve to prepare the organic modified montmorillonite;

Comparative example 11

(1) 45g of sodium montmorillonite is added into a beaker filled with 800mL of distilled water, and the stirring is continued for 30min until the montmorillonite is uniformly dispersed. And (3) carrying out ultrasonic dispersion on the beaker filled with the suspension for 30min, standing for 5-10min after the ultrasonic dispersion is finished, and removing the sediment at the bottom. Then adding 15g of polytetrahydrofuran, carrying out ultrasonic dispersion for 30min, stirring and reacting for 6h at the temperature of 80 ℃, carrying out suction filtration, and washing with distilled water for 4-5 times. Drying the product at 100 ℃, crushing the dried product, and sieving the crushed product with a 200-mesh sieve to prepare the organic modified montmorillonite;

Comparative example 12

(1) 45g of sodium montmorillonite is added into a beaker filled with 800mL of distilled water, and the stirring is continued for 30min until the montmorillonite is uniformly dispersed. And (3) carrying out ultrasonic dispersion on the beaker filled with the suspension for 30min, standing for 5-10min after the ultrasonic dispersion is finished, and removing the sediment at the bottom. Then adding 15g of imidazoline, carrying out ultrasonic dispersion for 30min, stirring and reacting for 6h at the temperature of 80 ℃, carrying out suction filtration, and washing with distilled water for 4-5 times. Drying the product at 100 ℃, crushing the dried product, and sieving the crushed product with a 200-mesh sieve to prepare the organic modified montmorillonite;

Comparative example 13

(1) 45g of sodium montmorillonite is added into a beaker filled with 800mL of distilled water, and the stirring is continued for 30min until the montmorillonite is uniformly dispersed. And (3) carrying out ultrasonic dispersion on the beaker filled with the suspension for 30min, standing for 5-10min after the ultrasonic dispersion is finished, and removing the sediment at the bottom. Adding KH 56015 g, ultrasonic dispersing for 30min, stirring at 80 deg.C for 6 hr, vacuum filtering, and washing with distilled water for 4-5 times. Drying the product at 100 ℃, crushing the dried product, and sieving the crushed product with a 200-mesh sieve to prepare the organic modified montmorillonite;

Comparative example 14

(1) 45g of sodium montmorillonite is added into a beaker filled with 800mL of distilled water, and the stirring is continued for 30min until the montmorillonite is uniformly dispersed. And (3) carrying out ultrasonic dispersion on the beaker filled with the suspension for 30min, standing for 5-10min after the ultrasonic dispersion is finished, and removing the sediment at the bottom. Adding KH 57015 g, ultrasonic dispersing for 30min, stirring at 80 deg.C for 6 hr, vacuum filtering, and washing with distilled water for 4-5 times. Drying the product at 100 ℃, crushing the dried product, and sieving the crushed product with a 200-mesh sieve to prepare the organic modified montmorillonite;

TABLE 10 influence of modifier types on the Properties of the high temperature resistant polyester Material

Specific example 21 and comparative examples 1-2 and 7-14 reflect the influence of the chain length of the modifier and the type of the modifier on the optical property, barrier property, mechanical property and thermal stability of the PET optical polyester film material, and the specific properties are shown in the table. The better the modifying effect of the modifier, the lower the fog of the high-temperature resistant polyester material, the lower the water vapor transmission rate, and the higher the tensile strength and the thermal decomposition temperature. Because the high temperature resistance of the modifier is different, the modifier can be decomposed to different degrees in the preparation process of the polyester material, and the optical performance of the PET high temperature resistant polyester material is obviously reduced. From the foregoing comparison, it can be seen that the effect of the organic montmorillonite obtained by epoxy modification is the best in the case of adding the same modified montmorillonite.

The patent provides a PET high-temperature resistant optical polyester material modified by montmorillonite and a preparation method thereof, wherein epoxy chloropropane with low price is used for replacing expensive epoxy iodopropane to react with triphenyl phosphorus to generate epoxy-containing quaternary phosphonium salt, and the montmorillonite is organically modified by the quaternary phosphonium salt. The surface of the lamella of the prepared organic montmorillonite contains a large amount of epoxy functional groups, and the organic montmorillonite can generate crosslinking reaction with a PET matrix to play a role of a crosslinking agent. And melting and blending the organic montmorillonite and the PET polyester material to prepare the PET high-temperature-resistant optical polyester film material. The obtained PET high-temperature-resistant optical polyester film material has the advantages of high light transmittance, low haze, high heat resistance, high tensile strength, high barrier property and the like.

The upper and lower limits and interval values of the raw materials and the upper and lower limits and interval values of the process parameters can all realize the invention, and examples are not listed here.

Claims

1. The organic montmorillonite modified PET high-temperature-resistant optical polyester material is characterized in that the organic montmorillonite is obtained by modifying sodium-based montmorillonite with 2-epoxy ethylene methyl triphenyl phosphorus chloride, the polyester material is prepared by blending the organic montmorillonite and PET and melt extrusion, and the dosage of each raw material is as follows: 0.5-2.5 wt% of organic montmorillonite and 97.5-99.5 wt% of PET.

2. The preparation method of the montmorillonite-modified PET high-temperature-resistant optical polyester material as claimed in claim 1, characterized by comprising the following steps:

(2) preparing organic montmorillonite: adding 45g of sodium montmorillonite into a beaker filled with 800mL of distilled water, continuously stirring for 30min until the montmorillonite is uniformly dispersed, carrying out ultrasonic dispersion on the beaker filled with the suspension for 30min, standing for 5-10min after the ultrasonic dispersion is finished, and removing bottom precipitates; then adding 10-20g of 2-oxiranylmethyl triphenyl phosphorus chloride prepared in the step (1), performing ultrasonic dispersion for 30min, stirring and reacting for 4-8 h at the temperature of room temperature-90 ℃, performing suction filtration, and washing for 4-5 times by using distilled water; drying the product at 100 ℃, crushing the dried product, and sieving the crushed product with a 200-mesh sieve to prepare the organic montmorillonite;

(3) the preparation of the montmorillonite modified PET high temperature resistant optical polyester material comprises the following steps: and (3) blending 0.5-2.5 wt% of the organic montmorillonite prepared in the step (2) and 97.5-99.5 wt% of PET by using a high-speed mixer, and then carrying out melt extrusion, granulation and drying by using a double-screw extruder to obtain the PET high-temperature-resistant optical polyester material.