CN109880075B - Preparation method of high-mercapto polythiol curing agent - Google Patents
Preparation method of high-mercapto polythiol curing agent Download PDFInfo
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- CN109880075B CN109880075B CN201910169715.2A CN201910169715A CN109880075B CN 109880075 B CN109880075 B CN 109880075B CN 201910169715 A CN201910169715 A CN 201910169715A CN 109880075 B CN109880075 B CN 109880075B
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Abstract
The invention provides a preparation method of high-sulfydryl polythiol curing agent, which takes polyether polyol as raw material, and generates ring-opening reaction with epichlorohydrin to form intermediate chloride under the action of catalyst 1, and further generates substitution reaction with NaHS under the action of catalyst 2 to generate polythiol curing agent, because the side reaction of the invention can generate H2S gas generation, increasing system H according to chemical reaction equilibrium constant2S can inhibit side reaction, so the inventor uses H in the synthesis process2S is used as protective gas for preparation, thereby providing a method which can control side reaction and increase the content of target products; the polythiol curing agent synthesized by the invention has higher proportion of sulfydryl and can reach 14.6 percent.
Description
Technical Field
The invention relates to the technical field of epoxy resin curing agents, in particular to a preparation method of a high-mercapto polythiol curing agent.
Background
The polythiol curing agent is a low-temperature quick epoxy curing agent used in recent years, has more than two-SH (hydroxyl groups) at the end group, and is mainly used for curing epoxy resin at room temperature. Compared with other epoxy curing agents, the epoxy curing agent has the remarkable advantages of low curing temperature, quick curing, thin-layer curing, light color and the like, and is a product which cannot be replaced by other curing agents. Meanwhile, due to the existence of the sulfur flexible chain segment and higher refractive index, the material also has great application value in the aspects of toughening resin and transparent resin.
However, the method for preparing the polythiol curing agent in the prior art mainly comprises a sodium hydrosulfide nucleophilic method, wherein sodium hydrosulfide is adopted as a raw material to synthesize polythiol; however, the method has obvious defects that the side reaction is difficult to control, the thioether generated by the side reaction not only reduces the mercapto content of the active group of the polythiol, but also greatly increases the product viscosity, and the adopted raw material sodium hydrosulfide is easy to generate the side reaction in the reaction process, so that the mercapto content is reduced, and the expected effect is difficult to achieve; the applicant has previously adopted a method of replacing reaction raw materials to overcome this problem, and in the previous application, thiourea was used to introduce the mercapto group, but this resulted in that the subsequent production processes all need to be adapted, which resulted in a great increase in production cost, and therefore how to overcome some of the side reactions caused by using sodium hydrosulfide as a raw material became one of the problems to be solved by those skilled in the art.
Disclosure of Invention
Aiming at various problems in the prior art, the invention provides a preparation method of a high-sulfydryl polythiol curing agent, which takes polyether polyol as a raw material, and performs ring-opening reaction with epoxy chloropropane under the action of a catalyst 1 to form an intermediate chloride, and further performs substitution reaction with NaHS under the action of a catalyst 2 to generate the polythiol curing agent, wherein H is generated due to side reaction in the invention2S gas generation, increasing system H according to chemical reaction equilibrium constant2S can inhibit side reaction, so the inventor introduces protective gas H in the synthesis process2S, the preparation provides a method which can control side reaction and increase the content of a target product; the polythiol curing agent synthesized by the invention has higher proportion of sulfydryl, and can reach 14.6%.
The specific technical scheme of the invention is as follows:
the invention relates to a method for preparing high-sulfydryl polythiol curing agent, which comprises the preparation of chlorinated polyether polyol and the preparation of polythiol curing agent, and the invention is characterized in that: in the preparation process of the polythiol curing agent, sodium hydrosulfide and chlorinated polyether polyol are used as raw materials to react, and the system pressure is controlled to be 0.02-4.5 Mpa in the reaction process;
in order to meet the reaction requirements, the preparation of the polythiol curing agent is carried out in a pressure vessel, and protective gas is introduced into the pressure vessel for pressure regulation; the protective gas is H2S；
Due to the fact thatThe invention adopts sodium hydrosulfide as reaction raw material, and side reaction occurs in the reaction process, thereby generating H2S gas, the inventors have found, based on the equilibrium constant of the chemical reaction, to increase the H of the reaction system of the present invention2S can inhibit side reaction and improve synthesis efficiency, so the inventor decides to use protective gas for pressure regulation in the synthesis process with sodium hydrosulfide, wherein the preferred protective gas is H2S, so that more H can be suppressed2S is generated, thereby reducing the occurrence of side reactions.
The preparation method comprises the following specific steps:
the first step is as follows: under the action of the catalyst 1, the catalyst is added,
polyether polyol + epichlorohydrin → chlorinated polyether polyol;
the second step is that: under the action of the catalyst 2, the catalyst is added,
chlorinated polyether polyol + sodium hydrosulfide → polythiol curing agent;
wherein the catalyst 1 is a weakly acidic metal salt; the catalyst 2 is a surfactant;
in the first step, the molecular weight of the polyether polyol is 200-3000, and the molar ratio of hydroxyl in epoxy chloropropane to hydroxyl in the polyether polyol is (0.8-2) to 1;
the molar ratio of the sodium hydrosulfide in the second step to the epoxy chloropropane in the first step is (0.8-2) to 1;
the first step is normal pressure reaction, the reaction pressure of the second step is 0.02-4.5 Mpa, and protective gas is introduced in the reaction process for pressure regulation.
Preferably, the catalyst 1 in the first step is selected from tin tetrachloride or antimony pentachloride or titanium tetrachloride or zinc chloride, and the dosage of the catalyst is 0.7 to 1.5 percent of the mass of the polyether polyol.
Preferably, the catalyst 2, i.e. the surfactant, in the second step is selected from glycerol or polyethylene glycol 400 or tetrabutylammonium halide or octadecyldimethylhydroxyethylammonium nitrate in an amount of 1% to 20% by weight of the chlorinated polyether polyol.
More preferably, catalyst 2 in the second step is selected from glycerol; this option can shorten the reaction time and improve the production efficiency.
The reaction temperature in the first step is preferably 80-120 ℃, the reaction time is 0.5-5 h, and the reaction pressure is normal pressure.
The reaction temperature in the second step is preferably 100-150 ℃, and the reaction time is 3-10 h.
The polyether polyol adopted by the invention can be directly prepared by adopting the prior art, or the polyether polyol on the market can be directly purchased, and the inventor does not need to describe any more;
and the first reaction step can also be directly referred to the prior art, such as the preparation of chlorinated polyether polyol by the method described in the applicant's prior application;
in conclusion, the inventors of the present invention used a shielding gas H in the synthesis process2S controls the side reaction, thereby increasing the content of the target product; the polythiol curing agent synthesized by the invention has higher proportion of sulfydryl, can reach 14.6 percent and is obviously higher than the prior art.
Detailed Description
The present invention is further illustrated below with reference to examples, which will enable those skilled in the art to more fully understand the present invention, but which are not intended to limit the invention in any way;
EXAMPLE 1 preparation of chlorinated polyether polyol
1) Into a 250mL four-necked flask equipped with a thermometer and a stirrer were charged 100g of polyether polyol and 1.2g of SnCl as a catalyst4·5H2O, starting a stirring and heating sleeve, and heating to 100 ℃;
2) slowly dripping 67.52g of epoxy chloropropane (99.5%) into a four-neck flask, controlling the system temperature at 100 ℃ and 110 ℃, and dripping for about 1 h;
3) after the dropwise addition, preserving the heat for 1h at the temperature of 110 ℃ to prepare light yellow transparent chlorinated polyether polyol;
4) the highest 3-Cl content of 36% was obtained by liquid chromatography.
EXAMPLE 2 preparation of chlorinated polyether polyol
The same step 1) as the step 1 of the example 1 is adopted, and in the step 2), epichlorohydrin (99.5 percent) is respectively dripped, and the mass is 75.02g, 82.52g and 90.02 g; the temperature of the system is controlled at 110 ℃ and the dropping time is about 1 h;
3) after the dropwise addition, preserving the heat for 1h at the temperature of 110 ℃ to prepare light yellow transparent chlorinated polyether polyol;
4) the content of 3-Cl was determined by liquid chromatography and found to be 46%, 50% and 45%, respectively.
Therefore, 82.52g of epoxy chloropropane is adopted as the best proportion, and the method is more suitable for being used in subsequent preparation.
EXAMPLE 3 preparation of polythiol curing agent (H)2S pressure of 0.2MPa)
1) 177.7g of the intermediate was weighed out into a pressure vessel while adding 18 wt% of NaHS solution (377 g) and 32g of catalyst glycerol in this order to the system, using as a starting material the chlorinated polyether polyol prepared in example 2 in which the amount of epichlorohydrin added was 82.52 g.
2) Filling a container with a protective gas H2S (the pressure is less than or equal to 0.1Mpa), and after 3 times of replacement, the protective gas is controlled to be 0.2 Mpa;
3) starting stirring and heating, raising the temperature to 125 ℃ of 120-;
4) and after the reaction is finished, carrying out liquid separation treatment on the reaction liquid, adding 500g of water into the oil phase, adding dilute hydrochloric acid, adjusting the pH value to be acidic, stirring for 3 hours, carrying out liquid separation, adding 500g of water into the oil phase, washing for 3 hours, carrying out liquid separation, and carrying out rotary evaporation to obtain the product, wherein the product is colorless and transparent, and the measured content of the sulfydryl in the product is 14.28%.
EXAMPLE 4 preparation of polythiol curing agent (H)2S pressure of 0.5MPa)
1) 27g of catalyst glycerol was added in the same manner as in step 1 of example 3;
2) filling a container with a protective gas H2S (the pressure is less than or equal to 0.1Mpa), and after 3 times of replacement, the protective gas is controlled to be 0.5 Mpa;
3) the same as the step 3 of the embodiment 3, the temperature is maintained at 120-125 ℃ for 5 hours from the time of temperature rise;
4) the product was found to have a mercapto content of 14.52% as measured in example 3, step 4.
EXAMPLE 5 polythiol solidPreparation of the Agents (H)2S pressure of 0.8MPa)
1) The same as example 3, step 1, 21g of catalyst glycerol was added;
2) filling a container with a protective gas H2S (the pressure is less than or equal to 0.1Mpa), and after 3 times of replacement, the protective gas is controlled to be 0.8 Mpa;
3) the same as the step 3 of the embodiment 3, the temperature is maintained at 120-125 ℃ for 4 hours from the time of temperature rise; (ii) a
4) The product was found to have a mercapto content of 14.6% as measured in example 3, step 4.
EXAMPLE 6 preparation of polythiol curing agent (H)2S pressure 1.2MPa)
1) The same as example 3, step 1, 16g of catalyst glycerol was added;
2) filling a container with a protective gas H2S (pressure is less than or equal to 0.1Mpa), and after 3 times of replacement, the protective gas is controlled at 1.2 Mpa.
3) The same as the step 3 of the embodiment 3, the temperature is increased to the end of heat preservation for 3 hours;
4) the product was found to have a mercapto content of 14.47% as measured in example 3, step 4.
The comparison between the above example 5 and examples 3, 4, and 6 shows that the thiol content of the polythiol curing agent finally obtained by the technical scheme of the present invention is significantly higher than that of the prior art, wherein the technical scheme of example 5 is the best embodiment, and the inventors have found through experiments that after the catalyst glycerol is replaced by polyethylene glycol 400 or tetrabutylammonium halide or octadecyl dimethyl hydroxyethyl ammonium nitrate, the thiol content of the final product is still higher than that of the prior art, and the method is also significantly improved compared with the prior art, but the effect is slightly worse than that of glycerol, so that the technical scheme provided by the present invention can solve many disadvantages of using sodium hydrosulfide as a raw material to prepare the polythiol curing agent, and can be better popularized and applied.
Claims (3)
1. A method for preparing high-sulfydryl polythiol curing agent, comprising the preparation of chlorinated polyether polyol and the preparation of polythiol curing agent, characterized in that: in the preparation process of the polythiol curing agent, sodium hydrosulfide and chlorinated polyether polyol are used as raw materials to react, and the system pressure is controlled to be 0.02-4.5 Mpa in the reaction process;
the polythiol curing agent is prepared under the protection gas, and the protection gas is H2S；
The method comprises the following specific steps:
the first step is as follows: under the action of the catalyst 1, the catalyst is added,
polyether polyol + epichlorohydrin → chlorinated polyether polyol;
the second step is that: under the action of the catalyst 2, the catalyst is added,
chlorinated polyether polyol + sodium hydrosulfide → polythiol curing agent;
wherein the catalyst 1 is a weakly acidic metal salt; the catalyst 2 is a surfactant;
in the first step, the molecular weight of the polyether polyol is 200-3000, and the molar ratio of hydroxyl in epoxy chloropropane to hydroxyl in the polyether polyol is (0.8-2) to 1;
the molar ratio of the sodium hydrosulfide in the second step to the epoxy chloropropane in the first step is (0.8-2) to 1;
the first step is a normal pressure reaction, and the protective gas in the second step is controlled to be 0.02-4.5 Mpa;
in the second step, the reaction temperature is 100-150 ℃, the reaction time is 3-10 h, and the catalyst 2 in the second step is selected from glycerol, and the dosage of the catalyst is 1-20% of the mass of the chlorinated polyether polyol.
2. The method of claim 1, wherein the curing agent is selected from the group consisting of:
the catalyst 1 in the first step is selected from tin tetrachloride or antimony pentachloride or titanium tetrachloride or zinc chloride, and the dosage of the catalyst is 0.7 to 1.5 percent of the mass of polyether polyol.
3. The method of claim 1, wherein the curing agent is selected from the group consisting of: the reaction temperature in the first step is 80-120 ℃, the reaction time is 0.5-5 h, and the reaction pressure is normal pressure.
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| CN110452370B (en) * | 2019-08-26 | 2020-10-20 | 山东益丰生化环保股份有限公司 | Polythiol curing agent, and preparation method and application thereof |
| CN112300370A (en) * | 2020-08-05 | 2021-02-02 | 山东益丰生化环保股份有限公司 | Viscosity-controllable polythiol epoxy resin curing agent and preparation method thereof |
| CN112250606B (en) * | 2020-10-27 | 2022-08-26 | 山东益丰生化环保股份有限公司 | Synthetic method of thiodiglycol for optical resin |
| EP4410865A1 (en) | 2021-09-29 | 2024-08-07 | Toray Fine Chemicals Co., Ltd. | Production method of thiol group-containing polyether polymer |
| WO2024053593A1 (en) * | 2022-09-06 | 2024-03-14 | 東レ・ファインケミカル株式会社 | Thiol group-containing polyether polymer, epoxy resin-containing composition, and curing agent for epoxy resin |
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Address after: 256500 Boxing Economic Development Zone, Shandong, Binzhou Patentee after: Yifeng New Material Co.,Ltd. Address before: 256500 Boxing Economic Development Zone, Shandong, Binzhou Patentee before: SHANDONG EFIRM BIOCHEMISTRY AND ENVIRONMENTAL PROTECTION Co.,Ltd. |