CN111116989B - Reactive flame retardant and preparation method and application thereof - Google Patents
Reactive flame retardant and preparation method and application thereof Download PDFInfo
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- CN111116989B CN111116989B CN201911353327.6A CN201911353327A CN111116989B CN 111116989 B CN111116989 B CN 111116989B CN 201911353327 A CN201911353327 A CN 201911353327A CN 111116989 B CN111116989 B CN 111116989B
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 83
- 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 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 22
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 12
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000008096 xylene Substances 0.000 claims abstract description 10
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
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- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 6
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
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- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 abstract description 15
- 239000011159 matrix material Substances 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 231100000053 low toxicity Toxicity 0.000 abstract description 5
- GWLKCPXYBLCEKC-UHFFFAOYSA-N 1,2-dichloro-3-methylbenzene Chemical compound CC1=CC=CC(Cl)=C1Cl GWLKCPXYBLCEKC-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 description 19
- 238000012360 testing method Methods 0.000 description 17
- 229910052736 halogen Inorganic materials 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 150000002367 halogens Chemical class 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 238000001746 injection moulding Methods 0.000 description 8
- 238000011160 research Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- BHTRKEVKTKCXOH-UHFFFAOYSA-N Taurochenodesoxycholsaeure Natural products OC1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(=O)NCCS(O)(=O)=O)C)C1(C)CC2 BHTRKEVKTKCXOH-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- AWDRATDZQPNJFN-VAYUFCLWSA-N taurodeoxycholic acid Chemical compound C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(=O)NCCS(O)(=O)=O)C)[C@@]2(C)[C@@H](O)C1 AWDRATDZQPNJFN-VAYUFCLWSA-N 0.000 description 4
- 229950005578 tidiacic Drugs 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- JXBAVRIYDKLCOE-UHFFFAOYSA-N [C].[P] Chemical group [C].[P] JXBAVRIYDKLCOE-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
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- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
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- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
-
- 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4025—Esters of poly(thio)phosphonic acids
-
- 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
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- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention disclosesA reactive flame retardant, a preparation method and an application thereof, wherein the structural formula of the reactive flame retardant is shown as the following formula (I); the preparation method comprises the following steps: mixing methyl dimethyl phosphate, terephthalaldehyde and a catalyst with a solvent, reacting in nitrogen or inert atmosphere, and performing post-treatment to obtain the reactive flame retardant; the catalyst is at least one selected from xylene, 2, 3-dichlorotoluene and trimethylbenzene; the solvent is selected from tetrahydrofuran and/or acetonitrile. The preparation method disclosed by the invention is simple, mild in condition, easy to control and high in product purity, and the prepared reactive flame retardant has the advantages of novel structure, high flame retardant efficiency, environmental friendliness and low toxicity; especially has excellent flame retardant property in an epoxy resin matrix.
Description
Technical Field
The invention belongs to the technical field of flame retardants, and particularly relates to a reactive flame retardant and a preparation method and application thereof.
Background
The epoxy resin is a thermosetting synthetic resin with excellent performance, is colorless and semitransparent thermosetting light general plastic, has extremely excellent mechanical and chemical properties, and is widely developed and applied in various fields such as adhesives, coatings, electronic and electrical materials, engineering plastics, composite materials and the like. However, the largest drawback in the application of epoxy resins is flammability, which is a problem of most high molecular materials. Due to flammability, the application range of epoxy resins is greatly limited. Therefore, the research on the flame retardant property of the epoxy resin is of great significance for expanding the application of the epoxy resin in various fields.
In recent years, the most popular problem in the flame retardant academia is the environmental pollution caused by halogen-containing materials, and a suitable novel flame retardant is sought to replace the halogen-containing flame retardant. With the research and analysis on the combustion products of materials, a large number of researchers believe that a small amount of dioxin or dibenzofuran is released when a halogen-containing flame retardant is combusted, which is also an important reason why plastic products of the halogen-containing flame retardant cannot be recycled or destroyed. Since there is currently no adequate replacement for all halogen-containing flame retardants, and at the same time, europe and japan have generally banned the use of halogen-containing flame retardants, which has resulted in some manufacturers being in double consideration of "environmental issues" and cost issues, and the use of flame retardants has been discontinued. Thus, manufacturers' practice to reduce manufacturing costs and "respond to environmental regulations" has resulted in serious fire hazards, allowing for the continued burning of non-flame retarded devices with a minimal ignition source. The use of halogen-free flame retardants is promoted by the fact that treatment specifications related to electronic and electric waste gas equipment have been promulgated in Europe and specify that halogen-containing waste needs to be specially treated.
Increasingly, flame retardant research for epoxy resins tends towards non-halogenation of flame retardants. The research of halogen is replaced by other flame retardant elements, the research of high-efficiency, low-toxicity and low-smoke halogen-free environment-friendly flame retardant and novel flame retardant polyolefin materials becomes a research hotspot of scholars at home and abroad, the flame retardant synthesized by DMMP and derivatives thereof becomes one of new flame retardant research directions due to the advantages of no halogen, no toxicity, no migration, long-lasting flame retardant property and the like, and has wide development prospect in the flame retardant application of high polymer materials, but 3 problems are urgently needed to be solved in the development and application of DMMP and derivatives thereof:
1. the research of enhancing the synergistic flame retardant effect of other non-halogen elements in DMMP and derivatives thereof;
2. expanding the types and application fields of DMMP and derivatives thereof;
3. the synthesis process of DMMP and the derivatives thereof is simplified, and the cost is reduced, so that the DMMP has better market competitiveness.
Disclosure of Invention
Aiming at the problems in the prior art, the invention discloses a reactive flame retardant and a preparation method thereof, the preparation method is simple, the condition is mild, the control is easy, the purity of the product is high, and the prepared reactive flame retardant has the advantages of novel structure, high flame retardant efficiency, environmental protection and low toxicity.
In order to solve the above technical problems, the technical solution is specifically adopted as follows:
a reactive flame retardant has a structural formula shown as the following formula (I):
the reactive flame retardant has a novel structure, and the carbon-phosphorus structure can better activate an acid source and a carbon source, accelerate the generation of reaction and form a more compact and compact carbon layer structure; when the flame retardant is further mixed with a resin matrix, such as epoxy resin, the C-O bond can form pi-pi bonds with the resin matrix, so that the flame retardant is more easily dissolved in the resin matrix, and the prepared epoxy resin composite material has good mechanical properties.
The invention also discloses a preparation method of the reactive flame retardant, which comprises the following steps:
mixing methyl dimethyl phosphate, terephthalaldehyde, a catalyst and a solvent, reacting in nitrogen or inert atmosphere, and performing post-treatment to obtain the reactive flame retardant;
the catalyst is selected from at least one of xylene, 2, 3-dichlorotoluene and trimethylbenzene;
the solvent is selected from tetrahydrofuran and/or acetonitrile.
The synthesis of the reactive flame retardant is carried out according to the following reaction formula:
the preparation process of the invention takes dimethyl methyl phosphate (DMMP) and Terephthalaldehyde (TDCA) as raw materials, screens proper catalyst and solvent, and prepares the target flame retardant with high yield.
In consideration of loss amount and side reaction in synthesis, the dimethyl methyl phosphate and the terephthalaldehyde are preferably fed in a molar ratio of 3-5: 1.
in order to ensure that the substrate can be completely dissolved in the solvent, the molar volume ratio of the methyl dimethyl phosphate to the solvent is preferably 1 mol: (80-100) mL; further preferably, the molar volume ratio is 1 mol: (80-85) mL.
In order to ensure the catalytic efficiency of the catalyst, the molar volume ratio of the dimethyl methyl phosphate to the catalyst is preferably 1 mol: (5-15) mL; further preferably, the molar volume ratio is 1 mol: 10 mL.
Aiming at the specific reaction taking dimethyl methylphosphonate and terephthalaldehyde as raw materials, a special catalyst and a special solvent variety are screened.
Tests show that the types of the catalysts are particularly important for the preparation process, and xylene, 2, 3-dichlorotoluene and trimethylbenzene are preferably used as the catalysts, so that the target product can be prepared with high yield.
When toluene, which is a common benzene solvent, is used as a catalyst for the reaction, the yield of the target product is greatly reduced.
Further preferred is xylene, which has been found by experiments to produce the highest yields of the desired product relative to other catalyst types using xylene as catalyst.
Further experiments show that the type of the solvent is particularly important for the preparation process, and tetrahydrofuran and acetonitrile are preferably used as the solvent, so that the target product can be prepared with high yield.
And when petroleum ether, which is a common organic solvent with similar performance to tetrahydrofuran and acetonitrile, is used as a solvent for the reaction, part of target products can be dissolved in the petroleum ether, and the extraction is difficult, so that the yield is seriously influenced.
The further preferred solvent is tetrahydrofuran, and experiments show that the target product is prepared by using tetrahydrofuran as the solvent in the highest yield compared with other solvent types. In tests, the inventor also unexpectedly finds that the flame-retardant epoxy resin composite material prepared by using the target product flame retardant has relatively higher mechanical properties by using tetrahydrofuran as a solvent.
The reaction temperature is 50-120 ℃, and the reaction time is 3-10 h.
The post-treatment comprises filtering, washing and drying; wherein the washing treatment adopts alcohol solvent such as methanol and ethanol, preferably ethanol.
Preferably:
the catalyst is selected from xylene;
the solvent is selected from tetrahydrofuran;
the feeding molar ratio of the dimethyl methylphosphonate to the terephthalaldehyde is 3: 1;
the molar volume ratio of the dimethyl methyl phosphate to the catalyst is 1 mol: 10 mL.
Tests show that the flame retardant prepared by adopting the specific raw materials has the highest yield, and the epoxy resin composite material further prepared by using the flame retardant not only has excellent flame retardant property, but also has excellent mechanical property and low conductivity.
The reaction type flame retardant prepared by the process has excellent flame retardant efficiency, is particularly suitable for preparing flame retardant epoxy resin, and tests prove that the flame retardant has extremely high flame retardant efficiency in the epoxy resin, can reach the flame retardant level of UL941.6mmV-0 at a lower content, and has an oxygen index as high as 31; more importantly, the C-O group in the flame retardant can be combined with the epoxy resin matrix through pi-pi bonds, so that the flame retardant is uniformly dispersed in the matrix resin, the prepared epoxy resin composite material has good mechanical property, hydrolysis is inhibited, and the conductivity is reduced.
Compared with the prior art, the invention has the following advantages:
1. the invention discloses a novel efficient flame retardant, wherein a carbon-phosphorus structure can better activate an acid source and a carbon source, accelerate the generation of reaction, form a more compact and compact carbon layer structure, can reach the flame retardant grade of UL941.6mmV-0 at a lower content, and has an oxygen index as high as 31; has the advantages of low toxicity and environmental protection, and is beneficial to the sustainable development.
2. The invention discloses a preparation process of the novel efficient flame retardant, which can prepare a target product at high yield under the action of a specific catalyst and a solvent, and has the advantages of simple preparation method, mild conditions, easy control and convenient post-treatment.
3. The novel efficient flame retardant and the epoxy resin are compounded to prepare the composite material, so that excellent flame retardant performance is obtained, meanwhile, the composite material is ensured to have excellent mechanical property due to the C-O bond in the structure of the flame retardant, and the conductivity is also remarkably reduced.
Drawings
FIG. 1 is a nuclear magnetic resonance phosphorous spectrum of the flame retardant prepared in example 1;
FIG. 2 is an infrared spectrum of a flame retardant prepared in example 1;
FIG. 3 is a NMR hydrogen spectrum of the flame retardant prepared in example 1.
Detailed Description
For the purpose of illustrating the technical content, the constructional features, the achieved objects and the effects of the invention in detail, reference will be made to the following detailed description of the embodiments in conjunction with the accompanying drawings.
Example 1
A100 mL three-necked flask equipped with a reflux condenser, a thermometer and a stirring rod was charged with 25mL of tetrahydrofuran as a solvent, 3mL of xylene was added thereto, the mixture was heated to 80 ℃ and stirred uniformly, and then 16.4g of TDCA (0.1mol) and 37.2g of DMMP (0.3mol) were added thereto, followed by addition of N2The reaction is carried out for 5h under the atmosphere and at the temperature of 80 ℃. After the reaction was completed, the mixture was filtered, washed, and dried to obtain a flame retardant as a white solid with a yield of 91%. The nuclear magnetic phosphorus spectrum, the infrared spectrum and the nuclear magnetic hydrogen spectrum of the obtained product are respectively shown in FIG. 1, FIG. 2 and FIG. 3. Observation of the above figures can prove that the target product has the structure shown in formula (I).
22 parts of the flame retardant prepared in this example were mixed with 78 parts of EP (model 4926) and compounded in a 190 ℃ twin-screw extruder.
With reference to the American standard ASTM D618, the composite material is made into UL941.6mm standard bars in an injection molding machine and subjected to standard tests on a horizontal and vertical combustion meter and an oxygen index tester. The flame retardant rating of the specimens tested was: UL941.6mm V-0 rating, oxygen index 31.
According to the national standard GB/T1040.1-2018, the composite material is made into a dumbbell type tensile standard sample bar in an injection molding machine, and standard test is carried out on a tensile tester. The test shows that the tensile strength of the sample strip is 32.14MPa, and the bending strength is 37.85 MPa.
10g of the above composite was added to 50mL of deionized water, and the conductivity was measured to be 3200. mu.s/cm.
Comparative example 1
The flame retardant was prepared by the same procedure as in example 1 except that the catalyst was replaced with toluene from xylene.
The comparative example was tested to produce a flame retardant yield of only 64%.
Comparative example 2
The preparation process of the flame retardant was the same as in example 1 except that the solvent was replaced with petroleum ether from tetrahydrofuran.
The test shows that the yield of the comparative example is greatly reduced to 25 percent, which proves that petroleum ether can not be used as a solvent.
Example 2
A250 mL three-necked flask equipped with a reflux condenser, a thermometer and a stirring rod was charged with 62.5mL of acetonitrile as a solvent, 7.5mL of xylene was added thereto, the mixture was heated to 80 ℃ and stirred uniformly, and then 41g of TDCA (0.25mol) and 93g of DMMP (0.75mol) were added thereto, followed by adding N2The reaction is carried out for 5h under the atmosphere and at the temperature of 80 ℃. After the reaction was completed, the mixture was filtered, washed, and dried to obtain a flame retardant as a white solid with a yield of 79%.
22 parts of the flame retardant obtained in this example were mixed with 78 parts of EP (model 4926) and compounded in a 190 ℃ twin-screw extruder.
The composite material is made into an UL941.6mm standard sample strip in an injection molding machine, and standard test is carried out on a horizontal and vertical combustion instrument and an oxygen index tester. The flame retardant rating of the specimens tested was: UL941.6mm V-0 rating, oxygen index 30.
The composite material is made into a dumbbell type tensile standard sample strip in an injection molding machine, and standard test is carried out on a tensile tester. The test shows that the tensile strength of the sample strip is 26.87MPa, and the bending strength is 29.53 MPa.
10g of the composite was added to 50mL of deionized water and the conductivity was tested to be 3200. mu.s/cm.
Example 3
250mL of tetrahydrofuran was added as a solvent to a 1000mL three-necked flask equipped with a reflux condenser, a thermometer and a stirring rod, 30mL of trimethylbenzene was added thereto, and the mixture was heatedAfter stirring uniformly at 80 ℃, 164g (1mol) of TDCA and 372g of DMMP (3mol) are added, and the mixture is stirred in the presence of N2The reaction is carried out for 5h under the atmosphere and at the temperature of 80 ℃. After the reaction was completed, the mixture was filtered, washed, and dried to obtain a white solid with a yield of 84%.
22 parts of the flame retardant obtained in this example were mixed with 78 parts of EP (model 4926) and compounded in a 190 ℃ twin-screw extruder.
The composite material is made into an UL941.6mm standard sample strip in an injection molding machine, and standard test is carried out on a horizontal and vertical combustion instrument and an oxygen index tester. The flame retardant rating of the specimens tested was: UL941.6mm V-0 rating, oxygen index 30.
The composite material is made into a dumbbell type tensile standard sample strip in an injection molding machine, and standard test is carried out on a tensile tester. The test shows that the tensile strength of the sample strip is 31.14MPa, and the bending strength is 35.85 MPa.
10g of the composite was added to 50ml of deionized water and the conductivity was measured to be 3200. mu.s/cm.
Comparative example 3
22 parts of DMMP were mixed with 78 parts of EP (model 4926) and compounded on a 190 ℃ twin-screw extruder.
The composite material is made into an UL941.6mm standard sample strip in an injection molding machine, and standard test is carried out on a horizontal and vertical combustion instrument and an oxygen index tester. The flame retardant rating of the specimens tested was: UL941.6mm V-2 rating, oxygen index 24.
The composite material is made into a dumbbell type tensile standard sample strip in an injection molding machine, and standard test is carried out on a tensile tester. The test shows that the tensile strength of the sample strip is 23.94MPa, and the bending strength is 25.65 MPa.
10g of the composite was added to 50mL of deionized water and tested for conductivity of 4500 uS/cm.
The novel efficient flame retardant disclosed by the invention contains phosphorus which is a flame retardant element, can participate in the solidification of polyolefin, has the characteristics of high flame retardant efficiency, no halogen, low smoke, low toxicity and the like, accords with the current concept of protecting the ecological environment, and reduces the generation of toxic gas and corrosive gas in the combustion process.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (4)
1. A method for preparing a reactive flame retardant is characterized by comprising the following steps:
mixing methyl dimethyl phosphate, terephthalaldehyde, a catalyst and a solvent, reacting in nitrogen or inert atmosphere, and performing post-treatment to obtain the reactive flame retardant;
the catalyst is selected from at least one of dimethylbenzene and trimethylbenzene;
the solvent is selected from tetrahydrofuran;
the feeding molar ratio of the dimethyl methylphosphonate to the terephthalaldehyde is 3-5: 1;
the molar volume ratio of the dimethyl methyl phosphate to the solvent is 1 mol: (80-100) mL;
the molar volume ratio of the dimethyl methyl phosphate to the catalyst is 1 mol: (5-15) mL;
the reaction temperature is 50-120 ℃, and the reaction time is 3-10 h;
the post-treatment comprises filtering, washing and drying.
2. The method of claim 1, wherein the catalyst is selected from xylene.
3. The method for producing a reactive flame retardant according to claim 1 or 2, characterized in that:
the feeding molar ratio of the dimethyl methylphosphonate to the terephthalaldehyde is 3: 1;
the molar volume ratio of the dimethyl methyl phosphate to the catalyst is 1 mol: 10 mL.
4. Use of a reactive flame retardant prepared according to the process of claim 1 in the preparation of a flame retardant epoxy resin.
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