CN110452387A - A kind of polysiloxanes of uV curable and its preparation method and application - Google Patents
A kind of polysiloxanes of uV curable and its preparation method and application Download PDFInfo
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- CN110452387A CN110452387A CN201910195350.0A CN201910195350A CN110452387A CN 110452387 A CN110452387 A CN 110452387A CN 201910195350 A CN201910195350 A CN 201910195350A CN 110452387 A CN110452387 A CN 110452387A
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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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
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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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
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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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/392—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing sulfur
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
Abstract
The invention discloses a kind of uV curable polysiloxanes and its preparation method and application.For the polysiloxanes of uV curable of the invention using Si-O-Si as main chain, branch contains aromatic radical, ultraviolet curing group and symmetrical epithio group modified organic silicon material.UV curable polysiloxanes of the invention not only refractive index with higher and light transmittance, have no irritating odor and with organosilicon polymer have good compatibility, but also have good elongation at break, excellent storage stability and mechanical property.Polysiloxanes has optical active group simultaneously, it can further react to obtain the silicone materials of higher refractive index and mechanical property, improve its light extraction efficiency, change heat-seal technique commonly used at present, industrialization efficiency is improved, can be widely applied to fields such as the higher flexible optical fibre of optical material requirement, optical lens, optical coating and flexible display screens.
Description
Technical field
The present invention relates to Functional polymer materials technology fields, more particularly, to a kind of poly- silicon of uV curable
Oxygen alkane and its preparation method and application.
Background technique
With the fast development and application of optical material, optical material product is to high refractive index, high transparency at present
Develop with high reliability direction, especially the application fields such as optical lens, optical glass, optical plastic and fiber optic materials, then wants
Material is asked to have refractive index higher, even as high as 1.7 or more, while also needing that there is good mechanical performance, workability
Deng.The method that high molecular material improves refractive index at present is primarily introduced into the group of high refractive index and small molecule volume, mainly has
Following several method: (1) introducing aromatic compound or fused ring compound, and refractive index, but the polymer dispersion prepared can be improved
Greatly；(2) halogen in addition to f is introduced, but the resin density being prepared increases, weatherability is poor, easy xanthochromia；(3) it introduces
Heavy metal ion such as lead, lanthanum or TiO2, PbS, FeS nanoparticle improves refractive index, and resin density is big, and impact resistance reduces,
Easy xanthochromia, practicability is difficult, there is environmentally friendly limitation；(4) aliphatic polycyclic compound is introduced, refractive index can be improved, and dispersion is lower；
(5) introducing the miscellaneous elements such as sulphur, nitrogen, phosphorus can be improved refractive index.In above-mentioned existing method, introducing element sulphur in polymer is to mention
The most efficient method of high refractive index, element sulphur is usually with thioether, thioesters, thiocarbamate and sulfuryl etc. in polymer
Form introduces.The problem of element sulphur is primarily present is introduced as the easy xanthochromia of product in above-mentioned form in polysiloxanes, introduces difficulty, instead
Answer condition harshness, refractive index promotion effect unobvious, and smell is larger.On the other hand, presently commercially available optics organosilicon material
It is main still to improve refractive index by introducing aromatic structure or Ppolynuclear aromatic mechanism, but the mechanical property of material is often
It is poor, the promotion of its refractive index is limited, to limit it in optical lens, lens materials, optical instrument, LED, flexible light
The application of the high-end fields such as fibre.Wherein, most important application is exactly the encapsulation of great power LED organosilicon, commercially available high folding organosilicon
Packaging plastic generally requires 100 DEG C of several hours or more heat cure, substantially reduces production efficiency, increases production cost, Er Qiechuan
The bi-component LED packaging plastic refractive index of system generally can only achieve 1.54, and it is big that there are viscosity, and colloid itself and colloid and fluorescent powder mix
Unevenness is closed, mechanical deaeration, complex steps, it is difficult to meet the needs of quick automatic production line are needed.High refractive index sulfur-bearing can at present
The cured polysiloxanes research of ultraviolet light is fewer, this is due primarily to the sulfur-bearing that sulfur-bearing monomer is prepared in conjunction with high molecular material
Polysiloxanes has penetrating odor, to greatly limit its industrial application, and organosilicon is introduced in the form of thia ring
In the preparation process of system, the stability of thia ring is poor, it is easy to which open loop during the reaction forms the thioether chain of straight-chain
Section, to increase the high molecular penetrating odor of sulfur-bearing.And organosilicon systems are introduced in the form of structure containing epithio (such as sulfuryl)
In, and the epithio structure of unsymmetric structure, not only there is biggish smell, but also epithio structure is also difficult to be introduced into silicone body
In system, and purity is not high, poor transparency, easy xanthochromia, and poor storage stability is poor with the compatibility of polysiloxanes.Preparation at present
The modified polyorganosiloxane of thia ring mainly uses ultralow temperature grignard reaction method to prepare, very high to experiment condition requirement, and investment is huge,
Industrialized production is difficult, and unstability factor is more, sulphur atom is introduced into relatively difficult in organosilicon systems.The prior art
CN106317898A discloses a kind of photo-curable silicone elastomer and its preparation method and application, which mainly passes through tune
The quantitative proportion of methyl segment and phenyl segment is controlled to promote the mechanical property, hardness and refraction index of organosilicon material, but is rolled over
Optical index is difficult more than 1.55, and optical material higher for optical performance requirements is difficult to use, and smell control, the storage of material
There is not any improvement enlightenment in terms of depositing stability and compatibility, very good solution side can not be provided in response to the above problems
Case.
Therefore, the present invention provides a kind of silicone materials of new uV curable, and material not only can be improved
Refractive index, and have good improvement for compatibility and storage stability, it has advanced optimized Photocurable Silicone Material and has existed
The application of the manufacture of advanced optical device etc. has very important meaning for the performance improvement of silicone photonic material
Justice.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the defects and deficiency of existing polysiloxanes optical material, provide one kind
The polysiloxanes of uV curable introduces ultraviolet curing group and symmetrical epithio group in silicon-oxygen backbone, significantly improves
The refractive index of material, storage stability, compatibility and mechanical property.
It is a further object of the present invention to provide a kind of preparation methods of the polysiloxanes of uV curable.
Another object of the present invention is to provide a kind of polysiloxanes of uV curable in optical material preparation
Using.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A kind of polysiloxanes of uV curable, the structural formula of the polysiloxanes are as follows:
Wherein 0≤a≤5,1≤m≤5,1≤n≤5,3≤b, c≤20,2≤d≤23,0 < e≤10, a, b, c, d, e, m,
N is positive integer,
R1For-CH3Or phenyl；
R2For-CH3；
R3For
R4For-CH3,-CH=CH2Or-H；
R5And R6For containing saturated fat univalence hydrocarbyl, have the saturated carbon chains or H of 1~10 carbon atom；
R7For methacryloxy double bond, epoxy bond or allyl ether, preferably methacrylic acid double bond.
Polysiloxanes of the invention using Si-O-Si as main chain, branch contain aromatic radical, while introduce UV curable group and
Accurate symmetrical epithio group, has no irritating odor, not only refractive index with higher, excellent storage stability and mechanical property
Can, and good compatibility is all had with organosilicon material, it can be used as the additive or synthesis material of organosilicon material.
25 DEG C of refractive index IR ranges of polysiloxanes of the invention be 1.55~1.70 have both simultaneously UV photo-curing rate it is fast,
The features such as low-temperature curable, energy-saving and environmental protection, and have the excellent thermal stability of organosilicon material, corrosion resistance, resistance to oxidation and stablize
Property, hydrophobicity, low-surface-energy, weatherability, non-toxic and tasteless and biocompatibility.
Preferably, the univalence hydrocarbyl of the saturated fat is the alkyl of 1~10 carbon atom.
Preferably, the alkyl of 1~10 carbon atom is methyl, ethyl, propyl, butyl, amyl, hexyl or heptyl.
More preferable methyl and H.
Preferably, the viscosity of the polysiloxanes is 500~20000mPas, and 25 DEG C of refractive index are 1.55~1.70.
A kind of preparation method of the polysiloxanes of above-mentioned uV curable, include the following steps: by carboxyl phenyl silicone oil,
The modified sulfur heterocyclic ring monomer mixing water removal of mixed solvent, catalyst, the agent of sulfur heterocyclic ring monomer stabilization, polymerization inhibitor and photocuring, it is lazy
Property atmosphere under, at 80~90 DEG C react 2~5h, be added inertia moisture absorber, the reaction was continued to acid value < 0.1mg KOH/
G, ice water washing take oil reservoir, and rectifying obtains the polysiloxanes, wherein in epithio heterocyclic monomer in hydroxyl and carboxyl phenyl silicone oil
The molar ratio of carboxyl is 1~2:1.
The polysiloxanes of the uV curable of high refractive index can be prepared by one-pot transesterification in the present invention,
The advantages that raw material is easy to get, preparation method is easy, reaction condition is mild, yield is high and smell is small, meets the requirement of industrialized production.
Preferably, the structural formula of the carboxyl phenyl silicone oil is as follows:
Wherein, R1For-CH3Or phenyl；
R2For-CH3；
R3For
R4For-CH3,-CH=CH2Or-H；
0≤a≤5,3≤b, c≤20, a, b, c are positive integer,
The viscosity of carboxyl phenyl silicone oil is 80~5000mPas, and acid value is 50~350mg KOH/g, 25 DEG C of refractive index n
It is 1.50~1.54.
Wherein the viscosity of carboxyl phenyl silicone oil can be 1350,3300 or 4800mPas, acid value can for 81.6,
139.5 or 177.2.
Preferably, the sulfur heterocyclic ring monomer is the thia ring hydroxylating containing >=2 symmetrical element sulphurs and ultraviolet curing group
Close object, sulfur heterocyclic ring monomer middle hydroxyl value be 125~275mg KOH/g, acrylic double bond degree of unsaturation (iodine number) be 50~
125gI2/100g.Such as sulfur heterocyclic ring monomer middle hydroxyl value can be 126.2,176.2 or 272mg KOH/g, acrylic double bond
Degree of unsaturation (iodine number) can be 123,57.1 or 79.7gI2/100g。
Preferably, the structural formula of the sulfur heterocyclic ring monomer is as follows:
Wherein 1≤m≤5,1≤n≤5,0 < e≤10, e, m, n is positive integer,
R5And R6For containing saturated fat univalence hydrocarbyl, have the saturated carbon chains or H of 1~10 carbon atom；
R7For methacrylic acid double bond, epoxy bond or allyl ether.
It is highly preferred that other atoms are carbon atom, sulfur heterocyclic ring in sulfur heterocyclic ring group in the sulfur heterocyclic ring monomer
Group is the sulfur heterocyclic ring group of saturation.
It is highly preferred that element sulphur has symmetrical six-membered ring structure in sulfur heterocyclic ring hydroxy compounds, and contain a hydroxyl
Group.
Preferably, the mixed solvent includes solvent A and solvent B, and wherein solvent A is insoluble or micro- Yu Shui, boiling point≤110
DEG C solvent, solvent B is miscible with water, the solvent of boiling point≤100 DEG C, and solvent A additional amount is that carboxyl phenyl silicone oil and light are solid
1~3 times for changing modified sulfur heterocyclic ring total monomer weight, solvent B are carboxyl phenyl silicone oil and the modified sulfur heterocyclic ring monomer of photocuring
0.3~0.8 times of total weight parts, and the weight ratio of solvent A and solvent B are 1:2~6.
Preferably, solvent A be toluene, benzene, chloroform, methylene chloride, ethyl acetate, petroleum ether, ether, pentane, naphtha,
The one or more of hexamethylene, n-hexane, carbon tetrachloride, dichloroethanes, trichloroethanes, heptane.
Preferably, solvent B is one or more of methanol, ethyl alcohol, isopropanol, tetrahydrofuran, acetone, butanone.
Preferably, the catalyst is one or more of organotin, organo-bismuth, organic zinc, and catalyst charge is
The 0.05~0.2% of carboxyl phenyl silicone oil and the modified sulfur heterocyclic ring total monomer weight of photocuring.
Wherein organotin can be dibutyl tin dilaurate, two stannous octoates, stannic chloride, stannous chloride, two neodecanoic acids
One or more of stannous methide, 2- methyl thio -4- (tri-n-butyl tin) pyrimidine, Bis(lauroyloxy)dioctyltin etc.；
Organo-bismuth can be one or more of isooctyl acid bismuth, bismuth neodecanoate and lauric acid bismuth etc.；Organic zinc includes neighbour
One or more of sulfonylbenzoylimine zinc and zinc Isoocatanoate etc.；
Organic zinc can be saccharin zinc and/or zinc Isoocatanoate.
Preferably, the catalyst is dibutyl tin dilaurate, two stannous octoates, stannic chloride, one in stannous chloride
Kind.
Preferably, the stabilizer is cyclic thiourea pyrimidine structure, and additional amount is the modified sulfur heterocyclic ring monomer matter of photocuring
The 0.2~1% of amount.Stabilizer can be prevented effectively in sulfurheterocyclic compound primarily as the stabilizer of epithio heterocyclic monomer
Cyclic structure not open loop at high temperature, forms the sulfide based structural of straight-chain, to ensure that in UV modified polyorganosiloxane of the present invention
The stabilization of epithio structure avoids the generation of smell while ensure that high refractive index.
Above stabilizer can be 2- deracil, methylthiouracil, 5- propyl -2- deracil, 5,6- diformazans
Base -- 2- deracil, the miscellaneous nitrogen -2- deracil of 6-, 2- methyl mercapto -4- pyrimidone, 6- phenyl -2- thiouracil, 4- thiocarbamide are phonetic
Pyridine, one or more of 2- paper substrate -4- carboxylic acid etc..
Preferably, polymerization inhibitor is vinyl monomer polymerization inhibitor, and additional amount is that carboxyl phenyl silicone oil and photocuring are modified containing thia
The 1.00~10.00% of ring monomer gross mass.Polymerization inhibitor is the substance for preventing vinyl monomer Raolical polymerizable, this hair
Bright middle addition polymerization inhibitor is primarily to prevent acrylic double bond open loop in (methyl) acrylic acid and its product, to generate gel
Risk.
Above-mentioned polymerization inhibitor can for polymerization inhibitor 701, polymerization inhibitor 705, p-hydroxyanisole, hydroquinone, phenthazine, to uncle
Butyl-catechol, N- nitroso-N-Phenylhydroxylamine aluminium, tert-butyl hydroquinone, 2,4,6- trinitrophenol, 1,4- benzoquinones,
One or more of 2,6- toluene di-tert-butyl phenol etc..
Inertia moisture absorber in the present invention be primarily to the moisture generated in reaction system of constantly going out, from
And improve the reaction speed and conversion ratio of UV modified silane.Inertia moisture absorber is preferably 4A active molecular sieve, anhydrous slufuric acid
One or more of in magnesium, anhydrous calcium oxide etc., additional amount is that carboxyl phenyl silicone oil and the modified sulfur heterocyclic ring monomer of photocuring are total
The 1.00~10.00% of quality.
In the present invention, inert gas can be nitrogen, argon gas etc., preferably nitrogen.
Preferably, the purifying is vacuum distillation purifying, and rectification temperature is 80~90 DEG C, and vacuum degree should maintain -0.095
~-0.10MPa.
A kind of application of the polysiloxanes of above-mentioned uV curable in optical material preparation is also in protection of the invention
Within the scope of.In the synthesis for being applied to prepare organosilicon associated materials, the optical active group of polysiloxanes of the invention is not only
Can obtain the modified polyorganosiloxane of higher refractive index further with polysiloxanes or polyurethane reaction, and can direct photocuring,
Solidification rate is fast, energy-saving and environmental protection.It is excellent for the production higher optical material of optical performance requirements, such as efficient production performance
Optical coating, adhesive, optical glass, optical plastic, LED encapsulation material and optical coating etc., there is far reaching significance.This
The polysiloxanes of invention has good compatibility, is particularly suitable for the excellent UV-LED of efficient production performance and encapsulates, in UV optical fiber
Outer layer coating, UV water resistant coating etc..
Compared with prior art, the beneficial effects of the present invention are:
(1) active group of polysiloxanes of the invention tool uV curable, it can be achieved that quickly under ultraviolet light irradiation
Solidification, green, energy conservation and environmental protection, while symmetrical epithio structure is introduced, while guaranteeing high refractive index, have no irritating odor,
For the superior optical coating of production performance, adhesive, optical glass, optical plastic, LED encapsulation material and optical coating
Deng especially in LED encapsulation, with important application value.
(2) polysiloxanes of high refractive index uV curable of the invention has photo curable group, with organosilicon
Material has good compatibility, can be used as raw material, further the polysiloxanes of reaction preparation higher refractive index and excellent properties
Material changes simultaneously existing heat curing process, using UV curing process, it can be achieved that rapid curing, simplifies curing process,
Curing efficiency is improved, the demand of industrialized production is more suitable for.
(3) polysiloxanes of the invention has excellent storage stability, can store 500 days or more.
(4) polysiloxanes of uV curable of the invention is applied in LED encapsulation, and not only refractive index is high, light transmittance
It is good, and there is excellent mechanical property, phenyl polysiloxane can be substituted completely for LED packaging plastic, improve its light extraction efficiency
Meanwhile changing existing organosilicon packaged type.
(5) polysiloxanes of uV curable of the invention is prepared by one-pot transesterification, preparation process is easy,
Step is simple, high production efficiency, and product is stablized, and at low cost, reaction condition is mild, and smell is low, it can be achieved that industrialized production.
Detailed description of the invention
Fig. 1 is synthetic route chart.
Specific embodiment
The present invention is further illustrated With reference to embodiment, but embodiment the present invention is not done it is any
The restriction of form.Unless otherwise indicated, source chemicals used in the embodiment of the present invention are the source chemicals routinely bought.
The detection method of the embodiment of the present invention and comparative example are as follows:
Gardner Color: it is tested according to GB/T 22295-2008；
Odor strength: it is tested according to GB/T 14675-93；
Refractive index: it is tested by GB/T 6488-2008；
Viscosity: 25 DEG C of dynamic viscosity value is tested by GB/T 10247-1988；
Storage stability: storage period is obtained, and with storage period length using viscosity as index by GB/T 7123.2-2002
Compare its storage stability；
Light transmittance: at 25 DEG C, sample is fitted into the absorption cell of 1cm specification, is tested with ultraviolet-uisible spectrophotometer
Its light transmittance in wavelength 405nm；
Compatibility: by ASTM D6887-2003 (2013) test UV modified polyorganosiloxane and DOW CORNING hydroxy silicon oil PMX-
0156 and DOW CORNING UV bonds silica gel VE-6001 by weight the compatibility of (2:1~6:1).
Ultraviolet light solidification rate: using dry method (indentation method) test is referred to, specific steps: embodiment and comparative example sample are applied
In in defined PET base material, solidify on ultraviolet light curing machine (2 × 5.6KW melts Baoding up to printed board equipment company), with hand
Refer to that light extrusion film is considered as and is fully cured if can not press trace, and fast to measure solidification with conveyer belt transmission speed (m/min)
The size of degree.(reference: Hunan University's master thesis, Xiong Pingfan " development that UV mixes cured offset printing ink "
Embodiment 1
A kind of polysiloxanes C of uV curable223H289Si18O37S10(theoretical value: C 61.08%, H6.60%, O
13.50%, S 7.30%) its structural formula is as follows:
Preparation method are as follows:
Agitating paddle, condenser pipe, N are being housed2In the four-hole bottle of gas feed and thermometer, 68.70g, 0.02mol carboxylic is added
Base phenyl silicone oil, toluene 206.20g, ethyl alcohol 51.55g, two stannous octoate 0.10g, methylthiouracil 0.52g, para hydroxybenzene
Methyl ether 1.03g and photocuring modified sulfur heterocyclic ring monomer 20.60g, 0.1mol, are removed water using division box, are reacted at 90 DEG C
After 2h, it is added 4A molecular sieve (5.15g), after continuing insulation reaction 7h, by testing acid value, as acid value < 0.1mg KOH/g,
It filters, after ice water washes 2 times, takes oil reservoir, reach at -0.095~-0.10MPa and 90 DEG C of temperature after rectifying 0.5h in vacuum degree, obtain
To colorless and transparent dope,
Wherein the structure of carboxyl phenyl silicone oil is as follows:
Refractive index n is 1.535, and viscosity 1350MPas, acid value is 81.6mg KOH/g, and-COOH group molal quantity is
0.1mol,
The structural formula of the modified sulfur heterocyclic ring monomer of photocuring is as follows:
Hydroxyl value: 272mg KOH/g, acrylic double bond (iodine number) content are 123.0g I2/100g ,-OH group molal quantity
For 0.1mol.
To the polysiloxanes C of uV curable223H289Si18O37S10Carry out elemental analysis, infrared analysis and1H-NMR points
Analysis,
Elemental analysis result are as follows: Found:C 60.82%, H 6.45%, O 13.72%, S 7.53%；
IR(cm-1) result are as follows: 2900~2960 (s, υC-H,-CH2,-CH3), 3000~3100 (s, υC-H,-CH=CH2,-
C6H5), 1710 (s, υC=O,-COO-), 1640 (s, δC=C,-CH=CH2), 1600,1590,1495 (s, υC-C,-C6H5), 1400
(m, δSi-C, Si-CH3), 1180 (m, υC-S-C,), 1260 (s, δSi-C, Si-CH3), 1000~1020 (s, υSi-O,
Si-O-Si), 700~800 (s, υSi-C, Si-CH3)。
1H-NMR (δ ppm, CDCl3, 400MHz): 7.35~7.50 (m, 5H, Si-Ph), 5.95~6.00 (m, 2H,), 2.90~3.20 (m, 4H,), 5.80~6.12 (m, 3H ,-CH=CH2), 1.60 (s, 2H ,-
COOCH2), 0~0.30 (m, 3H ,-CH3)。
Embodiment 2
A kind of polysiloxanes C of uV curable567H946Si34O93S30(theoretical value: C 61.02%, H8.48%, O
13.34%, S 8.61%) its structural formula is as follows:
Preparation method are as follows:
Agitating paddle, condenser pipe, N are being housed2In the four-hole bottle of gas feed and thermometer, carboxyl phenyl silicone oil is added
25.33g, 0.0053mol, ethyl acetate (209.43g), ethyl alcohol (27.92g), lauric acid bismuth (0.10g), 2- methyl mercapto -4- are phonetic
The modification sulfur heterocyclic ring monomer of pyridine ketone (0.21g), polymerization inhibitor 701 (0.35g) and uV curable, 44.48g, 0.1mol are adopted
It is removed water with division box, after reacting 5h at 80 DEG C, is added anhydrous magnesium sulfate (1.40g), after continuing insulation reaction 5h, passes through survey
Acid value is tried, as acid value < 0.1mgKOH/g, filters, after ice water washes 2 times, takes oil reservoir, reach -0.095 in vacuum degree~-
At 0.10MPa and 80 DEG C of temperature after rectifying 1h, pale yellow transparent dope is obtained,
Wherein the structure of carboxyl phenyl silicone oil is as follows:
Refractive index n is 1.524, and viscosity 4800mPas, acid value is 177.2mg KOH/g, and-COOH group molal quantity is
0.08moll,
The structural formula of the modified sulfur heterocyclic ring monomer of photocuring is as follows:
Hydroxyl value: 126.20mg KOH/g, double bond (iodine number) content are 57.10gI2/ 100g ,-OH group molal quantity is
0.1mol。
To the polysiloxanes C of uV curable567H946Si34O93S30Carry out elemental analysis, infrared analysis and1H-NMR points
Analysis,
Elemental analysis result are as follows: Found:C 61.46%, H 8.85%, O 12.95%, S 8.48%；
IR(cm-1) result are as follows: 2900~2960 (s, υC-H,-CH2,-CH3), 3000~3100 (s, υC-H,-CH=CH2,-
C6H5), 1720 (s, υC=O,-COO-), 1640 (s, δC=C,-CH=CH2), 1608,1580,1490 (s, υC-C,-C6H5), 1395
(m, δSi-C, Si-CH3), 1200 (m, υC-S-C,), 1256 (s, δSi-C, Si-CH3), 1000~1020 (s, υSi-O,
Si-O-Si), 700~800 (s, υSi-C, Si-CH3)；
1H-NMR (δ ppm, CDCl3, 400MHz): 7.10~7.30 (m, 5H, Si-Ph), 5.90~6.00 (m, 2H,), 2.80~3.20 (m, 4H,), 5.20~5.40 (d, 2H ,-CH=CH-), 2.40 (s, 2H ,-
COOCH2), 1.3~1.6,2.20 (s, 2H ,-CH2), 0~0.30 (m, 3H ,-CH3)。
Embodiment 3
A kind of polysiloxanes C of uV curable354H592Si21O60S20(theoretical value: C 60.44%, H8.42%, O
13.66%, S 9.11%), structural formula is as follows:
Preparation method are as follows:
Agitating paddle, condenser pipe, N are being housed2In the four-hole bottle of gas feed and thermometer, carboxyl phenyl silicone oil is added
24.17g, 0.006mol, n-hexane (56.02g), tetrahydrofuran (16.81g), stannic chloride (0.04g), 6- are miscellaneous, and nitrogen -2- thiocarbamide is phonetic
Modification sulfur heterocyclic ring monomer 31.85g, the 0.1mol of pyridine (0.45g), polymerization inhibitor 705 (0.84g) and uV curable are used
Division box water removal after reacting 3h at 85 DEG C, is added anhydrous calcium oxide (4.50g), after continuing insulation reaction 6h, passes through test
Acid value filters as acid value < 0.1mgKOH/g, after ice water washes 2 times, takes oil reservoir, reach -0.095 in vacuum degree~-
At 0.10MPa and 85 DEG C of temperature after rectifying 0.8h, pale yellow transparent dope is obtained,
Wherein, the structure of carboxyl phenyl silicone oil is as follows:
Refractive index n is 1.5158, and viscosity 3300mPas, acid value is 139.5mg KOH/g, and-COOH group molal quantity is
0.06mol；
The structural formula of modified sulfur heterocyclic ring monomer is as follows:
Hydroxyl value: 176.20mg KOH/g, double bond (iodine number) content are 79.70g I2/ 100g ,-OH group molal quantity is
0.1mol。
To the polysiloxanes C of uV curable354H592Si21O60S20Carry out elemental analysis, infrared analysis and1H-NMR points
Analysis,
Elemental analysis result: Found:C 60.86%, H 8.05%, O 13.15%, S 9.53%；
IR(cm-1): 2900~2960 (s, υC-H,-CH2,-CH3), 3000~3100 (s, υC-H,-CH=CH2,-C6H5),
1715 (s, υC=O,-COO-), 1635 (s, δC=C,-CH=CH2), 1602,1580,1480 (s, υC-C,-C6H5), 1370 (m,
δSi-C, Si-CH3), 747 (s, υC-S-S-C,), 1260 (s, δSi-C, Si-CH3), 1000~1020 (s, υSi-O, Si-
O-Si), 700~800 (s, υSi-C, Si-CH3)；
1H-NMR (δ ppm, CDCl3, 400MHz): 7.30~7.50 (m, 5H, Si-Ph), 5.50~5.60 (m, 2H,), 2.80~3.00 (m, 4H,), 5.0~5.20 (t, 2H ,-CH=CH2), 5.85 (d, 1H ,-CH=
CH2), 2.35 (s, 2H ,-COOCH2), 1.3~1.6,2.10 (s, 2H ,-CH2), 0~0.30 (m, 3H ,-CH3)。
Embodiment 4
A kind of polysiloxanes C of uV curable791H1378Si37O116S40(theoretical value: C 63.10%, H9.16%, O
12.34%, S 8.51%) its structural formula is as follows:
Preparation method are as follows:
Agitating paddle, condenser pipe, N are being housed2In the four-hole bottle of gas feed and thermometer, 29.30g, 0.0028mol is added
Carboxyl phenyl silicone oil, petroleum ether 116.50g, tetrahydrofuran 26.50g, stannous chloride 0.07g, 2- paper substrate -4- carboxylic acid
0.12g, p-tert-Butylcatechol 0.75g and photocuring modified sulfur heterocyclic ring monomer 23.60g, 0.1mol, using division box
Water removal after reacting 4h at 90 DEG C, is added 4A molecular sieve (4.36g), after continuing insulation reaction 5h, by testing acid value, works as acid
When value < 0.1mg KOH/g, filters, after ice water washes 2 times, take oil reservoir, reach -0.095~-0.10MPa and temperature in vacuum degree
At 90 DEG C after rectifying 0.5h, colorless and transparent dope is obtained,
Wherein the structure of carboxyl phenyl silicone oil is as follows:
Refractive index n is 1.508, and viscosity 4550MPas, acid value is 108.12mg KOH/g, and-COOH group molal quantity is
0.055mol,
The structural formula of the modified sulfur heterocyclic ring monomer of photocuring is as follows:
Hydroxyl value: 237.30mg KOH/g, acrylic double bond (iodine number) content are 107.54g I2/ 100g ,-OH group rub
Your number is 0.1mol.
To the polysiloxanes C of uV curable791H1378Si37O116S40Carry out elemental analysis, infrared analysis and1H-NMR
Analysis,
Elemental analysis result are as follows: Found:C 63.25%, H 9.01%, O 12.52%, S 8.75%；
IR(cm-1) result are as follows: 2900~2950 (s, υC-H,-CH2,-CH3), 3000~3150 (s, υC-H,-CH=CH2,-
C6H5), 1720 (s, υC=O,-COO-), 1635 (s, δC=C,-CH=CH2), 1600,1550,1490 (s, υC-C,-C6H5), 1410
(m, δSi-C, Si-CH3), 1200 (m, υC-S-C,), 1256 (s, δSi-C, Si-CH3), 1000~1100 (s, υSi-O,
Si-O-Si), 700~800 (s, υSi-C, Si-CH3)。
1H-NMR (δ ppm, CDCl3, 400MHz): 7.35~7.50 (m, 5H, Si-Ph), 5.95~6.00 (m, 2H,), 2.90~3.20 (m, 4H,), 5.80~6.12 (m, 3H ,-CH=CH2), 1.60 (s, 2H ,-
COOCH2), 1.3~1.5,2.00 (s, 2H ,-CH2), 0~0.30 (m, 3H ,-CH3)。
Comparative example 1
A kind of polysiloxanes C of uV curable223H289Si18O37S10(C 61.08%, H 6.60%, O13.50%,
S 7.30%).
Preparation method is as follows:
Agitating paddle, condenser pipe, N are being housed2In the four-hole bottle of gas feed and thermometer, carboxyl phenyl silicone oil is added
68.70g, 0.02mol, toluene (206.20g), ethyl alcohol (51.55g), two stannous octoates (0.10g), p-hydroxyanisole MEHQ
(1.03g) and photocuring are modified sulfur heterocyclic ring monomer 20.60g, 0.1mol, are removed water using division box, react 2h at 90 DEG C
Afterwards, 4A molecular sieve (5.15g) is added, after continuing insulation reaction 7h, by testing acid value, as acid value < 0.1mg KOH/g, takes out
Filter, after ice water washes 2 times, takes oil reservoir, reaches at -0.095~-0.10MPa and 90 DEG C of temperature after rectifying 0.5h in vacuum degree, obtains
Yellow paste,
Wherein the structural formula of carboxyl phenyl silicone oil is as follows:
Refractive index n is 1.535, and viscosity 1350mPas, acid value is 81.6mg KOH/g, and-COOH group molal quantity is
0.1mol
The structural formula of the modified sulfur heterocyclic ring monomer of photocuring is as follows:
Hydroxyl value:: 272mg KOH/g, acrylic double bond (iodine number) content are 123.0g I2/ 100g ,-OH group mole
Number is 0.1mol.
To the polysiloxanes C of uV curable223H289Si18O37S10Carry out elemental analysis, infrared analysis and1H-NMR points
Analysis,
Through elemental analysis, Found:C 64.22%, H 8.85%, O 8.36%, S 13.26%, with example structure
Theoretical value (C 61.08%, H 6.60%, O 13.50%, S 7.30%) is not consistent；
IR(cm-1): 2900~2960 (s, υC-H,-CH2,-CH3), 3000~3100 (s, υC-H,-CH=CH2,-C6H5),
1710 (s, υC=O,-COO-), 1640 (s, δC=C,-CH=CH2), 1600,1590,1495 (s, υC-C,-C6H5), 1400 (m,
δSi-C, Si-CH3), 670~680 (m, υC-S-C, C-S-C), 1260 (s, δSi-C, Si-CH3), 1000~1020 (s, υSi-O, Si-
O-Si), 700~800 (s, υSi-C, Si-CH3)；
1H-NMR (δ ppm, CDCl3, 400MHz): 7.35~7.50 (m, 5H, Si-Ph), 5.80~6.12 (m, 3H ,-CH=
CH2), 1.60 (s, 2H ,-COOCH2), 0~0.30 (m, 3H ,-CH3)。
As a result it detects
The correlated performance of the polysiloxanes of the uV curable of embodiment and comparative example preparation is detected, detection knot
Fruit is shown in Table 1:
Table 1.
From the data in table 1, it can be seen that the color of the polysiloxanes of uV curable prepared by the present invention is shallower, smell is smaller,
Refractive index is high, and light transmittance is higher, modest viscosity, excellent storage stability, can be seen that and organosilicon and market from compatibility ratio
The polysiloxanes of upper uV curable all has good compatibility, and UV solidification rate is higher, is fully applicable to
On the optical materials such as photo-LED, fiber optic conduction, optical lens and optical coating, and preparation method is simple, reaction condition temperature
With, have wide industrial prospect.
To the Ying Temei fluorescence that 1.5 parts by weight are added in the polysiloxanes of the uV curable of Examples 1 to 3 preparation
Powder, after mixing evenly, vacuum defoamation encapsulate 2835 lamp beads of 0.2W, In using Table top type two-component dispenser ZCX-DJ300
With rate 50.00m/min solidification on ultraviolet light curing machine (2 × 5.6kW melts Baoding up to printed board equipment company), its light is tested
Flux index.And the mechanical property table after pure glue curing is tested, performance table such as table 2.
Using DOW CORNING OE-6665 as matrix resin, OE-6665AB is uniformly mixed by A:B=1:1, obtains matrix silicon tree
Rouge sample.The Ying Temei fluorescent powder of 1.5 parts by weight is added, after mixing evenly, vacuum defoamation, using Table top type two-component dispenser
ZCX-DJ300 encapsulates 2835 lamp beads of 0.2W, forms under the conditions of 100 DEG C × 1h+150 DEG C × 3h, tests its luminous flux and refers to
Mark.And the mechanical property after pure OE-6665 solidifies is tested, measurement result is listed in table 2:
1, hardness
By Examples 1 to 4 and OE-6665, in ultraviolet light curing machine, (2 × 5.6kW melts Baoding up to printing panel device respectively
Company) on rate 50.00m/min solidification and 100 DEG C × 1h+150 DEG C × 3h under the conditions of completion of cure, by GB/T 531-
1999 test its shore hardness；
2, tensile strength
By Examples 1 to 4 and OE-6665, in ultraviolet light curing machine, (2 × 5.6kW melts Baoding up to printing panel device respectively
Company) on rate 50.00m/min solidification and 100 DEG C × 1h+150 DEG C × 3h under the conditions of completion of cure, by GB/T 7753-
2012 are tested；
3, elongation at break
By Examples 1 to 4 and OE-6665, in ultraviolet light curing machine, (2 × 5.6kW melts Baoding up to printing panel device respectively
Company) on rate 50.00m/min solidification and 100 DEG C × 1h+150 DEG C × 3h under the conditions of completion of cure, by GB/T 30776-
2014 are tested.
Table 2
As shown in Table 2, the polysiloxanes of uV curable prepared by the present invention, not only refractive index is high, light transmittance is good, and
And there is excellent mechanical property.Fast-photocurable after dispensing, hardness is high, has excellent performance.After ultraviolet light fast solidification, thoroughly
Light rate is higher.Phenyl polysiloxane can be substituted completely is used for LED packaging plastic, in the case where not sacrificing mechanical property and light transmittance,
Fast-photocurable, industrialization is high-efficient, can be widely applied to the higher flexible optical fibre of optical material requirement, UV-LED, light
The fields such as lens and optical coating in especially high performance LED encapsulation, have far-reaching significance.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention.For those of ordinary skill in the art, may be used also on the basis of the above description
To make other variations or changes in different ways.There is no necessity and possibility to exhaust all the enbodiments.It is all this
Made any modifications, equivalent replacements, and improvements etc., should be included in the claims in the present invention within the spirit and principle of invention
Protection scope within.
Claims (10)
1. a kind of polysiloxanes of uV curable, which is characterized in that the structural formula of the polysiloxanes is as follows:
Wherein 0≤a≤5,1≤m≤5,1≤n≤5,3≤b, c≤20,2≤d≤23,0 < e≤10, a, b, c, d, e, m, n are
Positive integer,
R1For-CH3Or phenyl；
R2For-CH3；
R3For
R4For-CH3,-CH=CH2Or-H；
R5And R6For containing saturated fat univalence hydrocarbyl, have the saturated carbon chains or H of 1~10 carbon atom；
Ultraviolet curing group R7For methacryloxy double bond, epoxy bond or allyl ether.
2. the polysiloxanes of uV curable as described in claim 1, which is characterized in that the univalence hydrocarbyl of the saturated fat
For the alkyl of 1~10 carbon atom.
3. the polysiloxanes of uV curable as described in claim 1, which is characterized in that the alkane of 1~10 carbon atom
Base is methyl, ethyl, propyl, butyl, amyl, hexyl or heptyl.
4. the polysiloxanes of uV curable as described in claim 1, which is characterized in that the viscosity of the polysiloxanes is
500~20000mPas, 25 DEG C of refractive index are 1.55~1.70.
5. a kind of preparation method of the polysiloxanes of uV curable described in Claims 1 to 4 any one, feature exist
In including the following steps: carboxyl phenyl silicone oil, mixed solvent, catalyst, the agent of sulfur heterocyclic ring monomer stabilization, polymerization inhibitor and light
Cured modified sulfur heterocyclic ring monomer mixing removes water, and under inert atmosphere, 2~5h is reacted at 80~90 DEG C, and inertia moisture is added and inhales
Agent is received, the reaction was continued to acid value < 0.1mg KOH/g, and ice water washing takes oil reservoir, and purifying obtains the polysiloxanes, wherein epithio
The molar ratio of hydroxyl and carboxyl in carboxyl phenyl silicone oil is 1~2:1 in heterocyclic monomer.
6. preparation method as claimed in claim 5, which is characterized in that the structural formula of the carboxyl phenyl silicone oil is as follows:
Wherein 0≤a≤5,3≤b, c≤20,2≤d≤20, and a, b, c are positive integer
R1For-CH3Or phenyl；
R2For-CH3
R3For
R4For-CH3,-CH=CH2Or-H；
The viscosity of carboxyl phenyl silicone oil is 80~5000mPas, and acid value is 50~350mg KOH/g, and 25 DEG C of refractive index n are
1.50~1.54.
7. preparation method as claimed in claim 5, which is characterized in that the sulfur heterocyclic ring monomer is containing >=2 symmetrical element sulphurs
And the thia ring hydroxy compounds of ultraviolet curing group, sulfur heterocyclic ring monomer middle hydroxyl value are 125~275mg KOH/g, acrylate
Double bond degree of unsaturation (iodine number) is 50~125gI2/100g。
8. preparation method as claimed in claim 5, which is characterized in that the mixed solvent includes solvent A and solvent B, wherein molten
Agent A is insoluble or micro- Yu Shui, and the solvent of boiling point≤110 DEG C, solvent B is miscible with water, the solvent of boiling point≤100 DEG C, solvent A
Additional amount is 1~3 times of carboxyl phenyl silicone oil and the modified sulfur heterocyclic ring total monomer weight of photocuring, and solvent B is carboxyl phenyl silicon
0.3~0.8 times of oil and the modified sulfur heterocyclic ring total monomer weight part of photocuring, and the weight ratio of solvent A and solvent B be 1:2~
6。
9. preparation method as claimed in claim 5, which is characterized in that the catalyst is organotin, in organo-bismuth, organic zinc
One or more, catalyst charge be the modified sulfur heterocyclic ring total monomer weight of carboxyl phenyl silicone oil and photocuring 0.05~
0.2%.
10. a kind of polysiloxanes of uV curable described in Claims 1 to 4 any one answering in optical material preparation
With.
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