CN113845699B - A kind of organometallic complex modified ammonium polyphosphate intumescent flame retardant and preparation method thereof - Google Patents
A kind of organometallic complex modified ammonium polyphosphate intumescent flame retardant and preparation method thereof Download PDFInfo
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- CN113845699B CN113845699B CN202111143397.6A CN202111143397A CN113845699B CN 113845699 B CN113845699 B CN 113845699B CN 202111143397 A CN202111143397 A CN 202111143397A CN 113845699 B CN113845699 B CN 113845699B
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- ammonium polyphosphate
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- 239000004114 Ammonium polyphosphate Substances 0.000 title claims abstract description 169
- 229920001276 ammonium polyphosphate Polymers 0.000 title claims abstract description 169
- 235000019826 ammonium polyphosphate Nutrition 0.000 title claims abstract description 169
- 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 95
- 239000003063 flame retardant Substances 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 150000003863 ammonium salts Chemical class 0.000 title claims description 68
- 125000002524 organometallic group Chemical group 0.000 title claims description 18
- 239000002262 Schiff base Substances 0.000 claims abstract description 23
- 150000004753 Schiff bases Chemical class 0.000 claims abstract description 15
- -1 metal complex modified ammonium Chemical class 0.000 claims abstract description 12
- 239000013110 organic ligand Substances 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
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- 238000006243 chemical reaction Methods 0.000 claims description 121
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- 239000002904 solvent Substances 0.000 claims description 6
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- IYROWZYPEIMDDN-UHFFFAOYSA-N 3-n-pentadec-8,11,13-trienyl catechol Natural products CC=CC=CCC=CCCCCCCCC1=CC=CC(O)=C1O IYROWZYPEIMDDN-UHFFFAOYSA-N 0.000 description 34
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- 238000001816 cooling Methods 0.000 description 14
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 8
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- 238000004458 analytical method Methods 0.000 description 3
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- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 description 2
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- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 description 2
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 description 2
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 235000001014 amino acid Nutrition 0.000 description 2
- OQRLVNFTCUZFSJ-UHFFFAOYSA-N benzene-1,2-diol;iron Chemical compound [Fe].OC1=CC=CC=C1O OQRLVNFTCUZFSJ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 description 2
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- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- LQZFQLVBZRVDLJ-DKWTVANSSA-N (2s)-2-aminobutanedioic acid;zinc Chemical compound [Zn].OC(=O)[C@@H](N)CC(O)=O LQZFQLVBZRVDLJ-DKWTVANSSA-N 0.000 description 1
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- XJGAELZYLAVUKK-UHFFFAOYSA-N 1h-1,2,4-triazol-5-amine;zinc Chemical compound [Zn].NC1=NC=NN1 XJGAELZYLAVUKK-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- HGSXDBRNFBJIMX-UHFFFAOYSA-N 2-aminoacetic acid;zinc Chemical compound [Zn].NCC(O)=O HGSXDBRNFBJIMX-UHFFFAOYSA-N 0.000 description 1
- UHGULLIUJBCTEF-UHFFFAOYSA-N 2-aminobenzothiazole Chemical compound C1=CC=C2SC(N)=NC2=C1 UHGULLIUJBCTEF-UHFFFAOYSA-N 0.000 description 1
- UEJVSOJRGUIWCY-UHFFFAOYSA-N 2-hydroxybenzoic acid;zinc Chemical compound [Zn].OC(=O)C1=CC=CC=C1O UEJVSOJRGUIWCY-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- JVTMLBYYQYMFLV-UHFFFAOYSA-N 2-methyl-1h-imidazole;zinc Chemical compound [Zn].CC1=NC=CN1 JVTMLBYYQYMFLV-UHFFFAOYSA-N 0.000 description 1
- 229930024421 Adenine Natural products 0.000 description 1
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 description 1
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 description 1
- 229910020647 Co-O Inorganic materials 0.000 description 1
- 229910020676 Co—N Inorganic materials 0.000 description 1
- 229910020704 Co—O Inorganic materials 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
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- 229910017135 Fe—O Inorganic materials 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
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- 239000004472 Lysine Substances 0.000 description 1
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- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
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- 229960000643 adenine Drugs 0.000 description 1
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- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
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- COZKIZRZDYVVHC-UHFFFAOYSA-N benzene-1,2-diol;zinc Chemical compound [Zn].OC1=CC=CC=C1O COZKIZRZDYVVHC-UHFFFAOYSA-N 0.000 description 1
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
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- 229910021641 deionized water Inorganic materials 0.000 description 1
- MGHPNCMVUAKAIE-UHFFFAOYSA-N diphenylmethanamine Chemical compound C=1C=CC=CC=1C(N)C1=CC=CC=C1 MGHPNCMVUAKAIE-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 229960002217 eugenol Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- PDDIPIDVUPWUML-UHFFFAOYSA-N oxalic acid;zinc Chemical compound [Zn].OC(=O)C(O)=O PDDIPIDVUPWUML-UHFFFAOYSA-N 0.000 description 1
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- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
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- 238000000967 suction filtration Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
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Classifications
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- 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
-
- 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
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
技术领域technical field
本发明属于高分子阻燃材料领域，具体涉及一种有机金属络合物修饰聚磷酸铵膨胀型阻燃剂及其制备方法。The invention belongs to the field of polymer flame retardant materials, and in particular relates to an organic metal complex modified ammonium polyphosphate intumescent flame retardant and a preparation method thereof.
技术背景technical background
高分子材料具有优异的耐化学性、机械性能、电绝缘性能和良好的加工性能，因此被应用于绝缘材料、房屋装修、航天航空、电子器件等各行各业中。普通的高分子材料都存在易燃性的缺点，这极大的限制了它们的应用，引起了广大学者对高分子阻燃材料的研究。Polymer materials have excellent chemical resistance, mechanical properties, electrical insulation properties and good processing properties, so they are used in various industries such as insulating materials, house decoration, aerospace, and electronic devices. Ordinary polymer materials have the disadvantage of flammability, which greatly limits their application, which has caused many scholars to study polymer flame retardant materials.
聚磷酸铵是商业中无毒无烟，热稳定性好的常见阻燃添加剂，含有大量的磷元素和氮元素，在燃烧过程中可以充当膨胀型阻燃剂。但是，由于聚磷酸铵是一种无机高分子化合物，存放于空气中容易吸收空气的水分，容易发生吸潮水解；单独使用聚磷酸铵充当阻燃剂对于高分子材料的阻燃效果不是非常的理想并且会引起高分子材料力学性能的下降。此外，由于聚磷酸铵不含碳源，为了增强聚磷酸铵的阻燃性效率，需要协同其它成炭剂来提高聚磷酸铵的阻燃效率。Ammonium polyphosphate is a common flame retardant additive that is non-toxic, smokeless and has good thermal stability. It contains a large amount of phosphorus and nitrogen, and can act as an intumescent flame retardant during combustion. However, since ammonium polyphosphate is an inorganic polymer compound, it is easy to absorb moisture in the air when stored in the air, and it is prone to moisture absorption and hydrolysis; using ammonium polyphosphate alone as a flame retardant is not very effective for the flame retardant of polymer materials. Ideal and will cause a decline in the mechanical properties of polymer materials. In addition, since ammonium polyphosphate does not contain a carbon source, in order to enhance the flame retardancy efficiency of ammonium polyphosphate, it is necessary to cooperate with other char-forming agents to improve the flame retardancy efficiency of ammonium polyphosphate.
发明内容Contents of the invention
本发明的目的是提供一种有机金属络合物修饰聚磷酸铵膨胀型阻燃剂及其制备方法，致力于解决高分子材料的易燃和烟释放量大问题。The purpose of the present invention is to provide an organometallic complex modified ammonium polyphosphate intumescent flame retardant and a preparation method thereof, which is dedicated to solving the problems of flammability and large smoke emission of polymer materials.
本发明有机金属络合物修饰聚磷酸铵膨胀型阻燃剂的化学结构通式为：The general chemical structure formula of the organometallic complex modified ammonium polyphosphate intumescent flame retardant of the present invention is:
其中，M2+为Zn2+、Cu2+、Mg2+、Mn2+、Ni2+、Co2+中的任一种金属离子，M3+为Al3+和Fe3+中的任一种金属离子；R为酚类、席夫碱、氮杂环、氨基酸、羧酸化合物中的任一种。Among them, M 2+ is any metal ion in Zn 2+ , Cu 2+ , Mg 2+ , Mn 2+ , Ni 2+ , Co 2+ , and M 3+ is any metal ion in Al 3+ and Fe 3+ Any metal ion; R is any one of phenols, Schiff bases, nitrogen heterocycles, amino acids, and carboxylic acid compounds.
进一步地，所述有机金属络合物修饰聚磷酸铵膨胀型阻燃剂的制备方法如下：Further, the preparation method of the organometallic complex modified ammonium polyphosphate intumescent flame retardant is as follows:
将聚磷酸铵和溶剂先后加入到装有机械搅拌器和温度计的三口烧瓶中；待原料混合均匀后，在常温下向三口烧瓶内滴加含金属离子溶液，边滴加边搅拌；滴加完毕后，常温反应一段时间，之后再向三口烧瓶内滴加有机配体溶液，然后在一定温度下反应一段时间；反应完毕后冷却至室温，抽滤，取滤饼，经溶剂洗数次，烘干，得到有机金属络合物修饰聚磷酸铵膨胀型阻燃剂。Add ammonium polyphosphate and solvent successively into a three-necked flask equipped with a mechanical stirrer and a thermometer; after the raw materials are mixed evenly, add the solution containing metal ions dropwise into the three-necked flask at room temperature, and stir while adding; Finally, react at room temperature for a period of time, then add the organic ligand solution dropwise into the three-necked flask, and then react at a certain temperature for a period of time; after the reaction is completed, cool to room temperature, filter with suction, take the filter cake, wash it several times with solvent, and dry dry to obtain an organometallic complex modified ammonium polyphosphate intumescent flame retardant.
其中，所述的溶剂为甲苯、二甲苯、四氢呋喃、水、二氧六环、甲醇、乙醇、丙酮、乙腈中的一种或几种。Wherein, the solvent is one or more of toluene, xylene, tetrahydrofuran, water, dioxane, methanol, ethanol, acetone, and acetonitrile.
所述的金属离子为Zn2+，Cu2+，Mg2+，Mn2+，Ni2+，Co2+，Al3+或Fe3+中的任一种。The metal ion is any one of Zn 2+ , Cu 2+ , Mg 2+ , Mn 2+ , Ni 2+ , Co 2+ , Al 3+ or Fe 3+ .
所述的配体为酚类、席夫碱、氮杂环、氨基酸、羧酸化合物的任一种。The ligand is any one of phenols, Schiff bases, nitrogen heterocycles, amino acids and carboxylic acid compounds.
所述的聚磷酸铵，金属离子和配体的质量比为1∶0.2～1∶0.2～2。In the ammonium polyphosphate, the mass ratio of metal ions and ligands is 1:0.2-1:0.2-2.
所述的常温反应时间为1～3小时。The normal temperature reaction time is 1 to 3 hours.
滴加有机配体后的反应温度为20℃～80℃，反应时间为18～36小时。The reaction temperature after the organic ligand is added dropwise is 20° C. to 80° C., and the reaction time is 18 to 36 hours.
本发明采用聚磷酸铵、金属离子和各类有机配体为原料合成一种有机金属络合物修饰聚磷酸铵膨胀型阻燃剂，从而将酸源、气源和碳源集于一体，且由于金属离子的存在，有望进一步提高聚磷酸铵的阻燃效率，适用于各类高分子材料的阻燃抑烟改性，且与高分子材料相容。The present invention uses ammonium polyphosphate, metal ions and various organic ligands as raw materials to synthesize an organometallic complex modified ammonium polyphosphate intumescent flame retardant, thereby integrating acid source, gas source and carbon source, and Due to the existence of metal ions, it is expected to further improve the flame retardant efficiency of ammonium polyphosphate, which is suitable for the modification of flame retardant and smoke suppression of various polymer materials, and is compatible with polymer materials.
本发明与现有技术相比，具有以下优点：Compared with the prior art, the present invention has the following advantages:
(1)本发明提供的有机金属络合物修饰聚磷酸铵膨胀型阻燃剂合成工艺简单，周期短，所得到的阻燃剂后处理过程简单，产率高，易于控制和工业化生产。(1) The organometallic complex modified ammonium polyphosphate intumescent flame retardant provided by the present invention has a simple synthesis process and a short cycle, and the obtained flame retardant has a simple post-treatment process, high yield, and is easy to control and industrialized production.
(2)本发明提供的有机金属络合物修饰聚磷酸铵膨胀型阻燃剂，集酸源、气源、碳源于一体，且含金属离子，是一种新型的膨胀型阻燃剂。(2) The organometallic complex modified ammonium polyphosphate intumescent flame retardant provided by the present invention integrates acid source, gas source and carbon source, and contains metal ions. It is a new type of intumescent flame retardant.
(3)本发明提供的有机金属络合物修饰聚磷酸铵膨胀型阻燃剂具有可调整性，可选用不同的金属离子和有机配体进行组合，解决各类高分子材料的易燃和烟毒性大问题。(3) The organometallic complex modified ammonium polyphosphate intumescent flame retardant provided by the present invention has adjustability, and can be combined with different metal ions and organic ligands to solve the problem of flammability and smoke of various polymer materials. Toxicity is a big problem.
附图说明Description of drawings
图1为漆酚-铁络合物修饰聚磷酸铵红外谱图。Fig. 1 is the infrared spectrogram of urushiol-iron complex modified ammonium polyphosphate.
图2为漆酚-铜络合物修饰聚磷酸铵红外谱图。Fig. 2 is the infrared spectrogram of ammonium polyphosphate modified by urushiol-copper complex.
图3为漆酚-钴络合物修饰聚磷酸铵红外谱图。Fig. 3 is the infrared spectrogram of ammonium polyphosphate modified by urushiol-cobalt complex.
图4为漆酚-镍络合物修饰聚磷酸铵红外谱图。Fig. 4 is the infrared spectrogram of ammonium polyphosphate modified by urushiol-nickel complex.
图5为漆酚-锌络合物修饰聚磷酸铵红外谱图。Fig. 5 is the infrared spectrum of ammonium polyphosphate modified by urushiol-zinc complex.
图6为儿茶酚-铁络合物修饰聚磷酸铵红外谱图。Fig. 6 is the infrared spectrogram of catechol-iron complex modified ammonium polyphosphate.
图7为腰果酚-铁络合物修饰聚磷酸铵红外谱图。Figure 7 is the infrared spectrum of cardanol-iron complex modified ammonium polyphosphate.
图8为水杨醛-二乙烯三胺席夫碱-钴络合物修饰聚磷酸铵红外谱图。Fig. 8 is the infrared spectrum of ammonium polyphosphate modified by salicylaldehyde-diethylenetriamine Schiff base-cobalt complex.
图9为水杨醛-氨基苯并噻唑席夫碱-铁络合物修饰聚磷酸铵红外谱图。Fig. 9 is the infrared spectrum of ammonium polyphosphate modified by salicylaldehyde-aminobenzothiazole Schiff base-iron complex.
图10为三唑衍生物-锌络合物修饰聚磷酸铵红外谱图。Fig. 10 is the infrared spectrum of triazole derivative-zinc complex modified ammonium polyphosphate.
具体实施方式Detailed ways
以下实施例对本发明设计的一种有机金属络合物修饰聚磷酸铵膨胀型阻燃剂及其制备方法进行具体描述，但本发明实施方式不限于此(可与金属配位的化合物均可采用本发明提供的技术进行实施)，实施例不应视作对本发明的限定。The following examples specifically describe an organometallic complex modified ammonium polyphosphate intumescent flame retardant designed by the present invention and its preparation method, but the embodiments of the present invention are not limited thereto (compounds that can coordinate with metals can be used The techniques provided by the present invention are implemented), and the examples should not be regarded as limiting the present invention.
实施例1Example 1
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴1.50gZn(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应1小时，之后再向三口烧瓶内滴加0.30g漆酚的50ml乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到漆酚-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, drop 1.50g of Zn(NO 3 ) 2 60ml of ethanol into the three-necked flask at room temperature solution, while stirring while adding dropwise, after the dropwise addition, react at room temperature for 1 hour, then add dropwise 50ml ethanol solution of 0.30g urushiol in the three-necked flask, then heat up to 60°C for reflux reaction for 18 hours, and cool to Suction filtration at room temperature, take the filter cake, wash with ethanol for several times, and dry to obtain urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
实施例2Example 2
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加1.50g Zn(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应2小时，之后再向三口烧瓶内滴加0.30g漆酚的50ml乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到漆酚-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 1.50g of Zn(NO 3 ) 2 ·6H 2 O dropwise into the three-necked flask at room temperature. 60ml ethanol solution, stirring while adding dropwise, after the dropwise addition, react at room temperature for 2 hours, then add dropwise 0.30g urushiol in 50ml ethanol solution into the three-necked flask, and then heat up to 60°C for reflux reaction for 18 hours, after the reaction is completed Cool to room temperature, filter with suction, take the filter cake, wash with ethanol for several times, and dry to obtain urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
实施例3Example 3
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加1.50g Zn(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加0.30g漆酚的50ml乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到漆酚-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 1.50g of Zn(NO 3 ) 2 ·6H 2 O dropwise into the three-necked flask at room temperature. 60ml ethanol solution, stirring while adding dropwise, after the dropwise addition, react at room temperature for 3 hours, then add dropwise 0.30g urushiol in 50ml ethanol solution into the three-necked flask, then raise the temperature to 60°C for reflux reaction for 18 hours, after the reaction is completed Cool to room temperature, filter with suction, take the filter cake, wash with ethanol for several times, and dry to obtain urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
实施例4Example 4
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加0.30g Zn(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加0.75g漆酚的50ml乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到漆酚-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 0.30g of Zn(NO 3 ) 2 ·6H 2 O dropwise into the three-necked flask at room temperature. 60ml ethanol solution, stirring while dropping, after the dropwise addition, react at room temperature for 3 hours, then add 0.75g urushiol in 50ml ethanol solution dropwise into the three-necked flask, then raise the temperature to 60°C for reflux reaction for 18 hours, after the reaction is completed Cool to room temperature, filter with suction, take the filter cake, wash with ethanol for several times, and dry to obtain urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
实施例5Example 5
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加0.30g Zn(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加1.50g漆酚的50ml乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到漆酚-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 0.30g of Zn(NO 3 ) 2 ·6H 2 O dropwise into the three-necked flask at room temperature. 60ml ethanol solution, stirring while adding dropwise, after the dropwise addition, react at room temperature for 3 hours, then add 1.50g urushiol in 50ml ethanol solution dropwise into the three-necked flask, then raise the temperature to 60°C for reflux reaction for 18 hours, after the reaction is completed Cool to room temperature, filter with suction, take the filter cake, wash with ethanol for several times, and dry to obtain urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
实施例6Example 6
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加0.30g Zn(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加3.00g漆酚的50ml乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到漆酚-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 0.30g of Zn(NO 3 ) 2 ·6H 2 O dropwise into the three-necked flask at room temperature. 60ml ethanol solution, stirring while adding dropwise, after the dropwise addition, react at room temperature for 3 hours, then add 3.00g urushiol in 50ml ethanol solution dropwise into the three-necked flask, and then heat up to 60°C for reflux reaction for 18 hours, after the reaction is completed Cool to room temperature, filter with suction, take the filter cake, wash with ethanol for several times, and dry to obtain urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
实施例7Example 7
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加0.75g Zn(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加0.30g漆酚的50ml乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到漆酚-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 0.75g of Zn(NO 3 ) 2 ·6H 2 O to the three-necked flask dropwise at room temperature. 60ml ethanol solution, stirring while adding dropwise, after the dropwise addition, react at room temperature for 3 hours, then add dropwise 0.30g urushiol in 50ml ethanol solution into the three-necked flask, then raise the temperature to 60°C for reflux reaction for 18 hours, after the reaction is completed Cool to room temperature, filter with suction, take the filter cake, wash with ethanol for several times, and dry to obtain urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
实施例8Example 8
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加0.75g Zn(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加0.75g漆酚的50ml乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到漆酚-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 0.75g of Zn(NO 3 ) 2 ·6H 2 O to the three-necked flask dropwise at room temperature. 60ml ethanol solution, stirring while dropping, after the dropwise addition, react at room temperature for 3 hours, then add 0.75g urushiol in 50ml ethanol solution dropwise into the three-necked flask, then raise the temperature to 60°C for reflux reaction for 18 hours, after the reaction is completed Cool to room temperature, filter with suction, take the filter cake, wash with ethanol for several times, and dry to obtain urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
实施例9Example 9
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加0.75g Zn(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加1.50g漆酚的50ml乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到漆酚-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 0.75g of Zn(NO 3 ) 2 ·6H 2 O to the three-necked flask dropwise at room temperature. 60ml ethanol solution, stirring while adding dropwise, after the dropwise addition, react at room temperature for 3 hours, then add 1.50g urushiol in 50ml ethanol solution dropwise into the three-necked flask, then raise the temperature to 60°C for reflux reaction for 18 hours, after the reaction is completed Cool to room temperature, filter with suction, take the filter cake, wash with ethanol for several times, and dry to obtain urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
实施例10Example 10
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加0.75g Zn(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加3.00g漆酚的50ml乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到漆酚-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 0.75g of Zn(NO 3 ) 2 ·6H 2 O to the three-necked flask dropwise at room temperature. 60ml ethanol solution, stirring while adding dropwise, after the dropwise addition, react at room temperature for 3 hours, then add 3.00g urushiol in 50ml ethanol solution dropwise into the three-necked flask, and then heat up to 60°C for reflux reaction for 18 hours, after the reaction is completed Cool to room temperature, filter with suction, take the filter cake, wash with ethanol for several times, and dry to obtain urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
实施例11Example 11
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加1.50g Zn(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加0.30g漆酚的50ml乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到漆酚-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 1.50g of Zn(NO 3 ) 2 ·6H 2 O dropwise into the three-necked flask at room temperature. 60ml ethanol solution, stirring while adding dropwise, after the dropwise addition, react at room temperature for 3 hours, then add dropwise 0.30g urushiol in 50ml ethanol solution into the three-necked flask, then raise the temperature to 60°C for reflux reaction for 18 hours, after the reaction is completed Cool to room temperature, filter with suction, take the filter cake, wash with ethanol for several times, and dry to obtain urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
实施例12Example 12
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加1.50g Zn(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加0.75g漆酚的50ml乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到漆酚-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 1.50g of Zn(NO 3 ) 2 ·6H 2 O dropwise into the three-necked flask at room temperature. 60ml ethanol solution, stirring while dropping, after the dropwise addition, react at room temperature for 3 hours, then add 0.75g urushiol in 50ml ethanol solution dropwise into the three-necked flask, then raise the temperature to 60°C for reflux reaction for 18 hours, after the reaction is completed Cool to room temperature, filter with suction, take the filter cake, wash with ethanol for several times, and dry to obtain urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
实施例13Example 13
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加1.50g Zn(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加1.50g漆酚的50ml乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到漆酚-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 1.50g of Zn(NO 3 ) 2 ·6H 2 O dropwise into the three-necked flask at room temperature. 60ml ethanol solution, stirring while adding dropwise, after the dropwise addition, react at room temperature for 3 hours, then add 1.50g urushiol in 50ml ethanol solution dropwise into the three-necked flask, then raise the temperature to 60°C for reflux reaction for 18 hours, after the reaction is completed Cool to room temperature, filter with suction, take the filter cake, wash with ethanol for several times, and dry to obtain urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
实施例14Example 14
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加1.50g Zn(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加1.50g漆酚的50ml乙醇溶液，然后升温至60℃回流反应24小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到漆酚-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 1.50g of Zn(NO 3 ) 2 ·6H 2 O dropwise into the three-necked flask at room temperature. 60ml ethanol solution, stirring while adding dropwise, after the dropwise addition, react at room temperature for 3 hours, then add 1.50g urushiol in 50ml ethanol solution dropwise into the three-necked flask, and then heat up to 60°C for reflux reaction for 24 hours, after the reaction is completed Cool to room temperature, filter with suction, take the filter cake, wash with ethanol for several times, and dry to obtain urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
实施例15Example 15
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加1.50g Zn(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加1.50g漆酚的50ml乙醇溶液，然后升温至60℃回流反应36小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到漆酚-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 1.50g of Zn(NO 3 ) 2 ·6H 2 O dropwise into the three-necked flask at room temperature. 60ml ethanol solution, stirring while adding dropwise, after the dropwise addition, react at room temperature for 3 hours, then add 1.50g urushiol in 50ml ethanol solution dropwise into the three-necked flask, then heat up to 60°C and reflux for 36 hours, after the reaction is completed Cool to room temperature, filter with suction, take the filter cake, wash with ethanol for several times, and dry to obtain urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
实施例16Example 16
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加1.50g Zn(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加1.50g漆酚的50ml乙醇溶液，然后升温至40℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到漆酚-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 1.50g of Zn(NO 3 ) 2 ·6H 2 O dropwise into the three-necked flask at room temperature. 60ml ethanol solution, stirring while adding dropwise, after the dropwise addition, react at room temperature for 3 hours, then add 1.50g urushiol in 50ml ethanol solution dropwise into the three-necked flask, and then heat up to 40°C for reflux reaction for 18 hours, after the reaction is completed Cool to room temperature, filter with suction, take the filter cake, wash with ethanol for several times, and dry to obtain urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
实施例17Example 17
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加1.50g Zn(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加1.50g漆酚的50ml乙醇溶液，然后升温至80℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到漆酚-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 1.50g of Zn(NO 3 ) 2 ·6H 2 O dropwise into the three-necked flask at room temperature. 60ml ethanol solution, stirring while adding dropwise, after the dropwise addition, react at room temperature for 3 hours, then add 1.50g urushiol in 50ml ethanol solution dropwise into the three-necked flask, then raise the temperature to 80°C for reflux reaction for 18 hours, after the reaction is completed Cool to room temperature, filter with suction, take the filter cake, wash with ethanol for several times, and dry to obtain urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
实施例18Example 18
将1.50g聚磷酸铵和40ml甲醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加1.50g Zn(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加1.50g漆酚的50ml乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经甲醇和乙醇泡洗数次，烘干，得到漆酚-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of methanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 1.50g of Zn(NO 3 ) 2 ·6H 2 O dropwise into the three-necked flask at room temperature. 60ml ethanol solution, stirring while adding dropwise, after the dropwise addition, react at room temperature for 3 hours, then add 1.50g urushiol in 50ml ethanol solution dropwise into the three-necked flask, then raise the temperature to 60°C for reflux reaction for 18 hours, after the reaction is completed Cool to room temperature, filter with suction, take the filter cake, wash with methanol and ethanol for several times, and dry to obtain the urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
实施例19Example 19
将1.50g聚磷酸铵和40ml水，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加2.96g(0.01mol)Zn(NO3)2·6H2O的60ml水溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加1.50g漆酚的50ml乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经水和乙醇泡洗数次，烘干，得到漆酚-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of water into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 2.96g (0.01mol) Zn(NO 3 ) 2 dropwise to the three-necked flask at room temperature. 60ml aqueous solution of 6H 2 O was added dropwise while stirring. After the dropwise addition, reacted at room temperature for 3 hours, then added dropwise 1.50g urushiol in 50ml ethanol solution into the three-necked flask, and then raised the temperature to 60°C for reflux reaction for 18 hours. After the reaction is completed, cool to room temperature, filter with suction, take the filter cake, soak it with water and ethanol for several times, and dry it to obtain an urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
实施例20Example 20
将1.50g聚磷酸铵和40ml甲苯，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加1.50g Zn(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加1.50g漆酚的50ml乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经甲苯和乙醇泡洗数次，烘干，得到漆酚-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of toluene into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 1.50g of Zn(NO 3 ) 2 ·6H 2 O dropwise into the three-necked flask at room temperature. 60ml ethanol solution, stirring while adding dropwise, after the dropwise addition, react at room temperature for 3 hours, then add 1.50g urushiol in 50ml ethanol solution dropwise into the three-necked flask, then raise the temperature to 60°C for reflux reaction for 18 hours, after the reaction is completed Cool to room temperature, filter with suction, take the filter cake, wash it several times with toluene and ethanol, and dry it to obtain the urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
实施例21Example 21
将1.50g聚磷酸铵和40ml二甲苯，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加1.50g Zn(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加1.50g漆酚的50ml乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经二甲苯和乙醇泡洗数次，烘干，得到漆酚-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of xylene into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 1.50g of Zn(NO 3 ) 2 ·6H 2 O to the three-necked flask at room temperature. 60ml ethanol solution of 1.50g urushiol was added dropwise while stirring. After the dropwise addition was completed, react at room temperature for 3 hours, then add 1.50g urushiol in 50ml ethanol solution dropwise into the three-necked flask, and then raise the temperature to 60°C for reflux reaction for 18 hours, and the reaction was completed. After cooling to room temperature, filter with suction, take the filter cake, wash it several times with xylene and ethanol, and dry it to obtain the urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
实施例22Example 22
将1.50g聚磷酸铵和40ml四氢呋喃，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加1.50g Zn(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加1.50g漆酚的50ml乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经四氢呋喃和乙醇泡洗数次，烘干，得到漆酚-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of tetrahydrofuran into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 1.50g of Zn(NO 3 ) 2 ·6H 2 O to the three-necked flask dropwise at room temperature. 60ml ethanol solution, stirring while adding dropwise, after the dropwise addition, react at room temperature for 3 hours, then add 1.50g urushiol in 50ml ethanol solution dropwise into the three-necked flask, then raise the temperature to 60°C for reflux reaction for 18 hours, after the reaction is completed Cool to room temperature, filter with suction, take the filter cake, soak and wash with tetrahydrofuran and ethanol several times, and dry to obtain the urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
实施例23Example 23
将1.50g聚磷酸铵和40ml二氧六环，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加1.50g Zn(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加1.50g漆酚的50ml乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经二氧六环和乙醇泡洗数次，烘干，得到漆酚-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of dioxane into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 1.50g of Zn(NO 3 ) 2 ·6H dropwise into the three-necked flask at room temperature 60ml ethanol solution of 2 O, stirring while dropping, after the dropwise addition, react at room temperature for 3 hours, then add 1.50g urushiol in 50ml ethanol solution dropwise into the three-necked flask, then heat up to 60°C for reflux reaction for 18 hours, After the reaction is completed, cool to room temperature, filter with suction, take the filter cake, soak and wash with dioxane and ethanol several times, and dry to obtain an urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
实施例24Example 24
将1.50g聚磷酸铵和40ml丙酮，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加1.50g Zn(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加1.50g漆酚的50ml乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经丙酮和乙醇泡洗数次，烘干，得到漆酚-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of acetone into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 1.50g of Zn(NO 3 ) 2 ·6H 2 O dropwise into the three-necked flask at room temperature. 60ml ethanol solution, stirring while adding dropwise, after the dropwise addition, react at room temperature for 3 hours, then add 1.50g urushiol in 50ml ethanol solution dropwise into the three-necked flask, then raise the temperature to 60°C for reflux reaction for 18 hours, after the reaction is completed Cool to room temperature, filter with suction, take the filter cake, wash with acetone and ethanol for several times, and dry to obtain the urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
实施例25Example 25
将1.50g聚磷酸铵和40ml乙腈入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加1.50g Zn(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加1.50g漆酚的50ml乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙腈洗数次，烘干，得到漆酚-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Put 1.50g of ammonium polyphosphate and 40ml of acetonitrile into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 60ml of 1.50g of Zn(NO 3 ) 2 ·6H 2 O dropwise to the three-necked flask at room temperature. Ethanol solution, stirring while adding dropwise, after the dropwise addition, react at room temperature for 3 hours, then add 1.50g urushiol in 50ml ethanol solution dropwise into the three-necked flask, then heat up to 60°C for reflux reaction for 18 hours, cool down after the reaction to room temperature, filter with suction, take the filter cake, wash it several times with acetonitrile, and dry it to obtain an urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
实施例26Example 26
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加1.50g Mg(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加1.50g漆酚的50ml乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到漆酚-镁络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 1.50g of Mg(NO 3 ) 2 ·6H 2 O to the three-necked flask at room temperature. 60ml ethanol solution, stirring while adding dropwise, after the dropwise addition, react at room temperature for 3 hours, then add 1.50g urushiol in 50ml ethanol solution dropwise into the three-necked flask, then raise the temperature to 60°C for reflux reaction for 18 hours, after the reaction is completed Cool to room temperature, filter with suction, take the filter cake, wash with ethanol for several times, and dry to obtain urushiol-magnesium complex modified ammonium polyphosphate intumescent flame retardant.
实施例27Example 27
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加1.50g Cu(NO3)2·3H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加1.50g漆酚的50ml乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到漆酚-铜络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 1.50g of Cu(NO 3 ) 2 ·3H 2 O to the three-necked flask dropwise at room temperature. 60ml ethanol solution, stirring while adding dropwise, after the dropwise addition, react at room temperature for 3 hours, then add 1.50g urushiol in 50ml ethanol solution dropwise into the three-necked flask, then raise the temperature to 60°C for reflux reaction for 18 hours, after the reaction is completed Cool to room temperature, filter with suction, take the filter cake, wash with ethanol for several times, and dry to obtain urushiol-copper complex modified ammonium polyphosphate intumescent flame retardant.
实施例28Example 28
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加1.50g Mn(NO3)2·4H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加1.50g漆酚的50ml乙醇溶液，然后升温至80℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到漆酚-锰络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 1.50g of Mn(NO 3 ) 2 ·4H 2 O to the three-necked flask at room temperature. 60ml ethanol solution, stirring while adding dropwise, after the dropwise addition, react at room temperature for 3 hours, then add 1.50g urushiol in 50ml ethanol solution dropwise into the three-necked flask, then raise the temperature to 80°C for reflux reaction for 18 hours, after the reaction is completed Cool to room temperature, filter with suction, take the filter cake, wash with ethanol for several times, and dry to obtain urushiol-manganese complex modified ammonium polyphosphate intumescent flame retardant.
实施例29Example 29
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加1.50g Ni(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加1.50g漆酚的50ml乙醇溶液，然后升温至80℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到漆酚-镍络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 1.50g of Ni(NO 3 ) 2 ·6H 2 O to the three-necked flask dropwise at room temperature. 60ml ethanol solution, stirring while adding dropwise, after the dropwise addition, react at room temperature for 3 hours, then add 1.50g urushiol in 50ml ethanol solution dropwise into the three-necked flask, then raise the temperature to 80°C for reflux reaction for 18 hours, after the reaction is completed Cool to room temperature, filter with suction, take the filter cake, wash with ethanol for several times, and dry to obtain the urushiol-nickel complex modified ammonium polyphosphate intumescent flame retardant.
实施例30Example 30
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加1.50g Co(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加1.50g漆酚的50ml乙醇溶液，然后升温至80℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到漆酚-钴络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 1.50g of Co(NO 3 ) 2 ·6H 2 O to the three-necked flask dropwise at room temperature. 60ml ethanol solution, stirring while adding dropwise, after the dropwise addition, react at room temperature for 3 hours, then add 1.50g urushiol in 50ml ethanol solution dropwise into the three-necked flask, then raise the temperature to 80°C for reflux reaction for 18 hours, after the reaction is completed Cool to room temperature, filter with suction, take the filter cake, wash with ethanol for several times, and dry to obtain the urushiol-cobalt complex modified ammonium polyphosphate intumescent flame retardant.
实施例31Example 31
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加1.50g Al(NO3)3·9H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加1.50g漆酚的50ml乙醇溶液，然后升温至80℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到漆酚-铝络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 1.50g of Al(NO 3 ) 3 9H 2 O to the three-necked flask dropwise at room temperature. 60ml ethanol solution, stirring while adding dropwise, after the dropwise addition, react at room temperature for 3 hours, then add 1.50g urushiol in 50ml ethanol solution dropwise into the three-necked flask, then raise the temperature to 80°C for reflux reaction for 18 hours, after the reaction is completed Cool to room temperature, filter with suction, take the filter cake, wash with ethanol for several times, and dry to obtain urushiol-aluminum complex modified ammonium polyphosphate intumescent flame retardant.
实施例32Example 32
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴1.50g Fe(NO3)3·9H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加1.50g漆酚的50ml乙醇溶液，然后升温至80℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到漆酚-铁络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, drop 60ml of 1.50g of Fe(NO 3 ) 3 9H 2 O into the three-necked flask at room temperature. Ethanol solution, stirring while adding dropwise, after the dropwise addition, react at room temperature for 3 hours, then add 1.50g urushiol in 50ml ethanol solution dropwise into the three-necked flask, then heat up to 80°C for reflux reaction for 18 hours, cool down after the reaction Return to room temperature, filter with suction, take the filter cake, wash with ethanol for several times, and dry to obtain the urushiol-iron complex modified ammonium polyphosphate intumescent flame retardant.
实施例33Example 33
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴1.50g Fe(NO3)3·9H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加1.50g儿茶酚的50ml乙醇溶液，然后升温至80℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到儿茶酚-铁络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, drop 60ml of 1.50g of Fe(NO 3 ) 3 9H 2 O into the three-necked flask at room temperature. Ethanol solution, stirring while adding dropwise, after the dropwise addition, react at room temperature for 3 hours, then add 1.50g of catechol in 50ml ethanol solution dropwise into the three-necked flask, and then heat up to 80°C for reflux reaction for 18 hours, after the reaction is completed Cool to room temperature, filter with suction, take the filter cake, wash with ethanol for several times, and dry to obtain catechol-iron complex modified ammonium polyphosphate intumescent flame retardant.
实施例34Example 34
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴1.50g Fe(NO3)3·9H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加1.50g腰果酚的50ml乙醇溶液，然后升温至80℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到腰果酚-铁络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, drop 60ml of 1.50g of Fe(NO 3 ) 3 9H 2 O into the three-necked flask at room temperature. Ethanol solution, stirring while adding dropwise, after the dropwise addition, react at room temperature for 3 hours, then add 1.50g cardanol in 50ml ethanol solution dropwise into the three-necked flask, then heat up to 80°C for reflux reaction for 18 hours, cool down after the reaction Return to room temperature, filter with suction, take the filter cake, soak and wash with ethanol several times, and dry to obtain cardanol-iron complex modified ammonium polyphosphate intumescent flame retardant.
实施例35Example 35
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加1.50g Zn(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加3.00g没食子酸的50ml乙醇溶液，然后升温至80℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到没食子酸-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 1.50g of Zn(NO 3 ) 2 ·6H 2 O dropwise into the three-necked flask at room temperature. 60ml of ethanol solution, stirring while dropping, after the dropwise addition, react at room temperature for 3 hours, then add 3.00g of gallic acid in 50ml of ethanol solution dropwise into the three-necked flask, and then heat up to 80°C for reflux reaction for 18 hours, after the reaction is completed Cool to room temperature, filter with suction, take the filter cake, wash with ethanol for several times, and dry to obtain gallic acid-zinc complex modified ammonium polyphosphate intumescent flame retardant.
实施例36Example 36
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加1.50g Zn(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加3.00单宁酸的50ml乙醇溶液，然后升温至80℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到单宁酸-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 1.50g of Zn(NO 3 ) 2 ·6H 2 O dropwise into the three-necked flask at room temperature. 60ml ethanol solution, stirring while adding dropwise, after the dropwise addition, react at room temperature for 3 hours, then add dropwise 50ml ethanol solution of 3.00 tannic acid into the three-necked flask, and then heat up to 80°C for reflux reaction for 18 hours, after the reaction is completed Cool to room temperature, filter with suction, take the filter cake, wash with ethanol for several times, and dry to obtain tannic acid-zinc complex modified ammonium polyphosphate intumescent flame retardant.
实施例37Example 37
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加1.50g Zn(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加3.00g腰果酚的50ml乙醇溶液，然后升温至80℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到腰果酚-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 1.50g of Zn(NO 3 ) 2 ·6H 2 O dropwise into the three-necked flask at room temperature. 60ml of ethanol solution, stirring while adding dropwise, after the dropwise addition, react at room temperature for 3 hours, then add 3.00g of cardanol in 50ml of ethanol solution dropwise into the three-necked flask, then heat up to 80°C for reflux reaction for 18 hours, after the reaction is completed Cool to room temperature, filter with suction, take the filter cake, wash with ethanol for several times, and dry to obtain cardanol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
实施例38Example 38
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加1.50g Zn(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加3.00g丁香酚的50ml乙醇溶液，然后升温至80℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到丁香酚-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 1.50g of Zn(NO 3 ) 2 ·6H 2 O dropwise into the three-necked flask at room temperature. 60ml of ethanol solution, stirring while adding dropwise, after the dropwise addition, react at room temperature for 3 hours, then add 3.00g of eugenol in 50ml of ethanol solution dropwise into the three-necked flask, and then heat up to 80°C for reflux reaction for 18 hours, after the reaction is completed Cool to room temperature, filter with suction, take the filter cake, wash with ethanol for several times, and dry to obtain the eugenol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
实施例39Example 39
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加1.50g Zn(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加3.00儿茶酚的50ml乙醇溶液，然后升温至68℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到儿茶酚-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 1.50g of Zn(NO 3 ) 2 ·6H 2 O dropwise into the three-necked flask at room temperature. 60ml ethanol solution, stirring while adding dropwise, after the dropwise addition, react at room temperature for 3 hours, then add dropwise 50ml ethanol solution of 3.00 catechol into the three-necked flask, then raise the temperature to 68°C for reflux reaction for 18 hours, after the reaction is completed Cool to room temperature, filter with suction, take the filter cake, wash with ethanol for several times, and dry to obtain catechol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
实施例40Example 40
步骤一将2.44g水杨醛和20ml乙醇溶液置于带有温度计搅拌装置的三口烧瓶中；待原料混合均匀后，在常温下向三口烧瓶滴加0.6g乙二胺的40ml乙醇溶液，边滴加边搅拌，升到60℃回流反应12小时，冷却至室温，得到水杨醛-乙二胺席夫碱。Step 1 Put 2.44g of salicylaldehyde and 20ml of ethanol solution in a three-necked flask with a thermometer stirring device; after the raw materials are mixed evenly, add 0.6g of ethylenediamine in 40ml of ethanol solution dropwise to the three-necked flask at room temperature, dropwise Stir while adding, rise to 60°C for reflux reaction for 12 hours, and cool to room temperature to obtain salicylaldehyde-ethylenediamine Schiff base.
步骤二将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴1.50gFe(NO3)3·9H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加步骤一中的席夫碱乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到水杨醛-乙二胺席夫碱-铁络合物修饰聚磷酸铵膨胀型阻燃剂。Step 2 Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, drop 1.50g of Fe(NO 3 ) 3 ·9H 2 O into the three-necked flask at room temperature. 60ml ethanol solution, stirring while dropping, after the dropwise addition, react at room temperature for 3 hours, then add dropwise the Schiff base ethanol solution in step 1 into the three-necked flask, then raise the temperature to 60°C and reflux for 18 hours, the reaction is complete After cooling to room temperature, filter with suction, take the filter cake, wash it several times with ethanol, and dry it to obtain salicylaldehyde-ethylenediamine Schiff base-iron complex modified ammonium polyphosphate intumescent flame retardant.
实施例41Example 41
步骤一将2.44g水杨醛和20ml乙醇溶液置于带有温度计搅拌装置的三口烧瓶中；待原料混合均匀后，在常温下向三口烧瓶滴加1.46g三乙烯四胺的40ml乙醇溶液，边滴加边搅拌，升到60℃回流反应12小时，冷却至室温，得到水杨醛-三乙烯四胺席夫碱。Step 1: Place 2.44g of salicylaldehyde and 20ml of ethanol solution in a three-necked flask with a thermometer stirring device; after the raw materials are mixed evenly, add 1.46g of triethylenetetramine in 40ml of ethanol solution to the three-necked flask at room temperature, while Stir while adding dropwise, rise to 60° C. for reflux reaction for 12 hours, and cool to room temperature to obtain salicylaldehyde-triethylenetetramine Schiff base.
步骤二将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴1.50gFe(NO3)3·9H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加步骤一中的席夫碱乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到水杨醛-三乙烯四胺席夫碱-铁络合物修饰聚磷酸铵膨胀型阻燃剂。Step 2 Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, drop 1.50g of Fe(NO 3 ) 3 ·9H 2 O into the three-necked flask at room temperature. 60ml ethanol solution, stirring while dropping, after the dropwise addition, react at room temperature for 3 hours, then add dropwise the Schiff base ethanol solution in step 1 into the three-necked flask, then raise the temperature to 60°C and reflux for 18 hours, the reaction is complete After cooling to room temperature, filter with suction, take the filter cake, soak and wash with ethanol for several times, and dry to obtain salicylaldehyde-triethylenetetramine Schiff base-iron complex modified ammonium polyphosphate intumescent flame retardant.
实施例42Example 42
步骤一将2.44g水杨醛和20ml乙醇溶液置于带有温度计搅拌装置的三口烧瓶中；待原料混合均匀后，在常温下向三口烧瓶滴加1.89g四乙烯五胺的40ml乙醇溶液，边滴加边搅拌，升到60℃回流反应12小时，冷却至室温，得到水杨醛-四乙烯五胺席夫碱。Step 1: Place 2.44g salicylaldehyde and 20ml ethanol solution in a three-necked flask with a thermometer stirring device; after the raw materials are mixed evenly, add 1.89g tetraethylenepentamine 40ml ethanol solution dropwise to the three-necked flask at room temperature, while Stir while adding dropwise, rise to 60° C. for reflux reaction for 12 hours, and cool to room temperature to obtain salicylaldehyde-tetraethylenepentamine Schiff base.
步骤二将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴1.50gFe(NO3)3·9H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加步骤一中的席夫碱乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到水杨醛-四乙烯五胺席夫碱-铁络合物修饰聚磷酸铵膨胀型阻燃剂。Step 2 Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, drop 1.50g of Fe(NO 3 ) 3 ·9H 2 O into the three-necked flask at room temperature. 60ml ethanol solution, stirring while dropping, after the dropwise addition, react at room temperature for 3 hours, then add dropwise the Schiff base ethanol solution in step 1 into the three-necked flask, then raise the temperature to 60°C and reflux for 18 hours, the reaction is complete After cooling to room temperature, filter with suction, take the filter cake, soak and wash with ethanol for several times, and dry to obtain salicylaldehyde-tetraethylenepentamine Schiff base-iron complex modified ammonium polyphosphate intumescent flame retardant.
实施例43Example 43
步骤一将1.22g水杨醛和20ml乙醇溶液置于带有温度计搅拌装置的三口烧瓶中；待原料混合均匀后，在常温下向三口烧瓶滴加1.2g聚乙烯亚胺的40ml乙醇溶液，边滴加边搅拌，升到60℃回流反应12小时，冷却至室温，得到水杨醛-聚乙烯亚胺席夫碱。Step 1: Place 1.22g of salicylaldehyde and 20ml of ethanol solution in a three-necked flask with a thermometer stirring device; after the raw materials are mixed evenly, add 1.2g of polyethyleneimine in 40ml of ethanol solution to the three-necked flask at room temperature, while Stir while adding dropwise, rise to 60° C. for reflux reaction for 12 hours, and cool to room temperature to obtain salicylaldehyde-polyethyleneimine Schiff base.
步骤二将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴1.50gFe(NO3)3·9H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加步骤一中的席夫碱乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到水杨醛-聚乙烯亚胺席夫碱-铁络合物修饰聚磷酸铵膨胀型阻燃剂。Step 2 Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, drop 1.50g of Fe(NO 3 ) 3 ·9H 2 O into the three-necked flask at room temperature. 60ml ethanol solution, stirring while dropping, after the dropwise addition, react at room temperature for 3 hours, then add dropwise the Schiff base ethanol solution in step 1 into the three-necked flask, then raise the temperature to 60°C and reflux for 18 hours, the reaction is complete After cooling to room temperature, filter with suction, take the filter cake, wash it several times with ethanol, and dry it to obtain salicylaldehyde-polyethyleneimine Schiff base-iron complex modified ammonium polyphosphate intumescent flame retardant.
实施例44Example 44
步骤一将1.22g水杨醛和20ml乙醇溶液置于带有温度计搅拌装置的三口烧瓶中；待原料混合均匀后，在常温下向三口烧瓶滴加1.83g氨基二苯甲烷的40ml乙醇溶液，边滴加边搅拌，升到60℃回流反应12小时，冷却至室温，得到水杨醛-胺基二苯甲烷席夫碱。Step 1: Place 1.22g of salicylaldehyde and 20ml of ethanol solution in a three-necked flask with a thermometer stirring device; after the raw materials are mixed evenly, add 1.83g of aminodiphenylmethane in 40ml of ethanol solution to the three-necked flask at room temperature, while Stir while adding dropwise, rise to 60° C. for reflux reaction for 12 hours, and cool to room temperature to obtain salicylaldehyde-aminodiphenylmethane Schiff base.
步骤二将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴1.50gFe(NO3)3·9H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加步骤一中的席夫碱乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到水杨醛-氨基二苯甲烷席夫碱-铁络合物修饰聚磷酸铵膨胀型阻燃剂。Step 2 Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, drop 1.50g of Fe(NO 3 ) 3 ·9H 2 O into the three-necked flask at room temperature. 60ml ethanol solution, stirring while dropping, after the dropwise addition, react at room temperature for 3 hours, then add dropwise the Schiff base ethanol solution in step 1 into the three-necked flask, then raise the temperature to 60°C and reflux for 18 hours, the reaction is complete After cooling to room temperature, filter with suction, take the filter cake, soak and wash with ethanol for several times, and dry to obtain salicylaldehyde-aminodiphenylmethane Schiff base-iron complex modified ammonium polyphosphate intumescent flame retardant.
实施例45Example 45
步骤一将1.22g水杨醛和20ml乙醇溶液置于带有温度计搅拌装置的三口烧瓶中；待原料混合均匀后，在常温下向三口烧瓶滴加1.5g 2-氨基苯并噻唑的40ml乙醇溶液，边滴加边搅拌，升到60℃回流反应12小时，冷却至室温，得到水杨醛-2-氨基苯并噻唑席夫碱。Step 1: Put 1.22g of salicylaldehyde and 20ml of ethanol solution in a three-necked flask with a thermometer stirring device; after the raw materials are mixed evenly, add 1.5g of 2-aminobenzothiazole in 40ml of ethanol solution to the three-necked flask at room temperature , Stirring while adding dropwise, rising to 60°C for reflux reaction for 12 hours, cooling to room temperature to obtain salicylaldehyde-2-aminobenzothiazole Schiff base.
步骤二将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴1.50gFe(NO3)3·9H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加步骤一中的席夫碱乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到水杨醛-2-氨基苯并噻唑-铁络合物修饰聚磷酸铵膨胀型阻燃剂。Step 2 Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, drop 1.50g of Fe(NO 3 ) 3 ·9H 2 O into the three-necked flask at room temperature. 60ml ethanol solution, stirring while dropping, after the dropwise addition, react at room temperature for 3 hours, then add dropwise the Schiff base ethanol solution in step 1 into the three-necked flask, then raise the temperature to 60°C and reflux for 18 hours, the reaction is complete After cooling to room temperature, filter with suction, take the filter cake, soak and wash with ethanol for several times, and dry to obtain salicylaldehyde-2-aminobenzothiazole-iron complex modified ammonium polyphosphate intumescent flame retardant.
实施例46Example 46
步骤一将1.22g水杨醛和20ml乙醇溶液置于带有温度计搅拌装置的三口烧瓶中；待原料混合均匀后，在常温下向三口烧瓶滴加0.84g 2-氨基-三氮唑的40ml乙醇溶液，边滴加边搅拌，升到60℃回流反应12小时，冷却至室温，得到水杨醛-2-氨基-三氮唑席夫碱。Step 1: Put 1.22g of salicylaldehyde and 20ml of ethanol solution in a three-necked flask with a thermometer stirring device; after the raw materials are mixed evenly, add 0.84g of 2-amino-triazole in 40ml of ethanol dropwise to the three-necked flask at room temperature The solution was stirred while being added dropwise, raised to 60° C. for reflux reaction for 12 hours, and cooled to room temperature to obtain salicylaldehyde-2-amino-triazole Schiff base.
步骤二将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴1.50gFe(NO3)3·9H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加步骤一中的席夫碱乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到水杨醛-2-氨基-三氮唑-铁络合物修饰聚磷酸铵膨胀型阻燃剂。Step 2 Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, drop 1.50g of Fe(NO 3 ) 3 ·9H 2 O into the three-necked flask at room temperature. 60ml ethanol solution, stirring while dropping, after the dropwise addition, react at room temperature for 3 hours, then add dropwise the Schiff base ethanol solution in step 1 into the three-necked flask, then raise the temperature to 60°C and reflux for 18 hours, the reaction is complete After cooling to room temperature, filter with suction, take the filter cake, soak and wash with ethanol for several times, and dry to obtain salicylaldehyde-2-amino-triazole-iron complex modified ammonium polyphosphate intumescent flame retardant.
实施例47Example 47
步骤一将1.22g水杨醛和20ml乙醇溶液置于带有温度计搅拌装置的三口烧瓶中；待原料混合均匀后，在常温下向三口烧瓶滴加0.85g 5-氨基-四氮唑的40ml乙醇溶液，边滴加边搅拌，升到60℃回流反应12小时，冷却至室温，得到水杨醛-5-氨基-四氮唑席夫碱。Step 1: Put 1.22g of salicylaldehyde and 20ml of ethanol solution in a three-necked flask with a thermometer stirring device; after the raw materials are mixed evenly, add 0.85g of 5-amino-tetrazolium in 40ml of ethanol dropwise to the three-necked flask at room temperature The solution was stirred while being added dropwise, raised to 60° C. for reflux reaction for 12 hours, and cooled to room temperature to obtain salicylaldehyde-5-amino-tetrazolium Schiff base.
步骤二将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴1.50gFe(NO3)3·9H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加步骤一中的席夫碱乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到水杨醛-5-氨基-四氮唑-铁络合物修饰聚磷酸铵膨胀型阻燃剂。Step 2 Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, drop 1.50g of Fe(NO 3 ) 3 ·9H 2 O into the three-necked flask at room temperature. 60ml ethanol solution, stirring while dropping, after the dropwise addition, react at room temperature for 3 hours, then add dropwise the Schiff base ethanol solution in step 1 into the three-necked flask, then raise the temperature to 60°C and reflux for 18 hours, the reaction is complete After cooling to room temperature, filter with suction, take the filter cake, wash it several times with ethanol, and dry it to obtain salicylaldehyde-5-amino-tetrazolium-iron complex modified ammonium polyphosphate intumescent flame retardant.
实施例48Example 48
步骤一将2.44g水杨醛和20ml乙醇溶液置于带有温度计搅拌装置的三口烧瓶中；待原料混合均匀后，在常温下向三口烧瓶滴加1.03g二乙烯三胺的40ml乙醇溶液，边滴加边搅拌，升到60℃回流反应12小时，冷却至室温，得到水杨醛-二乙烯三胺席夫碱。Step 1 Place 2.44g salicylaldehyde and 20ml ethanol solution in a three-necked flask with a thermometer stirring device; after the raw materials are mixed evenly, add 1.03g diethylenetriamine 40ml ethanol solution dropwise to the three-necked flask at room temperature, while Stir while adding dropwise, rise to 60° C. for reflux reaction for 12 hours, and cool to room temperature to obtain salicylaldehyde-diethylenetriamine Schiff base.
步骤二将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴1.50gCo(NO3)2·9H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加步骤一中的席夫碱乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到水杨醛-二乙烯三胺席夫碱-钴络合物修饰聚磷酸铵膨胀型阻燃剂。Step 2 Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, drop 1.50g of Co(NO 3 ) 2 ·9H 2 O into the three-necked flask at room temperature. 60ml ethanol solution, stirring while dropping, after the dropwise addition, react at room temperature for 3 hours, then add dropwise the Schiff base ethanol solution in step 1 into the three-necked flask, then raise the temperature to 60°C and reflux for 18 hours, the reaction is complete After cooling to room temperature, filter with suction, take the filter cake, soak and wash with ethanol for several times, and dry to obtain salicylaldehyde-diethylenetriamine Schiff base-cobalt complex modified ammonium polyphosphate intumescent flame retardant.
实施例49Example 49
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加1.50g Zn(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加3.00g漆酚的50ml乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到漆酚-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 1.50g of Zn(NO 3 ) 2 ·6H 2 O dropwise into the three-necked flask at room temperature. 60ml ethanol solution, stirring while adding dropwise, after the dropwise addition, react at room temperature for 3 hours, then add 3.00g urushiol in 50ml ethanol solution dropwise into the three-necked flask, and then heat up to 60°C for reflux reaction for 18 hours, after the reaction is completed Cool to room temperature, filter with suction, take the filter cake, wash with ethanol for several times, and dry to obtain urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
实施例50Example 50
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加1.50g Zn(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加3.00 2-甲基咪唑的50ml乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到2-甲基咪唑-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 1.50g of Zn(NO 3 ) 2 ·6H 2 O dropwise into the three-necked flask at room temperature. 60ml ethanol solution, stirring while dropping, after the dropwise addition, react at room temperature for 3 hours, then add dropwise 3.00 2-methylimidazole in 50ml ethanol solution into the three-necked flask, and then heat up to 60°C for reflux reaction for 18 hours, the reaction After completion, cool to room temperature, filter with suction, take out the filter cake, wash with ethanol for several times, and dry to obtain 2-methylimidazole-zinc complex modified ammonium polyphosphate intumescent flame retardant.
实施例51Example 51
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加1.50g Zn(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加3.00 3-氨基-1,2,4-三氮唑的50ml乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到3-氨基-1，2,4-三氮唑-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 1.50g of Zn(NO 3 ) 2 ·6H 2 O dropwise into the three-necked flask at room temperature. 60ml ethanol solution, stirring while dropping, after the dropwise addition, react at room temperature for 3 hours, then add dropwise 50ml ethanol solution of 3.00 3-amino-1,2,4-triazole in the three-necked flask, and then heat up to Reflux at 60°C for 18 hours, cool to room temperature after the reaction, filter with suction, take the filter cake, wash with ethanol for several times, and dry to obtain 3-amino-1,2,4-triazole-zinc complex Modified ammonium polyphosphate intumescent flame retardant.
实施例52Example 52
3-氨基-1,2,4-三氮唑衍生物(D-ATA)的合成:将4.45g DOPO和20ml二氯甲烷溶液加入到装有机械搅拌器的三口烧瓶中，加入3.15ml三乙胺，三口烧瓶温度降至5℃加入1.73g 3-氨基-1,2,4-三氮唑，待原料混合均匀后，滴加混有2.18ml CH2Cl2的5ml乙腈溶液，滴加完毕后，常温反应24小时，反应完毕后，抽滤，取滤饼，经去离子水溶液泡洗数次，烘干，得到D-ATA。Synthesis of 3-amino-1,2,4-triazole derivatives (D-ATA): 4.45g DOPO and 20ml dichloromethane solution were added to a three-necked flask equipped with a mechanical stirrer, and 3.15ml triethyl ether was added amine, the temperature of the three-necked flask was lowered to 5°C, and 1.73g of 3-amino-1,2,4-triazole was added. After the raw materials were mixed evenly, 5ml of acetonitrile solution mixed with 2.18ml of CH2Cl2 was added dropwise. React for 24 hours. After the reaction is completed, filter with suction, take the filter cake, soak it in deionized water for several times, and dry it to obtain D-ATA.
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加1.50g Zn(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加3.00D-ATA的50ml乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到D-ATA-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 1.50g of Zn(NO 3 ) 2 ·6H 2 O dropwise into the three-necked flask at room temperature. 60ml ethanol solution, stirring while adding dropwise, after the dropwise addition, react at room temperature for 3 hours, then add 50ml ethanol solution of 3.00D-ATA dropwise into the three-necked flask, then raise the temperature to 60°C for reflux reaction for 18 hours, after the reaction is completed Cool to room temperature, filter with suction, take the filter cake, wash with ethanol for several times, and dry to obtain D-ATA-zinc complex modified ammonium polyphosphate intumescent flame retardant.
实施例53Example 53
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加1.50g Zn(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加3.00g 5-氨基-四氮唑的50ml乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到5-氨基-四氮唑-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 1.50g of Zn(NO 3 ) 2 ·6H 2 O dropwise into the three-necked flask at room temperature. 60ml of ethanol solution, stirring while dropping, after the dropwise addition, react at room temperature for 3 hours, then add dropwise 3.00g of 5-amino-tetrazolium in 50ml of ethanol solution into the three-necked flask, and then heat up to 60°C for reflux reaction for 18 Hours, after the reaction is completed, cool to room temperature, filter with suction, take the filter cake, wash it several times with ethanol, and dry it to obtain a 5-amino-tetrazolium-zinc complex modified ammonium polyphosphate intumescent flame retardant.
实施例54Example 54
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加1.50g Zn(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加3.00g腺嘌呤的50ml乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到腺嘌呤-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 1.50g of Zn(NO 3 ) 2 ·6H 2 O dropwise into the three-necked flask at room temperature. 60ml of ethanol solution, stirring while dropping, after the dropwise addition, react at room temperature for 3 hours, then add 3.00g of adenine in 50ml of ethanol solution dropwise into the three-necked flask, then raise the temperature to 60°C for reflux reaction for 18 hours, after the reaction is completed Cool to room temperature, filter with suction, take the filter cake, wash with ethanol for several times, and dry to obtain an adenine-zinc complex modified ammonium polyphosphate intumescent flame retardant.
实施例55Example 55
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加1.50g Zn(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加3.00g天冬氨酸的50ml乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到天冬氨酸-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 1.50g of Zn(NO 3 ) 2 ·6H 2 O dropwise into the three-necked flask at room temperature. 60ml of ethanol solution, stirring while dropping, after the dropwise addition, react at room temperature for 3 hours, then add dropwise 3.00g of aspartic acid in 50ml of ethanol solution into the three-necked flask, and then heat up to 60°C for reflux reaction for 18 hours, the reaction After completion, cool to room temperature, filter with suction, take out the filter cake, wash with ethanol for several times, and dry to obtain aspartic acid-zinc complex modified ammonium polyphosphate intumescent flame retardant.
实施例56Example 56
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加1.50g Zn(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加3.00g赖氨酸的50ml乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到赖氨酸-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 1.50g of Zn(NO 3 ) 2 ·6H 2 O dropwise into the three-necked flask at room temperature. 60ml of ethanol solution, stirring while dropping, after the dropwise addition, react at room temperature for 3 hours, then add 3.00g of lysine in 50ml of ethanol solution dropwise into the three-necked flask, then raise the temperature to 60°C for reflux reaction for 18 hours, the reaction is complete After cooling to room temperature, filter with suction, take out the filter cake, wash with ethanol for several times, and dry to obtain the lysine-zinc complex modified ammonium polyphosphate intumescent flame retardant.
实施例57Example 57
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加1.50g Zn(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加3.00g谷氨酸的50ml乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到谷氨酸-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 1.50g of Zn(NO 3 ) 2 ·6H 2 O dropwise into the three-necked flask at room temperature. 60ml of ethanol solution, stirring while dropping, after the dropwise addition, react at room temperature for 3 hours, then add 3.00g of glutamic acid in 50ml of ethanol solution dropwise into the three-neck flask, then heat up to 60°C and reflux for 18 hours, the reaction is complete After cooling to room temperature, filter with suction, take out the filter cake, wash with ethanol for several times, and dry to obtain glutamic acid-zinc complex modified ammonium polyphosphate intumescent flame retardant.
实施例58Example 58
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加1.50g Zn(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加3.00g甘氨酸的50ml乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到甘氨酸-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 1.50g of Zn(NO 3 ) 2 ·6H 2 O dropwise into the three-necked flask at room temperature. 60ml ethanol solution, stirring while dropping, after the dropwise addition, react at room temperature for 3 hours, then add 3.00g glycine 50ml ethanol solution dropwise into the three-necked flask, then raise the temperature to 60°C for reflux reaction for 18 hours, cool down after the reaction Return to room temperature, filter with suction, take the filter cake, wash with ethanol for several times, and dry to obtain a glycine-zinc complex modified ammonium polyphosphate intumescent flame retardant.
实施例59Example 59
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加1.50g Zn(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加3.00g水杨酸的50ml乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到水杨酸-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 1.50g of Zn(NO 3 ) 2 ·6H 2 O dropwise into the three-necked flask at room temperature. 60ml of ethanol solution, stirring while dropping, after the dropwise addition, react at room temperature for 3 hours, then add 3.00g of salicylic acid in 50ml of ethanol solution dropwise into the three-necked flask, then raise the temperature to 60°C for reflux reaction for 18 hours, the reaction is complete After cooling to room temperature, filter with suction, take out the filter cake, wash with ethanol for several times, and dry to obtain salicylic acid-zinc complex modified ammonium polyphosphate intumescent flame retardant.
实施例60Example 60
将1.50g聚磷酸铵和40ml乙醇，加入到装有机械搅拌器的三口烧瓶中，待原料混合均匀后，在常温下向三口烧瓶内滴加1.50g Zn(NO3)2·6H2O的60ml乙醇溶液，边滴加边搅拌，滴加完毕后，常温反应3小时，之后再向三口烧瓶内滴加3.00g草酸的50ml乙醇溶液，然后升温至60℃回流反应18小时，反应完毕后冷却至室温，抽滤，取滤饼，经乙醇泡洗数次，烘干，得到草酸-锌络合物修饰聚磷酸铵膨胀型阻燃剂。Add 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-necked flask equipped with a mechanical stirrer. After the raw materials are mixed evenly, add 1.50g of Zn(NO 3 ) 2 ·6H 2 O dropwise into the three-necked flask at room temperature. 60ml of ethanol solution, stirring while adding dropwise, after the dropwise addition, react at room temperature for 3 hours, then add 3.00g of oxalic acid in 50ml of ethanol solution dropwise into the three-necked flask, then raise the temperature to 60°C for reflux reaction for 18 hours, cool down after the reaction is complete Return to room temperature, filter with suction, take the filter cake, wash with ethanol for several times, and dry to obtain an oxalic acid-zinc complex modified ammonium polyphosphate intumescent flame retardant.
实施例32漆酚-铁络合物修饰聚磷酸铵测试分析结果如下：Example 32 Urushiol-iron complex modified ammonium polyphosphate test analysis results are as follows:
FTIR(KBr，cm-1):3200(N-H)，2979(＝C-H),2927(-CH3),2856(-CH2),1635，1557苯环骨架，1256(P＝O)，1340(C-N)，1057(P-O)，880(C-N)，800(P-O-P)，680(Fe-O).FTIR (KBr, cm -1 ): 3200(NH), 2979(=CH), 2927(-CH 3 ), 2856(-CH 2 ), 1635, 1557 benzene ring skeleton, 1256(P=O), 1340( CN), 1057(PO), 880(CN), 800(POP), 680(Fe-O).
实施例48水杨醛-二乙烯三胺席夫碱-钴络合物修饰聚磷酸铵测试分析结果如下：Example 48 Salicylaldehyde-diethylenetriamine Schiff base-cobalt complex modified ammonium polyphosphate test and analysis results are as follows:
FTIR(KBr，cm-1):3200(N-H)，1635(C＝N)，1602(C＝N),1384(N-H),1256(P＝O)，1057(P-O)，880(C-N)，800(P-O-P)，443(Co-N),418(Co-O).FTIR (KBr, cm -1 ): 3200(NH), 1635(C=N), 1602(C=N), 1384(NH), 1256(P=O), 1057(PO), 880(CN), 800(POP), 443(Co-N), 418(Co-O).
实施例52D-ATA-锌络合物修饰聚磷酸铵测试分析结果如下：Example 52 D-ATA-zinc complex modified ammonium polyphosphate test analysis results are as follows:
FTIR(KBr，cm-1):3200(N-H)，1600(C＝N),1200(P＝O)，952(P-O)，880(C-N)，800(P-O-P)，500(Zn-N)。FTIR (KBr, cm -1 ): 3200(NH), 1600(C=N), 1200(P=O), 952(PO), 880(CN), 800(POP), 500(Zn-N).
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