CN107400237B - A kind of sulfur-containing polymer of high refractive index and the preparation method and application thereof - Google Patents
A kind of sulfur-containing polymer of high refractive index and the preparation method and application thereof Download PDFInfo
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- CN107400237B CN107400237B CN201610338990.9A CN201610338990A CN107400237B CN 107400237 B CN107400237 B CN 107400237B CN 201610338990 A CN201610338990 A CN 201610338990A CN 107400237 B CN107400237 B CN 107400237B
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- 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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
- C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
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Abstract
The present invention discloses a kind of sulfur-containing polymer and the preparation method and application thereof of high refractive index, belongs to polymeric optical Material Field.The sulfur-containing polymer of the high refractive index has structure shown in formula I or II；The present invention is using ester monomer containing mercaptan carboxylic acid, the triazines containing allyl or silane compound monomer as raw material, the sulfur-containing polymer of high refractive index is prepared by thermal curing method, entire preparation process is simple, the sulfur-containing polymer refractive index being prepared is high, good mechanical property, optical mirror slip, in terms of on application value with higher.
Description
Technical field
The invention belongs to polymeric optical Material Fields, and in particular to a kind of sulfur-containing polymer of high refractive index and its preparation
Method and application.
Background technique
High refractive index optical resin material can reduce the thickness of lens, mitigate quality, realize the lightweight of lens and small
Type.Currently, high refractive index optical resin material mainly include epoxy resin (refractive index 1.5~1.6), it is polysiloxane-based
(refractive index 1.5~1.6), polyurethanes (refractive index 1.55~1.65), sulfur-containing polymer class (refractive index 1.6~1.7), polyamides
Imines (refractive index 1.65~1.75) etc..The base with high molar refraction rate score is introduced in optical material molecular structure
Group, as halogen (bromine, iodine), aromatic ring and the metallic element other than element sulphur, fluorine removal are conducive to improve the refractive index of material.Simultaneously
It must also be taken into account that therefore the transparency and processing performance of material introduce element sulphur and heteroaromatic are to improve polymer light
Learn the ideal approach of Refractive Index of Material.As element sulphur in the sulfur-containing polymer of optical material usually with epithio, thioester bond,
The forms such as thioether bond, sulfuryl exist, and sulfur-containing epoxy resin class, sulfur-containing polyurethane can be divided into from sulfur-containing polymer chemical structure
Class, sulfur-bearing polyimide etc..
101665552 A of Chinese patent CN provides a kind of sulfur-containing polymer optical resin, by the list of six kinds of different components
Body material is prepared, and structure is complicated, refractive index 1.6 or so.101679596 B of Chinese patent CN provides a kind of thermal change
The high sulfur-containing polyurethane class optical resin of shape temperature, monomer material is mainly by diisocyanate cpd and sulfhydryl compound group
At prepared optical resin refractive index is 1.635~1.682, and Abbe number is 27~39, light transmittance about 98%, thermal deformation temperature
92 DEG C~105 DEG C of degree.
2013/0281651 A1 of United States Patent (USP) US provides a kind of novel sulfur-containing polymer, by the metal containing allyl
Organic compound or compound in triazine class monomer are polymerized with the organic compound containing double sulfydryls, refractive index be 1.570~
1.690, Abbe number is 24~45.For example, 5- pentane disulfide thioalcohol is the sulfur-containing polymer folding of raw material preparation with Tetraallylsilane and 1
Penetrating rate is 1.590, Abbe number 41.But double sulfydryl organic compounds used have niff mostly, and are more toxic.
Summary of the invention
For overcome the deficiencies in the prior art and disadvantage, the primary purpose of the present invention is that providing a kind of containing for high refractive index
Sulphur polymer.
Another object of the present invention is to provide the preparation methods of the sulfur-containing polymer of above-mentioned high refractive index.
A further object of the present invention is to provide the applications of the sulfur-containing polymer of above-mentioned high refractive index.
The purpose of the invention is achieved by the following technical solution:
A kind of sulfur-containing polymer of high refractive index has structure shown in formula I or II:
Wherein, n is 5~100；
The preparation method of the sulfur-containing polymer of the high refractive index, comprises the following steps:
Using ester monomer containing mercaptan carboxylic acid, the triazines containing allyl or silane compound monomer as raw material, pass through heat
The sulfur-containing polymer of high refractive index is prepared in solidification method；
The ester monomer containing mercaptan carboxylic acid is preferably four mercaptoacetate of pentaerythrite, (the 3- sulfydryl third of pentaerythrite four
Acid) ester, pentaerythrite four (4- sulfydryl) benzoic ether, trimethylolpropane tris (2- thioacetic acid) ester, trimethylolpropane tris
At least one of (3- mercaptopropionic acid) ester and trimethylolpropane tris (4- sulfydryl) benzoic ether；
Described triazines or silicon class compound monomer containing allyl are preferably tri- -2- acrylic -1,3,5- of 1,3,5-
Triazine -2,4,6 (1H, 3H, 5H)-triketone, 1,3,5- triacryl hexahydro -1,3,5- triazine, 1,3,5- triacryl six
At least one of hydrogen -1,3,5- triazine, Tetraallylsilane and tetra allylic tin；
It is also preferable to include release agents for the raw material；
The release agent be preferably in p isopropylbenzoic acid ester, diisopropyl phosphate, octyl phosphate and dioctylphosphoric acid ester extremely
Few one kind；
The preparation method of the sulfur-containing polymer of the high refractive index, preferably comprises following steps:
(1) raw material ester monomer containing mercaptan carboxylic acid, the triazines containing allyl or silane compound monomer are mixed, anti-
12~48h of pre-polymerization under temperature 50 C~60 DEG C or illumination condition is answered, gluey prepolymer is obtained；
(2) glue prepolymer made from step (1) is first placed under conditions of 20 DEG C~30 DEG C 24~72h, then existed
12~48h is reacted under conditions of 100 DEG C~120 DEG C, obtains the sulfur-containing polymer of high refractive index；
Ester monomer containing mercaptan carboxylic acid described in step (1) and triazines or silane compound monomer containing allyl
Molar ratio is preferably (1:9)~(9:1)；Preferably 1:1.36~1.57:1.
It is also preferable to include release agents for raw material described in step (1)；
The dosage of the release agent is the 0.01%~5% of overall reaction system quality；
Prepolymerization reaction is carried out again after preferably logical nitrogen displaced air after raw material mixing in step (1), and then avoids aoxidizing；
The sulfur-containing polymer of the high refractive index has many advantages, such as that satisfactory mechanical property, refractive index are high, the transparency is good,
Refractive index can reach 1.630 or more；It can be applied to polymeric optical Material Field；Especially optical mirror slip, optical lens,
The fields such as LED encapsulation material.
The present invention compared with the existing technology, have following advantages and effects
(1) present invention is using three of carboxylate and triallyl or tetraallyl containing more sulfydryls (tri-thiol or four sulfydryls)
The optical resin of piperazine class or silane compound reaction preparation high refractive index.In configuration aspects, the carboxylate and triolefin of more sulfydryls
The triazines or silane compound of propyl or tetraallyl reactivity with higher, it is prepared without adding initiator
High refractive index sulfur-containing polymer (high refractive index optical resin) refractive index and light transmittance height, satisfactory mechanical property etc..
(2) certain shortcomings compared with the existing technology, if monomer component is more, structure is complicated, operating procedure is more, anti-
Condition harshness etc. is answered, that the present invention provides a kind of structures is simple, preparation process is simple, reaction condition is easy to accomplish, is easy to scale
The preparation method of the sulfur-containing polymer (high refractive index optical resin) for the high refractive index that metaplasia produces.
(3) sulfur-containing polymer (high refractive index optical resin) of the high refractive index prepared by the present invention can be used for optical frames
The fields such as piece, optical lens, LED encapsulation material.
Detailed description of the invention
Fig. 1 is the infrared figure of the sulfur-containing polymer of high refractive index prepared by embodiment 1.
Specific embodiment
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this.
Reagent used in embodiment is all commercially available conventional reagent or raw material unless stated otherwise.
Embodiment 1
(1) 1.92g (7.7mmol) 1,3,5- tri--is separately added into the 50mL three-neck flask with electric mixing device
- 2,4,6 (1H, 3H, 5H)-triketone of 2- acrylic -1,3,5- triazine, four (3- sulfydryl third of 4.89g (10.2mmol) pentaerythrite
Acid) ester and 0.20g phosphoric acid dipropyl, it stirs evenly, is passed through nitrogen 10min displaced air, seal, illumination, at room temperature pre-polymerization
48h obtains gluey prepolymer；
(2) glue prepolymer made from step (1) is transferred in glass mold, places 72h under conditions of 20 DEG C；So
After be put into vacuum drying oven, vacuumize, the sulfur-containing polymer for obtaining high refractive index for 24 hours reacted at 120 DEG C；
(3) index of refraction of the sulfur-containing polymer of high refractive index made from step (2) and Abbe number are surveyed by Abbe refractometer
Fixed, light transmittance passes through spectrophotometric determination；Its stretching strength determination is executed referring to national standard GB1040-2006 standard, stretches speed
Degree is 10mm/min.
The optical property and mechanical properties results of the sulfur-containing polymer of high refractive index made from embodiment 1 are as shown in table 1:
The optical property and mechanical performance of 1 embodiment of table, 1 gained sulfur-containing polymer
| Refractive index nd | Abbe number | Light transmittance (%) | Tensile strength (MPa) |
| 1.613±0.015 | 38.6±1.8 | 96.2±1.2 | 3.83±0.26 |
The infrared figure of the sulfur-containing polymer of high refractive index prepared by embodiment 1, as shown in Figure 1.As can be known from Fig. 1, mainly
Absorption peak have: 1736cm-1、1686cm-1, C=O, by force；1236cm-1、1143cm-1, C-O-C, by force；1043cm-1, C-S,
It is weak；1349cm-1, C-N, in；2967cm-1、2923cm-1、1461cm-1、1381cm-1、1287cm-1、762cm-1,CH2.Illustrate:
Their position and strength condition and polymer phase seemingly, and in 2550cm-1The absorption for not finding-SH group, 990-
910cm-1Do not find-CH=CH2The absorption of group, so without SH, CH=CH2Group residual.
Embodiment 2
(1) in the 50mL three-neck flask with electric mixing device, it is separately added into 4.98g (20.5mmol) 1,3,5-
- 2,4,6 (1H, 3H, 5H)-triketone of three -2- acrylic -1,3,5- triazines, four (3- sulfydryl of 7.33g (14.9mmol) pentaerythrite
Propionic acid) ester and 0.20g phosphoric acid dipropyl, it stirs evenly, is passed through nitrogen 10min displaced air, seal, pre-polymerization 48h at 50 DEG C is obtained
To gluey prepolymer；
(2) glue prepolymer made from step (1) is transferred in glass mold, is placed for 24 hours under conditions of 30 DEG C；So
After be put into vacuum drying oven, vacuumize, the sulfur-containing polymer for obtaining high refractive index for 24 hours reacted at 120 DEG C；
(3) index of refraction of the sulfur-containing polymer of high refractive index made from step (2) and Abbe number are surveyed by Abbe refractometer
Fixed, light transmittance passes through spectrophotometric determination；Its stretching strength determination is executed referring to national standard GB1040-2006 standard, stretches speed
Degree is 10mm/min.
The optical property and mechanical properties results of the sulfur-containing polymer of high refractive index made from embodiment 2 are as shown in table 2:
The optical property and mechanical performance of 2 embodiment of table, 2 gained sulfur-containing polymer
| Refractive index nd | Abbe number | Light transmittance (%) | Tensile strength (MPa) |
| 1.635±0.010 | 42.4±1.5 | 95.5±1.0 | 4.43±0.22 |
Embodiment 3
(1) in the 50mL three-neck flask with electric mixing device, it is separately added into 5.38g (22.1mmol) 1,3,5-
- 2,4,6 (1H, 3H, 5H)-triketone of three -2- acrylic -1,3,5- triazines, four (3- sulfydryl of 6.93g (14.1mmol) pentaerythrite
Propionic acid) ester and 0.20g phosphoric acid dipropyl, it stirs evenly, is passed through nitrogen 10min displaced air, seal, pre-polymerization 12h at 60 DEG C is obtained
To gluey prepolymer；
(2) glue prepolymer made from step (1) is transferred in glass mold, places 48h under conditions of 25 DEG C；So
After be put into vacuum drying oven, vacuumize, react 48h at 100 DEG C, obtain the sulfur-containing polymer of high refractive index；
(3) index of refraction of the sulfur-containing polymer of high refractive index made from step (2) and Abbe number are surveyed by Abbe refractometer
Fixed, light transmittance passes through spectrophotometric determination；Its stretching strength determination is executed referring to national standard GB1040-2006 standard, stretches speed
Degree is 10mm/min.
The optical property and mechanical properties results of the sulfur-containing polymer of high refractive index made from embodiment 3 are as shown in table 3:
The optical property and mechanical performance of 3 embodiment of table, 3 gained sulfur-containing polymer
| Refractive index nd | Abbe number | Light transmittance (%) | Tensile strength (MPa) |
| 1.621±0.011 | 41.3±1.7 | 95.7±1.1 | 4.38±0.21 |
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of sulfur-containing polymer of high refractive index, it is characterised in that: the sulfur-containing polymer has structure shown in formula I or II:
Formula I；
Formula II；
Wherein, n is 5~100.
2. the preparation method of the sulfur-containing polymer of high refractive index described in claim 1, characterized by comprising the steps of:
Using ester monomer containing mercaptan carboxylic acid, the triazines containing allyl or silane compound monomer as raw material, pass through heat cure
The sulfur-containing polymer of high refractive index is prepared in method.
3. the preparation method of the sulfur-containing polymer of high refractive index according to claim 2, it is characterised in that:
The ester monomer containing mercaptan carboxylic acid is four mercaptoacetate of pentaerythrite, pentaerythrite four (3- mercaptopropionic acid) ester, season
At least one of penta tetrol four (4- sulfydryl) benzoic ether.
4. the preparation method of the sulfur-containing polymer of high refractive index according to claim 2, it is characterised in that:
Described triazines or silane compound monomer containing allyl are tri- triazine-2-2- acrylic-1,3,5- 1,3,5-,
At least one of 4,6 (1H, 3H, 5H)-triketones, 1,3,5- triacryl hexahydro -1,3,5- triazine, Tetraallylsilane.
5. the preparation method of the sulfur-containing polymer of high refractive index according to claim 2, it is characterised in that:
The raw material further includes release agent.
6. the preparation method of the sulfur-containing polymer of high refractive index according to claim 5, it is characterised in that:
The release agent is at least one of p isopropylbenzoic acid ester, diisopropyl phosphate, octyl phosphate and dioctylphosphoric acid ester.
7. the preparation method of the sulfur-containing polymer of high refractive index according to claim 2, it is characterised in that:
The preparation method of the sulfur-containing polymer of the high refractive index, comprises the following steps:
(1) raw material ester monomer containing mercaptan carboxylic acid, the triazines containing allyl or silane compound monomer are mixed, in reaction temperature
12~48 h of pre-polymerization under 50 DEG C~60 DEG C of degree or illumination condition, obtains gluey prepolymer；
(2) glue prepolymer made from step (1) is first placed into 24~72 h under conditions of 20 DEG C~30 DEG C, then 100
DEG C~120 DEG C under conditions of react 12~48 h, obtain the sulfur-containing polymer of high refractive index.
8. the preparation method of the sulfur-containing polymer of high refractive index according to claim 7, it is characterised in that:
Mole of ester monomer containing mercaptan carboxylic acid as described in step (1) and triazines or silane compound monomer containing allyl
Than for (1:9)~(9:1).
9. the preparation method of the sulfur-containing polymer of high refractive index according to claim 7, it is characterised in that:
Raw material as described in step (1) further includes release agent；
The dosage of the release agent is the 0.01%~5% of overall reaction system quality.
10. application of the sulfur-containing polymer of high refractive index described in claim 1 in polymeric optical Material Field.
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| US8470948B2 (en) * | 2009-08-28 | 2013-06-25 | Florida State University Research Foundation, Inc. | High refractive index polymers |
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