CN107721892B - Thio-polythiol, preparation method and application in transparent polyurethane material - Google Patents
Thio-polythiol, preparation method and application in transparent polyurethane material Download PDFInfo
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- CN107721892B CN107721892B CN201711044489.2A CN201711044489A CN107721892B CN 107721892 B CN107721892 B CN 107721892B CN 201711044489 A CN201711044489 A CN 201711044489A CN 107721892 B CN107721892 B CN 107721892B
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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
The invention discloses a preparation method of thio-polythiol and application thereof in preparation of transparent polyurethane. The method is simple, the raw materials are easy to obtain, no organic reagent is used in the preparation process of the S monomer, the harm to the environment and the human body is greatly reduced, and the prepared polyurethane has high light transmittance, high refractive index, high hardness and stable chemical properties.
Description
Technical Field
The invention relates to a thio-polythiol, a preparation method and application thereof in a transparent polyurethane material.
Background
With the progress of technology and the widening of application fields, polyurethane becomes a versatile polymer and is widely used in the global range. The novel transparent polyurethane is one of polyurethanes, overcomes the defects of poor opacity and heat resistance of the traditional polyurethane, can be used as transparent coating, heat insulation materials, optical materials and the like, and is a new research direction in recent years.
In recent years, polyurethane is rapidly developed in basic research and application development, so that the application of polyurethane in the optical field is more and more extensive, the development and research of optical plastics, which is the most important part of optical materials, is particularly prominent, the polyurethane is used in many fields to replace inorganic optical glass, and the research of transparent polyurethane is in the practical stage. Although the traditional inorganic optical glass has the advantages of larger refractive index, lower dispersion force, good light transmission and the like, the glass material has larger brittleness, larger processing difficulty and easy cracking, and the application of the inorganic optical glass in many aspects is limited. Compared with inorganic optical glass, the optical plastic has the advantages of good processability, high impact strength, low price and the like. The polymer material has the defects of poor refractivity, low hardness, poor wear resistance, large linear expansion coefficient, low surface hardness and the like, so that the application of the polymer material in certain fields is limited.
The refractive index and the dispersion force are basic performances of the optical material, and the high-refraction low-dispersion polyurethane optical plastic can eliminate chromatic aberration of a relative aperture optical system, so that a lighter, thinner and easier-to-process material is prepared. The high refractive optical materials currently used in the market include Polycarbonate (PC), Allyl diethylene glycol Carbonate (CR-39), and Polymethacrylate (PMMA). Of these, CR-39 resin lenses are most used mainly because of its high refractive index and high impact resistance. PC has higher refractive index, but has larger chromatic dispersion; the other two types of optical glass have small dispersion but small refractive index, the highest refractive index of the optical glass is only 1.590, and the performance of the optical glass in other aspects is not satisfactory, so that the synthesis of a high-performance optical plastic becomes an inevitable trend in the development of optical materials.
The introduction of aromatic ring and condensed ring, sulfur-containing group, halogen atom (except fluorine atom), heavy metal ion with higher equimolar refractivity and smaller molecular volume into the molecular structure is the most used method for improving the refractive index of the material at present.
Disclosure of Invention
The invention aims to design a monomer with high S content, which is used as a reaction type raw material and added into a polyurethane material by a simple method, thereby obtaining an optical resin with high transparency, high refractive index and low dispersion. In the process of consulting documents, the fact that S-containing monomers with asymmetric structures are rarely reported, and the asymmetry of the molecular structure can effectively prevent crystallization of soft segments (carbon-carbon main chain polymer polyol is good in flexibility and is a flexible segment in a polyurethane main chain) and hard segments (segments formed by reaction of isocyanate, a chain extender and a cross-linking agent on a polyurethane molecular main chain, and the groups have large cohesive energy, large space volume and high rigidity), so that the light transmittance and the refractive index of the material can be improved to a great extent. The technical solution of the invention is as follows: (1) the method is characterized in that a novel polythiol monomer with high refractive index is designed and synthesized by combining a modern theoretical method through a large amount of experimental data such as a large database and the like on the molecular and electronic level and correcting the defects in the previous experiment; (2) the high refractive property of sulfur element and the high strength performance of polyurethane are combined, and the thiopolyurethane resin is synthesized through proper reaction conditions to obtain the polymer optical material with high refractive index, low dispersion and high strength.
In a first aspect of the present invention, there is provided:
a thiopolythiol having the structure shown in formula (I):
in a second aspect of the present invention, there is provided:
a preparation method of thio-polythiol comprises the following steps:
In one embodiment, in the step 1, the weight ratio of mercaptoethanol, epichlorohydrin, base and phase transfer catalyst is 1: 2-3: 0.8-1.2: 0.1 to 0.3.
In one embodiment, the base used in step 1 is NaOH, KOH or NH3•H2O、Na2CO3And the like, or a combination of any of them.
In one embodiment, in step 1, the phase transfer catalyst is one or a combination of any of triethylbenzylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride and tetrabutylammonium hydrogen sulfate.
In one embodiment, in the step 1, the step of purifying the product is to neutralize the pH of the reaction system to 5-6 with an acid, and then to remove water by distillation, remove salts by suction filtration, and evaporate ethanol.
In one embodiment, the reaction is carried out in an ice-water bath at a temperature of less than 10 ℃ in step 1.
In one embodiment, in the step 2, the weight ratio of the thiopolyol to the thiourea is 1: 0.7-1.3, and the reaction temperature is 100-120 ℃.
In one embodiment, in the step 2, the acid catalyst is one or any combination of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid.
In one embodiment, the step 2 of purifying the product comprises acidifying the reactant with hydrochloric acid, washing the product with water and ethanol in sequence, and distilling under reduced pressure to remove the solvent and the small molecular substances.
In a third aspect of the present invention, there is provided:
a transparent polyurethane material is prepared from thiopolythiol, isocyanate and polyether polyol through cross-linking.
In a fourth aspect of the present invention, there is provided:
the preparation method of the transparent polyurethane material comprises the following steps:
mixing the thiopolythiol with isocyanate, polyether glycol, a chain extender and an auxiliary agent, uniformly mixing, preheating for 2min by microwave high fire, mechanically stirring for reaction, pouring into a mold after vacuum defoaming, and curing at room temperature to obtain the colorless and transparent polyurethane.
The transparent polyurethane material comprises the following raw materials in percentage by mass: 10-20% of thiopolythiol, 30-50% of isocyanate, 25-40% of polyether polyol, 1-10% of chain extender and 1-3% of auxiliary agent.
The isocyanate is isophorone diisocynateCyanate ester (IPDI), Hexamethylene Diisocyanate (HDI), dicyclohexylmethane diisocyanate (H)12MDI), or any combination thereof.
The polyether polyol is one or any combination of PPG2000, PPG3000, PEG2000 and PEG 300.
The micromolecule chain-extending cross-linking agent is one or the combination of any more of 1, 4-butanediol, ethylene glycol, diethylene glycol, tetraethylene glycol, 1, 2-propylene glycol, 1, 3-butanediol and trimethylolpropane.
The auxiliary agent comprises one or the combination of any more of a catalyst, a mildew inhibitor, a defoaming agent, an antioxidant and an ultraviolet absorbent.
In a fifth aspect of the present invention, there is provided:
the application of thio-polythiol in preparing transparent polyurethane material.
Advantageous effects
(1) Through the understanding of reference documents and the summary of previous experiments, sulfhydryl compounds and thiourea are selected as reaction raw materials, monomers with high S content are obtained through simple substitution reaction, the operation is simple, the reaction conditions are mild, the requirement on equipment is not high, and the method is suitable for industrial production. (2) The S-containing monomer designed and prepared by utilizing the molecular theory has the S content of more than 60 percent, not only can improve the refractive index of polyurethane to a great extent and reduce the dispersion force, but also can prevent the microphase separation of a soft segment and a hard segment of the polyurethane to a great extent due to the asymmetry of the molecular structure. (3) In the preparation process, the molecular utilization rate of the raw materials is high, most of the raw materials are converted into products, and the byproducts are inorganic salts which are non-toxic and harmless to the environment, so that the green chemistry concept is met. (4) The process for synthesizing the polyurethane is simple and easy for expanding production.
Drawings
FIG. 1 is a mass spectrum of a thiopolyol in example 1
FIG. 2 is an IR spectrum of a thiopolyol of example 1
FIG. 3 is a mass spectrum of thiopolythiol in example 1
FIG. 4 is an IR spectrum of thiopolythiol in example 1
Detailed Description
The present invention will be described in further detail with reference to the following embodiments. It will be understood by those skilled in the art that the following examples are illustrative of the present invention only and should not be taken as limiting the scope of the invention. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Reference throughout this specification to "one embodiment," "another embodiment," "an implementation," or the like, means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment described generally throughout this application. The appearances of the same phrase in various places in the specification are not necessarily all referring to the same embodiment. Further, when a particular feature, structure, or characteristic is described in connection with any embodiment, it is submitted that it is within the purview of this application to effect such feature, structure, or characteristic in connection with other ones of the embodiments.
The words "include," "have," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to those elements, but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The percentages recited in the present invention refer to mass percentages unless otherwise specified.
The invention provides thio-polythiol which can be used as a monomer to remarkably improve the performance of a transparent polyurethane material, wherein the thio-polythiol has a structure shown in a formula (I).
The preparation method comprises the following steps: (1) under the existence of alkali and a phase transfer catalyst, water is used as a solvent, mercaptoethanol is used for carrying out ring opening addition on epoxy chloropropane in an ice water bath, after the reaction is finished, acid is added to neutralize the pH value of a reaction system, water is removed by distillation, salts are removed by suction filtration, and ethanol is evaporated to obtain the thiopolyol. (2) And (2) under the action of an acid catalyst, reacting the product in the step (1) with metered thiourea at a certain temperature to obtain isothiuronium salt, adding alkali for hydrolysis after the reaction is finished, mechanically stirring, and extracting a lower organic layer to obtain a crude product of the thiopolythiol. The obtained crude product is firstly acidified by hydrochloric acid, washed by deionized water at 70 ℃ for three times, washed by absolute ethyl alcohol for one time, and subjected to reduced pressure distillation to remove small molecules to obtain the thio-polythiol.
In one embodiment, in the step 1, the weight ratio of mercaptoethanol, epichlorohydrin, base and phase transfer catalyst is 1: 2-3: 0.8-1.2: 0.1 to 0.3. The alkali is NaOH, KOH, NH3•H2O、Na2CO3And the like, or a combination of any of them. The phase transfer catalyst is one or the combination of any more of triethyl benzyl ammonium chloride, tetrabutyl ammonium bromide, tetrabutyl ammonium chloride and tetrabutyl ammonium hydrogen sulfate. And the step of purifying the product comprises the steps of neutralizing the pH value of the reaction system to 5-6 with acid, distilling to remove water, carrying out suction filtration to remove salt, and evaporating to remove ethanol. The reaction was carried out in an ice-water bath at a temperature below 10 ℃.
In one embodiment, in the step 2, the weight ratio of the thiopolyol to the thiourea is 1: 0.7-1.3, and the reaction temperature is 100-120 ℃. The acid catalyst is one or any combination of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid. The step of purifying the product is to acidify the reactant by hydrochloric acid, wash the product by water and ethanol in turn, and remove the solvent and the micromolecular substances by reduced pressure distillation.
The transparent polyurethane material can be obtained after the thiopolythiol, the isocyanate and the polyether polyol are mutually crosslinked.
The preparation method of the transparent polyurethane material comprises the following steps:
mixing the thiopolythiol, isocyanate, polyether glycol, chain extender and auxiliary agent, and mixingAnd after the mixture is uniform, preheating for 2min by microwave high fire, mechanically stirring for reaction, pouring the mixture into a mold after vacuum defoaming, and curing at room temperature to obtain colorless and transparent polyurethane. The transparent polyurethane material comprises the following raw materials in percentage by mass: 3-6% of thiopolythiol, 40-50% of isocyanate, 30-40% of polyether polyol, 1-10% of chain extender and 1-3% of auxiliary agent. The isocyanate is isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI) and hydrogenated diphenylmethane diisocyanate (H)12MDI), or any combination thereof. The polyether polyol is one or any combination of PPG2000, PPG3000, PEG2000 and PEG300, and the end group of the polyethylene glycol can be modified by an active group so as to improve the physical properties of the material, such as hardness, impact resistance and the like. The micromolecule chain-extending cross-linking agent is one or the combination of any more of 1, 4-butanediol, ethylene glycol, diethylene glycol, tetraethylene glycol, 1, 2-propylene glycol, 1, 3-butanediol and trimethylolpropane. The auxiliary agent comprises one or the combination of any more of a catalyst, a mildew inhibitor, an antioxidant and an ultraviolet absorbent. The used micromolecule chain-extending cross-linking agent is one or any combination of 1, 4-butanediol, ethylene glycol, diethylene glycol, tetraethylene glycol, 1, 2-propylene glycol, 1, 3-butanediol, trimethylolpropane and the like. The used auxiliary agents are catalysts, antifoaming agents, antioxidants and ultraviolet absorbers, and the catalysts are organic tin compounds including dibutyltin dilaurate, dibutyl acetate and dibutyltin dilauryl sulfide; the antioxidant is 2, 6-di-tert-butyl-p-cresol; the defoamer can be a polysiloxane defoamer; the ultraviolet absorbent is N- (ethoxycarbonylphenyl) -N '-methyl-N' -phenylformamidine (UV-1).
EXAMPLE 1 preparation of thiopolythiol
Preparation of thiopolyol:
(1) accurately weighing 10g of NaOH and 2g of triethyl benzyl ammonium chloride (TEBA), dissolving 40ml of water, and transferring the dissolved solution into a 250ml three-neck flask; (2) placing the three-neck flask in an ice-water bath, adding 9.75 g of 2-mercaptoethanol when the temperature is reduced to less than 5 ℃, mechanically stirring, controlling the temperature of the mixed solution in the reactor to be less than 10 ℃, and dropwise adding 23 g of epoxy chloropropane. (3) TLC monitors until the raw material is completely reacted, the mixed solution is neutralized by concentrated hydrochloric acid until the pH is =5-6, reduced pressure distillation is carried out to remove small molecules, and suction filtration is carried out to remove salts, so as to obtain 17.2 g of colorless and odorless transparent liquid with the yield of 64.9%.
The mass spectrum of the thiopolyol is shown in FIG. 1, and the infrared spectrum is shown in FIG. 2.
1H NMR characterization results: (400 MHz, D)2O） 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（d，J=6.4 Hz，1H）。
Preparation of thiopolythiol:
(1) taking 10.6g of the product in the step 1, putting the product in a three-neck flask, adding 11.7g of thiourea and 30ml of hydrochloric acid in sequence, quickly heating to 110 ℃, and monitoring by TLC until the reaction is finished. (2) And after the reaction is finished, cooling to 60 ℃, adding 20wt% of NaOH under the protection of nitrogen to neutralize until the solution has alkalescent pH of 8-9, hydrolyzing for 1h under nitrogen atmosphere, stopping stirring, standing for layering, and taking a lower-layer organic phase to obtain a crude product of the thiopolythiol. (3) The crude reaction product was extracted with 3X 30ml of ethanol, the extract phases were combined and the small molecules were removed by distillation under reduced pressure, giving 10.13 g of colorless transparent thiopolythiol in 78% yield.
The mass spectrum of thiopolythiol is shown in FIG. 3, and the infrared spectrum is shown in FIG. 4.
1H NMR characterization results: (400 MHz, CDCl)3） 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）。
EXAMPLE 2 preparation of thiopolythiol
Preparation of thiopolyol:
(1) accurately weighing 12g of NaOH and 2.4g of triethyl benzyl ammonium chloride (TEBA), dissolving in 50ml of water, and transferring to a 250ml three-neck flask; (2) placing the three-neck flask in an ice-water bath, adding 9.00g of 2-mercaptoethanol when the temperature is reduced to less than 5 ℃, mechanically stirring, controlling the temperature of the mixed solution in the reactor to be lower than 10 ℃, and dropwise adding 25g of epoxy chloropropane. (3) TLC monitoring until the raw material completely reacted, neutralizing the reaction mixture with concentrated hydrochloric acid to pH =5-6, distilling under reduced pressure to remove small molecules, and filtering with suction to remove salts to obtain 16.8g colorless and odorless transparent liquid with yield of 60.2%.
The results of the structural characterization of the thiopolyol are the same as in example 1.
Preparation of thiopolythiol:
(1) taking 10.8g of the product in the step 1, putting the product in a three-neck flask, sequentially adding 12.4g of thiourea and 40ml of hydrochloric acid, quickly heating to 115 ℃, and monitoring by TLC until the reaction is finished. (2) And after the reaction is finished, cooling to 65 ℃, adding 20wt% of NaOH under the protection of nitrogen to neutralize until the solution has alkalescent pH of 8-9, hydrolyzing for 1h under nitrogen atmosphere, stopping stirring, standing for layering, and taking a lower-layer organic phase to obtain a crude product of the thiopolythiol. (3) The crude reaction product was extracted with 3X 30ml of ethanol, the extract phases were combined and the small molecules were removed by distillation under reduced pressure to give 9.98g of colorless transparent thiopolythiol in 74% yield.
The structural characterization of the thiopolythiol is the same as in example 1.
EXAMPLE 3 preparation of thiopolythiol
Preparation of thiopolyol:
(1) accurately weighing 8g of NaOH and 1.8g of triethyl benzyl ammonium chloride (TEBA), dissolving in 35 ml of water, and transferring to a 250ml three-neck flask; (2) placing the three-neck flask in an ice-water bath, adding 10.05g of 2-mercaptoethanol when the temperature is reduced to less than 5 ℃, mechanically stirring, controlling the temperature of the mixed solution in the reactor to be less than 10 ℃, and dropwise adding 26 g of epoxy chloropropane. (3) TLC monitoring until the raw material completely reacted, neutralizing the reaction mixture with concentrated hydrochloric acid to pH =5-6, distilling under reduced pressure to remove small molecules, and filtering with suction to remove salts to obtain 18.1 g colorless and odorless transparent liquid with a yield of 68.4%.
The results of the structural characterization of the thiopolyol are the same as in example 1.
Preparation of thiopolythiol:
(1) and taking 11.0g of the product in the step 1, putting the product in a three-neck flask, sequentially adding 13.5g of thiourea and 30ml of hydrochloric acid, quickly heating to 105 ℃, and monitoring by TLC until the reaction is finished. (2) And after the reaction is finished, cooling to 60 ℃, adding 20wt% of NaOH under the protection of nitrogen to neutralize until the solution has alkalescent pH of 8-9, hydrolyzing for 1h under nitrogen atmosphere, stopping stirring, standing for layering, and taking a lower-layer organic phase to obtain a crude product of the thiopolythiol. (3) The crude reaction product was extracted with 3X 30ml of ethanol, the extract phases were combined and the small molecules were removed by distillation under reduced pressure, giving 10.78 g of colorless transparent thiopolythiol in 80.1% yield.
The structural characterization of the thiopolythiol is the same as in example 1.
EXAMPLE 4 preparation of clear polyurethane
The preparation method comprises the steps of putting 8g of 1, 4-butanediol, 200035 g of PPG and 15g of thiopolythiol in an example 1 into a three-neck flask, adding 0.4g of catalyst, 0.4g of antioxidant, 0.4g of ultraviolet absorbent, 0.4g of mildew preventive and 0.4g of defoaming agent, dehydrating in vacuum at 105 ℃ for 2 hours, adding 40g of isophorone diisocyanate (IPDI), uniformly mixing, preheating by microwave and high fire for 2 minutes, mechanically stirring to a certain viscosity, discharging, defoaming in a vacuum drying oven at 50 ℃ for 20 minutes, taking out, pouring into a preheated mold, and curing and molding at room temperature to obtain the transparent polyurethane.
EXAMPLE 5 preparation of clear polyurethane
Adopting 3g of ethylene glycol, 30040 g of PEG and 10g of thiopolythiol in the embodiment 2, putting 3g of ethylene glycol, 30040 g of PEG and 10g of thiopolythiol in a three-neck flask, adding 0.5g of catalyst, 0.3g of antioxidant, 0.3g of ultraviolet absorbent, 0.5g of mildew preventive and 0.4g of defoamer, dehydrating in vacuum at 115 ℃ for 2h, adding 45g of isophorone diisocyanate (IPDI), uniformly mixing, preheating by microwave and high fire for 2min, mechanically stirring to a certain viscosity, discharging, defoaming in a vacuum drying oven at 55 ℃ for 25 min, taking out, pouring into a preheated mold, and curing and molding at room temperature to obtain the transparent polyurethane.
EXAMPLE 6 preparation of clear polyurethane
Adopting the thiopolythiol in the embodiment 2, taking 10g of ethylene glycol, 200030 g of PEG and 12g of thiopolythiol, adding 0.4g of catalyst, 0.4g of antioxidant, 0.4g of ultraviolet absorbent, 0.4g of mildew preventive and 0.4g of defoaming agent into a three-neck flask, dehydrating for 1h in vacuum at 110 ℃, adding 46g of isophorone diisocyanate (IPDI), uniformly mixing, preheating for 2min by microwave high fire, mechanically stirring to a certain viscosity, discharging, defoaming for 15min in a vacuum drying oven at 60 ℃, taking out, pouring into a preheated mold, and curing and molding at room temperature to obtain the transparent polyurethane.
EXAMPLE 7 preparation of clear polyurethane
In this example, polyethylene glycol with maleate end groups was used as the polyurethane raw material. The preparation method comprises the following steps: mixing PEG2000 and maleic anhydride according to a weight ratio of 4: 1, adopting toluene as a water-carrying agent and a solvent, reacting for 7h at 170 ℃ in a nitrogen atmosphere, cooling the product to room temperature, and washing the product with water to obtain the modified PEG 2000.
Taking 10g of ethylene glycol, 200030 g of modified PEG and 12g of thiopolythiol in the embodiment 2, adding 0.4g of catalyst, 0.4g of antioxidant, 0.4g of ultraviolet absorbent, 0.4g of mildew preventive and 0.4g of defoaming agent into a three-neck flask, dehydrating for 1h in vacuum at 110 ℃, adding 46g of isophorone diisocyanate (IPDI), uniformly mixing, preheating for 2min by microwave high fire, mechanically stirring to a certain viscosity, discharging, defoaming for 15min in a vacuum drying oven at 60 ℃, taking out, pouring into a preheated mold, and curing and molding at room temperature to obtain the transparent polyurethane.
The transparent polyurethane materials prepared in the above examples were characterized as follows:
as can be seen from the above table, the transparent polyurethane material prepared by the invention has higher transmittance and lower refractive index (n)d) And simultaneously has better hardness and impact resistance.
Claims (1)
1. The application of polyethylene glycol with maleate end groups in improving the light transmittance of a transparent polyurethane material is characterized in that the preparation method of the transparent polyurethane material comprises the following steps:
preparation of maleate-terminated polyethylene glycol:
mixing PEG2000 and maleic anhydride according to a weight ratio of 4: 1, mixing, reacting for 7 hours at 170 ℃ in a nitrogen atmosphere by using toluene as a water-carrying agent and a solvent, cooling a product to room temperature, and washing the product with water to obtain modified PEG 2000;
preparation of thiopolyol:
weighing 2.4g of NaOH and triethyl benzyl ammonium chloride 12g, dissolving with 50ml of water, and transferring to a 250ml three-neck flask; placing the three-neck flask in an ice-water bath, adding 9.00g of 2-mercaptoethanol when the temperature is reduced to less than 5 ℃, mechanically stirring, controlling the temperature of the mixed solution in the reactor to be lower than 10 ℃, and dropwise adding 25g of epoxy chloropropane; TLC monitoring until the raw materials completely react, neutralizing the reaction mixture with concentrated hydrochloric acid until the pH is =5-6, distilling under reduced pressure to remove small molecules, and performing suction filtration to remove salts to obtain 16.8g of colorless and odorless transparent liquid which is thiopolyol;
preparation of thiopolythiol:
taking 10.8g of thiopolyol into a three-neck flask, sequentially adding 12.4g of thiourea and 40ml of hydrochloric acid, rapidly heating to 115 ℃, monitoring by TLC until the reaction is finished, cooling to 65 ℃, adding 20wt% of NaOH for neutralization under the protection of nitrogen until the pH of the solution is = 8-9, hydrolyzing for 1h under a nitrogen atmosphere, stopping stirring, standing for layering, taking a lower layer organic phase to obtain a crude thiopolythiol product, extracting the crude product by using 3 x 30ml of ethanol, combining extraction phases, and carrying out reduced pressure distillation to remove small molecules to obtain 9.98g of colorless and transparent thiopolythiol;
the thiopolythiol has a structure shown in a formula (I):
preparation of transparent polyurethane:
taking 10g of ethylene glycol, 200030 g g of modified PEG and 12g of thio-polyhydric mercaptan, adding 0.4g of catalyst, 0.4g of antioxidant, 0.4g of ultraviolet absorbent, 0.4g of mildew preventive and 0.4g of defoaming agent into a three-neck flask, dehydrating for 1 hour in vacuum at 110 ℃, adding 46g of isophorone diisocyanate, uniformly mixing, preheating for 2 minutes by microwave high fire, mechanically stirring to a certain viscosity, discharging, defoaming in a vacuum drying oven at 60 ℃ for 15 minutes, taking out, pouring into a preheated mold, and curing and molding at room temperature to obtain the transparent polyurethane.
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| CN111018756A (en) * | 2019-12-13 | 2020-04-17 | 山东益丰生化环保股份有限公司 | Preparation method of 2-2-dimercaptomethyl-1-3-propanedithiol |
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| JP2007187865A (en) * | 2006-01-13 | 2007-07-26 | Seiko Epson Corp | Optical resin composition, method for producing the same and optical goods |
| CN104321307A (en) * | 2012-08-14 | 2015-01-28 | 三井化学株式会社 | Production method for polythiol compound, polymerizable composition for optical material and use therefor |
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