CN117247553A - Triazine polyphosphate flame retardant, and preparation method and application thereof - Google Patents
Triazine polyphosphate flame retardant, and preparation method and application thereof Download PDFInfo
- Publication number
- CN117247553A CN117247553A CN202311315870.3A CN202311315870A CN117247553A CN 117247553 A CN117247553 A CN 117247553A CN 202311315870 A CN202311315870 A CN 202311315870A CN 117247553 A CN117247553 A CN 117247553A
- Authority
- CN
- China
- Prior art keywords
- triazine
- flame retardant
- polyphosphate
- polyphosphate flame
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 108
- 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 98
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229920000388 Polyphosphate Polymers 0.000 title claims abstract description 57
- 239000001205 polyphosphate Substances 0.000 title claims abstract description 57
- 235000011176 polyphosphates Nutrition 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 44
- -1 triazine compound Chemical class 0.000 claims abstract description 37
- 239000000178 monomer Substances 0.000 claims abstract description 32
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- KVHMUDRYVFJMEQ-UHFFFAOYSA-N phosphoric acid;triazine Chemical compound OP(O)(O)=O.C1=CN=NN=C1 KVHMUDRYVFJMEQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 12
- 229920000098 polyolefin Polymers 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 238000005086 pumping Methods 0.000 claims description 10
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 6
- OHRVBDRGLIWLPA-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] dihydrogen phosphate Chemical compound OCC(CO)(CO)COP(O)(O)=O OHRVBDRGLIWLPA-UHFFFAOYSA-N 0.000 claims description 5
- 125000002723 alicyclic group Chemical group 0.000 claims description 4
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- TVUMQLGIWIIUBP-UHFFFAOYSA-N 1,1-bis(trimethylsilyl)hydrazine Chemical compound C[Si](C)(C)N(N)[Si](C)(C)C TVUMQLGIWIIUBP-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000018044 dehydration Effects 0.000 abstract description 20
- 238000006297 dehydration reaction Methods 0.000 abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052799 carbon Inorganic materials 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 10
- 239000002904 solvent Substances 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 150000003918 triazines Chemical class 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 description 37
- 238000001816 cooling Methods 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 17
- 125000003277 amino group Chemical group 0.000 description 13
- 229940125904 compound 1 Drugs 0.000 description 12
- 229940125782 compound 2 Drugs 0.000 description 11
- 229940126214 compound 3 Drugs 0.000 description 11
- 238000002411 thermogravimetry Methods 0.000 description 10
- 229910019142 PO4 Inorganic materials 0.000 description 9
- 238000007599 discharging Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 239000010452 phosphate Substances 0.000 description 9
- 238000007873 sieving Methods 0.000 description 9
- 238000000967 suction filtration Methods 0.000 description 9
- 229910004856 P—O—P Inorganic materials 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 230000004580 weight loss Effects 0.000 description 6
- 239000001177 diphosphate Substances 0.000 description 5
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 5
- 235000011180 diphosphates Nutrition 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005452 bending Methods 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 2
- UMVBXBACMIOFDO-UHFFFAOYSA-N [N].[Si] Chemical compound [N].[Si] UMVBXBACMIOFDO-UHFFFAOYSA-N 0.000 description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical group C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- MWFNQNPDUTULBC-UHFFFAOYSA-N phosphono dihydrogen phosphate;piperazine Chemical compound C1CNCCN1.OP(O)(=O)OP(O)(O)=O MWFNQNPDUTULBC-UHFFFAOYSA-N 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
- C08G79/04—Phosphorus linked to oxygen or to oxygen and carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The application is suitable for the technical field of flame-retardant materials, and provides a triazine polyphosphate flame retardant, a preparation method and application thereof, compared with the existing triazine flame retardant, the triazine polyphosphate flame retardant contains an acid source, a carbon source and an air source, has good thermal stability and high carbon residue rate, and has good flame-retardant performance on polyolefin; in addition, pure water is used as a solvent in the synthesis process, so that the problems of toxic and harmful solvents and solvent recovery in the existing triazine flame retardant synthesis technology are avoided; a series of novel phosphoric acid triazine salt monomers are synthesized by designing various triazine compounds and regulating the proportion of the triazine compounds to phosphoric acid, and then the novel triazine compound polyphosphate-based flame retardant is prepared by high-temperature dehydration, so that a novel thought is provided for the synthesis of novel triazine compound polyphosphate flame retardants.
Description
Technical Field
The application belongs to the technical field of flame retardant materials, and particularly relates to a triazine polyphosphate flame retardant, and a preparation method and application thereof.
Background
At present, people pay more attention to physical health and environmental protection, and the progress of the development of the flame retardant to harmless and green is accelerated. As a novel flame retardant which is clean, efficient and environment-friendly, the halogen-free intumescent flame retardant is considered as one of effective ways for realizing harmless and environment-friendly flame retardant, and is widely applied to flame retardant modification of polymers in recent years. Intumescent flame retardants generally consist of three parts, an acid source, a carbon source, and an air source. Since the carbon forming effect of the carbon forming agent in the components plays a crucial role in the flame retardant performance of the intumescent flame retardant, the development of the efficient carbon forming agent is also an important direction of the research of the current intumescent flame retardant. The traditional expansion flame retardant char forming agent is mainly pentaerythritol, but the traditional expansion flame retardant char forming agent is easy to migrate, has large addition amount, low char forming rate and the like, so that the traditional expansion flame retardant char forming agent is gradually replaced by some novel char forming agents. As a compound rich in tertiary nitrogen structure, the triazine compound has the advantages of high carbon forming efficiency, low water solubility and good thermal stability, and has bright prospect in the application aspect of intumescent flame retardants.
As research is advanced, some triazine compounds having a specific structure have been synthesized and reported. The introduction of P in triazine compounds to increase the P-N synergistic flame retardant effect is a hot spot for developing novel triazine flame retardants currently. There are two main ways reported to introduce the P element in triazine compounds. Firstly, cyanuric chloride and a phosphorus-containing compound are subjected to organic reaction to form the P-containing triazine flame retardant, and the prepared P-containing triazine flame retardant has good flame retardant performance, but a large amount of organic solvent is required in the synthesis or/and purification process, so that the recovery of the solvent is difficult and the cost is increased. Secondly, the phosphate radical and the amino group on the triazine compound are combined to form a monomer, and then the monomer is dehydrated at high temperature to obtain the polyphosphoric triazine salt flame retardant. The flame retardant synthesized by the method mainly comprises melamine polyphosphate and melamine polyphosphate. However, these two flame retardants need to be used in combination with other flame retardants (such as piperazine pyrophosphate) to achieve good flame retardant effect, and have certain limitations in application.
Therefore, the existing technology for synthesizing the triazine flame retardant with phosphorus has the problems of large organic solvent consumption, difficult solvent recovery and limited flame retardant effect.
Disclosure of Invention
The embodiment of the application aims to provide a triazine polyphosphate flame retardant, and aims to solve the problems of large organic solvent consumption, difficult solvent recovery and limited flame retardant effect in the existing phosphorus-containing triazine flame retardant synthesis technology.
The embodiment of the application is realized in such a way, and the triazine polyphosphate flame retardant is characterized in that the structural formula of the triazine polyphosphate flame retardant is shown in any one of the following I to VI:
wherein the R is 1 、R 2 Independently selected from one of aromatic amino, nitrogen heterocyclic group amino, alicyclic amino, silicon nitrogen compound amino, enamine compound amino and pentaerythritol phosphate;
the structural formula of the X isor-NH (CH) 2 ) m NH-，2≤m≤6。
Another object of the embodiments of the present application is to provide a method for preparing the triazine polyphosphate flame retardant, including:
dropwise adding phosphoric acid into a triazine compound and pure water system, heating to 70-100 ℃ after dropwise adding, and stirring for reacting for 1-5 hours to obtain a triazine phosphate monomer;
and (3) vacuumizing the triazine phosphate monomer, heating to 220-350 ℃ and dehydrating for 0.5-5 hours to obtain the triazine phosphate monomer.
Another object of the embodiments of the present application is the use of the triazine polyphosphate flame retardant in flame retardant modification of polymers, wherein the addition amount of the triazine polyphosphate flame retardant is 18-30 wt% of polyolefin.
Compared with the existing triazine flame retardant, the triazine polyphosphate flame retardant provided by the embodiment of the application contains an acid source, a carbon source and an air source, can be used singly or in combination with other flame retardants, has good thermal stability and high carbon residue rate, and has great application potential in flame retardant modification of various polymers.
According to the preparation method of the triazine polyphosphate flame retardant, pure water is used as a solvent in the synthesis process, so that the problems of using toxic and harmful solvents and recovering the solvents in the existing synthesis technology of the triazine flame retardant are avoided; in addition, a series of novel phosphoric acid triazine salt monomers are synthesized by designing various triazine compounds and regulating the proportion of the triazine compounds to phosphoric acid, and then the novel triazine compound polyphosphate-based flame retardant is prepared through high-temperature dehydration, so that a novel thought is provided for the synthesis of novel triazine compound polyphosphate flame retardants.
Drawings
Fig. 1 is a TGA profile of a triazine compound 1 polyphosphate-based flame retardant provided in example 1 of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application will be further described in detail with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the present application.
The embodiment of the application provides a triazine polyphosphate flame retardant, and the structural formula of the triazine polyphosphate flame retardant is shown in any one of the following I-VI:
wherein n in the general structure only represents that the obtained product polyphosphate has a certain degree of polymerization. The R is 1 、R 2 Can be independently aromatic amino groups such as amino groups, anilino groups and the like, azacyclic groups such as amino groups such as morpholine, piperidine and the like, alicyclic amine groups such as cyclohexylamino and the like, -NHC y H 2y An amine group of a silicon nitrogen compound such as an OH (1-8) amine group or a hexamethyldisilazane group, an enamine compound such as an acrylamide group, or a caged pentaerythritol phosphate group;
the structural formula of the X isor-NH (CH) 2 ) m NH-, wherein m is more than or equal to 2 and less than or equal to 6.
The embodiment of the application also provides a preparation method of the triazine polyphosphate flame retardant, which comprises the following steps:
step S1: and (3) dropwise adding phosphoric acid into a triazine compound and pure water system, heating to 70-100 ℃ after dropwise adding, and stirring for reacting for 1-5 hours to obtain a triazine phosphate monomer.
Optionally, adding pure water and triazine compound into a 5L four-neck flask, starting stirring, then slowly dripping phosphoric acid, heating to 70-100 ℃ after the adding, and stirring for reacting for 1-5 hours. Cooling after the reaction is finished, carrying out suction filtration, drying and crushing to obtain the triazine phosphate monomer.
Optionally, the phosphoric acid is 85% phosphoric acid.
In the embodiment of the application, the pure water amount is 3-10 times of the total feeding amount of the phosphoric acid and the triazine compound.
In the embodiment of the present application, the structural formula of the triazine compound described in step S1 is shown as (1) or (2) below:
the structural formula of the triazine phosphate monomer in the step S1 is shown in any one of the following (a) to (f):
wherein R in the above (1) to (2) and (a) to (f) 1 、R 2 Can be independently aromatic amino groups such as amino groups, anilino groups and the like, azacyclic groups such as amino groups such as morpholine, piperidine and the like, alicyclic amine groups such as cyclohexylamino and the like, -NHC y H 2y An amine group of a silicon nitrogen compound such as an OH (1-8) amine group or a hexamethyldisilazane group, an enamine compound such as an acrylamide group, or a caged pentaerythritol phosphate group; the structural formula of X isor-NH (CH) 2 ) m NH-, wherein m is more than or equal to 2 and less than or equal to 6.
In the embodiment of the application, the mass ratio of the phosphoric acid to the triazine compound in the step S1 is 1-4:1.
In the embodiment of the present application, the phosphoric acid dropwise adding time described in step S1 is 0.5 to 3 hours.
Step S2: and vacuumizing the triazine phosphate monomer, heating to 220-350 ℃ and dehydrating for 0.5-5 hours to obtain the triazine polyphosphate flame retardant.
Optionally, adding the triazine phosphate monomer into a reactor capable of being vacuumized, starting vacuumizing, then heating to 220-350 ℃ for high-temperature dehydration, reacting for 0.5-5 hours, cooling to room temperature after dehydration, discharging, crushing, and sieving to obtain the novel flame retardant based on the triazine compound polyphosphate. The structural formula of the novel flame retardant based on the triazine compound polyphosphate is shown as I-VI.
The vacuum-pumping reactor can be a double-screw extruder, a double-cone dryer, a kneader dryer, a blade dryer, a vertical stirring dryer, a rotary kiln dryer and the like.
Wherein, the vacuum degree of the vacuumizing treatment is required to be between-0.1 MPa and-0.05 MPa.
In the embodiment of the application, the triazine polyphosphate flame retardant prepared in the step S2 can be used singly or can be used as an intumescent flame retardant after being compounded with other flame retardants.
In addition, the triazine polyphosphate flame retardant provided by the embodiment of the application can be applied to polymer flame retardant modification, for example, a proper amount of triazine polyphosphate flame retardant is added into a polymer matrix for compounding to obtain a flame retardant polymer material, so that the thermal stability and flame retardant property of the polymer are improved. The addition amount of the triazine polyphosphate flame retardant is 18-30 wt% of the polyolefin.
Examples of certain embodiments of the present application are given below, which are not intended to limit the scope of the present application.
In addition, the materials and the processing means used in the present application are common materials and familiar technical means in the art unless otherwise specified. The numerical values set forth in the following examples are reported as precisely as possible, but those of ordinary skill in the art will understand that, due to unavoidable measurement errors and experimental operating problems, each numerical value should be understood as a divisor rather than an absolute accurate numerical value.
Example 1: a process for the preparation of a triazine compound 1 polyphosphate based flame retardant comprising the steps of:
2000mL of water, 278.28g of triazine compound 1 was added to a 5L four-necked flask, stirring was started, and then 115.3g of phosphoric acid (85% by weight) was slowly dropped thereto, and after the addition was completed, the temperature was raised to 98℃and the reaction was stirred for 4 hours. Cooling after the reaction is finished, carrying out suction filtration, drying and crushing to obtain the triazine compound 1 phosphate monomer (yield 96.2%). The triazine compound 1 has the structure shown below:
adding a triazine compound 1 phosphate monomer into a kneader, starting vacuum pumping, then heating to 290 ℃ for high-temperature dehydration for 1.5 hours, cooling to room temperature after dehydration, discharging, crushing, and sieving to obtain the triazine compound 1 polyphosphate-based flame retardant, wherein the structural formula is shown as follows:
the thermogravimetric analysis (TGA) test results are shown in figure 1. TGA 1% weight loss temperature was 296.2 ℃and 600℃residual carbon rate was 49.95%. Infrared spectral structure information: 1646cm -1 And 1585cm -1 For C=N, C-N telescopic vibration absorption peak on triazine ring, 1270cm -1 Expansion and contraction vibration absorption peak of P=O, 1072cm -1 、977cm -1 The bending vibration absorption peak of P-O-P was 3343cm -1 And 3177cm -1 Is N-H and NH 3 + Is a stretching vibration absorption peak of (a).
Example 2: a process for the preparation of a triazine compound 1 polydiphosphate based flame retardant comprising the steps of:
3000mL of water, 278.28g of triazine compound 1 was added to a 5L four-necked flask, stirring was started, and then 330.6g of phosphoric acid (85% by weight) was slowly dropped thereto, and after the addition was completed, the temperature was raised to 98℃and the reaction was stirred for 6 hours. Cooling after the reaction is finished, carrying out suction filtration, drying and crushing to obtain a triazine compound 1 diphosphate monomer (the yield is 94.7%);
adding a triazine compound 1 diphosphate monomer into a kneader, starting vacuum pumping, heating to 280 ℃ for high-temperature dehydration for 2.5 hours, cooling to room temperature after dehydration, discharging, crushing, and sieving to obtain the triazine compound 1 polyphosphate-based flame retardant, wherein the structural formula is shown as follows:
TGA 1% weight loss temperature 314.6 ℃,600 ℃ carbon residue 60.45%); infrared structural information: 1666cm -1 And 1536cm -1 For c=n, C-N telescopic vibration absorption peak on triazine ring, 1256cm -1 For P=O stretching vibration absorption peak, 1067cm -1 、971cm -1 Is the flexural vibration absorption peak of P-O-P, 3348cm -1 And 3192cm -1 Is N-H and NH 3 + Is a stretching vibration absorption peak of (a).
Example 3: a process for the preparation of a triazine compound 2 polyphosphate based flame retardant comprising the steps of:
2000mL of water, 320.19g of triazine compound 2 was added to a 5L four-necked flask, stirring was started, and then 115.3g of phosphoric acid (85% by weight) was slowly dropped thereto, and after the addition was completed, the temperature was raised to 98℃and the reaction was stirred for 4 hours. Cooling after the reaction is finished, carrying out suction filtration, drying and crushing to obtain the triazine compound 2 phosphate monomer (yield 98.4%). The triazine compound 2 has the structure shown below:
adding a triazine compound 2 phosphate monomer into a kneader, starting vacuum pumping, then heating to 260 ℃ for high-temperature dehydration for 2.5 hours, cooling to room temperature after dehydration, discharging, crushing, and sieving to obtain the triazine compound 2 polyphosphate-based flame retardant, wherein the structural formula is shown as follows:
TGA 1% weight loss temperature was 269.7 ℃and 600℃residual carbon rate was 40.74%. Infrared spectral structure information: infrared structural information: 1638cm -1 And 1538cm -1 For C=N, C-N telescopic vibration absorption peak on triazine ring, 2932cm -1 ，2855cm -1 Is C-H telescopic vibration absorption peak on hexamethylenediamine, 1242cm -1 For P=O stretching vibration absorption peak, 1084cm -1 、966cm -1 Is the flexural vibration absorption peak of P-O-P, 3328cm -1 And 3174cm -1 Is N-H and NH 3 + Is a stretching vibration absorption peak of (a).
Example 4: a process for the preparation of a triazine compound 2 polydiphosphate based flame retardant comprising the steps of:
3000mL of water, 320.19g of triazine compound 2 was added to a 5L four-necked flask, stirring was started, and then 330.6g of phosphoric acid (85% by weight) was slowly dropped thereto, and after the addition was completed, the temperature was raised to 98℃and the reaction was stirred for 3 hours. Cooling after the reaction is finished, carrying out suction filtration, drying and crushing to obtain a triazine compound 2 diphosphate monomer (yield 92.9%);
adding a triazine compound 2 polyphosphate monomer into a kneader, starting vacuum pumping, heating to 250 ℃ for high-temperature dehydration for 3.5 hours, cooling to room temperature after dehydration, discharging, crushing and sieving to obtain the triazine compound 2 polyphosphate-based flame retardant, wherein the structural formula is shown as follows:
TGA 1% weight loss temperature was 261.0 ℃and 600℃residual carbon rate was 46.77%. Infrared spectral structure information: 1636cm -1 And 1538cm -1 For C=N, C-N telescopic vibration absorption peak on triazine ring, 2857cm -1 And 2924cm -1 Is C-H telescopic vibration absorption peak on hexamethylenediamine of 1250cm -1 1079cm for P=O stretching vibration absorption peak -1 、972cm -1 Is a bending vibration absorption peak of P-O-P, 3401cm -1 And 3210cm -1 Is N-H and NH 3 + Is a stretching vibration absorption peak of (a).
Example 5: a process for the preparation of a triazine compound 3 polyphosphate based flame retardant comprising the steps of:
1700mL of water, 194.24g of triazine compound 3 was added to a 5L four-necked flask, stirring was started, and then 115.3 (85% by weight) of phosphoric acid was slowly dropped thereto, and after the addition was completed, the temperature was raised to 75℃and the reaction was stirred for 4 hours. Cooling after the reaction is finished, carrying out suction filtration, drying and crushing to obtain the triazine compound 3 phosphate monomer (the yield is 93.4%). The triazine compound 3 has the structure shown below:
adding a triazine compound 3 phosphate monomer into a kneader, starting vacuum pumping, then heating to 280 ℃ for high-temperature dehydration for 2.5 hours, cooling to room temperature after dehydration, discharging, crushing, and sieving to obtain the triazine compound 3 polyphosphate-based flame retardant, wherein the structural formula is shown as follows:
TGA 1% weight loss temperature is: 266.9 ℃,600 ℃ carbon residue rate of 53.13 percent); infrared structural information: 1637cm -1 And 1534cm -1 For C=N, C-N telescopic vibration absorption peak on triazine ring, 2866cm -1 And 2906cm -1 Is C-H telescopic vibration absorption peak on piperidine ring, 1254cm -1 For P=O stretching vibration absorption peak, 1061cm -1 、1018cm -1 、899cm -1 Is the flexural vibration absorption peak of P-O-P, 3341cm -1 And 3157cm -1 Is N-H and NH 3 + Is a stretching vibration absorption peak of (a).
Example 6: a process for the preparation of a triazine compound 3 polydiphosphate based flame retardant comprising the steps of:
3000mL of water, 194.24g of triazine compound 3 was added to a 5L four-necked flask, stirring was started, and then 330.6g of phosphoric acid (85% by weight) was slowly dropped, and after the addition was completed, the temperature was raised to 70℃and the reaction was stirred for 6 hours. Cooling after the reaction is finished, carrying out suction filtration, drying and crushing to obtain a triazine compound 3 diphosphate monomer (the yield is 89.8%);
adding a triazine compound 3 polyphosphate monomer into a kneader, starting vacuum pumping, heating to 250 ℃ for high-temperature dehydration for 2.5 hours, cooling to room temperature after dehydration, discharging, crushing and sieving to obtain the triazine compound 3 polyphosphate-based flame retardant, wherein the structural formula is shown as follows:
TGA:1% decomposition temperature 268.9 ℃,600 ℃ carbon residue 46.83%); infrared structural information: 1630cm -1 And 1538cm -1 For C=N, C-N telescopic vibration absorption peak on triazine ring, 1281cm -1 For P=O stretching vibration absorption peak, 1049cm -1 、1002cm -1 、959cm -1 The bending vibration absorption peak of P-O-P was 3139cm -1 NH 3 + Is a stretching vibration absorption peak of (a).
Example 7: a process for the preparation of a triazine compound 4 polyphosphate based flame retardant comprising the steps of:
2000mL of water, 196.21g of triazine compound 4 was added to a 5L four-necked flask, stirring was started, 115.3g (85% by weight of phosphoric acid) was slowly dropped, and after the addition was completed, the temperature was raised to 90℃and the reaction was stirred for 3 hours. Cooling after the reaction is finished, carrying out suction filtration, drying and crushing to obtain the triazine compound 4 phosphate monomer (yield 88.4%). The triazine compound 4 has the structure shown below:
adding a triazine compound 4 phosphate monomer into a kneader, starting vacuum pumping, then heating to 260 ℃ for high-temperature dehydration for 1.5 hours, cooling to room temperature after dehydration, discharging, crushing, and sieving to obtain the triazine compound 4 polyphosphate-based flame retardant, wherein the structural formula is shown as follows:
TGA 1% weight loss temperature is 253.3 ℃,600 ℃ residual carbon rate is 48.16%; infrared structural information: 1642cm -1 And 1529cm -1 C=N, C-N telescopic vibration absorption peak on triazine ring, 1014cm -1 Is a flexible vibration absorption peak on morpholine ring C-O-C, 1262cm -1 Peak of vibration absorption, 1057c, is p=o telescopicm -1 、1012cm -1 、876cm -1 Is the flexural vibration absorption peak of P-O-P, 3338cm -1 And 3201cm -1 Is N-H and NH 3 + Is a stretching vibration absorption peak of (a).
Example 8: a process for the preparation of a triazine compound 4 polydiphosphate based flame retardant comprising the steps of:
3000mL of water, 196.21g of triazine compound 4 was added to a 5L four-necked flask, stirring was started, and then 330.6g of phosphoric acid (85% by weight) was slowly dropped, and after the addition was completed, the temperature was raised to 90℃and the reaction was stirred for 3 hours. Cooling after the reaction is finished, carrying out suction filtration, drying and crushing to obtain a triazine compound 4 diphosphate monomer (yield 87%);
adding a triazine compound 4 polyphosphate monomer into a kneader, starting vacuum pumping, heating to 250 ℃ for high-temperature dehydration for 2.5 hours, cooling to room temperature after dehydration, discharging, crushing, and sieving to obtain the triazine compound 4 polyphosphate-based flame retardant, wherein the structural formula is shown as follows:
TGA is 1% decomposition temperature 285.1 ℃,600 ℃ residual carbon rate is 49.65%; infrared structural information: 1645cm -1 And 1524cm -1 For C=N, C-N telescopic vibration absorption peak on triazine ring, 1010cm -1 Is a telescopic vibration absorption peak on morpholine ring C-O-C, 1258cm -1 For P=O stretching vibration absorption peak, 1052cm -1 、1019cm -1 、889cm -1 Bending vibration absorption peak of P-O-P, 3201cm -1 Is NH 3 + Is a stretching vibration absorption peak of (a).
Preparation of PP spline and flame retardant data: adding the flame retardant and the auxiliary agent in each embodiment into a mixer according to the amount listed in the following table 1, setting the rotating speed to 1000 revolutions per minute, stirring for 3 minutes, extruding the mixed materials by using a homodromous double-screw extruder (Nanjiao) with the length-diameter ratio of 48:1 and the screw diameter of 36 millimeters, wherein the temperature of the extruder is set to 170-195 ℃, the rotating speed is 200 revolutions per minute, the vacuum degree is-0.8 MPa, and the mixed materials are subjected to water cooling at 25+/-5 ℃ and granulating; the pellets were put into a blow dryer, set at a temperature of 85℃and dried for 3 hours to prepare flame retardant PP materials containing examples 1 to 8, respectively. Setting the injection molding temperature to be 180-195 ℃, and then injecting each particle into a standard spline for UL 94 flame retardance test.
TABLE 1 raw materials composition table (parts by mass) of flame retardant PP material
The flame retardant PP materials in the table are prepared into samples (samples 1 to 8 in sequence), and the flame retardant performance test and the precipitation performance test are carried out, wherein the test results are shown in the following table 2, and the prepared flame retardant has good flame retardant performance on PP.
Table 2 flame retardant property test results of flame retardant PP materials
The foregoing examples are provided merely for the purpose of describing particular embodiments of the present application and are not intended to limit the scope of the present application thereto. It should be noted that it would be apparent to those skilled in the art that various modifications and improvements could be made without departing from the spirit of the present application, which would be within the scope of the present application. Accordingly, the scope of protection of the present application is to be determined by the claims appended hereto.
The foregoing description of the preferred embodiments of the present application is not intended to be limiting, but is intended to cover any and all modifications, equivalents, and alternatives falling within the spirit and principles of the present application.
Claims (10)
1. The triazine polyphosphate flame retardant is characterized by having a structural formula shown in any one of the following I to VI:
wherein the R is 1 、R 2 Independently selected from one of aromatic amino, nitrogen heterocyclic group amino, alicyclic amino, silicon nitrogen compound amino, enamine compound amino and pentaerythritol phosphate;
the structural formula of the X isor-NH (CH) 2 ) m NH-，2≤m≤6。
2. The triazine polyphosphate flame retardant of claim 1, wherein R 1 、R 2 Independently selected from amino, anilino, morpholinium, piperidine, cyclohexylamino, -NHC y H 2y One of OH amino, hexamethyldisilazane, acrylamide and caged pentaerythritol phosphate is more than or equal to 1 and less than or equal to 8.
3. A process for the preparation of the triazine polyphosphate flame retardant of claim 1 or 2, comprising:
dropwise adding phosphoric acid into a triazine compound and pure water system, heating to 70-100 ℃ after dropwise adding, and stirring for reacting for 1-5 hours to obtain a triazine phosphate monomer;
and (3) vacuumizing the triazine phosphate monomer, heating to 220-350 ℃ and dehydrating for 0.5-5 hours to obtain the triazine phosphate monomer.
4. The method for preparing a triazine polyphosphate flame retardant of claim 3, wherein the pure water is used in an amount 3 to 10 times the total amount of phosphoric acid and triazine compound.
5. A process for the preparation of triazine polyphosphate flame retardants according to claim 3, wherein the mass ratio of phosphoric acid to triazine compound is 1-4:1.
6. The method for producing a triazine polyphosphate flame retardant according to claim 3, wherein the dropping time of phosphoric acid is 0.5 to 3 hours.
7. The method for preparing a triazine polyphosphate flame retardant according to claim 3, wherein the vacuum degree is-0.1 to-0.05 MPa in the vacuum-pumping treatment.
8. The method for preparing a triazine polyphosphate flame retardant according to claim 3, wherein the structural formula of the triazine compound is as follows (1) or (2):
9. the method for preparing a triazine polyphosphate flame retardant according to claim 3, wherein the structural formula of the triazine phosphate monomer is shown in any one of the following (a) to (f):
10. use of the triazine polyphosphate flame retardant according to claim 1 or 2 in flame retardant modification of polyolefin, characterized in that the addition amount of the triazine polyphosphate flame retardant is 18-30% by weight of polyolefin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311315870.3A CN117247553A (en) | 2023-10-10 | 2023-10-10 | Triazine polyphosphate flame retardant, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311315870.3A CN117247553A (en) | 2023-10-10 | 2023-10-10 | Triazine polyphosphate flame retardant, and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117247553A true CN117247553A (en) | 2023-12-19 |
Family
ID=89129168
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311315870.3A Pending CN117247553A (en) | 2023-10-10 | 2023-10-10 | Triazine polyphosphate flame retardant, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117247553A (en) |
-
2023
- 2023-10-10 CN CN202311315870.3A patent/CN117247553A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107417912B (en) | Phosphorus-nitrogen-silicon intumescent flame retardant containing triazine ring and cage structure and synthesis method thereof | |
| TWI585099B (en) | A cyclic triphosphazene halogen-free flame retardant with an imide structure, preparation method and use thereof | |
| CN101362819B (en) | Triazines cross-linking compounds, preparation method and application thereof | |
| CN102675895A (en) | Flame-retardant composite material with DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) modified nano mesoporous molecular sieve | |
| CN105669970B (en) | Polyamide-based expandable flame retardant carbon forming agent and its preparation method and application of the main chain containing piperazine structure | |
| CN111662332B (en) | Organophosphorus flame retardant with active amino groups, and preparation method and application thereof | |
| CN114015051B (en) | Preparation method and application of DOPO-POSS flame retardant | |
| CN111548479A (en) | Phosphine-modified triazole flame-retardant co-curing agent for epoxy resin and preparation method thereof | |
| CN103044708A (en) | High-efficiency N/P flame retardant, as well as preparation method and application thereof | |
| CN106397778A (en) | Method for increasing yield and polymerization degree of polymeric phosphorus-nitrogen intumescent flame retardant | |
| CN109021287A (en) | A kind of phosphorus nitrogen sulfur type fire retardant and its application in the epoxy | |
| CN110563944B (en) | Polyphosphazene covalent triazine polymer and preparation method and application thereof | |
| CN111040248A (en) | Preparation method of Melamine Cyanurate (MCA) flame retardant and application of flame retardant in PA6 | |
| CN113372616A (en) | Triazine ring-containing intumescent flame retardant and preparation method thereof | |
| CN102875816B (en) | Organosilicone modified halogen-free intumescent flame retardant and preparation method thereof | |
| CN117247553A (en) | Triazine polyphosphate flame retardant, and preparation method and application thereof | |
| Tian et al. | Effect of char-forming agents rich in tertiary carbon on flame retardant properties of polypropylene | |
| CN110922637B (en) | DOPO derivative flame-retardant photo-thermal stabilizer and preparation method and application thereof | |
| CN106892943B (en) | A kind of compound in triazine class, preparation method and applications | |
| CN115340574A (en) | Reactive flame retardant, flame-retardant epoxy resin, and preparation method and application thereof | |
| CN113651854B (en) | Phosphazene compound and preparation method and application thereof | |
| CN110938235B (en) | Triazine structure-containing DOPO amino derivative flame retardant, and preparation method and application thereof | |
| CN111362981B (en) | Phosphonate ammonium salt flame retardant and synthesis method thereof | |
| CN102757563A (en) | Intumescent polymer phosphorus nitrogen halogen-free flame retardant and preparation method thereof | |
| CN113402712A (en) | Phosphorus-containing ladder-shaped polysiloxane and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |