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CN111748069B - Optical resin composition and optical resin material prepared from same - Google Patents

Optical resin composition and optical resin material prepared from same Download PDF

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Publication number
CN111748069B
CN111748069B CN201910247404.3A CN201910247404A CN111748069B CN 111748069 B CN111748069 B CN 111748069B CN 201910247404 A CN201910247404 A CN 201910247404A CN 111748069 B CN111748069 B CN 111748069B
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optical resin
compound
episulfide
resin composition
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CN111748069A (en
Inventor
谢毓
刘振东
王凯
罗建勋
巴龙翰
高彦升
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Wanhua Chemical Group Co Ltd
Wanhua Chemical Ningbo Co Ltd
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Wanhua Chemical Group Co Ltd
Wanhua Chemical Ningbo Co Ltd
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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
    • C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto groups
    • 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
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
    • 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
    • C08G18/387—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 in addition to a perfluoroalkyl group

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses an optical resin composition and an optical resin material prepared from the same, wherein the composition comprises the following components in parts by weight: based on the total mass of the composition, (a) an isocyanate-terminated prepolymer in an amount of 45 to 65 wt%, preferably 50 to 60 wt%; (b) a thiol compound having at least two mercapto groups in an amount of 35 to 55 wt%, preferably 40 to 50 wt%; the raw materials for preparing the isocyanate-terminated prepolymer comprise aliphatic isocyanate, episulfide compound and thioether compound with at least one hydroxyl group. The optical resin material prepared by using the composition as a raw material has high refractive index, and also has excellent impact resistance and optical transparency.

Description

Optical resin composition and optical resin material prepared from same
Technical Field
The invention relates to the field of optical resin, in particular to an optical resin composition and an optical resin material prepared from the same.
Background
In recent years, the Chinese glasses industry has realized soaring and qualitative changes, and is becoming a sunrise industry with unlimited vitality and potential. At present, the market capacity of the Chinese eyeglass industry reaches 400 hundred million RMB. In recent 5 years, the Chinese eyeglass industry has increased by 17% in every year. China has not only become the world with the greatest potential for the consumption of glasses, but also the world's leading country for the production of glasses. China has huge market potential of glasses, and the number of the old people exceeds 1.3 hundred million in the whole country, and 90 percent of the people need glasses. College students across the country are over 2000 million people, of which at least 80% require glasses. Meanwhile, China is a typical high-myopia high-incidence country, and the prevalence rate of high myopia of teenagers in China is between 6.69 and 38.4 percent, showing a youthful trend. The lens of high refracting index has frivolous advantage, can provide more comfortable experience sense and reach pleasing to the eye effect for high myopia wearer. The high impact resistance can protect the lens from cracking easily under the action of larger external force, and the safety of a wearer is protected to the maximum extent. Therefore, with the development of lenses, high refractive index and high impact resistance have become important indexes for measuring the excellence of lenses.
CN105646835B discloses an optical resin composition with high refractive index and high heat resistance. The composition comprises toluene diisocyanate and aliphatic polyisocyanate with 4-8 carbon atoms as an isocyanate component. However, toluene diisocyanate monomer has relatively high toxicity, so it is not widely used in the current lens production industry.
CN1601306B discloses a high refractive index, high impact resistance plastic lens. The composition from which the lens is synthesized comprises a prepolymer component obtained by mixing sulfur and an epithio group-containing compound and reacting the sulfur and the epithio group-containing compound. The solid sulfur in the formulation has problems of dissolution in the episulfide compound and insufficient reaction to cause deviation in the amount of the charge, and thus the stability of the optical lens prepared from the formulation is not optimistic.
CN105294974 discloses a preparation method of a polyurethane optical material with high impact toughness, which comprises the steps of polymerizing diol containing mesogen and general anti-yellowing diisocyanate into a polyurethane liquid crystal polymer to obtain a liquid crystal polymer modifier, adding the liquid crystal polymer into isocyanate and mercaptan, and curing to obtain a product. The optical material cannot provide a high refractive index while ensuring impact resistance, which limits the development of lens performance.
In order to solve the defects of high toxicity and various raw materials in the prior art, and the like, the optical resin composition which has high refractive index, excellent impact resistance and high light transmittance simultaneously needs to be provided aiming at the defects in the prior art.
Disclosure of Invention
The invention provides an optical resin composition and an optical resin material prepared from the same. The optical resin material has high refractive index, excellent impact resistance and good optical performance, and can be used for preparing optical lenses.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
an optical resin composition comprising, based on the total mass of the composition, (a) an isocyanate terminated prepolymer in an amount of 45 to 65 wt%, preferably 50 to 60 wt%; (b) a thiol compound having at least two mercapto groups in an amount of 35 to 55 wt%, preferably 40 to 50 wt%; the raw materials for preparing the isocyanate-terminated prepolymer comprise aliphatic isocyanate, episulfide compound and thioether compound with at least one hydroxyl group.
As a preferred embodiment, the method for preparing an isocyanate terminated prepolymer comprises the following steps: in the preparation process, the temperature is kept at 20-40 ℃, a catalyst is added into aliphatic isocyanate, then a thioether compound with at least one hydroxyl group is added, stirring is carried out for 1-3 hours, then an episulfide compound is added, and stirring is continued for 2-4 hours, so that the isocyanate-terminated prepolymer is obtained.
The molar ratio of the aliphatic isocyanate to the episulfide compound is 2-9: 1, such as 2,3, 4, 5, 6, 7, 8 and 9; preferably 3-7: 1.
The thioether compound having at least one hydroxyl group according to the invention represents 0.5 to 5% of the total mass of the aliphatic isocyanate and the episulfide compound, such as 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5.0%, preferably 1 to 4.5%.
The catalyst accounts for 0.005-0.015 percent of the mass of the isocyanate-terminated prepolymer (calculated by the mass sum of the aliphatic isocyanate, the episulfide compound and the thioether compound with at least one hydroxyl group), and preferably 0.008-0.013 percent.
The catalyst used in the preparation of the isocyanate terminated prepolymer according to the present invention is selected from amine catalysts, preferably one or more selected from triethanolamine, N-dimethylcyclohexylamine, triethylamine, N-dimethylbenzylamine.
The aliphatic isocyanate is selected from at least one of isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, cyclohexane dimethylene diisocyanate, 2, 5-bis (isocyanatomethyl) -bicyclo [2.2.1] heptane and 2, 6-bis (isocyanatomethyl) -bicyclo [2.2.1] heptane.
The episulfide compound described in the invention is selected from the group consisting of episulfide ethane, hexylepisulfide ethylene, 2-methylcyclothiopropane, 4,7, 7-trimethyl-6-thiobicyclo [3.2.1] octane, 1, 2-bis (2, 3-episulfide propylthio) ethane, 1, 2-bis (2, 3-episulfide propylthio) propane, 1, 3-bis (2, 3-episulfide propylthio) -2-methylpropane, 1, 4-bis (2, 3-episulfide propylthio) butane, 1, 4-bis (2, 3-episulfide propylthio) -2-methylbutane, 1, 3-bis (2, 3-episulfide propylthio) butane, 1, 5-bis (2, 3-episulfide propylthio) pentane, One or more of 1, 5-bis (2, 3-epithiopropylthio) -2-methylpentane, 1, 5-bis (2, 3-epithiopropylthio) -3-thiapentane, 1, 6-bis (2, 3-epithiopropylthio) hexane, 1, 6-bis (2, 3-epithiopropylthio) -2-methylhexane, 3, 8-bis (2, 3-epithiopropylthio) -3, 6-dithiaoctane.
The thioether compound of the present invention comprises at least one hydroxyl group, and is preferably one or more selected from the group consisting of 4,4 '-dihydroxydiphenyl sulfide, 4' -dihydroxydiphenyl disulfide, ethyl-2-hydroxyethyl sulfide, 2-hydroxyethylisopropyl sulfide, and 2-hydroxyanisole.
Preferably, the thioether compound of the invention is a monohydroxy thioether. The use of polyhydroxy thioethers can lead to the simultaneous presence of one or more isocyanates attached to a thioether with a certain degree of impairment of the regularity of the molecular structure. The use of the monohydroxy sulfide can ensure that one thioether is connected to one isocyanate, and the consistency of the molecular structure is ensured.
The reason for selecting thioethers with hydroxyl groups instead of thioethers with mercapto groups is that the reactivity of mercapto groups with isocyanate groups is much higher than that of hydroxyl groups with isocyanate, and since the reaction of episulfide compounds with isocyanate requires a catalyst at the end of the prepolymerization reaction, the catalytic activity of the catalyst used in the reaction can also catalyze the reaction of hydroxyl groups with isocyanate, so that the reaction can be carried out at a suitable rate to avoid unnecessary side reactions.
In the present invention, the viscosity of the isocyanate terminated prepolymer at 25 ℃ is 50 to 5000 mPa.s, preferably 1000 to 2500 mPa.s.
In the present invention, the viscosity is a value measured at 25 ℃ in accordance with JIS Z8803 using a vibration viscometer VISCOMATE VM-10A manufactured by SEKONIC.
The invention also provides an optical resin material which is prepared by taking the optical resin composition as a raw material.
The invention also provides a preparation method of the optical resin material, which comprises the following steps: uniformly mixing the isocyanate-terminated prepolymer, an internal release agent, a catalyst and an ultraviolet absorbent, and then adding a thiol compound with at least two mercapto groups for uniform mixing to obtain a combined solution; and (3) defoaming the combined solution, filtering, injecting into a mold, heating to 100-130 ℃ after 6-20 hours, and demolding to obtain the optical resin lens material.
The defoaming according to the present invention preferably comprises the steps of: and (3) defoaming at 300-900 Pa for at least 30 minutes.
The filtering of the invention preferably uses a polytetrafluoroethylene filter screen with the aperture of 0.5-1 μm.
The thiol compound having at least two mercapto groups according to the present invention is selected from trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (2-mercaptoacetate), trimethylolethane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), bis (mercaptomethyl) sulfide, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) sulfide, bis (mercaptoethyl) disulfide, bis (mercaptopropyl) sulfide, bis (mercaptomethylthio) methane, bis (2-mercaptoethylthio) methane, bis (3-mercaptopropylthio) methane, 1, 2-bis (mercaptomethylthio) ethane, 1, 2-bis (thio (2-mercaptoethyl)) -1-n-propanethiol, 1, 2-bis (3-mercaptopropylthio) ethane, 1,2, 3-tris (mercaptomethylthio) propane, 1,2, 3-tris (2-mercaptoethylthio) propane, 1,2, 3-tris (3-mercaptopropylthio) propane, 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane, 5, 7-dimercapto-1, 11-dimercapto-3, 6, 9-trithiaundecane, 4, 8-dimercapto-1, 11-dimercapto-3, 6, 9-trithiaundecane, tetrakis (mercaptomethylthiomethyl) methane, At least one of tetrakis (2-mercaptoethylthiomethyl) methane, 2-mercaptoethylether bis (2-mercaptoacetate), 2-mercaptoethylether bis (3-mercaptopropionate), thiodiglycolic acid bis (2-mercaptoethyl ester), thiodipropionic acid bis (2-mercaptoethyl ester), thiodiglycolic acid bis (2-mercaptoethyl ester), 1,3, 3-tetrakis (mercaptomethylthio) propane, and 1,1,2, 2-tetrakis (mercaptomethylthio) ethane.
Examples of the catalyst for polymerization of an optical resin include amine compounds and organometallic compounds. Examples of the amine compound include: triethylene diamine, hexamethylene tetramine, N-dimethyl octylamine, 4' -trimethylene bis (1-methylpiperidine), and the like. Examples of the organic metal compound include organic tin, copper oleate, copper acetylacetonate, iron naphthenate, and 2-ethylhexyl titanate. The amount of the catalyst added is 0.0001 to 3% by mass, preferably 0.0002 to 1% by mass of the optical resin composition (based on the sum of the mass of (a) the isocyanate-terminated prepolymer and (b) the thiol compound having at least two mercapto groups).
Examples of the ultraviolet absorber of the present invention include benzophenone compounds, triazine compounds, and benzotriazole compounds. Specific examples thereof include benzophenone-based compounds such as 2-hydroxy-4-acryloyloxy-5-tert-butylbenzophenone and 2-hydroxy-4-acryloyloxy-2 ', 4' -dichlorobenzophenone; triazine compounds such as 2- (2-hydroxy-4- [ 1-octyloxycarbonylethoxy ] phenyl) -4, 6-bis (4-phenylphenyl) -1,3, 5-triazine; 2- (2H-benzotriazol-2-yl) -4-methylphenol, 2- (2H-benzotriazol-2-yl) -4-tert-octylphenol, 2- (2H-benzotriazol-2-yl) -4, 6-bis (1-methyl-1-phenylethyl) phenol, benzotriazole-based compounds such as 2- (5-chloro-2H-benzotriazol-2-yl) -4-methyl-6-tert-butylphenol, 2- (5-chloro-2H-benzotriazol-2-yl) -2, 4-tert-butylphenol, and 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -chlorobenzotriazole. The amount of the ultraviolet absorber added is 0.0001 to 3% by mass, preferably 0.0004 to 1.5% by mass of the optical resin composition (based on the sum of the mass of (a) the isocyanate terminated prepolymer and (b) the thiol compound having at least two mercapto groups).
As the internal mold release agent of the present invention, a phosphate ester is preferably used, and specific examples thereof include phosphoric monoesters such as isopropyl acid phosphate, butyl acid phosphate, octyl acid phosphate, propylphenyl acid phosphate, butylphenyl acid phosphate and butoxyethyl acid phosphate; phosphoric acid diesters such as diisopropyl acid phosphate, dibutyl acid phosphate, dioctyl acid phosphate, diisodecyl acid phosphate, and dibutoxyethyl acid phosphate. These phosphoric esters may be used alone or in combination. The amount of the internal mold release agent added is 0.0001 to 5% by mass, preferably 0.00015 to 2% by mass of the optical resin composition (based on the sum of the mass of (a) the isocyanate terminated prepolymer and (b) the thiol compound having at least two mercapto groups).
In addition, various additives known in the art, such as a chain extender, a crosslinking agent, a light stabilizer, an antioxidant, an oil-soluble dye, a filler, and a bluing agent, may be added to the optical resin composition depending on the purpose of use.
In the present invention, an aliphatic isocyanate is reacted with a thioether compound having at least one hydroxyl group, and then reacted with an episulfide compound to obtain a prepolymer. The aliphatic isocyanate is firstly reacted with a thioether compound with at least one hydroxyl group, particularly a monohydroxy thioether compound, so that on one hand, the molecular chain length of the polymer is increased, and the toughness of the polymer can be improved due to mutual dragging of molecular chains when the polymer is subjected to an external force; on the other hand, long molecular chains often exhibit a state of being wound in a coil in the polymer, and also play an unexpected positive role in light transmittance of the optical resin.
The optical resin prepared from the composition has high refractive index, high impact strength and high light transmittance.
Detailed Description
The advantages of the present invention will be described in more detail with reference to examples. The resin properties were evaluated by the following experimental methods.
1. Refractive index, abbe number: measured using an ATAGO NAR-4T refractometer;
2. light transmittance: measured according to GBT 2410-2008 by using a Hunterlab USVIS1839 colorimeter;
3. impact resistance: according to the GBT 1843-2008 requirement, the sample is made into a shape of 80 × 10 × 4mm, the impact resistance of unnotched sample strips is tested by adopting cantilever beam impact, 5 sample strips are tested in each group of experiments, and the final result is averaged.
Preparation of isocyanate terminated prepolymer J1
46g of isophorone diisocyanate were taken in a round bottom flask and the oil bath temperature was set to 35 ℃. 5.16mg triethanolamine (alatin) catalyst was added to the flask, stirred until the catalyst was completely mixed, then 1.5g 4, 4' -dihydroxydiphenyl sulfide (carbofuran) was stirred for 1.5 hours, 4.1g ethylene Thiuram (TCI) was further added, and the reaction was carried out for 2 hours to obtain an isocyanate terminated prepolymer. The viscosity of the prepolymer J1 thus prepared was found to be 1200 mPa.s at 25 ℃.
With reference to the process of J1, the preparation of prepolymers J2 to J6 was carried out, the proportions of the charges and indices of the prepolymers prepared being as given in Table 1.
TABLE 1 composition and indices of isocyanate terminated prepolymer (J1-J6)
Figure BDA0002011434040000071
Figure BDA0002011434040000081
In the preparation process of J2-6, the related compounds comprise:
j2: the isocyanate is hexamethylene diisocyanate, the episulfide compound is 2-methyl epithiopropane (TCI), the thioether compound is 4, 4' -dihydroxy diphenyl disulfide (carbofuran), and the catalyst is triethylamine (Annigii).
J3: the isocyanate is dicyclohexylmethane diisocyanate, the episulfide compound is 4,7, 7-trimethyl-6-thiobicyclo [3.2.1] octane (advanced technology limited), the thioether compound is ethyl 2-hydroxyethyl thioether (carbofuran), and the catalyst is triethylamine (Annigii).
J4: the isocyanate is hexamethylene diisocyanate, the episulfide compound is 2-methylcyclothiopropane (TCI), the thioether compound is 2-hydroxyethyl isopropyl sulfide (Affaesar), and the catalyst is triethylamine (Annage).
J5: the isocyanate is cyclohexanedimethylene diisocyanate, the episulfide compound is 4,7, 7-trimethyl-6-thiobicyclo [3.2.1] octane (advanced technology, Inc.), the thioether compound is 2-hydroxyanisole (TCI), and the catalyst is N, N-dimethylcyclohexylamine (Sigma-Aldrich).
J6: the isocyanate is isophorone diisocyanate, the episulfide compound is episulfide ethane (TCI), the thioether compound is 4' 4-dimercaptodiphenyl sulfide (carbofuran), and the catalyst is triethanolamine (alatin).
Example 1
The isocyanate terminated prepolymer obtained in 25.8g J1 was taken at 20 ℃ and added with 0.008g of catalyst di-n-butyltin dichloride (carbofuran), 0.05g of internal mold release agent ZELEC UN (Stepan) and 0.03g of ultraviolet absorber 2- (2-hydroxy-5-tert-octylphenyl) Benzotriazole (BASF) to dissolve sufficiently to obtain solution A. 27g of trimethylolpropane tris (2-mercaptoacetate) (carbofuran) was added to the solution A, and the mixture was stirred at 25 ℃ for 30 minutes and mixed uniformly, and the uniformly mixed combined solution was defoamed under a pressure of 600Pa for half an hour, and then filtered through a filter of 1. mu. m TFE. Pouring the filtered combined liquid into a mold at 30 ℃, heating to 120 ℃ for 18h for curing, and finally demolding to obtain the product.
Example 2
The isocyanate terminated prepolymer obtained in 28.7g J2 was taken at 15 ℃ and added with 0.007g of triethylenediamine catalyst (Hangzhou Dayang chemical), 0.05g of internal release agent ZELEC UN (Stepan) and 0.03g of ultraviolet absorber 2- (2H-benzotriazol-2-yl) -4-methylphenol (Guanghao Biotech, Hubei) and dissolved sufficiently to obtain solution A. 20.3g of pentaerythritol tetrakis (3-mercaptopropionate) (Jingbo) was added to the solution A, and the mixture was stirred at 25 ℃ for 30 minutes to be mixed uniformly, and the uniformly mixed combined solution was defoamed under a gas pressure of 600Pa for half an hour, and then filtered through a filter of 1. mu. mTFE. Pouring the filtered combined liquid into a mold at 30 ℃, heating to 110 ℃ for 15h for curing, and finally demolding to obtain the product.
Example 3
The isocyanate terminated prepolymer obtained in 29g J3 was taken at 25 ℃ and added with 0.007g of di-n-butyltin dichloride (carbofuran) as a catalyst, 0.06g of diisopropyl acid phosphate as an internal mold release agent (Shanghai Homing chemical), and 0.025g of 2- (5-chloro-2H-benzotriazol-2-yl) -4-methyl-6-tert-Butylphenol (BASF) as an ultraviolet absorber, and sufficiently dissolved to obtain a solution A. 17g of bis (2-mercaptoethylthio) methane (Henan Possian chemical Co., Ltd.) was added to the solution A, and the mixture was stirred at 25 ℃ for 30 minutes and mixed uniformly, and the mixed combined solution was defoamed under a gas pressure of 600Pa for half an hour, and then filtered through a filter of 1. mu. mPTE. Pouring the filtered combined liquid into a mold at 25 ℃, heating to 110 ℃ for 16h for curing, and finally demolding to obtain the product.
Example 4
The isocyanate terminated prepolymer obtained in 28.7g J4 was taken at 15 ℃ and added with 0.007g of triethylenediamine catalyst (Hangzhou Dayang chemical), 0.05g of internal release agent ZELEC UN (Stepan) and 0.03g of ultraviolet absorber 2- (2H-benzotriazol-2-yl) -4-methylphenol (Guanghao Biotech, Hubei) and dissolved sufficiently to obtain solution A. 20.3g of pentaerythritol tetrakis (3-mercaptopropionate) (Jingbo) was added to the solution A, and the mixture was stirred at 25 ℃ for 30 minutes to be mixed uniformly, and the uniformly mixed combined solution was defoamed under a gas pressure of 600Pa for half an hour, and then filtered through a filter of 1. mu. mTFE. Pouring the filtered combined liquid into a mold at 30 ℃, heating to 110 ℃ for 15h for curing, and finally demolding to obtain the product.
Example 5
The isocyanate terminated prepolymer obtained in 23.4g J5 was taken at 25 ℃ and added with 0.006g of catalyst di-n-butyltin dichloride (carbofuran), 0.045g of internal mold release agent dibutyl phosphate (daoyang chemical, Hangzhou) and 0.023g of ultraviolet absorber 1164(TCI) to dissolve sufficiently to obtain solution A. 21.6g of bis (2-mercaptoethylthio) methane (Henan Possian chemical Co., Ltd.) was added to the solution A, and the mixture was stirred at 25 ℃ for 30 minutes and mixed uniformly, and the mixed combined solution was defoamed under a pressure of 600Pa for half an hour, and then filtered through a filter of 1. mu. mPTE. Pouring the filtered combined liquid into a mold at 25 ℃, heating to 110 ℃ for 16h for curing, and finally demolding to obtain the product.
Comparative example 1
23g of isophorone diisocyanate was put in a flask at 20 ℃ and 0.008g of di-n-butyltin dichloride (carbofuran), an internal mold release agent ZELEC UN (Stepan), and 0.03g of an ultraviolet absorber 2- (2-hydroxy-5-tert-octylphenyl) Benzotriazole (BASF) were added thereto and sufficiently dissolved to obtain a solution A. 27g of trimethylolpropane tris (2-mercaptoacetate) (carbofuran), 0.75g of 4, 4' -dihydroxybiphenyl sulfide (carbofuran) and 2.05g of Thiirane (TCI) were added to the solution A in this order, and the mixture was stirred and mixed uniformly at 25 ℃ for 30 minutes, and the uniformly mixed combined solution was defoamed under a pressure of 600Pa for half an hour, and then filtered through a filter of 1. mu. mPTEF. Pouring the filtered combined liquid into a mold at 30 ℃, heating to 120 ℃ for 18h for curing, and finally demolding to obtain the product.
Comparative example 2
43g of dicyclohexylmethane diisocyanate were taken in a round-bottomed flask and the oil bath temperature was set at 35 ℃. 0.004g of triethylamine (Annage) as a catalyst was added to the flask and stirred until the catalyst was thoroughly mixed. To the combined solution was added 1.29g of ethyl 2-hydroxyethyl sulfide (carbofuran), and the mixture was stirred to react for 2 hours to obtain an isocyanate terminated prepolymer.
29g of the isocyanate terminated prepolymer obtained as described above was taken at 25 ℃ and added with 0.007g of di-n-butyltin dichloride (carbofuran) as a catalyst, 0.06g of diisopropyl acid phosphate as an internal mold release agent (Shanghai Homing chemical), and 0.025g of 2- (5-chloro-2H-benzotriazol-2-yl) -4-methyl-6-tert-Butylphenol (BASF) as an ultraviolet absorber, and sufficiently dissolved to obtain a solution A. 17g of bis (2-mercaptoethylthio) methane (Henan Possian chemical Co., Ltd.) was added to the solution A, and the mixture was stirred at 25 ℃ for 30 minutes and mixed uniformly, and the mixed combined solution was defoamed under a gas pressure of 600Pa for half an hour, and then filtered through a filter of 1. mu. mPTE. Pouring the filtered combined liquid into a mold at 25 ℃, heating to 110 ℃ for 16h for curing, and finally demolding to obtain the product.
Comparative example 3
According to the technical scheme of patent CN1601306, a comparative example is made:
the flask was charged with 66.16g of di (. beta. -epithiopropyl) sulfide and 3.31g of sulfur (manufactured by Wako Pure chemical industries, Ltd.), and the mixture was dissolved by heating at 55 ℃ for 30 minutes. After this, 0.53g of methimazole was added immediately and dissolved, after which the mixture was cooled to 25 ℃ immediately. This is referred to as "solution 1".
10.71g of bis (isocyanatomethyl) bicyclo [2.2.1] heptane, 0.035g of an ultraviolet absorber SEESORB707(Shipro Kasei Kaisha, manufactured by Ltd.), 0.04g of an internal mold release agent JP-506H (Jojoku chemical), and 0.004g of a catalyst tetrabutylphosphonium bromide were charged into the flask at 20 ℃ and the mixture was stirred and dissolved. After the dissolution, 19.29g of bis (mercaptomethyl) -1, 4-dithiane was added as a polythiol compound, and the mixture was further uniformly dissolved. Then, 70g of "solution 1" was added, and the mixture was stirred and mixed uniformly. The resulting mixture was degassed under vacuum at 600Pa for half an hour and filtered through a 1 μm TFE filter. Pouring the filtered combined liquid into a mold at 20 ℃, heating to 110 ℃ for 16h for curing, and finally demolding to obtain the product.
Comparative example 4
The isocyanate terminated prepolymer obtained in 25.8g J6 was taken at 20 ℃ and added with 0.008g of catalyst di-n-butyltin dichloride (carbofuran), 0.05g of internal mold release agent ZELEC UN (Stepan) and 0.03g of ultraviolet absorber 2- (2-hydroxy-5-tert-octylphenyl) Benzotriazole (BASF) to dissolve sufficiently to obtain solution A. 27g of trimethylolpropane tris (2-mercaptoacetate) (carbofuran) was added to the solution A, and the mixture was stirred at 25 ℃ for 30 minutes and mixed uniformly, and the uniformly mixed combined solution was defoamed under a pressure of 600Pa for half an hour, and then filtered through a filter of 1. mu. m TFE. Pouring the filtered combined liquid into a mold at 30 ℃, heating to 120 ℃ for 18h for curing, and finally demolding to obtain the product.
The articles obtained from examples 1-5 and comparative examples 1-4 were tested for properties, and the specific test data are shown in Table 2.
TABLE 2 Performance indices of the examples and comparative examples
Figure BDA0002011434040000121
According to the above results, the article obtained by reacting the isocyanate terminated prepolymer with the polythiol compound of the present invention has a high refractive index, a high light transmittance, and a high impact strength, as compared with the sample prepared by the conventional method.
The experimental data of example 2 and example 4 are compared, and the thioether compound of the prepolymer in example 2 is bis-mercapto sulfide, while the thioether compound of the prepolymer in example 4 is monohydroxy sulfide. It can be seen from the experimental data obtained by the test that the use of the bishydroxy sulfide destroys the stability of the molecular structure to some extent, resulting in that the optical resin finally obtained has lower light transmittance than the optical resin obtained by the reaction of the monohydroxy sulfide, and the impact resistance is also affected.
As can be seen from the comparison of example 1 with comparative example 1, the optical resin obtained by using the same raw materials and by a different process, i.e., comparative example 1, without first synthesizing the prepolymer, has quite different properties. This is because in comparative example 1, when all the raw materials were mixed together, the respective raw materials reacted with each other irregularly, and the resulting molecular structure was disordered. In example 1, the raw materials are sequentially reacted to exert the positive effects of the raw materials, so that the optical resin prepared has more excellent performances.
As can be seen by comparing example 3 with comparative example 2, the absence of the addition of the episulfide compound in the prepolymerization results in the optical resin article having significant drawbacks in optical properties and impact properties. The episulfide compound plays an extremely important role as a main raw material for reacting with isocyanate in the prepolymer.
By comparing example 1 with comparative example 4, the prepolymer obtained in comparative example 4 with the thioethers with mercapto groups added has a significantly increased viscosity, which in turn affects the subsequent mixing and reaction with the thiol, resulting in a substantial decrease in the light transmittance and impact resistance of the cured optical resin material.
According to the technical scheme of CN1601306, compared with the optical resin obtained by the method of the invention, the optical resin obtained by the invention has more excellent light transmittance as compared with the optical resin obtained by the method of the invention.

Claims (13)

1. An optical resin composition comprising the following composition: based on the total mass of the composition, (a) isocyanate-terminated prepolymer, the using amount is 45-65 wt%; (b) 35-55 wt% of thiol compound with at least two sulfydryl groups; the preparation raw materials of the isocyanate-terminated prepolymer comprise aliphatic isocyanate, episulfide compound and thioether compound with at least one hydroxyl; the thioether compound having at least one hydroxyl group is selected from monohydroxy sulfides and/or bishydroxy sulfides.
2. The optical resin composition according to claim 1, wherein the isocyanate terminated prepolymer (a) is used in an amount of 50 to 60 wt%; the amount of the thiol compound (b) having at least two mercapto groups is 40 to 50 wt%.
3. The optical resin composition according to claim 1, wherein the isocyanate terminated prepolymer is prepared by a method comprising the steps of: in the preparation process, the temperature is kept at 20-40 ℃, a catalyst is added into aliphatic isocyanate, then a thioether compound with at least one hydroxyl group is added, stirring is carried out for 1-3 hours, then an episulfide compound is added, and stirring is continued for 2-4 hours, so that the isocyanate-terminated prepolymer is obtained.
4. The optical resin composition according to claim 1, wherein the molar ratio of the aliphatic isocyanate to the episulfide compound is 2 to 9: 1.
5. The optical resin composition according to claim 1, wherein the molar ratio of the aliphatic isocyanate to the episulfide compound is 3 to 7: 1.
6. The optical resin composition according to claim 1, wherein the thioether compound having at least one hydroxyl group is present in an amount of 0.5 to 5% by mass based on the total mass of the aliphatic isocyanate and the episulfide compound.
7. The optical resin composition according to claim 1, wherein the thioether compound having at least one hydroxyl group accounts for 1 to 4.5% of the total mass of the aliphatic isocyanate and the episulfide compound.
8. The optical resin composition according to claim 1, wherein the episulfide compound is selected from the group consisting of episulfide ethane, hexylepisulfide ethylene, 2-methylcyclothiopropane, 4,7, 7-trimethyl-6-thiobicyclo [3.2.1] octane, 1, 2-bis (2, 3-episulfide propylthio) ethane, 1, 2-bis (2, 3-episulfide propylthio) propane, 1, 3-bis (2, 3-episulfide propylthio) -2-methylpropane, 1, 4-bis (2, 3-episulfide propylthio) butane, 1, 4-bis (2, 3-episulfide propylthio) -2-methylbutane, 1, 3-bis (2, 3-episulfide propylthio) butane, 1, 5-bis (2, 3-epithiopropylthio) pentane, 1, 5-bis (2, 3-epithiopropylthio) -2-methylpentane, 1, 5-bis (2, 3-epithiopropylthio) -3-thiapentane, 1, 6-bis (2, 3-epithiopropylthio) hexane, 1, 6-bis (2, 3-epithiopropylthio) -2-methylhexane, 3, 8-bis (2, 3-epithiopropylthio) -3, 6-dithiaoctane.
9. The optical resin composition according to claim 1, wherein the sulfide compound having at least one hydroxyl group is one or more selected from the group consisting of 4,4 '-dihydroxydiphenyl sulfide, 4' -dihydroxydiphenyl disulfide, ethyl-2-hydroxyethyl sulfide, 2-hydroxyethylisopropyl sulfide and 2-hydroxyanisole.
10. The optical resin composition according to claim 1, wherein the viscosity of the isocyanate terminated prepolymer at 25 ℃ is 50 to 5000 mPa-s.
11. The optical resin composition according to claim 1, wherein the viscosity of the isocyanate terminated prepolymer at 25 ℃ is 1000 to 2500 mpa-s.
12. The optical resin composition according to claim 1, wherein the thiol compound having at least two mercapto groups is selected from trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (2-mercaptoacetate), trimethylolethane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), bis (mercaptomethyl) sulfide, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) sulfide, bis (mercaptoethyl) disulfide, bis (mercaptopropyl) sulfide, bis (mercaptomethylthio) methane, bis (2-mercaptoethylthio) methane, bis (3-mercaptopropylthio) methane, 1, 2-bis (mercaptomethylthio) ethane, mixtures thereof, and mixtures thereof, 1, 2-bis (thio (2-mercaptoethyl)) -1-n-propanethiol, 1, 2-bis (3-mercaptopropylthio) ethane, 1,2, 3-tris (mercaptomethylthio) propane, 1,2, 3-tris (2-mercaptoethylthio) propane, 1,2, 3-tris (3-mercaptopropylthio) propane, 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane, 5, 7-dimercapto-methyl-1, 11-dimercapto-3, 6, 9-trithiaundecane, 4, 7-dimercapto-1, 11-dimercapto-3, 6, 9-trithiaundecane, 4, 8-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithioundecane, tetrakis (mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethylthiomethyl) methane, 2-mercaptoethylether bis (2-mercaptoacetate), 2-mercaptoethylether bis (3-mercaptopropionate), thiodiglycolic acid bis (2-mercaptoethyl ester), 1,3, 3-tetrakis (mercaptomethylthio) propane, 1,2, 2-tetrakis (mercaptomethylthio) ethane.
13. An optical resin material prepared from the optical resin composition according to any one of claims 1 to 12.
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