CN119528978B - Intumescent flame retardant and preparation method and application thereof - Google Patents
Intumescent flame retardant and preparation method and application thereofInfo
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- CN119528978B CN119528978B CN202411478111.3A CN202411478111A CN119528978B CN 119528978 B CN119528978 B CN 119528978B CN 202411478111 A CN202411478111 A CN 202411478111A CN 119528978 B CN119528978 B CN 119528978B
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
- C07D251/70—Other substituted melamines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
- C07F9/3817—Acids containing the structure (RX)2P(=X)-alk-N...P (X = O, S, Se)
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
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Abstract
本发明公开了一种膨胀型阻燃剂及其制备方法与应用，所述膨胀型阻燃剂是由三嗪化合物和氨基膦酸以离子键结合形成的化合物，其中氨基膦酸类化合物同时含有磷元素和氮元素，三嗪类化合物是一类富含叔氮结构，因此结合两者的特性可制得“三源”一体膨胀型阻燃剂，并且三嗪类化合物可使得该阻燃剂的磷氮均衡。本发明的三嗪基化合物以离子键结合，所得到的离子型阻燃剂可在聚合物中均匀分散，其在高分子材料中溶解或散布后，利用三嗪化合物氨基膦酸盐的阻燃性能从而达到阻燃高效的效果。本发明的阻燃聚丙烯以三嗪基化合物作为阻燃剂，不仅阻燃剂添加量少，还具有良好的阻燃性能。This invention discloses an intumescent flame retardant, its preparation method, and its application. The intumescent flame retardant is a compound formed by the ionic bonding of a triazine compound and aminophosphonic acid. The aminophosphonic acid compound contains both phosphorus and nitrogen elements, while the triazine compound is rich in tertiary nitrogen structures. Therefore, combining the characteristics of both allows for the preparation of a "three-source" integrated intumescent flame retardant, and the triazine compound ensures a balanced phosphorus and nitrogen content in the flame retardant. The triazine-based compound of this invention is ionicly bonded, resulting in an ionic flame retardant that can be uniformly dispersed in polymers. After dissolving or dispersing in polymer materials, the flame-retardant properties of the triazine compound and aminophosphonate salt achieve a highly efficient flame-retardant effect. The flame-retardant polypropylene of this invention uses a triazine-based compound as the flame retardant, resulting in a low addition amount of flame retardant while exhibiting excellent flame-retardant properties.
Description
Technical Field
The invention belongs to the technical field of flame retardants, and particularly relates to an intumescent flame retardant as well as a preparation method and application thereof.
Background
The intumescent flame retardant has huge application prospect in the today with the increasingly serious environmental problems due to the advantages of high efficiency, environmental protection and the like, and simultaneously attracts more and more researchers and flame retardant manufacturers to widely and deeply research the development and preparation of the high-performance intumescent flame retardant. Because the intumescent flame retardant consists of an acid source, a carbon source and an air source, the realization of reasonable collocation of the three sources is always the key of the development and preparation of the high-performance intumescent flame retardant. The traditional intumescent flame retardant is prepared by mixing and compounding three components of an acid source, a carbon source and an air source, and is generally prepared by mixing ammonium polyphosphate (APP), pentaerythritol (PER) and Melamine (MEL). The three components are often not uniformly dispersed in the polymer matrix, so that the components cannot be well cooperated with each other, and the flame retardant efficiency of the polymer matrix is affected. In addition, the traditional intumescent flame retardant has the problems of poor thermal stability and difficult processing.
It has been reported that an ionic flame retardant, which is also called an "ionic solid flame retardant", is a molecule or an ion group composed of anions and cations, and can interact with a polymer material after being dissolved or dispersed in the polymer material, thereby having an effect of preventing combustion. However, in the prior art, ionic flame retardants are low in flame retardant efficiency because of few types of ionic flame retardants, so that the development of ionic flame retardants with high flame retardant efficiency is required.
Disclosure of Invention
In order to overcome the problems of the prior art, one of the purposes of the present invention is to provide an intumescent flame retardant. The second object of the present invention is to provide a method for preparing the intumescent flame retardant. It is a further object of the present invention to provide a flame retardant polyolefin.
The amino phosphonic acid compound is a compound containing both phosphorus and nitrogen, and is very suitable for intumescent flame retardants. However, in general, the phosphorus content of the compound is far higher than that of nitrogen, and the compound is unfavorable for realizing high-performance flame retardance due to the unbalanced phosphorus and nitrogen content. The triazine compound is a compound rich in tertiary nitrogen structure, can be used as a carbon source and a gas source in the intumescent flame retardant, has higher nitrogen content, and can be combined with the amino phosphonic acid compound to obtain the intumescent flame retardant with balanced phosphorus and nitrogen. Therefore, the application combines the structure and physical property advantages of the amino phosphonic acid compound and the triazine compound, combines the amino phosphonic acid compound and the triazine compound in an ionic bond form, and provides a triazine-based compound which is used as a three-source integrated intumescent flame retardant.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
In a first aspect, the present invention provides an intumescent flame retardant which is a compound formed from a triazine compound and an aminophosphonic acid in ionic bonding.
Preferably, the molar ratio of the triazine compound to the aminophosphonic acid is (0.5-3): 1.
More preferably, the molar ratio of the triazine compound to the aminophosphonic acid is (0.75-2): 1.
Preferably, the structural formula of the aminophosphonic acid is shown in the following formulas 1 to 6:
preferably, the structural formula of the triazine compound is shown as formula a or formula b:
wherein R 1 and R 2 are independently selected from one of amino, nitrogen-containing alicyclic heterocyclic group, nitrogen-containing aromatic heterocyclic group, alicyclic amino and aryl amino aliphatic amino, and X is alkanediamino.
Preferably, the triazine compound has a structural formula shown in the following formulas 7 to 10:
In a second aspect, the invention provides a method for preparing the intumescent flame retardant of the first aspect, comprising the step of reacting a triazine compound with an aminophosphonic acid in water to prepare the intumescent flame retardant.
Preferably, the temperature of the reaction is 70-100 ℃.
More preferably, the temperature of the reaction is 85-95 ℃.
Preferably, the reaction time is 3-7 hours.
More preferably, the reaction time is 3 to 5 hours.
Preferably, the mass ratio of water to aminophosphonic acid is (10-30): 1.
More preferably, the mass ratio of water to aminophosphonic acid is (10-20): 1.
A third aspect of the present invention provides a flame retardant polyolefin comprising the intumescent flame retardant of the first aspect.
Preferably, the mass percentage of the triazinyl compound in the flame retardant polypropylene is 15-25%.
More preferably, the triazinyl compound is present in the flame retardant polypropylene in a mass percentage of 20 to 23%.
Preferably, the flame retardant polyolefin comprises polyolefin, lubricant, antioxidant, coupling agent and the triazinyl compound of the first aspect.
Preferably, the flame-retardant polyolefin is prepared from 75 to 84 mass percent of polyolefin, 0.3 to 0.5 mass percent of lubricant, 0.1 to 0.3 mass percent of antioxidant, 0.2 to 0.4 mass percent of coupling agent and 15 to 25 mass percent of triazinyl compound of the first aspect.
More preferably, the flame retardant polypropylene is prepared by extrusion granulating the components to obtain the flame retardant polypropylene.
Further preferably, the temperature of the extrusion is 170-195 ℃.
More preferably, the lubricant is a combination of an inner lubricant and an outer lubricant.
More preferably, the coupling agent is a titanate coupling agent.
Preferably, the flame retardant polyolefin is flame retardant polypropylene.
The beneficial effects of the invention are as follows:
The invention provides an intumescent flame retardant which is a compound formed by combining a triazine compound and amino phosphonic acid through ionic bonds, wherein the amino phosphonic acid compound contains phosphorus and nitrogen at the same time, and the triazine compound is a tertiary nitrogen-rich structure, so that the three-source integrated intumescent flame retardant can be prepared by combining the characteristics of the three-source integrated intumescent flame retardant, and the triazine compound can balance phosphorus and nitrogen of the flame retardant. The triazinyl compound is combined by ionic bond, the obtained ionic flame retardant can be uniformly dispersed in a polymer, and after the ionic flame retardant is dissolved or dispersed in a high polymer material, the flame retardant performance of the triazinyl compound amino phosphonate is utilized, so that the flame retardant effect is achieved.
In particular, compared with the prior art, the invention has the following advantages:
(1) The invention also provides a preparation method of the intumescent flame retardant, which is characterized by simple process, environment protection and convenient industrial production, and the intumescent flame retardant is prepared under a water reaction system without using an organic solution.
(2) The invention also provides a flame-retardant polyolefin, the flame-retardant efficiency of the three-source integrated intumescent flame retardant which is synthesized is low for polyolefin materials, the addition amount of the flame-retardant polypropylene needs to be more than 25wt% in order to achieve the UL-94V-0 level of a vertical combustion test, and the flame-retardant polypropylene takes the triazinyl compound as the flame retardant, so that the flame-retardant polypropylene has the advantages of less addition amount of the flame retardant, good flame retardant performance and UL-94V-0 level flame retardant effect under the condition that the addition amount is 21 wt%.
Drawings
FIG. 1 is an infrared spectrum of a triazine compound 1 isocyanate flame retardant provided in example 1;
FIG. 2 is an infrared spectrum of the triazine compound 2-cyanate flame retardant provided in example 2;
FIG. 3 is an infrared spectrum of the triazine compound 3-cyanate flame retardant provided in example 3;
Fig. 4 is an infrared spectrum of the triazine compound 4-isocyanate flame retardant provided in example 4.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The starting materials used in the examples below, unless otherwise specified, were either commercially available or isolated by simple synthetic preparation, and the procedures employed, unless otherwise specified, were all conventional in the art.
Example 1
The embodiment provides an intumescent flame retardant, and the preparation method of the intumescent flame retardant comprises the following steps:
Triazine compound 1 (55.6 g,0.2 mol), an amino trimethylene phosphonic acid aqueous solution (concentration 50%,119.6g,0.2 mol) and 1500mL of water are placed in a 2L round bottom flask, then stirred and reacted for 4 hours at 90 ℃, cooled to room temperature after the reaction is finished, and subjected to suction filtration, drying and crushing treatment to prepare triazine compound 1 amino trimethylene phosphonate, namely an intumescent flame retardant;
wherein the structural formula of the triazine compound 1 is as follows:
The structural formula of the triazine compound 1 amino trimethylene phosphonate is:
The infrared spectrum of the triazine compound 1 amino trimethylene phosphonate is shown in figure 1.
Example 2
The embodiment provides an intumescent flame retardant, and the preparation method of the intumescent flame retardant comprises the following steps:
Triazine compound 2 (67.6 g,0.2 mol), an amino trimethylene phosphonic acid aqueous solution (concentration 50%,119.6g,0.2 mol) and 1500mL of water are placed in a 2L round bottom flask, then stirred and reacted for 4 hours at 90 ℃, cooled to room temperature after the reaction is finished, and subjected to suction filtration, drying and crushing treatment to prepare triazine compound 2 amino trimethylene phosphonate, namely an intumescent flame retardant;
the structural formula of the triazine compound 2 is as follows:
the structural formula of the triazine compound 2 amino trimethylene phosphonate is:
the infrared spectrum of the triazine compound 2 amino trimethylene phosphonate is shown in figure 2.
Example 3
The embodiment provides an intumescent flame retardant, and the preparation method of the intumescent flame retardant comprises the following steps:
Triazine compound 3 (38.8 g,0.2 mol), an amino trimethylene phosphonic acid aqueous solution (concentration 50%,119.6g,0.2 mol) and 1500mL of water are placed in a 2L round bottom flask, stirred and reacted for 4 hours at 90 ℃, cooled after the reaction is finished, and subjected to suction filtration, drying and crushing treatment to prepare triazine compound 3 amino trimethylene phosphonate, namely an intumescent flame retardant;
the structural formula of the triazine compound 3 is as follows:
the structural formula of the triazine compound 3 amino trimethylene phosphonate is:
the infrared spectrum of the triazine compound 3 amino trimethylene phosphonate is shown in figure 3.
Example 4
The embodiment provides an intumescent flame retardant, and the preparation method of the intumescent flame retardant comprises the following steps:
Triazine compound 4 (58 g,0.2 mol), an amino trimethylene phosphonic acid aqueous solution (concentration 50%,119.6g,0.2 mol) and 1500mL of water are placed in a 5L round bottom flask, stirred and reacted for 4 hours at 90 ℃, cooled after the reaction is finished, and subjected to suction filtration, drying and crushing treatment to prepare triazine compound 4 amino trimethylene phosphonate, namely an intumescent flame retardant;
The structural formula of the triazine compound 4 is as follows:
the structural formula of the triazine compound 4 amino trimethylene phosphonate is:
the IR spectrum of the triazine compound 4 amino trimethylene phosphonate is shown in FIG. 4.
Experimental analysis
The products of examples 1-4 were tested for flame retardant properties, with the following specific test methods and results:
The flame-retardant PP material sample is prepared according to the formula shown in the following table 1, specifically, raw materials are added into a mixer, the rotating speed is set to 1000 revolutions per minute, stirring is carried out for 3 minutes, then the mixed materials are extruded by a homodromous double-screw extruder (Nanjaka) with the length-diameter ratio of 48:1 and the screw diameter of 36 millimeters, the temperature of the extruder is set to 170-195 ℃, the rotating speed is 200 revolutions per minute, the vacuum degree is-0.8 MPa, water cooling is carried out at 25+/-5 ℃, granulating is carried out, the particles are put into a blast drier, the temperature is set to 85 ℃, and drying is carried out for 3 hours, so that the flame retardant corresponding to the flame-retardant PP material sample of the embodiment 1-4 is prepared. Setting the injection molding temperature to 180-195 ℃, and then injecting each particle into a standard spline for UL 94 flame retardance test, wherein the test results are shown in Table 2.
TABLE 1 raw materials composition table (parts by mass) of flame retardant PP material
Table 2 flame retardant property test results of flame retardant PP materials
From the test results of the flame retardants of examples 1-4 in the PP flame retardant application, the flame retardants of examples 1-4 have good flame retardant performance. This is because examples 1-4 contain the complete and balanced intumescent flame retardant "three-source" component within a single molecule, thus having good flame retardant properties.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that changes and modifications may be made without departing from the principles of the invention, such changes and modifications are also intended to be within the scope of the invention.
Claims (7)
1. An intumescent flame retardant, characterized in that it is a compound formed by ionic bonding of a triazine compound and an aminophosphonic acid;
The structural formula of the aminophosphonic acid is shown in the following formulas 1-6:
A formula 1, A formula 2,
3(S),4 (V),
5,Formula 6;
the structural formula of the triazine compound is shown in the following formulas 7-10:
7, 8 (V),
9. A step of,Formula 10.
2. The intumescent flame retardant of claim 1, characterized in that the molar ratio of triazine compound to aminophosphonic acid is (0.5-3): 1.
3. The method for preparing the intumescent flame retardant as claimed in any one of claims 1-2, characterized by comprising the step of reacting a triazine compound with an aminophosphonic acid in water to prepare the intumescent flame retardant.
4. The method according to claim 3, wherein the reaction temperature is 70-100 ℃ and/or the reaction time is 3-7 h.
5. The process according to claim 3, wherein the mass ratio of water to aminophosphonic acid is (10-30): 1.
6. Flame retardant polyolefin comprising an intumescent flame retardant as claimed in any one of claims 1-2.
7. The flame retardant polyolefin of claim 6, further comprising polyolefin, lubricant, antioxidant, coupling agent.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101429438A (en) * | 2008-12-23 | 2009-05-13 | 山东天一化学有限公司 | Phosphor-nitrogen expansion type combustion inhibitor and method of producing the same |
| CN101921599A (en) * | 2010-04-30 | 2010-12-22 | 中国科学院宁波材料技术与工程研究所 | Bicyclic phosphate-based triazine derivative flame retardant and preparation method thereof |
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| WO2017096519A1 (en) * | 2015-12-08 | 2017-06-15 | 东北林业大学 | Triazine-based highly-effective intumescent flame retardant and intumescent flame retardant polypropylene |
| CN106519295A (en) * | 2016-09-26 | 2017-03-22 | 天津科技大学 | Novel phosphorus-based flame retardant and halogen-free intumescent anti-flaming ABS (Acrylonitrile Butadiene Styrene) resin containing same |
| JP7244085B2 (en) * | 2017-11-10 | 2023-03-22 | 大八化学工業株式会社 | FLAME RETARDANT COMPOSITION AND FLAME RETARDANT THERMOPLASTIC RESIN COMPOSITION CONTAINING THE FLAME RETARDANT COMPOSITION |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101429438A (en) * | 2008-12-23 | 2009-05-13 | 山东天一化学有限公司 | Phosphor-nitrogen expansion type combustion inhibitor and method of producing the same |
| CN101921599A (en) * | 2010-04-30 | 2010-12-22 | 中国科学院宁波材料技术与工程研究所 | Bicyclic phosphate-based triazine derivative flame retardant and preparation method thereof |
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