CN115819453A - Phosphorus-containing epoxy curing agent and preparation method thereof - Google Patents
Phosphorus-containing epoxy curing agent and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a phosphorus-containing epoxy curing agent and a preparation method thereof. The epoxy curing agent has multiple functions, and has the advantages of simple preparation process, high product purity, nontoxic and harmless production process and easy large-scale production.
Description
Technical Field
The invention belongs to the technical field of curing agents, and particularly relates to a phosphorus-containing epoxy curing agent and a preparation method thereof.
Background
Epoxy resins are well known for their excellent adhesion, chemical and heat resistance, good to excellent mechanical properties and good electrical insulation properties. Cured epoxy systems have a wide range of applications including adhesives, coatings, inks, and composites. For example: protective coatings for metal surfaces, and building products for concrete, cement or ceramic substrates, commonly referred to as civil engineering applications; a sealant for electronic 3C products or for LEDs. The related industries comprise the aspects of building, chemical engineering, automobiles, ships, electrical insulation and the like.
The epoxy resin is a compound with a linear structure, has stable performance, and has practical value only by using the epoxy resin and a curing agent together. The curing agent is therefore an essential component of the epoxy resin during use. Curing agents for epoxy resins are widely varied, and there are common: aliphatic diamines and polyamines, aromatic polyamines, other nitrogen-containing compounds and modified aliphatic amines, acid anhydrides, polyamides, organic acids, boron trifluoride and the like, with diamine polyamines and acid anhydride curing agents being the most common.
Epoxy resin is widely applied to a plurality of fields, but the limit oxygen index of the epoxy resin is very low, usually lower than 20, the epoxy resin is easy to burn, the application of the epoxy resin is greatly limited, and the epoxy resin used in the electronic packaging industry and the transportation equipment industry needs to have flame retardance, so the research and development of the flame retardant epoxy resin are not slow.
The organic phosphorus flame retardant has the advantages of low smoke, no toxicity, low halogen, no halogen and the like, accords with the development direction of the flame retardant, and has good development prospect. The organic phosphorus flame retardant comprises phosphate, phosphite, phosphonate, organic phosphorus salt, phosphorus heterocyclic compound, polymer phosphate (phosphonate) ester and the like, but the phosphate and phosphonate are the most widely used, the research and development of the phosphorus flame retardant is underway, and a lot of reports are reported every year, for example, patent application 202011344498.5 discloses a preparation method of a low-halogen high-polymerization degree phosphate flame retardant, which comprises the following steps: (1) Preparing oligomeric phosphate solution by using dihydroxyl or diamine compounds and phosphorus oxychloride compounds as raw materials; (2) Concentrating the oligomeric phosphate solution to form a viscous mixture, adding a solvent into the viscous mixture to dissolve the viscous mixture into a solution state, then heating to the boiling point temperature of the solvent, carrying out heat preservation polymerization reaction for 1-6 h at the temperature, and filtering to obtain a polyphosphate aggregate; (3) After the polyphosphate ester aggregate is polymerized at high temperature, the phosphate ester flame retardant with low halogen and high polymerization degree is prepared by cooling. Patent application 201910314499.6 discloses a nitrogen-containing phosphonate flame retardant and a synthetic method thereof, wherein the chemical name of the nitrogen-containing phosphonate flame retardant is polymethylpiperazine phosphonate; the preparation method comprises the following steps: adding piperazine and a catalyst into dimethyl methylphosphate in a reaction vessel, fully stirring to dissolve the dimethyl methylphosphate, heating and reacting for several hours, and collecting fraction methanol; and cooling after the reaction is finished to obtain the product of the polymethyl piperazine phosphonate.
The action mechanism of the organic phosphorus flame retardant is that the flame retardant can generate a cross-linked solid substance or a carbonized layer with a more stable structure when being heated. The carbonized layer can prevent the polymer from further pyrolysis on one hand and prevent the thermal decomposition products in the carbonized layer from entering the gas phase to participate in the combustion process on the other hand.
At present, the most common methods for people mainly comprise external addition type and reaction type flame retardance, and the addition type adopts a physical dispersion mode, so that the compatibility is poor, the flame retardance efficiency is low, and the physical properties of the material are influenced; the reactive halogen is widely applied due to excellent flame-retardant and mechanical and electrical properties, but toxic and harmful substances are generated, so that the reactive halogen is forbidden by many countries, and the development of a high-performance and multifunctional halogen-free flame-retardant epoxy curing agent is necessary.
Disclosure of Invention
In order to solve the above problems, a primary object of the present invention is to provide a phosphorous epoxy hardener and a method for preparing the same, in which a short chain contains phosphorous or cyclic phosphorous, and the phosphorous is in a main chain, thereby improving a flame retardant effect and having various functions.
The invention also aims to provide the phosphorus-containing epoxy curing agent and the preparation method thereof, and the epoxy curing agent and the preparation method thereof have the advantages of simple preparation process, high product purity, nontoxic and harmless production process and easy large-scale production.
In order to achieve the above object, the technical solution of the present invention is as follows.
A phosphorus-containing epoxy curing agent, the molecular structure of which is as follows:
wherein R is alkyl, alkoxy, aryl, aryloxy; r' is alkyl chain, ether chain or aryl chain.
The invention improves the performance of the curing agent by short-chain phosphorus or cyclic phosphorus, so that the curing agent has excellent flame retardant performance, and can increase the hardness, water resistance and other functions of the product.
The preparation process of the phosphorus-containing epoxy curing agent is as follows:
dissolving the C or D-represented divinyl phosphate (one equivalent) in water or ethanol, then dropwise adding into the aqueous solution of hydroxylamine hydrochloride at 0 ℃ within three hours, heating to room temperature after dropwise adding, and reacting at room temperature overnight; TLC (thin layer chromatography) is used for monitoring the reaction end point, and after the reaction is finished, low boiling point substances are distilled off under reduced pressure to obtain transparent viscous liquid.
Further, the concentration of the hydroxylamine solution is 30%.
Further, the amount of the solution of the bisvinylphosphate representing C or D and the hydroxylamine solution is as follows: 14-25mmol of bisvinylphosphate (the amount is summarized in the examples, please confirm), 120ml of 30% hydroxylamine solution.
Further, after confirming that the reaction was completed, the reaction system was depressurized to remove residual ammonia and water or ethanol, and finally a colorless and transparent viscous liquid was obtained.
After the epoxy curing agent and the epoxy resin are cured into a polymer, the short chain contains phosphorus or cyclic phosphorus, so that the phosphorus is in the main chain, the hardness of the product can be improved, and the coating has no foaming, no wrinkling, no obvious color change, no shedding and other phenomena within 240 hours; meanwhile, in the aspect of limiting oxygen index, the limiting oxygen index is over 27, and the flame retardant effect is greatly improved.
And the preparation process is simple, the product purity is high, the production process is non-toxic and harmless, and the large-scale production is easy to carry out.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of a compound A2 realized by the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. 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 phosphorus-containing epoxy curing agent has the following molecular structure:
wherein R is alkyl, alkoxy, aryl, aryloxy; r' is alkyl chain, ether chain or aryl chain.
The phosphorus-containing epoxy curing agent is prepared as follows:
dissolving the bisvinylphosphate (equivalent) representing C or D in water or ethanol, then dropwise adding into the aqueous solution (30%) of hydroxylamine hydrochloride at 0 ℃ within several hours, heating to room temperature after dropwise adding, and reacting at room temperature overnight; TLC monitors the reaction end point, and after the reaction is finished, ammonia and water or ethanol are decompressed and distilled to obtain transparent viscous liquid.
The following describes implementations of the present invention with reference to specific embodiments.
Example 1
Preparation of phosphorus-containing epoxy hardener A1 using divinylbutanediol diphosphate C1: c1 (2.18 g, 7.3 mmol) was dissolved in 120mL of water, the temperature was controlled at 0 deg.C, and the C1 solution was added dropwise over three hours to a three-necked flask with mechanical stirring containing 120mL of hydroxylamine solution (30%). After the completion of the dropwise addition, the temperature of the reaction system was raised to room temperature and reacted overnight. The reaction was monitored by TLC to confirm completion of the reaction. The reaction system was depressurized to remove residual ammonia and water. Finally, 2.39 g of A1 as a colorless transparent viscous liquid was obtained in a yield of 98.8%.
Example 2
Preparation of A2 using C2: c2 (1.97 g, 7.3 mmol) was dissolved in 120mL of water, the temperature was controlled at 0 deg.C, and the C2 solution was added dropwise over three hours to a three-necked flask with mechanical stirring containing 120mL of hydroxylamine solution (30%). After the completion of the dropwise addition, the temperature of the reaction system was raised to room temperature and reacted overnight. The reaction was monitored by TLC to confirm completion of the reaction. The reaction system was depressurized to remove residual ammonia and water. Finally, 2.20 g of A2 as colorless and transparent viscous liquid is obtained, and the yield is 99.1%.
Example 3
Preparation of A3 using C3: c3 (2.18 g, 7.3 mmol) was dissolved in 120mL of water, the temperature was controlled at 0 deg.C, and the C3 solution was added dropwise over three hours to a three-necked flask with mechanical stirring containing 120mL of hydroxylamine solution (30%). After the completion of the dropwise addition, the temperature of the reaction system was raised to room temperature and reacted overnight. The reaction was monitored by TLC to confirm completion of the reaction. The reaction system was depressurized to remove residual ammonia and water. Finally, 2.40 g of A2 as colorless and transparent viscous liquid is obtained, and the yield is 99.2%.
Example 4
Preparation of A4 using C4: c4 (3.29 g, 7.3 mmol) was dissolved in 120mL of water, the temperature was controlled at 0 deg.C, and the C4 solution was added dropwise over three hours to a three-necked flask with mechanical stirring containing 120mL of hydroxylamine solution (30%). After the completion of the dropwise addition, the temperature of the reaction system was raised to room temperature and reacted overnight. The reaction was monitored by TLC to confirm completion of the reaction. The reaction system was depressurized to remove residual ammonia and water. Finally, 3.45 g of A4 as a colorless transparent viscous liquid was obtained in 97.7% yield.
Example 5
Preparation of A5 using C5: c5 (2.82 g, 7.3 mmol) was dissolved in 120mL of water, the temperature was controlled at 0 deg.C, and the C5 solution was added dropwise over three hours to a three-necked flask with mechanical stirring containing 120mL of hydroxylamine solution (30%). After the completion of the dropwise addition, the temperature of the reaction system was raised to room temperature and reacted overnight. The reaction was monitored by TLC to confirm completion of the reaction. The reaction system was depressurized to remove residual ammonia and water. Finally, 3 g of A5 as a colorless transparent viscous liquid was obtained in 97.7% yield.
Example 6
Preparation of A6 using C6: c6 (2.69 g, 7.3 mmol) was dissolved in 120mL of water, the temperature was controlled at 0 ℃ and added dropwise over three hours to a three-necked flask with mechanical stirring containing 120mL of hydroxylamine solution (30%). After the completion of the dropwise addition, the temperature of the reaction system was raised to room temperature and reacted overnight. The reaction was monitored by TLC to confirm completion of the reaction. The reaction system was depressurized to remove residual ammonia and water. Finally, 3 g of A6 as a colorless transparent viscous liquid is obtained with a yield of 98.7%.
Example 7
Preparation of A7 using C7: c7 (3.27 g, 7.3 mmol) was dissolved in 120mL of water, the temperature was controlled at 0 ℃ and added dropwise over three hours to a three-necked flask with mechanical stirring containing 120mL of a hydroxylamine solution (30%). After the completion of the dropwise addition, the temperature of the reaction system was raised to room temperature and reacted overnight. The reaction was monitored by TLC to confirm completion of the reaction. The reaction system was depressurized to remove residual ammonia and water. Finally, 3.45 g of A7 was obtained as a colorless transparent viscous liquid with a yield of 98.0%.
Example 8
Preparation of B using D: d (2.04 g, 7.3 mmol) was dissolved in 120mL of water, the temperature was controlled at 0 ℃ and added dropwise over three hours to a three-necked flask with mechanical stirring containing 120mL of hydroxylamine solution (30%). After the completion of the dropwise addition, the temperature of the reaction system was raised to room temperature and reacted overnight. The reaction was monitored by TLC to confirm completion of the reaction. The reaction system was depressurized to remove residual ammonia and water. Finally, 2.28 g of B was obtained as a colorless transparent viscous liquid with a yield of 99.6%.
Taking A2 as an example, as shown in fig. 1, the nuclear magnetic hydrogen spectrum carbon spectrum data of the compound A2 is as follows:
1 H NMR(500MHz,CDCl 3 )δ4.40(td,J＝3.9,1.5Hz,2H),3.65(d,J＝21.8Hz,3H),2.96(t,J＝16.6Hz,2H),2.03(dt,J＝23.8,16.6Hz,2H),1.18(s,2H). 13 CNMR(125MHz,CDCl 3 )δ63.95(t,J＝6.2Hz),53.21(d,J＝6.7Hz),38.90(d,J＝6.7Hz),30.93(s),30.17(s)。
see also table 1.
TABLE 1
As can be seen from table 1: the flame-retardant epoxy curing agents A1, A7 and D prepared in the embodiments 1,7 and 8 are respectively added with 10 percent (mass fraction, curing agent 1) of the flame-retardant epoxy curing agent A1, A7 and D and the traditional epoxy curing agent polyether amine D230 (curing agent 2), and then the leveling agent and the accelerator are added to respectively form the components B in the embodiments 9, 10 and 11. Comparative example 1, comparative example 2 had only a single curing agent 2 (D230), comparative example 1 had no flame retardant added, and comparative example 2 had 2% of the conventional flame retardant tetrabutylphosphonium chloride added. The component A resin 1 is south Asia epoxy resin 128, and the component A resin 2 is Jiangsu Taite Er New Material familyThe Technology Ltd is a cycloaliphatic epoxy 821E. The leveling agent is selected from the mechanical energy chemical industry Co., ltd, dongguan city
The promoter is JSC-1120 of Hangzhou Jessica chemical Co.
The above examples were subjected to performance characterization tests, and the test results are shown in table 2:
1. adhesion force: the coating film samples provided in the examples were tested for adhesion according to the GB/T5210-85 pull-off method, the results are shown in Table 2.
2. Pencil hardness: the film coating samples provided in the examples were tested for pencil hardness according to GB/T6739-86 and the results are shown in Table 2.
3. Limiting oxygen index: the coated film samples provided in the examples were tested for limiting oxygen index according to GB/T2406-2008 and the results are shown in Table 2.
4. Water impermeability: the coating film samples provided in the examples were tested for water impermeability according to GB/T16777-2008, 0.4MPa,2 hours. The results are shown in Table 2.
5. Water resistance: the coating film samples provided in the examples were tested for water resistance according to GB/T1733-1993, and the water resistance was tested for 240 hours, and the phenomena of coating blistering, wrinkling, obvious discoloration, peeling and the like were observed.
TABLE 2
From table 2 we can see that examples 9, 10, 11 and comparative examples 1,2 differ more than 2.1MPa in adhesion performance. In the pencil hardness test, the hardness of examples 9, 10 and 11 was 3H, while that of comparative examples 1 and 2 was only 2H. This is because the comparative example has only a single polyetheramine curing agent D230, which is long-chained and results in a softer final material. The example curing agent added synthetic short chain phosphorus curing agent A1 or cyclic phosphorus curing agent A7, D, so that the hardness ratio was higher than the comparative example. In terms of water impermeability and water resistance, examples 9, 10 and 11 were all good in comparison with comparative example 1 and comparative example 2, were not permeable to water, and had no foaming, no wrinkling, no significant discoloration, no peeling, and the like in 240 hours. In terms of limiting oxygen index, the examples are greatly superior to the comparative examples, the limiting oxygen index is over 27, the limiting oxygen index of the coating film completely without the flame retardant component in the comparative example 1 is only 17, and the limiting oxygen index of the coating film added with the two-point flame retardant in the comparative example 2 is also only 20.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalents and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. A phosphorus-containing epoxy curing agent is characterized in that the molecular structure of the phosphorus-containing epoxy curing agent is as follows:
wherein R is alkyl, alkoxy, aryl, aryloxy; r' is alkyl chain, ether chain or aryl chain.
2. A preparation method of a phosphorus-containing epoxy curing agent is characterized by comprising the following preparation processes:
dissolving C or D-representing divinyl phosphate into water or ethanol, dropwise adding into the aqueous solution of hydroxylamine hydrochloride at 0 ℃ within three hours, heating to room temperature after dropwise adding is finished, and reacting at room temperature overnight; TLC monitors the reaction end point, and after the reaction is finished, the low boiling point substance is distilled off under reduced pressure to obtain transparent viscous liquid.
3. The method of claim 2, wherein the concentration of the hydroxylamine solution is 30%.
4. The method for preparing the phosphorus-containing epoxy curing agent according to claim 2, wherein the amount of the solution of the bisvinylphosphate representing C or D and the hydroxylamine is: 14-25mmol of bisvinylphosphate and 120ml of 30% hydroxylamine solution.
5. The process for producing a phosphorus-containing epoxy curing agent according to claim 2, wherein after completion of the reaction, the reaction system is depressurized to remove residual ammonia and water or ethanol, and finally a colorless transparent viscous liquid is obtained.
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