CN110790691A - Hyperbranched secondary thiol compound, preparation method thereof and epoxy resin composition containing hyperbranched secondary thiol compound - Google Patents
Hyperbranched secondary thiol compound, preparation method thereof and epoxy resin composition containing hyperbranched secondary thiol compound Download PDFInfo
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- CN110790691A CN110790691A CN201911087448.0A CN201911087448A CN110790691A CN 110790691 A CN110790691 A CN 110790691A CN 201911087448 A CN201911087448 A CN 201911087448A CN 110790691 A CN110790691 A CN 110790691A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/52—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
- C07C319/12—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols by reactions not involving the formation of mercapto groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/26—Separation; Purification; Stabilisation; Use of additives
- C07C319/28—Separation; Purification
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
Abstract
The invention relates to the technical field of organic synthesis, and discloses a hyperbranched secondary thiol compound, which is shown as a formula 1:
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a hyperbranched secondary thiol compound and a preparation method thereof.
Background
The polythiol compound can be used as an industrial organic intermediate, a connecting agent, a polymerization modifier and a light curing agent, and can be widely used for light curing coatings, photosensitive materials, printed circuit boards and other functional materials. The coating is applied to a photocuring coating system, can improve the properties of the coating such as adhesive force, hardness, toughness, yellowing resistance and the like, and improves the curing property and the apparent property of the coating. Meanwhile, the modified polyvinyl alcohol can be used as a light-cured comonomer or a light-cured agent of polymers such as vinyl, (meth) acrylic acid, polyiso (thio) cyanate and the like to prepare an optical transparent material, improve the transparency and the refractive index of resin, and improve the impact resistance, the dyeing property, the processability and the like of the resin. In addition, the epoxy resin curing agent is used as a curing agent in an epoxy resin system, has the unique advantages of low-temperature rapid curing, improvement of the production efficiency of terminal customers, protection of heat-sensitive electronic components from damage and the like, and is widely applied.
The conventional mercaptan compound is in a primary ternary or quaternary mercaptan structure, has the advantages of high chemical activity and the defects of poor storage stability and the like, so that the problem of storage stability needs to be overcome in practical application. The secondary mercaptan has a significant advantage in storage stability compared with the primary mercaptan, but the reaction activity of the existing secondary mercaptan is insufficient.
The hyperbranched secondary thiol compound prepared by the invention is taken as a novel structural compound, has good storage stability and higher reaction activity, and is certainly favored by the market.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a hyperbranched secondary thiol structure compound and a preparation method thereof, which have good storage stability and higher reaction activity; meanwhile, the preparation process is simple, the product yield is high, and the production cost of the compound is greatly reduced. The compound can be widely applied to UV curing coatings and UV curing high polymer materials, and can be used as a curing agent for low-temperature rapid curing of epoxy resin, so that the compound has a very wide application prospect.
In order to achieve the above purpose, the invention provides the following technical scheme:
a hyperbranched secondary thiol compound has a structure shown in formula 1:
the R radical is a linear or branched or cyclic monovalent hydrocarbon radical of 1 to 18C atoms.
The reaction process of the hyperbranched secondary thiol compound is shown as formula 2:
further, the preparation method comprises the following steps: and (2) reacting the hyperbranched polyol with 3-mercaptobutyric acid in the presence of a solvent and a catalyst, and purifying after the reaction is finished to obtain the hyperbranched polyol.
Specifically, the preparation method of the hyperbranched secondary thiol compound comprises the following steps:
1) respectively adding hyperbranched polyol, a solvent and a catalyst into a reaction kettle with a high-speed stirrer, a water separator and an electronic sensing temperature controller;
2) setting the reaction temperature, and starting heating and stirring;
3) when the hyperbranched polyol, the solvent, the catalyst and other materials are completely dissolved and uniformly stirred and the material temperature reaches the set temperature, dropwise adding 3-mercaptobutyric acid;
4) after the dropwise addition of the 3-mercaptobutyric acid is finished, the reaction is continued for 3-5 hours at constant temperature, and then the reaction can be stopped;
5) cooling to room temperature, stopping stirring, and purifying to obtain the final product.
In the invention, further, the molar ratio of the hyperbranched polyol to the 3-mercaptobutyric acid is 1: 5-1: 10
In the invention, further, the solvent is one or a mixture of toluene, xylene and butyl acetate; preferably toluene; the mass of the solvent is 1-20 times of that of the hyperbranched polyol.
In the invention, further, the catalyst is one of hydrochloric acid, sulfuric acid and p-toluenesulfonic acid, preferably p-toluenesulfonic acid; the mass of the catalyst is 0.1-5% of that of the hyperbranched polyol.
In the invention, further, the reaction temperature is 70-160 ℃, preferably 90-140 ℃, and preferably 110-120 ℃; the reaction time is 2-5 hours.
In the invention, further, the purification treatment method includes but is not limited to water washing, extraction, drying and reduced pressure distillation, and if the requirement of high light transmittance on the appearance of the product is required, activated carbon powder decoloration treatment can be added.
The hyperbranched secondary mercaptan compound is a novel structural compound, has greatly improved structural stability compared with the conventional mercaptan compound which is primary ternary or quaternary mercaptan, has higher reaction activity compared with the common secondary mercaptan, and fills the defect of the common secondary mercaptan in reaction activity. The acrylate copolymer can be widely applied to acrylate compositions and epoxy resin compositions, and the comprehensive performance of the compositions is obviously improved.
Meanwhile, the preparation method of the hyperbranched secondary thiol compound has the advantages of simple preparation process, high product yield, greatly reduced material production cost and very wide application prospect.
Specifically, the hyperbranched secondary mercaptan compound is applied to an epoxy resin composition, and the epoxy resin composition comprises the secondary mercaptan compound, bisphenol A epoxy resin, silicon dioxide, black pigment and an accelerator.
The accelerator includes, but is not limited to, tertiary amines.
In the invention, further, the components of the epoxy resin composition are as follows according to the parts by weight:
in the invention, further, the components of the epoxy resin composition are as follows according to the parts by weight:
in the present invention, further, the epoxy resin composition is prepared by the following steps: after all the materials are added into the planetary stirrer, the materials are stirred and kneaded uniformly at a low speed and then stirred uniformly at a high speed.
Compared with the prior art, the invention has the beneficial effects that: the invention has the beneficial effects that:
the hyperbranched secondary mercaptan compound prepared by the invention has high transparency, high purity and low odor, is convenient to use in a laboratory or a production workshop, and can greatly reduce the discomfort of a user particularly in an environment with relatively closed space of the production workshop.
The hyperbranched secondary mercaptan compound and the preparation method thereof have the advantages of simple preparation process, high product yield, convenience for large-scale industrial production and great reduction of the production cost of the product.
Compared with the conventional primary mercaptan, the hyperbranched secondary mercaptan compound prepared by the invention has the effects of good product storage stability, quicker reaction speed, good humidity resistance and heat resistance of a cured product and the like in the practical application of UV coating, thermosetting epoxy resin system and the like.
Detailed Description
In order to make the technical means, the creation features, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the embodiment. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The raw materials used in the invention can be purchased from the market.
Example 1
A method for synthesizing a hyperbranched secondary thiol structural compound comprises the following steps:
1) adding 2000g of hyperbranched polyol, 10L of toluene and 50g of p-toluenesulfonic acid into a reaction kettle with a high-speed stirrer, a water separator and an electronic sensing temperature controller respectively; the R group in the hyperbranched polyol is methyl;
2) setting the reaction temperature to 120 ℃, and starting heating and stirring;
3) completely dissolving all materials in the reaction kettle and uniformly stirring, and beginning to dropwise add 3960g of 3-mercaptobutyric acid into the reaction kettle when the material temperature reaches the set temperature;
4) the dripping speed is controlled to be about 30 min;
5) after the dropwise addition is finished, the reaction is stopped after the constant-temperature reaction is continued for 3 hours;
6) cooling to room temperature, adding 5L of saturated salt water into the reaction kettle, stirring for 5min, standing for layering, discharging water layer, and repeating the steps for 3 times;
7) adding anhydrous sodium sulfate drying agent to remove residual water in the crude product;
8) filtering to remove the drying agent, distilling under reduced pressure, removing the solvent under 5000Pa, and removing low molecules for 1 hr after reducing the vacuum to within 100 Pa;
9) and finally, sealing and storing the product at normal temperature.
The hydrogen spectrum data of the product are as follows:
1H NMR(500MHz,Chloroform-d)δ5.06(p,J＝7.0Hz,1H),4.34(dd,J＝12.5,7.0Hz,1H),4.28–4.15(m,6H),4.14(dd,J＝12.4,7.1Hz,1H),4.06(dd,J＝12.5,7.0Hz,1H),3.85–3.74(m,2H),3.74–3.56(m,5H),3.52–3.40(m,2H),3.35(dd,J＝12.4,7.0Hz,1H),3.33–3.20(m,6H),3.19(s,3H),3.05(t,J＝6.9Hz,5H),2.67–2.55(m,10H),2.45(p,J＝7.0Hz,1H),1.33(dd,J＝6.8,3.5Hz,15H).
the target product is confirmed by analysis, and after purification, the yield of the hyperbranched secondary thiol compound TS2 is calculated to be 92.8%.
Example 2
A method for synthesizing a hyperbranched secondary thiol structural compound is different from that of example 1 only in that 2L of toluene and 2g of p-toluenesulfonic acid are added, the reaction temperature is 70 ℃ and 3510g of 3-mercaptobutyric acid is added dropwise. After purification, the yield of the hyperbranched secondary thiol compound TS2 was calculated to be 90.5%.
Example 3
A method for synthesizing a hyperbranched secondary thiol structural compound is different from that of example 1 only in that 12L of toluene and 50g of p-toluenesulfonic acid are added, the reaction temperature is 100 ℃ and the amount of dropwise added 3-mercaptobutyric acid is 4200 g. After purification, the yield of the secondary thiol compound TS2 was calculated to be 92.2%.
Example 4
A method for synthesizing a hyperbranched secondary thiol structural compound is different from that of example 1 only in that 15L of toluene and 60g of p-toluenesulfonic acid are added, the reaction temperature is 140 ℃ and 5600g of 3-mercaptobutyric acid is added dropwise. After purification, the yield of the secondary thiol compound TS2 was calculated to be 91.2%.
Example 5
A method for synthesizing a hyperbranched secondary thiol structural compound is different from that of example 1 only in that 34L of toluene and 100g of p-toluenesulfonic acid are added, the reaction temperature is 160 ℃ and 7010g of 3-mercaptobutyric acid is added dropwise. After purification, the yield of the secondary thiol compound TS2 was calculated to be 91.0%.
When the R group is other substituent, the specific reaction regulation and yield are shown in the following table 1:
TABLE 1
Note: the feeding molar ratio is the molar ratio of the hyperbranched polyol to the 3-mercaptobutyric acid, and the reaction temperature is 120 ℃.
Example 6
An epoxy resin composition was prepared using the secondary thiol compound obtained in example 1 as a curing agent:
(1) the epoxy resin composition material and the parts thereof are as follows:
(2) the preparation method of the epoxy resin composition comprises the following steps: e51, commercially available carbon black, R972, TS2 and tertiary amine are added into a planetary stirrer, and then the mixture is uniformly stirred and kneaded at a low speed and then uniformly stirred at a high speed.
Comparative example 1: preparation of an epoxy resin composition with pentaerythritol tetrakis (3-mercaptopropionate) as curing agent: the other components, the proportion and the preparation method are all consistent with those of the example 6.
The epoxy resin combinations of example 6 and comparative example 1 were tested and the product characteristics are shown in table 2:
TABLE 2
Note: the data are the average of at least 5 tests.
As can be seen from the data in Table 1, the epoxy resin composition using the hyperbranched secondary thiol compound TS2 obtained in example 6 as a curing agent has high curing speed and low curing temperature; meanwhile, the opening time at normal temperature is long enough to ensure that the product has enough service time; and after the product is cured, the mechanical property is excellent, the water absorption rate is low, and the comprehensive performance is excellent.
The above experiments were also conducted on hyperbranched secondary thiol compound TS2 prepared in other examples of the present invention as a curing agent to prepare epoxy resin compositions, and similar results were obtained.
In this example 6, too much consideration and optimization are not made to the formulation, but the effect of the product TS2 prepared by the present invention in practical application is considered for the first time. In practical application, more excellent products can be optimized according to the characteristics of the epoxy resin system, so that the epoxy resin curing agent has a very wide application prospect.
The invention is not limited to the foregoing embodiments. The invention extends to any novel feature or any novel combination of features disclosed in this specification and any novel method or process steps or any novel combination of features disclosed.
Claims (10)
1. A hyperbranched secondary thiol compound is characterized in that the structure of the compound is shown as formula 1:
the R radical is a linear or branched or cyclic monovalent hydrocarbon radical of 1 to 18C atoms.
2. A method for preparing the hyperbranched secondary thiol compound of claim 1, wherein the synthetic reaction process is as shown in formula 2:
3. the method of claim 2, comprising the steps of: and (2) reacting the hyperbranched polyol with 3-mercaptobutyric acid in the presence of a solvent and a catalyst, and purifying after the reaction is finished to obtain the hyperbranched polyol.
4. The method according to claim 3, wherein the molar ratio of the hyperbranched polyol to the 3-mercaptobutanoic acid is 1:5 to 1: 10.
5. The method for preparing a hyperbranched secondary thiol compound as claimed in claim 3, wherein the solvent is one or more of toluene, xylene, and butyl acetate; preferably toluene; the mass of the solvent is 1-20 times of that of the hyperbranched polyol.
6. The method for preparing a hyperbranched secondary thiol compound as claimed in claim 3, wherein the catalyst is one of hydrochloric acid, sulfuric acid, and p-toluenesulfonic acid, preferably p-toluenesulfonic acid; the mass of the catalyst is 0.1-5% of that of the hyperbranched polyol.
7. The method for preparing a hyperbranched secondary thiol compound as claimed in claim 3, wherein the purification treatment includes but is not limited to water washing, extraction, drying and distillation under reduced pressure, and the purification treatment further includes activated carbon powder decolorization treatment.
8. The method for preparing a hyperbranched secondary thiol compound as claimed in claim 3, wherein the reaction temperature is 70 ℃ to 160 ℃, preferably 90 ℃ to 140 ℃, preferably 110 ℃ to 120 ℃; the reaction time is 2-5 hours.
9. An epoxy resin composition comprising a hyperbranched secondary thiol compound according to claim 1.
10. The epoxy resin composition as claimed in claim 9, further comprising bisphenol a epoxy resin, silica, black pigment, accelerator;
preferably, the components are as follows according to parts by weight:
more preferably, the components are as follows according to parts by weight:
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Cited By (3)
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| CN111040133A (en) * | 2019-12-17 | 2020-04-21 | 山东益丰生化环保股份有限公司 | High-temperature-resistant epoxy resin curing agent, and preparation method and application thereof |
| CN115124906A (en) * | 2022-07-29 | 2022-09-30 | 华南理工大学 | Underwater construction curing coating and preparation method and application thereof |
| CN115181484A (en) * | 2022-07-29 | 2022-10-14 | 华南理工大学 | Underwater construction in-situ curing antifouling paint and preparation method and application thereof |
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| CN102449021A (en) * | 2009-05-28 | 2012-05-09 | 昭和电工株式会社 | Epoxy resin-based coating composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111040133A (en) * | 2019-12-17 | 2020-04-21 | 山东益丰生化环保股份有限公司 | High-temperature-resistant epoxy resin curing agent, and preparation method and application thereof |
| CN115124906A (en) * | 2022-07-29 | 2022-09-30 | 华南理工大学 | Underwater construction curing coating and preparation method and application thereof |
| CN115181484A (en) * | 2022-07-29 | 2022-10-14 | 华南理工大学 | Underwater construction in-situ curing antifouling paint and preparation method and application thereof |
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