Flexible hydroxyl bisphenol A glycidyl ether epoxy compound, preparation method thereof and application of epoxy compound as polyurethane optical material modifier

Abstract

The invention discloses a flexible hydroxyl bisphenol A glycidyl ether epoxy compound as shown in a formula i, a preparation method thereof and application of the flexible hydroxyl bisphenol A glycidyl ether epoxy compound as a polyurethane optical material modifier. The preparation method comprises the following steps: (1) single-side epoxidation reaction: carrying out epoxidation reaction on bisphenol A and epoxy chloropropane under an alkaline condition to obtain bisphenol A monoglycidyl ether; (2) flexible chain introduction reaction: bisphenol A monoglycidyl ether and diethylene glycol are subjected to protonation activation under acid catalysis, phenolic hydroxyl attacks protonated carbon atoms to form ether bonds, the ether bonds preferentially react with one end of diethylene glycol, and finally the flexible hydroxyl bisphenol A glycidyl ether epoxy compound (formula i) is obtained. The modified polyurethane resin can be used as a modified material of a polyurethane optical resin material, improves toughness, enhances interface interaction, reduces curing stress, avoids element failure caused by stress concentration and is used for pouring, assembling and the like of precise optical components through structural optimization designs such as super-flexible chain segment increase, terminal hydroxylation and gradient epoxy distribution. (i)

Description

Technical Field

[0001] This invention belongs to the field of optical material preparation technology, specifically relating to a flexible hydroxy bisphenol A glycidyl ether epoxy compound, its preparation method, and its application as a polyurethane optical material. Background Technology

[0003] Bisphenol A glycidyl ether epoxy resin, as the most widely used and abundant type of epoxy resin, exhibits excellent comprehensive properties such as high rigidity, high strength, high temperature resistance, creep resistance, and chemical corrosion resistance due to the synergistic effect of aromatic rings and ether bonds in its molecular structure. The cured product has a Young's modulus of 2-4 GPa, a tensile strength generally exceeding 60 MPa, and a glass transition temperature (Tg) mostly in the range of 120-180℃. After immersion in organic solvents for 1000 hours, the weight change rate is usually less than 5%. These characteristics make it occupy a core position in fields such as marine anti-corrosion coatings, electronic packaging adhesives, and composite matrix.

[0004] However, the inherent defects in its molecular structure also significantly limit its application range: the highly cross-linked three-dimensional network results in a curing elongation at break of less than 5% and an impact strength of only 10-20 kJ / m², making it prone to microcracks in vibration or temperature cycling environments; the melt viscosity increases sharply with the increase of molecular weight, for example, products with an epoxy equivalent of 180-200 can reach a viscosity of 5000-8000 mPa·s at 100℃, requiring heating to above 120℃ or adding 10-30% organic solvent for dilution during processing, which not only increases energy consumption but may also introduce volatile residues; during the curing process, due to the superposition of chemical shrinkage and thermal shrinkage, the volume shrinkage rate is as high as 2-3%, which can easily generate internal stress during the molding of precision optical components or the application of large-area coatings, leading to deformation or interface peeling, especially in fields with strict requirements for dimensional stability such as optical lenses and optical packaging, making it difficult to meet the application requirements. Summary of the Invention

[0006] To address the aforementioned problems in the prior art, this invention provides a flexible hydroxylated bisphenol A glycidyl ether epoxy compound with the structure shown in Formula i. This compound can be used as a modifying raw material for polyurethane optical resin materials. Through structural optimization design, such as adding ultra-flexible segments, terminal hydroxylation, and gradient epoxy distribution to the bisphenol A glycidyl ether epoxy compound, it improves toughness, enhances interfacial interactions, reduces curing stress, and avoids component failure due to stress concentration. It can be used for casting and assembling precision optical components.

[0007] To achieve the above objectives, the present invention provides the following technical solution: On the one hand, the present invention provides a flexible hydroxy bisphenol A glycidyl ether epoxy compound, the structure of which is shown in formula i:

[0008] On the other hand, the present invention provides a method for preparing the flexible hydroxybisphenol A glycidyl ether epoxy compound as described above.

[0009] This invention employs a "stepwise selective synthesis" method to prepare flexible hydroxy bisphenol A glycidyl ether epoxy compounds. The specific reaction is as follows: Step 1: Bisphenol A reacts with epichlorohydrin under alkaline conditions in an epoxidation reaction. The phenoxy anion attacks the α-carbon of epichlorohydrin, causing the chloride ion to leave and forming an ether bond while maintaining the epoxy structure. The reaction is controlled on one side by limiting the amount of epichlorohydrin. The specific reaction process is as follows: Step 2: The phenolic hydroxyl group of bisphenol A monoglycidyl ether (a) is protonated and activated by diethylene glycol under the catalysis of p-toluenesulfonamide (PTSA). The phenolic hydroxyl group attacks the protonated carbon atom, loses the proton to form an ether bond, and preferentially reacts with one end of the diethylene glycol, finally yielding the flexible hydroxyl bisphenol A glycidyl ether epoxy compound (i). The specific reaction process is as follows:

[0010] Specifically, the method includes the following steps: (1) One-sided epoxidation reaction: Bisphenol A and epichlorohydrin were added to a reaction vessel containing N,N-dimethyldiamide solvent with stirring. The weight ratio of bisphenol A to epichlorohydrin was 1:(0.37~0.44). N2 was continuously introduced and the temperature was controlled to 65~90℃. Potassium carbonate powder was added with stirring and the reaction was stirred for 3~7 hours. The organic phase was separated and eluted, and the solvent was collected by vacuum distillation to obtain bisphenol A monoglycidyl ether.

[0011] (2) Flexible chain introduction reaction: Bisphenol A monoglycidyl ether and diethylene glycol prepared in step (1) are added to a reaction vessel containing xylene solvent with stirring. N2 is continuously introduced and the temperature is raised to 60~70℃. p-Toluenesulfonamide is added in batches with stirring and the temperature is raised to 70~100℃ for 4~7 hours.

[0012] The reaction process was monitored using a combination of thin-layer chromatography (TLC) and acid value determination. TLC: Samples were taken periodically, using ethyl acetate / petroleum ether (1:3-1:5) as the developing solvent. Judgment criteria: Under UV light, the spot of the raw material bisphenol A monoglycidyl ether gradually weakened, while the product spot gradually strengthened, and the Rf value was smaller than that of the raw material (due to increased polarity). Acid value determination: Samples were titrated with KOH standard solution. As the reaction proceeded, the acid value of the system should gradually decrease (due to the reduction of phenolic hydroxyl groups).

[0013] After the reaction was completed, the acid was neutralized with alkali, the catalyst was removed by washing with water, the solvent was collected by vacuum distillation, and finally the flexible hydroxybisphenol A glycidyl ether epoxy compound (i) was obtained.

[0014] In the preparation method described above, preferably, the weight ratio of potassium carbonate, epichlorohydrin, bisphenol A and N,N-dimethyldiamide in step (1) is (0.28~0.37):(0.37~0.44):1:(2~5).

[0015] In the preparation method described above, preferably, the weight ratio of p-toluenesulfonamide, diethylene glycol, bisphenol A monoglycidyl ether (a) and xylene in step (2) is (0.01~0.1):(1~1.2):(1.2~1.7):(3~7).

[0016] In another aspect, the present invention provides the application of the flexible hydroxybisphenol A glycidyl ether epoxy compound as described above as a polymer optical material.

[0017] In the applications described above, preferably, the flexible hydroxybisphenol A glycidyl ether epoxy compound is used as a modifier for polyurethane optical materials.

[0018] In the application described above, preferably, the polyurethane optical material is polymerized from flexible hydroxybisphenol A glycidyl ether epoxy compound, polyisocyanate and polythiol compound.

[0019] In the application described above, preferably, the polyisocyanate is selected from at least one of toluene diisocyanate, diphenylmethane diisocyanate, diphenyl ether diisocyanate, dicyclohexylmethane diisocyanate, diethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, hexamethylene diisocyanate, dithiodiethyl diisocyanate, dithiodipropyl diisocyanate, thiodihexyl diisocyanate, thiodipropyl diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, lysine triisocyanate, triphenylmethane triisocyanate, m-phenylenedimethyl isocyanate, phenylenedimethyl diisocyanate, and o-toluidine diisocyanate.

[0020] In the application described above, preferably, the polythiol compound is selected from 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, methanedithiol, methanetrithiol, bis(2-mercaptoethyl) ether, tetra(mercaptomethyl)methane, 1,3-dimercaptopropane, 1,4-dimercaptobutane, 1,6-dimercaptohexane, 2,2-dimercaptopropane, 1,2-bis(2-mercaptoethoxy)ethane, 1,2-bis(2-mercaptoethylthio)ethane, and 2,3-dimercapto-1-propanol. 1,3-Dimercapto-2-propanol, 2-Mercaptomethyl-1,3-dimercaptopropane, 2-Mercaptomethyl-1,4-dimercaptobutane, 1,2,3-trimercaptopropane, 2-(2-mercaptoethylthio)-1,3-dimercaptopropane, 1,2-dimercaptopropane, 2,4-dimercaptomethyl-1,5-dimercapto-3-thiapentane, bis(2-mercaptoethyl) sulfide, ethylene glycol bis(3-mercaptopropionate), diethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(2-mercaptoacetate), 1,4-butanediol bis(2-mercaptoacetate), trimethylolpropane trimercaptopropionate, pentaerythritol tetramercaptoacetate, diethylene glycol bis(3-mercaptopropionate), pentaerythritol tetramercaptopropionate Ester, 1,2-dimercaptocyclohexane, 1,1,1-tris(mercaptomethyl)propane, 1,4-butanediol bis(3-mercaptopropionate), 1,3-dimercaptocyclohexane, trimethylolpropane trimercaptoacetate, 1,4-dimercaptocyclohexane, 1,3-bis(mercaptomethyl)cyclohexane, 1,4-bis(mercaptomethyl)cyclohexane, 2,5-dimercaptomethyl-1,4-dithiane, 2,5-bis(2-mercaptoethylthiomethyl)-1,4-dithiane, 2,5-dimercaptomethyl-1-thiane, 1,2-dimercaptoethane, 2,5-dimercaptoethyl-1-thiane, 2,5-dimercaptomethylthiophene, bis(4-mercaptophenyl)sulfone, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, At least one of 1,4-dimercaptobenzene, bis(4-mercaptophenyl) sulfide, 1,3-bis(mercaptomethyl)benzene, 2,5-dimercaptomethyl-1,4-dithiane, 1,4-bis(mercaptomethyl)benzene, 2,2-bis(4-mercaptophenyl)propane, 2,2'-dimercaptobiphenyl, 4,4'-dimercaptobiphenyl, bis(4-mercaptophenyl) ether, bis(4-mercaptomethylphenyl)methane, 1,1,3,3-tetra(mercaptomethylthio)propane, 2,2-bis(4-mercaptomethylphenyl)propane, bis(4-mercaptomethylphenyl) ether, bis(4-mercaptomethylphenyl) sulfide, bis(4-mercaptophenyl)methane, 2,5-dimercapto-1,3,4-thiadiazole, and 3,4-thiophene dithiol.

[0021] The beneficial effects of this invention are as follows: 1. The flexible hydroxybisphenol A glycidyl ether epoxy compound of the present invention introduces flexible ether bond segments into the molecular chain, which significantly improves the flexibility of the molecular chain and improves the toughness of the material while maintaining the rigid skeleton.

[0022] 2. The terminal hydroxyl group provides active hydrogen, which enhances the reactivity with the curing agent and the intermolecular hydrogen bonding.

[0023] 3. During the curing process, the epoxy groups and hydroxyl groups form a reaction gradient, achieving stepwise curing, reducing curing stress, minimizing deformation or cracks caused by internal stress, and avoiding defects in optical components due to stress concentration. Attached Figure Description

[0024] Figure 1 The image shows the FT-IR infrared spectrum of the flexible hydroxy bisphenol A glycidyl ether epoxy compound prepared in Example 1.

[0025] Figure 2 The image shows the 1H NMR spectrum of the flexible hydroxy bisphenol A glycidyl ether epoxy compound prepared in Example 1. Detailed Implementation

[0026] The present invention will be further described below through specific embodiments, but this does not imply a limitation on the scope of protection of the present invention.

[0027] Example 1: Preparation of flexible hydroxybisphenol A glycidyl ether epoxy compound (1) Add 150g of bisphenol A and 58g of epichlorohydrin to a reaction vessel containing 500g of DMF solvent, continuously introduce N2, control the temperature to 80°C, add 46g of potassium carbonate powder, stir and react for 5 hours, separate and elute the organic phase, collect the solvent by vacuum distillation, and obtain 142.4g of bisphenol A monoglycidyl ether (compound a).

[0028] (2) Take 120g of bisphenol A monoglycidyl ether (a) and 85g of diethylene glycol prepared in step (1) and stir them into a reaction vessel containing 400g of xylene solvent. Continuously introduce N2 and heat to 65°C. Stir and add 3g of p-toluenesulfonamide. Heat to 85°C and add another 2g of p-toluenesulfonamide. Titrate the acid value of the system with KOH standard solution every hour. Keep the reaction at this temperature for 6 hours. When the acid value no longer changes, cool down to 50°C and neutralize with 10% NaHCO3 solution. Separate and elute the organic phase. Distill under reduced pressure to obtain 132.4g of colorless, transparent, flexible hydroxy bisphenol A glycidyl ether epoxy compound (i), with a yield of 80.4%.

[0029] Fourier transform infrared (FT-IR) spectroscopy was performed on the product prepared in Example 1. Figure 1As shown in the figure, the curve analysis shows that the range is 3250~3567cm. -1 The strong absorption peak at 3056 cm⁻¹ is due to the stretching vibration of the hydroxyl group (OH) (broad peak). -1 The peak at 2855-2960 cm⁻¹ represents the stretching vibration of the aromatic CH bond; the peaks at 1605 cm⁻¹, 1580 cm⁻¹, 1510 cm⁻¹, and 1467 cm⁻¹ represent the characteristic peak combination of the stretching vibration of the aromatic ring (C=C) in the bisphenol A structure; the absorption peaks at 1460-1375 cm⁻¹ represent the CH bending vibration of the methyl and methylene groups; the peak at 1385 cm⁻¹ represents the characteristic peak of the symmetric bending vibration of the -C(CH₃)₂ group; the peak at 1261 cm⁻¹ represents the symmetric breathing vibration of the epoxy ring; and the peak at 1231 cm⁻¹ represents the symmetric breathing vibration of the epoxy ring. -1 The vibration at 1180 cm⁻¹ is an asymmetric stretching vibration of an aromatic ether bond (Ph-OC); the vibration at 1110–1030 cm⁻¹ is an asymmetric stretching vibration of an aliphatic ether bond (COC); the vibration at 1110–1030 cm⁻¹ is a symmetric stretching vibration of an ether bond (CO); and the vibration at 915 cm⁻¹ is a symmetric stretching vibration of an ether bond (CO). -1 The strong absorption peak at 860-833 cm⁻¹ is a characteristic absorption peak of the epoxy group; the peak at 825 cm⁻¹ is a characteristic peak of the para-disubstituted benzene ring; and the peak at 729-693 cm⁻¹ is an out-of-plane bending vibration of the aromatic ring.

[0030] 1H NMR spectroscopy analysis: Results are as follows Figure 2 As shown, δ = 7.15~6.86 ppm (m, 8H, 2×Ph hydrogen); 4.19~3.95 (dd, 2H, epoxy-CH2-O-Ph); 3.89~3.77 (t, 2H, -CH2OH- with hydroxyl group); 376~3.63 (m, 6H, OCH2CH2OCH2); 3.18~3.15 (m, 1H, epoxy-CH-); 2.80~2.65 (dd, 2H, epoxy-CH2-); 2.50 ppm (t, 1H, -OH); 1.63 (s, 6H, -C(CH3)2).

[0031] Example 2 Preparation of flexible hydroxybisphenol A glycidyl ether epoxy compound (1) Add 100g of bisphenol A and 42g of epichlorohydrin to a reaction vessel containing 400g of DMF solvent, continuously introduce N2, control the temperature to 80℃, add 32g of potassium carbonate powder, stir and react for 5 hours, separate and elute the organic phase, collect the solvent by vacuum distillation, and obtain 105.4g of bisphenol A monoglycidyl ether (a).

[0032] (2) Take 100g of bisphenol A monoglycidyl ether (a) and 70g of diethylene glycol prepared in step (1) and stir them into a reaction vessel containing 380g of xylene solvent. Continuously introduce N2 and heat to 65°C. Stir and add 2g of p-toluenesulfonamide. Heat to 85°C and add 3g of p-toluenesulfonamide. Keep the reaction at this temperature for 6 hours. Cool down to 50°C and neutralize with 10% NaHCO3 solution. Separate and elute the organic phase. Distill under reduced pressure to obtain 116.4g of colorless, transparent, flexible hydroxy bisphenol A glycidyl ether epoxy compound (i), with a yield of 80.5%.

[0033] Example 3 Preparation of flexible hydroxybisphenol A glycidyl ether epoxy compound (1) Add 100g of bisphenol A and 42g of epichlorohydrin to a reaction vessel containing 450g of DMF solvent, continuously introduce N2, control the temperature to 85°C, add 33g of potassium carbonate powder, stir and react for 5 hours, separate and elute the organic phase, collect the solvent by vacuum distillation, and obtain 106.4g of bisphenol A monoglycidyl ether (a).

[0034] (2) Take 100g of bisphenol A monoglycidyl ether (a) and 65g of diethylene glycol prepared in step (1) and stir them into a reaction vessel containing 360g of xylene solvent. Continuously introduce N2 and heat to 60°C. Stir and add 3g of p-toluenesulfonamide. Heat to 85°C and add 2g of p-toluenesulfonamide. Keep the reaction at this temperature for 6 hours. Cool down to 50°C and neutralize with 10% NaHCO3 solution. Separate and elute the organic phase. Distill under reduced pressure to obtain 116.2g of colorless, transparent, flexible hydroxy bisphenol A glycidyl ether epoxy compound (i), with a yield of 80.4%.

[0035] Example 4: Preparation of Flexible Hydroxybisphenol A Glycidyl Ether Epoxide (1) Add 75g of bisphenol A and 30g of epichlorohydrin to a reaction vessel containing 340g of DMF solvent, continuously introduce N2, control the temperature to 85°C, add 25g of potassium carbonate powder, stir and react for 5 hours, separate and elute the organic phase, collect the solvent by vacuum distillation, and obtain 79.8g of bisphenol A monoglycidyl ether (a).

[0036] (2) Take 75g of bisphenol A monoglycidyl ether and 49g of diethylene glycol prepared in step (1) and stir them into a reaction vessel containing 280g of xylene solvent. Continuously introduce N2 and heat to 60°C. Stir and add 2.0g of p-toluenesulfonamide. Heat to 85°C and add 1.75g ​​of p-toluenesulfonamide. Keep the reaction at this temperature for 6 hours, cool to 50°C, neutralize with 5% NaHCO3 solution, separate and elute the organic phase, and distill under reduced pressure to obtain 87.2g of colorless, transparent, flexible hydroxy bisphenol A glycidyl ether epoxy compound (i), with a yield of 80.5%.

[0037] Example 5: Preparation of Flexible Hydroxybisphenol A Glycidyl Ether Epoxide (1) Add 120g of bisphenol A and 46g of epichlorohydrin to a reaction vessel containing 400g of DMF solvent, continuously introduce N2, control the temperature to 80℃, add 36g of potassium carbonate powder, stir and react for 5 hours, separate and elute the organic phase, collect the solvent by vacuum distillation, and obtain 113.9g of bisphenol A monoglycidyl ether (a).

[0038] (2) Take 95g of bisphenol A monoglycidyl ether (a) and 68g of diethylene glycol prepared in step (1) and stir them into a reaction vessel containing 320g of xylene solvent. Continuously introduce N2 and heat to 65°C. Stir and add 2g of p-toluenesulfonamide. Heat to 85°C and add another 2g of p-toluenesulfonamide. Keep the reaction at this temperature for 6 hours. Cool down to 50°C and neutralize with 10% NaHCO3 solution. Separate and elute the organic phase. Distill under reduced pressure to obtain 105.9g of colorless, transparent, flexible hydroxy bisphenol A glycidyl ether epoxy compound (i), with a yield of 80.6%.

[0039] Example 6: Preparation of Modified Polyurethane Optical Materials

[0040] (I) Add 90g of diphenylmethane diisocyanate to a reactor containing 90g of 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (Formula I), and stir at 80 rpm for 50 minutes. Add 10g of the flexible hydroxy bisphenol A glycidyl ether epoxy compound (i) prepared in Example 1, and stir for 10 minutes. Then add 40g of diphenylmethane diisocyanate and 0.45g of dibutyltin dilaurate, and stir at 80 rpm for 50 minutes. After degassing under vacuum for 15 minutes, pour the mixture into a tempered mold at a pouring temperature controlled at 50°C. Place the tempered mold containing the prepolymer in a curing oven and cure at 45°C for 2.5 hours → 55°C for 2.5 hours → Annealing process: 70℃×1.5h→90℃×1h→110℃×1.5h, annealing at 110℃→30℃, slow cooling at 2℃ / min, and sampling to obtain modified polyurethane optical material.

[0041] Comparative Example 1: Preparation of Polyurethane Optical Materials Using the same raw materials and reaction conditions as in Example 6, except without the flexible hydroxy bisphenol A glycidyl ether epoxy compound (i), polyurethane optical material was obtained after curing and demolding.

[0042] Comparative Example 2: Preparation of Modified Polyurethane Optical Materials Using the same raw materials and reaction conditions as in Example 6, except that the flexible hydroxy bisphenol A glycidyl ether epoxy compound (i) was replaced with E51 type bisphenol A epoxy resin (whose main component is bisphenol A diglycidyl ether) from Nantong Xingchen Synthetic Materials Co., Ltd., the modified polyurethane optical material was obtained after curing and demolding.

[0043] Example 7: Optical performance testing experiment on modified polyurethane optical materials. The optical properties of the polyurethane optical materials prepared in Example 6 and Comparative Examples 1-2 were tested. Transmittance was measured using a Lambda 650S UV-Vis spectrophotometer (PerkinElmer Chemical Analysis Instruments, Inc.), and refractive index was measured using an Rx-7000 digital refractometer (Shanghai Optical Instrument Equipment Co., Ltd.). The testing method involved placing the polyurethane optical material sample directly on the prism of the UV-Vis spectrophotometer or the prism of the refractometer. The yellow index was calculated from the spectrophotometer reading using the formula: YI = 100(1.28X - 1.06Z) ÷ Y, where X, Y, and Z are the tristimulus values ​​of the C light source. The test results are shown in Table 1.

[0044]

[0045] The test results show that the modified polyurethane optical material containing flexible hydroxy bisphenol A glycidyl ether epoxy compound (i) prepared in this invention meets the optical performance design requirements.

[0046] Example 8: Impact Strength Test of Modified Polyurethane Optical Materials The polyurethane optical materials prepared in Example 6, Comparative Example 1, and Comparative Example 2 were subjected to impact strength tests. The highest steel ball mass at which cracks appeared in the optical material was used as the benchmark. For example, if the material did not crack after three impacts with a 90g steel ball, but cracked after impact with a 95g steel ball, then the impact strength of this material was less than 95g. Testing method: A substrate with a certain curvature at its center thickness was fixed to the bottom of the instrument with the convex side facing upwards. Steel balls of different masses (90g, 95g, 100g, and 105g) were dropped vertically from a height of 1.30m onto the center of the substrate surface, and each mass of steel ball was measured three times. The test results are shown in Table 2.

[0047]

[0048] The steel ball impact test results show that the impact strength of the sample in Example 6 is greater than that of the sample in Comparative Example 2, which is greater than that of the sample in Comparative Example 1.

[0049] Example 9: Comparative Experiment on Curing Deformation Detection Internal stress was tested using the thin-sheet bending method. The testing instrument was a coating internal stress tester, model PN683, from Specialtytest, USA. The testing method and steps were as follows: Stainless steel sheet substrates were selected. The prepolymers prepared in Example 6, Comparative Example 1, and Comparative Example 2 were coated onto one side of each stainless steel sheet substrate, with 5 sheets per group. These were labeled A, B, and C. After curing, the maximum bending value and the final bending value were read, and the average of the maximum and final bending values ​​was recorded.

[0050] Warpage deformation was detected using a three-dimensional contour scanning method. The instrument used was a laser three-dimensional contour analyzer, model: Novator432, manufactured by Shenzhen Zhongtu Instrument Co., Ltd. The detection method and steps were as follows: Warpage deformation was detected on the polyurethane optical materials prepared in Example 6, Comparative Example 1, and Comparative Example 2, respectively. The warpage deformation was measured as the difference between the volume of the tempered mold and the volume of the polymer.

[0051] Volume shrinkage rate was measured using the density method. The testing instrument was a curing shrinkage rate tester, model MAY-S3233, manufactured by Shenzhen Lidaxin Instrument Co., Ltd. The testing method consisted of liquid density measurement (ρ0) and cured density measurement (ρ1). Volume shrinkage rate (%) = (ρ1 - ρ0) / ρ1 × 100%. The test results are shown in Table 3.

[0052]

[0053] Curing deformation testing results show that the modified polyurethane optical material prepared from flexible hydroxyl bisphenol A glycidyl ether epoxy compound has lower internal stress, warpage deformation, and curing shrinkage than the polyurethane optical material prepared from ordinary bisphenol A epoxy resin, exhibiting better mechanical and processing properties. This is because the bifunctionality of the i-type compound ensures a chemical reaction gradient, the flexible chain provides stress buffering, and avoids macroscopic separation; while ordinary bisphenol A epoxy monomers, with epoxy groups at both ends, cannot be pre-anchored and lack flexible transition, resulting in high interfacial stress.

Claims

1. A flexible hydroxy bisphenol A glycidyl ether epoxy compound, characterized in that, Its structure is shown in equation i:

2. The method for preparing the flexible hydroxybisphenol A glycidyl ether epoxy compound as described in claim 1, characterized in that, The method includes the following steps: (1) One-sided epoxidation reaction: Bisphenol A and epichlorohydrin were added to a reaction vessel containing N,N-dimethyldiamide solvent with stirring. The weight ratio of bisphenol A to epichlorohydrin was 1:(0.37~0.44). N2 was continuously introduced and the temperature was controlled to 65~90℃. Potassium carbonate powder was added with stirring and the reaction was stirred for 3~7 hours. The organic phase was separated and eluted. The solvent was collected by vacuum distillation to obtain bisphenol A monoglycidyl ether. (2) Flexible chain introduction reaction: Bisphenol A monoglycidyl ether (formula a) and diethylene glycol prepared in step (1) above are added to a reaction vessel containing xylene solvent with stirring. N2 is continuously introduced and the temperature is raised to 60~70℃. p-Toluenesulfonamide is added in batches with stirring. The temperature is raised to 70~100℃ and the reaction is carried out for 4~7 hours. After the reaction is completed, the acidity is neutralized with alkali solution, the catalyst is removed by washing with water, the solvent is collected by vacuum distillation, and finally the flexible hydroxy bisphenol A glycidyl ether epoxy compound (i) is obtained.

3. The preparation method according to claim 2, characterized in that, In step (1), the weight ratio of potassium carbonate, epichlorohydrin, bisphenol A and N,N-dimethyldiamide is (0.28~0.37):(0.37~0.44):1:(2~5).

4. The preparation method according to claim 2 or 3, characterized in that, In step (2), the weight ratio of p-toluenesulfonamide, diethylene glycol, bisphenol A monoglycidyl ether (formula a) and xylene is (0.01~0.1):(1~1.2):(1.2~1.7):(3~7).

5. The application of the flexible hydroxybisphenol A glycidyl ether epoxy compound as described in claim 1 as a polymer optical material modifier.

6. The application as described in claim 5, characterized in that, The polyurethane optical material is polymerized from flexible hydroxybisphenol A glycidyl ether epoxy compound, polyisocyanate and polythiol compound.

7. The application as described in claim 6, characterized in that, The polyisocyanate is selected from at least one of toluene diisocyanate, diphenylmethane diisocyanate, diphenyl ether diisocyanate, dicyclohexylmethane diisocyanate, diethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, hexamethylene diisocyanate, dithiodiethyl diisocyanate, dithiodipropyl diisocyanate, thiodihexyl diisocyanate, thiodipropyl diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, lysine triisocyanate, triphenylmethane triisocyanate, m-phenylenedimethyl isocyanate, phenylenedimethyl diisocyanate, and o-toluidine diisocyanate.

8. The application as described in claim 6 or 7, characterized in that, The polythiol compound is selected from 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecan, 4,8-dimercaptomethyl-1 ,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, methane dithiol, methane trithiol, bis(2-mercaptoethyl) ether, tetra(mercaptomethyl)methane, 1,3-dimercaptopropane, 1,4-dimercaptobutane, 1,6-dimercaptohexane, 2,2-dimercaptopropane, 1,2-bis(2-mercaptoethoxy)ethane, 1,2-bis(2-mercaptoethylthio)ethane, 2,3-dimercapto-1-propanol, 1,3-dimercapto-2-propanol, 2-mercaptomethyl-1,3-dimercaptopropane, 2-mercaptomethyl-1,4-dimercaptobutane, 1 2,3-Trimercaptopropane, 2-(2-mercaptoethylthio)-1,3-dimercaptopropane, 1,2-dimercaptopropane, 2,4-dimercaptomethyl-1,5-dimercapto-3-thiapentane, bis(2-mercaptoethyl) sulfide, ethylene glycol bis(3-mercaptopropionate), diethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(2-mercaptoacetate), 1,4-butanediol bis(2-mercaptoacetate), trimethylolpropane trimercaptopropionate, pentaerythritol tetramercaptoacetate, diethylene glycol bis(3-mercaptopropionate), pentaerythritol tetramercaptopropionate, 1,2-dimercaptocyclohexane, 1,1,1-tris(mercaptomethyl)propane, 1,4 Butylene glycol bis(3-mercaptopropionate), 1,3-dimercaptocyclohexane, trimethylolpropane trimercaptoacetate, 1,4-dimercaptocyclohexane, 1,3-bis(mercaptomethyl)cyclohexane, 1,4-bis(mercaptomethyl)cyclohexane, 2,5-dimercaptomethyl-1,4-dithiane, 2,5-bis(2-mercaptoethylthiomethyl)-1,4-dithiane, 2,5-dimercaptomethyl-1-thiane, 1,2-dimercaptoethane, 2,5-dimercaptoethyl-1-thiane, 2,5-dimercaptomethylthiophene, bis(4-mercaptophenyl)sulfone, 1,2-dimercaptophenyl, 1,3-dimercaptophenyl, 1,4-dimercaptophenyl, bis(4-mercaptophenyl)sulfone The following are included in the list of at least one of the following: thioether, 1,3-bis(mercaptomethyl)benzene, 2,5-dimercaptomethyl-1,4-dithiane, 1,4-bis(mercaptomethyl)benzene, 2,2-bis(4-mercaptophenyl)propane, 2,2'-dimercaptobiphenyl, 4,4'-dimercaptobiphenyl, bis(4-mercaptophenyl)ether, bis(4-mercaptomethylphenyl)methane, 1,1,3,3-tetra(mercaptomethylthio)propane, 2,2-bis(4-mercaptomethylphenyl)propane, bis(4-mercaptomethylphenyl)ether, bis(4-mercaptomethylphenyl)thioether, bis(4-mercaptophenyl)methane, 2,5-dimercapto-1,3,4-thiadiazole, and 3,4-thiophene dithiol.

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