CN107721892A - A kind of thio multi-thiol, preparation method and the application in transparent polyurethane material - Google Patents
A kind of thio multi-thiol, preparation method and the application in transparent polyurethane material Download PDFInfo
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- CN107721892A CN107721892A CN201711044489.2A CN201711044489A CN107721892A CN 107721892 A CN107721892 A CN 107721892A CN 201711044489 A CN201711044489 A CN 201711044489A CN 107721892 A CN107721892 A CN 107721892A
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- thio
- thiol
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- transparent polyurethane
- polyurethane material
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
- C07C321/12—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms
- C07C321/14—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
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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
Abstract
Application the invention discloses a kind of preparation method of thio multi-thiol and its in transparent polyurethane preparation, first, it is higher that sulfur content is obtained by a kind of relatively simple and less pollution method, the larger thio multi-thiol of refractive index, then mixed by suitable method with other auxiliary agents such as chain extender, catalyst, antioxidant, IPDI is added, transparent polyurethane is obtained after stirring deaeration.The method of the present invention is simple, and raw material is easy to get, and without using any organic reagent in S monomer preparation process, mitigates the harm to environment and human body significantly, and obtained polyurethane light transmittance is high, refractive index is high, hardness is big, chemical property is relatively stable.
Description
Technical field
The present invention relates to a kind of thio multi-thiol, preparation method and the application in transparent polyurethane material.
Background technology
Widened with advances in technology with application field, polyurethane becomes Almightiness type polymer, in the world
It is widely used.And the one kind of new transparent polyurethane as polyurethane, the opacity of conventional urethane is overcome, it is heat-resisting
The shortcomings of property is poor, may be used as clear dope, heat-barrier material, optical material etc., is research direction new in recent years.
In recent years, polyurethane is fast-developing in basic research and application and development so that it gets in the application of optical field
Come it is more extensive, and as a most important part in optical material --- the developmental research of optical plastic is especially prominent, very
The multi-field use instead of inorganic optical glass, the research of transparent polyurethane enter practical stage.Traditional inorganic optical glass
Although glass has the advantages that larger index of refraction, relatively low dispersion force, good translucency, but due to glass material fragility ratio itself
Larger, difficulty of processing is larger, easy fragmentation, and these all limit inorganic optical glass in very many applications.With inorganic light
Learn glass to compare, optical plastic has the advantages that processability is good, impact strength is high, cheap.Certainly due to macromolecule material
The material shortcoming such as existing refractivity is poor, hardness is low, wear no resistance, linear expansion coefficient is big, case hardness is low in itself, is limited
Its application in some fields.
Refractive index and dispersion force are the basic performances of optical material, and high refractive low dispersive type polyurethane optical plastic can disappear
Except the aberration of relative aperture optical system, so as to prepare more frivolous, easy processing material.High folding currently used in the market
Penetrate the main makrolon of optical material（Polycarbonate, PC）, acrylic diglycol carbonates（Allyl Diethylene
Glycol Carbonate CR-39）And polymethacrylates（Polymethacrylate, PMMA）Etc. several.Wherein use
Most is CR-39 resin lens, is primarily due to its high refractive index and higher impact resistance.PC has higher refractive power
Rate, but its dispersion is larger；And other two kinds of dispersions are smaller, but index of refraction is also small, the refractive index highest of this kind of optical glass
Only 1.590, and otherwise performance is also not fully up to expectations, so a kind of high performance optical plastic of synthesis turns into optics material
Expect the inexorable trend of development.
Aromatic ring and condensed ring, sulfur-containing group, halogen atom are introduced in the molecular structure（In addition to fluorine atom）, heavy metal ion etc.
Molar refraction is higher, the less group of molecular volume is the method for improving Refractive Index of Material most commonly used at present.
The content of the invention
The monomer higher it is an object of the invention to design a kind of amount containing S, and response type raw material are used as, by simple
Method is added in polyurethane material, so as to obtain a kind of optical resin of high transparency high-refractivity and low-dispersion.In Literature Consult
Process for the monomer containing S of dissymmetrical structure it was found that be rarely reported, and the asymmetry of this molecular structure can be effective
Prevention soft segment（Carbon carbon backbone chain polymer polyatomic alcohol, compliance is preferable, is soft segment in polyurethane backbone.）And hard section
（Formed segment is reacted by isocyanates, chain extender, crosslinking agent on polyurethane molecular main chain, these group cohesive energys are larger,
Spatial volume is larger, rigidity is larger）Crystallization, can largely improve the translucency and refractivity of material.The present invention
Technical solution be：（1）By lot of experimental data such as large database concepts from molecule, electronic horizon, with reference to modern theory
Method, corrects the weak point in experiment in the past, and design synthesizes a kind of new multi-thiol monomer with high index of refraction；
（2）The high refractive properties of element sulphur are combined with the high-intensity performance of polyurethane, sulphur is synthesized by suitable reaction condition
For polyurethane resin, the polymeric optical material of acquisition high-refractivity and low-dispersion rate high intensity.
The first aspect of the invention, there is provided：
A kind of thio multi-thiol, it has such as formula（I）Shown structure：
（I）.
The second aspect of the invention, there is provided：
A kind of preparation method of thio multi-thiol, comprises the following steps：
1st step, the preparation of thio polyol：In the presence of alkali and phase transfer catalyst, using water as solvent, mercaptoethanol is to epoxy
Chloropropane carries out open loop addition, after reaction terminates, carries out product purification, obtains thio polyol；
2nd step, the preparation of polynary thio mercaptan：Under acid catalyst effect, thio polyol and thiocarbamide that the 1st step is obtained react
Isothiuronium salts is obtained, reaction adds alkali after terminating and is hydrolyzed, and takes lower organic layer, carries out product purification, obtain thio more
First mercaptan.
In one embodiment, in the 1st described step, mercaptoethanol, epoxychloropropane, alkali, the weight of phase transfer catalyst
It is 1 to measure ratio：2~3：0.8~1.2：0.1~0.3.
In one embodiment, in the 1st described step, alkali used is NaOH, KOH, NH3•H2O、Na2CO3Etc. therein
A kind of or any several combination.
In one embodiment, in the 1st described step, phase transfer catalyst is triethyl benzyl ammonia chloride, tetrabutyl bromine
Change ammonium, tetrabutylammonium chloride, one kind in 4-butyl ammonium hydrogen sulfate or any several combination.
In one embodiment, in the 1st described step, carry out product purification the step of be first with sour neutralization reaction system
PH to 5~6, redistillation water removal, filter desalination, boil off ethanol.
In one embodiment, in the 1st described step, reaction is carried out under ice-water bath, and reaction temperature is less than 10 DEG C.
In one embodiment, in the 2nd described step, thio polyol, the weight ratio of thiocarbamide are 1：0.7~1.3, reaction
Temperature is 100~120 DEG C.
In one embodiment, in the 2nd described step, acid catalyst be hydrochloric acid, sulfuric acid, nitric acid, one kind in phosphoric acid or
Several any combination of person.
In one embodiment, in the 2nd described step, carry out product purification the step of be that first reactant is carried out with hydrochloric acid
Acidifying, then water and ethanol washed product are used successively, vacuum distillation removes solvent and small-molecule substance.
The third aspect of the invention, there is provided：
A kind of transparent polyurethane material, it is to be cross-linked with each other to obtain by thio multi-thiol and isocyanates, PPG.
The fourth aspect of the invention, there is provided：
The preparation method of transparent polyurethane material, comprises the following steps：
After thio multi-thiol is mixed with isocyanates, PPG, chain extender and auxiliary agent, after being well mixed, microwave is high
Fire preheating 2min, mechanical agitation is reacted, then is poured into after vacuum defoamation in mould, and solidification at room temperature obtains water white transparency
Polyurethane.
The mass percent of each raw material of transparent polyurethane material is：Thio multi-thiol 10~20%, isocyanates 30
~50%, PPG 25~40%, chain extender 1~10%, auxiliary agent 1~3%.
Described isocyanates is IPDI（IPDI）, hexamethylene diisocyanate（HDI）, two rings
Hexyl methane diisocyanate（H12MDI）In one kind or any combination.
Described PPG is one kind or any combination in PPG2000, PPG3000, PEG2000, PEG300.
Described small molecule chain extension-crosslinking agent be BDO, ethylene glycol, diglycol, tetraethylene-glycol,
One kind or any several combinations in 1,2-PD, 1,3-BDO, trimethylolpropane.
Described auxiliary agent includes catalyst, mould inhibitor, defoamer, antioxidant, one kind in ultra-violet absorber or appointed
Anticipate several combinations.
The fifth aspect of the invention, there is provided：
Application of the thio multi-thiol in transparent polyurethane material is prepared.
Beneficial effect
（1）By the understanding to bibliography and the summary to testing in the past, select sulfhydryl compound and thiocarbamide former as reaction
Material, obtains the higher monomer of amount containing S, simple to operate, reaction condition is gentle, to equipment requirement not by simple substitution reaction
Height, it is adapted to industrialized production.（2）The monomer containing S for being designed and being prepared using molecular theory, S contents, not only can be with more than 60%
Largely improving the refractive index of polyurethane reduces dispersion force, and the asymmetry of molecular structure, can be largely
The upper microphase-separated for preventing polyurethane soft segment and hard section.（3）The molecule utilization rate of raw material is higher in preparation process, most of conversion
For product, accessory substance is the nontoxic inorganic salts of environment, meets the theory of Green Chemistry.（4）The process of synthesis of polyurethane
Simply, it is easily enlarged production.
Brief description of the drawings
Fig. 1 is the mass spectrogram of thio polyol in embodiment 1
Fig. 2 is the infrared spectrum of thio polyol in embodiment 1
Fig. 3 is the mass spectrogram of thio multi-thiol in embodiment 1
Fig. 4 is the infrared spectrum of thio multi-thiol in embodiment 1
Embodiment
The present invention is described in further detail below by embodiment.But those skilled in the art will manage
Solution, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.Unreceipted specific skill in embodiment
Art or condition person, carried out according to the technology described by document in the art or condition or according to product description.Examination used
Agent or the unreceipted production firm person of instrument, being can be by the conventional products of acquisition purchased in market.
" one embodiment " for addressing in this manual, " another embodiment ", " embodiment " etc., are referred to
With reference to the specific features of embodiment description, structure or it is included at least one embodiment of the application generality description.
It is not necessarily to refer to same embodiment that statement of the same race, which occur, in multiple places in the description.Furthermore, it is understood that with reference to any
When embodiment describes a specific features, structure or feature, what is advocated is to combine other embodiment to realize this spy
Sign, structure or feature also fall in the application scope of the claimed.
Word " comprising " used herein, "comprising", " having " or its any other variant are intended to cover non-exclusionism
Including.Technique, method, article or the equipment for e.g., including listing key element are not necessarily limited by those key elements, but can include
Other are not expressly set out or belonged to this technique, method, article or the intrinsic key element of equipment.
Heretofore described percentage refers to mass percent in the case of without special instruction.
The invention provides a kind of thio multi-thiol, and it can significantly improve the property of transparent polyurethane material as monomer
Can, thio multi-thiol has such as formula（I）Structure.
（I）.
Its preparation methods steps are：（1）In the presence of alkali and phase transfer catalyst, using water as solvent, under ice-water bath, use
Mercaptoethanol carries out open loop addition to epoxychloropropane, after reaction terminates, adds the pH of sour neutralization reaction system, and distillation removes water,
Suction strainer desalination, boils off ethanol, obtains thio polyol.（2）, will under acid catalyst effect（1）Middle product and the thiocarbamide of metering exist
Reaction obtains isothiuronium salts under certain temperature, and reaction adds basic hydrolysis, mechanical agitation, extracts lower organic layer, obtain after terminating
To thio multi-thiol crude product.Obtained crude product is first acidified with hydrochloric acid, and three times, absolute ethyl alcohol washes one for 70 DEG C of deionization washings
It is secondary, it is evaporated under reduced pressure, removes small molecule and obtain thio multi-thiol.
In one embodiment, in the 1st described step, mercaptoethanol, epoxychloropropane, alkali, the weight of phase transfer catalyst
It is 1 to measure ratio：2~3：0.8~1.2：0.1~0.3.Alkali used is NaOH, KOH, NH3•H2O、Na2CO3Etc. therein a kind of or
Any several combination.Phase transfer catalyst is triethyl benzyl ammonia chloride, TBAB, tetrabutylammonium chloride, four fourths
One kind or any several combination in base ammonium hydrogen sulfate.The step of carrying out product purification is first with the pH of sour neutralization reaction system
To 5~6, redistillation water removal, filter desalination, boil off ethanol.Reaction is carried out under ice-water bath, and reaction temperature is less than 10 DEG C.
In one embodiment, in the 2nd described step, thio polyol, the weight ratio of thiocarbamide are 1：0.7~1.3, reaction
Temperature is 100~120 DEG C.Acid catalyst is one or several kinds of any combination in hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid.Carry out
The step of product purification is that first reactant is acidified with hydrochloric acid, then is removed successively with water and ethanol washed product, vacuum distillation
Solvent and small-molecule substance.
Above-mentioned thio multi-thiol can obtain transparent polyurethane material after being cross-linked with each other with isocyanates, PPG
Material.
The preparation method of transparent polyurethane material, comprises the following steps：
After thio multi-thiol is mixed with isocyanates, PPG, chain extender and auxiliary agent, after being well mixed, microwave is high
Fire preheating 2min, mechanical agitation is reacted, then is poured into after vacuum defoamation in mould, and solidification at room temperature obtains water white transparency
Polyurethane.The mass percent of each raw material of transparent polyurethane material is：Thio multi-thiol 3~6%, isocyanates 40
~50%, PPG 30~40%, chain extender 1~10%, auxiliary agent 1~3%.Described isocyanates is the isocyanide of isophorone two
Acid esters（IPDI）, hexamethylene diisocyanate（HDI）, hydrogenated diphenyl methane diisocyanate（H12MDI）In one kind or
Any combination.Described PPG is one kind or any combination in PPG2000, PPG3000, PEG2000, PEG300,
The end group of polyethylene glycol can also be modified using active group, to improve the physical properties such as the hardness of material, impact resistance.
Described small molecule chain extension-crosslinking agent is BDO, ethylene glycol, diglycol, tetraethylene-glycol, 1,2- the third two
One kind or any several combinations in alcohol, 1,3-BDO, trimethylolpropane.Described auxiliary agent include catalyst, mould inhibitor,
One kind or any several combinations in antioxidant, ultra-violet absorber.Small molecule chain extension-crosslinking agent used is Isosorbide-5-Nitrae-fourth two
Alcohol, ethylene glycol, diglycol, tetraethylene-glycol, 1,2-PD, 1,3-BDO, trimethylolpropane etc. are wherein
One kind or any several combinations.Auxiliary agent used is catalyst, defoamer, antioxidant, ultra-violet absorber, and catalyst is
Organic tin compound, including dibutyl tin laurate, acetic acid dibutyl, two (dodecyl sulphur) dibutyl tins；Antioxidant
For 2,6- toluene di-tert-butyl phenols；Defoamer can be polysiloxane defoaming agent；Ultra-violet absorber is N-（Ethoxy carbonyl
Phenyl）- N '-methyl-N '-phenyl formamidine（UV-1）.
The preparation of 1 thio multi-thiol of embodiment
The preparation of thio polyol：
（1）Accurately weigh 10g NaOH, triethyl benzyl ammonia chloride（TEBA）2g, 250 ml tri- are transferred to after the dissolving of 40 ml water
In mouth flask；（2）Three-necked flask is placed in ice-water bath, treats that temperature is dropped to less than 5 DEG C, adds 9.75 g 2 mercapto ethanols, machine
Tool stirs, and controls the temperature of mixed solution in reactor to be less than 10 DEG C, 23 g epoxychloropropane are added dropwise.（3）TLC monitor to
Raw material reacts completely, using mixed solution after concentrated hydrochloric acid neutralization reaction to pH=5-6, is evaporated under reduced pressure, removes small molecule, filters
Desalination, obtain the transparency liquid of 17.2 g no color or smells, yield 64.9%.
The mass spectrogram of thio polyol is as shown in figure 1, infrared spectrogram is as shown in Figure 2.
1H NMR characterization results：（400MHz, D2O） δ 3.82-3.77 （M, 1H）, 3.61（T, J=6.4 Hz, 4H）,
2.75（D, J=4.8 Hz, 1H）, 2.71（D, J=8.8 Hz, 1H）, 2.64（T, J=13.6 Hz, 4H）, 2.57（The Hz of d, J=6.4,
1H）.
The preparation of thio multi-thiol：
（1）Product 10.6g sequentially adds 11.7g thiocarbamides and 30ml hydrochloric acid in three-necked flask in taking 1, is rapidly heated to 110
DEG C, TLC, which is monitored to reaction, to be terminated.（2）Reaction is cooled to 60 DEG C after terminating, the lower addition 20wt% NaOH of nitrogen protection are neutralized to molten
Liquid alkalescent pH8~9,1h is hydrolyzed under nitrogen atmosphere, stop stirring, stratification, remove a layer organic phase, obtain thio polynary sulphur
Alcohol crude product.（3）Reacting coarse product is extracted using 3 × 30 ml ethanol, merges extraction phase, is evaporated under reduced pressure and is removed small molecule, obtains
The g of thio multi-thiol 10.13 of water white transparency, yield 78%.
The mass spectrogram of thio more sulphur member alcohol is as shown in figure 3, infrared spectrogram is as shown in Figure 4.
1H NMR characterization results：（400 MHz, CDCl3） δ 2.99-2.94（M, 1H）, 2.91（T, J=8 Hz, 4H）,
2.82（T, J=6.8 Hz, 4H）,2.76（D, J=6.8 Hz, 4H）, 1.81（S, 3H）.
The preparation of 2 thio multi-thiol of embodiment
The preparation of thio polyol：
（1）Accurately weigh 12g NaOH, triethyl benzyl ammonia chloride（TEBA）2.4g, 250 ml are transferred to after the dissolving of 50 ml water
In three-necked flask；（2）Three-necked flask is placed in ice-water bath, treats that temperature is dropped to less than 5 DEG C, adds 9.00 g 2 mercapto ethanols,
Mechanical agitation, control the temperature of mixed solution in reactor to be less than 10 DEG C, 25 g epoxychloropropane are added dropwise.（3）TLC is monitored
Reacted completely to raw material, using mixed solution after concentrated hydrochloric acid neutralization reaction to pH=5-6, be evaporated under reduced pressure, remove small molecule, take out
Salt is filtered out, obtains the transparency liquid of 16.8 g no color or smells, yield 60.2%.
The structural characterization result of thio polyol is the same as embodiment 1.
The preparation of thio multi-thiol：
（1）Product 10.8g sequentially adds 12.4g thiocarbamides and 40ml hydrochloric acid in three-necked flask in taking 1, is rapidly heated to 115
DEG C, TLC, which is monitored to reaction, to be terminated.（2）Reaction is cooled to 65 DEG C after terminating, the lower addition 20wt% NaOH of nitrogen protection are neutralized to molten
Liquid alkalescent pH8~9,1h is hydrolyzed under nitrogen atmosphere, stop stirring, stratification, remove a layer organic phase, obtain thio polynary sulphur
Alcohol crude product.（3）Reacting coarse product is extracted using 3 × 30 ml ethanol, merges extraction phase, is evaporated under reduced pressure and is removed small molecule, obtains
The thio multi-thiol 9.98g of water white transparency, yield 74%.
The structural characterization result of thio more sulphur member alcohol is the same as embodiment 1.
The preparation of 3 thio multi-thiol of embodiment
The preparation of thio polyol：
（1）Accurately weigh 8g NaOH, triethyl benzyl ammonia chloride（TEBA）1.8g, 250 ml tri- are transferred to after the dissolving of 35 ml water
In mouth flask；（2）Three-necked flask is placed in ice-water bath, treats that temperature is dropped to less than 5 DEG C, adds 10.05g 2 mercapto ethanols, machine
Tool stirs, and controls the temperature of mixed solution in reactor to be less than 10 DEG C, 26 g epoxychloropropane are added dropwise.（3）TLC monitor to
Raw material reacts completely, using mixed solution after concentrated hydrochloric acid neutralization reaction to pH=5-6, is evaporated under reduced pressure, removes small molecule, filters
Desalination, obtain the transparency liquid of 18.1 g no color or smells, yield 68.4%.
The structural characterization result of thio polyol is the same as embodiment 1.
The preparation of thio multi-thiol：
（1）Product 11.0g sequentially adds 13.5g thiocarbamides and 30ml hydrochloric acid in three-necked flask in taking 1, is rapidly heated to 105
DEG C, TLC, which is monitored to reaction, to be terminated.（2）Reaction is cooled to 60 DEG C after terminating, the lower addition 20wt% NaOH of nitrogen protection are neutralized to molten
Liquid alkalescent pH8~9,1h is hydrolyzed under nitrogen atmosphere, stop stirring, stratification, remove a layer organic phase, obtain thio polynary sulphur
Alcohol crude product.（3）Reacting coarse product is extracted using 3 × 30 ml ethanol, merges extraction phase, is evaporated under reduced pressure and is removed small molecule, obtains
The g of thio multi-thiol 10.78 of water white transparency, yield 80.1%.
The structural characterization result of thio more sulphur member alcohol is the same as embodiment 1.
The preparation of the transparent polyurethane of embodiment 4
Using the thio multi-thiol in embodiment 1, the 35g of BDO 8g, PPG 2000, thio multi-thiol 15g parts are taken
In three-necked flask, catalyst 0.4g, antioxidant 0.4g, ultraviolet absorber 0.4g, mould inhibitor 0.4g, defoamer 0.4g are added,
IPDI is added after 105 DEG C of vacuum dehydration 2h（IPDI）40g, after being well mixed, the high fire preheating 2min of microwave,
Discharge, 50 DEG C of min of vacuum drying chamber deaeration 20, take out in the mould after pouring into preheating, room temperature after mechanical agitation to certain viscosity
Lower curing molding, obtains transparent polyurethane.
The preparation of the transparent polyurethane of embodiment 5
Using the thio multi-thiol in embodiment 2, the g of ethylene glycol 3g, PEG 300 40, thio multi-thiol 10g parts are taken in three
In mouthful flask, catalyst 0.5g, antioxidant 0.3g, ultraviolet absorber 0.3g, mould inhibitor 0.5g, defoamer 0.4g are added, 115 DEG C
IPDI is added after vacuum dehydration 2h（IPDI）45g, after being well mixed, the high fire preheating 2min machineries of microwave stir
Discharged after mixing to certain viscosity, 55 DEG C of min of vacuum drying chamber deaeration 25, take out in the mould after pouring into preheating, solidify at room temperature
Shaping, obtains transparent polyurethane.
The preparation of the transparent polyurethane of embodiment 6
Using the thio multi-thiol in embodiment 2, take the 30g of ethylene glycol 10g, PEG 2000, thio multi-thiol 12g parts in
In three-necked flask, catalyst 0.4g, antioxidant 0.4g, ultraviolet absorber 0.4g, mould inhibitor 0.4g, defoamer 0.4g are added, 110
IPDI is added after DEG C vacuum dehydration 1h（IPDI）46g, after being well mixed, the high fire preheating 2min machineries of microwave
Discharge, 60 DEG C of min of vacuum drying chamber deaeration 15, take out in the mould after pouring into preheating after stirring to certain viscosity, it is solid at room temperature
Chemical conversion type, obtains transparent polyurethane.
The preparation of the transparent polyurethane of embodiment 7
Using the polyethylene glycol of maleate end group as urethane raw in the present embodiment.Preparation method is：By PEG2000 with
Maleic anhydride is according to weight than 4：1 mixing, using toluene as water entrainer and solvent, reacts 7h in nitrogen atmosphere at 170 DEG C,
After product is cooled to room temperature, product has obtained modified PE G2000 after water washing.
Using the thio multi-thiol in embodiment 2, ethylene glycol 10g, the 30g of modified PE G 2000, thio multi-thiol are taken
12g parts add catalyst 0.4g, antioxidant 0.4g, ultraviolet absorber 0.4g, mould inhibitor 0.4g, defoamer in three-necked flask
IPDI is added after 0.4g, 110 DEG C of vacuum dehydration 1h（IPDI）46g, after being well mixed, the high fire preheating of microwave
Discharge, 60 DEG C of min of vacuum drying chamber deaeration 15, take out in the mould after pouring into preheating after 2min mechanical agitations to certain viscosity,
Curing molding at room temperature, obtain transparent polyurethane.
The characterization result of transparent polyurethane material prepared by above example is as follows：
As can be seen from the above table, the transparent polyurethane material that prepared by the present invention has higher transmitance and relatively low refractive index
（nd）, while also there is preferable hardness and impact resistance.
Claims (10)
1. a kind of thio multi-thiol, it is characterised in that it has such as formula（I）Shown structure：
（I）.
2. the preparation method of the thio multi-thiol described in claim 1, it is characterised in that comprise the following steps：
1st step, the preparation of thio polyol：In the presence of alkali and phase transfer catalyst, using water as solvent, mercaptoethanol is to epoxy
Chloropropane carries out open loop addition, after reaction terminates, carries out product purification, obtains thio polyol；
2nd step, the preparation of polynary thio mercaptan：Under acid catalyst effect, thio polyol and thiocarbamide that the 1st step is obtained react
Isothiuronium salts is obtained, reaction adds alkali after terminating and is hydrolyzed, and takes lower organic layer, carries out product purification, obtain thio more
First mercaptan.
3. the preparation method of thio multi-thiol according to claim 2, it is characterised in that in the 1st described step, sulfydryl
Ethanol, epoxychloropropane, alkali, the weight ratio of phase transfer catalyst are 1：2~3：0.8~1.2：0.1~0.3；The 1st described step
In, alkali used is NaOH, KOH, NH3•H2O、Na2CO3Etc. therein a kind of or any several combination；The 1st described step
In, phase transfer catalyst is in triethyl benzyl ammonia chloride, TBAB, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate
One kind or any several combination.
4. the preparation method of thio multi-thiol according to claim 2, it is characterised in that in the 1st described step, carry out
The step of product purification is first redistillation water removal, to be filtered desalination with the pH to 5~6 of sour neutralization reaction system, boil off ethanol；Institute
In the 1st step stated, reaction is carried out under ice-water bath, and reaction temperature is less than 10 DEG C.
5. the preparation method of thio multi-thiol according to claim 2, it is characterised in that thio in the 2nd described step
Polyalcohol, the weight ratio of thiocarbamide are 1：0.7~1.3, reaction temperature is 100~120 DEG C；In the 2nd described step, acid catalyst is
One or several kinds of any combination in hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid；In the 2nd described step, the step of product purification is carried out
Suddenly it is that first reactant is acidified with hydrochloric acid, then uses water and ethanol washed product successively, vacuum distillation removes solvent and small molecule
Material.
6. a kind of transparent polyurethane material, it is characterised in that be as the thio multi-thiol and isocyanic acid described in claim 1
Ester, PPG are cross-linked with each other to obtain.
7. the preparation method of the transparent polyurethane material described in claim 6, it is characterised in that comprise the following steps：Will be thio
After multi-thiol mixes with isocyanates, PPG, chain extender and auxiliary agent, after being well mixed, the high fire preheating 2min of microwave,
Mechanical agitation is reacted, then is poured into after vacuum defoamation in mould, and solidification at room temperature obtains the polyurethane of water white transparency.
8. the preparation method of transparent polyurethane material according to claim 7, it is characterised in that transparent polyurethane material
The mass percent of each raw material is：Thio multi-thiol 10~20%, isocyanates 30~50%, PPG 25~40%,
Chain extender 1~10%, auxiliary agent 1~3%.
9. the preparation method of transparent polyurethane material according to claim 8, it is characterised in that described isocyanates is
IPDI（IPDI）, hexamethylene diisocyanate（HDI）, dicyclohexyl methyl hydride diisocyanate
（H12MDI）In one kind or any combination；Described PPG is in PPG2000, PPG3000, PEG2000, PEG300
One kind or any combination；Described small molecule chain extension-crosslinking agent is BDO, ethylene glycol, diglycol, three contractings
One kind or any several combinations in tetraethylene glycol, 1,2-PD, 1,3-BDO, trimethylolpropane；Described auxiliary agent
Including one kind in catalyst, mould inhibitor, defoamer, antioxidant, ultra-violet absorber or any several combinations.
10. application of the thio multi-thiol in transparent polyurethane material is prepared described in claim 1.
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