阅读说明：本技术 光学树脂及其制备方法及应用 (Optical resin and preparation method and application thereof ) 是由 王少飞 施文昌 于 2021-08-13 设计创作，主要内容包括：本发明公开了一种光学树脂,其结构式中含有式1单元、式2单元、以及式3的单元；式1：式2：其中,R8、R9各自独立选自H、C1-C7的烷基、芳基、或芳烷基；a、b为1-7的自然数；式3：其中,R1选自C2-C4的亚烷基；R2、R3、R4、R5各自独立的选自H、C1-C4的烷基、芳基、或芳烷基。上述光学树脂,同时具有良好的折射率以及阿贝数；且上述光学树脂原料不含特殊异氰酸酯原料,对保存要求低；原料对环境和人体健康基本无影响；还容易加工。本发明还提供上述光学树脂的制备方法及应用。(The invention discloses an optical resin, which comprises a unit of a formula 1, a unit of a formula 2 and a unit of a formula 3 in a structural formula; formula 1: formula 2: wherein R8 and R9 are independently selected from alkyl, aryl or aralkyl of H, C1-C7; a. b is a natural number of 1-7; formula 3: wherein R1 is selected from C2-C4 alkylene; r2, R3, R4 and R5 are independently selected from H, C1-C4 alkyl, aryl or aralkyl. The optical resin has good refractive index and Abbe number; and the raw material of the optical resin does not contain special materialsIsocyanate raw material, the requirement for storage is low; the raw materials basically have no influence on the environment and the human health; and also easy to process. The invention also provides a preparation method and application of the optical resin.)

1. An optical resin is characterized in that the structural formula of the optical resin contains a unit of formula 1, a unit of formula 2 and a unit of formula 3;

formula 1:

formula 2:

wherein R8 and R9 are independently selected from alkyl, aryl or aralkyl of H, C1-C7; a. b is a natural number of 1-7;

formula 3:

wherein R1 is selected from C2-C4 alkylene; r2, R3, R4 and R5 are independently selected from H, C1-C4 alkyl, aryl or aralkyl.

2. An optical resin according to claim 1 wherein the unit of formula 3 is

Formula 2 is a unit of

3. The optical resin according to claim 1, wherein the molar ratio of the unit of formula 1 to the unit of formula 2 to the unit of formula 3 is 0.5 to 100: 0.5-100: 0.5 to 100.

4. An optical resin according to any one of claims 1 to 3, wherein the structural formula further comprises a unit of formula 4;

formula 4:

wherein X is a natural number of 1-100.

5. The optical resin according to claim 4, wherein the molar ratio of the unit of formula 1 to the unit of formula 2 to the unit of formula 3 to the unit of formula 4 is 0.5 to 100: 0.5-100: 0.5-100: 0.5 to 30.

6. A method for producing an optical resin, comprising: polymerizing raw material monomers; wherein the raw material monomers comprise a compound of formula I, a compound of formula II and a compound of formula III;

a compound of formula I:

a compound of formula II:

wherein R8 and R9 are independently selected from alkyl, aryl or aralkyl of H, C1-C7; a. b is a natural number of 1-7;

a compound of formula III:

wherein R1 is selected from C2-C4 alkylene; r2, R3, R4 and R5 are independently selected from H, C1-C4 alkyl, aryl or aralkyl.

7. The process of claim 5, wherein the compound of formula III is

The compound of the formula II is

8. The method of claim 6 or 7, wherein the starting monomers further comprise a compound of formula IV;

a compound of formula IV:

wherein X is a natural number of 1-100.

9. Use of the optical resin according to claim 1 in an optical lens.

10. Use of the optical resin according to claim 1 in lenses for electronic products.

11. Use of the optical resin according to claim 1 in an LED backlight, an LCD backlight, or an ITO film.

Technical Field

The invention belongs to the technical field of optical resin, and relates to optical resin and a preparation method and application thereof.

Background

The refractive index and the abbe number are two important optical parameters of optical resin, especially when the optical resin is applied to optical lenses and electronic product lenses. For an optical lens, the thickness of the lens is directly influenced by the refractive index, and the higher the refractive index is, the thinner the lens is under the same myopia degree; the abbe number directly affects the imaging quality, and the higher the abbe number is, the smaller the dispersion is, the clearer the imaging is. The lens of the electronic product is also formed by matching lenses made of materials with different refractive indexes and Abbe numbers, so that the more clear the photographing quality is, the higher the pixels are.

Currently, optical resins are compared with representative polycarbonate materials and three-well MR series materials in the field of optical lenses. The abbe number of polycarbonate materials is very low and the market applications are limited. The advantage of MR materials is that they have both a high refractive index and a high Abbe number, but MR materials are generally made mainly from special isocyanates (NBDI/XDI, etc.) and thiol starting materials (polythiol 504), the manufacturing process being that of CPU. The special isocyanate raw material has strict storage requirements (low temperature, oxygen and water vapor isolation), belongs to dangerous chemicals and has harm to the health of production personnel; the mercaptan raw material has serious peculiar smell and has influence on the environment and human health; the processing cost is high: the processing period is long (12-24h), and the yield is difficult to control.

The optical lens is a field with wide application, except the field of a mobile phone camera module, in other fields such as security video monitoring, vehicle-mounted cameras and the like, the optical lens is related to government policies and law regulations of various countries. Currently, in the field of electronic product lenses, optical resin is typically prepared by matching a high refractive index lens EP material (refractive index >1.60, abbe number about 20) of MGC company with a high abbe number APL material (refractive index 1.52, abbe number 56) of mitsui company. However, these combinations tend to increase the thickness of the lens assembly, and the lens is protruded, which affects the aesthetic appearance of the electronic product and also limits the quality of the photographed image.

In recent years, a series of industrial support policies are developed in the fields of optical lenses and the application in China, and a good policy environment is provided for the continuous development of the optical lens industry. An optical camera, a night vision system and the like in an important field technical route map has image processing and vision enhancement functions, has the performance equivalent to that of an international brand, has cost advantage and has more than 80 percent of independent market share "

Therefore, a new optical resin material is needed to satisfy the requirements of the optical resin for higher and higher refractive index and abbe number.

Disclosure of Invention

In view of the above-mentioned disadvantages, it is necessary to provide a new optical resin.

An optical resin, the structural formula of which contains a unit of formula 1, a unit of formula 2 and a unit of formula 3;

formula 1:

formula 2:

wherein R8 and R9 are independently selected from alkyl, aryl or aralkyl of H, C1-C7; a. b is a natural number of 1-7;

formula 3:

wherein R1 is selected from C2-C4 alkylene; r2, R3, R4 and R5 are independently selected from H, C1-C4 alkyl, aryl or aralkyl.

The optical resin has good refractive index and Abbe number; the raw materials of the optical resin do not contain special isocyanate raw materials, and the requirement on storage is low; the raw materials basically have no influence on the environment and the human health; and also easy to process.

Preferably, the unit of formula 3 is

Formula 2 is a unit of

Preferably, the molar ratio of the unit of formula 1 to the unit of formula 2 to the unit of formula 3 is 0.5 to 100: 0.5-100: 0.5 to 100.

Preferably, the structural formula also contains a unit of formula 4;

formula 4:

wherein X is a natural number of 1-100.

Preferably, the molar ratio of the unit of formula 1 to the unit of formula 2 to the unit of formula 3 to the unit of formula 4 is 0.5 to 100: 0.5-100: 0.5-100: 0.5 to 30.

The invention also provides a preparation method of the optical resin.

A method for producing an optical resin, the method comprising: polymerizing raw material monomers in extrusion; wherein the raw material monomers comprise a compound of formula I, a compound of formula II and a compound of formula III;

a compound of formula I:

a compound of formula II:

wherein R8 and R9 are independently selected from alkyl, aryl or aralkyl of H, C1-C7; a. b is a natural number of 1-7;

a compound of formula III:

wherein R1 is selected from C2-C4 alkylene; r2, R3, R4 and R5 are independently selected from H, C1-C4 alkyl, aryl or aralkyl.

The optical resin obtained by the preparation method has good refractive index and Abbe number; the raw materials do not contain special isocyanate raw materials, and the requirement on storage is low; the raw materials basically have no influence on the environment and the human health; the preparation method has simple and convenient process.

Preferably, the compound of formula III is

The compounds of formula II are:

preferably, the starting monomers further comprise a compound of formula IV;

a compound of formula IV:

wherein X is a natural number of 1-100.

The invention also provides an application of the optical resin.

An application of the optical resin in optical lenses.

An application of the optical resin in an electronic product lens.

The application of the optical resin in an LED backlight plate, an LCD backlight plate or an ITO film.

Drawings

FIG. 1 is a transmission spectrum of an optical resin of example 1.

FIG. 2 is a transmission spectrum of an optical resin of example 2.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to specific embodiments. It should be understood that the detailed description and specific examples, while indicating the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

An optical resin having a structural formula containing units of formula 1, 2, and 3;

formula 1:

formula 2:

wherein R8 and R9 are independently selected from alkyl, aryl or aralkyl of H, C1-C7; a. b is a natural number of 1-7;

formula 3:

wherein R1 is selected from C2-C4 alkylene; r2, R3, R4 and R5 are independently selected from H, C1-C4 alkyl, aryl or aralkyl.

It is understood that, in the above optical resin, the units of formula 1, the units of formula 2, and the units of formula 3 are linked to each other, and the units of formula 1, the units of formula 2, and the units of formula 3 are segments in a copolymer.

Preferably, the unit of formula 2 is

That is, when R8 and R9 in formula 2 are selected from H, the formula is shown in the specification.

Preferably, the unit of formula 3 is

That is, when R1 in formula 3 is selected from ethylene; r2, R3, R4 and R5 are all selected from H structural formulas.

Preferably, the molar ratio of the unit of formula 1 to the unit of formula 2 to the unit of formula 3 is 0.5 to 100: 0.5-50: 0.5 to 50. Wherein the unit of formula 1 can provide the present invention with excellent low-temperature fluidity in subsequent thermal processing, particularly in extrusion (extrusion) molding and injection (injection) molding. The refractive index, glass transition temperature and birefringence (birefringence) of the present invention can be further adjusted by the content of different formula 2 units, but too high a content of two units causes difficulties in subsequent thermal processing, and particularly, the flowability during injection molding is greatly reduced. The Abbe number of the present invention increases with the content of the unit of formula 3, but the refractive index of the present invention is also decreased due to the proportion of the unit of formula 3 that is too high in the present invention, so that the content of the unit of formula 1, the unit of formula 2, and the unit of formula 3 needs to be balanced in response to the requirements of the application on the thermal processing characteristics, the glass transition temperature, the refractive index, and the Abbe number.

In another embodiment, the formula further comprises a unit of formula 4;

formula 4:

wherein X is a natural number of 1-100.

The introduction of the unit of formula 4 can improve the flowability of the subsequent thermal processing and improve the affinity and anchoring force (anchoring Effect) of the optical resin to the organic solvent coating.

Preferably, the molar ratio of the unit of formula 1 to the unit of formula 2 to the unit of formula 3 to the unit of formula 4 is 0.5 to 100: 0.5-50: 0.5-50: 0.5 to 30. Within this range, the optical resin is most effective in terms of the requirements of thermal processing characteristics, glass transition temperature, refractive index, Abbe number, and organic base coating (organic base coating).

The invention also provides a preparation method of the optical resin.

A method for producing an optical resin, the method comprising: polymerizing raw material monomers in extrusion; wherein the raw material monomers comprise a compound of formula I, a compound of formula II and a compound of formula III;

a compound of formula I:

a compound of formula II:

wherein R8 and R9 are independently selected from alkyl, aryl or aralkyl of H, C1-C7; a. b is a natural number of 1-7;

a compound of formula III:

wherein R1 is selected from C2-C4 alkylene; r2, R3, R4 and R5 are independently selected from H, C1-C4 alkyl, aryl or aralkyl.

Reacting a compound of formula I with a compound of formula I to produce a unit of formula 1; reacting a compound of formula I with a compound of formula II to produce a unit of formula 2; reacting the compound of formula I with the compound of formula III to produce a unit of formula 3.

Preferably, the compound of formula II is:

(TCD DM)。

preferably, the compound of formula III is

(BPEF，CAS-No.117344-32-8)。

That is, when R1 in the compound of formula III is selected from ethylene; r2, R3, R4 and R5 are all selected from H.

Preferably, the starting monomers further comprise a compound of formula IV;

a compound of formula IV:

wherein X is a natural number of 1-100.

Reacting the compound of formula I with the compound of formula IV to produce a unit of formula 4.

Preferably, each raw material monomer is added into a reaction tank, heated under an inert environment to melt the reactants, and then fully stirred and mixed for reaction for a period of time.

Preferably, the raw material monomers are polymerized and pelletized in a reaction kettle and then processed in a screw extruder. Further preferably, the extruder is in three stages.

More preferably, the front-section injection temperature is 210-; the middle-section injection temperature is 210-260 ℃; the injection temperature of the rear section is 210-250 ℃; the outlet injection temperature is 210-240 ℃.

The invention also provides an application of the optical resin.

An application of the optical resin in optical lenses.

An application of the optical resin in an electronic product lens.

The application of the optical resin in an LED backlight plate, an LCD backlight plate or an ITO film.

The invention is further illustrated by the following examples.

Example 1

Adding 30phr of a compound of a formula III (BPEF, CAS-No.117344-32-8), 10phr of a compound of a formula II (TCD DM) and 100 parts of a compound of a formula I into a reaction tank, heating to 245 ℃ in a nitrogen environment to melt reactants, controlling a stirrer to rotate at 150rpm after the reactants are completely melted, fully mixing the reactants, stirring at 245 ℃ and 150rpm for 10 minutes, starting to heat and depressurize the reaction tank, slowly heating to 280 ℃ and lowering the pressure to below 1mmHg, and maintaining for 40 minutes. And continuously observing the torque change of the stirrer, and when the torque of the stirrer reaches 13kg-cm, determining the end point of the polymerization reaction.

The resulting optical resin was designated as A1.

Example 2

Adding 30phr of a compound of a formula III (BPEF, CAS-No.117344-32-8), 20phr of a compound of a formula II (TCD DM) and 100 parts of a compound of a formula I into a reaction tank, heating to 245 ℃ in a nitrogen environment to melt reactants, controlling a stirrer to rotate at 150rpm after the reactants are completely melted, fully mixing the reactants, stirring at 245 ℃ and 150rpm for 10 minutes, starting to heat and depressurize the reaction tank, slowly heating to 280 ℃ and lowering the pressure to below 1mmHg, and maintaining for 40 minutes. And continuously observing the torque change of the stirrer, and when the torque of the stirrer reaches 13kg-cm, determining the end point of the polymerization reaction.

The resulting optical resin was designated as A2.

Example 3

Adding 20phr of a compound of a formula III (BPEF, CAS-No.117344-32-8), 10phr of a compound of a formula II (TCD DM), 20phr of a compound of a formula IV (x is 1) and 100 parts of a compound of a formula I into a reaction tank, heating to 245 ℃ under a nitrogen environment to melt reactants, controlling a stirrer to rotate at 150rpm after the reactants are completely melted, fully mixing the reactants, stirring at 245 ℃ and 150rpm for 10 minutes, starting to heat and reduce the pressure of the reaction tank, slowly heating to 280 ℃ and reducing the pressure to below 1mmHg, and maintaining for 40 minutes. And continuously observing the torque change of the stirrer, and when the torque of the stirrer reaches 13kg-cm, determining the end point of the polymerization reaction.

The resulting optical resin was designated as A3.

Example 4

Adding 20phr of a compound of a formula III (BPEF, CAS-No.117344-32-8), 20phr of a compound of a formula II (TCD DM), 10phr of a compound of a formula IV (x is 1) and 100 parts of a compound of a formula I into a reaction tank, heating to 245 ℃ under a nitrogen environment to melt reactants, controlling an agitator to rotate at 150rpm after the reactants are completely melted, fully mixing the reactants, stirring at 245 ℃ and 150rpm for 10 minutes, starting to heat and reduce the pressure of the reaction tank, slowly heating to 280 ℃ and reducing the pressure to below 1mmHg for 40 minutes. And continuously observing the torque change of the stirrer, and when the torque of the stirrer reaches 13kg-cm, determining the end point of the polymerization reaction.

The resulting optical resin was designated as A4.

Performance testing

And (3) testing a transmission spectrum:

the products A1-A2 were subjected to transmission spectrum testing, the results of which are shown in FIGS. 1-2.

Refractive index and abbe number test:

the products A1-A4 were tested for refractive index and Abbe number and the results are shown in Table 1.

TABLE 1

Examples	Refractive index	Abbe number
			Example 1	1.645	25
Example 2	1.608	45
			Example 3	1.607	30
Example 4	1.6032	27

As can be seen from Table 1, the optical resins of examples 1-4, both of which have a higher refractive index and Abbe number, are provided with good refractive index and Abbe number.

The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.