CN108864392A - A kind of optical resin product and preparation method thereof - Google Patents
A kind of optical resin product and preparation method thereof Download PDFInfo
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- CN108864392A CN108864392A CN201810845420.8A CN201810845420A CN108864392A CN 108864392 A CN108864392 A CN 108864392A CN 201810845420 A CN201810845420 A CN 201810845420A CN 108864392 A CN108864392 A CN 108864392A
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- component
- optical resin
- resin product
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3863—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms
- C08G18/3865—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms
- C08G18/3868—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms the sulfur atom belonging to a sulfide group
-
- 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
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a kind of optical resin products, and comprising the polymer obtained by using component A and component B, the component A is multi-thioalcohol compound shown in structural formula (1), and the component B is polyisocyanates.A kind of optical resin product proposed by the present invention and preparation method thereof, prepolymer by being formed using after multi-thioalcohol compound and isocyanate polymeric comprising the big sulfur-bearing electron rich conjugated structure unit-thio binaphthalene of molar refraction and thioether bond effectively increases the refractive index of the product as optical resin product.
Description
Technical field
The present invention relates to the technical fields of optical resin more particularly to a kind of optical resin product and preparation method thereof.
Background technique
Optical resin is a kind of organic material, the space network that inside is in for the connection of macromolecule chain structure, point
Structure relative relaxation between son, molecule interchain have the space that can produce relative displacement, and light-transmissive rate is 84-90%, translucency
It is good, while the anti-impact force of optical resin is strong.Optical resin has a wide range of applications, and produces especially as optical resin lens
Product, it is therefore, right with the obvious superiority such as light, good impact resistance, easily processed into type compared to traditional glass lens
The research of optical resin has broad application prospects.
Polyurethane optical resin product is polymerized by isocyanates and multi-thiol, has light transmittance height, refractive power
The features such as rate is high, manufactured eyeglass is thinner and lighter to be full of；The routine that refractive index is high and Abbe number is low is broken, has made its imaging more
Clearly；Also, the perfect combination of multi-thiol and isocyanates makes it possess higher impact strength in mechanical property.
However, the difference of raw material will lead to the reduced performance of polyurethane optical resin product, due to domestic thermosetting property tree
Rouge starting is too late, especially using polyurethane resin as representative：Domestic technique Innovation Input is few, and based on small-sized manufacturing enterprise；
And overseas enterprise monopolizes the raw materials for production of polyurethane optical resin product, domestic enterprise can not obtain high performance different
The optical articles that cyanate polymerize with multi-thiol, can only be produced by the general raw material that possesses currently on the market relative quality compared with
Low naval stores.
Summary of the invention
The problem of based on background technique, the invention proposes a kind of optical resin products and preparation method thereof, lead to
It crosses with the sulfur-bearing electron rich conjugated structure unit-thio binaphthalene and thioether bond multi-thioalcohol compound big comprising molar refraction
With the prepolymer that is formed after isocyanate polymeric as optical resin product, the refractive index of the product is effectively increased.
A kind of sulfur-bearing optical resin monomer proposed by the present invention, includes the polymerization obtained by using component A and component B
Object, the component A are multi-thioalcohol compound shown in structural formula (1), and the component B is polyisocyanates；
The preparation method of the multi-thioalcohol compound, includes the following steps：
S1, beta naphthal is added to and is dissolved completely, under condition of ice bath by the in the mixed solvent that toluene and ethyl acetate form
The molar ratio of addition sulfur dichloride, sulfur dichloride and beta naphthal is 1:1.9-2.2 is stirred to react 2-4h at 10-20 DEG C, obtains
Intermediate (A)；
S2, intermediate (A) is added in epoxychloropropane, the molar ratio of intermediate (A) and epoxychloropropane is 1:5-10,
Catalyst tetra-n-butyl ammonium bromide is added, is warming up to 80-90 DEG C under inert gas protection, is stirred to react 3-5h, is stopped anti-
Should after be cooled to room temperature, remove excessive epoxychloropropane, purify, obtain intermediate (B)；
S3, intermediate (B) is dissolved in toluene, be added dropwise under agitation dissolved with potassium rhodanate ethanol water mixing it is molten
The molar ratio of liquid, intermediate (B) and potassium rhodanate is 1:5-15 is warming up to 50-60 DEG C of reaction 8-10h, obtains after being added dropwise
Intermediate (C)；
S4, the sodium hydroxide solution that concentration is 25-35wt% is added dropwise into 2 mercapto ethanol under conditions of nitrogen protection,
Control reaction temperature is 25-30 DEG C during being added dropwise, be added dropwise rear insulated and stirred to reaction solution pH be 8-9, then in stirring bar
Isosorbide-5-Nitrae-dioxane solution dissolved with intermediate (C) is added dropwise under part, the molar ratio of intermediate (C) and 2 mercapto ethanol is 1:2-4,
Insulated and stirred 3-5h after being warming up to 80-90 DEG C removes Isosorbide-5-Nitrae-dioxane, adds methylene chloride dissolution, washes, dry, dense
Contracting, obtains compound (D), i.e., the described optical resin material multi-thioalcohol compound, H1NMR：8.16 (d, 2H), 8.05 (d,
2H), 7.63 (q, 2H), 7.55 (d, 2H), 7.54 (q, 2H), 7.12 (d, 2H), 4.45 (t, 4H), 3.65 (s, 2H), 3.45 (t,
4H), 3.33 (q, 2H), 2.65 (d, 4H), 2.65 (t, 4H), 2.491 (t, 2H), 1.5 (s, 2H)；
Preferably, the polyisocyanates is selected from sub- xylene diisocyanate, 3,3 '-dichlorobenzene -4,4 '-two isocyanides
Acid esters, 4,4 '-methyl diphenylene diisocyanates, hexylidene diisocyanate, tolylene diisocyanate, two isocyanide of hexamethylene
The combination of one or more of acid esters, different Buddhist ketone diisocyanate.
Preferably, the molar ratio of the component A and component B is 1:1.2-1.7.
Preferably, it is obtained in polymer process using component A and component B, with organic per-compounds or azo
Object and organo-tin compound or aminated compounds are closed as catalyst, the dosage of catalyst is the 0.01-0.05mol% of component A.
It preferably, further include UV absorbent, antioxidant, fade inhibitor or fluorescent dye.
Preferably, the organic per-compounds are selected from tert-butyl hydroperoxide 2- ethylhexyl carbonate, t-butyl peroxy
Change butylperoxyisopropyl carbonate, diisopropyl peroxydicarbonate, peroxidating two (2,4- dichloro-benzoyl), two isobutyl of peroxidating
One or more of acyl, benzoyl peroxide；The azo compound is selected from azodiisobutyronitrile, azo two (2,4-
Methyl pentane nitrile)；The organo-tin compound is selected from dibutyl tin dilaurate, dibutyltin chloride, stannous octoate, methyl three
One or more of stannic chloride and trimethyltin chloride；The aminated compounds is selected from N, N- dimethyl cyclohexyl amine, diethyl
Alkene triamine, three ethyl mercaptan amine, triethanolamine, N, one of N- di-n-butyl ethanol amine, triethylamine, triethylenediamine or
It is a variety of.
Preferably, the UV absorbent is selected from UV-P, UV-O, UV-9, UV-531, UV-327, UV-234, UV-326, UV-
329, one of nano-titanium dioxide, nano zine oxide and nano zircite or a variety of combinations.
On the other hand, the present invention also proposes the preparation method of this kind of optical resin product, including：Component A and component B are mixed
After conjunction, catalyst is added, insulated and stirred reacts 1-2h after being warming up to 70-80 DEG C under conditions of inert gas shielding, obtains pre-
Polymers；By the first curing reaction 3-5h at 90-100 DEG C of prepolymer, curing reaction 1-3h, is obtained after being continuously heating to 120-130 DEG C
To the optical resin product.
Preferably, the dosage of catalyst is the 1-3mol% of component A.
The beneficial effects of the present invention are the present invention uses the sulfur-bearing electron rich conjugated structure list big comprising molar refraction
It is same in multi-thioalcohol compound structure while multi-thioalcohol compound and the isocyanates polycondensation of member-thio binaphthalene and thioether bond
When acrylate group, be conducive to the cross-linking reaction of condensation polymer molecule interchain, the final corresponding optical resin product obtained is simultaneously
Refractive index and heat resistance with higher.
Specific embodiment
In the following, technical solution of the present invention is described in detail by specific embodiment.
Embodiment 1
A kind of optical resin product, comprising being 1 by using molar ratio:The polymer that 1.2 component A and component B is obtained,
The component A is multi-thioalcohol compound shown in structural formula (1), and the component B is polyisocyanates, and polyisocyanates is selected from Asia
Xylene diisocyanate, 3,3 '-dichlorobenzene -4, the combination of 4 '-diisocyanate；
Preparing the optical resin product includes：After component A and component B is mixed, catalyst, the dosage of catalyst is added
For the 0.01mol% of component A, insulated and stirred reacts 1h after 80 DEG C are warming up under conditions of inert gas shielding, obtains pre-polymerization
Object；By prepolymer, first curing reaction 3h, curing reaction 1h after being continuously heating to 130 DEG C at 100 DEG C obtain the optical resin
Product；Wherein the catalyst is organic per-compounds and organo-tin compound；The organic per-compounds are selected from tertiary fourth
Base peroxidating 2- ethylhexyl carbonate；The organo-tin compound is selected from dibutyl tin dilaurate.
Embodiment 2
A kind of optical resin product, comprising being 1 by using molar ratio:The polymer that 1.7 component A and component B is obtained,
The component A is multi-thioalcohol compound shown in structural formula (1), and the component B is polyisocyanates, and polyisocyanates is selected from 4,
4 '-methyl diphenylene diisocyanates, hexylidene diisocyanate；
Preparing the optical resin product includes：After component A and component B is mixed, catalyst, the dosage of catalyst is added
For the 0.05mol% of component A, insulated and stirred reacts 2h after 70 DEG C are warming up under conditions of inert gas shielding, obtains pre-polymerization
Object；By prepolymer, first curing reaction 5h, curing reaction 3h after being continuously heating to 120 DEG C at 90 DEG C obtain the optical resin
Product；
Wherein the catalyst is azo compound and aminated compounds；It is different that the azo compound is selected from azo two
Butyronitrile；The aminated compounds is selected from N, N- dimethyl cyclohexyl amine.
Embodiment 3
A kind of optical resin product, comprising being 1 by using molar ratio:The polymer that 1.5 component A and component B is obtained,
The component A is multi-thioalcohol compound shown in structural formula (1), and the component B is polyisocyanates, the polyisocyanates choosing
From hexylidene diisocyanate；
Preparing the optical resin product includes：After component A and component B is mixed, catalyst, the dosage of catalyst is added
For the 0.03mol% of component A, insulated and stirred reacts 1.6h after 75 DEG C are warming up under conditions of inert gas shielding, obtains pre-
Polymers；By prepolymer, first curing reaction 4h, curing reaction 2h after being continuously heating to 125 DEG C at 95 DEG C obtain the optics tree
Fat prod；
Wherein the catalyst is organic per-compounds and organo-tin compound；The organic per-compounds were selected from
Aoxidize the combination of two dimethyl isopropyl esters, peroxidating two (2,4- dichloro-benzoyl)；The organo-tin compound is selected from two fourths
The combination of base stannic chloride, stannous octoate.
Embodiment 4
A kind of optical resin product, comprising being 1 by using molar ratio:The polymer that 1.6 component A and component B is obtained,
The component A is multi-thioalcohol compound shown in structural formula (1), and the component B is polyisocyanates, the polyisocyanates choosing
From the combination of tolylene diisocyanate, cyclohexane diisocyanate, different Buddhist ketone diisocyanate；
Preparing the optical resin product includes：After component A and component B is mixed, catalyst, the dosage of catalyst is added
For the 0.04mol% of component A, insulated and stirred reacts 1.6h after 78 DEG C are warming up under conditions of inert gas shielding, obtains pre-
Polymers；By prepolymer, first curing reaction 4h, curing reaction 2.5h after being continuously heating to 128 DEG C at 98 DEG C obtain the optics
Naval stores；
Wherein the catalyst is azo compound and aminated compounds；The azo compound is selected from azo two
(2,4- methyl pentane nitrile)；The aminated compounds is selected from the combination of triethylamine, triethylenediamine.
Optical property detection is carried out respectively to the optical resin product of embodiment 1-4 preparation, wherein transmitance detection is selected
Ultraviolet-visible photometer, is subject to the light transmittance of 550nm；Abbe refractometer is selected in refractive index detection；Heat resistance detection：Using
The measurement of TMA analyzer.As a result as shown in table 1 below：
The performance test results of optical resin product described in 1 embodiment 1-4 of table
| Transmitance (T/%) | Refractive index (nd) | Yellow colour index (YI) | Heat resistance (DEG C) | |
| Embodiment 1 | 83.3 | 1.677 | 1.66 | 121 |
| Embodiment 2 | 84.2 | 1.687 | 1.67 | 120 |
| Embodiment 3 | 82.3 | 1.689 | 1.68 | 122 |
| Embodiment 4 | 82.1 | 1.681 | 1.64 | 124 |
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (9)
1. a kind of optical resin product, which is characterized in that comprising the polymer obtained by using component A and component B, described group
Dividing A is multi-thioalcohol compound shown in structural formula (1), and the component B is polyisocyanates；
2. optical resin product according to claim 1, which is characterized in that the polyisocyanates is selected from sub- dimethylbenzene two
Isocyanates, 3,3 '-dichlorobenzene -4,4 '-diisocyanate, 4,4 '-methyl diphenylene diisocyanates, two isocyanide of hexylidene
The group of one or more of acid esters, tolylene diisocyanate, cyclohexane diisocyanate, different Buddhist ketone diisocyanate
It closes.
3. optical resin product according to claim 1 or 2, which is characterized in that the molar ratio of the component A and component B
It is 1:1.2-1.7.
4. optical resin product according to claim 1-3, which is characterized in that obtained using component A and component B
In polymer process, using organic per-compounds or azo compound and organo-tin compound or aminated compounds as urging
Agent, the dosage of catalyst are the 0.01-0.05mol% of component A.
5. optical resin product according to claim 1-4, which is characterized in that further include UV absorbent, antioxygen
Agent, fade inhibitor or fluorescent dye.
6. optical resin product according to claim 4, which is characterized in that the organic per-compounds are selected from tert-butyl
Peroxidating 2- ethylhexyl carbonate, t-butylperoxyisopropyl carbonic ester, diisopropyl peroxydicarbonate, peroxidating
The combination of one or more of two (2,4- dichloro-benzoyls), diisobutyryl peroxide, benzoyl peroxide；The azo
Class compound is selected from one or more kinds of combinations of azodiisobutyronitrile, azo two (2,4- methyl pentane nitrile)；It is described organic
Tin compound is selected from dibutyl tin dilaurate, dibutyltin chloride, stannous octoate, tin methyltrichloride and trimethyltin chloride
One or more of combination；The aminated compounds is selected from N, N- dimethyl cyclohexyl amine, diethylenetriamine, three ethyl mercaptans
Amine, triethanolamine, N, the combination of one or more of N- di-n-butyl ethanol amine, triethylamine, triethylenediamine.
7. optical resin product according to claim 5, which is characterized in that the UV absorbent be selected from UV-P, UV-O,
In UV-9, UV-531, UV-327, UV-234, UV-326, UV-329, nano-titanium dioxide, nano zine oxide and nano zircite
One or more combinations.
8. a kind of preparation method of optical resin product of any of claims 1-7, which is characterized in that including：It will
After component A and component B mixing, catalyst is added, insulated and stirred is anti-after being warming up to 70-80 DEG C under conditions of inert gas shielding
1-2h is answered, prepolymer is obtained；It is solid after being continuously heating to 120-130 DEG C by the first curing reaction 3-5h at 90-100 DEG C of prepolymer
Change reaction 1-3h, obtains the optical resin product.
9. the preparation method of optical resin product according to claim 8, which is characterized in that the dosage of catalyst is component
The 1-3mol% of A.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111499822A (en) * | 2020-03-19 | 2020-08-07 | 江苏新视客光电科技有限公司 | Polyurethane resin lens with refractive index of 1.70 and preparation method thereof |
| CN113461658A (en) * | 2021-06-15 | 2021-10-01 | 深圳市勇泰运科技有限公司 | High-refraction high-temperature-resistant optical monomer, optical resin and preparation method thereof |
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| CN113461658A (en) * | 2021-06-15 | 2021-10-01 | 深圳市勇泰运科技有限公司 | High-refraction high-temperature-resistant optical monomer, optical resin and preparation method thereof |
| CN113461658B (en) * | 2021-06-15 | 2022-07-01 | 深圳市勇泰运科技有限公司 | High-refraction high-temperature-resistant optical monomer, optical resin and preparation method thereof |
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