ORGANIC PHOSPHOROUS COMPOUND FLAME RETARDANT, PREPARATION METHOD AND APPLICATIONS THEREOF

Abstract

The invention relates to an organic phosphorous compound flame retardant, their preparation methods and applications. The organic phosphorous compound flame retardants are prepared by drop-wise adding at least one from the soluble salts of di-alkyl hypophosphorous acid or soluble salts of mono-alkyl hypophosphorous acid as well as at least one from the soluble salts of alkyl phosphorous acid or soluble salts of phosphorous acid into the solution of soluble non-halogen salt of II-IV valent metal to react, or drop-wise adding at least one from the di-alkyl hypophosphorous acid or mono-alkyl hypophosphorous acid, and at least one from the alkyl phosphorous acid or phosphorous acid into at least one from the active oxides or hydroxides of II-IV valent metal to react.

Claims

1. A preparation method for organic phosphorus compound flame retardant, wherein the preparation method for organic phosphorus compound flame retardant comprises the following steps: first drop-wise adding at least one from the soluble salts of alkyl phosphorous acid or soluble salts of phosphorous acid into a solution of soluble non-halogen II˜IV valent metal salt to react and obtain a clear aqueous solution, then continuing to drop-wise at least one from the soluble salts of di-alkyl hypophosphorous acid or soluble salts of mono-alkyl hypophosphorous acid into the obtained clear aqueous solution, the adding ratios of various substances are as follows: the molar mass ratio between the total di-alkyl hypophosphite or mono-alkyl hypophosphite versus the total alkyl phosphite or phosphite is 1˜10, the molar mass ratio between the total metal ions versus the total di-alkyl hypophosphite or mono-alkyl hypophosphite and alkyl phosphite or phosphite is 0.01˜0.5, reaction temperature controlled to 0° C.˜90° C., then continuing to agitate them 0˜10 hours after the adding ended, finally filtering, washing, drying and comminuting the yielded turbid solution to obtain compound salt particles having a grain size of 0.001 μm to 100 μm, that is, the organic phosphorus compound flame retardant described above, wherein the structural formula (3) of the organic phosphorous compound flame retardants described above is: ##STR00004## wherein: in the structural formula (3), the R1 and R2 are the same or not, and both at least one selected from hydrogen, saturated alkyl groups of C1˜C6, aralkyl groups of C7˜C18 or alkaryl groups of C7˜C18 and form no, one or more rings between them; the R3 is at least one selected from hydrogen, saturated alkyl groups of C1˜C6, alkyl naphthenic group of C3˜C18, aralkyl groups of C7˜C18 or alkaryl groups of C7˜C18; M is a II˜IV valent metal element, m is 2˜4, x and y are both positive numbers of no less than 0.01 but no more than 10, including but not limited to a positive integer.

2. The preparation methods for an organic phosphorous compound flame retardant according to claim 1, wherein the soluble salts of di-alkyl hypophosphorous acid or soluble salts of mono-alkyl hypophosphorous acid described above, and the soluble salts of alkyl phosphorous acid or soluble salts of phosphorous acid salt described above, are prepared respectively by means of a reaction between the corresponding di-alkyl hypophosphorous acid, mono-alkyl hypophosphorous acid, alkyl phosphorous acid and phosphorous acid, with any one from an alkali metal or their oxide or their cyanide or hydroxide.

3. The preparation methods for an organic phosphorous compound flame retardant according claim 1, wherein the II˜IV valent metal described above is at least one from Mg, Ca, Fe, Al, Zn, Sn, Mn, Ni, Ti, Ge, Ba, Sr, Ce and Zr.

4. An organic phosphorous compound flame retardant, wherein the organic phosphorous compound flame retardant described above is prepared according to method described in claim 1.

5. The organic phosphorous compound flame retardants according to claim 4, wherein M bonds to at least one from di-alkyl hypophosphite or mono-alkyl hypophosphite and at least one from alkyl phosphite and phosphite together to form a molecular structure.

6. The application of an organic phosphorous compound flame retardant, wherein it comprises that organic phosphorous compound flame retardant prepared by the preparation method according to claim 1 can be applied singly in polyester resin, polyamide resin, polyurethane, polyolefin or rubber, and can also be applied together with a synergistic flame retardant including N based, Si based, P based, P and N based, aluminium hydroxide or magnesium hydroxide.

Description

DESCRIPTION OF THE EMBODIMENTS

[0035] The present invention is further explained in combination with the following embodiments in order to help understand the invention contents. Unless specified otherwise, the methods employed in the present invention are all conventional ones and the raw materials and devices are all the regular commercial products.

Example 1

[0036] Dissolve both 121 g di-ethyl hypophosphorous acid and 110 g ethyl phosphorous acid in 1000 g water to obtain Solution (1), then add 120 g sodium hydroxide into Solution (1) to obtain the corresponding Na salt mixture solution (2). Dissolve 333 g Al.sub.2(SO.sub.4).sub.3.18H.sub.2O into 1000 g water to obtain Solution (3). Add Solution (2) drop-wise into Solution (3) to react and get a turbid solution. Continue agitation for 0.5 h after the adding ends and control the reaction temperature to 0° C. Finally, filter, wash, dry and comminute the yielded turbid solution to get the compound salt ADEP.

[0037] Or first dissolve 122 g di-ethyl hypophosphorous acid in 500 g water and add 40 g NaOH to obtain Solution (4) then dissolve 110 g ethyl phosphorous acid in 500 g water and also add 80 g NaOH to obtain Solution (5). Then dissolve 333 g Al.sub.2(SO.sub.4).sub.3.18H.sub.2O into 1000 g water to obtain Solution (6). First add Solution (5) drop-wise into Solution (6) to react and get a clear solution (7). Then add Solution (4) drop-wise into Solution (7) to react further and get a turbid solution. Continue agitation for 5 h after the adding ends and control the reaction temperature to 0° C. Finally, filter, wash, dry and comminute the yielded turbid solution to get the compound salt ADEP.

Example 2

[0038] Dissolve both 244 g di-ethyl hypophosphorous acid and 110 g ethyl phosphorous acid in 1500 g water to obtain Solution (8), then add 160 g sodium hydroxide into Solution (8) to obtain the corresponding Na salt mixture Solution (9). Dissolve 444 g Al.sub.2(SO.sub.4).sub.3.18H.sub.2O into 1500 g water to obtain Solution (10). Add Solution (9) drop-wise into Solution (10) to react and get a turbid solution. Continue agitation for 3 h after the adding ends and control the reaction temperature to 50° C. Finally, filter, wash, dry and comminute the yielded turbid solution to get the compound salt ADEP.

[0039] Or first dissolve 244 g di-ethyl hypophosphorous acid in 1000 g water and add 80 g NaOH to obtain Solution (11). Then dissolve 110 g ethyl phosphorous acid in 500 g water and also add 80 g NaOH to obtain Solution (12). Then dissolve 444 g Al.sub.2(SO.sub.4).sub.3.18H.sub.2O into 1500 g water to obtain Solution (13). First add Solution (12) drop-wise into Solution (13) to react and get a clear Solution (14). Then add Solution (11) drop-wise into Solution (14) to react further and get a turbid solution. Continue agitation for 8 h after the adding ends and control the reaction temperature to 70° C. Finally, filter, wash, dry and comminute the yielded turbid solution to get the compound salt ADEP.

Example 3

[0040] Dissolve both 732 g di-ethyl hypophosphorous acid and 110 g ethyl phosphorous acid in 2500 g water to obtain Solution (15), then add 320 g sodium hydroxide into Solution (15) to obtain the corresponding Na salt mixture solution (16). Dissolve 888 g Al.sub.2(SO.sub.4).sub.3.18H.sub.2O into 2500 g water to obtain Solution (17). Add Solution (16) drop-wise into Solution (17) to react and get a turbid solution. Continue agitation for 9 h after the adding ends and control the reaction temperature to 80° C. Finally, filter, wash, dry and comminute the yielded turbid solution to get the compound salt ADEP.

[0041] Or first dissolve 732 g di-ethyl hypophosphorous acid in 2000 g water and add 240 g NaOH to obtain Solution (18). Then dissolve 110 g ethyl phosphorous acid in 500 g water and also add 80 g NaOH to obtain Solution (19). Then dissolve 888 g Al.sub.2(SO.sub.4).sub.3.18H.sub.2O into 2500 g water to obtain Solution (20). First add Solution (19) drop-wise into Solution (20) to react and get a clear solution (21). Then add Solution (18) drop-wise into Solution (21) to react further and get a turbid solution. Continue agitation for 9 h after the adding ends and control the reaction temperature to 80° C. Finally, filter, wash, dry and comminute the yielded turbid solution to get the compound salt ADEP.

Example 4

[0042] Dissolve both 122 g di-ethyl hypophosphorous acid and 11g methyl phosphorous acid in 250 g water to obtain Solution (22). Then add 48 g NaOH into Solution (22) to get the corresponding Na salt mixture Solution (23). Dissolve 84.9 g zirconium sulfate in 250 g water to obtain Solution (24). Then add Solution (23) drop-wise into Solution (24) to react and get a turbid solution. Continue agitation for 10 h after the adding ends and control the reaction temperature to 90° C. Finally, filter, wash, dry and comminute the yielded turbid solution to get the compound salt ADEP.

[0043] Or first dissolve 122 g di-ethyl hypophosphorous acid in 200 g water and add 40 g NaOH to obtain Solution (25). Then dissolve 11g methyl phosphorous acid in 50 g water and also add 8 g NaOH to obtain Solution (26). Then dissolve 84.9 g zirconium sulfate in 250 g water to obtain Solution (27). Then first add Solution (26) drop-wise into Solution (27) to react further and obtain a clear Solution (29). Then add Solution (25) drop-wise into Solution (29) to react and get a turbid solution. Continue agitation for 10 h after the adding ends and control the reaction temperature to 90° C. Finally, filter, wash, dry and comminute the turbid solution to get the compound salt ADEP.

Example 5

[0044] Add 750 g zirconium hydroxide in a small kneading machine and set the temperature of the kneading machine to 130° C. Then mix 1220 g di-ethyl hypophosphorous acid and 110 g methyl phosphorous acid evenly before adding them drop-wise into the kneading machine to react for 6 h at the temperature. Then increase the temperature to 200° C. to continue the kneading for 6 h. Finally, move the materials out from the kneading machine and comminute them to get the compound salt ADEP.

Comparison of Experiment Effects

[0045] Take Example 2 as the example, add the ADEP prepared in Example 2 into various polyester, polyamide, polyolefin, polyurethane or rubber to test the flame retardation.

Group 1 of Example 2

[0046] Mix 50 g PBT, 20 g ADEP and 30 g GF (glass fiber reinforced material) evenly and then put them into a torque rheometer to mix where the temperature of the rheometer is controlled to 240° C.-260° C. Then use the extrusion kit to produce strips and granulate to obtain the flame retardant and reinforced PBT. This PBT does not yellow, shows no bubble and breaking and produces a flame retardant rating of UL-94-V0 (2 mm).

Group 2 of Example 2

[0047] Mix 50 g PET, 20 g ADEP and 30 g GF evenly and then put them into a torque rheometer to mix where the temperature of the rheometer is controlled to 240° C.-260° C. Then use the extrusion kit to produce strips and granulate to obtain the flame retardant and reinforced PET. This PET does not yellow, shows no bubble and breaking and produces a flame retardant rating of UL-94-V0 (2 mm).

Group 3 of Example 2

[0048] Mix 50 g TPEE, 20 g ADEP and 30 g GF evenly and then put them into a torque rheometer to mix where the temperature of the rheometer is controlled to 260° C.-300° C. Then use the extrusion kit to produce strips and granulate to obtain the flame retardant and reinforced TPEE. This TPEE does not yellow, shows no bubble and breaking and produces a flame retardant rating of UL-94-V0 (2 mm).

Group 4 of Example 2

[0049] Mix 50 g PA6, 20 g ADEP and 30 g GF evenly and then put them into a torque rheometer to mix where the temperature of the rheometer is controlled to 240° C.-260° C. Then use the extrusion kit to produce strips and granulate to obtain the flame retardant and reinforced PA6. This PA6 does not yellow, shows no bubble and breaking and produces a flame retardant rating of UL-94-V0 (2 mm).

Group 5 of Example 2

[0050] Mix 50 g PA66, 20 g ADEP and 30 g GF evenly and then put them into a torque rheometer to mix where the temperature of the rheometer is controlled to 260° C.-300° C. Then use the extrusion kit to produce strips and granulate to obtain the flame retardant and reinforced PA66. This PA66 does not yellow, shows no bubble and breaking and produces a flame retardant rating of UL-94-V0 (2 mm).

Group 6 of Example 2

[0051] Mix 58 g PA66, 12 g ADEP and 30 g GF evenly and then put them into a torque rheometer to mix where the temperature of the rheometer is controlled to 260° C.-300° C. Then use the extrusion kit to produce strips and granulate to obtain the flame retardant and reinforced PA66. This PA66 does not yellow, shows no bubble and breaking and produces a flame retardant rating of UL-94-V0 (2 mm).

Group 7 of Example 2

[0052] Mix 50 g PE, 20 g ADEP and 13 g MPP (synergetic P—N based flame retardant) evenly and then put them into a torque rheometer to mix where the temperature of the rheometer is controlled to 180° C.-200° C. Then use the extrusion kit to produce strips and granulate to obtain the flame retardant PE. This PE does not yellow, shows no bubble and breaking and produces a flame retardant rating of UL-94-V0 (2 mm).

Group 8 of Example 2

[0053] Mix 50 g TPU, 20 g ADEP and 13 g MPP evenly and then put them into a torque rheometer to mix where the temperature of the rheometer is controlled to 160° C.-200° C. Then use the extrusion kit to produce strips and granulate to obtain the flame retardant TPU. This TPU does not yellow, shows no bubble and breaking and produces a flame retardant rating of UL-94-V0 (2 mm).

Control Group

[0054] Mix 50 g PA66, 20 g ADP and 30 g GF evenly and then put them into a torque rheometer to mix where the temperature of the rheometer is controlled to 260° C.-300° C. Then use the extrusion kit to produce strips and granulate to obtain the flame retardant and reinforced PA66. This PA66 does not yellow, shows no bubble and breaking and produces a flame retardant rating of only UL-94-V2 (2 mm) which is far from UL-94-V0 (2 mm).

[0055] The experiment result revealed that: [0056] when the organic phosphorous compound flame retardants prepared according to the present invention are added into polyester, polyamide, polyolefin, polyurethane or rubber, the products did not yellow and showed no bubbling and breaking. The flame retardation performance of those materials were obviously improved and the flame retardant ratings of PBT, PET, TPEE, PA6, PA66, PE, TPU reached UL-94-V0 (2 mm). Nevertheless, the PA66 added with ADP showed yellowing as well as bubbling and breaking and only a flame retardant rating of UL-94-V2 (2 mm). The flame retardant effects of the polyester, polyamide, polyolefin, polyurethane or rubber added with ADEP were far better than those added with ADP. Moreover, the excellent flame retardant effects can still be realized at a lower adding ratio of the flame retardant. Thus, the production cost was greatly reduced for the enterprise.

[0057] The examples described above are only the preferred implementations. Nevertheless, the implementations of the present invention shall not be limited by those examples. Any other changes, modifications, substitutions, combinations and simplifications that do not deviate from the spirit and principle of the present invention should be equivalent replacements and shall be included in the protection scope of the present invention.