Aminophosphonic acid metal compound as well as preparation method and application thereof

Abstract

The invention discloses an amino phosphonic acid metal compound as well as a preparation method and application thereof. The amino phosphonic acid metal compound is a compound formed by combining amino phosphonic acid radicals and aluminum ions through ionic bonds. The invention provides a UL94V2 flame retardant scheme based on an amino phosphonic acid metal salt flame retardant / melamine and a hydrobromide of a derivative thereof / a free radical initiator. Compared with an aluminum hypophosphite component, the amino phosphonic acid metal compound disclosed by the invention is used for producing and processing the flame retardant, so that hydrogen phosphide gas can be prevented from being decomposed, the risk of fire is avoided, and the problem of yellowing of a polymer product cannot be caused. Besides, the aminophosphonic acid metal aluminum flame retardant also contains a flame-retardant element N, inert gas N2 can be released in the combustion process, O2 around comburent can be diluted, the flame-retardant effect of the flame retardant is further improved, and the flame-retardant UL94V2 level can be realized when the additive amount of the aminophosphonic acid metal aluminum flame retardant acting on polypropylene is required to be 1wt%.

Description

Technical Field

[0001] This invention belongs to the field of flame retardant technology, specifically relating to an aminophosphonic acid metal compound, its preparation method, and its application. Background Technology

[0002] UL94 V2 flame retardants are widely used in applications requiring lower flame retardancy ratings, such as automotive components and home appliances, due to their low addition amount and minimal damage to the mechanical properties of polymer substrates. Conventional UL94 V2 flame retardants are divided into bromine-antimony synergistic flame retardant systems and free radical-initiated dripping flame retardant systems. The bromine-antimony synergistic flame retardant system is generally obtained by compounding bromine-based flame retardants such as decabromodiphenyl ether with antimony trioxide. However, this system has drawbacks, including the easy release of bromine from polymers such as PP and the generation of large amounts of toxic smoke during combustion, which limits its application in countries and regions with relevant environmental regulations. The free radical-initiated dripping flame retardant system is generally obtained by compounding melamine and its derivatives' hydrobromide, metal phosphate salts, and free radical initiators. The composition of 2,3-dimethyl-2,3-diphenylbutane (bichlorobenzene) / aluminum hypophosphite / melamine hydrobromide is currently the most classic free radical-initiated dripping flame retardant system on the market.

[0003] However, the aluminum hypophosphite component in this system decomposes under severe impact and high temperatures, releasing flammable and highly reducing phosphine gas. This not only easily causes fires during production and processing but also leads to yellowing of polymer products due to its oxidation. Therefore, it is necessary to develop a novel flame retardant as a substitute for aluminum hypophosphite in this classic free radical-initiated dripping flame retardant system. Summary of the Invention

[0004] To overcome the problems existing in the prior art, one objective of the present invention is to provide an aminophosphonic acid metal compound. A second objective of the present invention is to provide a method for preparing the above-mentioned aminophosphonic acid metal compound. A third objective of the present invention is to provide applications of the above-mentioned aminophosphonic acid metal compound. A fourth objective of the present invention is to provide a flame-retardant composition. A fifth objective of the present invention is to provide a flame-retardant polyolefin.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0006] The first aspect of this invention provides an aminophosphonic acid metal compound, wherein the aminophosphonic acid aluminum compound is a compound formed by the ionic bonding of aminophosphonate ions and aluminum ions;

[0007] The structural formulas of the aminophosphonate group are shown in Formulas 1-5 below:

[0008]

[0009]

[0010] x represents the number of hydrogen ions that are neutralized by aminophosphonic acid.

[0011] Preferably, the molar ratio of aluminum ions to aminophosphonate is 1-3:1.

[0012] A second aspect of the present invention provides a method for preparing the aminophosphonic acid metal compound described in the first aspect, comprising the following steps: reacting aminophosphonic acid with a water-soluble aluminum salt in an aqueous solution containing an inorganic base to obtain the aminophosphonic acid metal compound.

[0013] Preferably, the aminophosphonic acid has the following structural formulas a-e:

[0014]

[0015] That is, ethylenediaminetetramethylenephosphonic acid (CAS: 1429-50-1);

[0016]

[0017] That is, 1,6-hexanediaminetetramethylenephosphonic acid (CAS: 23605-74-5);

[0018]

[0019] That is, polyamine polyether phosphonic acid (CAS: 130668-24-5);

[0020]

[0021] That is, diethylenetriaminepentamethylenephosphonic acid (CAS No. 15827-60-8);

[0022]

[0023] That is, dihexytriamine pentamethylenephosphonic acid (CAS: 34690-00-1).

[0024] Preferably, the reaction temperature is 80–100°C.

[0025] More preferably, the reaction temperature is 85–95°C.

[0026] Preferably, the reaction time is 10-20 hours.

[0027] More preferably, the reaction time is 10-15 hours.

[0028] Preferably, the inorganic base includes at least one of sodium hydroxide and potassium hydroxide.

[0029] Preferably, the water-soluble aluminum salt includes at least one of aluminum chloride, aluminum sulfate, and aluminum nitrate.

[0030] Preferably, the molar ratio of the water-soluble aluminum salt to the inorganic base is 1:(3-6).

[0031] Preferably, the molar ratio of the water-soluble aluminum salt to aminophosphonic acid is 1-6:1.

[0032] Preferably, the process includes the following steps: mixing an inorganic base with aminophosphonic acid in water and carrying out a neutralization reaction at 70–100°C; adding a water-soluble aluminum salt to the reaction system after the neutralization reaction is completed and carrying out a metathesis reaction to obtain the aminophosphonic acid metal compound.

[0033] More preferably, the method specifically includes the following steps: first, adding aminophosphonic acid to water, then slowly adding an inorganic base, and carrying out a neutralization reaction at 70-100°C for 0.5-2 hours.

[0034] More preferably, the neutralization reaction is carried out under stirring conditions.

[0035] More preferably, water-soluble aluminum salt is slowly added dropwise to the reaction system after the neutralization reaction is completed.

[0036] More preferably, the metathesis reaction is carried out under stirring conditions.

[0037] More preferably, the ratio of the water-soluble aluminum salt to the water solvent in the reaction system is 0.2 mol:(500-2000 mL).

[0038] The third aspect of this invention provides the application of the aminophosphonic acid metal compound described in the first aspect in the field of flame retardants.

[0039] A fourth aspect of the present invention provides a flame retardant composition comprising the following components: the aminophosphonic acid metal compound described in the first aspect, the hydrobromide of polycyanamide and its derivatives, and a free radical initiator.

[0040] Preferably, the hydrobromide of the polycyanamide and its derivatives includes at least one of melamine hydrobromide, melamine dihydrobromide, melamine hydrobromide, melamine dihydrobromide, melamine hydrobromide, and melamine dihydrobromide.

[0041] Preferably, the free radical initiator includes 2,3-dimethyl-2,3-diphenylbutane (Liquid), poly(phenyl-1,3-diylethane-1,2-diyl), poly(phenyl-1,4-diyl-1,1,2,2-tetramethylethane-1,2-diyl), poly(phenyl-1,3-diyl-1,1,2,2-tetramethylethane-1,2-diyl), poly(phenyl-1,2-diyl-1,1,2,2-tetramethylethane-1,2-diyl), poly(phenyl-1,2-diyl-1,1,2,2-tetramethylethane-1,2-diyl), poly (Benzene-1,4-diyl-1,1,2,2-tetraoctylethane-1,2-diyl), poly(3-nitrobenzene-1,5-diyl-1,1,2-trimethyl-2-butylethane-1,2-diyl), poly(3-aminophenyl-1,4-diyl-1,1,2,2-tetramethylethane-1,2-diyl), poly(2,5-dimethylphenyl-1,4-diyl-1,2-dimethyl-1-butyl-2-propylethane-1,2-diyl), poly( 2,5,6-Trimethylbenzene-1,4-diyl-1,2-dimethyl-1-propyl-2-ethylethane-1,2-diyl), poly(2,5,6-trimethylbenzene-1,4-diyl-1,2-dimethyl-1-propyl-2-ethylethane-1,2-diyl), poly(3-methyl-7-nitronaphthalene-1,6-diyl-1,2,3-trimethyl-2-ethylethane-1,2-diyl), poly(2-chloro-4,8-dimethylphenidate-1,5-diyl) At least one of the following: -1,2,3-trimethyl-2-ethylethane-1,2-diyl, poly(3-methyl-7-nitronaphthalene-1,6-diyl-1,2,3-trimethyl-2-ethylethane-1,2-diyl), poly(2-chloro-3-methylphenanthrene-1,6-diyl-1,23-trimethyl-2-ethylethane-1,2-diyl), and poly(4-ethylpyridine-2,5-diyl-1,1,2,2-tetramethylethane-1,2-yl).

[0042] Preferably, by weight, it comprises the following components: 30 to 80 parts of the aminophosphonic acid metal compound described in the first aspect, 5 to 50 parts of hydrobromide of polycyanamide and its derivatives, and 2 to 30 parts of free radical initiator.

[0043] The fifth aspect of the present invention provides a flame-retardant polyolefin, comprising the intumescent flame retardant described in the first aspect, or the flame-retardant composition described in the fourth aspect.

[0044] Preferably, the flame retardant composition comprises 0.5%-10% by mass of the flame retardant polyolefin.

[0045] More preferably, the flame retardant composition comprises 1%-3% by mass of the flame retardant polyolefin.

[0046] Preferably, the flame-retardant polyolefin comprises the following components: polyolefin, excipients, and the flame-retardant composition described in the fourth aspect.

[0047] Preferably, the flame-retardant polyolefin is prepared by the following steps: mixing the components and extruding and granulating to obtain the flame-retardant polyolefin.

[0048] More preferably, the extrusion temperature is 150-200°C.

[0049] Preferably, the flame-retardant polyolefin is flame-retardant polypropylene.

[0050] Specifically, compared with the prior art, the present invention has the following advantages:

[0051] (1) This invention provides an aminophosphonic acid metal compound, which replaces the aluminum hypophosphite in a composition of 2,3-dimethyl-2,3-diphenylbutane (L-carboxyl) / aluminum hypophosphite / melamine hydrobromide, proposing a UL94 V2 flame retardant scheme based on aminophosphonic acid metal salt flame retardant / melamine and its derivatives hydrobromide / free radical initiator. Compared to the aluminum hypophosphite component, the aminophosphonic acid metal compound of this invention, when used as a flame retardant in the production and processing process, avoids the decomposition of phosphine gas, thus eliminating the risk of ignition and preventing yellowing of polymer products. In addition, the aminophosphonic acid metal aluminum flame retardant also contains nitrogen (N) flame retardant element, which releases inert gas N2 during combustion, diluting the O2 around the burning material and further improving the flame retardant effect. When added to polypropylene, an addition amount of 1 wt% is sufficient to achieve a UL94 V2 flame retardant rating.

[0052] (2) The method for synthesizing the aminophosphonic acid aluminum flame retardant of the present invention is simple and easy to industrialize. Attached Figure Description

[0053] Figure 1 The infrared spectrum of aluminum ethylenediaminetetramethylenephosphonate in Example 1;

[0054] Figure 2 The infrared spectrum is shown for the composition comprising aluminum ethylenediaminetetramethylenephosphonate of Example 1. Detailed Implementation

[0055] The present invention will be further described in detail below through specific embodiments. Unless otherwise specified, the raw materials used in the following embodiments can be obtained from conventional commercial channels or prepared and isolated through simple synthesis; unless otherwise specified, the processes employed are conventional processes in the art.

[0056] Example 1

[0057] This embodiment provides an aminophosphonic acid metal compound, the preparation method of which is as follows:

[0058] 87.2 g of ethylenediaminetetramethylenephosphonic acid (CAS: 429-50-1) and 1000 mL of water were placed in a 2 L round-bottom flask. Then, 160 g of 30% sodium hydroxide solution (water as solvent) was added dropwise. The mixture was then heated to 90 °C and stirred for 1 h. Subsequently, 228.2 g of 30% aluminum sulfate solution (water as solvent) was added dropwise. After the addition was complete, the mixture was stirred at 90 °C for 13 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, dried, and pulverized to obtain aluminum ethylenediaminetetramethylenephosphonic acid.

[0059] Figure 1 The infrared spectrum of aluminum ethylenediaminetetramethylenephosphonate from Example 1 shows that aluminum ethylenediaminetetramethylenephosphonate was successfully prepared in Example 1.

[0060] Example 2

[0061] This embodiment provides an aminophosphonic acid metal compound, the preparation method of which is as follows:

[0062] 98.9 g of hexamethylenediaminetetramethylenephosphonic acid (CAS: 23605-74-5) and 1000 mL of water were placed in a 2 L round-bottom flask. Then, 160 g of 30% sodium hydroxide solution was added dropwise. The mixture was heated to 90 °C and stirred for 1 h. Subsequently, 228.2 g of 30% aluminum sulfate solution was added dropwise. After the addition was complete, the mixture was stirred at 90 °C for 13 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, dried, and pulverized to obtain aluminum hexamethylenediaminetetramethylenephosphonic acid.

[0063] Example 3

[0064] This embodiment provides an aminophosphonic acid metal compound, the preparation method of which is as follows:

[0065] 120 g of polyamine polyether phosphonic acid (CAS: 130668-24-5) and 1000 mL of water were placed in a 2 L round-bottom flask. Then, 160 g of 30% sodium hydroxide solution was added dropwise. The mixture was heated to 90 °C and stirred for 1 h. Subsequently, 228.2 g of 30% aluminum sulfate solution was added dropwise. After the addition was complete, the mixture was stirred at 90 °C for 15 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, dried, and pulverized to obtain aluminum polyamine polyether phosphonate.

[0066] Example 4

[0067] This embodiment provides an aminophosphonic acid metal compound, the preparation method of which is as follows:

[0068] 114.6 g of diethylenetriaminepentamethylenephosphonic acid (CAS: 15827-60-8) and 1000 mL of water were placed in a 2 L round-bottom flask. Then, 160 g of 30% sodium hydroxide solution was added dropwise. The mixture was heated to 90 °C and stirred for 1 h. Subsequently, 228.2 g of 30% aluminum sulfate solution was added dropwise. After the addition was complete, the mixture was stirred at 90 °C for 15 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, dried, and pulverized to obtain aluminum diethylenetriaminepentamethylenephosphonate.

[0069] Example 5

[0070] This embodiment provides an aminophosphonic acid metal compound, the preparation method of which is as follows:

[0071] 139.6 g of hexamethylenetriaminepentamethylenephosphonic acid (CAS: 34690-00-1) and 1000 mL of water were placed in a 2 L round-bottom flask. Then, 160 g of 30% sodium hydroxide solution was added dropwise. The mixture was heated to 90 °C and stirred for 1 h. Subsequently, 228.2 g of 30% aluminum sulfate solution was added dropwise. After the addition was complete, the mixture was stirred at 90 °C for 18 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, dried, and pulverized to obtain aluminum hexamethylenetriaminepentamethylenephosphonate.

[0072] Example 6

[0073] This embodiment provides a flame retardant composition, the preparation method of which is as follows:

[0074] Take 40 parts by weight of the aluminum aminophosphonate flame retardant prepared in Example 1, 40 parts by weight of melamine hydrobromide and 20 parts by weight of methyl methacrylate, and mix them evenly in a low-speed mixer to obtain the aluminum aminophosphonate / melamine hydrobromide / methyl methacrylate flame retardant composition 1 of Example 1.

[0075] Using the same method, the aluminum aminophosphonate flame retardant prepared in Examples 2-5 was used to prepare flame retardant compositions 2-5.

[0076] Comparative Example 1

[0077] Take 40 parts by weight of aluminum hypophosphite, 40 parts by weight of melamine hydrobromide, and 20 parts by weight of methyl methacrylate, and mix them evenly in a low-speed mixer to obtain comparative aluminum hypophosphite / melamine hydrobromide / methyl methacrylate comparative flame retardant compositions.

[0078] Flame retardant application testing

[0079] Polypropylene, flame retardant compositions 1-5, comparative flame retardant compositions, and additives were mixed evenly in a low-speed mixer (proportions shown in Table 1). The mixtures were then extruded at 170°C to form granules, yielding flame-retardant polypropylene particles. These particles were then injection molded at 200°C to form flame-retardant test strips, and their flame retardancy rating was evaluated based on the UL94 flame retardancy standard. The test results are shown in Table 2.

[0080] Table 1. Raw material composition of flame-retardant PP materials (parts by mass)

[0081]

[0082]

[0083] Table 2. Flame retardant PP material and flame retardant performance test results.

[0084]

[0085] As shown in Table 2 above, compared to the traditional aluminum hypophosphite / melamine hydrobromide / Lycorite flame retardant system, the aminophosphonic acid aluminum metal / melamine hydrobromide / Lycorite flame retardant system can pass the UL94 V2 flame retardant test at a lower addition amount when used in PP, exhibiting higher flame retardant efficiency. This may be due to the nitrogen (N) flame retardant element contained in the aminophosphonic acid aluminum metal flame retardant component, which releases inert gas N2 during combustion. This helps dilute the O2 around the burning material, exerting a gas-phase flame retardant effect and improving the flame retardant performance.

[0086] The above description represents the preferred embodiments of the present invention. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of the present invention, and these improvements and modifications are also considered to be within the scope of protection of the present invention.

Claims

1. An aminophosphonic acid metal compound, characterized in that, The aluminum aminophosphonate compound is a compound formed by the ionic bonding of aminophosphonate ions and aluminum ions. The structural formulas of the aminophosphonate group are shown in Formulas 1-5 below: Where x = 1-10; x represents the number of hydrogen ions neutralized by aminophosphonic acid.

2. The aminophosphonic acid metal compound according to claim 1, characterized in that, The molar ratio of aluminum ions to aminophosphonate is (1-3):

1.

3. The method for preparing the aminophosphonic acid metal compound according to claim 1 or 2, characterized in that, The process includes the following steps: reacting aminophosphonic acid with a water-soluble aluminum salt in an aqueous solution containing an inorganic base to obtain the aminophosphonic acid metal compound.

4. The method for preparing the aminophosphonic acid metal compound according to claim 3, characterized in that, The reaction temperature is 80–100°C; and / or the reaction time is 10–20 h.

5. The method for preparing the aminophosphonic acid metal compound according to claim 3, characterized in that, Specifically, the steps include: mixing an inorganic base with aminophosphonic acid in water and carrying out a neutralization reaction at 70–100°C; adding a water-soluble aluminum salt to the reaction system after the neutralization reaction is completed and carrying out a metathesis reaction to obtain the aminophosphonic acid metal compound.

6. The method for preparing the aminophosphonic acid metal compound according to claim 3, characterized in that, The inorganic base includes at least one of sodium hydroxide and potassium hydroxide.

7. The application of the aminophosphonic acid metal compound according to claim 1 or 2 in the field of flame retardants.

8. A flame-retardant composition, characterized in that, It includes the following components: the aminophosphonic acid metal compound as described in claim 1 or 2, the hydrobromide of melamine and its derivatives, and a free radical initiator.

9. The flame-retardant composition according to claim 8, characterized in that, The hydrobromide salts of melamine and its derivatives include at least one of melamine hydrobromide, melamine dihydrobromide, melamine hydrobromide, melamine dihydrobromide, and melamine dihydrobromide.

10. A flame-retardant polyolefin, characterized in that, It includes the intumescent flame retardant as described in claim 1 or 2, or the flame retardant composition as described in claim 8 or 9.

Images