CN105175608B - A kind of high index of refraction lens resin monomer - Google Patents

Abstract

The invention belongs to the technical field of optical resin materials, and in particular relates to a high-refractive-index lens resin monomer, which consists of the following components by weight percentage: 5-15% of dibenzyl maleate, styrene compounds 5-15%, diallyl terephthalate or diallyl isophthalate or a mixture of the two 30-60%, bromoether 30-40%. The preparation method comprises the following steps: taking the components according to the proportion, mixing and stirring evenly, adding an initiator, degassing, putting into an oven after injection molding, raising the temperature to 120 DEG C by program, and then cooling down to room temperature to obtain the product. The high refractive index lens resin monomer provided by the invention, the monomer formed after the polymerization of each component, has a higher refractive index and stronger impact resistance and wear resistance, and its refractive index can reach more than 1.60; the present invention The preparation method provided has the advantages of simple process, good process controllability and repeatability, mild reaction conditions, no pollution and low cost.

Description

A high refractive index lens resin monomer

technical field

The invention belongs to the technical field of optical resin materials, and in particular relates to a high refractive index lens resin monomer.

Background technique

In recent years, optical resin lenses have sprung up in the domestic and foreign eyewear markets, especially high-refractive index optical resin lenses because of their unique advantages such as light texture, high strength, non-fragile, high light transmittance, UV protection, and ultra-thin shape. Very popular with visually impaired groups. Generally, in the lens industry, those with a refractive index above 1.60 are high refractive index, those with a refractive index above 1.56 are medium refractive index, and those with a refractive index below 1.56 are low refractive index. There are optical resin lenses with a refractive index of 1.56 made of chemical monomers whose main components are phenylacrylates and other components, but their thickness is relatively thick, and their thermal resistance and visible light transmittance are relatively low. Therefore, it is necessary to have an optical resin monomer material for making high refractive index resin lenses.

Contents of the invention

One of the objectives of the present invention is to provide a high-refractive-index lens resin monomer with high refractive index and strong impact resistance against the shortcomings of the prior art.

In order to solve the problems of the technologies described above, the technical solution of the present invention is:

A high-refractive index lens resin monomer, which is composed of the following components by weight percentage: 5-15% of dibenzyl maleate, 5-15% of styrene compounds, and diene terephthalate Propyl ester or diallyl isophthalate or a mixture of the two is 30-60%, and bromoether is 30-40%.

Wherein, the structural formula of bromoether is as follows:

Its chemical name is 2,2-bis(4-(3-allyloxy-2-hydroxypropoxy)3,5-dibromophenyl)propane, and its English name is 2,2-bis(4-( 3-(allyloxy)-2-hydroxypropoxy)-3,5-dibromophenyl)propane.

As an improvement, the monomer is composed of the following components by weight percentage: 7-10% of dibenzyl maleate, 7-10% of styrene compounds, diallyl terephthalate or m-phenylene 45-50% of diallyl diformate or a mixture of the two, 35-40% of bromoether.

As a further improvement, the styrene compound is styrene or divinylbenzene.

The second object of the present invention is to provide a method for preparing high refractive index lens resin monomer with low cost and simple process.

In order to solve the problems of the technologies described above, the technical solution of the present invention is:

A kind of preparation method of high refractive index lens resin monomer, described preparation method comprises the following steps: according to the weight ratio described in claim 1, take diallyl terephthalate or diallyl isophthalate or two The mixture, dibenzyl maleate, styrene compounds and brominated ethers are mixed and stirred evenly, the initiator is added, degassed, put into an oven after injection molding, and rise from 20°C to 30°C within 1 to 2 hours. Raise from 30°C to 70°C within 2-5 hours, keep warm for 4-10 hours, rise from 70°C to 120°C within 2-5 hours, keep warm for 2-6 hours, and cool down from 120°C to room temperature within 1-5 hours.

Preferably, the initiator is azobisisobutyronitrile or azobisisoheptanonitrile.

As an improvement, the bromine-containing ether is synthesized according to the following steps: take the reactant tetrabromobisphenol A and allyl glycidyl ether, add an organic solvent, then mix and stir evenly, and the weight of the organic solvent is the reaction 30-60% of the total weight of the reactants, then add a catalyst, the weight of the catalyst is 0.3-3% of the total weight of the reactants, stir at 30-80°C, react for 5-15h, after the reaction, decompress Remove the solvent by distillation, wash with distilled water, separate liquid, and purify the product by distillation under reduced pressure.

The synthesis process of bromoether is as follows:

As an improvement, the molar ratio of the tetrabromobisphenol A to the allyl glycidyl ether is 1:1-2.

Preferably, the organic solvent is methanol, ethanol or isopropanol.

Preferably, the catalyst is triethylamine, tripropylamine, tri-n-butylamine, N,N-dimethylbenzylamine or N,N-diethylbenzylamine.

Owing to adopted above-mentioned technical scheme, the beneficial effect of the present invention is:

In the high refractive index lens resin monomer provided by the present invention, bromoether is introduced into the component, which effectively improves the refractive index of the monomer, and dibenzyl maleate, styrene compounds and phthalic acid are introduced into the component. Diallyl ester compound, the monomer formed after the polymerization of each component, has a higher refractive index and stronger impact resistance and abrasion resistance, and its refractive index can reach more than 1.60. The preparation method provided by the invention has the advantages of simple process, good process controllability and repeatability, mild reaction conditions, no pollution, low cost, and the prepared product has high refractive index and good impact resistance.

detailed description

In order to make the object, technical solution and advantages of the present invention more clear, the present invention will be further described in detail below in conjunction with the examples. It should be understood that the specific embodiments described here are only used to explain the present invention, not to limit the present invention.

Embodiment one

A high refractive index lens resin monomer, the monomer is composed of the following components by weight percentage: 5% dibenzyl maleate, 15% styrene compounds, diallyl terephthalate compounds 50%, containing bromoether 30%; among them, the styrene compound is styrene.

Embodiment two

A high-refractive index lens resin monomer, which is composed of the following components by weight percentage: 10% dibenzyl maleate, 10% styrene compound, diallyl isophthalate compound 40%, containing 40% bromoether; among them, the styrene compound is divinylbenzene.

Embodiment three

A high refractive index lens resin monomer, which is composed of the following components by weight percentage: 15% dibenzyl maleate, 5% styrene compounds, diallyl terephthalate and m- 45% mixture of diallyl phthalate, 35% bromoether-containing; wherein, the styrene compound is styrene, diallyl terephthalate and diallyl isophthalate in the mixture according to Mix in any proportion.

Embodiment Four

A high refractive index lens resin monomer, which is composed of the following components by weight percentage: 15% dibenzyl maleate, 15% styrene compounds, diallyl isophthalate compounds 30%, 40% containing bromoether; Among them, styrene compounds are styrene.

Embodiment five

A high refractive index lens resin monomer, which is composed of the following components by weight percentage: 7% of dibenzyl maleate, 13% of styrene compounds, and 60% of diallyl terephthalate , containing 30% bromoether; among them, the styrene compound is divinylbenzene.

Embodiment six

A high refractive index lens resin monomer, which is composed of the following components by weight percentage: 13% of dibenzyl maleate, 7% of styrene compounds, and 30% of diallyl terephthalate , containing 40% bromoether; wherein, the styrene compound is styrene.

Embodiment seven

A preparation method of a high refractive index lens resin monomer, the preparation method comprising the following steps:

(1) Synthesis of bromoether: take the reactant Tetrabromobisphenol A 271.9g and allyl glycidyl ether 85.6g, join in the four-neck flask with stirring paddle, add the organic solvent methanol, then mix and stir evenly , the weight of the organic solvent is 30% of the total weight of the reactants, then add the catalyst triethylamine, the weight of the catalyst is 0.3% of the total weight of the reactants, stir and react for 5h at 30°C, after the reaction is completed, remove it by distillation under reduced pressure The solvent is washed with distilled water, separated, and the product is purified by distillation under reduced pressure to obtain final product;

(2) Preparation of lens resin monomer: get dibenzyl maleate, styrene, diallyl terephthalate and bromine-containing ether according to the weight ratio described in Example 1, mix and stir evenly, add initiator Azobisisobutyronitrile, degassed, put into the oven after injection molding, rise from 20°C to 30°C within 1-2 hours, rise from 30°C to 70°C within 2-5 hours, keep warm for 4-10 hours, within 2-5 hours Raise from 70°C to 120°C, keep it warm for 2 to 6 hours, and drop from 120°C to room temperature within 1 to 5 hours to obtain the product.

Embodiment eight

A preparation method of a high refractive index lens resin monomer, the preparation method comprising the following steps:

(1) Synthesis of bromoether: take the reactant tetrabromobisphenol A271.9g and allyl glycidyl ether 114.0g, join in the four-neck flask with stirring paddle, add the organic solvent ethanol, then mix and stir evenly , the weight of the organic solvent is 60% of the total weight of the reactants, then add catalyst tripropylamine, the weight of the catalyst is 3% of the total weight of the reactants, stir and react for 15h at 80°C, after the reaction is completed, the solvent is removed by distillation under reduced pressure , washed with distilled water, liquid separation, and vacuum distillation to purify the product to obtain final product;

(2) Preparation of lens resin monomer: take dibenzyl maleate, divinylbenzene, diallyl isophthalate and bromine-containing ether according to the weight ratio described in Example 2, mix and stir evenly, add Initiator azobisisoheptanonitrile, degassed, put into oven after injection molding, rise from 20°C to 30°C within 1~2h, rise from 30°C to 70°C within 2~5h, keep warm for 4~10h, 2~ Raise from 70°C to 120°C within 5 hours, keep warm for 2-6 hours, and cool down from 120°C to room temperature within 1-5 hours.

Embodiment nine

A preparation method of a high refractive index lens resin monomer, the preparation method comprising the following steps:

(1) Synthesis of bromoether: get reactant Tetrabromobisphenol A271.9g and allyl glycidyl ether 52.6g, join in the four-necked flask that stirring paddle is placed, then add organic solvent isopropanol, mix Stir evenly, the weight of the organic solvent is 40% of the total weight of the reactant, then add catalyst tri-n-butylamine, the weight of the catalyst is 1% of the total weight of the reactant, stir and react for 7h at 50°C, after the reaction finishes, reduce Remove the solvent by distillation under pressure, wash with distilled water, separate liquid, and purify the product by distillation under reduced pressure to get final product;

(2) Preparation of lens resin monomer: take dibenzyl maleate, styrene, diallyl terephthalate, diallyl isophthalate and bromine-containing Ether, mix and stir evenly, add the initiator azobisisoheptanonitrile, degas, put it into the oven after injection molding, rise from 20°C to 30°C within 1-2 hours, and rise from 30°C to 70°C within 2-5 hours, Keep warm for 4-10 hours, raise from 70°C to 120°C within 2-5 hours, keep warm for 2-6 hours, and drop from 120°C to room temperature within 1-5 hours.

Embodiment ten

A preparation method of a high refractive index lens resin monomer, the preparation method comprising the following steps:

(1) Synthesis of bromoether: take the reactants tetrabromobisphenol A271.9g and allyl glycidyl ether 87.9g, join in the four-necked flask with stirring paddle, then add the organic solvent methanol, mix and stir evenly , the weight of the organic solvent is 50% of the total weight of the reactants, then add the catalyst N,N-dimethylbenzylamine, the weight of the catalyst is 2% of the total weight of the reactants, stir and react for 8h at 60°C, and the reaction ends Finally, remove the solvent by distillation under reduced pressure, wash with distilled water, separate liquids, and purify the product by distillation under reduced pressure to obtain final product;

(2) Preparation of lens resin monomer: get dibenzyl maleate, styrene, diallyl isophthalate and bromine-containing ether according to the weight ratio described in Example 4, mix and stir evenly, add initiator Azobisisobutyronitrile, degassed, put into the oven after injection molding, rise from 20°C to 30°C within 1-2 hours, rise from 30°C to 70°C within 2-5 hours, keep warm for 4-10 hours, within 2-5 hours Raise from 70°C to 120°C, keep it warm for 2 to 6 hours, and drop from 120°C to room temperature within 1 to 5 hours to obtain the product.

Embodiment Eleven

A preparation method of a high refractive index lens resin monomer, the preparation method comprising the following steps:

(1) Synthesis of bromoether: get reactant Tetrabromobisphenol A271.9g and allyl glycidyl ether 102.8g, join in the four-necked flask that stirring paddle is placed, then add organic solvent isobutanol, mix Stir evenly, the weight of the organic solvent is 30% of the total weight of the reactants, then add the catalyst N,N-diethylbenzylamine, the weight of the catalyst is 0.5% of the total weight of the reactants, stir and react at 60°C for 5h, After the reaction is completed, the solvent is removed by distillation under reduced pressure, washed with distilled water, separated, and purified by distillation under reduced pressure to obtain the product;

(2) Preparation of lens resin monomer: take dibenzyl maleate, divinylbenzene, diallyl terephthalate and bromine-containing ether according to the weight ratio described in Example 5, mix and stir evenly, add Initiator azobisisobutyronitrile, degassed, put into oven after injection molding, rise from 20°C to 30°C within 1~2h, rise from 30°C to 70°C within 2~5h, keep warm for 4~10h, 2~ Raise from 70°C to 120°C within 5 hours, keep warm for 2-6 hours, and cool down from 120°C to room temperature within 1-5 hours.

Embodiment 12

A preparation method of a high refractive index lens resin monomer, the preparation method comprising the following steps:

(1) Synthesis of bromoether: get reactant Tetrabromobisphenol A271.9g and allyl glycidyl ether 68.5g, join in the four-necked flask that stirrer paddle is placed, then add organic solvent isobutanol, mix Stir evenly, the weight of the organic solvent is 360% of the total weight of the reactants, then add the catalyst triethylamine, the weight of the catalyst is 3% of the total weight of the reactants, stir and react at 70°C for 12h, after the reaction is completed, depressurize Distill to remove the solvent, wash with distilled water, separate liquid, and purify the product by distillation under reduced pressure to get final product;

(2) Preparation of lens resin monomer: get dibenzyl maleate, styrene, diallyl terephthalate and bromine-containing ether according to the weight ratio described in Example 6, mix and stir evenly, add initiator Azobisisobutyronitrile, degassed, put into the oven after injection molding, rise from 20°C to 30°C within 1-2 hours, rise from 30°C to 70°C within 2-5 hours, keep warm for 4-10 hours, within 2-5 hours Raise from 70°C to 120°C, keep it warm for 2 to 6 hours, and drop from 120°C to room temperature within 1 to 5 hours to obtain the product.

The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present invention should be included in the protection of the present invention. within range.

Claims (9)

1. a kind of high index of refraction lens resin monomer, it is characterised in that by weight percentage, the monomer is by following components group Into：Dibenzyl maleate 5~15%, styrene compound 5~15%, diallyl p phthalate or M-phthalic acid two The mixture 30~60% of allyl ester or both, containing bromo-ether 30~40%；Wherein, the structural formula containing bromo-ether is as follows：

2. high index of refraction lens resin monomer as claimed in claim 1, it is characterised in that by weight percentage, the monomer It is composed of the following components：Dibenzyl maleate 7~10%, styrene compound 7~10%, diallyl p phthalate or The mixture 45~50% of DAIP or both, containing bromo-ether 35~40%.

3. high index of refraction lens resin monomer as claimed in claim 1 or 2, it is characterised in that the styrene compound It is styrene or divinylbenzene.

4. a kind of preparation method of high index of refraction lens resin, it is characterised in that the preparation method comprises the following steps：By power Profit require weight described in 1 than take diallyl p phthalate or DAIP or both mixture, Dibenzyl maleate, styrene compound and containing bromo-ether, mixing and stirring is put into baking after adding initiator, degassing, injection molding Rise to be risen in 70 DEG C, insulation 4~10h, 2~5h by 30 DEG C in 30 DEG C, 2~5h by 20 DEG C in case, 1~2h and is risen to by 70 DEG C 120 DEG C, it is incubated in 2~6h, 1~5h and is down to room temperature by 120 DEG C, produce.

5. the preparation method of high index of refraction lens resin as claimed in claim 4, it is characterised in that the initiator is azo Bis-isobutyronitrile or ABVN.

6. the preparation method of high index of refraction lens resin as claimed in claim 4, it is characterised in that described to press following containing bromo-ether Step is synthesized：Reactant tetrabromobisphenol A and allyl glycidyl ether are taken, mixing and stirring adds organic solvent, then mixed Conjunction stirs, and the weight of the organic solvent is the 30~60% of the reactant gross weight, adds catalyst, described to urge The weight of agent is the 0.3~3% of the reactant gross weight, and in being stirred at 30~80 DEG C, reacting 5~15h, reaction terminates Afterwards, vacuum distillation removes solvent, is washed with distilled water, divides liquid, vacuum distillation purified product, produced.

7. the preparation method of high index of refraction lens resin as claimed in claim 6, it is characterised in that the tetrabromobisphenol A with The mol ratio of the allyl glycidyl ether is 1：1~2.

8. the preparation method of high index of refraction lens resin as claimed in claim 6, it is characterised in that the organic solvent is first Alcohol, ethanol or isopropanol.

9. the preparation method of high index of refraction lens resin as claimed in claim 6, it is characterised in that the catalyst is three second Amine, tripropyl amine (TPA), tri-n-butylamine, N, N- dimethyl benzylamines or N, N- diethyl benzylamine.