CN116874814B - Tannic acid flame retardant taking water as solvent and preparation method and application thereof - Google Patents
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Abstract
本发明公开了一种以水为溶剂的单宁酸阻燃剂及其制备方法和应用，属于阻燃材料技术领域。本发明以天然可再生生物资源单宁酸为原料，水为溶剂，采用氮杂环磷酸对单宁酸进行化学接枝改性，得到所述单宁酸阻燃剂。本发明所制备的单宁酸阻燃剂不含卤素、磷氮含量高、阻燃性能优异、与硬质聚氨酯泡沫等聚合物相容性好，且制备工艺简单、条件温和、生产成本低、绿色环保，适于工业化推广应用。The present invention discloses a tannic acid flame retardant with water as solvent, a preparation method and application thereof, and belongs to the technical field of flame retardant materials. The present invention uses tannic acid, a natural renewable biological resource, as raw material, water as solvent, and adopts nitrogen heterocyclic phosphoric acid to chemically graft and modify tannic acid to obtain the tannic acid flame retardant. The tannic acid flame retardant prepared by the present invention does not contain halogen, has high phosphorus and nitrogen content, has excellent flame retardant performance, has good compatibility with polymers such as rigid polyurethane foam, and has a simple preparation process, mild conditions, low production cost, and is green and environmentally friendly, and is suitable for industrial promotion and application.
Description
Technical Field
The invention belongs to the technical field of flame-retardant materials, and particularly relates to a tannic acid flame retardant taking water as a solvent, and a preparation method and application thereof.
Background
The rigid polyurethane foam material is a building heat-insulating material with excellent comprehensive performance, and has the advantages of light weight, small density, low heat conductivity coefficient, high specific strength, heat insulation and the like. However, rigid polyurethane foam is a flammable material, and when burned, has high flame propagation speed and high heat release rate, and is usually accompanied by toxic smoke, thus greatly threatening the life and property safety of people. Flame retardancy is the most common route to rigid polyurethane foams by flame retardants.
Among commercial flame retardants, the market scale and application area of halogen-containing flame retardants have long been the top of the leadership. However, halogen-containing flame retardants are increasingly limited in their use at present because they release a large amount of smoke when burned and produce toxic gases such as hydrogen halide and dioxin, which cause secondary damage. Among the halogen-free flame retardants, the phosphorus-nitrogen flame retardant has the advantages of no halogen, low toxicity, low smoke, high flame retardant efficiency and the like, and has good application prospect.
Patent CN 115612089B discloses a nitrogen-phosphorus composite hydrolysis-resistant reaction type flame retardant and a preparation method and application thereof, patent CN 115678103B reports a long-chain alkane cyclotriphosphazene flame retardant and a preparation method and application thereof, and although a lot of researchers present a preparation method of the phosphorus-nitrogen flame retardant, the synthesis of the phosphorus-nitrogen flame retardant mainly depends on petrochemical raw materials, and a large amount of organic solvents such as tetrahydrofuran, N-dimethylformamide and the like are needed in the synthesis process, so that the cost is high and the environmental load is large, which is contrary to sustainable and green development concepts. Patent CN 109912650B discloses a phosphorus-nitrogen bio-based flame retardant, and its synthesis method and application, the method uses bio-based aldehydes or amines as raw materials, but a large amount of organic solvents are still used in the synthesis process. Therefore, developing a phosphorus-nitrogen type flame retardant with wide sources of raw materials, reproducibility, environmental protection, low production cost, mild reaction conditions, good compatibility with polymers and high flame retardant efficiency is a problem to be solved by the technicians in the field.
Tannic acid is a natural plant polyphenol compound widely distributed in the skin, shell, root, leaf and pulp of plants, such as Chinese five gallol, pericarpium Granati, folium lacquer, hamamelis mollis, etc. Tannic acid has the characteristics of abundant resources, low price, excellent water solubility, and 25 phenolic hydroxyl groups in a molecular structure, and the like, thereby laying a foundation for realizing chemical grafting modification of azacyclic phosphoric acid under the condition that water is a solvent.
Disclosure of Invention
In order to solve the problems that the phosphorus-nitrogen flame retardant in the prior art mainly depends on petrochemical raw materials, a large amount of organic solvents are needed in the synthesis process, the production cost is high, the compatibility with polymers is poor, the flame retardant effect is not ideal, and the like, the invention provides a tannic acid flame retardant taking water as a solvent, and a preparation method and application thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
The invention aims at protecting a preparation method of a tannic acid flame retardant taking water as a solvent, which comprises the following steps:
(1) The preparation of the azacyclic phosphoric acid comprises the steps of dispersing amine compounds and phosphorous acid in deionized water, dropwise adding formaldehyde under the protection of nitrogen atmosphere, and reacting to obtain the azacyclic phosphoric acid, wherein the reaction formula is as follows:
;
(2) The preparation of the tannic acid flame retardant comprises the steps of dispersing tannic acid and the prepared azacyclic phosphoric acid in deionized water together, reacting under the protection of nitrogen atmosphere, cooling, distilling under reduced pressure, washing and vacuum drying after the reaction is finished, and the tannic acid flame retardant is obtained, wherein the reaction formula is as follows:
。
In the reaction scheme, only graft modification of a single phenolic hydroxyl group is exemplified. The molecular structure of tannic acid is rich in 25 phenolic hydroxyl groups, and the quantity of tannic acid phenolic hydroxyl modification can be regulated and controlled by regulating the molar ratio of tannic acid to azacyclic phosphoric acid, so that tannic acid flame retardants with different phosphorus and nitrogen element contents are obtained.
Further, the amine compound in the step (1) is any one of melamine, methyl guanamine, piperazine, N-ethylpiperazine, N-phenylpiperazine, N-aminoethylpiperazine, 2-aminopyrimidine, 2,4, 6-triaminopyrimidine, 3-aminopyridine, 4-aminopyridine, 2, 6-diaminopyridine, guanine or adenine.
Further, the molar ratio of the amine compound, the phosphorous acid and the formaldehyde used in the step (1) is 1 (1-6): 1-6.
Further, the temperature of the reaction in the step (1) is 60-100 ℃ and the time is 2-6 hours.
Further, the molar ratio of tannic acid to azacyclic phosphoric acid used in the step (2) is 1 (5-20).
Further, the temperature of the reaction in the step (2) is 40-80 ℃ and the time is 2-6 hours.
The second object of the present invention is to protect the tannic acid flame retardant prepared by the above method. The tannic acid flame retardant prepared by the method disclosed by the invention does not contain halogen, has high phosphorus and nitrogen content, and has a molecular structure rich in structures such as benzene rings, phenolic hydroxyl groups and nitrogen heterocycles, so that good compatibility of the tannic acid flame retardant and a polymer matrix is ensured, and high-efficiency flame retardance of various polymer materials can be realized on the premise of ensuring the physicochemical properties of the polymer matrix.
The invention also aims to protect the application of the tannic acid flame retardant in preparing flame-retardant high polymer materials, such as flame-retardant rigid polyurethane foam.
Further, 10-20wt% of tannic acid flame retardant is added into the flame-retardant rigid polyurethane foam, and the limiting oxygen index is more than 28%.
Besides flame-retardant rigid polyurethane foam, the tannic acid flame retardant obtained by the invention is also suitable for preparing other flame-retardant products.
Compared with the prior art, the invention has the remarkable advantages that:
(1) The tannic acid flame retardant provided by the invention adopts natural plant polyphenol tannic acid which is rich in resources, low in price, low in carbon, environment-friendly and excellent in water solubility as a raw material, and uses water as a solvent, and the azacyclic phosphoric acid is obtained through chemical grafting in a certain proportioning relationship.
(2) The tannic acid flame retardant has the advantages of easy regulation and control of the structure and components, no halogen, high phosphorus and nitrogen content, and high compatibility with a polymer matrix, and can be used for high-efficiency flame retardance of various polymer materials.
(3) The flame-retardant rigid polyurethane foam containing 10-20% of tannic acid flame retardant by mass percent has excellent flame retardant property, does not reduce the physical and chemical properties of polyurethane, and can be widely popularized and applied.
Drawings
FIG. 1 is a comparative graph of UL-94 vertical burning test conducted on a rigid polyurethane foam prepared in comparative example and a flame retardant rigid polyurethane foam prepared in example 3. As can be seen from FIG. 1, the flame retardant rigid polyurethane foam prepared by the invention has good flame retardant effect.
Fig. 2 is an SEM image of the rigid polyurethane foam prepared in the comparative example and the flame retardant rigid polyurethane foam prepared in example 8. As can be seen from fig. 2, the addition of the tannic acid flame retardant has no significant effect on the morphology of the prepared rigid polyurethane foam.
Detailed Description
A tannic acid flame retardant taking water as a solvent, and a preparation method thereof comprises the following steps:
(1) The preparation of the azacyclic phosphoric acid comprises the steps of dispersing amine compounds and phosphorous acid in deionized water together, dropwise adding formaldehyde under the protection of nitrogen atmosphere, and reacting at 60-100 ℃ for 2-6 hours to obtain the azacyclic phosphoric acid, wherein the molar ratio of the amine compounds to the phosphorous acid to the formaldehyde is 1 (1-6): 1-6;
(2) The preparation of the tannic acid flame retardant comprises the steps of dispersing tannic acid and the prepared azacyclic phosphoric acid in deionized water according to a molar ratio of 1 (5-20), reacting for 2-6 hours at 40-80 ℃ under the protection of nitrogen atmosphere, and cooling, distilling under reduced pressure, washing and drying in vacuum after the reaction is finished to obtain the tannic acid flame retardant.
Wherein the amine compound is any one of melamine, methyl guanamine, piperazine, N-ethylpiperazine, N-phenylpiperazine, N-aminoethylpiperazine, 2-aminopyrimidine, 2,4, 6-triaminopyrimidine, 3-aminopyridine, 4-aminopyridine, 2, 6-diaminopyridine, guanine or adenine.
In order to describe the technical contents of the technical solution in detail, the construction features, the achieved objects and effects are described in detail below with reference to specific embodiments.
Reference herein to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment may be included in at least one embodiment of the application. The appearances of the phrase "in various places in the specification are not necessarily all referring to the same embodiment, nor are they particularly limited to independence or relevance from other embodiments. In principle, in the present application, as long as there is no technical contradiction or conflict, the technical features mentioned in each embodiment may be combined in any manner to form a corresponding implementable technical solution.
Unless defined otherwise, technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present application pertains, and the use of related terms herein is intended only to describe specific embodiments, not to limit the present application.
The following examples of the invention will now be described with reference to the following raw materials:
tannic acid, phosphorous acid, formaldehyde, amine compounds, and rigid polyurethane foam preparation materials are all from commercially available conventional products.
The compression performance, limiting oxygen index and UL-94 vertical burning rating measurements referred to in the examples listed below are specifically described as follows:
The compression performance test method performs the relevant specifications in ASTM D1621, the limiting oxygen index measurement method performs the relevant specifications in ASTM D-2863, and the UL-94 vertical burn rating measurement method performs the relevant specifications in ASTM D-3801.
Comparative example
This comparative example provides a method for preparing rigid polyurethane foam
A one-step free foaming process is adopted to prepare the rigid polyurethane foam, which comprises the specific steps of uniformly mixing 40g of polyether polyol LY-4110, 0.3g of water, 0.04g of dibutyltin dilaurate and 4g g of silicone oil, adding 54g of polyarylene polymethylene isocyanate PM-200 under the condition of high-speed stirring, fully reacting for 10 seconds, rapidly pouring the product into a grinding tool, and curing for 24 hours to obtain the rigid polyurethane foam.
Example 1
This example provides a method for preparing tannic acid flame retardant using water as solvent and flame-retardant rigid polyurethane foam containing the same
(1) Dispersing 1.0mol of guanine and 2.0mol of phosphorous acid in deionized water, dropwise adding 2.0mol of formaldehyde under the protection of nitrogen atmosphere, and reacting for 5 hours at 70 ℃ after the dropwise adding is finished to obtain azacyclic phosphoric acid;
(2) Dispersing 0.1mol of tannic acid and 1.0mol of prepared azacyclic phosphoric acid in deionized water, reacting for 4 hours at 60 ℃ under the protection of nitrogen atmosphere, and cooling, distilling under reduced pressure, washing and drying in vacuum after the reaction to obtain the tannic acid flame retardant.
The tannic acid flame retardant was uniformly mixed with polyether polyol LY-4110, water, dibutyl tin dilaurate and silicone oil, and a flame retardant rigid polyurethane foam was prepared by the one-step free foaming process described in comparative example, wherein the tannic acid flame retardant content was 10wt%.
Example 2
This example provides a method for preparing tannic acid flame retardant using water as solvent and flame-retardant rigid polyurethane foam containing the same
(1) Dispersing 1.0mol of methyl guanamine and 2.0mol of phosphorous acid in deionized water, dropwise adding 2.0mol of formaldehyde under the protection of nitrogen atmosphere, and reacting for 2 hours at 100 ℃ after the dropwise adding is finished to obtain nitrogen heterocyclic phosphoric acid;
(2) Dispersing 0.1mol of tannic acid and 0.5mol of prepared azacyclic phosphoric acid in deionized water, reacting for 3 hours at 80 ℃ under the protection of nitrogen atmosphere, and cooling, distilling under reduced pressure, washing and drying in vacuum after the reaction to obtain the tannic acid flame retardant.
The tannic acid flame retardant was uniformly mixed with polyether polyol LY-4110, water, dibutyl tin dilaurate and silicone oil, and a flame retardant rigid polyurethane foam was prepared by the one-step free foaming process described in comparative example, wherein the tannic acid flame retardant content was 16wt%.
Example 3
This example provides a method for preparing tannic acid flame retardant using water as solvent and flame-retardant rigid polyurethane foam containing the same
(1) Dispersing 1.0mol of N-aminoethylpiperazine and 3.0mol of phosphorous acid in deionized water, dropwise adding 3.0mol of formaldehyde under the protection of nitrogen atmosphere, and reacting at 75 ℃ for 6 hours after the dropwise adding is finished to obtain azacyclic phosphoric acid;
(2) Dispersing 0.1mol of tannic acid and 1.2mol of prepared azacyclic phosphoric acid in deionized water, reacting for 6 hours at 40 ℃ under the protection of nitrogen atmosphere, and cooling, distilling under reduced pressure, washing and drying in vacuum after the reaction to obtain the tannic acid flame retardant.
The tannic acid flame retardant was uniformly mixed with polyether polyol LY-4110, water, dibutyl tin dilaurate and silicone oil, and a flame retardant rigid polyurethane foam was prepared by the one-step free foaming process described in comparative example, wherein the tannic acid flame retardant content was 20wt%.
Example 4
This example provides a method for preparing tannic acid flame retardant using water as solvent and flame-retardant rigid polyurethane foam containing the same
(1) Dispersing 1.0mol of piperazine and 2.0mol of phosphorous acid in deionized water, dropwise adding 2.0mol of formaldehyde under the protection of nitrogen atmosphere, and reacting for 2 hours at 60 ℃ after the dropwise adding is finished to obtain azacyclic phosphoric acid;
(2) Dispersing 0.1mol of tannic acid and 2.0mol of prepared azacyclic phosphoric acid in deionized water, reacting for 3 hours at 65 ℃ under the protection of nitrogen atmosphere, and cooling, distilling under reduced pressure, washing and drying in vacuum after the reaction to obtain the tannic acid flame retardant.
The tannic acid flame retardant was uniformly mixed with polyether polyol LY-4110, water, dibutyl tin dilaurate and silicone oil, and a flame retardant rigid polyurethane foam was prepared by the one-step free foaming process described in comparative example, wherein the tannic acid flame retardant content was 15wt%.
Example 5
This example provides a method for preparing tannic acid flame retardant using water as solvent and flame-retardant rigid polyurethane foam containing the same
(1) Dispersing 1.0mol of N-ethylpiperazine and 1.0mol of phosphorous acid in deionized water, dropwise adding 1.0mol of formaldehyde under the protection of nitrogen atmosphere, and reacting at 80 ℃ for 5 hours after the dropwise adding is finished to obtain azacyclic phosphoric acid;
(2) Dispersing 0.1mol of tannic acid and 1.5mol of prepared azacyclic phosphoric acid in deionized water, reacting for 5 hours at 70 ℃ under the protection of nitrogen atmosphere, and cooling, distilling under reduced pressure, washing and drying in vacuum after the reaction to obtain the tannic acid flame retardant.
The tannic acid flame retardant was uniformly mixed with polyether polyol LY-4110, water, dibutyl tin dilaurate and silicone oil, and a one-step free foaming process was used to prepare a flame retardant rigid polyurethane foam as described in comparative example, wherein the tannic acid flame retardant content was 12wt%.
Example 6
This example provides a method for preparing tannic acid flame retardant using water as solvent and flame-retardant rigid polyurethane foam containing the same
(1) Dispersing 1.0mol of N-phenylpiperazine and 1.0mol of phosphorous acid in deionized water, dropwise adding 1.0mol of formaldehyde under the protection of nitrogen atmosphere, and reacting for 4 hours at 90 ℃ after the dropwise adding is finished to obtain azacyclic phosphoric acid;
(2) Dispersing 0.1mol of tannic acid and 0.8mol of prepared azacyclic phosphoric acid in deionized water, reacting for 2 hours at 80 ℃ under the protection of nitrogen atmosphere, and cooling, distilling under reduced pressure, washing and drying in vacuum after the reaction to obtain the tannic acid flame retardant.
The tannic acid flame retardant was uniformly mixed with polyether polyol LY-4110, water, dibutyl tin dilaurate and silicone oil, and a flame retardant rigid polyurethane foam was prepared by the one-step free foaming process described in comparative example, wherein the tannic acid flame retardant content was 15wt%.
Example 7
This example provides a method for preparing tannic acid flame retardant using water as solvent and flame-retardant rigid polyurethane foam containing the same
(1) Dispersing 1.0mol of 2, 6-diaminopyridine and 4.0mol of phosphorous acid in deionized water, dropwise adding 4.0mol of formaldehyde under the protection of nitrogen atmosphere, and reacting at 80 ℃ for 6 hours after the dropwise adding is finished to obtain azacyclic phosphoric acid;
(2) Dispersing 0.1mol of tannic acid and 0.7mol of prepared azacyclic phosphoric acid in deionized water, reacting for 4 hours at 75 ℃ under the protection of nitrogen atmosphere, and cooling, distilling under reduced pressure, washing and drying in vacuum after the reaction to obtain the tannic acid flame retardant.
The tannic acid flame retardant was uniformly mixed with polyether polyol LY-4110, water, dibutyl tin dilaurate and silicone oil, and a flame retardant rigid polyurethane foam was prepared by the one-step free foaming process described in comparative example, wherein the tannic acid flame retardant content was 14wt%.
Example 8
This example provides a method for preparing tannic acid flame retardant using water as solvent and flame-retardant rigid polyurethane foam containing the same
(1) Dispersing 1.0mol of 2,4, 6-triaminopyrimidine and 6.0mol of phosphorous acid in deionized water, dropwise adding 6.0mol of formaldehyde under the protection of nitrogen atmosphere, and reacting for 5 hours at 100 ℃ after the dropwise adding is finished to obtain azacyclic phosphoric acid;
(2) Dispersing 0.1mol of tannic acid and 1.0mol of prepared azacyclic phosphoric acid in deionized water, reacting for 6 hours at 70 ℃ under the protection of nitrogen atmosphere, and cooling, distilling under reduced pressure, washing and drying in vacuum after the reaction to obtain the tannic acid flame retardant.
The tannic acid flame retardant was uniformly mixed with polyether polyol LY-4110, water, dibutyl tin dilaurate and silicone oil, and a flame retardant rigid polyurethane foam was prepared by the one-step free foaming process described in comparative example, wherein the tannic acid flame retardant content was 10wt%.
Example 9
This example provides a method for preparing tannic acid flame retardant using water as solvent and flame-retardant rigid polyurethane foam containing the same
(1) Dispersing 1.0mol of adenine and 3.0mol of phosphorous acid in deionized water, dropwise adding 3.0mol of formaldehyde under the protection of nitrogen atmosphere, and reacting for 3 hours at 65 ℃ after the dropwise adding is finished to obtain azacyclic phosphoric acid;
(2) Dispersing 0.1mol of tannic acid and 1.5mol of prepared azacyclic phosphoric acid in deionized water, reacting for 2 hours at 50 ℃ under the protection of nitrogen atmosphere, and cooling, distilling under reduced pressure, washing and drying in vacuum after the reaction to obtain the tannic acid flame retardant.
The tannic acid flame retardant was uniformly mixed with polyether polyol LY-4110, water, dibutyl tin dilaurate and silicone oil, and a flame retardant rigid polyurethane foam was prepared by the one-step free foaming process described in comparative example, wherein the tannic acid flame retardant content was 13wt%.
The parameters and test results for the preparation of rigid polyurethane foam products from examples and comparative examples were statistically aligned and the results are shown in Table 1.
Table 1 parameters and properties for preparing rigid polyurethane foam products in examples and comparative examples
As can be seen from the results shown in Table 1, the tannic acid flame retardants prepared in examples 1 to 9 are applied to rigid polyurethane foam, so that the limiting oxygen index is higher than 28%, the vertical burning test grade is V-0, and the flame retardant product has a uniform cell structure, and the compression strength is basically unchanged compared with that of pure rigid polyurethane foam, so that the tannic acid flame retardant provided by the invention can be used as an excellent flame retardant for high polymer materials such as rigid polyurethane foam.
It should be noted that, although the foregoing embodiments have been described herein, the scope of the present invention is not limited thereby. Therefore, changes and modifications made to the embodiments described herein, or equivalent structures or equivalent flow transformations by employing the principles of the present invention, based on the innovative concepts of the present invention, will be apparent to those skilled in the art and may be practiced, directly or indirectly, in other relevant fields.
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| CN115678102A (en) * | 2022-11-08 | 2023-02-03 | 福州大学 | A kind of tannic acid-based single-component intumescent flame retardant and its preparation method and application |
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| CN105085575A (en) * | 2015-09-05 | 2015-11-25 | 四川大学 | Flame-retardant polyol containing phosphorus linked pendant groups and preparation method of polyol |
| CN106632958B (en) * | 2016-09-29 | 2019-04-12 | 四川大学 | The preparation method of fire-retardant water-based polyurethane based on response type Graphene fire retardant |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111718463A (en) * | 2020-07-03 | 2020-09-29 | 华北科技学院 | A kind of preparation method of bio-based flame retardant and method for preparing flame retardant polyurethane foam |
| CN115678102A (en) * | 2022-11-08 | 2023-02-03 | 福州大学 | A kind of tannic acid-based single-component intumescent flame retardant and its preparation method and application |
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