CN113831441A - Preparation method and reaction system of optical resin monomer - Google Patents
Preparation method and reaction system of optical resin monomer Download PDFInfo
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- CN113831441A CN113831441A CN202111128549.5A CN202111128549A CN113831441A CN 113831441 A CN113831441 A CN 113831441A CN 202111128549 A CN202111128549 A CN 202111128549A CN 113831441 A CN113831441 A CN 113831441A
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Abstract
The invention relates to the field of optical resin monomers, and discloses a preparation method and a reaction system of an optical resin monomer, which are carried out according to the following steps: s1, preparing diallyl terephthalate; s2, purifying diallyl terephthalate; s3, preparing a mixture I; s4, preparing a mixture II; s5, preparing an optical resin monomer; according to the invention, after the mixture II is added into the optical resin monomer, the mechanical property of the optical resin monomer is increased, the hardness and the stamping resistance of the material are increased, the later-stage lens processing is facilitated, the weather resistance and corrosion resistance of the lens prepared from the optical resin monomer are improved, and finally, the unsaturated double bond of the polyester part of the mixture II provides the free radical addition polymerization capability, and can be further polymerized with the diallyl terephthalate polymer to generate a macromolecular compound, so that the mechanical property of the optical resin monomer is increased.
Description
Technical Field
The invention relates to the technical field of optical resin, in particular to a preparation method of an optical resin monomer and a reaction system thereof.
Background
The optical resin monomer is used as a raw material for preparing the lens, and has the requirements of light transmission of more than 90 percent, no color, transparency, excellent cementing property, small shrinkage during curing, curing at a lower temperature and the like, but the existing optical resin monomer has the technical problems of poor stamping resistance, difficult processing and forming of the lens and difficult production.
Disclosure of Invention
The invention aims to provide a preparation method of an optical resin monomer and a reaction system thereof, and aims to solve the problem of difficult forming caused by poor stamping resistance of the optical resin monomer.
The technical purpose of the invention is realized by the following technical scheme: the preparation method of the optical resin monomer comprises the following steps:
s1: according to the mass parts, sequentially adding 150 parts of dimethyl terephthalate 140-containing organic silicon, 320 parts of allyl alcohol 280-containing organic silicon and 1-2 parts of calcium hydroxide into a glass reaction kettle, introducing nitrogen for protection, then reacting for 12-15 hours in a programmed heating mode to obtain a reaction solution, and meanwhile, arranging a condensation reflux device on the glass reaction kettle to carry out condensation reflux on the allyl alcohol and recover a product methanol;
s2: transferring the reaction liquid obtained in the step S1 into a reduced pressure distillation kettle, heating to 140 ℃, carrying out reduced pressure distillation for 6-10h, and collecting front fraction and rear fraction of generated steam through a condensing device respectively;
s3: adding the post fraction obtained in the step S2, 10-15 parts of propylene glycol and 1-2 parts of calcium hydroxide into a condensation reaction kettle, stirring and heating to about 110-120 ℃, then keeping the temperature and stirring for reacting for 17-19h to obtain a mixture I;
s4: putting 86-96 parts of bisphenol A diglycidyl ether into a blending kettle, heating to 90 ℃, keeping the temperature constant, starting stirring, after solid materials are completely dissolved, adding 17-20 parts of terephthalic acid, 0.3-0.5 part of triphenylphosphine and 0.3-0.5 part of 4-methoxyphenol, heating to 100 ℃, keeping the temperature for reaction for 2 hours, heating to 120 ℃ within 1 hour, reacting for 8 hours, sampling to test the acid value, stopping heating when the acid value is not more than 20, cooling the reactant to 85 ℃, adding 18-20 parts of acrylic acid, heating to 90 ℃, keeping the temperature for reaction for 5 hours, heating to 95-100 ℃, reacting for 10 hours, sampling to test the acid value, and stopping the reaction when the acid value is less than 1.5 to obtain a mixture II;
s5, preparing optical resin monomer: adding the mixture I obtained in the step S3 and the mixture II obtained in the step S4 into a mixing kettle, adding 15-17 parts of styrene and 15-17 parts of dibutyl maleate according to parts by weight, mixing and stirring for 2 hours at 48-52 ℃, and filtering to obtain the optical resin monomer.
Through the technical scheme, in the S1 reaction, the existing diallyl terephthalate production process is improved, the raw material proportion is adjusted, meanwhile, the glass reaction kettle is provided with the condensation reflux device, the programmed heating mode is adopted, the generated methanol is continuously distilled out of the glass reaction kettle and collected, the raw material allyl alcohol is refluxed back into the glass reaction kettle again, the reaction is promoted to be carried out in the forward direction, and the yield of the diallyl terephthalate can be improved to be more than 95%.
In the reaction of S3, diallyl terephthalate is subjected to a condensation reaction to form diallyl terephthalate polymers, and the molecular chain length of diallyl terephthalate is increased, thereby increasing the mechanical properties of the optical resin monomer.
Meanwhile, in the S4 reaction, bisphenol A diglycidyl ether is used as a raw material, firstly, the bisphenol A diglycidyl ether reacts with terephthalic acid to generate a dimer, so that a molecular chain grows, then, the dimer reacts with acrylic acid to generate hydrogen ions, the hydrogen ions provided by the acrylic acid can attack the oxygen of epoxy groups to form onium ions, lone pair electrons on the carboxyl oxygen attack carbon with strong positive electricity connected with the epoxy groups, the epoxy groups open rings, the hydrogen ions on the carboxyl oxygen are removed, and finally, the terephthalic acid bisphenol A diglycidyl ether diacrylate is generated, and a benzene ring chain is arranged in the molecular structure of the mixture II to extend the chain, so that the density of the bisphenol A structure carried by the mixture II is increased, the prepared lens maintains higher refractive index, the dispersion coefficient of the material is reduced, the Abbe number is improved, the visual effect is better, and the desired refractive index can be reached by adding a small amount of the bisphenol A diglycidyl ether; in addition, due to the introduction of bromine and the unsaturated double bond of the polyester part at the molecular tail end, the weather resistance and corrosion resistance of the prepared lens are improved, and the UV irradiation is obviously improved, so that the thermal deformation temperature of the optical resin monomer is obviously improved, the optical resin monomer is not easy to deform, and the process qualification rate in the later processing process is improved; after the acrylate is added, the reactivity of the whole system is higher, and the activity of the required initiator is lower, so that the definition of the lens manufactured in the later stage is higher.
After the mixture II is added with the optical resin monomer (according to the material charging amount, the ratio of the mixture I to the mixture II is in the range of 1:1-3: 2), firstly, the mechanical property of the optical resin monomer is integrally increased through a macromolecular structure, the hardness and the stamping resistance of the material are increased, and the later-stage lens processing is facilitated; secondly, by adding the mixture II, the addition amount of the diallyl terephthalate polymer can be reduced on the basis of ensuring the mechanical property of the product, so that the heat release of the whole system is more stable during curing, and the curing splinters are not easy to occur; then, due to the introduction of brominated bisphenol A and an acrylate structure, the weather resistance and corrosion resistance of the lens prepared from the optical resin monomer are improved, a higher refractive index is maintained, the dispersion coefficient of the material is reduced, the Abbe number is improved, and the visual effect is better; finally, the unsaturated double bond of the polyester part of the mixture II provides the free radical addition polymerization capability, and can be further polymerized with diallyl terephthalate polymer to generate macromolecular compounds, so that the mechanical property of the optical resin monomer is improved.
The structural formula of mixture II is:
the invention is further provided with: in step S1, the temperature programming process comprises the steps of firstly heating to 70 ℃, starting a stirring device, then heating to 80 ℃, boiling in a glass reaction kettle, gradually raising the temperature to 100 ℃ along with the reaction time when the boiling is slowed down, reacting for 10 hours, sampling and testing the product yield, heating to 120 ℃ when the product yield is more than 90%, reacting for 0.5-1 hour, then sampling and testing the product yield, and stopping the reaction when the product yield is more than 95%.
Through the technical scheme, firstly, the temperature is raised to 70 ℃, the stirring device is started to fully mix the raw materials, the reaction is started, then, the temperature is raised to 80 ℃, the product methanol is greatly evaporated from the reaction liquid (the boiling point of the raw material allyl alcohol is not reached at this moment, the allyl alcohol cannot be evaporated), so that the glass reaction kettle is boiled, in this stage, the condensation recovery device is utilized to collect a large amount of product methanol, the amount of methanol in the reaction liquid system is reduced, the boiling of the glass reaction kettle is slowed, the amount of the raw material is reduced at this moment, the reaction speed of the system is slowed, therefore, the temperature is raised to 100 ℃, the reaction speed is improved, a small amount of product methanol is evaporated out with the large amount of raw material allyl alcohol, the allyl alcohol flows back into the glass reaction kettle through the condensation recovery device, the methanol is collected at the same time, the forward progress of the reaction is promoted through the continuous recovery of the methanol, after reacting for a period of time, sampling and detecting, calculating the yield of the product diallyl terephthalate (allyl alcohol is added excessively) according to the feeding amount of dimethyl terephthalate, when the yield of the product is more than 90%, further increasing the temperature of a reaction system to 120 ℃ to improve the reaction rate and promote the forward progress of the reaction, after reacting for 0.5-1h, sampling and detecting, and when the yield of the product is more than 95%, stopping the reaction; in the preparation reaction of the diallyl terephthalate, the reaction process is regulated by programmed temperature of four stages, so that the product yield is improved to be more than 95%.
The invention is further provided with: in step S2, the front cut fraction includes methanol and allyl alcohol, and the back cut fraction is diallyl terephthalate.
According to the technical scheme, the diallyl terephthalate product in the reaction liquid is collected through reduced pressure distillation, so that the purity of the diallyl terephthalate is ensured, and simultaneously, the methanol and the allyl alcohol in the reaction liquid are recovered and reused as the heat-conducting oil furnace fuel.
The invention is further provided with: in step S5, 30-34 parts by weight of diethylene glycol allyl carbonate is added.
By adopting the technical scheme, after the diethylene glycol allyl carbonate and the mixture II are mixed, the mixture has better aging resistance and impact resistance; the mixture II has high aging resistance and heat distortion temperature, high hardness and good light transmittance; the diethylene glycol allyl carbonate has higher flexibility, but has a single reaction structure, and the molding effect is not as good as the combination of the two; therefore, the diethylene glycol allyl carbonate and the mixture II have complementary properties and can comprehensively exert mutual effects after being mixed.
The invention is further provided with: the device comprises the glass reaction kettle and a condensation reflux device arranged on the glass reaction kettle, wherein a first collecting pipe used for refluxing the allyl alcohol is arranged on the condensation reflux device, and one end of the first collecting pipe is communicated with the glass reaction kettle.
The invention is further provided with: the condensation reflux device comprises a cylindrical tank body, cooling pipelines with drum-shaped cross sections and spiral clapboards, wherein the cooling pipelines are arranged in the tank body, the spiral clapboards are arranged among the cooling pipelines, a spiral downward steam condensation pipeline is formed among the clapboard, the cooling pipeline and the tank body, one end of the cooling pipeline close to the outer wall of the tank body is communicated with a refrigerant inflow pipe, the bottom end of the cooling pipeline is communicated with a refrigerant outflow pipe, the top of the glass reaction kettle is communicated with a steam inflow pipe communicated with the top end of the steam condensation pipeline, the clapboard is respectively provided with a first collecting pipe and a second collecting pipe for collecting methanol in a communication way along the vertical direction, the second collecting pipe is located below the first collecting pipe, and a tail gas treatment device used for recycling uncondensed gas is arranged at the bottom end of the partition plate in a vertical direction in a communicated mode.
With the above technical solution, (it should be noted that, the condensing device used in the S2 reaction may be a common condensing device, or a condensing and refluxing device used in the S1 reaction may be used, except that, in the S2 reaction, one end of the first collecting pipe is communicated with the recovery device of allyl alcohol and methanol, and one end of the second collecting pipe is communicated with the collection device of diallyl terephthalate), in the S1 reaction, the control valve of the coolant inflow pipe is opened to allow cooling water to flow into the cooling pipe, the generated methanol vapor and allyl alcohol vapor enter the vapor condensing pipe from the inflow pipe, the vapor contacts the outer wall of the winding cooling pipe along the spiral vapor condensing pipe to cool the vapor, allyl alcohol in the vapor is liquefied first, the liquefied allyl alcohol flows down along the spiral downward pipe, and is refluxed into the glass reaction vessel from the first collecting pipe, then, methanol in the steam is liquefied, the liquefied methanol continuously flows downwards along a spiral downward pipeline, enters a methanol recovery device from a second collecting pipe, and finally enters a tail gas treatment device from the bottom end of a steam condensation pipeline; by arranging the drum-shaped cooling pipeline, the contact time and the contact area of the steam and the cooling pipeline are increased, and the heat exchange effect is improved; simultaneously through the decurrent steam condensation pipeline of spiral for automatic along the baffle downstream (the boiling point of allyl alcohol and methyl alcohol is different, and the liquefaction temperature is different, consequently the liquefaction position in the steam condenser pipe is different) after allyl alcohol and the methyl alcohol liquefaction, get into first collecting pipe and second collecting pipe respectively, thereby make the fractionation effect of allyl alcohol and methyl alcohol better, be convenient for carry out the backward flow of allyl alcohol and the recovery of methyl alcohol.
The invention is further provided with: the top of cooling duct evenly is provided with the first baffle of a plurality of along vertical decurrent direction, the bottom of cooling duct evenly is provided with a plurality of second baffle along vertical decurrent direction, first baffle with the second baffle from top to bottom in proper order staggered distribution in on the inner wall of cooling duct.
Through above-mentioned technical scheme, after cooling water got into cooling tube from the refrigerant inflow pipe, flowed along the first baffle and the second baffle that set gradually from top to bottom, ensured that cooling water can flow through all positions of cooling tube, steam can carry out the heat exchange with the abundant contact of cooling water to ensure the condensation effect of steam.
The invention is further provided with: the baffle is V-shaped.
According to the technical scheme, liquefied allyl alcohol and methanol are collected at the middle position of the partition plate along the V-shaped partition plate and then flow downwards along the spiral partition plate until the liquefied allyl alcohol and the methanol enter the first collecting pipe and the second collecting pipe respectively; through setting up the baffle into the V style of calligraphy, the liquid of being convenient for is gathered to the centre for the mobile speed of liquid also avoids a small amount of liquid adhesion in the juncture of baffle and condensation duct, causes the waste.
Compared with the prior art, the invention has the beneficial effects that:
1. after the optical resin monomer is added into the mixture II, the mechanical property of the optical resin monomer is integrally increased through the macromolecular structure, the hardness and the stamping resistance of the material are increased, and the later processing of the lens is facilitated; secondly, by adding the mixture II, the addition amount of the diallyl terephthalate polymer can be reduced on the basis of ensuring the mechanical property of the product, so that the heat release of the whole system is more stable during curing, and the curing splinters are not easy to occur; then, the introduction of brominated bisphenol A and an acrylate structure improves the weather resistance and corrosion resistance of the lens prepared from the optical resin monomer, maintains higher refractive index, reduces the dispersion coefficient of the material, improves the Abbe number and has better visual effect; finally, the unsaturated double bond of the polyester part of the mixture II provides the free radical addition polymerization capability, and can be further polymerized with diallyl terephthalate polymer to generate macromolecular compounds, so that the mechanical property of the optical resin monomer is improved.
2. The reaction process is regulated by programmed temperature rise of four stages, and the yield of the product is improved to be more than 95%.
3. By arranging the drum-shaped cooling pipeline, the contact time and the contact area of the steam and the cooling pipeline are increased, and the heat exchange effect is improved; simultaneously, the allyl alcohol and the methanol automatically flow downwards along the partition plate after being liquefied through the spiral downward steam condensation pipeline and respectively enter the first collecting pipe and the second collecting pipe, so that the fractionation effect of the allyl alcohol and the methanol is better, and the reflux of the allyl alcohol and the recovery of the methanol are facilitated.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a schematic structural diagram of an embodiment of a method for preparing an optical resin monomer and a reaction system thereof according to the present invention;
FIG. 2 is a schematic diagram of a partial cross-sectional structure of an embodiment of a method for preparing an optical resin monomer and a reaction system thereof according to the present invention;
FIG. 3 is a schematic diagram of a partial cross-sectional structure of an embodiment of a method for preparing an optical resin monomer and a reaction system thereof according to the present invention.
In the figure, 1, a glass reaction kettle; 2. a condensing reflux unit; 21. a tank body; 22. a cooling duct; 23. a partition plate; 3. a first collection tube; 4. a steam condensing line; 5. a refrigerant inflow pipe; 6. a refrigerant outflow pipe; 7. a steam inflow pipe; 8. a second collection tube; 9. a tail gas treatment device; 10. a first baffle plate; 11. a second baffle.
Detailed Description
Example 1:
the preparation method of the optical resin monomer comprises the following steps:
s1: according to the mass parts, 150 parts of dimethyl terephthalate, 320 parts of allyl alcohol and 2 parts of calcium hydroxide are sequentially added into a glass reaction kettle, nitrogen is introduced for protection, then the temperature is directly raised to 120 ℃, the reaction is carried out for 12-15 hours, reaction liquid is obtained, the yield of the product is 78% through detection, meanwhile, a condensation reflux device is arranged on the glass reaction kettle, condensation reflux is carried out on the allyl alcohol, and the product methanol is recovered;
s2: transferring the reaction liquid obtained in the step S1 into a reduced pressure distillation kettle, heating to 140 ℃, carrying out reduced pressure distillation for 6-10h, and collecting front fraction and rear fraction of generated steam through a condensing device respectively;
s3: adding the post fraction obtained in the step S2, 15 parts of propylene glycol and 2 parts of calcium hydroxide into a condensation reaction kettle, stirring and heating to about 110-120 ℃, then keeping the temperature and stirring for reacting for 17-19h to obtain a mixture I;
s4: putting 96 parts of bisphenol A diglycidyl ether into a blending kettle, heating to 90 ℃, keeping the temperature constant, starting stirring, after solid materials are completely dissolved, adding 20 parts of terephthalic acid, 0.5 part of triphenylphosphine and 0.5 part of 4-methoxyphenol, heating to 100 ℃, keeping the temperature for reaction for 2 hours, heating to 120 ℃ within 1 hour, reacting for 8 hours, sampling and testing the acid value, stopping heating when the acid value is not more than 20, then cooling the reactant to 85 ℃, adding 20 parts of acrylic acid, heating to 90 ℃, keeping the temperature for reaction for 5 hours, heating to 95-100 ℃, reacting for 10 hours, sampling and testing the acid value, and stopping the reaction when the acid value is less than 1.5 to obtain a mixture II;
s5, preparing optical resin monomer: adding the mixture I obtained in the step S3 and the mixture II obtained in the step S4 into a mixing kettle, adding 17 parts by weight of styrene and 17 parts by weight of dibutyl maleate, mixing and stirring at 48-52 ℃ for 2 hours, and filtering to obtain the optical resin monomer.
Example 2:
the preparation method of the optical resin monomer comprises the following steps:
s1: according to the mass parts, 140 parts of dimethyl terephthalate, 280 parts of allyl alcohol and 1 part of calcium hydroxide are sequentially added into a glass reaction kettle, nitrogen is introduced for protection, then a programmed heating mode is adopted for reaction for 12-15 hours to obtain a reaction solution, and meanwhile, a condensation reflux device is arranged on the glass reaction kettle for condensation reflux of the allyl alcohol and recovery of a product methanol;
s2: transferring the reaction liquid obtained in the step S1 into a reduced pressure distillation kettle, heating to 140 ℃, carrying out reduced pressure distillation for 6-10h, and collecting front fraction and rear fraction of generated steam through a condensing device respectively;
s3: adding the post fraction obtained in the step S2, 10 parts of propylene glycol and 1 part of calcium hydroxide into a condensation reaction kettle, stirring and heating to about 110-120 ℃, then keeping the temperature and stirring for reacting for 17-19h to obtain a mixture I;
s4: putting 86 parts of bisphenol A diglycidyl ether into a blending kettle, heating to 90 ℃, keeping the temperature constant, starting stirring, after solid materials are completely dissolved, adding 17 parts of terephthalic acid, 0.3 part of triphenylphosphine and 0.3 part of 4-methoxyphenol, heating to 100 ℃, keeping the temperature for reaction for 2 hours, heating to 120 ℃ within 1 hour, reacting for 8 hours, sampling and testing the acid value, stopping heating when the acid value is not more than 20, then cooling the reactant to 85 ℃, adding 18 parts of acrylic acid, heating to 90 ℃, keeping the temperature for reaction for 5 hours, heating to 95-100 ℃, reacting for 10 hours, sampling and testing the acid value, and stopping the reaction when the acid value is less than 1.5 to obtain a mixture II;
s5, preparing optical resin monomer: adding the mixture I obtained in the step S3 and the mixture II obtained in the step S4 into a mixing kettle, adding 15 parts of styrene and 15 parts of dibutyl maleate according to parts by mass, mixing and stirring at 48-52 ℃ for 2 hours, and filtering to obtain the optical resin monomer.
The temperature programming process comprises the steps of firstly heating to 70 ℃, starting a stirring device, then heating to 80 ℃, boiling in a glass reaction kettle, reacting for 10 hours with the reaction time, gradually heating to 100 ℃ after the boiling is slowed down, sampling to test the product yield, heating to 120 ℃ when the product yield is more than 90%, reacting for 0.5-1 hour, then sampling to test the product yield, and stopping the reaction when the product yield is more than 95%.
Example 3:
the preparation method of the optical resin monomer comprises the following steps:
s1: according to the mass parts, 140 parts of dimethyl terephthalate, 280 parts of allyl alcohol and 1 part of calcium hydroxide are sequentially added into a glass reaction kettle, nitrogen is introduced for protection, then a programmed heating mode is adopted for reaction for 12-15 hours to obtain a reaction solution, and meanwhile, a condensation reflux device is arranged on the glass reaction kettle for condensation reflux of the allyl alcohol and recovery of a product methanol;
s2: transferring the reaction liquid obtained in the step S1 into a reduced pressure distillation kettle, heating to 140 ℃, carrying out reduced pressure distillation for 6-10h, and collecting front fraction and rear fraction of generated steam through a condensing device respectively;
s3: adding the post fraction obtained in the step S2, 1 part of propylene glycol and 1-2 parts of calcium hydroxide into a condensation reaction kettle, stirring and heating to about 110-120 ℃, then keeping the temperature and stirring for reacting for 17-19h to obtain a mixture I;
s4, preparing optical resin monomer: adding the mixture I obtained in the step S3 into a mixing kettle, adding 15 parts of styrene and 15 parts of dibutyl maleate according to parts by mass, mixing and stirring for 2 hours at 48-52 ℃, and filtering to obtain the optical resin monomer.
The temperature programming process comprises the steps of firstly heating to 70 ℃, starting a stirring device, then heating to 80 ℃, boiling in a glass reaction kettle, reacting for 10 hours with the reaction time, gradually heating to 100 ℃ after the boiling is slowed down, sampling to test the product yield, heating to 120 ℃ when the product yield is more than 90%, reacting for 0.5-1 hour, then sampling to test the product yield, and stopping the reaction when the product yield is more than 95%.
Example 4:
the preparation method of the optical resin monomer comprises the following steps:
s1: according to the mass parts, 140 parts of dimethyl terephthalate, 280 parts of allyl alcohol and 1 part of calcium hydroxide are sequentially added into a glass reaction kettle, nitrogen is introduced for protection, then a programmed heating mode is adopted for reaction for 12-15 hours to obtain a reaction solution, and meanwhile, a condensation reflux device is arranged on the glass reaction kettle for condensation reflux of the allyl alcohol and recovery of a product methanol;
s2: transferring the reaction liquid obtained in the step S1 into a reduced pressure distillation kettle, heating to 140 ℃, carrying out reduced pressure distillation for 6-10h, and collecting front fraction and rear fraction of generated steam through a condensing device respectively;
s3: adding the post fraction obtained in the step S2, 12 parts of propylene glycol and 1 part of calcium hydroxide into a condensation reaction kettle, stirring and heating to about 110-120 ℃, then keeping the temperature and stirring for reaction for 17-19h, and obtaining a mixture I after the reaction;
s4: putting 86 parts of bisphenol A diglycidyl ether into a blending kettle, heating to 90 ℃, keeping the temperature constant, starting stirring, after solid materials are completely dissolved, adding 20 parts of terephthalic acid, 0.3 part of triphenylphosphine and 0.3 part of 4-methoxyphenol, heating to 100 ℃, keeping the temperature for reaction for 2 hours, heating to 120 ℃ within 1 hour, reacting for 8 hours, sampling and testing the acid value, stopping heating when the acid value is not more than 20, then cooling the reactant to 85 ℃, adding 18 parts of acrylic acid, heating to 90 ℃, keeping the temperature for reaction for 5 hours, heating to 95-100 ℃, reacting for 10 hours, sampling and testing the acid value, and stopping the reaction when the acid value is less than 1.5 to obtain a mixture II;
s5, preparing optical resin monomer: adding the mixture I obtained in the step S3 and the mixture II obtained in the step S4 into a mixing kettle, adding 15 parts by weight of styrene, 15 parts by weight of dibutyl maleate and 30 parts by weight of diethylene glycol allyl carbonate, mixing and stirring at 48-52 ℃ for 2 hours, and filtering to obtain the optical resin monomer.
The temperature programming process comprises the steps of firstly heating to 70 ℃, starting a stirring device, then heating to 80 ℃, boiling in a glass reaction kettle, reacting for 10 hours with the reaction time, gradually heating to 100 ℃ after the boiling is slowed down, sampling to test the product yield, heating to 120 ℃ when the product yield is more than 90%, reacting for 0.5-1 hour, then sampling to test the product yield, and stopping the reaction when the product yield is more than 95%.
Example 5:
the preparation method of the optical resin monomer comprises the following steps:
s1: according to the mass parts, 150 parts of dimethyl terephthalate, 320 parts of allyl alcohol and 2 parts of calcium hydroxide are sequentially added into a glass reaction kettle, nitrogen is introduced for protection, then a programmed heating mode is adopted for reaction for 12-15 hours to obtain reaction liquid, meanwhile, a condensation reflux device is arranged on the glass reaction kettle for condensation reflux of the allyl alcohol, and a product methanol is recovered;
s2: transferring the reaction liquid obtained in the step S1 into a reduced pressure distillation kettle, heating to 140 ℃, carrying out reduced pressure distillation for 6-10h, and collecting front fraction and rear fraction of generated steam through a condensing device respectively;
s3: adding the post fraction obtained in the step S2, 15 parts of propylene glycol and 2 parts of calcium hydroxide into a condensation reaction kettle, stirring and heating to about 110-120 ℃, then keeping the temperature and stirring for reacting for 17-19h to obtain a mixture I;
s4: putting 96 parts of bisphenol A diglycidyl ether into a blending kettle, heating to 90 ℃, keeping the temperature constant, starting stirring, after solid materials are completely dissolved, adding 20 parts of terephthalic acid, 0.5 part of triphenylphosphine and 0.5 part of 4-methoxyphenol, heating to 100 ℃, keeping the temperature for reaction for 2 hours, heating to 120 ℃ within 1 hour, reacting for 8 hours, sampling and testing the acid value, stopping heating when the acid value is not more than 20, then cooling the reactant to 85 ℃, adding 20 parts of acrylic acid, heating to 90 ℃, keeping the temperature for reaction for 5 hours, heating to 95-100 ℃, reacting for 10 hours, sampling and testing the acid value, and stopping the reaction when the acid value is less than 1.5 to obtain a mixture II;
s5, preparing optical resin monomer: adding the mixture I obtained in the step S3 and the mixture II obtained in the step S4 into a mixing kettle, adding 17 parts by weight of styrene, 17 parts by weight of dibutyl maleate and 34 parts by weight of diethylene glycol allyl carbonate, mixing and stirring at 48-52 ℃ for 2 hours, and filtering to obtain the optical resin monomer.
The temperature programming process comprises the steps of firstly heating to 70 ℃, starting a stirring device, then heating to 80 ℃, boiling in a glass reaction kettle, reacting for 10 hours with the reaction time, gradually heating to 100 ℃ after the boiling is slowed down, sampling to test the product yield, heating to 120 ℃ when the product yield is more than 90%, reacting for 0.5-1 hour, then sampling to test the product yield, and stopping the reaction when the product yield is more than 95%.
It should be noted that, since the reaction temperature cannot be accurately adjusted, the reaction temperature in the examples is only required to be within the above range to satisfy the requirements, and the specific time of the reaction is determined according to the actual reaction progress, but is within the time range described in the examples.
The experimental method comprises the following steps: the optical resin monomers prepared in the above embodiments are respectively used as raw materials to prepare lenses, and the related performance detection is carried out
Preparation of the lens: (1) weighing the raw materials in parts by mass according to the following mixture ratio
Wherein: UV 5411: 2- (2 '-hydroxy-5' -tert-butylphenyl) benzotriazole
IPP: peroxydicarbonate diisopropyl ester
(2) The raw materials are put into a mixing tank and stirred for about 3 hours at 25 ℃, and vacuumization is carried out to ensure that no bubbles exist in the stirred materials.
(3) And (3) installing an injection port on the mixing tank, tearing the adhesive tape on the assembled mould until a small opening is exposed, placing the injection port at the small opening for injection, re-attaching the adhesive tape on the mould after material injection, and placing the mould on a curing frame after no leakage phenomenon is observed.
(4) And placing the mold filled with the materials on a cured iron frame, placing the mold in an oven, performing thermosetting molding, and curing for 20-24 hours to mold the lens. (curing procedure as shown in the following table)
The evaluation method comprises the following steps:
(1) refractive index: measuring the nd value by using a multi-wavelength Abbe refractometer, wherein the instrument manufacturer and the model are Japanese Atago, DR-M4;
(2) transmittance and yellow index: measuring full-wavelength light transmittance by using spectrophotometer, and manufacturer and model of instrument
Number HunterLab, UltraScan, usa;
(3) impact resistance: measuring the weight of a steel ball which can be borne by the lens by adopting a ball drop impact tester, and measuring the height of the steel ball by 1.30 meters and the weight of the steel ball by 16g, 32g, 43g, 50g, 60g, 70g, 80g, 90g, 105g and 500g according to an FDA standard measuring method; the test object is a 500-degree optical resin lens, and the center thickness is 1.2 mm;
(4) heat distortion temperature: detecting a Tg point by using a differential scanning calorimeter, wherein the manufacturer and the model of the instrument are Mettlerlington, and DSC 1;
(5) QUV test: the ultraviolet aging test box has the instrument manufacturer and model of American Q-Lab, QUV. Aging conditions are as follows: 340nm, 0.69 w/square meter and 48 h.
The experimental results are as follows:
table 1 optical lens test results:
as can be seen from Table 1, in example 1, compared with example 2, in the step S1, in example 1, the temperature is not programmed, so that the yield of the mixture I (diallyl terephthalate and polymers thereof) is low, the proportion of the mixture I in the optical resin monomer is low, and the refractive index, light transmittance, aging resistance, heat distortion temperature and impact resistance of the prepared lens are reduced, which indicates that the proportion of the mixture I to the mixture II in the optical resin monomer should be in a reasonable range (1:1-3: 2); compared with the example 3, the example 2 has the advantages that the mixture II is not added in the example 3, so that the prepared lens is poor in refractive index, light transmittance, aging resistance, heat distortion temperature, impact resistance and the like, and the mixture II is added into an optical resin monomer, so that the refractive index, light transmittance, aging resistance, heat distortion temperature and impact resistance of the obtained lens can be remarkably improved; example 2 compared with example 4, the addition of diethylene glycol allyl carbonate in example 4 results in the improvement of the aging resistance, heat distortion temperature and impact resistance of the prepared lens, which shows that the addition of diethylene glycol allyl carbonate in the optical resin monomer can improve the aging resistance and impact resistance of the product; in comparison with example 5, the lens prepared by adjusting the dosage within the range of example 4 has substantially the same properties, which means that the adjustment of the dosage within the range of example 4 does not affect the properties of the optical resin monomer.
A reaction system for producing the optical resin monomer comprises the glass reaction kettle 1 and the condensation reflux device 2 arranged on the glass reaction kettle 1, wherein a first collecting pipe 3 used for refluxing the allyl alcohol is arranged on the condensation reflux device 2, and one end of the first collecting pipe 3 is communicated with the glass reaction kettle 1.
Further, the condensation and reflux device 2 comprises a cylindrical tank 21, a cooling pipeline 22 with a reel-shaped cross section arranged in the tank 21, and a spiral partition plate 23 arranged between the cooling pipeline 22, a spiral downward steam condensation pipeline 4 is formed among the partition plate 23, the cooling pipeline 22 and the tank 21, one end of the cooling pipeline 22 close to the outer wall of the tank 21 is communicated with a refrigerant inflow pipe 5, the bottom end of the cooling pipeline 22 is communicated with a refrigerant outflow pipe 6, the top of the glass reaction kettle 1 is communicated with a steam inflow pipe 7 communicated with the top end of the steam condensation pipeline 4, the partition plate 23 is respectively communicated with a first collecting pipe 3 and a second collecting pipe 8 for collecting methanol along the vertical direction, and the second collecting pipe 8 is positioned below the first collecting pipe 3, and the bottom end of the partition plate 23 is communicated with a tail gas treatment device 9 for recovering uncondensed gas along the vertical direction.
Further, a plurality of first baffles 10 are evenly arranged on the top end of the cooling pipeline 22 along the vertical downward direction, a plurality of second baffles 11 are evenly arranged on the bottom end of the cooling pipeline 22 along the vertical upward direction, and the first baffles 10 and the second baffles 11 are sequentially distributed on the inner wall of the cooling pipeline 22 in a staggered manner from top to bottom.
Further, the partition 23 is V-shaped.
The working process is as follows: (Note that, in the S2 reaction, a common condensing device may be used, or a condensing reflux device 2 in the S1 reaction may be used, except that in the S2 reaction, one end of a first collecting pipe 3 is communicated with a recovery device of allyl alcohol and methanol, and one end of a second collecting pipe 8 is communicated with a collection device of diallyl terephthalate). in the S1 reaction, a control valve of a coolant inflow pipe 5 is opened, so that cooling water flows into a cooling pipe 22, generated methanol vapor and allyl alcohol vapor enter a vapor condensing pipe 4 from an inflow pipe 7, the vapor contacts with the outer wall of a drum-shaped cooling pipe 22 along a spiral vapor condensing pipe 4 to cool the vapor, allyl alcohol in the vapor is liquefied first, the liquefied allyl alcohol flows down along a spiral downward pipe and is refluxed into a glass reaction vessel 1 from the first collecting pipe 3, then, methanol in the steam is liquefied, the liquefied methanol continuously flows downwards along a spiral downward pipeline, enters a methanol recovery device from a second collecting pipe 8, and finally enters a tail gas treatment device 9 from the bottom end of a steam condensation pipeline 4; by arranging the reel-shaped cooling pipeline 22, the contact time and the contact area of the steam and the cooling pipeline 22 are increased, and the heat exchange effect is improved; simultaneously through spiral decurrent steam condensation pipeline 4 for automatic along baffle 23 downstream (the boiling point of allyl alcohol and methyl alcohol is different, and the liquefaction temperature is different, consequently the liquefaction position in the steam condenser pipe is different) after allyl alcohol and the methyl alcohol liquefaction, get into first collecting pipe 3 and second collecting pipe 8 respectively, thereby make the fractionation effect of allyl alcohol and methyl alcohol better, be convenient for carry out the backward flow of allyl alcohol and the recovery of methyl alcohol.
After cooling water enters the cooling pipeline 22 from the refrigerant inflow pipe 5, the cooling water flows along the first baffle 10 and the second baffle 11 which are sequentially arranged from top to bottom, so that all positions of the cooling pipeline 22 can be ensured to flow through, and steam can be in full contact with the cooling water to perform heat exchange, thereby ensuring the condensation effect of the steam.
After the liquefied allyl alcohol and methanol are collected at the middle position of the partition plate 23 along the V-shaped partition plate 23, the liquefied allyl alcohol and methanol flow downwards along the spiral partition plate 23 until entering the first collecting pipe 3 and the second collecting pipe 8 respectively; through setting up baffle 23 to the V style of calligraphy, the liquid of being convenient for is gathered to the centre for the speed of flow of liquid also avoids a small amount of liquid adhesion at baffle 23 and condensation duct's juncture, causes the waste.
It should be noted that, in the present specification, the embodiments are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments may be referred to each other.
The above description is only for the purpose of describing the preferred embodiments of the present invention, and is not intended to limit the scope of the present invention, and any variations and modifications made by those skilled in the art based on the above disclosure are within the scope of the appended claims.
Claims (8)
1. A method for preparing an optical resin monomer is characterized by comprising the following steps: the method comprises the following steps:
s1: according to the mass parts, sequentially adding 150 parts of dimethyl terephthalate 140-one-material, 320 parts of allyl alcohol 280-one-material and 1-2 parts of calcium hydroxide into a glass reaction kettle (1), introducing nitrogen for protection, then reacting for 12-15 hours in a programmed heating mode to obtain a reaction liquid, and meanwhile, arranging a condensation reflux device (2) on the glass reaction kettle (1) to carry out condensation reflux on the allyl alcohol and recover a product methanol;
s2: transferring the reaction liquid obtained in the step S1 into a reduced pressure distillation kettle, heating to 140 ℃, carrying out reduced pressure distillation for 6-10h, and collecting front fraction and rear fraction of generated steam through a condensing device respectively;
s3: adding the post fraction obtained in the step S2, 10-15 parts of propylene glycol and 1-2 parts of calcium hydroxide into a condensation reaction kettle, stirring and heating to about 110-120 ℃, then keeping the temperature and stirring for reacting for 17-19h to obtain a mixture I;
s4: putting 86-96 parts of bisphenol A diglycidyl ether into a blending kettle, heating to 90 ℃, keeping the temperature constant, starting stirring, after solid materials are completely dissolved, adding 17-20 parts of terephthalic acid, 0.3-0.5 part of triphenylphosphine and 0.3-0.5 part of 4-methoxyphenol, heating to 100 ℃, keeping the temperature for reaction for 2 hours, heating to 120 ℃ within 1 hour, reacting for 8 hours, sampling to test the acid value, stopping heating when the acid value is not more than 20, cooling the reactant to 85 ℃, adding 18-20 parts of acrylic acid, heating to 90 ℃, keeping the temperature for reaction for 5 hours, heating to 95-100 ℃, reacting for 10 hours, sampling to test the acid value, and stopping the reaction when the acid value is less than 1.5 to obtain a mixture II;
s5, preparing optical resin monomer: adding the mixture I obtained in the step S3 and the mixture II obtained in the step S4 into a mixing kettle, adding 15-17 parts of styrene and 15-17 parts of dibutyl maleate according to parts by weight, mixing and stirring for 2 hours at 48-52 ℃, and filtering to obtain the optical resin monomer.
2. The method for preparing an optical resin monomer according to claim 1, wherein: in the step S1, the procedure of temperature programming includes firstly raising the temperature to 70 ℃, starting a stirring device, then raising the temperature to 80 ℃, boiling in the glass reaction kettle (1), gradually raising the temperature to 100 ℃ along with the reaction time after the boiling is slowed down, reacting for 10 hours, sampling to test the product yield, raising the temperature to 120 ℃ when the product yield is more than 90%, reacting for 0.5-1 hour, then sampling to test the product yield, and stopping the reaction when the product yield is more than 95%.
3. The method for preparing an optical resin monomer according to claim 1, wherein: in step S2, the front cut fraction includes methanol and allyl alcohol, and the back cut fraction is diallyl terephthalate.
4. A method for producing an optical resin monomer according to claim 1, characterized in that: in step S5, 30-34 parts by weight of diethylene glycol allyl carbonate is added.
5. A reaction system for realizing the method for producing an optical resin monomer according to any one of claims 1 to 4, characterized in that: the device comprises a glass reaction kettle (1) and a condensation reflux device (2) arranged on the glass reaction kettle (1), wherein a first collecting pipe (3) used for refluxing the allyl alcohol is arranged on the condensation reflux device (2), and one end of the first collecting pipe (3) is communicated with the glass reaction kettle (1).
6. The system of claim 5, wherein: the condensation reflux device (2) comprises a cylindrical tank body (21), a cooling pipeline (22) with a reel-shaped cross section and a spiral partition plate (23) arranged between the cooling pipeline (22), wherein the cooling pipeline (22) is arranged in the tank body (21), a spiral downward steam condensation pipeline (4) is formed among the partition plate (23), the cooling pipeline (22) and the tank body (21), one end, close to the outer wall of the tank body (21), of the cooling pipeline (22) is communicated with a refrigerant inflow pipe (5), the bottom end of the cooling pipeline (22) is communicated with a refrigerant outflow pipe (6), the top of the glass reaction kettle (1) is communicated with a steam inflow pipe (7) communicated with the top end of the steam condensation pipeline (4), and the partition plate (23) is respectively communicated with a first collecting pipe (3) and a second collecting pipe (8) used for collecting methanol in the vertical direction, the second collecting pipe (8) is positioned below the first collecting pipe (3), and the bottom end of the partition plate (23) is provided with a tail gas treatment device (9) used for recycling uncondensed gas in a vertical direction in a communicated mode.
7. The system of claim 6, wherein: the top of cooling duct (22) evenly is provided with a plurality of first baffle (10) along vertical decurrent direction, the bottom of cooling duct (22) evenly is provided with a plurality of second baffle (11) along vertical decurrent direction, first baffle (10) with second baffle (11) are crisscross distribute in proper order from top to bottom on the inner wall of cooling duct (22).
8. The system of claim 6, wherein: the partition plate (23) is V-shaped.
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