CN117966517A - Waterproof flame-retardant corrugated paper and preparation method thereof - Google Patents
Waterproof flame-retardant corrugated paper and preparation method thereof Download PDFInfo
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- CN117966517A CN117966517A CN202410188897.9A CN202410188897A CN117966517A CN 117966517 A CN117966517 A CN 117966517A CN 202410188897 A CN202410188897 A CN 202410188897A CN 117966517 A CN117966517 A CN 117966517A
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000003063 flame retardant Substances 0.000 title claims abstract description 105
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000004114 Ammonium polyphosphate Substances 0.000 claims abstract description 50
- 229920001276 ammonium polyphosphate Polymers 0.000 claims abstract description 50
- 229920002472 Starch Polymers 0.000 claims abstract description 31
- 235000019698 starch Nutrition 0.000 claims abstract description 31
- 239000008107 starch Substances 0.000 claims abstract description 31
- 239000003094 microcapsule Substances 0.000 claims abstract description 27
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims abstract description 25
- 239000011248 coating agent Substances 0.000 claims abstract description 22
- 238000000576 coating method Methods 0.000 claims abstract description 22
- -1 4,4' -biphenyl di (diaminotriazine) Chemical compound 0.000 claims abstract description 18
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract description 17
- 239000000853 adhesive Substances 0.000 claims abstract description 15
- 230000001070 adhesive effect Effects 0.000 claims abstract description 15
- 239000001254 oxidized starch Substances 0.000 claims abstract description 14
- 235000013808 oxidized starch Nutrition 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 10
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 10
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 17
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 230000010355 oscillation Effects 0.000 claims description 14
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 12
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- FVFVNNKYKYZTJU-UHFFFAOYSA-N 6-chloro-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(Cl)=N1 FVFVNNKYKYZTJU-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000005859 coupling reaction Methods 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000004305 biphenyl Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- VBXDEEVJTYBRJJ-UHFFFAOYSA-N diboronic acid Chemical compound OBOBO VBXDEEVJTYBRJJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 239000002775 capsule Substances 0.000 abstract description 6
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 125000003277 amino group Chemical group 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 238000004132 cross linking Methods 0.000 abstract description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 abstract description 3
- 125000003172 aldehyde group Chemical group 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- WEWFIUPOLKEEJP-UHFFFAOYSA-N triazine-4,6-diamine Chemical compound NC1=CC(N)=NN=N1 WEWFIUPOLKEEJP-UHFFFAOYSA-N 0.000 description 6
- SLHKDOGTVUCXKX-UHFFFAOYSA-N 4,4'-biphenyldiboronic acid Chemical compound C1=CC(B(O)O)=CC=C1C1=CC=C(B(O)O)C=C1 SLHKDOGTVUCXKX-UHFFFAOYSA-N 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
Landscapes
- Paper (AREA)
Abstract
The invention relates to the technical field of corrugated paper and discloses waterproof flame-retardant corrugated paper and a preparation method thereof, wherein 4,4' -biphenyl di (diaminotriazine) contains a plurality of amino groups, cross-linking polymerization reaction is carried out on the amino groups and aldehyde groups of aldehyde starch, a starch capsule wall is formed on the surface of ammonium polyphosphate through an in-situ polymerization method, coating of the ammonium polyphosphate is realized, a starch-ammonium polyphosphate microcapsule flame retardant is obtained, and the starch-ammonium polyphosphate microcapsule flame retardant is compounded with oxidized starch adhesive as an adhesive, magnesium hydroxide or aluminum hydroxide synergistic flame retardant to obtain a flame retardant solution, and then the surface of the corrugated paper is coated. The starch-ammonium polyphosphate microcapsule flame retardant takes starch as a carbon source, ammonium polyphosphate as an acid source and a triazine group as a steam source to form an intumescent flame retardant system, so that the flame retardant and waterproof performance of corrugated paper are improved.
Description
Technical Field
The invention relates to the technical field of corrugated paper, in particular to waterproof flame-retardant corrugated paper and a preparation method thereof.
Background
The corrugated paper has low cost and easy recycling, is suitable for automatic high-speed production, and has wide application in the packaging field. However, the corrugated paper is easy to burn when meeting open fire, has larger potential safety hazard, has poor waterproof property, is easy to absorb moisture, and has much influence on mechanical strength. At present, the surface of the corrugated paper is generally coated with the flame retardant liquid, so that the performance of the corrugated paper is improved. Patent CN109109424B discloses that a flame-retardant layer is formed on the surface of corrugated paper by using cerium oxide, nano silicon dioxide, phosphazene compound, polychlorinated ester, ammonium polyphosphate, melamine, terpene phenolic resin and the like as raw materials, so that the fireproof flame-retardant durability of the corrugated paper is improved. However, the patent has excessive raw materials, is unfavorable for practical production, and the ammonium polyphosphate flame retardant is easy to absorb moisture and water, so that the flame retardant property of the ammonium polyphosphate flame retardant is affected.
Disclosure of Invention
The invention solves the technical problems that: the waterproof flame-retardant corrugated paper and the preparation method thereof are provided, and the problems that the corrugated paper does not have flame retardance and has poor waterproof performance are solved.
The technical scheme provided by the invention is as follows: a preparation method of waterproof flame-retardant corrugated paper comprises the following steps:
adding water and aldehyde starch into a reaction container, adding ethanol and 4,4' -biphenyl di (diamino triazine) after ultrasonic oscillation, adding an aqueous solution containing ammonium polyphosphate after uniform mixing, stirring and reacting for 6-12h at 70-80 ℃, filtering a solvent, washing with ethanol, and drying to obtain the starch-ammonium polyphosphate microcapsule flame retardant.
And (2) adding water, oxidized starch adhesive, starch-ammonium polyphosphate microcapsule flame retardant and hydroxide flame retardant into a reaction container, and preparing a flame retardant solution after ultrasonic oscillation.
And (3) coating the surface of the corrugated paper with the flame retardant solution by using a coating machine, and then drying at 50-60 ℃ for 4-8 hours to obtain the waterproof flame-retardant corrugated paper.
Preferably, the ratio of aldehyde starch, 4' -biphenylbis (diaminotriazine), ammonium polyphosphate is 1g: (0.3-0.8) g: (2-5) g.
Preferably, the proportion of the oxidized starch adhesive, the starch-ammonium polyphosphate microcapsule flame retardant and the hydroxide flame retardant is 1g: (2-8) g: (1.2-2.5) g.
Preferably, the hydroxide flame retardant comprises magnesium hydroxide, aluminum hydroxide.
Preferably, the preparation method of the aldehyde starch comprises the following steps: adding water and sodium periodate into a reaction container, dripping sulfuric acid to regulate the pH value to 2-3, adding starch, carrying out light-proof reaction for 2-3h at 45-55 ℃, adding ethylene glycol to neutralize and remove residual sodium periodate, filtering, washing with water, and drying to obtain aldehyde starch.
Preferably, the preparation method of the 4,4' -biphenyl di (diaminotriazine) comprises the following steps: adding ethylene glycol dimethyl ether solvent, 2-chloro-4, 6-diamino-1, 3, 5-triazine, 4 '-biphenyl diboronic acid, sodium carbonate and tetra (triphenylphosphine) palladium into a reaction vessel, carrying out coupling reaction for 18-36h at 75-85 ℃, filtering, rotationally evaporating filtrate, and recrystallizing methylene dichloride to obtain 4,4' -biphenyl di (diamino triazine). The reaction route is as follows:
Preferably, the ratio of 2-chloro-4, 6-diamino-1, 3, 5-triazine, 4' -biphenyldiboronic acid, sodium carbonate, tetrakis (triphenylphosphine) palladium is (2-2.2) mol:1mol: (2.4-3.5) mol: (0.013-0.018) mol.
The invention has the technical effects that: the 2-chloro-4, 6-diamino-1, 3, 5-triazine and 4,4' -biphenyl diboronic acid are utilized for carrying out coupling reaction to obtain 4,4' -biphenyl di (diamino triazine), the 4,4' -biphenyl di (diamino triazine) contains a plurality of amino groups, the cross-linking polymerization reaction is carried out with aldehyde groups of aldehyde starch, a starch capsule wall is formed on the surface of ammonium polyphosphate by an in-situ polymerization method, the coating of the ammonium polyphosphate is realized, the starch-ammonium polyphosphate microcapsule flame retardant is obtained, and meanwhile, the starch capsule wall contains biphenyl hydrophobic groups, so that the hydrophobicity of the starch capsule wall can be improved, the ammonium polyphosphate is prevented from absorbing moisture and affecting the flame retardant performance.
The invention combines the oxidized starch adhesive, magnesium hydroxide or aluminum hydroxide synergistic flame retardant and the starch-ammonium polyphosphate microcapsule flame retardant to obtain a flame retardant solution, and then coats the surface of the corrugated paper. The starch-ammonium polyphosphate microcapsule flame retardant takes starch as a carbon source, ammonium polyphosphate as an acid source and a triazine group as a steam source to form an intumescent flame retardant system, and a continuous carbon layer is formed on the surface of corrugated paper during combustion, so that flame retardant effects of isolating oxygen, suppressing smoke, preventing combustion reaction and the like can be achieved. The average after-burning time and the average burning time are low, the minimum is only 2.2s and 1.5s, and the limiting oxygen index reaches 29.6 percent. Has excellent flame retardant property.
The starch-ammonium polyphosphate microcapsule flame retardant contains biphenyl hydrophobic groups, so that the hydrophobicity of the flame retardant solution film can be enhanced to a certain extent, and a hydrophobic film can be formed on the surface of corrugated paper, thereby being beneficial to improving the water resistance and the water resistance of the corrugated paper.
Detailed Description
The invention is further illustrated below with reference to examples. These examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. The experimental procedures in the examples below, without specific details, are generally performed under conditions conventional in the art or recommended by the manufacturer; the raw materials, reagents and the like used, unless otherwise specified, are those commercially available from conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art in light of the above teachings are intended to be within the scope of the invention as claimed.
50ML of water and 4.5g of sodium periodate are added into a reaction vessel, sulfuric acid is added dropwise to adjust the pH to 2-3, 1g of starch is added, the reaction is carried out for 2 hours at 50 ℃ in the dark, ethylene glycol is added for neutralization to remove the residual sodium periodate, and the aldehyde starch is obtained after filtering, washing with water and drying.
Example 1
To the reaction vessel were added 10mL of ethylene glycol dimethyl ether solvent, 4.4mmol of 2-chloro-4, 6-diamino-1, 3, 5-triazine, 2mmol of 4,4 '-biphenyldiboronic acid, 4.8mmol of sodium carbonate, 0.036mmol of tetrakis (triphenylphosphine) palladium, and the coupling reaction was performed at 85℃for 24 hours, filtered, the filtrate was rotary evaporated, and methylene chloride was recrystallized to obtain 4,4' -biphenylbis (diaminotriazine).
Adding 25mL of water and 5g of aldehyde starch into a reaction vessel, adding 10mL of ethanol and 1.5g of 4,4' -biphenyl di (diaminotriazine) after ultrasonic oscillation, adding an aqueous solution containing 10g of ammonium polyphosphate after uniform mixing, stirring and reacting for 6h at 80 ℃, filtering a solvent, washing with ethanol, and drying at 60 ℃ for 12h to obtain the starch-ammonium polyphosphate microcapsule flame retardant.
Adding 100mL of water, 10g of oxidized starch adhesive, 20g of starch-ammonium polyphosphate microcapsule flame retardant and 12g of magnesium hydroxide into a reaction vessel, and preparing a flame retardant solution after ultrasonic oscillation;
And coating the surface of the corrugated paper with the flame retardant solution by using a coating machine, and then drying at 60 ℃ for 4 hours to obtain the waterproof flame-retardant corrugated paper.
Example 2
To the reaction vessel were added 20mL of ethylene glycol dimethyl ether solvent, 4.4mmol of 2-chloro-4, 6-diamino-1, 3, 5-triazine, 2mmol of 4,4 '-biphenyldiboronic acid, 4.8mmol of sodium carbonate, 0.03mmol of tetrakis (triphenylphosphine) palladium, and the reaction vessel was subjected to coupling reaction at 85℃for 18 hours, filtration, rotary evaporation of the filtrate, and recrystallization of methylene chloride to obtain 4,4' -biphenylbis (diaminotriazine).
40ML of water and 5g of aldehyde starch are added into a reaction vessel, 20mL of ethanol and 2.8g of 4, 4-biphenyl di (diamino triazine) are added after ultrasonic oscillation, an aqueous solution containing 17g of ammonium polyphosphate is added after uniform mixing, the mixture is stirred and reacted for 12 hours at 75 ℃, the solvent is filtered, the ethanol is used for washing, and the mixture is dried for 12 hours at 60 ℃ to prepare the starch-ammonium polyphosphate microcapsule flame retardant.
150ML of water, 10g of oxidized starch adhesive, 50g of starch-ammonium polyphosphate microcapsule flame retardant and 18g of aluminum hydroxide are added into a reaction vessel, and a flame retardant solution is prepared after ultrasonic oscillation;
And coating the surface of the corrugated paper with the flame retardant solution by using a coating machine, and then drying at 60 ℃ for 6 hours to obtain the waterproof flame-retardant corrugated paper.
Example 3
To the reaction vessel were added 10mL of ethylene glycol dimethyl ether solvent, 4mmol of 2-chloro-4, 6-diamino-1, 3, 5-triazine, 2mmol of 4,4 '-biphenyldiboronic acid, 7mmol of sodium carbonate, 0.026mmol of tetrakis (triphenylphosphine) palladium, and the coupling reaction was performed at 75℃for 36 hours, filtered, the filtrate was rotary evaporated, and methylene chloride was recrystallized to obtain 4,4' -biphenylbis (diaminotriazine).
50ML of water and 5g of aldehyde starch are added into a reaction vessel, 25mL of ethanol and 4g of 4,4' -biphenyl di (diamino triazine) are added after ultrasonic oscillation, an aqueous solution containing 25g of ammonium polyphosphate is added after uniform mixing, stirring reaction is carried out for 12h at 70 ℃, a solvent is filtered, ethanol washing is carried out, and drying is carried out for 18h at 60 ℃, thus obtaining the starch-ammonium polyphosphate microcapsule flame retardant.
200ML of water, 10g of oxidized starch adhesive, 80g of starch-ammonium polyphosphate microcapsule flame retardant and 25g of aluminum hydroxide are added into a reaction vessel, and a flame retardant solution is prepared after ultrasonic oscillation;
And coating the surface of the corrugated paper with the flame retardant solution by using a coating machine, and then drying at 50 ℃ for 8 hours to obtain the waterproof flame-retardant corrugated paper.
Comparative example 1
Adding 100mL of water, 10g of oxidized starch adhesive and 12g of magnesium hydroxide into a reaction container, and preparing a flame retardant solution after ultrasonic oscillation;
And coating the surface of the corrugated paper with the flame retardant solution by using a coating machine, and then drying at 60 ℃ for 4 hours to obtain the waterproof flame-retardant corrugated paper.
Comparative example 2
To the reaction vessel were added 25mL of water, 5g of aldehyde starch, 10mL of ethanol and 1.5g of 4,4' -biphenyl di (diaminotriazine) after ultrasonic vibration, stirred at 80℃for reaction for 6 hours, filtered the solvent, washed with ethanol, and dried at 60℃for 12 hours to prepare a starch microcapsule.
100ML of water, 10g of oxidized starch adhesive, 20g of starch microcapsule and 12g of magnesium hydroxide are added into a reaction vessel, and the solution is prepared into a flame retardant solution after ultrasonic oscillation.
And coating the surface of the corrugated paper with the flame retardant solution by using a coating machine, and then drying at 60 ℃ for 4 hours to obtain the waterproof flame-retardant corrugated paper.
Comparative example 3
100ML of water, 10g of oxidized starch adhesive, 20g of ammonium polyphosphate and 12g of magnesium hydroxide are added into a reaction vessel, and the solution is prepared into a flame retardant solution after ultrasonic oscillation.
And coating the surface of the corrugated paper with the flame retardant solution by using a coating machine, and then drying at 60 ℃ for 4 hours to obtain the waterproof flame-retardant corrugated paper.
Comparative example 4
To the reaction vessel were added 25mL of water, 5g of aldehyde starch, an aqueous solution containing 10g of ammonium polyphosphate, and the mixture was stirred at 80℃for reaction for 6 hours, the solvent was filtered, washed with ethanol, and dried at 60℃for 12 hours to prepare a starch-ammonium polyphosphate composite.
100ML of water, 10g of oxidized starch adhesive, 20g of starch-ammonium polyphosphate compound and 12g of magnesium hydroxide are added into a reaction vessel, and after ultrasonic oscillation, a flame retardant solution is prepared.
And coating the surface of the corrugated paper with the flame retardant solution by using a coating machine, and then drying at 60 ℃ for 4 hours to obtain the waterproof flame-retardant corrugated paper.
Comparative example 5 is a conventional corrugated paper, and the surface was not coated with a flame retardant solution.
And testing the vertical combustion performance of the corrugated paper by adopting a vertical combustion tester according to the method of GB/T14656-2009. And testing the limiting oxygen index of the corrugated paper by adopting an oxygen index tester.
Table 1 test of flame retardant Properties of corrugated paper
Examples 1-3 utilize a plurality of amino groups of 4,4' -biphenyl di (diamino triazine) to carry out cross-linking polymerization reaction with aldehyde groups of aldehyde starch, and form a starch capsule wall on the surface of ammonium polyphosphate by an in-situ polymerization method to realize the coating of the ammonium polyphosphate, thereby obtaining the starch-ammonium polyphosphate microcapsule flame retardant, preventing the ammonium polyphosphate from absorbing moisture and affecting the flame retardant property. And then, compounding the modified starch with oxidized starch adhesive, magnesium hydroxide or aluminum hydroxide synergistic flame retardant to obtain flame retardant solution, and then, coating the surface of the corrugated paper. The starch-ammonium polyphosphate microcapsule flame retardant takes starch as a carbon source, ammonium polyphosphate as an acid source and a triazine group as a steam source to form an intumescent flame retardant system, and a continuous carbon layer is formed on the surface of corrugated paper during combustion, so that flame retardant effects of isolating oxygen, suppressing smoke, preventing combustion reaction and the like can be achieved. The average after-burning time and the average burning time are low, the minimum is only 2.2s and 1.5s, and the limiting oxygen index reaches 29.6 percent. Has excellent flame retardant property.
Comparative example 1 did not add starch-ammonium polyphosphate microcapsule flame retardant, did not form an intumescent flame retardant system, and had poor flame retardant properties for corrugated paper. Comparative example 2 when preparing starch microcapsules, ammonium polyphosphate was not added, and the flame retardant property of corrugated paper was poor.
Comparative example 4 does not add 4,4' -biphenylbis (diaminotriazine), does not contain flame retardant nitrogen element, does not expand a flame retardant system, does not generate cross-linking reaction to form capsule walls and microcapsules, does not coat ammonium polyphosphate, and is easy to absorb moisture and influence flame retardant performance in the long-term use process of corrugated paper.
Pouring the flame retardant solution on the surface of a clean glass plate, casting to form a film, drying at 60 ℃ for 4 hours, and measuring the contact angle by adopting a contact angle tester.
Table 2 test of water resistance and water resistance of corrugated paper
Examples 1-3 use a plurality of amino groups of 4,4' -biphenyl di (diamino triazine) as cross-linking agents to obtain the starch-ammonium polyphosphate microcapsule flame retardant, and the biphenyl hydrophobic groups contained in the flame retardant can enhance the hydrophobicity of the flame retardant solution film to a certain extent, improve the water contact angle and facilitate improving the water resistance and water resistance of corrugated paper.
Comparative examples 1, 3 and 4 all have no 4,4' -biphenylbis (diaminotriazine) added, no biphenyl hydrophobic groups, and low water contact angles.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (9)
1. A preparation method of waterproof flame-retardant corrugated paper is characterized by comprising the following steps:
Adding water and aldehyde starch into a reaction container, adding ethanol and 4,4' -biphenyl di (diaminotriazine) after ultrasonic oscillation, uniformly mixing, adding an aqueous solution containing ammonium polyphosphate, stirring for reaction, filtering, washing and drying to obtain the starch-ammonium polyphosphate microcapsule flame retardant;
Adding water, oxidized starch adhesive, starch-ammonium polyphosphate microcapsule flame retardant and hydroxide flame retardant into a reaction container, and preparing a flame retardant solution after ultrasonic oscillation;
and (3) coating the surface of the corrugated paper with the flame retardant solution by using a coating machine, and then drying at 50-60 ℃ for 4-8 hours to obtain the waterproof flame-retardant corrugated paper.
2. The method for preparing waterproof and flame-retardant corrugated paper according to claim 1, wherein the proportion of the aldehyde starch, the 4,4' -biphenyl di (diamino triazine) and the ammonium polyphosphate is 1g (0.3-0.8 g) (2-5 g).
3. The method for producing waterproof and flame-retardant corrugated paper according to claim 1, wherein the reaction in step (1) is carried out at 70 to 80 ℃ for 6 to 12 hours.
4. The method for preparing waterproof and flame-retardant corrugated paper according to claim 1, wherein the proportion of the oxidized starch adhesive, the starch-ammonium polyphosphate microcapsule flame retardant and the hydroxide flame retardant is 1g (2-8 g) (1.2-2.5 g).
5. The method for preparing waterproof and flame-retardant corrugated paper according to claim 4, wherein the hydroxide flame retardant comprises magnesium hydroxide and aluminum hydroxide.
6. The method for preparing waterproof and flame-retardant corrugated paper according to claim 1, wherein the method for preparing aldehyde starch comprises the following steps: adding water and sodium periodate into a reaction container, dripping sulfuric acid to regulate the pH value to 2-3, adding starch, carrying out light-proof reaction for 2-3h at 45-55 ℃, adding ethylene glycol to neutralize sodium periodate, filtering, washing with water, and drying to obtain aldehyde starch.
7. The method for preparing waterproof and flame-retardant corrugated paper according to claim 1, wherein the preparation method of the 4,4' -biphenyl di (diaminotriazine) comprises the following steps: adding ethylene glycol dimethyl ether solvent, 2-chloro-4, 6-diamino-1, 3, 5-triazine, 4 '-biphenyl diboronic acid, sodium carbonate and tetra (triphenylphosphine) palladium into a reaction vessel, filtering after coupling reaction, rotationally evaporating filtrate, and recrystallizing to obtain 4,4' -biphenyl di (diamino triazine).
8. The method for producing waterproof flame-retardant corrugated paper according to claim 7, wherein the ratio of 2-chloro-4, 6-diamino-1, 3, 5-triazine, 4' -biphenyldiboronic acid, sodium carbonate, tetrakis (triphenylphosphine) palladium is (2-2.2) mol to 1mol (2.4-3.5) mol (0.013-0.018) mol.
9. The method for preparing waterproof and flame-retardant corrugated paper according to claim 7, wherein the coupling reaction is carried out at 75-85 ℃ for 18-36 hours.
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