Triazine-containing cycloalkyl phosphinate as well as preparation method and application thereof

Abstract

The invention relates to a triazine-containing cycloalkyl phosphinate and a preparation method and application thereof, and belongs to the technical field of organic phosphinates, and the triazine-containing cycloalkyl phosphinate has a structure as shown in the specification. ; the preparation method comprises the following steps: taking cyanuric chloride, alkyl phosphinate and polyamine as raw materials, and reacting to obtain triazine-containing cycloalkyl phosphinate; during application, the triazine naphthenic base-containing phosphinate and a high polymer material are subjected to melt blending and injection molding to prepare the flame-retardant high polymer material. Or the triazine naphthenic base-containing phosphinate, epoxy resin, urea resin, polyurethane or acrylic resin are prepared into paint or glue, and the paint or glue is coated on the surface of the material to form the flame-retardant coating. The preparation process is simple, the product yield is high, raw materials are wide in source and easy to obtain, and industrial production is easy; the prepared triazine-containing cycloalkyl phosphinate is good in thermal stability and excellent in hydrolysis resistance; the application range is wide.

Description

Technical Field

[0001] This invention belongs to the field of organic phosphonates technology, and relates to a triazine cycloalkyl phosphonate, its preparation method and application. Background Technology

[0002] Organic phosphines are an important class of phosphorus-containing flame retardants, especially aluminum diethylphosphines and inorganic aluminum phosphines, which are widely used in the flame retardant field of various polymer materials. These phosphorus-containing flame retardants have advantages such as halogen-free and low toxicity, low smoke emission, environmental friendliness, and significant flame retardant effects, making them a research hotspot in the field of flame retardants in recent years. They are widely used in the flame retardant of polymer materials such as polyamides, polyesters, polyurethanes, and polyolefins. Charring agents containing triazine rings are currently important components of halogen-free flame-retardant polyolefins, playing a crucial role in improving the charring performance of materials. However, flame retardants containing both phosphines and triazine rings in a single molecule, especially polymeric triazine ring-containing organic phosphines with a certain molecular chain length, have not yet been reported.

[0003] Patent CN202011470971.4 discloses a method for preparing and applying melamine alkyl phosphate esters. The resulting flame retardant contains phosphorus and nitrogen elements at a content between 22% and 25%, exhibiting a synergistic effect on flame retardancy. Patent CN201810901824.4 discloses a method for improving the high-temperature thermal stability of melamine derivative flame retardants using inorganic phosphite metal salts. This invention enables melamine derivatives to have high thermal decomposition temperatures, avoiding the disadvantages of flame retardants such as decomposition, degradation of the matrix polymer, migration, and equipment corrosion. It also allows for synergistic use with other flame retardants, broadening the application range of flame retardants. Patent CN201910072035.9 discloses a method for preparing the organophosphorus flame retardant 1-hydroxyphosphonite, which involves reacting hypophosphite with aldehydes in a polar solvent, followed by reaction with melamine or aluminum / zinc compounds to prepare aluminum hydroxyphosphonate, zinc hydroxyphosphonate, and melamine hydroxyphosphonate salts. This preparation method is more environmentally friendly, safer, and lower in cost. However, the flame retardants prepared by the above methods are all single organophosphonate flame retardants, and their structures are organophosphonate metal salts or organophosphonate organic amine salts.

[0004] Patent CN202310615394.0 reports the synthesis of a bio-based triazine char foaming agent using cyanuric chloride, alanine, and ethylenediamine as raw materials. However, it needs to be used in combination with a phosphorus-containing flame retardant. The flame retardant efficiency is related to dispersion and uniformity, and the performance is unstable.

[0005] Patent CN201210570170.4 discloses an organic phosphonate containing a triazine ring structure and its preparation method. The organic phosphonate containing a triazine ring structure referred to in this patent is prepared from hypophosphite and triglycidyl isocyanurate as the main raw materials. Its target compound is still a phosphonate.

[0006] Therefore, it is of great significance to study a non-phosphonate structure containing triazine cycloalkyl phosphonates with high flame retardancy and excellent moisture resistance, as well as its preparation method and application. Summary of the Invention

[0007] The purpose of this invention is to solve the problems existing in the prior art and to provide a triazine cycloalkylphosphinate, its preparation method and application.

[0008] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0009] A triazine cycloalkyl phosphonate having the structure shown below;

[0010] ;

[0011] Wherein, n is 2~20; a value less than 2 indicates a small molecular weight, making it easy to migrate and precipitate; a value greater than 20 indicates a large molecular weight, which is not conducive to dispersion; R1 and R2 are independently selected from hydrogen, alkyl groups with or without heteroatom substituents, aromatic groups with or without heteroatom substituents, and cyclic groups formed by carbon atoms and other atoms. R1 and R2 can also be selected from cyclic groups within the same molecule; R3 is an alkylene group with or without heteroatoms, including chain alkylene groups and cyclic alkylene groups; R4 is... R5 is y is 2~20; R' and R'' are each independently selected from alkyl groups with or without heteroatoms, the alkyl group being a chain alkyl group or a cyclic alkyl group, and R' and R'' can be alkylene groups that are bridged together.

[0012] The present invention also provides a method for preparing a triazine cycloalkyl phosphonate as described above, wherein cyanuric chloride, alkyl phosphonate and polyamine are used as raw materials to react and obtain a triazine cycloalkyl phosphonate.

[0013] As a preferred technical solution:

[0014] The method for preparing a triazine cycloalkyl phosphonate as described above, wherein the structural formula of the alkyl phosphonate is as follows:

[0015] ;

[0016] Where x is 1, 2, or 3; R6 and R7 are each independently selected from hydrogen, alkyl groups with or without heteroatom substituents, aromatic groups with or without heteroatom substituents, and cyclic groups formed by carbon atoms and other atoms; M x+ It can be lithium ions, sodium ions, potassium ions, magnesium ions, calcium ions, aluminum ions, zinc ions, or ammonium ions.

[0017] In the preparation method of the triazine cycloalkylphosphonate as described above, the polyamine is one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, propylenediamine, butanediamine, pentanediamine, hexanediamine, decanediamine, p-phenylenediamine, cyclohexanediamine, and piperazine.

[0018] The preparation method of the triazine cycloalkyl phosphonate as described above is as follows: cyanuric chloride and polyamine are added to a reactor, water and / or acetone are added, and the reaction is carried out at 0~10℃ for 1~12 hours. Then, alkyl phosphonates are added, and the reaction is continued at 10~100℃ for 1~24 hours to obtain the triazine cycloalkyl phosphonate.

[0019] The preparation method of the triazine cycloalkyl phosphonate as described above, or the specific preparation process is as follows: cyanuric chloride and alkyl phosphonate are put into a reactor, water and / or acetone are added, and the reaction is carried out at 0~10℃ for 1~12 hours, then polyamine is added, and the reaction is continued at 10~100℃ for 1~24 hours.

[0020] In the preparation method of the triazine cycloalkyl phosphonate as described above, the molar ratio of cyanuric chloride, polyamine and alkyl phosphonate is 1:0.5~1:0.5~3.0.

[0021] The present invention also provides an application of the triazine cycloalkyl phosphinate as described above, wherein the triazine cycloalkyl phosphinate is melt-blended with a thermoplastic polymer and then injection-molded to obtain a flame-retardant polymer material; when the amount of triazine cycloalkyl phosphinate added is 10~25wt%, the flame-retardant polymer material has a flame retardant rating of UL94 V0 and a limiting oxygen index of 30~40%.

[0022] The present invention also provides an application of the triazine cycloalkyl phosphonate as described above, wherein the triazine cycloalkyl phosphonate is formulated with epoxy resin, urea-formaldehyde resin, polyurethane or acrylic resin to form a coating or adhesive which is then applied to the surface of a material to form a flame-retardant coating.

[0023] When the content of triazine cycloalkyl phosphine esters in the flame-retardant coating is 5-20 wt%, the limiting oxygen index (LOI) of the flame-retardant coating is above 28%. Specifically, for polyolefin materials, when the flame-retardant coating contains 15-20 wt% triazine cycloalkyl phosphine esters, the LIO of the flame-retardant coating is 28-32%; for polyester materials, when the flame-retardant coating contains 10-20 wt% triazine cycloalkyl phosphine esters, the LIO of the flame-retardant coating is 28-35%; for polyamide materials, when the flame-retardant coating contains 8-15 wt% triazine cycloalkyl phosphine esters, the LIO of the flame-retardant coating is 30-38%; and for cellulosic fiber fabrics and paper, when the flame-retardant coating contains 5-15 wt% triazine cycloalkyl phosphine esters, the LIO of the flame-retardant coating is 32-40%.

[0024] The mechanism of this invention is:

[0025] This invention provides a method for preparing triazine cycloalkyl phosphinates. The flame retardant obtained by this method is rich in phosphorus and triazine structures. Because this molecular structure lacks the metal ions found in traditional organic phosphinates, it effectively improves the compatibility of the flame retardant with polymers and also solves the problems of flame retardant precipitation and deterioration of water resistance. In the prior art, some compounds containing triazine structures are often used as char-forming components in flame retardant systems. This invention unexpectedly yields a triazine cycloalkyl phosphinate flame retardant with a molecular chain size within a certain range, whose char-forming effect exhibits excellent synergistic flame-retardant properties with phosphorus and nitrogen elements.

[0026] The triazine cycloalkyl phosphinate provided by this invention, through a rational combination of the composition and ratio of triazine rings and phosphino acid groups, as well as the molecular structure of the target material, provides halogen-free flame-retardant elements for phosphino acid groups and triazine char formation within the same molecule. In the early stages of combustion, the microreactor formed by the multiple flame-retardant elements exhibits excellent synergistic effects, resulting in high flame-retardant efficiency and overcoming the problems of insufficient dispersion and contact caused by multi-component compounding. Furthermore, due to the high flame-retardant efficiency, a relatively small amount of flame retardant is required. In particular, the organic groups in the molecule effectively improve the hydrophobicity of the molecule compared to phosphinoates, thus effectively solving the problems of hygroscopicity and easy precipitation in flame-retardant materials. Moreover, the raw materials for preparing this triazine cycloalkyl phosphinate are readily available, facilitating industrial production and application. The triazine cycloalkyl phosphinate synthesized by this invention can be widely used in flame retardant applications of polyolefins, polyamides, polyesters, and polyurethanes, showing promising application prospects as a flame retardant.

[0027] This invention relates to a triazine cycloalkyl phosphinate molecule containing both hypophosphite and triazine structures, eliminating the need for compounding and overcoming the dispersion difficulties and insufficient contact issues associated with traditional hypophosphite and triazine flame retardants. The macromolecular triazine cycloalkyl phosphinate of this invention achieves coupling of gas-phase and condensed-phase flame retardant mechanisms through molecular design. Its core lies in the fact that the triazine structure and hypophosphite group are both present in the same molecule, achieving efficient free radical termination, dense char layer reinforcement, and thermodynamic complementarity through chemical bonding. The triazine structure primarily plays a continuous char-forming role, while the hypophosphite group can decompose to generate phosphorus-containing oxygen (PO) free radicals, exerting a gas-phase flame retardant mechanism. Simultaneously, the decomposition is endothermic, reducing the temperature of the combustion zone. The hypophosphite structure can decompose to generate phosphoric acid-based catalytic materials for dehydration and carbonization, forming a dense, porous char layer that isolates oxygen and heat transfer.

[0028] The triazine structure of this invention is located in the same molecule as the phosphonic acid group, resulting in good hydrolysis resistance, electrical properties, and mechanical properties.

[0029] (1) Hydrolysis resistance: The triazine ring forms a stable chemical bond with the hypophosphite group, and the high steric hindrance of hypophosphite can effectively prevent hydrolysis;

[0030] (2) Electrical properties (conductivity): When the triazine ring and the phosphonic acid group are in the same molecule, the triazine ring can regulate the electron cloud distribution of the molecule and promote electron transport, thereby improving the electrical properties of the material.

[0031] (3) Triazine rings can enhance intermolecular interactions, and phosphonic acid groups can enhance intermolecular forces by forming chemical bonds or physical entanglements with polymer materials, both of which can improve the mechanical properties of materials.

[0032] The triazine cycloalkyl phosphinate of this invention is a macromolecular flame retardant. Besides possessing excellent thermal stability, its longer molecular chain segments containing the triazine structure and hypophosphite groups result in good compatibility between the char formation of the triazine structure and the char-promoting effect of the hypophosphite groups, leading to a better synergistic flame retardant effect. Compared to small-molecule flame retardants containing triazine structures and hypophosphite groups, it exhibits superior flame retardant efficiency.

[0033] Beneficial effects:

[0034] (1) The present invention provides a method for preparing triazine cycloalkyl phosphonates, which uses readily available raw materials, has a simple and easy-to-implement process, and is easy to industrialize.

[0035] (2) A method for preparing a triazine cycloalkyl phosphinate of the present invention, by rationally designing the composition, ratio and molecular structure of the triazine ring and phosphinate groups and the target material, and providing all the flame retardant elements required by the flame retardant system in one molecule, not only improves the flame retardant efficiency, but also solves the problem of the hygroscopicity of flame retardant materials;

[0036] (3) The triazine cycloalkyl phosphonate of the present invention has good thermal stability and excellent hydrolysis resistance, and can be widely used in flame retardancy of various polymer materials.

[0037] (4) An application of the triazine cycloalkyl phosphinate of the present invention is a flame retardant material that has both good mechanical properties and flame retardant properties, and has a wide range of applications. Attached Figure Description

[0038] Figure 1 The infrared spectrum of the triazine cycloalkylphosphonate of Example 6 is shown. Detailed Implementation

[0039] The present invention will be further described below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0040] The test methods involved in the performance indicators in the embodiments and comparative examples of this invention are as follows:

[0041] Limiting oxygen index: Tested in accordance with GB / T 2406.2-2009.

[0042] Water contact angle: The test was conducted in accordance with GB / T 30693-2014 Measurement of water contact angle between plastic film and water.

[0043] Water resistance: Tested according to GB / T 1034-2008 Determination of water absorption of plastics.

[0044] Volume resistivity: Tested according to GB / T 1410-2006 Test methods for volume resistivity and surface resistivity of solid insulating materials.

[0045] Tensile strength: Refer to GB / T 1040.1-2025. Method: The specimen must be dumbbell-shaped without scratches or burrs. The draft angle of the injection molded part should be ≤2°. The specimen should be conditioned in an environment of 23℃±2℃ and 50%±10% RH for at least 24 hours. The specimen should be stretched at a speed of 50mm / min using a universal testing machine. The tensile strength should be calculated based on the ratio of the maximum tensile force to the original cross-sectional area. Five specimens should be tested in each group, and the average value should be taken.

[0046] Notched impact strength (cantilever beam): Refer to GB / T 1843-2008. Method: The specimen size is 63.5mm×12.7mm×3.2mm. The specimen has a V-shaped notch with a notch depth of 2.54mm and a notch bottom radius of 0.25mm. It is impacted by a pendulum at a speed of 3.5m / s. The strength is calculated based on the ratio of absorbed energy to the width of the notch.

[0047] Example 1

[0048] A method for preparing a triazine cycloalkyl phosphonate, the specific steps of which are as follows:

[0049] (1) Preparation of raw materials:

[0050] Cyanide trichloroethylene;

[0051] Alkylphosphonates: Sodium diethylphosphonate;

[0052] Polyamines: Ethylenediamine;

[0053] water;

[0054] (2) Add cyanuric chloride and polyamine to the reactor, add water, react at 5°C for 8 hours, then add alkyl phosphonates, and continue to react at 80°C for 8 hours to obtain triazine cycloalkyl phosphonates.

[0055] The molar ratio of cyanuric chloride, polyamine and alkyl phosphonate is 1:0.5:0.5; the mass-volume ratio of cyanuric chloride to water is 100g:100mL.

[0056] The final structure of the triazine cycloalkyl phosphonate is as follows:

[0057] .

[0058] Comparative Example 1

[0059] A method for preparing a polyaminoalkylphosphino acid metal composite salt is basically the same as in Example 1, except that the raw material cyanuric chloride is omitted, that is, cyanuric chloride is not added in step (2).

[0060] The final obtained sodium ethylenediamine diethyl hypophosphite has the following structural formula: .

[0061] Comparative Example 2

[0062] A method for preparing a triazine ring polyamine is basically the same as in Example 1, except that the raw material alkylphosphinate is omitted, that is, alkylphosphinate is not added in step (2).

[0063] The final structure of the triazine cycloethylenediamine is as follows: .

[0064] Example 2

[0065] A method for preparing a triazine cycloalkyl phosphonate, the specific steps of which are as follows:

[0066] (1) Preparation of raw materials:

[0067] Cyanide trichloroethylene;

[0068] Alkylphosphonates: Sodium methyl ethyl phosphonate;

[0069] Polyamines: Triethylenetetramine;

[0070] acetone;

[0071] (2) Add cyanuric chloride and polyamine to a reactor, add acetone, react at 0°C for 12 hours, then add alkyl phosphonates, and continue to react at 80°C for 20 hours to obtain triazine cycloalkyl phosphonates.

[0072] The molar ratio of cyanuric chloride, polyamine and alkylphosphinate is 1:0.75:2; the mass-volume ratio of cyanuric chloride to acetone is 100g:1000mL.

[0073] The final structure of the triazine cycloalkyl phosphonate is as follows:

[0074] .

[0075] Example 3

[0076] A method for preparing a triazine cycloalkyl phosphonate, the specific steps of which are as follows:

[0077] (1) Preparation of raw materials:

[0078] Cyanide trichloroethylene;

[0079] Alkylphosphonates: Sodium diisobutylphosphonate;

[0080] Polyamines: Pentylene diamine;

[0081] water;

[0082] (2) Add cyanuric chloride and polyamine to the reactor, add water, react at 10°C for 12 hours, then add alkyl phosphonates, and continue to react at 60°C for 12 hours to obtain triazine cycloalkyl phosphonates.

[0083] The molar ratio of cyanuric chloride, polyamine and alkyl phosphonate is 1:1:0.5; the mass-volume ratio of cyanuric chloride to acetone is 100g:2000mL.

[0084] The final structure of the triazine cycloalkyl phosphonate is as follows:

[0085] .

[0086] Example 4

[0087] A method for preparing a triazine cycloalkyl phosphonate, the specific steps of which are as follows:

[0088] (1) Preparation of raw materials:

[0089] Cyanide trichloroethylene;

[0090] Alkylphosphonates: Sodium hypophosphite;

[0091] Polyamines: p-phenylenediamine;

[0092] water;

[0093] (2) Add cyanuric chloride and alkyl phosphonates into the reactor in 5 portions over 6 hours, add water, react at 3°C ​​for 8 hours, then add polyamine, and continue to react at 10°C for 24 hours to obtain triazine cycloalkyl phosphonates.

[0094] The molar ratio of cyanuric chloride, polyamine and alkyl phosphonate is 1:0.5:1.5; the molar ratio of cyanuric chloride to water is 100g:500ml.

[0095] The final structure of the triazine cycloalkyl phosphonate is as follows:

[0096] .

[0097] Example 5

[0098] A method for preparing a triazine cycloalkyl phosphonate, the specific steps of which are as follows:

[0099] (1) Preparation of raw materials:

[0100] Cyanide trichloroethylene;

[0101] Alkylphosphonates: Sodium ethyl hypophosphite;

[0102] Polyamines: Cyclohexanediamine;

[0103] acetone;

[0104] (2) Add cyanuric chloride and alkyl phosphonates into the reactor in 8 portions over 8 hours, add acetone, react at 5°C for 10 hours, then add polyamine, and continue to react at 100°C for 8 hours to obtain triazine cycloalkyl phosphonates.

[0105] The molar ratio of cyanuric chloride, polyamine and alkyl phosphonate is 1:0.75:2.5; the molar ratio of cyanuric chloride to acetone is 100g:800ml.

[0106] The final structure of the triazine cycloalkyl phosphonate is as follows:

[0107] .

[0108] Example 6

[0109] A method for preparing a triazine cycloalkyl phosphonate, the specific steps of which are as follows:

[0110] (1) Preparation of raw materials:

[0111] Cyanide trichloroethylene;

[0112] Alkylphosphonates: Aluminum diethylphosphinate;

[0113] Polyamines: piperazine;

[0114] Water and acetone in a 1:1 mass ratio;

[0115] (2) Add cyanuric chloride and alkyl phosphonate into the reactor in 10 portions over 10 hours, add water and acetone in a mass ratio of 1:1, react at 3°C ​​for 5 hours, then add polyamine, and continue to react at 85°C for 4 hours to obtain triazine cycloalkyl phosphonate.

[0116] The molar ratio of cyanuric chloride, polyamine and alkyl phosphonate is 1:1:1; the molar ratio of cyanuric chloride to water and acetone is 100g:1000ml.

[0117] The final structure of the triazine cycloalkyl phosphonate is as follows:

[0118] .

[0119] pass Figure 1 The infrared spectrum shown verifies the synthesis of this triazine cycloalkylphosphinate structure: 2800~3000 cm⁻¹ in the spectrum. -1 The weak absorption in this region corresponds to the saturated CH stretching vibration of the ethyl group in the molecule, 1500~1600 cm⁻¹. -1 The absorption peak matches the skeletal vibration of the triazine ring (-N=CN-), 1200~1300 cm⁻¹ -1 The absorption in this region includes characteristic peaks of the P=O double bond of alkyl phosphonates, while the 1000–1200 cm⁻¹ region contains these peaks. -1The complex absorption corresponds to the vibration of the POC bond, and the characteristic peaks of these functional groups all match the groups in the target structure, proving the successful synthesis of the compound. This infrared spectrum, with wavenumbers (4000~500 cm⁻¹), shows... -1 The x-axis represents the area of ​​light and the y-axis represents the transmittance (0~100%), with an overall range of 4000~3000 cm. -1 The area has high transmittance, only 3000cm. -1 Weak absorption nearby; 3000~2000cm -1 No strong characteristic peaks in the region; 2000~1500cm -1 The regional transmittance gradually decreases, to 1500cm -1 A strong absorption zone appears nearby; 1500~500cm -1 The region exhibits significant fluctuations in transmittance and multiple strong absorption peaks, which are the main characteristic regions of the molecule's functional group vibrations.

[0120] Example 7

[0121] An application of a triazine cycloalkylphosphinate, the specific process of which is as follows:

[0122] The triazine cycloalkyl phosphine ester and hindered amine stabilizer NOR116 (manufacturer: Shanghai Kaiyin Chemical Co., Ltd., brand name: FLAMESTAB®NOR 116 FF) from Example 1 were melt-blended with polypropylene PP (manufacturer: Yanshan Petrochemical Co., Ltd., brand name: K8303) and then injection-molded to obtain a flame-retardant polymer material. The flame-retardant polymer material contained 25 wt% triazine cycloalkyl phosphine ester and 5 wt% hindered amine stabilizer.

[0123] The specific steps of melt blending are as follows: First, a high-speed mixer physically mixes all the above materials according to the formula; second, the mixed materials are added to the main feeder of a twin-screw extruder; third, the temperature of the twin-screw extruder is set to 190℃ in zone one, 205℃ in zone two, 220℃ in zone three, and 210℃ in zone four. After the set temperatures are reached, the twin-screw extruder is started to melt blend and extrude the mixture; fourth, the mixture is drawn into strips and granulated; fifth, the granules are dried at 80℃ and then injection molded into test strips that meet the testing standards.

[0124] The final flame-retardant polymer material has a flame retardancy rating of UL94 V0, a ​​limiting oxygen index of 35%, a water contact angle of 105°, and a volume resistivity of 10. 14 Ω, tensile strength of 30MPa, notched impact strength of 3.5KJ / m 2Flame-retardant polymer materials showed no significant changes in appearance when immersed in water at room temperature (26℃) for 1 hour, 12 hours, 24 hours, 48 ​​hours, and 96 hours in a simulated humid environment. After removal, mechanical and flame-retardant performance tests were conducted, and no adverse effects were observed, indicating good water resistance.

[0125] Comparative Example 3

[0126] The application of a polyaminoalkylphosphonic acid metal complex salt is basically the same as in Example 7, except that the triazine cycloalkylphosphonate ester in Example 1 is replaced with the polyaminoalkylphosphonic acid metal complex salt of Comparative Example 1.

[0127] The final flame-retardant polymer material has a flame retardant rating of UL94 V2, a limiting oxygen index of 26%, and a water contact angle of 90°.

[0128] Comparing Comparative Example 3 and Example 7, it can be found that the flame retardant performance and water contact angle of Comparative Example 3 decreased. This is because the polyaminoalkyl hypophosphite metal composite salt does not have the flame retardant synergistic effect of nitrogen element. At the same time, due to its higher water solubility, the water contact angle decreased after the addition of flame retardant.

[0129] Comparative Example 4

[0130] The application of a triazine cyclic polyamine is basically the same as in Example 7, except that the triazine cyclic alkyl phosphonate of Example 1 is replaced with the triazine cyclic polyamine of Comparative Example 2.

[0131] The final flame-retardant polymer material has a flame retardant rating of UL94 HB, a limiting oxygen index of 18%, and a water contact angle of 90°.

[0132] Comparing Comparative Example 4 and Example 7, it can be found that the flame retardant performance of Comparative Example 4 is reduced. This is because the triazine cyclopolyamine does not contain phosphorus, and its flame retardant effect is significantly worse than that of the phosphorus-containing triazine cycloalkylphosphinate.

[0133] Example 8

[0134] An application of a triazine cycloalkylphosphinate, the specific process of which is as follows:

[0135] The triazine cycloalkyl phosphonate from Example 2 was formulated with epoxy resin (manufacturer: China Petroleum & Chemical Corporation, grade: epoxy resin CYD-128) to form a coating, which was then applied to the surface of polypropylene (PP) (manufacturer: Yanshan Petrochemical Company, grade: K8303) to form a flame-retardant coating.

[0136] The coating contains 20 wt% triazine cycloalkylphosphinate and has a coating weight of 2.5 wt%.

[0137] The final material with the flame-retardant coating has a flame retardancy rating of UL94 V0, a ​​limiting oxygen index of 32%, a water contact angle of 102°, and a volume resistivity of 10. 14 Ω, tensile strength is 30MPa, notched impact strength is 3.1KJ / m 2 The material was subjected to prolonged immersion in simulated humid environments at room temperature (26℃) water for 1 hour, 12 hours, 24 hours, 48 ​​hours, and 96 hours. No significant changes in appearance were observed. Mechanical and flame retardant performance tests were conducted after removal, showing no adverse effects, indicating good water resistance. By mixing triazine cycloalkyl hypophosphite as a coating additive with epoxy resin and coating it onto electronic devices, changes in current before and after coating were measured using an oscilloscope. The results showed low resistance, stable electrical performance, low current loss, and good electrical properties.

[0138] Example 9

[0139] An application of a triazine cycloalkylphosphinate, the specific process of which is as follows:

[0140] The triazine cycloalkyl phosphinate from Example 3 was melt-blended with polycarbonate (PC, manufacturer: Shanghai Shien Plastics Co., Ltd., brand: PC-110) and then injection-molded to obtain a flame-retardant polymer material. The content of triazine cycloalkyl phosphinate in the flame-retardant polymer material was 15 wt%.

[0141] The specific steps of melt blending are as follows: First, a high-speed mixer physically mixes all the above materials according to the formula; second, the mixed materials are added to the main feeder of a twin-screw extruder; third, the temperature of the twin-screw extruder is set to 255℃ in zone one, 265℃ in zone two, 275℃ in zone three, and 265℃ in zone four. After the set temperatures are reached, the twin-screw extruder is started to melt blend and extrude the mixture; fourth, the mixture is drawn into strips and granulated; fifth, the granules are dried at 80℃ and then injection molded into test strips that meet the testing standards.

[0142] The final flame-retardant polymer material has a flame retardant rating of UL94 V0, a ​​limiting oxygen index of 40%, a water contact angle of 105°, and a volume resistivity of 10. 14 Ω, tensile strength of 35MPa, notched impact strength of 3.2KJ / m 2 The flame-retardant polymer material was observed to have no significant changes in appearance after being immersed in room temperature water for 1 hour, 12 hours, 24 hours, 48 ​​hours, and 96 hours in a simulated humid environment. After removal, mechanical properties and flame-retardant properties were tested, and no effect was found.

[0143] Example 10

[0144] An application of a triazine cycloalkylphosphinate, the specific process of which is as follows:

[0145] The triazine cycloalkyl phosphonate from Example 4 was formulated with urea-formaldehyde resin (manufacturer: Shandong Baiqian Chemical Co., Ltd., grade: 5631) to form a coating, which was then applied to the surface of nylon PA6 (manufacturer: Jisheng Industrial Co., Ltd., grade: TP-4204) to form a flame-retardant coating.

[0146] The coating contains 8 wt% triazine cycloalkylphosphinate and has a coating amount of 2 wt%.

[0147] The resulting material with the flame-retardant coating has a flame retardant rating of UL94 V0, a ​​limiting oxygen index of 30%, and a water contact angle of 110°.

[0148] Example 11

[0149] An application of a triazine cycloalkylphosphinate, the specific process of which is as follows:

[0150] The triazine cycloalkyl phosphinate from Example 3 was melt-blended with high-density polyethylene (HDPE, manufacturer: Beijing Yanshan Branch, grade: HDPE 5000S) and then injection-molded to obtain a flame-retardant polymer material. The content of triazine cycloalkyl phosphinate in the flame-retardant polymer material was 10 wt%.

[0151] The process parameters for melt blending are as follows: First, a high-speed mixer physically mixes all the above materials according to the formula. Second, the mixed materials are added to the main feeder of a twin-screw extruder. Third, the temperature of the twin-screw extruder is set to 160℃ in zone one, 170℃ in zone two, 180℃ in zone three, and 190℃ in zone four. After the set temperatures are reached, the twin-screw extruder is started to melt blend and extrude the mixture. Fourth, the mixture is drawn into strips and granulated. Fifth, the granules are dried at 80℃ and then injection molded into test strips that meet the testing standards.

[0152] The final flame-retardant polymer material achieved a UL94 V0 flame retardancy rating, a limiting oxygen index of 26.8%, and a water contact angle of 105°. Triazine cycloalkyl phosphonates were added to polyethylene and other polymer materials to form injection-molded samples. Tensile, bending, hardness, and shear properties were measured using a universal testing machine. Compared with pure polyethylene, the mechanical properties were improved in various aspects.

[0153] Example 12

[0154] An application of a triazine cycloalkylphosphinate, the specific process of which is as follows:

[0155] The triazine cycloalkyl phosphonate of Example 6 was formulated with polyurethane resin (manufacturer: Wanhua Chemical Group Co., Ltd., brand name: WANTHANE® HD-190) to form a coating, which was then applied to the surface of flax fiber fabric (manufacturer: Suzhou Jianglong Hemp Textile Co., Ltd., brand name: Shuchang) to form a flame-retardant coating.

[0156] The coating contains 5 wt% triazine cycloalkylphosphinate and has a coating amount of 1 wt%.

[0157] The final material with the flame-retardant coating has a flame retardant rating of UL94 V0, a ​​limiting oxygen index of 32%, a water contact angle of 105°, and a volume resistivity of 10. 14 Ω, tensile strength is 32MPa, notched impact strength is 3.8KJ / m 2 The material was observed to have no significant changes in appearance after being immersed in room temperature water for 1 hour, 12 hours, 24 hours, 48 ​​hours, and 96 hours in a simulated humid environment. After being removed, mechanical properties and flame retardant properties were tested, and no adverse effects were found.

Claims

1. A triazine cycloalkylphosphonate, characterized in that: It has the structure shown below; ； Wherein, n is 2~20; R1 and R2 are each independently selected from hydrogen, alkyl groups with or without heteroatom substituents, aromatic groups with or without heteroatom substituents, and cyclic groups formed by carbon atoms and other atoms; R3 is an alkylene group with or without heteroatoms; R4 is... R5 is y is 2~20; R' and R'' are each independently selected from alkyl groups with or without heteroatoms.

2. The method for preparing a triazine cycloalkyl phosphonate as described in claim 1, characterized in that: Triazine cycloalkyl phosphonates were obtained by reacting cyanuric chloride, alkyl phosphonates and polyamines.

3. The method for preparing a triazine cycloalkyl phosphonate according to claim 2, characterized in that, The structural formula of alkyl phosphines is as follows: ； R6 and R7 are each independently selected from hydrogen, alkyl groups with or without heteroatom substituents, aromatic groups with or without heteroatom substituents, and cyclic groups formed by carbon atoms and other atoms; M x+ It can be lithium ions, sodium ions, potassium ions, magnesium ions, calcium ions, aluminum ions, zinc ions, or ammonium ions.

4. The method for preparing a triazine cycloalkyl phosphonate according to claim 2, characterized in that, The polyamine is one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, propylenediamine, butanediamine, pentanediamine, hexanediamine, decanediamine, p-phenylenediamine, cyclohexanediamine, and piperazine.

5. The method for preparing a triazine cycloalkyl phosphonate according to claim 2, characterized in that, The specific preparation process is as follows: cyanuric chloride and polyamine are added to a reactor, water and / or acetone are added, and the reaction is carried out at 0~10℃ for 1~12 hours. Then, alkyl phosphonates are added, and the reaction is carried out at 10~100℃ for 1~24 hours to obtain triazine cycloalkyl phosphonates.

6. The method for preparing a triazine cycloalkyl phosphonate according to claim 2, characterized in that, The specific preparation process is as follows: cyanuric chloride and alkyl phosphonates are added to a reactor, water and / or acetone are added, and the reaction is carried out at 0~10℃ for 1~12 hours. Then, polyamine is added, and the reaction is continued at 10~100℃ for 1~24 hours.

7. A method for preparing a triazine cycloalkylphosphonate according to claim 5 or 6, characterized in that, The molar ratio of cyanuric chloride, polyamine and alkyl phosphonate is 1:0.5~1:0.5~3.

0.

8. The application of a triazine cycloalkylphosphonate as described in claim 1, characterized in that: Flame-retardant polymer materials are prepared by melt blending triazine cycloalkyl phosphonates with thermoplastic polymers and then injection molding.

9. The application of a triazine cycloalkylphosphinate as described in claim 1, characterized in that: Triazine cycloalkyl phosphonates are formulated with epoxy resin, urea-formaldehyde resin, polyurethane or acrylic resin to form a coating or adhesive, which is then applied to the surface of the material to form a flame-retardant coating.

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