CN113150386A - Modified ammonium polyphosphate intumescent flame retardant and preparation method and application thereof - Google Patents
Modified ammonium polyphosphate intumescent flame retardant and preparation method and application thereof Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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- C08L2201/02—Flame or fire retardant/resistant
Abstract
The invention discloses a modified ammonium polyphosphate intumescent flame retardant, a preparation method and application thereof. The chemically modified ammonium polyphosphate is prepared from ammonium ions (NH) of ammonium polyphosphate4 +) Amino group (-NH) with amino group-containing silane coupling agent2) The silane coupling agent is prepared by the cation exchange reaction in the mixed solution of sodium hydroxide aqueous solution and polyhydric alcohol, and a new mode of modifying the silane coupling agent is created; the introduced silicon hydroxyl is modified, so that the condensed phase flame retardant effect is improved; in cooperation with the gas-phase flame retardance of the raw materials, the flame retardant can be independently used as an intumescent flame retardantThe flame retardant is applied to high polymer materials, and has the advantages of small dosage and good flame retardant effect. The invention has simple and easily controlled reaction, convenient synthesis and preparation and easy industrialization.
Description
Technical Field
The invention belongs to the technical field of modified ammonium polyphosphate flame retardants and application thereof, and particularly relates to a preparation method of an amino-containing silane coupling agent chemically modified ammonium polyphosphate intumescent flame retardant and flame retardant application thereof.
Background
Ammonium polyphosphate is one of the most widely used intumescent flame retardant materials, and is favored by wide practitioners because of its high phosphorus-nitrogen ratio and the functions of an intumescent flame retardant acid source and a gas source. However, in order to achieve a better flame retardant effect, ammonium polyphosphate is usually used in combination with a char-forming agent in a larger amount. In addition, the compatibility of ammonium polyphosphate and a substrate is poor, so that the mechanical property of the polymer is reduced, and the like. The current research on the improvement of ammonium polyphosphate is mainly focused on the aspects of water resistance, thermal stability and substrate compatibility. Chinese patent CN 101235221A discloses a preparation method of modified ammonium polyphosphate by using an aminosilane coupling agent, wherein the surface organic modification treatment is carried out on the ammonium polyphosphate dispersed in an inert solvent by using silicon hydroxyl groups in hydrolysate of the aminosilane coupling agent, so that the water solubility of the ammonium polyphosphate is obviously reduced; the amino at the other end of the hydrolysate and the hydroxyl in the ammonium polyphosphate molecule form a hydrogen bond to promote the condensation of the coupling agent on the surface of the ammonium polyphosphate, and simultaneously improve the compatibility of the ammonium polyphosphate with a polymer substrate. However, the modified ammonium polyphosphate of the patent still needs to be matched with a carbon forming agent and the addition amount is 20 wt%. Chinese patents CN 103382267A and CN 103756013A disclose organic amine modified ammonium polyphosphate and a preparation method and application thereof, and flame-retardant modified ammonium polyphosphate and a preparation method and application thereof, and continuously report the application of chemically modified ammonium polyphosphate which is independently used as a flame retardant of a high polymer material. Both of which utilize ammonium ion (NH) of ammonium polyphosphate4 +) With amino groups (-NH) in the modifier2) Or the amido (-NH-) has cation exchange reaction, thus obtaining the chemically modified ammonium polyphosphate. However, the addition amount of the organic amine modified ammonium polyphosphate is generally more than or equal to 30 wt%, so that the vertical combustion of the high polymer material can reach the UL-94 (3.2 mm) V-0 standard, and the flame retardant efficiency is not high. And piperazines are mainly usedOr the flame retardant effect of the aliphatic diamine modified ammonium polyphosphate is improved; furthermore, because piperazine and aliphatic diamine retain partial amino/amino groups in the modification, the modified ammonium polyphosphate can be used as a flame retardant and a curing agent when used for flame retardance of epoxy resin, so that the cost is reduced, the process is simplified, and the flame retardant effect is better. However, the chemical reaction of these chemically modified ammonium polyphosphates occurs in the aqueous phase, i.e., the ammonium polyphosphate is required to be well dissolved in water, which is contradictory to the property that the ammonium polyphosphate with high polymerization degree is difficult to dissolve in water. Thereby improving the difficulty of the preparation process and restricting the optional range of the polymerization degree of the ammonium polyphosphate in the chemical modification process. Meanwhile, the research of chemically modifying the ammonium polyphosphate by utilizing the amino group of the silane coupling agent containing the amino group is not reported.
Disclosure of Invention
The invention aims to provide a modified ammonium polyphosphate intumescent flame retardant and a preparation method thereof, which is ammonium polyphosphate chemically modified by amino of amino-containing silane coupling agent hydrolysate and is different from the traditional ammonium polyphosphate surface-modified by silicon hydroxyl of amino silane coupling agent hydrolysate. The chemically modified ammonium polyphosphate is prepared from ammonium ions (NH) of ammonium polyphosphate4 +) Amino group (-NH) with amino group-containing silane coupling agent2) The product is prepared by cation exchange reaction in the mixed solution of sodium hydroxide water solution and polyhydric alcohol, and silicon hydroxyl groups are still remained in the obtained product. The invention also provides application of the chemically modified ammonium polyphosphate in flame retardance of high polymer materials.
The invention provides a modified ammonium polyphosphate intumescent flame retardant, which has a structural general formula shown in any one of the following formulas:
wherein R and R' are NH3 +–(CH2)3–Si(OH)3、NH3 +–(CH2)3–SiCH3(OH)2、NH3 +–(CH2)2–NH–(CH2)3–Si(OH)3、NH3 +–(CH2)2–NH–(CH2)3–SiCH3(OH)2、NH3 +–(CH2)2–NH–(CH2)2–NH–(CH2)3–Si(OH)3、NH3 +–(CH2)2–NH–(CH2)2–NH–(CH2)3–SiCH3(OH)2、NH3 +–Q1–Si(OH)3、NH3 +–Q3–SiCH3(OH)2、NH3 +–Q5–NH–Q6–Si(OH)3、NH3 +–Q9–NH–Q10–SiCH3(OH)2、NH3 +–Q13–NH–Q14–NH–Q15–Si(OH)3、NH3 +–Q16–NH–Q17–NH–Q18–SiCH3(OH)2、NH3 +–CO–NH–(CH2)3–Si(OH)3、NH3 +–CO–NH–Q19–Si(OH)3Wherein R and R' are different in the same structural formula, wherein Q1~Q19Is C1–C4Linear or branched alkyl.
The invention provides a preparation method of the modified ammonium polyphosphate intumescent flame retardant, which comprises the following steps: firstly, at room temperature, mixing a solvent and a sodium hydroxide aqueous solution (0.1-1 mol/L) according to a volume ratio of 100: 10-40, and then mixing according to a molar ratio of 1: 0.1-1, adding ammonium polyphosphate and an amino-containing silane coupling agent, uniformly stirring, heating to 30-90 ℃, reacting for 3-10 h, washing with industrial alcohol, and drying in vacuum to obtain chemically modified ammonium polyphosphate with a structural general formula I or III; the silane coupling agent is a silane coupling agent NH containing amino2–Q1–Si(OCH3)3、NH2–Q2–Si(OCH2CH3)3、NH2–Q3–SiCH3(OCH3)2、NH2–Q4–SiCH3(OCH2CH3)2、NH2–Q5–NH–Q6–Si(OCH3)3、NH2–Q7–NH–Q8–Si(OCH2CH3)3、NH2–Q9–NH–Q10–SiCH3(OCH3)2、NH2–Q11–NH–Q14–SiCH3(OCH2CH3)2、NH2–Q13–NH–Q14–NH–Q15–Si(OCH3)3、NH2–Q16–NH–Q17–NH–Q18–SiCH3(OCH3)2，NH2–CO–NH–Q19–Si(OCH3)3、NH2–CO–NH–Q20–Si(OCH2CH3)3Any one of (1), wherein Q1~Q20Is a straight chain or branched chain alkyl of C1-C4; the solvent used is a water-miscible polyol.
The above method for preparing chemically modified ammonium polyphosphate having a structural formula of i or iii is further described as follows:
the ammonium polyphosphate is I-type ammonium polyphosphate or II-type ammonium polyphosphate, and the polymerization degree is more than 50; the volume ratio of the solvent to the aqueous sodium hydroxide solution used was 100: 2-35; the solvent is ethylene glycol or propylene glycol or glycerol; the concentration of the sodium hydroxide aqueous solution is 0.1-1 mol/L; the modification ratio of the ammonium polyphosphate can be changed by adjusting the reaction conditions, and when the modification ratio is higher than 40%, the adjacent silicon hydroxyl groups can be dehydrated and condensed to form Si-O-Si bonds.
The invention provides a preparation method of the modified ammonium polyphosphate intumescent flame retardant, which comprises the following steps: firstly, at room temperature, mixing a solvent and a sodium hydroxide aqueous solution (0.1-1 mol/L) according to a volume ratio of 100: 10-40, and then mixing according to a molar ratio of 1: 0.1-1, adding any one of ammonium polyphosphate and a first silane coupling agent, uniformly stirring, heating to 30-90 ℃, reacting for 3-5 h, dropwise adding a mixture of a second silane coupling agent and a solvent, reacting for 3-5 h after dropwise adding is completed within 10-30 min, washing with industrial alcohol, and drying in vacuum to obtain the chemically modified ammonium polyphosphate with the structural general formula II or IV;
the molar ratio of the second silane coupling agent to the ammonium polyphosphate in the mixture is 0.1-0.5: 1, the volume ratio of the solvent to the second silane coupling agent is 1-20: 1, the first silane coupling agent and the second silane coupling agent are respectively a silane coupling agent NH containing amino2–Q1–Si(OCH3)3、NH2–Q2–Si(OCH2CH3)3、NH2–Q3–SiCH3(OCH3)2、NH2–Q4–SiCH3(OCH2CH3)2、NH2–Q5–NH–Q6–Si(OCH3)3、NH2–Q7–NH–Q8–Si(OCH2CH3)3、NH2–Q9–NH–Q10–SiCH3(OCH3)2、NH2–Q11–NH–Q14–SiCH3(OCH2CH3)2、NH2–Q13–NH–Q14–NH–Q15–Si(OCH3)3、NH2–Q16–NH–Q17–NH–Q18–SiCH3(OCH3)2，NH2–CO–NH–Q19–Si(OCH3)3、NH2–CO–NH–Q20–Si(OCH2CH3)3Wherein Q is1~Q20Is a straight chain or branched chain alkyl of C1-C4; the solvent used is a water-miscible polyol.
The method for preparing the chemically modified ammonium polyphosphate with the structural general formula II or IV is further described as follows:
the volume ratio of the solvent to the second silane coupling agent is 1-18: 1; the molar ratio of the second silane coupling agent to the ammonium polyphosphate is 0.1-0.4: 1; the proportion range of the first silane coupling agent and the second silane coupling agent is 0.1-10; the ammonium polyphosphate is I-type ammonium polyphosphate or II-type ammonium polyphosphate, and the polymerization degree is more than 50; the volume ratio of the solvent to the aqueous sodium hydroxide solution used was 100: 2-35; the solvent is ethylene glycol or propylene glycol or glycerol; the modification proportion of the ammonium polyphosphate can be changed by adjusting the reaction conditions when the concentration of the sodium hydroxide aqueous solution is 0.1-1 mol/L, and when the modification proportion is higher and exceeds 40%, adjacent silicon hydroxyl groups can be dehydrated and condensed to form Si-O-Si bonds.
The silane coupling agent containing an amino group involved in the production method of the present invention is preferably as follows: 3-aminopropyltrimethoxysilane (NH)2–(CH2)3–Si(OCH3)3) 3-aminopropyltriethoxysilane (NH)2–(CH2)3–Si(OCH2CH3)3) 3-aminopropylmethyldimethoxysilane (NH)2–(CH2)3–SiCH3(OCH3)2) 3-aminopropylmethyldiethoxysilane (NH)2–(CH2)3–SiCH3(OCH2CH3)2) Aminoethylaminopropyltrimethoxysilane (NH)2–(CH2)2–NH–(CH2)3–Si(OCH3)3) Aminoethylaminopropyltriethoxysilane (NH)2–(CH2)2–NH–(CH2)3–Si(OCH2CH3)3) Aminoethylaminopropylmethyldimethoxysilane (NH)2–(CH2)2–NH–(CH2)3–SiCH3(OCH3)2) Aminoethylaminopropylmethyldiethoxysilane (NH)2–(CH2)2–NH–(CH2)3–SiCH3(OCH2CH3)2) Diethylenetriaminopropyltrimethoxysilane (NH)2–(CH2)2–NH–(CH2)2–NH–(CH2)3–Si(OCH3)3) Diethylenetriaminopropylmethyldimethoxysilane (NH)2–(CH2)2–NH–(CH2)2–NH–(CH2)3–SiCH3(OCH3)2) 3-Urea propyl trimethoxy silane (NH)2–CO–NH–(CH2)3–Si(OCH3)3) 3-Urea propyl triethoxysilane (NH)2–CO–NH–(CH2)3–Si(OCH2CH3)3) One or two of them. When preparing chemically modified ammonium polyphosphate with a structural general formula I or III, selecting any one of the coupling agents; when the chemically modified ammonium polyphosphate with the structural general formula II or IV is prepared, two different coupling agents (respectively corresponding to the first silane coupling agent and the second silane coupling agent in the method) are selected.
The invention also provides the application of the modified ammonium polyphosphate intumescent flame retardant in epoxy resin or polyolefin.
In the application, the addition amount of the modified ammonium polyphosphate is 8-25% by mass percent, the Limit Oxygen Index (LOI) of the obtained flame-retardant epoxy resin is 26.0-45.0%, and the grade of a vertical combustion test (UL-94) is V-0; the LOI of the obtained flame-retardant polyolefin is 15.8-35.0%, and UL-94 is V-2-V-0.
Further, when in application, the modified ammonium polyphosphate can also be mixed with ammonium polyphosphate according to the mass ratio of 1: 0.1-10 of the composition is applied to the flame retardance of epoxy resin and polyolefin.
The invention has the beneficial effects that:
(1) the modified ammonium polyphosphate is prepared by chemical modification of a silane coupling agent containing amino, modifies introduced silicon hydroxyl, endows a new condensed phase flame retardant effect, and can be independently used as an intumescent flame retardant to be applied to a high polymer material in cooperation with gas phase flame retardance of the ammonium polyphosphate, so that a new modification mode of the silane coupling agent is created, and new products are provided for the application field of the flame retardant ammonium polyphosphate.
(2) Due to the inventionThe modified ammonium polyphosphate can adjust the ammonium ion (NH) of the ammonium polyphosphate by controlling reaction conditions such as alcohol-water ratio and reaction temperature4 +) And amino group (-NH) of silane coupling agent2) The proportion of the reaction is different from the main gas-phase flame retardance of the ammonium polyphosphate, and the modified part of the silane coupling agent focuses on condensed-phase flame retardance, so that the modified ammonium polyphosphate with different flame-retardant effects can be prepared aiming at different high polymers.
(3) Because the modified ammonium polyphosphate provided by the invention is prepared by chemically modifying the silane coupling agent containing amino, the modified ammonium polyphosphate can be independently used as an intumescent flame retardant to be applied to a high polymer material, and has small addition amount and good flame retardant effect, namely the addition amount of the flame retardant is less than or equal to 25 wt%, so that UL-94 (1.6 mm) can achieve the effect of V-0, the negative influence on the mechanical property of a base material can be reduced, and the cost is reduced.
(4) The preparation method provided by the invention is simple and convenient to operate and easy to control, so that the industrialization is easy to realize.
Drawings
FIG. 1 is an FTIR spectrum of ammonium polyphosphate as a starting material for use in the present invention.
FIG. 2 is a TG curve of the ammonium polyphosphate as a raw material used in the present invention.
FIG. 3 shows the complete spectrum (a) of the ammonium polyphosphate used as a raw material in the present invention and its N1s（b），O1s(c) XPS spectra of (a).
FIG. 4 is an FTIR spectrum of modified ammonium polyphosphate obtained by the products of examples 5 and 14 in the invention.
FIG. 5 is a TG curve of modified ammonium polyphosphate obtained by the products of examples 5 and 14 in the present invention.
FIG. 6 shows the full spectra (a) and N of modified ammonium polyphosphate obtained in examples 5 and 14 of the present invention1s（b），O1s(c) XPS spectra of (a).
FIG. 7 is an FTIR spectrum of modified ammonium polyphosphate obtained by the products of examples 1 and 13 in the invention.
FIG. 8 is a TG curve of modified ammonium polyphosphate obtained in examples 1 and 13 of the present invention.
FIG. 9 is a schematic view ofFull spectrum (a) and N of modified ammonium polyphosphate of products obtained in examples 1 and 13 of the invention1s（b），O1s(c) XPS spectra of (a).
Detailed Description
The following examples are given to further illustrate the invention. It is necessary to note here that the following examples, application examples and comparative examples are only illustrative of the present invention and are not intended to limit the scope of the present invention. If various changes or modifications of the present invention are made by those skilled in the art after reading the contents of the present invention, these equivalents also fall within the scope of the present invention as defined by the appended claims.
It is worth to be noted that, 1) the parts of the solvent and the water in the following examples are all parts by volume, and the parts of other materials are all parts by mass; 2) the parts of materials used in the following application examples are all parts by mass; 3) the limiting oxygen indices given in the following application examples and comparative examples were obtained by testing according to ASTM D2863-19 using a digital display limiting oxygen index tester (ZR-01, Qingdao, China); the vertical burn rating was obtained by performing a test using a horizontal vertical burn tester (JR-SSC-A, Shenzhen, China) according to ASTM D3801-19.
Example 1
Mixing 300 parts of ethylene glycol and 100 parts of 0.1 mol/L sodium hydroxide aqueous solution at room temperature to serve as a solvent, adding 100 parts of ammonium polyphosphate I with a polymerization degree of 200, uniformly stirring, adding 166 parts of 3-aminopropyltrimethoxysilane, stirring, heating to 90 ℃, reacting for 3 hours, filtering, washing with industrial alcohol, and drying in vacuum to obtain a product, wherein the yield is 95%.
Example 2
At room temperature, 400 parts of propylene glycol and 100 parts of 0.4 mol/L sodium hydroxide aqueous solution are mixed to be used as a solvent, 100 parts of ammonium polyphosphate I with 500 polymerization degrees are added into the solvent, 84 parts of 3-aminopropyl methyl dimethoxy silane is added after the mixture is uniformly stirred, then the mixture is stirred and heated to 70 ℃, the reaction is carried out for 5 hours, the mixture is filtered, washed by industrial alcohol and dried in vacuum, and a product is obtained, wherein the yield is 89%.
Example 3
Mixing 600 parts of glycerol and 100 parts of 0.6 mol/L sodium hydroxide aqueous solution at room temperature to serve as a solvent, adding 100 parts of ammonium polyphosphate II with the polymerization degree of 800, stirring uniformly, adding 91.5 parts of aminoethyl aminopropyltrimethoxysilane, stirring, heating to 80 ℃, reacting for 4 hours, filtering, washing with industrial alcohol, and drying in vacuum to obtain a product, wherein the yield is 92%.
Example 4
At room temperature, 500 parts of glycerol and 100 parts of 0.7 mol/L sodium hydroxide aqueous solution are mixed to be used as a solvent, 100 parts of ammonium polyphosphate II with the polymerization degree of 1000 is added, after the mixture is uniformly stirred, 63.7 parts of aminoethyl aminopropyl methyl dimethoxy silane is added, then the mixture is stirred and heated to 80 ℃, the reaction is carried out for 5 hours, the mixture is filtered, washed by industrial alcohol and dried in vacuum, and a product is obtained, wherein the yield is 92%.
Example 5
Mixing 600 parts of ethylene glycol and 100 parts of 1mol/L sodium hydroxide aqueous solution at room temperature to serve as a solvent, adding 100 parts of ammonium polyphosphate II with the polymerization degree of 1500, uniformly stirring, adding 45.6 parts of 3-aminopropyltriethoxysilane, stirring, heating to 50 ℃, reacting for 4 hours, filtering, washing with industrial alcohol, and drying in vacuum to obtain a product, wherein the yield is 96%.
Example 6
At room temperature, 500 parts of propylene glycol and 100 parts of 0.5 mol/L sodium hydroxide aqueous solution are mixed to be used as a solvent, 100 parts of ammonium polyphosphate I with the polymerization degree of 200 is added, after uniform stirring, 218 parts of diethylenetriaminopropyltrimethoxysilane is added, then the mixture is stirred and heated to 80 ℃, the reaction is carried out for 5 hours, the filtration is carried out, the product is obtained by washing with industrial alcohol and vacuum drying, and the yield is 90%.
Example 7
Mixing 800 parts of propylene glycol and 100 parts of 0.8 mol/L sodium hydroxide aqueous solution at room temperature to serve as a solvent, adding 100 parts of ammonium polyphosphate II with the polymerization degree of 1000, stirring uniformly, adding 77 parts of diethylenetriaminopropylmethyldimethoxysilane, stirring, heating to 60 ℃, reacting for 3 hours, filtering, washing with industrial alcohol, and drying in vacuum to obtain a product, wherein the yield is 93%.
Example 8
At room temperature, 900 parts of glycerol and 100 parts of 1mol/L sodium hydroxide aqueous solution are mixed to be used as a solvent, 100 parts of ammonium polyphosphate II with 1500 polymerization degrees is added, after uniform stirring, 46 parts of 3-urea propyl trimethoxy silane is added, then the mixture is stirred and heated to 80 ℃, the reaction is carried out for 6 hours, the mixture is filtered, washed by industrial alcohol and dried in vacuum, and a product is obtained, wherein the yield is 88%.
Example 9
At room temperature, 700 parts of propylene glycol and 100 parts of 0.7 mol/L sodium hydroxide aqueous solution are mixed to be used as a solvent, 100 parts of ammonium polyphosphate II with 1500 polymerization degrees is added into the solvent, after the mixture is uniformly stirred, 40 parts of 3-aminopropylmethyldiethoxysilane is added, then the mixture is stirred and heated to 70 ℃, the reaction is carried out for 9 hours, the mixture is filtered, washed by industrial alcohol and dried in vacuum, and a product is obtained, wherein the yield is 96%.
Example 10
Mixing 400 parts of ethylene glycol and 100 parts of 0.2 mol/L sodium hydroxide aqueous solution at room temperature to serve as a solvent, adding 100 parts of ammonium polyphosphate II with 500 polymerization degrees, uniformly stirring, adding 136 parts of aminoethyl aminopropyl triethoxysilane, stirring, heating to 70 ℃, reacting for 3 hours, filtering, washing with industrial alcohol, and drying in vacuum to obtain a product, wherein the yield is 92%.
Example 11
Mixing 600 parts of glycerol and 100 parts of 1mol/L sodium hydroxide aqueous solution at room temperature to serve as a solvent, adding 100 parts of ammonium polyphosphate II with the polymerization degree of 1500, uniformly stirring, adding 48 parts of aminoethyl aminopropyl methyl diethoxysilane, stirring, heating to 50 ℃, reacting for 5 hours, filtering, washing with industrial alcohol, and drying in vacuum to obtain a product, wherein the yield is 91%.
Example 12
Mixing 300 parts of ethylene glycol and 100 parts of 0.1 mol/L sodium hydroxide aqueous solution at room temperature to serve as a solvent, adding 100 parts of ammonium polyphosphate II with a polymerization degree of 200, uniformly stirring, adding 218 parts of 3-urea propyl triethoxysilane, stirring, heating to 80 ℃, reacting for 4 hours, filtering, washing with industrial alcohol, and drying in vacuum to obtain a product, wherein the yield is 95%.
Example 13
Mixing 600 parts of ethylene glycol and 100 parts of 0.1 mol/L sodium hydroxide aqueous solution at room temperature to serve as a solvent, adding 100 parts of ammonium polyphosphate II with the polymerization degree of 200, uniformly stirring, adding 73.8 parts of 3-aminopropyltrimethoxysilane and 67.2 parts of 3-aminopropyltriethoxysilane, stirring, heating to 80 ℃, reacting for 4 hours, filtering, washing with industrial alcohol, and drying in vacuum to obtain a product, wherein the yield is 90%.
Example 14
At room temperature, 600 parts of glycerol and 100 parts of 1mol/L sodium hydroxide aqueous solution are mixed to be used as a solvent, 100 parts of ammonium polyphosphate II with 1500 polymerization degrees are added, after uniform stirring, 18.4 parts of 3-aminopropyltrimethoxysilane and 22.8 parts of 3-aminopropyltriethoxysilane are added, then stirring and heating are carried out to 50 ℃, reaction is carried out for 4 hours, filtering is carried out, washing is carried out by using industrial alcohol, and vacuum drying is carried out to obtain the product, wherein the yield is 93%.
Example 15
At room temperature, 400 parts of glycerol and 100 parts of 0.5 mol/L sodium hydroxide aqueous solution are mixed to be used as a solvent, 100 parts of ammonium polyphosphate I with 500 polymerization degrees are added, after the mixture is uniformly stirred, 19.7 parts of 3-aminopropylmethyldiethoxysilane and 91.5 parts of aminoethylaminopropyltrimethoxysilane are added, then the mixture is stirred and heated to 60 ℃, the reaction is carried out for 6 hours, the mixture is filtered, washed by industrial alcohol and dried in vacuum, and a product is obtained, wherein the yield is 96%.
Example 16
At room temperature, 700 parts of propylene glycol and 100 parts of 0.3 mol/L aqueous solution of sodium hydroxide are mixed to serve as a solvent, 100 parts of ammonium polyphosphate II with the polymerization degree of 1500 is added, after the mixture is uniformly stirred, 27.2 parts of aminoethyl aminopropyl triethoxysilane and 21.2 parts of aminoethyl aminopropyl methyl dimethoxysilane are added, then the mixture is stirred and heated to 80 ℃, the reaction is carried out for 7 hours, the mixture is filtered, washed by industrial alcohol and dried in vacuum, and a product is obtained, wherein the yield is 91%.
Example 17
At room temperature, 500 parts of propylene glycol and 100 parts of 0.7 mol/L aqueous solution of sodium hydroxide are mixed to be used as a solvent, 100 parts of ammonium polyphosphate I with the polymerization degree of 800 are added, after the mixture is uniformly stirred, 48.2 parts of aminoethyl aminopropyl methyl diethoxy silane and 54.6 parts of diethylenetriaminopropyl trimethoxy silane are added, then the mixture is stirred and heated to 50 ℃, the reaction is carried out for 4 hours, the mixture is filtered, washed by industrial alcohol and dried in vacuum, and a product is obtained, wherein the yield is 93 percent.
Example 18
Mixing 800 parts of ethylene glycol and 100 parts of 0.5 mol/L aqueous solution of sodium hydroxide at room temperature to serve as a solvent, adding 100 parts of ammonium polyphosphate II with the polymerization degree of 800, stirring uniformly, adding 77 parts of diethylenetriaminopropylmethyldimethoxysilane and 27.3 parts of diethylenetriaminopropyltrimethoxysilane, stirring and heating to 50 ℃, reacting for 7 hours, filtering, washing with industrial alcohol, and drying in vacuum to obtain a product, wherein the yield is 96%.
Example 19
Mixing 600 parts of ethylene glycol and 100 parts of 0.9 mol/L aqueous solution of sodium hydroxide at room temperature to serve as a solvent, adding 100 parts of ammonium polyphosphate II with the polymerization degree of 1000, uniformly stirring, adding 25.7 parts of diethylenetriaminopropylmethyldimethoxysilane and 45.8 parts of 3-ureidopropyltrimethoxysilane, stirring, heating to 70 ℃, reacting for 5 hours, filtering, washing with industrial alcohol, and drying in vacuum to obtain a product, wherein the yield is 88%.
Example 20
At room temperature, 500 parts of glycerol and 100 parts of 1mol/L sodium hydroxide aqueous solution are mixed to be used as a solvent, 100 parts of ammonium polyphosphate II with 1500 polymerization degrees are added, after uniform stirring, 54.4 parts of 3-urea propyl triethoxysilane and 45.6 parts of 3-amino propyl triethoxysilane are added, then stirring and heating are carried out to 80 ℃, reaction is carried out for 3 hours, filtering is carried out, washing is carried out by industrial alcohol, and vacuum drying is carried out to obtain a product, wherein the yield is 98%.
Example 21
At room temperature, 900 parts of propylene glycol and 100 parts of 1mol/L sodium hydroxide aqueous solution are mixed to be used as a solvent, 100 parts of ammonium polyphosphate II with 800 polymerization degrees are added, after uniform stirring, 50.4 parts of 3-aminopropylmethyldimethoxysilane and 72.4 parts of aminoethylaminopropylmethyldiethoxysilane are added, then stirring and heating are carried out to 50 ℃, reaction is carried out for 6 hours, filtering is carried out, washing is carried out by industrial alcohol, and vacuum drying is carried out to obtain the product, wherein the yield is 90%.
Example 22
At room temperature, 400 parts of ethylene glycol and 100 parts of 0.4 mol/L sodium hydroxide aqueous solution are mixed to be used as a solvent, 100 parts of ammonium polyphosphate II with the polymerization degree of 1000 is added, after the mixture is uniformly stirred, 45.8 parts of aminoethyl aminopropyl trimethoxysilane and 77 parts of diethylenetriaminopropyl methyl dimethoxysilane are added, then the mixture is stirred and heated to 70 ℃, the reaction is carried out for 8 hours, the mixture is filtered, washed by industrial alcohol and dried in vacuum, and a product is obtained, wherein the yield is 88%.
As can be seen from the infrared spectra of figures 1, 4 and 7, the chemically modified ammonium polyphosphate is 1600-1665 cm‒1NH appears at the left and right3 +The asymmetric variable angle absorption peak of (1); 3300-3645 cm‒1Characteristic absorption peaks of-OH appear on the left and right, and the characteristic absorption peaks are obviously attributed to silicon hydroxyl groups after the silane coupling agent is hydrolyzed; in the modified ammonium polyphosphates of examples 1 and 13, 1000 to 1100cm‒1The peak of antisymmetric stretching vibration of Si-O-Si newly appeared, and no corresponding peak was observed in the modified ammonium polyphosphates of examples 5 and 14, because the modified ammonium polyphosphates obtained in examples 1 and 13 had a modification ratio of more than 40%, and adjacent silicon hydroxyl groups were dehydrated and condensed to form Si-O-Si bonds. These all indicate that silane coupling agents have successfully chemically modified ammonium polyphosphate. The XPS spectra of FIGS. 3, 6 and 9 demonstrate that, in the modified ammonium polyphosphates of examples 5 and 14, N is present1sNH newly appears in the spectrum3 +And part of NH is retained4 +And peak of-P-NH-P-, O1sA peak of silicon hydroxyl is newly appeared in the spectrum; in the modified ammonium polyphosphates of examples 1 and 13, NH in N spectrum3 +Occupy a dominant position, O1sPeaks of-Si-O-Si-were observed in the spectra. As can be seen from the thermogravimetric curves of fig. 2, 5 and 8, the residual weight of the raw material ammonium polyphosphate at 800 ℃ is about 15%, the residual weight of the modified ammonium polyphosphates of examples 5 and 14 is about 25%, and the residual weight of the modified ammonium polyphosphates of examples 1 and 13 is increased to more than 67%, which shows that the improvement of the modification ratio of the silane coupling agent is beneficial to the enhancement of the flame retardance of the modified ammonium polyphosphate coacervate phase, and further proves that the ammonium polyphosphates with different modification ratios of the silane coupling agent are successfully prepared.
Application example 1
After 8 parts of modified ammonium polyphosphate, 61.4 parts of epoxy resin and 30.6 parts of polyamide curing agent in the embodiment 5 of the invention are uniformly mixed, the mixture is cured for 3 hours at 100 ℃. The LOI of the resulting sample was 26%, and UL-94 (1.6 mm) was V-0.
Application example 2
After 16 parts of modified ammonium polyphosphate, 56 parts of epoxy resin and 28 parts of polyamide curing agent in the embodiment 5 of the invention are uniformly mixed, the mixture is cured for 3 hours at 100 ℃. The LOI of the resulting sample was 37%, and UL-94 (1.6 mm) was V-0.
Application example 3
After 25 parts of modified ammonium polyphosphate, 50 parts of epoxy resin and 25 parts of polyamide curing agent in the embodiment 5 of the invention are uniformly mixed, curing is carried out for 3 hours at 100 ℃. The LOI of the resulting sample was 45% and UL-94 (1.6 mm) was V-0.
Application example 4
2 parts of modified ammonium polyphosphate, 8 parts of ammonium polyphosphate with the polymerization degree of more than or equal to 1000, 60 parts of epoxy resin and 30 parts of polyamide curing agent in the embodiment 1 are uniformly mixed and then cured for 3 hours at 100 ℃. The LOI of the resulting sample was 26%, and UL-94 (1.6 mm) was V-0.
Application example 5
4 parts of modified ammonium polyphosphate, 16 parts of ammonium polyphosphate with the polymerization degree of more than or equal to 1000, 53.4 parts of epoxy resin and 26.6 parts of polyamide curing agent in the embodiment 1 of the invention are uniformly mixed and then cured for 3 hours at 100 ℃. The LOI of the resulting sample was 38%, and UL-94 (1.6 mm) was V-0.
Application example 6
20 parts of modified ammonium polyphosphate and 80 parts of polypropylene in the embodiment 5 of the invention are premixed uniformly and then put into a double-screw extruder, and the heating temperature of each section from a feeding hole to a discharging hole is as follows in sequence: 170, 175, 180, 185, 180, 170 ℃ and melt blending and extruding. The LOI of the resulting sample was 28.0%, and UL-94 (1.6 mm) was V-0.
Application example 7
After uniformly premixing 25 parts of modified ammonium polyphosphate and 75 parts of polypropylene in the embodiment 5 of the invention, putting the mixture into a double-screw extruder (the temperature of each section is the same as that in the application example 6, but not shown). The LOI of the resulting sample was 35.0%, and UL-94 (1.6 mm) was V-0.
Application example 8
5 parts of modified ammonium polyphosphate, 20 parts of ammonium polyphosphate with the polymerization degree of more than or equal to 1000 and 75 parts of polypropylene in the embodiment 1 are premixed uniformly and then put into a double-screw extruder (the temperature of each section is the same as that of the application example 6, but is not shown). The LOI of the resulting sample was 31.0%, and UL-94 (1.6 mm) was V-0.
Application example 9
After 22 parts of modified ammonium polyphosphate and 78 parts of polyethylene in the embodiment 5 of the invention are premixed uniformly, the mixture is put into a double-screw extruder, and the heating temperatures of all sections from a feeding hole to a discharging hole are as follows in sequence: 145, 150, 160, 155, 150, 145 ℃ and extruding. The LOI of the resulting sample was 27.5%, and UL-94 (1.6 mm) was V-0.
Application example 10
After 25 parts of modified ammonium polyphosphate and 75 parts of polyethylene in the embodiment 5 of the invention are uniformly premixed, the mixture is put into a double-screw extruder (the temperature of each section is the same as that of the application example 9, but is not shown). The LOI of the resulting sample was 31.0%, and UL-94 (1.6 mm) was V-0.
Application example 11
5 parts of modified ammonium polyphosphate, 20 parts of ammonium polyphosphate with the polymerization degree of more than or equal to 1000 and 75 parts of polyethylene in the embodiment 1 are premixed uniformly and then put into a double-screw extruder (the temperature of each section is the same as that of the application example 9, but is not shown). The LOI of the resulting sample was 28.5%, and UL-94 (1.6 mm) was V-0.
Comparative example 1
60 parts of epoxy resin and 30 parts of polyamide curing agent are uniformly premixed and then cured for 3 hours at 100 ℃. The LOI of the resulting sample was 18.2% and UL-94 was no grade.
Comparative example 2
100 parts of pure polypropylene were directly put into a twin-screw extruder and melt-coextruded (the temperature in each stage was the same as that in application example 6, but omitted). The LOI of the resulting sample was 17.2% and UL-94 was no grade.
Comparative example 3
100 parts of pure polyethylene were directly put into a twin-screw extruder and melt-coextruded (the temperature in each stage was the same as in application example 9, not shown). The LOI of the resulting sample was 16.5% and UL-94 was no grade.
It can be seen that the flame retardant properties of the pure samples of the epoxy resin, polypropylene and polyethylene of the comparative examples were poor, the LOI values were all below 20%, and the vertical burning test could not be passed. After the modified ammonium polyphosphate or the mixture of the modified ammonium polyphosphate and the ammonium polyphosphate is added into the polymer, the composite material in the application example can pass the V-0 level of UL-94, and the LOI value is obviously improved.
Claims (10)
1. A modified ammonium polyphosphate intumescent flame retardant is characterized in that: the structural general formula of the modified ammonium polyphosphate is any one of the following formulas:
wherein R and R' are NH3 +–(CH2)3–Si(OH)3、NH3 +–(CH2)3–SiCH3(OH)2、NH3 +–(CH2)2–NH–(CH2)3–Si(OH)3、NH3 +–(CH2)2–NH–(CH2)3–SiCH3(OH)2、NH3 +–(CH2)2–NH–(CH2)2–NH–(CH2)3–Si(OH)3、NH3 +–(CH2)2–NH–(CH2)2–NH–(CH2)3–SiCH3(OH)2、NH3 +–Q1–Si(OH)3、NH3 +–Q3–SiCH3(OH)2、NH3 +–Q5–NH–Q6–Si(OH)3、NH3 +–Q9–NH–Q10–SiCH3(OH)2、NH3 +–Q13–NH–Q14–NH–Q15–Si(OH)3、NH3 +–Q16–NH–Q17–NH–Q18–SiCH3(OH)2、NH3 +–CO–NH–(CH2)3–Si(OH)3、NH3 +–CO–NH–Q19–Si(OH)3Wherein R and R' are different in the same structural formula, wherein Q1~Q19Is C1–C4Linear or branched alkyl.
2. A method for preparing the modified ammonium polyphosphate intumescent flame retardant of claim 1, which is characterized in that: firstly, at room temperature, mixing a solvent and an aqueous solution of sodium hydroxide according to a volume ratio of 100: 10-40, and then mixing according to a molar ratio of 1: 0.1-1, adding ammonium polyphosphate and an amino-containing silane coupling agent, uniformly stirring, heating to 30-90 ℃, reacting for 3-10 h, washing with industrial alcohol, and drying in vacuum to obtain chemically modified ammonium polyphosphate with a structural general formula I or III;
the silane coupling agent is a silane coupling agent NH containing amino2–Q1–Si(OCH3)3、NH2–Q2–Si(OCH2CH3)3、NH2–Q3–SiCH3(OCH3)2、NH2–Q4–SiCH3(OCH2CH3)2、NH2–Q5–NH–Q6–Si(OCH3)3、NH2–Q7–NH–Q8–Si(OCH2CH3)3、NH2–Q9–NH–Q10–SiCH3(OCH3)2、NH2–Q11–NH–Q14–SiCH3(OCH2CH3)2、NH2–Q13–NH–Q14–NH–Q15–Si(OCH3)3、NH2–Q16–NH–Q17–NH–Q18–SiCH3(OCH3)2，NH2–CO–NH–Q19–Si(OCH3)3、NH2–CO–NH–Q20–Si(OCH2CH3)3Any one of (1), wherein Q1~Q20Is C1-C4Linear or branched alkyl of (a); the solvent used is a water-miscible polyol.
3. A method for preparing the modified ammonium polyphosphate intumescent flame retardant of claim 1, which is characterized in that: firstly, at room temperature, mixing a solvent and an aqueous solution of sodium hydroxide according to a volume ratio of 100: 10-40, and then mixing according to a molar ratio of 1: 0.1-1 adding ammonium polyphosphate and a first silane coupling agent, uniformly stirring, heating to 30-90 ℃, reacting for 3-5 h, dropwise adding a mixture of a second silane coupling agent and a solvent, finishing dropwise adding within 10-30 min, reacting for 3-5 h, washing with industrial alcohol, and drying in vacuum to obtain chemically modified ammonium polyphosphate with a structural general formula II or IV;
the molar ratio of the second silane coupling agent to the ammonium polyphosphate in the mixture is 0.1-0.5: 1, the volume ratio of the solvent to the second silane coupling agent is 1-20: 1, the first silane coupling agent and the second silane coupling agent are respectively a silane coupling agent NH containing amino2–Q1–Si(OCH3)3、NH2–Q2–Si(OCH2CH3)3、NH2–Q3–SiCH3(OCH3)2、NH2–Q4–SiCH3(OCH2CH3)2、NH2–Q5–NH–Q6–Si(OCH3)3、NH2–Q7–NH–Q8–Si(OCH2CH3)3、NH2–Q9–NH–Q10–SiCH3(OCH3)2、NH2–Q11–NH–Q14–SiCH3(OCH2CH3)2、NH2–Q13–NH–Q14–NH–Q15–Si(OCH3)3、NH2–Q16–NH–Q17–NH–Q18–SiCH3(OCH3)2，NH2–CO–NH–Q19–Si(OCH3)3、NH2–CO–NH–Q20–Si(OCH2CH3)3Wherein Q is1~Q20Is a straight chain or branched chain alkyl of C1-C4; the solvent used is a water-miscible polyol.
4. The preparation method of the modified ammonium polyphosphate intumescent flame retardant of claim 3, characterized in that: the volume ratio of the solvent to the second silane coupling agent is 1-18: 1; the molar ratio of the second silane coupling agent to the ammonium polyphosphate is 0.1-0.4: 1; the proportion range of the first silane coupling agent and the second silane coupling agent is 0.1-10.
5. The preparation method of the modified ammonium polyphosphate intumescent flame retardant of claim 2 or 3, characterized in that: the ammonium polyphosphate used is I-type ammonium polyphosphate or II-type ammonium polyphosphate, and the polymerization degree is more than 50.
6. The preparation method of the modified ammonium polyphosphate intumescent flame retardant of claim 2 or 3, characterized in that: the volume ratio of the solvent to the aqueous sodium hydroxide solution used was 100: 2-35; the solvent is ethylene glycol or propylene glycol or glycerol; the concentration of the sodium hydroxide aqueous solution is 0.1-1 mol/L.
7. The preparation method of the modified ammonium polyphosphate intumescent flame retardant of claim 2 or 3, characterized in that: the modification proportion of the ammonium polyphosphate is changed by adjusting the reaction conditions, and when the modification proportion is higher than 40 percent, adjacent silicon hydroxyl groups can be dehydrated and condensed to form Si-O-Si bonds.
8. Use of the modified ammonium polyphosphate intumescent flame retardant of claim 1 in epoxy resins or polyolefins.
9. Use according to claim 8, characterized in that: according to the mass percentage, the addition amount of the modified ammonium polyphosphate is 8-25%, the LOI of the obtained flame-retardant epoxy resin is 26.0-45.0%, and the UL-94 is V-0; the LOI of the obtained flame-retardant polyolefin is 15.8-35.0%, and UL-94 is V-2-V-0.
10. Use according to claim 8, characterized in that: the modified ammonium polyphosphate and the ammonium polyphosphate are mixed according to the mass ratio of 1: 0.1-10 of the composition is applied to the flame retardance of epoxy resin and polyolefin.
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