CN113248667B - Super-tough acrylate resin and preparation process thereof - Google Patents
Super-tough acrylate resin and preparation process thereof Download PDFInfo
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- CN113248667B CN113248667B CN202110479193.3A CN202110479193A CN113248667B CN 113248667 B CN113248667 B CN 113248667B CN 202110479193 A CN202110479193 A CN 202110479193A CN 113248667 B CN113248667 B CN 113248667B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
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Abstract
A super tough acrylate resin and its preparation process, which comprises monomer mixture, initiator, antioxidant and toner; the monomer mixture comprises methyl butenoic acid polyethylene glycol diester, tetrabromobisphenol A diethoxy acrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate and a polymerization regulator; according to the invention, 3-methyl-2-butenoic acid is modified by polyethylene glycol esterification to obtain methyl butenoic acid polyethylene glycol diester, the polyethylene glycol has a simple structure, a molecular chain is soft and smooth, the flexibility and the polarity are better, the rigidity of esters is improved, the molecular structure of the long-chain acrylic acid super-tough lens is in a net-shaped cross-linked structure, when the lens is impacted by external force, the lens can interact and support, the impact resistance is super-strong, the lens is not easy to break, and fragments are less and not sharp even if the lens is crushed.
Description
Technical Field
The invention relates to the technical field of optical elements, in particular to a super-tough acrylate resin and a preparation process thereof.
Background
With the continuous development of the technology, optical elements are applied more and more widely in life and work of people, optical materials for preparing the optical elements are a material which is applied to optical experiments and optical instruments and can transmit and use light, and the optical materials are divided into inorganic optical glass and organic optical resin from the structural category, and compared with the inorganic optical glass, the organic optical resin has the advantages of light weight, easy dyeing, difficult breakage and the like, and is widely applied to the fields of spectacle lenses, optical disk substrates, optical lenses, prisms and the like; in recent years, the lenses made of glass materials have the defects of fragility, heavier weight and the like, which greatly affect the safety and comfort of wearing glasses by myopes, and are gradually replaced by resin lenses;
the resin materials for mainstream lenses in the market at present mainly comprise four materials, namely injection-molded PC particles, acrylic resin, allyl ester resin and thiourethane lenses, and the refractive index of the lenses made of the acrylic resin is between 1.56 and 1.61, so that the lenses have good imaging effect, but the toughness is poor, and the impact resistance is not enough, so that the preparation of the super-tough acrylic resin is urgently needed.
Disclosure of Invention
The invention aims to solve the defects of the prior art, and provides a super-tough acrylate resin which comprises 80-110 parts of a monomer mixture, 1-2 parts of an initiator, 0.5-1 part of an antioxidant and 0.05-0.1 part of a toner in parts by weight; the monomer mixture comprises 40-60 parts of methyl butenoic acid polyethylene glycol diester, 20-30 parts of tetrabromobisphenol A diethoxy acrylate, 15-25 parts of polyethylene glycol dimethacrylate, 10-20 parts of trimethylolpropane trimethacrylate and 1-3 parts of polymerization regulator;
the preparation method of the methyl butenoic acid polyethylene glycol diester comprises the following steps: adding polyethylene glycol into a reaction kettle, simultaneously adding a catalyst and a polymerization inhibitor, uniformly stirring, dissolving 3-methyl-2-butenoic acid in a proper amount of diethyl ether, dropwise adding into the reaction kettle under a reflux condition, dropwise adding for three times, wherein the dropwise adding time is 0.5-1h each time, after the dropwise adding is finished, heating the reactant to 120 plus 130 ℃, reacting for 1-1.5h, carrying out reduced pressure distillation for 1-2h after the reaction is finished, adjusting the pH of the finally obtained reaction liquid to be neutral, layering after washing to obtain a polyethylene glycol diester layer of the methyl butenoic acid, and carrying out reduced pressure distillation to remove the solvent to obtain the polyethylene glycol diester of the methyl butenoic acid.
Preferably, the catalyst is concentrated sulfuric acid.
Preferably, the polymerization inhibitor is hydroquinone.
Preferably, the molar ratio of the polyethylene glycol to the 3-methyl-2-butenoic acid is 1 (2.5-3.5), and the dosages of the catalyst and the polymerization inhibitor are respectively 1-2% and 0.5-1% of the mass of the 3-methyl-2-butenoic acid.
Preferably, the toner is a heterocyclic aminoketone dye and an anthraquinone dye.
Preferably, the polymerization regulator is at least one of dodecyl mercaptan or methyl styrene dimer.
The preparation process of the super-tough acrylate resin comprises the following steps: weighing the monomer mixture, the initiator, the antioxidant and the toner in parts by weight, stirring for 30-40min under the assistance of ultrasonic waves, stopping stirring, and performing temperature programming reaction to obtain the super-tough acrylate resin.
Further, the temperature programming comprises three stages, wherein the first stage is room temperature, and the reaction time is 0.8-1.5 h; the second stage is at 60-80 deg.C for 1.5-2.0 hr, and the third stage is at 80-100 deg.C for 1.5-2.5 hr.
The invention has the following beneficial effects:
(1) according to the invention, 3-methyl-2-butenoic acid is modified by polyethylene glycol esterification to obtain methyl butenoic acid polyethylene glycol diester, the polyethylene glycol has a simple structure, a molecular chain is soft and smooth, the flexibility and the polarity are better, the rigidity of esters is improved, the molecular structure of the long-chain acrylic acid super-tough lens is of a net-shaped cross-linking structure, and after being impacted by an external force, the long-chain acrylic acid super-tough lens can interact and support, has super-strong impact resistance and is not easy to break, and even if the lens is broken, fragments are less and not sharp;
(2) tetrabromobisphenol A diethoxy acrylate, polyethylene glycol dimethacrylate and trimethylolpropane trimethacrylate are used as auxiliary materials, so that the resin is guaranteed to have a high refractive index, and is low in yellowing degree, and the yellowing factor is smaller than 1.0.
Detailed Description
For the purpose of enhancing understanding of the present invention, the present invention will be further described in detail with reference to the following examples, which are provided for illustration only and are not to be construed as limiting the scope of the present invention.
Example 1
The super-tough acrylate resin comprises, by weight, 95 parts of a monomer mixture, 1.5 parts of an initiator, 0.8 part of an antioxidant and 0.08 part of a toner heterocyclic aminoketone dye; the monomer mixture comprises 55 parts of methyl butenoic acid polyethylene glycol diester, 26 parts of tetrabromobisphenol A diethoxy acrylate, 18 parts of polyethylene glycol dimethacrylate, 16 parts of trimethylolpropane trimethacrylate and 2 parts of polymerization regulator dodecyl mercaptan.
The preparation process of the super-tough acrylate resin specifically comprises the following steps:
(1) preparing methyl butenoic acid polyethylene glycol diester: adding polyethylene glycol into a reaction kettle, simultaneously adding catalyst concentrated sulfuric acid and polymerization inhibitor hydroquinone, uniformly stirring, dissolving 3-methyl-2-butenoic acid in a proper amount of diethyl ether, dropwise adding into the reaction kettle under a reflux condition, dropwise adding for three times, wherein the dropwise adding time is 0.6h each time, after the dropwise adding is finished, heating the reactant to 120 plus 130 ℃, reacting for 1.2h, carrying out reduced pressure distillation for 1.6h after the reaction is finished, adjusting the pH of the finally obtained reaction liquid to be neutral, layering to obtain a polyethylene glycol diester layer of the methyl butenoic acid, and removing the solvent by reduced pressure distillation to obtain the polyethylene glycol diester of the methyl butenoic acid; wherein, the molar ratio of the polyethylene glycol to the 3-methyl-2-butenoic acid is 1:2.8, and the using amounts of the catalyst and the polymerization inhibitor are respectively 1.5 percent and 0.8 percent of the mass of the 3-methyl-2-butenoic acid;
(2) weighing a monomer mixture, an initiator, an antioxidant and a toner according to parts by weight, stirring for 35min under the assistance of ultrasonic waves, stopping stirring, and performing temperature programming reaction to obtain the lens resin, wherein the temperature programming comprises three stages, the first stage is room temperature, and the reaction time is 1.0 h; the second stage is at 60-80 deg.C for 1.5 hr, and the third stage is at 80-100 deg.C for 1.8 hr.
Example 2
The super-tough acrylate resin comprises, by weight, 100 parts of a monomer mixture, 1.2 parts of an initiator, 0.6 part of an antioxidant and 0.08 part of a toner heterocyclic aminoketone dye; the monomer mixture comprises 46 parts of methyl butenoic acid polyethylene glycol diester, 28 parts of tetrabromobisphenol A diethoxy acrylate, 17 parts of polyethylene glycol dimethacrylate, 16 parts of trimethylolpropane trimethacrylate and 1.5 parts of polymerization regulator dodecyl mercaptan.
The preparation process of the super-tough acrylate resin specifically comprises the following steps:
(1) preparing methyl butenoic acid polyethylene glycol diester: adding polyethylene glycol into a reaction kettle, simultaneously adding catalyst concentrated sulfuric acid and polymerization inhibitor hydroquinone, uniformly stirring, dissolving 3-methyl-2-butenoic acid in a proper amount of diethyl ether, dropwise adding into the reaction kettle under a reflux condition, dropwise adding for three times, wherein the time of each dropwise adding is 0.5h, after the dropwise adding is finished, heating the reactant to 120 plus 130 ℃, reacting for 1.5h, carrying out reduced pressure distillation for 2h after the reaction is finished, adjusting the pH of the finally obtained reaction liquid to be neutral, layering to obtain a polyethylene glycol diester layer of the methyl butenoic acid, and carrying out reduced pressure distillation to remove the solvent to obtain the polyethylene glycol diester of the methyl butenoic acid; wherein, the molar ratio of the polyethylene glycol to the 3-methyl-2-butenoic acid is 1:3.0, and the using amounts of the catalyst and the polymerization inhibitor are respectively 1.3 percent and 0.8 percent of the mass of the 3-methyl-2-butenoic acid;
(2) weighing a monomer mixture, an initiator, an antioxidant and a toner according to parts by weight, stirring for 35min under the assistance of ultrasonic waves, stopping stirring, and performing temperature programming reaction to obtain the lens resin, wherein the temperature programming comprises three stages, the first stage is room temperature, and the reaction time is 0.8 h; the second stage is at 60-80 deg.C for 1.8 hr, and the third stage is at 80-100 deg.C for 2.5 hr.
Example 3
The super-tough acrylate resin comprises, by weight, 110 parts of a monomer mixture, 1.8 parts of an initiator, 0.7 part of an antioxidant and 0.09 part of a toner heterocyclic aminoketone dye; the monomer mixture comprises 55 parts of methyl butenoic acid polyethylene glycol diester, 30 parts of tetrabromobisphenol A diethoxy acrylate, 18 parts of polyethylene glycol dimethacrylate, 14 parts of trimethylolpropane trimethacrylate and 1-3 parts of polymerization regulator dodecyl mercaptan.
The preparation process of the super-tough acrylate resin specifically comprises the following steps:
(1) preparing methyl butenoic acid polyethylene glycol diester: adding polyethylene glycol into a reaction kettle, simultaneously adding catalyst concentrated sulfuric acid and polymerization inhibitor hydroquinone, uniformly stirring, dissolving 3-methyl-2-butenoic acid in a proper amount of diethyl ether, dropwise adding into the reaction kettle under a reflux condition, dropwise adding for three times, wherein the dropwise adding time is 1 hour each time, heating reactants to 120 plus 130 ℃ after the dropwise adding is finished, reacting for 1.5 hours, carrying out reduced pressure distillation for 1 hour after the reaction is finished, adjusting the pH of the finally obtained reaction liquid to be neutral, layering after washing to obtain a polyethylene glycol diester methacrylate layer, and carrying out reduced pressure distillation to remove the solvent to obtain the polyethylene glycol diester methacrylate; wherein, the molar ratio of the polyethylene glycol to the 3-methyl-2-butenoic acid is 1:2.8, and the dosages of the catalyst and the polymerization inhibitor are respectively 1-2 percent and 0.5-1 percent of the mass of the 3-methyl-2-butenoic acid;
(2) weighing a monomer mixture, an initiator, an antioxidant and a toner according to parts by weight, stirring for 30-40min under the assistance of ultrasonic waves, stopping stirring, and performing temperature programming reaction to obtain the lens resin, wherein the temperature programming comprises three stages, the first stage is room temperature, and the reaction time is 1.0 h; the second stage is at 60-80 deg.C for 1.8 hr, and the third stage is at 80-100 deg.C for 1.8 hr.
Example 4
The super-tough acrylate resin comprises, by weight, 80 parts of a monomer mixture, 1 part of an initiator, 0.6 part of an antioxidant and 0.08 part of a toner heterocyclic aminoketone dye; the monomer mixture comprises 46 parts of methyl butenoic acid polyethylene glycol diester, 25 parts of tetrabromobisphenol A diethoxy acrylate, 22 parts of polyethylene glycol dimethacrylate, 14 parts of trimethylolpropane trimethacrylate and 2 parts of polymerization regulator dodecyl mercaptan.
The preparation process of the super-tough acrylate resin specifically comprises the following steps:
(1) preparing methyl butenoic acid polyethylene glycol diester: adding polyethylene glycol into a reaction kettle, simultaneously adding catalyst concentrated sulfuric acid and polymerization inhibitor hydroquinone, uniformly stirring, dissolving 3-methyl-2-butenoic acid in a proper amount of diethyl ether, dropwise adding into the reaction kettle under a reflux condition, dropwise adding for three times, wherein the dropwise adding time is 0.6h each time, after the dropwise adding is finished, heating the reactant to 120 plus 130 ℃, reacting for 1.5h, carrying out reduced pressure distillation for 1-2h after the reaction is finished, adjusting the pH of the finally obtained reaction liquid to be neutral, layering to obtain a polyethylene glycol diester layer of the methyl butenoic acid, and removing the solvent by reduced pressure distillation to obtain the polyethylene glycol diester of the methyl butenoic acid; wherein, the molar ratio of the polyethylene glycol to the 3-methyl-2-butenoic acid is 1:3.0, and the dosages of the catalyst and the polymerization inhibitor are respectively 1.5 percent and 0.6 percent of the mass of the 3-methyl-2-butenoic acid;
weighing a monomer mixture, an initiator, an antioxidant and a toner according to parts by weight, stirring for 30-40min under the assistance of ultrasonic waves, stopping stirring, and performing temperature programming reaction to obtain the lens resin, wherein the temperature programming comprises three stages, the first stage is room temperature, and the reaction time is 1.2 h; the second stage is at 60-80 deg.C for 1.5 hr, and the third stage is at 80-100 deg.C for 2.5 hr.
Performance testing
The lens resins obtained in examples 1 to 4 were used for producing resin lenses, and the dispersion coefficient, yellowing factor and falling ball test were measured, and the test data are shown in table 1; wherein the measurement of the yellowing factor is detected according to a method specified by QB2506-2006 optical resin spectacle lens, and in a ball dropping experiment, the weight of a ball is 16.3g, and the height is 127 cm;
TABLE 1
| Item | Refractive index | Coefficient of dispersion | Yellowing factor | Falling ball experiment |
| Example 1 | 1.60 | 42 | 0.96 | By passing |
| Example 2 | 1.60 | 42 | 0.94 | By passing |
| Example 3 | 1.60 | 40 | 0.93 | By passing |
| Example 4 | 1.60 | 41 | 0.94 | By passing |
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. The super-tough acrylate resin is characterized by comprising, by weight, 80-110 parts of a monomer mixture, 1-2 parts of an initiator, 0.5-1 part of an antioxidant and 0.05-0.1 part of a toner; the monomer mixture comprises 40-60 parts of methyl butenoic acid polyethylene glycol diester, 20-30 parts of tetrabromobisphenol A diethoxy acrylate, 15-25 parts of polyethylene glycol dimethacrylate, 10-20 parts of trimethylolpropane trimethacrylate and 1-3 parts of polymerization regulator;
the preparation method of the methyl butenoic acid polyethylene glycol diester comprises the following steps: adding polyethylene glycol into a reaction kettle, simultaneously adding a catalyst and a polymerization inhibitor, uniformly stirring, dissolving 3-methyl-2-butenoic acid in a proper amount of diethyl ether, dropwise adding into the reaction kettle under a reflux condition, dropwise adding for three times, wherein the dropwise adding time is 0.5-1h each time, after the dropwise adding is finished, heating the reactant to 120 plus 130 ℃, reacting for 1-1.5h, carrying out reduced pressure distillation for 1-2h after the reaction is finished, adjusting the pH of the finally obtained reaction liquid to be neutral, layering after washing to obtain a polyethylene glycol diester layer of the methyl butenoic acid, and carrying out reduced pressure distillation to remove the solvent to obtain the polyethylene glycol diester of the methyl butenoic acid.
2. The super tough type acrylate resin according to claim 1, wherein the catalyst is concentrated sulfuric acid.
3. The super tough type acrylate resin according to claim 1, wherein the polymerization inhibitor is hydroquinone.
4. The super-tough acrylate resin according to claim 1, wherein the molar ratio of the polyethylene glycol to the 3-methyl-2-butenoic acid is 1 (2.5-3.5), and the amounts of the catalyst and the polymerization inhibitor are respectively 1-2% and 0.5-1% of the mass of the 3-methyl-2-butenoic acid.
5. The super tough type acrylate resin according to claim 1, wherein the toner is heterocyclic amino ketone dye and anthraquinone type dye.
6. The super tough type acrylate resin according to claim 1, wherein the polymerization regulator is at least one of dodecyl mercaptan or methyl styrene dimer.
7. The process for preparing a super tough type acrylate resin according to any one of claims 1 to 6, which is carried out by the steps of: weighing the monomer mixture, the initiator, the antioxidant and the toner in parts by weight, stirring for 30-40min under the assistance of ultrasonic waves, stopping stirring, and performing temperature programming reaction to obtain the super-tough acrylate resin.
8. The method for preparing the super tough type acrylate resin according to claim 7, wherein the temperature programming comprises three stages, the first stage is room temperature, the reaction time is 0.8-1.5 h; the second stage is at 60-80 deg.C for 1.5-2.0 hr, and the third stage is at 80-100 deg.C for 1.5-2.5 hr.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1756814A (en) * | 2003-03-03 | 2006-04-05 | 索拉国际控股有限公司 | Toned optical substrate |
| CN102690386A (en) * | 2012-06-07 | 2012-09-26 | 常州大学 | Method for preparing crosslinked copolymerized organic glass |
| CN105254816A (en) * | 2015-10-22 | 2016-01-20 | 瑞洲树脂（东莞）有限公司 | Radiation cured perfusion adhesive, radiation cured lens, radiation cured camera lens and radiation cured optical sheet |
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- 2021-04-30 CN CN202110479193.3A patent/CN113248667B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1756814A (en) * | 2003-03-03 | 2006-04-05 | 索拉国际控股有限公司 | Toned optical substrate |
| CN102690386A (en) * | 2012-06-07 | 2012-09-26 | 常州大学 | Method for preparing crosslinked copolymerized organic glass |
| CN105254816A (en) * | 2015-10-22 | 2016-01-20 | 瑞洲树脂（东莞）有限公司 | Radiation cured perfusion adhesive, radiation cured lens, radiation cured camera lens and radiation cured optical sheet |
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