BIO-BASED FIRE RETARDANT DERIVED FROM POLYACRYLAMIDE GRAFTED STARCH AND USE THEREOF

Abstract

A bio-based fire retardant derived from polyacrylamide grafted starch and use thereof. This disclosure relates to the field of polymer additives for improving fire safety of materials. Specifically, the present disclosure is bio-based material derived from polyacrylamide grafted starch as fire retardants to polymers. Moreover, the disclosure relates to their uses in the fields of coating, adhesive, etc.

Claims

1. A compound characterized by the following general formula: ##STR00019## wherein: n is 100-10000; ST is starch; R.sub.1 is selected from the list group consisting of ##STR00020## wherein m is 100-5000, R.sub.3 is selected from the list group consisting of NH.sub.4.sup.+, ##STR00021## and ##STR00022## wherein R.sub.4 is selected from the group consisting of CH.sub.3, CH.sub.2CH.sub.3, CH.sub.2CH.sub.2CH.sub.3, and ##STR00023## wherein X is selected from the group consisting of NH.sub.4.sup.+, Na.sup.+, and K.sup.+, R.sub.2 is selected from the group consisting of ##STR00024## wherein m is 100-5000, R.sub.5 is selected from the list group consisting of NH.sub.4.sup.+, ##STR00025## and ##STR00026## wherein R6 is selected from the list group consisting of CH.sub.3, CH.sub.2CH.sub.3, CH.sub.2CH.sub.2CH.sub.3, and ##STR00027## wherein X is selected from the group consisting of NH.sub.4.sup.+, Na.sup.+, and K.sup.+.

2. A method for preparing the compound of claim 1, comprising: providing a solvent comprising water and, optionally, an organic solvent; adding polyacrylamide grafted starch and a compound selected from the group consisting of ammonium polyphosphate, glycidylpropyltrimethoxysilane, H.sub.3PO.sub.4, and 3-(hydroxyphenylphosphinyl)-propanoic acid to the solvent; stirring under N.sub.2 to form a mixture, heating the mixture to 40-80 C. for 2 to 6 h such that the polyacrylamide grafted starch and the compound react to form a solid product; cooling the mixture down to room temperature; filtering the solid product from the mixture, cleaned, and dried in a vacuum oven at 80 C. for 12 h.

3. The method of claim 2, wherein the organic solvent is selected from the group consisting of acetone, methanol, ethanol, isopropanol, chloroform and tetrahydrofuran.

4. The method of claim 2, wherein the ratio of organic solvent and to water ratio is 0-0.1:1.

5. (canceled) .

6. The fire retardant formulation of claim 10, wherein the one or more additives are selected from the group consisting of nanoclay, metal oxides, talc, Mg(OH).sub.2, ammonium polyphosphate, Al(OH).sub.3, intumescent flame retardants and Sb.sub.2O.sub.3 etc.

7. The fire retardant formulation of claim 10, wherein the polymers are selected from the group consisting of polyurethane, polypropylene, polyethylene, rubber, polyvinyl chloride, polylactic acid, epoxy, ethylene vinyl acetate, polyamide, polyvinyl alcohol, and polyimide.

8. A fire retardant compound, formulation, and/or composite comprising the compound according to claim 1.

9. (canceled)

10. A fire retardant formulation comprising: the compound of claim 1; and one or more additives and/or polymers.

11. The method of claim 3, wherein the organic solvent is ethanol or acetone.

12. The compound of claim 1, wherein R.sub.3 is NH.sub.4.sup.+.

13. The compound of claim 1, wherein R.sub.5 is NH.sub.4.sup.+.

Description

DETAILED DESCRIPTION OF THE INVENTION

EXAMPLE 1

[0030] The mixed solvent of water and acetone (ratio 100:5) was added in a three-neck round-bottom flask equipped with a stirrer in N2. Polyacrylamide grafted starch (5 g) and APP (10 g) were added in the flask. Then, the mixture was heated up to 75 C. with the release of ammonia for 6 h. Then, the reaction mixture was cooled down to room temperature.

[0031] After that, the mixture was concentrated and washed with ethanol. The white solid was filtered, and then the sample was dried in a vacuum oven at 80 C. for 12 h, the compound having the following structure was obtained.(yield>80%):

##STR00010##

EXAMPLE 2

[0032] The mixed solvent of water and ethanol (ratio 100:8) was added in a three-neck round-bottom flask equipped with a stirrer in N2. Polyacrylamide grafted starch (5 g) and APP (10 g) were added in the flask. Then, the mixture was heated up to 80 C. with the release of ammonia for 6 h. Then, the reaction mixture was cooled down to room temperature.

[0033] After that, the mixture was concentrated and washed with ethanol. The white solid was filtered, and then the sample was dried in a vacuum oven at 80 C. for 12 h, the compound having the following structure was obtained (yield>85%):

##STR00011##

EXAMPLE 3

[0034] The mixed solvent of water and ethanol (ratio 100:5) was added in a three-neck round-bottom flask equipped with a stirrer in N2. Glycidylpropyltrimethoxysilane (KH560, 3 g) and Polyacrylamide grafted starch (10 g) were added in the flask. Then, the mixture was heated up to 60 C. and kept for 4 h with stirring. Then, the reaction mixture was cooled down to room temperature. After that, the mixture was concentrated and washed with ethanol. The white solid was filtered, and then the sample was dried in a vacuum oven at 80 C. for 12 h, the compound having the following structure was obtained (yield>82%):

##STR00012##

EXAMPLE 4

[0035] The mixed solvent of water and ethanol (ratio 100:10) was added in a three-neck round-bottom flask equipped with a stirrer in N2. Glycidylpropyltrimethoxysilane (KH560, 4 g) and Polyacrylamide grafted starch (10 g) were added in the flask. Then, the mixture was heated up to 70 C. and kept for 5 h with stirring. Then, the reaction mixture was cooled down to room temperature. After that, the mixture was concentrated and washed with ethanol. The white solid was filtered, and then the sample was dried in a vacuum oven at 80 C. for 12 h, the compound having the following structure was obtained (yield>85%):

##STR00013##

EXAMPLE 5

[0036] The mixed solvent of water and ethanol (ratio 100:10) was added in a three-neck round-bottom flask equipped with a stirrer in N2. Polyacrylamide grafted starch (3 g) and APP (10 g) were added in the flask. Then, the mixture was heated up to 80 C. with the release of ammonia for 6 h. Then, the reaction mixture was cooled down to room temperature. After that, the mixture was concentrated and washed with ethanol. The white solid was filtered, and then the sample was dried in a vacuum oven at 80 C. for 12 h, the compound having the following structure was obtained (yield>88%):

##STR00014##

EXAMPLE 6

[0037] The mixed solvent of water and ethanol (ratio 100:5) was added in a three-neck round-bottom flask equipped with a stirrer in N2. Polyacrylamide grafted starch (3 g) and H.sub.3PO.sub.4(10 g) were added in the flask. Then, the mixture was heated up to 40 C. with the release of ammonia for 2 h. Then, the reaction mixture was cooled down to room temperature. After that, the mixture was concentrated and washed with water. The white solid was filtered, and then the sample was dried in a vacuum oven at 70 C. for 12 h, the compound having the following structure was obtained (yield>80%):

##STR00015##

EXAMPLE 7

[0038] The water was added in a three-neck round-bottom flask equipped with a stirrer in N2. Polyacrylamide grafted starch (2 g) and H.sub.3PO.sub.4(12 g) were added in the flask. Then, the mixture was heated up to 60 C. for 6 h. Then, the reaction mixture was cooled down to room temperature. After that, the mixture was concentrated and washed with water. The white solid was filtered, and then the sample was dried in a vacuum oven at 70 C. for 12 h, the compound having the following structure was obtained (yield>82%):

##STR00016##

EXAMPLE 8

[0039] The water was added in a three-neck round-bottom flask equipped with a stirrer in N2. Polyacrylamide grafted starch (2 g) and 3-(hydroxyphenylphosphinyl)-propanoic acid (10 g) were added in the flask. Then, the mixture was heated up to 60 C. or 2 h. Then, the reaction mixture was added NaOH solution (0.1M) untill pH value in the range of 6-8. Finally, the reaction was cooled down to room temperature. After that, the mixture was concentrated and washed with water. The white solid was filtered, and then the sample was dried in a vacuum oven at 70 C. for 12 h, the compound having the following structure was obtained (yield>82%):

##STR00017##

EXAMPLE 9

[0040] The water was added in a three-neck round-bottom flask equipped with a stirrer in N2. Polyacrylamide grafted starch (2 g) and 3-(hydroxyphenylphosphinyl)-propanoic acid (10 g) were added in the flask. Then, the mixture was heated up to 60 C. or 4 h. Then, the reaction mixture was added KOH solution (0.1M) untill pH value in the range of 6-8. Finally, the reaction was cooled down to room temperature. After that, the mixture was concentrated and washed with water. The white solid was filtered, and then the sample was dried in a vacuum oven at 70 C. for 12 h, the compound having the following structure was obtained (yield>80%):

##STR00018##

EXAMPLE 10

[0041] Compound obtained according to example 1 was added into the commercialized PU resin at 15 wt % in order to prepare fire retardant coating resin. The fire retardant coating was used to treat wood board with the thickness of 0.50.1 mm. After fully cured of the resin, two fire tests, vertical burning test from profile (45 degree) and cone calorimeter test, were used to investigate the fire retardant efficiency of the fire retardant coating. Moreover, the polyacrylamide grafted starch in the Examples was used as reference.

TABLE-US-00001 TABLE 1 Fire retardant performance of PU coating and fire retardant PU coating pHRR THR TSP Extinguishement in (kW/m.sup.2) (MJ/m2) (m.sup.2) vertical burning test PU coating 362 5.4 0.27 No PU/Compound-1 240 4.5 0.23 Yes PU/Reference 320 5.0 0.26 No

EXAMPLE 11

[0042] Compound obtained according to example 3 was added into the commercialized PU resin at 15 wt % in order to prepare fire retardant coating resin. The fire retardant coating was used to treat wood board with the thickness of 0.50.1 mm. After fully cured of the resin, two fire tests, vertical burning test from profile (45 degree) and cone calorimeter test, were used to investigate the fire retardant efficiency of the fire retardant coating. Moreover, the polyacrylamide grafted starch in the Examples was used as reference.

TABLE-US-00002 TABLE 2 Fire retardant performance of PU coating and fire retardant PU coating pHRR THR TSP Extinguishment in (kW/m.sup.2) (MJ/m2) (m.sup.2) vertical burning test PU coating 362 5.4 0.27 No PU/Compound-3 260 4.7 0.24 Yes PU/Reference 320 5.0 0.26 No

EXAMPLE 12

[0043] Compound obtained according to example 6 was added into the commercialized PU resin at 15 wt % in order to prepare fire retardant coating resin. The fire retardant coating was used to treat wood board with the thickness of 0.50.1 mm. After fully cured of the resin, two fire tests, vertical burning test from profile (45 degree) and cone calorimeter test, were used to investigate the fire retardant efficiency of the fire retardant coating. Moreover, the polyacrylamide grafted starch in the Examples was used as reference.

TABLE-US-00003 TABLE 3 Fire retardant performance of PU coating and fire retardant PU coating pHRR THR TSP Extinguishment in (kW/m.sup.2) (MJ/m2) (m.sup.2) vertical burning test PU coating 362 5.4 0.27 No PU/Compound-6 268 4.8 0.25 Yes PU/Reference 320 5.0 0.26 No

EXAMPLE 13

[0044] Compound obtained according to example 6 was added into the commercialized PU resin at 15 wt % in order to prepare fire retardant coating resin. The fire retardant coating was used to treat wood board with the thickness of 0.50.1 mm. After fully cured of the resin, two fire tests, vertical burning test from profile (45 degree) and cone calorimeter test, were used to investigate the fire retardant efficiency of the fire retardant coating. Moreover, the polyacrylamide grafted starch in the Examples was used as reference.

TABLE-US-00004 TABLE 4 Fire retardant performance of PU coating and fire retardant PU coating pHRR THR TSP Extinguishment in (kW/m.sup.2) (MJ/m2) (m.sup.2) vertical burning test PU coating 362 5.4 0.27 No PU/Compound-8 262 4.7 0.24 Yes PU/Reference 320 5.0 0.26 No

EXAMPLE 14

[0045] Compound obtained according to example 2 was combined with ammonium polyphosphate with mass ration at 1:2 (compound mix-1), then the mixture was added into the commercialized PU resin at 15 wt % in order to prepare fire retardant coating resin. The fire retardant coating was used to treat wood board with the thickness of 0.50.1 mm. After fully cured of the resin, two fire tests, vertical burning test from profile (45 degree) and cone calorimeter test, were used to investigate the fire retardant efficiency of the fire retardant coating. Moreover, the polyacrylamide grafted starch in the Examples was used as reference.

TABLE-US-00005 TABLE 5 Fire retardant performance of PU coating and fire retardant PU coating pHRR THR TSP Extinguishment in (kW/m.sup.2) (MJ/m2) (m.sup.2) vertical burning test PU coating 362 5.4 0.27 No PU/Compound-mix1 220 4.0 0.21 Yes PU/Reference 320 5.0 0.26 No

EXAMPLE 15

[0046] Compound obtained according to example 2 was combined with ammonium polyphosphate and nanoclay with mass ration at 1:2:0.2 (compound mix-2), then the mixture was added into the commercialized PU resin at 15 wt % in order to prepare fire retardant coating resin. The fire retardant coating was used to treat wood board with the thickness of 0.50.1 mm. After fully cured of the resin, two fire tests, vertical burning test from profile (45 degree) and cone calorimeter test, were used to investigate the fire retardant efficiency of the fire retardant coating. Moreover, the polyacrylamide grafted starch in the Examples was used as reference.

TABLE-US-00006 TABLE 6 Fire retardant performance of PU coating and fire retardant PU coating pHRR THR TSP Extinguishment in (kW/m.sup.2) (MJ/m2) (m.sup.2) vertical burning test PU coating 362 5.4 0.27 No PU/Compound-mix2 210 3.9 0.19 Yes PU/Reference 320 5.0 0.26 No

EXAMPLE 16

[0047] Compound obtained according to example 3 was combined with ammonium polyphosphate with mass ration at 1:2 (compound mix-3), then the mixture was added into the commercialized PU resin at 15 wt % in order to prepare fire retardant coating resin. The fire retardant coating was used to treat wood board with the thickness of 0.50.1 mm. After fully cured of the resin, two fire tests, vertical burning test from profile (45 degree) and cone calorimeter test, were used to investigate the fire retardant efficiency of the fire retardant coating. Moreover, the polyacrylamide grafted starch in the Examples was used as reference.

TABLE-US-00007 TABLE 7 Fire retardant performance of PU coating and fire retardant PU coating pHRR THR TSP Extinguishment in (kW/m.sup.2) (MJ/m2) (m.sup.2) vertical burning test PU coating 362 5.4 0.27 No PU/Compound-mix3 232 4.2 0.22 Yes PU/Reference 320 5.0 0.26 No

EXAMPLE 17

[0048] Compound obtained according to example 3 was combined with ammonium polyphosphate and nanoclay with mass ration at 1:2:0.2 (compound mix-4), then the mixture was added into the commercialized PU resin at 15 wt % in order to prepare fire retardant coating resin. The fire retardant coating was used to treat wood board with the thickness of 0.50.1 mm. After fully cured of the resin, two fire tests, vertical burning test from profile (45 degree) and cone calorimeter test, were used to investigate the fire retardant efficiency of the fire retardant coating. Moreover, the polyacrylamide grafted starch in the Examples was used as reference.

TABLE-US-00008 TABLE 8 Fire retardant performance of PU coating and fire retardant PU coating pHRR THR TSP Extinguishment in (kW/m.sup.2) (MJ/m2) (m.sup.2) vertical burning test PU coating 362 5.4 0.27 No PU/Compound-mix4 215 4.0 0.20 Yes PU/Reference 320 5.0 0.26 No