CN110922595A - Catalyst for preparing polythiol curing agent and application thereof - Google Patents
Catalyst for preparing polythiol curing agent and application thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/66—Mercaptans
Abstract
The invention relates to the technical field of polythiol compounds, in particular to a catalyst for preparing a polythiol curing agent and application thereof. The quaternary ammonium salt three-phase transfer catalyst is obtained by carrying out halogenation modification on a mesoporous molecular sieve and reacting with tertiary amine, and is applied to the preparation of a polythiol curing agent. The catalyst obtained by the method has high catalytic activity, can be used for preparing colorless and transparent high-quality polythiol curing agents with low halogen residue, is easy to recover and low in separation cost, and has a very good industrial application prospect.
Description
Technical Field
The invention relates to the technical field of polythiol compounds, in particular to a catalyst for preparing a polythiol curing agent and application thereof.
Background
There are many known methods for preparing thiol compounds, for example: (1) disulfide compound reduction; (2) the method comprises the steps of reacting organic halide or alcohol with thiourea to generate isothiourea salt, and hydrolyzing isothiourea; (3) a process via Bunte salt; (4) a method of reacting an organic halide with a metal salt such as sodium hydrosulfide or potassium hydrosulfide; (5) a method of hydrolysis from dithiocarbamates; (6) and a method of adding an alkene to hydrogen sulfide or thioacetic acid. Among these, the method (2) and the method (4) using an organic halide as a starting material are the most commonly used methods for producing a thiol compound, and these methods have a high yield, a small amount of by-products, and a good product quality as compared with other methods, but the method (2) involves many reaction steps, and is not as convenient as a direct sulfhydrylation operation using a metal salt.
Chinese patent publication No. CN109180926A discloses a method for producing a polyether polythiol compound, which can produce a polythiol compound efficiently and inexpensively in high yield by direct sulfhydrylation using an organic halogen compound to react with sodium hydrosulfide; in addition, in a method for preparing a polythiol curing agent disclosed in Liao Yibin et al (preparation of polythiol curing agent and its activity research, academic master paper of Xiamen university, 2014.4), polyether polythiol was prepared.
However, most of the polythiol curing agents obtained by the preparation method are yellow green or light yellow, and have poor transparency, and most of the polythiol curing agents used in the preparation method are quaternary ammonium salt phase transfer catalysts, so that the polythiol curing agents can remain in products after being used, and halogen and the like are excessively remained, and if the content of chloride ions in the obtained products is high, the polythiol curing agents cannot meet the requirement of green environmental protection; and the catalyst is not easy to recover, the production and separation cost is high, and the industrial scale production and application limitations are large.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a catalyst for preparing a polythiol curing agent and application thereof. The quaternary ammonium salt three-phase transfer catalyst is obtained by carrying out halogenation modification on a mesoporous molecular sieve and reacting with tertiary amine, and is applied to the preparation of a polythiol curing agent. The catalyst obtained by the method has high catalytic activity, can be used for preparing colorless and transparent high-quality polythiol curing agents with low halogen residue, is easy to recover and low in separation cost, and has a very good industrial application prospect.
Firstly, the catalyst for preparing the polythiol curing agent is mesoporous molecular sieve SBA-15 with modified surface groups, marked as QA-SBA-15, and the surface groups of the catalyst comprise a structure shown as formula I:
wherein, the left vertical thick black line represents the matrix skeleton of the mesoporous molecular sieve SBA-15, and R1, R2 and R3 are straight-chain or branched alkanes of C1-C10, which can be the same or different.
The inventor further provides a preparation method of the catalyst, which comprises the following specific steps:
under the protective atmosphere, carrying out reflux reaction on a halogenating reagent and mesoporous molecular sieve SBA-15 in an organic solvent, and carrying out surface halogenation modification on the mixture to obtain halogenated SBA-15; and reacting the obtained halogenated SBA-15 with tertiary amine to obtain the quaternary ammonium salt three-phase transfer catalyst QA-SBA-15.
The protective atmosphere is preferably nitrogen;
the mass ratio of the halogenating agent to the mesoporous molecular sieve SBA-15 is preferably (0.5-4): 1, more preferably (0.5 to 3): 1, more preferably (0.8 to 1.5): 1, more preferably (0.8 to 1.2): 1, most preferably (1-1.2): 1; the molar ratio of halogen atoms in the reaction of halogenated SBA-15 with tertiary amine to nitrogen in the tertiary amine is preferably 1: (2-4);
the halogenating agent is preferably selected from 3-chloropropyltrimethoxysilane or 3-chloropropyltriethoxysilane or 3-bromopropyltrimethoxysilane or 3-bromopropyltriethoxysilane or a combination thereof; more preferably, the halogenating agent is selected from 3-chloropropyltriethoxysilane or 3-bromopropyltriethoxysilane.
Preferably, the tertiary amine has a structural formula shown in a formula II, wherein R1, R2 and R3 are straight chain or branched chain alkanes of C1-C10, and can be the same or different;
more preferably, the tertiary amine is selected from tri-n-propylamine or tri-n-butylamine, or combinations thereof.
The organic solvent is preferably an alcohol solvent, more preferably absolute ethyl alcohol;
the concentration of the halogenation reagent in the reaction system is preferably 30-100 mmol/L, more preferably 40-80 mmol/L, further preferably 40-60 mmol/L, and most preferably 50 mmol/L;
the time of the reflux reaction is preferably 20-24 h;
the reaction temperature of the halogenated SBA-15 and the tertiary amine is preferably 70-120 ℃, and is preferably 80 ℃; the reaction time of the halogenated SBA-15 and the tertiary amine is preferably 8-12 h;
preferably, after the reflux reaction is finished, the method further comprises the steps of filtering, washing and drying. The washing is preferably performed by using an alcohol solvent, and more preferably absolute ethyl alcohol; the drying is preferably vacuum drying; the drying temperature is preferably 60-100 ℃, more preferably 70-90 ℃, and further preferably 80 ℃; the time of vacuum drying is preferably 6-12 h.
When the obtained halogenated SBA-15 is reacted with tertiary amine, dichloroethane and absolute ethyl alcohol are preferably added as solvents;
the reaction of halogenated SBA-15 with a tertiary amine is preferably carried out with stirring; after the reaction is finished, carrying out suction filtration and separation, washing with ethanol, and airing; and then adding absolute ethyl alcohol into a Soxhlet extractor for extraction for 12 hours to remove tertiary amine which does not react in the pore channel, and finally drying in vacuum at room temperature to constant weight to obtain the catalyst QA-SBA-15.
The following reaction scheme for preparing QA-SBA-15 using 3-chloropropyltriethoxysilane as the halogenating agent is shown below:
in addition, mesoporous molecular sieves MCM-41 and MCM-48 can also be subjected to halogenation modification by referring to the method disclosed by the invention, and then react with tertiary amine to obtain modified mesoporous molecular sieves MCM-41 and MCM-48, and the modified mesoporous molecular sieves can also be used for synthesizing catalytic polythiol curing agents.
The catalyst QA-SBA-15 is further used for synthesizing the polythiol curing agent, and the method comprises the following steps: NaSH, a catalyst QA-SBA-15 and halogenated polyether polyol are added at normal pressure H2S, reacting in a gas environment, and separating out the catalyst to obtain a crude product; and then washing and drying the crude product in sequence to obtain the high-quality polythiol curing agent for the epoxy resin.
Preferably, the adding amount of the catalyst QA-SBA-15 is 0.1-10% of the mass of the halogenated polyether polyol, and more preferably 0.5-6%; the adding amount of NaSH is preferably determined according to the molar ratio (0.5-3) of NaSH to halogen atoms in halogenated polyether polyol: 1, more preferably (0.9 to 1.5): 1.
preferably, the NaSH is added in the form of an aqueous NaSH solution; the mass fraction of the NaSH aqueous solution is preferably 10-50%, more preferably 20-44%, and most preferably 20-25%.
In the synthesis of the polythiol curing agent, the reaction temperature is preferably 60-150 ℃, more preferably 80-110 ℃, and most preferably 90 ℃; the reaction time is preferably 2 to 20 hours, more preferably 5 to 7 hours, and most preferably 6 hours.
In the synthesis of the polythiol curing agent, the washing process preferably comprises the following steps: adding the obtained crude product into water for primary washing, adjusting the pH value of an organic phase to 5-7, standing for layering after stabilization, taking out substances on the lower layer, uniformly mixing the substances with the water, standing for 10-14 h, and then cutting out a product to finish the washing process; more preferably, the lower layer material is taken out and uniformly mixed with water, and then is kept stand for 12 hours. The method is favorable for removing the salt generated by the reaction by the water washing mode of acid washing and water washing.
In the synthesis of the polythiol curing agent, the drying mode is preferably vacuum dehydration; the vacuum degree of the vacuum dehydration is preferably less than or equal to-0.095 MPa; the temperature of the vacuum dehydration is preferably 60-70 ℃, and more preferably 65 ℃; the time for vacuum dehydration is preferably 1 to 3 hours, more preferably 2 hours. According to the invention, through the drying process, the high-quality polythiol curing agent for epoxy resin is obtained by evaporating water.
The sources of the mesoporous molecular sieve SBA-15, the halogenated polyether polyol and NaSH are not particularly limited in the invention, and commercial products or self-products (NaSH is mainly prepared by introducing hydrogen sulfide into an alkali solution) which are well known to a person skilled in the art can be adopted.
Preferably, the mesoporous molecular sieve SBA-15 is prepared in the references "Xiaoyao Fei, Shaoyun Chen, Dai Liu, Chunjie Huang, Yongchun Zhang. company of amino and epoxy funtionality SBA-15used for carbonic and hydrolytic enzyme immobilization. journal of Bioscience and Biogenetic engineering [ J ] 2016,122(3): 314-.
Preferably, the halogenated polyether polyol has a structure shown in formula III:
wherein m, n and p are independently selected from integers of 2-5, R is a linear alkyl group of C1-C10, a branched alkyl group of C1-C10, a substituted aryl group or an unsubstituted aryl group, and X is one or more of F, Cl and Br.
Preferably, R is C2-C4 straight-chain alkyl or C2-C4 branched-chain alkyl; and X is Cl.
The synthesis of the polythiol curing agent also comprises the recycling of the separated catalyst QA-SBA-15.
In the present invention, the reaction of the halogenated polyether polyol with NaSH is carried out in H2The reaction can be carried out efficiently in the presence of S, and meanwhile, the product quality can be improved. The invention is directed to said H2The source of S is not particularly limited.
The invention provides a catalyst for preparing a polythiol curing agent, which is used for synthesizing a polythiol curing agent for epoxy resin. Compared with the traditional method, the catalyst QA-SBA-15 has high activity and good mechanical strength, is easy to separate from the product and can be recycled, reduces the discharge amount of wastewater, can greatly reduce the cost of raw materials, production and separation, greatly reduces the reaction time, and has very good industrial application prospect. Experimental results show that the chroma of the polythiol curing agent for epoxy resin obtained by the catalyst and the preparation method provided by the invention is less than 20, and the halogen content is within 200 ppm.
Compared with the prior art, the invention adopts a specific kind of catalyst to synthesize the polythiol curing agent for the epoxy resin by the solvent-free three-phase transfer catalysis under a specific preparation process. The prepared product is colorless and transparent, and has low halogen residue; and the used catalyst is easy to recover, low in separation cost, recyclable and has a very good industrial application prospect.
The preparation method provided by the invention has the advantages of good conversion rate (the product conversion rate exceeds 90 percent) and high yield, simple process, mild condition, great reduction of waste water generation amount, suitability for industrial manufacture, great reduction of reaction time and production cost compared with the traditional method, and wide application prospect.
Drawings
FIG. 1 is a chart of detection of hydrogen nuclear magnetic 1H NMR of a product obtained by the preparation method provided in example 4 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but it should not be construed that the scope of the above subject matter is limited to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention, and the following embodiments are all completed by adopting the conventional prior art except for the specific description.
The halogenated polyether polyols used in the following examples were prepared by laboratory synthesis, specifically according to the method described in patent CN109180926A, and specifically:
89.6g of polyether polyol and 0.46g of Lewis acid catalyst BF3 are taken, the temperature is raised to 65 ℃ to completely dissolve the catalyst, 87.9g of epoxy chloropropane is dripped, the reaction temperature is controlled at 100 ℃ in the dripping process, the reaction time is 7 hours, and after the reaction is finished, the chlorinated polyether polyol is obtained.
The mesoporous molecular sieve SBA-15 is prepared according to the method of the literature "Xiaoyao Fei, Shaoyun Chen, Dai Liu, Chunjie Huang, Yongchun Zhang. comparative of amino and epoxy functionalized SBA-15used for carboxylic and enzymatic immobilization. journal of Bioscience and Biochemical [ J ].2016,122(3): 314-" 321 ".
Other raw materials are all commercial products.
Example 1
Preparation of catalyst QA-SBA-15:
(1) halogenated SBA-15 Process: in N2Under the atmosphere, 2g of SBA-15 is added into an absolute ethyl alcohol solution of 3-chloropropyltriethoxysilane (2g) with the concentration of 50mM, the mixture is filtered after refluxing for 24h, the mixture is washed by absolute ethyl alcohol and dried overnight under the vacuum condition of 80 ℃, and the obtained solid is halogenated SBA-15.
(2) Synthesis of QA-SBA-15: 2g of the dried halogenated SBA-15 was put in a 150mL three-necked flask, and a mixed solvent of 50mL of 1, 2-dichloroethane and 50mL of anhydrous ethanol was added. According to a molar ratio n (Cl): n (amine) ═ 1: 3 adding tri-n-butylamine, carrying out reflux reaction for 12h, carrying out suction filtration separation, washing with ethanol, and drying. And then adding absolute ethyl alcohol into a Soxhlet extractor for extraction for 12 hours to remove tertiary amine which does not react in the pore channel, and finally drying in vacuum at room temperature to constant weight to obtain the catalyst QA-SBA-15.
Example 2
Referring to the preparation of catalyst QA-SBA-15 in example 1, 3-bromopropyltriethoxysilane (1.2) is selected as halogenating agent, and when QA-SBA-15 is synthesized, n (amine) is 1:4.2, and the rest of reaction conditions are not changed.
Example 3
Referring to example 1 for preparing catalyst QA-SBA-15, 3-chloropropyltriethoxysilane (3.2g) was used as halogenating agent, and when QA-SBA-15 was synthesized, n (amine) was 1:2.7, tri-n-propane was used as tertiary amine, and the remaining reaction conditions were not changed.
Example 4
Synthesizing polythiol curing agent:
(1) 258.4g of 23 percent NaSH aqueous solution and 3.5g of the catalyst QA-SBA-15 prepared in example 1 were added into the reaction kettle, 168.4g of chlorinated polyether was then added, the reaction kettle was closed and the airtightness was checked, and then the reaction kettle was chargedIntroduction of H2S gas makes the kettle at normal pressure, the reaction system is heated to 90 ℃ through oil bath, then the reaction is carried out for 6 hours under heat preservation, then the vent valve of the reaction kettle is opened and N is used2And (4) displacing, filtering out the catalyst, and standing and layering the product to obtain a crude product A.
(2) Adding the crude product A into 175g of deionized water for primary washing, adjusting the pH of an organic phase to 5-7 by using hydrochloric acid, standing for layering after stabilization, and taking out a lower-layer substance, namely a crude product B; and adding 175g of deionized water into the crude product B, uniformly mixing, standing for 12h, cutting out the product, and dehydrating under the condition that the vacuum degree is less than or equal to-0.095 MPa, wherein the dehydrating temperature is 65 ℃ and the dehydrating time is 2h to obtain 152.7g of the high-quality polythiol curing agent for the epoxy resin.
The product obtained by the preparation method of example 4 was colorless and transparent, and had a chroma (Hazen) of 16 as measured by a hunter colorimeter and a halogen content (chlorine residue) of 154ppm as measured by a coulometer; meanwhile, the obtained product is subjected to hydrogen nuclear magnetic 1HNMR detection, the result is shown in figure 1, and as can be seen from figure 1, the product is a polyether polythiol compound with a structure shown in formula IV.
In the formula IV, m, n and p are independently selected from 2-5, and R is a C3 straight-chain alkyl group.
Example 5
Synthesizing polythiol curing agent: 237.9g of NaSH aqueous solution with the mass fraction of 18% (the molar ratio of NaSH to epichlorohydrin is 1.2: 1) and 5.5g of QA-SBA-15 catalyst prepared in example 2 were added to a reaction kettle, the reaction kettle was sealed, the airtightness was checked, and H was introduced into the kettle after the replacement2S gas makes the kettle at normal pressure, the reaction system is heated to 85 ℃ through oil bath, then the reaction is carried out for 6 hours under heat preservation, then the vent valve of the reaction kettle is opened and N is used2Replacing, and standing and layering the product to obtain a crude product A; adding the crude product A into 180g of deionized water for primary washing, adjusting the pH value of an organic phase to 3-4 by using hydrochloric acid, standing for layering after stabilization, and taking out a lower-layer substance, namely a crude product B; to the crude product B was added 180g of deionized waterAfter mixing uniformly, standing for 10 hours, cutting out the product, and dehydrating under the condition that the vacuum degree is less than or equal to-0.095 MPa, wherein the dehydration temperature is 65 ℃ and the time is 2 hours, thus obtaining 156.8g of colorless and transparent polyether type polythiol product.
The product obtained by the preparation method provided by the embodiment 2 of the invention is colorless and transparent, the chroma (Hazen) is 18 by a Hunter chroma meter, and the halogen content (chlorine residue) is 181ppm by a coulometer.
Example 6
220.6g of NaSH aqueous solution with the mass fraction of 18% (the molar ratio of NaSH to epichlorohydrin is 1.2: 1) and 4.2g of the phase transfer catalyst QA-SBA-15 prepared in example 3 are added into a reaction kettle, 161.0g of chlorinated polyether is added, the reaction kettle is sealed and checked for airtightness, H is introduced into the kettle after replacement2S gas makes the kettle at normal pressure, the reaction system is heated to 85 ℃ through oil bath, then the reaction is carried out for 6 hours under heat preservation, then the vent valve of the reaction kettle is opened and N is used2Replacing, and standing and layering the product to obtain a crude product A; adding the crude product A into 175g of deionized water for primary washing, adjusting the pH of an organic phase to 5-7 by using hydrochloric acid, standing for layering after stabilization, and taking out a lower-layer substance, namely a crude product B; and adding 175g of deionized water into the crude product B, uniformly mixing, standing for 10 hours, cutting out the product, and dehydrating under the condition that the vacuum degree is less than or equal to-0.095 MPa at the temperature of 65 ℃ for 2 hours to obtain 154.2g of colorless and transparent polyether type polythiol product.
Comparative example 1
Polythiol curing agents were obtained by the preparation method provided in example 4; the difference lies in that: 12.5g of the phase transfer catalyst tetrabutylammonium chloride was used instead of 3.5g of the catalyst QA-SBA-15 in example 4.
The product obtained by the preparation process provided in comparative example 1 was colorless and transparent, and had a color (Hazen) of 27 as measured by a hunter colorimeter and a halogen content (chlorine residue) of 589ppm as measured by a coulometer.
Comparative example 2
Polythiol curing agents were obtained by the preparation method provided in example 4; the difference lies in that: 16g of the phase transfer catalyst benzyltriethylammonium chloride was used instead of the catalyst QA-SBA-15 in example 4.
The product obtained by the preparation process provided in comparative example 2 was colorless and transparent, and had a color (Hazen) of 21 as measured by a hunter colorimeter and a halogen content (chlorine residual) of 673ppm as measured by a coulometer.
In conclusion, by adopting the preparation method provided by the invention, the polythiol curing agent for epoxy resin obtained by solvent-free three-phase transfer catalytic synthesis is colorless and transparent in appearance, the chroma is less than 20, the chlorine residue is only 100-200 ppm, and the polythiol curing agent is obviously superior to the polythiol curing agent prepared by the conventional method in the comparative example. Therefore, the preparation method provided by the invention can be used for preparing the environment-friendly colorless, transparent and high-viscosity polythiol product with low chlorine residue, an organic solvent is not required in the reaction process, the aim of recycling the expensive catalyst is fulfilled after the phase transfer catalyst is immobilized by using the organic high molecular polymer, and the catalyst is easy to recycle, so that the treatment difficulty of desalting and halogen removing of the product is reduced, and the obtained product chlorine residue is in the range of 100-200 ppm. Therefore, the invention reduces the raw material cost and the production cost, simultaneously reduces the post-treatment difficulty and the three-waste treatment difficulty, can further expand the application field of the product due to environmental protection of the product, and has very good industrial application prospect.
Claims (10)
1. The catalyst for preparing the polythiol curing agent is characterized in that the catalyst is a mesoporous molecular sieve SBA-15 with modified surface groups, and is marked as QA-SBA-15, wherein the surface groups of the catalyst comprise a structure shown as a formula I:
wherein, the left vertical thick black line represents the matrix skeleton of the mesoporous molecular sieve SBA-15, and R1, R2 and R3 are straight-chain or branched alkanes of C1-C10, which can be the same or different.
2. The method of claim 1, wherein the catalyst for preparing polythiol curing agent is prepared by subjecting a halogenating agent and the mesoporous molecular sieve SBA-15 to a reflux reaction in an organic solvent under a protective atmosphere, and subjecting the mixture to surface halogenation modification to obtain halogenated SBA-15; and reacting the obtained halogenated SBA-15 with tertiary amine to obtain the quaternary ammonium salt three-phase transfer catalyst QA-SBA-15.
3. The method of claim 2, wherein the mass ratio of the halogenating agent to the mesoporous molecular sieve SBA-15 is (0.5-4): 1; the molar ratio of halogen atoms in the reaction of halogenated SBA-15 with tertiary amine to nitrogen in tertiary amine is 1: (2-4).
4. The method for preparing a catalyst for polythiol curing agent according to claim 2, characterized in that said protective atmosphere is nitrogen; the halogenating agent is selected from 3-chloropropyltrimethoxysilane or 3-chloropropyltriethoxysilane or 3-bromopropyltrimethoxysilane or 3-bromopropyltriethoxysilane or a combination thereof; the organic solvent is an alcohol solvent; the tertiary amine has a structural formula shown in formula II:
wherein R1, R2 and R3 are straight-chain or branched alkanes of C1-C10, which can be the same or different;
the concentration of the halogenating reagent in the reaction system is 30-100 mmol/L; the reflux reaction time is 20-24 h; the reaction temperature of the halogenated SBA-15 and tertiary amine is 70-120 ℃; the reaction time of the halogenated SBA-15 and the tertiary amine is 8-12 h.
5. The method of claim 4, wherein the tertiary amine is selected from tri-n-propylamine, tri-n-butylamine, or a combination thereof.
6. The method of claim 2, wherein dichloroethane and absolute ethanol are added as a solvent in the reaction of the halogenated SBA-15 with a tertiary amine.
7. The method for synthesizing polythiol curing agent by using the catalyst of claim 1, which comprises the following steps: NaSH, a catalyst QA-SBA-15 and halogenated polyether polyol are added at normal pressure H2S, reacting in a gas environment, and separating out the catalyst to obtain a crude product; and then washing and drying the crude product in sequence to obtain the high-quality polythiol curing agent for the epoxy resin.
8. The method for synthesizing polythiol curing agent according to claim 7, characterized in that the catalyst QA-SBA-15 is added in an amount of 0.1-10% by mass of halogenated polyether polyol; the adding amount of NaSH is determined according to the molar ratio (0.5-3) of NaSH to halogen atoms in halogenated polyether polyol: 1, adding; the NaSH is added in the form of NaSH aqueous solution, and the mass fraction of the NaSH aqueous solution is 10-50%; the structure of the halogenated polyether polyol is shown as the formula III:
wherein m, n and p are independently selected from integers of 2-5, R is a linear alkyl group of C1-C10, a branched alkyl group of C1-C10, a substituted aryl group or an unsubstituted aryl group, and X is one or more of F, Cl and Br.
9. The method for synthesizing polythiol curing agent according to claim 7, wherein the reaction temperature is 60 ℃ to 150 ℃ and the reaction time is 2h to 20 h.
10. The method for preparing the catalyst for preparing the polythiol curing agent according to claim 2, wherein the washing process comprises: adding the obtained crude product into water for primary washing, adjusting the pH value of an organic phase to 5-7, standing for layering after stabilization, taking out substances on the lower layer, uniformly mixing the substances with the water, standing for 10-14 h, and then cutting out a product to finish the washing process; the drying mode is vacuum dehydration, the vacuum degree of the vacuum dehydration is less than or equal to-0.095 MPa, the temperature of the vacuum dehydration is 60-70 ℃, and the time of the vacuum dehydration is 1-3 h.
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| CN112250606A (en) * | 2020-10-27 | 2021-01-22 | 山东益丰生化环保股份有限公司 | Synthetic method of thiodiglycol for optical resin |
| WO2021114920A1 (en) * | 2019-12-13 | 2021-06-17 | 山东益丰生化环保股份有限公司 | Catalyst for preparing polythiol curing agent and use thereof |
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