CN111574751B - Preparation method of modified melamine polyphosphate - Google Patents
Preparation method of modified melamine polyphosphate Download PDFInfo
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- CN111574751B CN111574751B CN202010393980.1A CN202010393980A CN111574751B CN 111574751 B CN111574751 B CN 111574751B CN 202010393980 A CN202010393980 A CN 202010393980A CN 111574751 B CN111574751 B CN 111574751B
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- 229920000388 Polyphosphate Polymers 0.000 title claims abstract description 60
- 239000001205 polyphosphate Substances 0.000 title claims abstract description 60
- 235000011176 polyphosphates Nutrition 0.000 title claims abstract description 60
- 150000007974 melamines Chemical class 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 51
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 37
- 239000004698 Polyethylene Substances 0.000 claims abstract description 19
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 19
- -1 polyethylene Polymers 0.000 claims abstract description 19
- 229920000573 polyethylene Polymers 0.000 claims abstract description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 44
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000006482 condensation reaction Methods 0.000 claims description 8
- 230000018044 dehydration Effects 0.000 claims description 8
- 238000006297 dehydration reaction Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229920001903 high density polyethylene Polymers 0.000 claims description 4
- 239000004700 high-density polyethylene Substances 0.000 claims description 4
- 229920001684 low density polyethylene Polymers 0.000 claims description 4
- 239000004702 low-density polyethylene Substances 0.000 claims description 4
- NLSFWPFWEPGCJJ-UHFFFAOYSA-N 2-methylprop-2-enoyloxysilicon Chemical compound CC(=C)C(=O)O[Si] NLSFWPFWEPGCJJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 2
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical group [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 2
- 239000003063 flame retardant Substances 0.000 abstract description 47
- 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 abstract description 46
- 239000002131 composite material Substances 0.000 abstract description 13
- 239000011248 coating agent Substances 0.000 abstract description 12
- 238000000576 coating method Methods 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 239000002245 particle Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 9
- 238000011161 development Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000002861 polymer material Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 description 3
- 229920000137 polyphosphoric acid Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010053567 Coagulopathies Diseases 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- 206010024769 Local reaction Diseases 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000035602 clotting Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- ZZMPGNVAROSUSZ-UHFFFAOYSA-N triazanium;1,3,5-triazine-2,4,6-triamine;phosphate Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O.NC1=NC(N)=NC(N)=N1 ZZMPGNVAROSUSZ-UHFFFAOYSA-N 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having three nitrogen atoms as the only ring hetero atoms
- C07F9/6521—Six-membered rings
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34928—Salts
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- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention relates to a preparation method of a melamine polyphosphate composite flame retardant, in particular to a novel preparation method of a coated water-resistant melamine polyphosphate flame retardant. The method directly synthesizes the coating modified melamine polyphosphate, and adopts the silane coupling agent and the polyethylene as coating materials for graded coating, so that the effect is better, the efficiency is higher, the flame retardant product is mixed more uniformly, the flame retardant efficiency of the product is improved, and the use cost of the flame retardant is reduced.
Description
Technical Field
The invention relates to a preparation method of modified melamine polyphosphate, in particular to a novel method for preparing a coated water-resistant melamine polyphosphate flame retardant.
Background
The research and development and formula development of the novel flame retardant can obviously improve the performance level of military equipment such as spaceflight, ships and the like; can meet the development and application requirements in the fields of novel fire-resistant protective materials, fire protection, safety protection and the like, and has important significance for promoting the development of national economy.
With the rapid development of the chemical synthesis industry and the promotion of the fire-proof safety consciousness, the trend of flame retardance of high polymer materials is more and more obvious, and the rapid development of the flame retardant industry is promoted. At present, the domestic flame retardant is still mainly halogen, but with the enhancement of domestic environmental awareness, the development potential of the halogen-free flame retardant is huge.
The melamine polyphosphate self-expansion flame retardant has no halogen, low smoke and low toxicity; the polymer is well compatible with the treated polymer material and has little influence on the performance of the polymer material; can be decomposed to release water and melamine by heating to play a role in fire retardation, can generate a P-N synergistic flame-retardant effect, can generate a uniform and compact carbon layer, has good heat insulation, oxygen isolation, flame retardance and smoke suppression functions, can effectively prevent a dripping phenomenon, and prevents flame from spreading and spreading.
At present, the synthesis methods of melamine polyphosphate mainly comprise the following two methods:
(1) heat treatment method
The heat treatment method refers to a method for preparing MPP by calcining a substance containing phosphoric acid and melamine components at high temperature, and can be subdivided into a two-step method and a one-step method according to different synthesis steps. The two-step process refers to the first preparation of Melamine Phosphate (MP) from phosphoric acid and melamine at room temperature followed by high temperature thermal polycondensation to produce MPP. The method is a main method for domestic industrial production at present. The method has the advantages of cheap and easily-obtained raw materials, mild conditions and simple and convenient operation method. However, the acceleration of the phosphoric acid drop in the reaction process of synthesizing MP in the first step is not easy to control, and clotting is easy to generate, so that the reaction mixing is not uniform, and local reaction or side reaction occurs. Kanayma A and the like disclose a one-step solid phase reaction process of MPP, which comprises the steps of calcining substances containing melamine and phosphoric acid components, such as MPP, melamine, ammonium phosphate, melamine ammonium phosphate and the like at a high temperature (300-350 ℃), controlling the melamine/phosphoric acid ratio of raw materials to be 1.05-1.5, and preparing the MPP with low water solubility.
(2) Solvent process
Aiming at the defects of large energy consumption of a heat treatment method, large amount of irritant gas emission in the production process, poor flame retardant property caused by low product purity and the like, a method for preparing MPP by directly utilizing polyphosphoric acid and melamine to react in an organic solvent in one step is provided by few people. Zhang Yanjiang et al reported a synthesis process for directly preparing MPP by using silicotungstic acid as a catalyst and reacting melamine with polyphosphoric acid in a methanol reaction medium, wherein the whole reaction process has no caking phenomenon, the reaction temperature is easy to control, the local overheating phenomenon does not occur, and the product is relatively pure. The solvent method has the advantages that the reaction temperature is easy to control, and MPP with higher purity can be prepared. However, the organic solvent used in large quantities in industrial production has potential risks of burning and explosion under the condition of improper control, and the use of polyphosphoric acid and catalysts in certain systems greatly increases the process cost, and the application is limited to a certain extent and is difficult to popularize.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the method simplifies the production process of the product, improves the water resistance, the flame retardant efficiency and the compatibility with high polymer materials of the melamine polyphosphate flame retardant, and is a novel method suitable for preparing the melamine polyphosphate flame retardant in batch production.
The solution of the invention is:
a preparation method of modified melamine polyphosphate comprises the following steps: in the kneading machine, melamine, phosphoric acid, a silane coupling agent and polyethylene are used as raw materials, melamine polyphosphate is synthesized through neutralization reaction and dehydration condensation reaction, and the water-resistant melamine polyphosphate composite flame retardant is obtained through thermal coating treatment of the silane coupling agent and the polyethylene.
The reaction formula of the synthetic route of the water-resistant melamine polyphosphate is as follows:
in the kneading machine, melamine, phosphoric acid, a silane coupling agent and polyethylene are used as raw materials, melamine polyphosphate is synthesized through neutralization reaction and dehydration condensation reaction, and the modified melamine polyphosphate composite flame retardant is obtained through thermal coating treatment of the silane coupling agent and the polyethylene.
The preparation method is divided into three steps, wherein in the first step, melamine and phosphoric acid are used as reaction raw materials and react for 1-10 hours at the temperature of 60-100 ℃; the second step is that under the vacuum condition, the temperature is raised to 200-300 ℃ for dehydration condensation reaction for 2-8 h; the third step is that the temperature is reduced to 90-130 ℃, the vacuum is relieved, firstly, the silane coupling agent is added, the stirring is carried out for 1-2h, then, the polyethylene in a melting state is added, the mixture is continuously mixed uniformly, and the mixture is discharged after being reduced to the room temperature; the three steps of reactions are continuously carried out. The molar ratio of the phosphoric acid to the melamine is 0.5: 1-4: 1, the mass ratio of the silane coupling agent to the phosphoric acid is 1: 100-20: 100, the mass ratio of polyethylene to phosphoric acid is 1: 100-40: 100.
the mass concentration of the phosphoric acid is not lower than 50 percent;
the silane coupling agent for surface treatment of melamine polyphosphate is several types of vinyl silane, amino silane, epoxy silane and methacryloxy silane, and specific grades include but are not limited to KH-540, KH-550, KH-560, KH-570, KH-590, A-151, A-171, A-172, Si-563 and YDH-201.
The polyethylene for coating the melamine polyphosphate is High Density Polyethylene (HDPE), Low Density Polyethylene (LDPE) or Linear Low Density Polyethylene (LLDPE).
The modified melamine polyphosphate flame retardant synthesized by the method does not need other treatment, and is flame retardant powder which can be directly used for modified plastics.
The invention not only can realize the one-step direct synthesis of the melamine polyphosphate composite flame retardant product by a chemical method, but also has better performance than the traditional melamine polyphosphate flame retardant product because of the coating modification treatment, and compared with the prior art, the invention also has the advantages that:
(1) compared with the prior foreign literature reports, the method adopts a one-step method to directly synthesize the melamine polyphosphate, and directly utilizes the phosphoric acid aqueous solution to carry out reaction, so that the reaction process is green and environment-friendly, and the production cost is low.
(2) In the preparation process, the modified melamine polyphosphate composite flame retardant is obtained through thermal coating treatment of the silane coupling agent and the polyethylene, the lipophilicity of the melamine polyphosphate is improved, the dispersing capacity and compatibility of the melamine polyphosphate in a high polymer material are improved, the water-resistant composite flame retardant which meets the market demand and can be directly used is prepared, and the energy consumption of product production is reduced.
(3) The method directly synthesizes the coating modified melamine polyphosphate, and adopts the silane coupling agent and the polyethylene as coating materials for graded coating, so that the effect is better, the efficiency is higher, the flame retardant product is more uniformly mixed, the flame retardant efficiency of the product is improved, and the use cost of the flame retardant is reduced.
The preparation method of the modified melamine polyphosphate composite flame retardant introduced by the invention is a synthetic method with high efficiency, low cost and easy operation. The modified melamine polyphosphate composite flame retardant prepared by the method can directly obtain the flame retardant with good water resistance and good material compatibility without changing the conventional synthesis production condition, thereby reducing the cost and enhancing the comprehensive competitiveness of the flame retardant as the composite flame retardant.
A preparation method of modified melamine polyphosphate. In the kneading machine, melamine, phosphoric acid, a silane coupling agent and polyethylene are used as raw materials, melamine polyphosphate is synthesized through neutralization reaction and dehydration condensation reaction, and the modified melamine polyphosphate composite flame retardant is obtained through thermal coating treatment of the silane coupling agent and the polyethylene. The preparation method of the modified melamine polyphosphate composite flame retardant introduced by the invention is a synthetic method with high efficiency, low cost and easy operation. The modified melamine polyphosphate composite flame retardant prepared by the method can directly obtain the flame retardant with good water resistance and good material compatibility without changing the conventional synthesis production condition, thereby reducing the cost and enhancing the comprehensive competitiveness of the flame retardant as the composite flame retardant.
Drawings
FIG. 1 is a graph of the results of particle size testing of the product prepared in example 1;
FIG. 2 is a graph of the results of particle size testing of the product prepared in example 2;
FIG. 3 is a graph of the results of particle size testing of the product prepared in example 3.
Detailed Description
Example 1
1260g of melamine and 50% of phosphorus were added to a 5L vacuum kneader980g of aqueous acid solution. After 10 hours of reaction at the temperature of 60 ℃, starting vacuum, raising the temperature to 200 ℃ for dehydration condensation reaction for 5 hours, then reducing the temperature to 90 ℃, relieving the vacuum, adding 4.9g of silane coupling agent KH-550, continuing stirring for 1 hour, adding 4.9g of low-density polyethylene in a molten state, continuing mixing for 1 hour, reducing the temperature to room temperature, and discharging. 1.42 kg of modified melamine polyphosphate flame retardant is obtained, and the yield is 95%. The obtained melamine polyphosphate flame retardant was subjected to particle size testing by a laser particle sizer, the test results are shown in table 1, and the particle size D of the product was506.668 μm, D90At 17.371 μm, the particle size distribution of the melamine polyphosphate flame retardant is shown in FIG. 1:
TABLE 1
| D10 | 1.778μm | D25 | 4.093μm | D50 | 6.668μm | D75 | 10.879μm | D90 | 17.371μm |
Example 2
12.6kg of melamine and 16.3kg of a 60% phosphoric acid aqueous solution were charged into a 50L vacuum kneader. After 6 hours of reaction at the temperature of 80 ℃, starting vacuum, raising the temperature to 260 ℃ for dehydration condensation reaction for 4 hours, then reducing the temperature to 110 ℃, removing the vacuum, adding 0.29kg of Si-602 silane coupling agent, continuously stirring for 1.5 hours, adding 0.49kg of linear low density polyethylene in a melting state, continuously mixing for 3 hours, reducing the temperature to room temperature, and discharging. 17.3 kg of modified melamine polyphosphate flame retardant was obtained, the yield being 97%. The obtained melamine polyphosphate flame retardant is subjected to particle size test by using a laser particle size analyzer, the test result is shown in table 2, the particle size D50 of the product is 10.467 μm, the particle size D90 of the product is 22.511 μm, and the particle size distribution of the melamine polyphosphate flame retardant is shown in figure 2:
TABLE 2
| D10 | 3.657μm | D25 | 6.447μm | D50 | 10.467μm | D75 | 16.030μm | D90 | 22.511μm |
Example 3
126kg of melamine and 560kg of a 70% phosphoric acid aqueous solution were added to a 1000L vacuum kneader. After 5 hours of reaction at the temperature of 100 ℃, starting vacuum, raising the temperature to 300 ℃ for dehydration condensation reaction for 3 hours, then reducing the temperature to 130 ℃, relieving the vacuum, adding 68.4kg of A-151 silane coupling agent, continuing stirring for 2 hours, adding 136.8kg of high-density polyethylene in a molten state, continuing mixing for 2 hours, reducing the temperature to room temperature, and discharging. 665.8 kg of modified melamine polyphosphate flame retardant was obtained, the yield being 98%. The obtained melamine polyphosphate flame retardant is subjected to particle size test by using a laser particle size analyzer, the test result is shown in table 3, the particle size D50 of the product is 9.4735 μm, the particle size D90 of the product is 26.959 μm, and the particle size distribution of the melamine polyphosphate flame retardant is shown in fig. 3:
TABLE 3
| D10 | 2.741μm | D25 | 5.257μm | D50 | 9.473μm | D75 | 16.928μm | D90 | 26.959μm |
Claims (9)
1. A preparation method of modified melamine polyphosphate is characterized by comprising the following steps:
firstly, mixing melamine and phosphoric acid aqueous solution, and then reacting for 1-10h at the temperature of 60-100 ℃; the molar ratio of phosphoric acid to melamine is 0.5-4: 1;
secondly, vacuumizing the reaction system obtained in the first step, and raising the temperature to 200-300 ℃ for dehydration condensation reaction for 2-8 h;
step three, reducing the temperature of the reaction system obtained in the step two to 90-130 ℃, and then removing the vacuum;
step four, adding a silane coupling agent into the reaction system obtained in the step three, wherein the mass ratio of the silane coupling agent to the phosphoric acid in the step one is 1-20: 100, stirring for 1-2h, and then adding polyethylene, wherein the mass ratio of the polyethylene to the phosphoric acid is 1-40: 100, continuously mixing uniformly, and cooling to room temperature to obtain modified melamine polyphosphate;
in the first step, melamine and phosphoric acid are mixed in a vacuum kneader.
2. The method for preparing modified melamine polyphosphate according to claim 1, wherein the melamine polyphosphate comprises: the mass concentration of the phosphoric acid aqueous solution is not less than 50%.
3. The method for preparing modified melamine polyphosphate according to claim 1, wherein the melamine polyphosphate comprises: the silane coupling agent is vinyl silane, amino silane, epoxy silane or methacryloxy silane.
4. The method for preparing modified melamine polyphosphate according to claim 3, wherein: the silane coupling agent has the brand number of KH-540, KH-550, KH-560, KH-570, KH-590, A-151, A-171, A-172 or Si-563.
5. The method for preparing modified melamine polyphosphate according to claim 1, wherein the melamine polyphosphate comprises: the polyethylene is high-density polyethylene.
6. The method for preparing modified melamine polyphosphate according to claim 1, wherein the melamine polyphosphate comprises: the polyethylene is low-density polyethylene.
7. The method for preparing modified melamine polyphosphate according to claim 1, wherein the melamine polyphosphate comprises: the polyethylene is linear low density polyethylene.
8. The method for preparing modified melamine polyphosphate according to claim 1, wherein the melamine polyphosphate comprises: in the fourth step, the polyethylene added is molten polyethylene.
9. The method for preparing modified melamine polyphosphate according to claim 1, wherein the melamine polyphosphate comprises: and in the fourth step, after continuously and uniformly mixing for 1 hour, cooling to room temperature.
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| CN111961254A (en) * | 2020-08-27 | 2020-11-20 | 湖北航天化学技术研究所 | Preparation method of modified aluminum hypophosphite flame retardant |
| CN113264890A (en) * | 2020-11-30 | 2021-08-17 | 上海普利特复合材料股份有限公司 | Synthesis and application of stain-resistant flame retardant |
| CN113150383B (en) * | 2021-04-02 | 2022-10-28 | 奇瑞新能源汽车股份有限公司 | Polycyanamide polyphosphate and preparation method thereof |
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| US9822239B2 (en) * | 2014-09-24 | 2017-11-21 | Shanghai Huihai Chemical Technology Co., Ltd. | Low-corrosion fire-resistant thermoplastic resin composition |
| CN104693483B (en) * | 2015-03-02 | 2017-04-19 | 镇江森华阻燃工程科技有限公司 | Preparation method of high-dispersibility melamine pyrophosphate fire retardant |
| CN105968060B (en) * | 2016-05-09 | 2019-02-26 | 东华大学 | A kind of preparation method of the melamine polyphosphate of Narrow Molecular Weight Distribution |
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