BPEF-based polyester optical resin preparation method

Abstract

The invention discloses a BPEF-based polyester optical resin preparation method, and particularly relates to the technical field of optical resin preparation, and the specific preparation method comprises the following steps: 1, preparing raw materials; step 2, preparing a BPEF oligomer; step 3, preparing polyester polyol; and 4, preparing the polyester optical resin. The prepared optical resin has high refractive index and good heat resistance and can keep good performance in a high-temperature environment, BPEF has high light transmittance and can improve the light transmittance performance of the optical resin, the refractive index, the heat resistance and the light transmittance of the optical resin can be further improved through the added modifier and additive, and the optical resin has the advantages of being high in heat resistance and good in heat resistance. The preparation method is simple to operate, renewable resources or recycled organic wastes can be used as raw materials to prepare the BPEF oligomer and the polyester polyol, so that the preparation method is greener and sustainable, and the preparation method can be widely applied to the fields of optical instruments, laser technologies, photoelectric sensing and the like.

Description

Technical Field

[0001] The invention relates to the technical field of optical resin preparation, and more specifically to a method for preparing a polyester optical resin based on BPEF. Background Art

[0002] Optical resin generally refers to resin synthesized to achieve certain optical properties. It is commonly used in glasses, indoor lighting products, etc. The optical production industry has developed rapidly in China, especially optical lenses have become a new industry in China, and the original cold-processed inorganic materials have gradually been replaced by thermoformed polymer materials. The domestic industry of thermosetting polymer optical resin materials started late and the starting point of process technology is low. Most manufacturers import optical resin monomers from abroad for polymerization processing and are highly dependent on foreign raw material supplies. In recent years, domestic manufacturers have realized the importance of raw materials and have begun to develop optical resin materials, and have achieved considerable results.

[0003] The Chinese invention patent with publication number CN111748069B discloses an optical resin composition and an optical resin material prepared therefrom, which improves the shortcomings of the prior art, such as high toxicity and variety of raw materials. The optical resin material prepared from the composition has a high refractive index, as well as excellent impact resistance and optical transparency.

[0004] The above technical scheme designs a method for preparing an optical resin material, which can make the prepared optical resin material have a high refractive index and excellent impact resistance and optical transparency. Nevertheless, the preparation of optical resin is not limited to the above patent design. Optical resins with high refractive index and light transmittance can also be obtained by adopting different preparation raw materials and preparation methods. Therefore, in order to prepare better optical resins, nowadays, in view of the refractive index, heat resistance and light transmittance of optical resins that need to be improved in the prior art, it is also necessary to improve the preparation method of optical resins to improve the refractive index, heat resistance and light transmittance of optical resins, and in view of the problem of high toxicity of raw materials, it is also necessary to design a more green and sustainable preparation method. Summary of the invention

[0005] In order to overcome the above-mentioned defects of the prior art, the present invention provides a method for preparing a polyester optical resin based on BPEF.

[0006] To achieve the above object, the present invention provides the following technical solution: a method for preparing a polyester optical resin based on BPEF, the specific preparation method steps are as follows:

[0007] Step 1: prepare raw materials, BPEF (diphenyl dichloroethane), diphenol methane, terminator, diol, catalyst, modifier, initiator, stabilizer and additives;

[0008] Step 2: preparing BPEF oligomers, mixing BPEF (diphenyl dichloroethane) and diphenol methane, adding a catalyst to obtain a mixture, and then heating the mixture for polycondensation reaction. When the reaction mixture becomes thick, the heating is stopped, and a terminator is added to the reaction mixture and stirred. After the terminator is stirred evenly, the temperature is lowered, and then the BPEF oligomers are obtained by discharging the mixture;

[0009] Step 3: preparing polyester polyol, adding BPEF oligomer to diol, adding catalyst under inert gas protection, and then carrying out polymerization reaction at a certain temperature, controlling the temperature and time of the polymerization reaction, and then cooling to below 50°C, adding terminator, and obtaining polyester polyol;

[0010] Step 4: Prepare polyester optical resin, add polyester polyol to the modifier and stir evenly, add initiator and additives at a certain temperature, carry out polymerization reaction, control the polymerization reaction temperature within a certain range to make the reaction complete, cool to below 50°C, add stabilizer, stir evenly, remove unreacted monomers and additives by filtering, washing and drying, and finally obtain polyester optical resin.

[0011] As a further improvement of the technical solution of the present invention, in the step 2, BPEF (diphenyldichloroethane) and diphenol methane are mixed in a molar ratio of 1:1, and the added catalyst is any one of tetrabutyl titanate, organotin or organoboron.

[0012] As a further improvement of the technical solution of the present invention, the heating temperature of the mixture during the condensation reaction in step 2 is 100-130°C, the terminator added is phenol, the molar ratio of phenol to BPEF is 1:20, and after the terminator is stirred evenly, the temperature is lowered to below 50°C, and the stirring rate is 100-200r / min.

[0013] As a further improvement of the technical solution of the present invention, in the step three, the mixing ratio of the BPEF oligomer to the diol is 1:10, and the diol is any one of ethylene glycol or propylene glycol.

[0014] As a further improvement of the technical solution of the present invention, the catalyst in step three is stannous octoate, the polymerization temperature is 90-120° C., the reaction time is 30-60 min, and the terminator in step three is any one of terminal hydroxyl polyester or terminal amino polyester.

[0015] As a further improvement of the technical solution of the present invention, in the step 4, the mixing ratio of the polyester polyol to the modifier is 1:1, and the modifier is any one of styrene or methyl methacrylate.

[0016] As a further improvement of the technical solution of the present invention, the temperature range for adding the initiator and the additive in step 4 is controlled to be 60-80°C, the initiator is benzoyl peroxide, and the additive is any one or a combination of two or more of silicon dioxide, aluminum oxide, titanium dioxide, silicone oil, quartz and polycarbonate.

[0017] As a further improvement of the technical solution of the present invention, the polymerization reaction temperature in step 4 is controlled to be 90-120°C, the reaction time is 30-45min, the stabilizer added in step 4 is stearic acid, and the stirring rate after adding the stabilizer is 120-200r / min.

[0018] Beneficial effects of the present invention:

[0019] In the present technical scheme, by adding BPEF, a polyester material with good heat resistance, and utilizing the high refractive index of BPEF, the refractive index performance of the optical resin can be improved, so that the prepared optical resin has a higher refractive index and better heat resistance, and can maintain good performance in a high temperature environment. BPEF has high light transmittance, which can improve the light transmittance performance of the optical resin, so that the prepared optical resin has better light transmittance. The added modifiers and additives can also further improve the refractive index, heat resistance and light transmittance of the optical resin. The preparation method is simple to operate, and renewable resources or recycled organic waste can be used as raw materials to prepare BPEF oligomers and polyester polyols, thereby making the preparation method more green and sustainable, and can be widely used in optical instruments, laser technology, photoelectric sensing and other fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 It is a preparation flow chart of the present invention. DETAILED DESCRIPTION

[0021] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0022] As attached Figure 1 A method for preparing a polyester optical resin based on BPEF is shown, and the specific preparation steps are as follows:

[0023] Step 1: prepare raw materials, BPEF (diphenyl dichloroethane), diphenol methane, terminator, diol, catalyst, modifier, initiator, stabilizer and additives;

[0024] Step 2: preparing BPEF oligomers, mixing BPEF (diphenyl dichloroethane) and diphenol methane, adding a catalyst to obtain a mixture, and then heating the mixture for polycondensation reaction. When the reaction mixture becomes thick, the heating is stopped, and a terminator is added to the reaction mixture and stirred. After the terminator is stirred evenly, the temperature is lowered, and then the BPEF oligomers are obtained by discharging the mixture;

[0025] Step 3: preparing polyester polyol, adding BPEF oligomer to diol, adding catalyst under inert gas protection, and then carrying out polymerization reaction at a certain temperature, controlling the temperature and time of the polymerization reaction, and then cooling to below 50°C, adding terminator, and obtaining polyester polyol;

[0026] Step 4: Prepare polyester optical resin, add polyester polyol to the modifier and stir evenly, add initiator and additives at a certain temperature, carry out polymerization reaction, control the polymerization reaction temperature within a certain range to make the reaction complete, cool to below 50°C, add stabilizer, stir evenly, remove unreacted monomers and additives by filtering, washing and drying, and finally obtain polyester optical resin.

[0027] Preferably, in step 2, BPEF (diphenylethylene dichloride) and diphenol methane are mixed in a molar ratio of 1:1, and the added catalyst is any one of tetrabutyl titanate, organotin or organoboron.

[0028] Preferably, the heating temperature of the mixture during the polycondensation reaction in step 2 is 100-130°C, the terminator added is phenol, the molar ratio of phenol to BPEF is 1:20, and after the terminator is stirred evenly, the temperature is lowered to below 50°C, and the stirring rate is 100-200r / min.

[0029] Preferably, in step three, the mixing ratio of BPEF oligomer to diol is 1:10, and the diol is any one of ethylene glycol or propylene glycol.

[0030] Preferably, the catalyst in step three is stannous octoate, the polymerization temperature is 90-120° C., the reaction time is 30-60 min, and the terminator in step three is any one of hydroxyl-terminated polyester or amino-terminated polyester.

[0031] Preferably, in step 4, the mixing ratio of polyester polyol to modifier is 1:1, and the modifier is any one of styrene or methyl methacrylate.

[0032] Preferably, the temperature range for adding the initiator and the additive in step 4 is controlled to be 60-80° C., the initiator is benzoyl peroxide, and the additive is any one or a combination of two or more of silicon dioxide, aluminum oxide, titanium dioxide, silicone oil, quartz and polycarbonate.

[0033] Preferably, in step 4, the polymerization reaction temperature is controlled to be 90-120° C., the reaction time is 30-45 min, the stabilizer added in step 4 is stearic acid, and the stirring rate after adding the stabilizer is 120-200 r / min.

[0034] Working principle: The present invention designs a method for preparing a polyester optical resin based on BPEF. The specific process is as shown in the attached manual. Figure 1 As shown, the specific preparation steps in this technical solution are as follows:

[0035] First, prepare raw materials BPEF (diphenyl dichloroethane), diphenol methane, terminator, diol, catalyst, modifier, initiator, stabilizer and additives;

[0036] Secondly, BPEF (diphenyl dichloroethane) and diphenol methane are mixed, a catalyst is added to obtain a mixture, and then the mixture is heated for polycondensation reaction. When the reaction mixture becomes thick, the heating is stopped, and a terminator is added to the reaction mixture and stirred. After the terminator is stirred evenly, the temperature is lowered, and then the BPEF oligomer is obtained by discharging the material, wherein BPEF (diphenyl dichloroethane) and diphenol methane are mixed in a molar ratio of 1:1, the added catalyst is any one of tetrabutyl titanate, organotin or organoboron, the heating temperature of the mixture during the polycondensation reaction is 100-130°C, the added terminator is phenol, the molar ratio of phenol to BPEF is 1:20, and after the terminator is stirred evenly, the temperature is lowered to below 50°C, and the stirring rate is 100-200r / min;

[0037] Then, the BPEF oligomer is added to the diol, and a catalyst is added under the protection of an inert gas, and then a polymerization reaction is carried out at a certain temperature, and the temperature and time of the polymerization reaction are controlled, and then the temperature is lowered to below 50° C., and a terminator is added to obtain a polyester polyol, wherein the mixing ratio of the BPEF oligomer to the diol is 1:10, the diol is any one of ethylene glycol or propylene glycol, the catalyst is stannous octoate, the polymerization reaction temperature is 90-120° C., the reaction time is 30-60 min, and the terminator in step three is any one of a terminal hydroxyl polyester or an amino-terminated polyester;

[0038] Finally, the polyester polyol is added to the modifier and stirred evenly, the mixing ratio of the polyester polyol to the modifier is 1:1, the modifier is any one of styrene or methyl methacrylate, and an initiator and an additive are added at a temperature of 60-80°C to carry out a polymerization reaction, wherein the initiator is benzoyl peroxide, and the additive is any one of silicon dioxide, aluminum oxide, titanium dioxide, silicone oil, quartz and polycarbonate or a combination of two or more thereof, and the polymerization reaction temperature is controlled within a certain range to complete the reaction, and the temperature is lowered to below 50°C, a stabilizer is added, and the mixture is stirred evenly, and unreacted monomers and additives are removed by filtering, washing and drying to finally obtain a polyester optical resin, wherein the polymerization reaction temperature is controlled to be 90-120°C, and the reaction time is 30-45min. The stabilizer added in step 4 is stearic acid, and the stirring rate is 120-200r / min after the stabilizer is added.

[0039] In summary, in the present technical scheme, by adding the polyester material BPEF with good heat resistance and utilizing the high refractive index of BPEF, the refractive index performance and heat resistance of the optical resin can be improved, and good performance can be maintained in a high temperature environment. BPEF has high light transmittance, which can improve the light transmittance of the optical resin, so that the prepared optical resin has better light transmittance. The added modifiers and additives can also further improve the refractive index, heat resistance and light transmittance of the optical resin. The preparation method is simple to operate, and renewable resources or recycled organic waste can be used as raw materials to prepare BPEF oligomers and polyester polyols, thereby making the preparation method more green and sustainable, and can be widely used in optical instruments, laser technology, optoelectronic sensing and other fields. The industrial feasibility and sustainability can provide a good foundation for future development.

[0040] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing a polyester optical resin based on BPEF, characterized in that: The specific preparation steps are as follows: Step 1: prepare raw materials, BPEF (diphenyl dichloroethane), diphenol methane, terminator, diol, catalyst, modifier, initiator, stabilizer and additives; Step 2: preparing BPEF oligomers, mixing BPEF (diphenyl dichloroethane) and diphenol methane, adding a catalyst to obtain a mixture, and then heating the mixture for polycondensation reaction. When the reaction mixture becomes thick, the heating is stopped, and a terminator is added to the reaction mixture and stirred. After the terminator is stirred evenly, the temperature is lowered, and then the BPEF oligomers are obtained by discharging the mixture; Step 3: preparing polyester polyol, adding BPEF oligomer to diol, adding catalyst under inert gas protection, and then carrying out polymerization reaction at a certain temperature, controlling the temperature and time of the polymerization reaction, and then cooling to below 50°C, adding terminator, and obtaining polyester polyol; Step 4: Prepare polyester optical resin, add polyester polyol to the modifier and stir evenly, add initiator and additives at a certain temperature, carry out polymerization reaction, control the polymerization reaction temperature within a certain range to make the reaction complete, cool to below 50°C, add stabilizer, stir evenly, remove unreacted monomers and additives by filtering, washing and drying, and finally obtain polyester optical resin.

2. The method for preparing a polyester optical resin based on BPEF according to claim 1, characterized in that: In the step 2, BPEF (diphenylethylene dichloride) and diphenol methane are mixed in a molar ratio of 1:1, and the added catalyst is any one of tetrabutyl titanate, organotin or organoboron.

3. The method for preparing a polyester optical resin based on BPEF according to claim 1, characterized in that: In the step 2, the heating temperature of the mixture during the polycondensation reaction is 100-130° C., the terminator added is phenol, the molar ratio of phenol to BPEF is 1:20, and after the terminator is stirred evenly, the temperature is lowered to below 50° C., and the stirring rate is 100-200 r / min.

4. The method for preparing a polyester optical resin based on BPEF according to claim 1, characterized in that: In the step 3, the mixing ratio of the BPEF oligomer to the diol is 1:10, and the diol is any one of ethylene glycol or propylene glycol.

5. The method for preparing a polyester optical resin based on BPEF according to claim 1, characterized in that: The catalyst in step 3 is stannous octoate, the polymerization temperature is 90-120° C., the reaction time is 30-60 min, and the terminator in step 3 is any one of hydroxyl-terminated polyester and amino-terminated polyester.

6. The method for preparing a polyester optical resin based on BPEF according to claim 1, characterized in that: In the step 4, the mixing ratio of the polyester polyol to the modifier is 1:1, and the modifier is any one of styrene or methyl methacrylate.

7. The method for preparing a polyester optical resin based on BPEF according to claim 1, characterized in that: The temperature range for adding the initiator and the additive in step 4 is controlled to be 60-80° C., the initiator is benzoyl peroxide, and the additive is any one or a combination of two or more of silicon dioxide, aluminum oxide, titanium dioxide, silicone oil, quartz and polycarbonate.

8. The method for preparing a polyester optical resin based on BPEF according to claim 1, characterized in that: In the step 4, the polymerization reaction temperature is controlled to be 90-120° C., the reaction time is 30-45 min, the stabilizer added in the step 4 is stearic acid, and the stirring rate after adding the stabilizer is 120-200 r / min.

Images