CN114874266A - Biomass flame retardant applied to epoxy resin and preparation method thereof - Google Patents
Biomass flame retardant applied to epoxy resin and preparation method thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 55
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 54
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 54
- 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 47
- 239000002028 Biomass Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- -1 aldehyde compounds Chemical class 0.000 claims abstract description 16
- GPXCORHXFPYJEH-UHFFFAOYSA-N 3-[[3-aminopropyl(dimethyl)silyl]oxy-dimethylsilyl]propan-1-amine Chemical compound NCCC[Si](C)(C)O[Si](C)(C)CCCN GPXCORHXFPYJEH-UHFFFAOYSA-N 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 5
- 125000004207 3-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(OC([H])([H])[H])=C1[H] 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 5
- 229910018557 Si O Inorganic materials 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 229910052710 silicon Inorganic materials 0.000 abstract description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 abstract description 4
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 abstract 1
- 238000007039 two-step reaction Methods 0.000 abstract 1
- 238000002485 combustion reaction Methods 0.000 description 7
- 238000005452 bending Methods 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 4
- 229910002808 Si–O–Si Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 3
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 3
- 235000012141 vanillin Nutrition 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- JVTZFYYHCGSXJV-UHFFFAOYSA-N isovanillin Chemical compound COC1=CC=C(C=O)C=C1O JVTZFYYHCGSXJV-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- WMPDAIZRQDCGFH-UHFFFAOYSA-N 3-methoxybenzaldehyde Chemical compound COC1=CC=CC(C=O)=C1 WMPDAIZRQDCGFH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
-
- 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
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Silicon Polymers (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a biomass flame retardant applied to epoxy resin and a preparation method thereof, the flame retardant is prepared by taking 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane (BTDS), 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and aldehyde compounds as main raw materials through two-step reaction, in the first step, reacting-NH 2 of BTDS and-C ═ O of the aldehyde compounds under certain conditions to generate an intermediate; and in the second step, reacting-HC ═ N-of the intermediate obtained in the first step with P-H of DOPO to obtain the biomass flame retardant containing the silicon-oxygen bond and the DOPO structure. The invention has the advantages that: the Si-O flexible structure is designed in the flame retardant structural unit, so that the toughness of the modified epoxy resin can be improved, and the modified epoxy resin has good impact resistance; meanwhile, P, N, Si and other elements, DOPO and phenyl rigid groups in the structure can endow the modified epoxy resin with good thermal stability and flame retardant property, and the modified epoxy resin has wide application prospect.
Description
Technical Field
The invention relates to a biomass flame retardant applied to epoxy resin and a preparation method thereof, in particular to a biomass flame retardant applied to epoxy resin and containing a silicon-oxygen bond and a DOPO structure and a preparation method thereof, belonging to the technical field of flame retardants.
Background
Thermosetting resins have excellent corrosion resistance, dimensional stability, thermodynamic properties, etc., exhibit good comprehensive functions, and are an indispensable composition in the plastics and rubber industries in recent years. The epoxy resin is particularly representative thermosetting resin, has excellent chemical resistance, dielectric property, mechanical property, caking property and the like, can be used as an adhesive, a coating, an electronic packaging material, a civil engineering material and the like, and is widely applied to the fields of electronics, electricity, mechanical manufacturing, aerospace, automobile tracks, chemical engineering, building metallurgy and the like. However, the epoxy resin is not only extremely easy to burn, but also has the defects of insufficient toughness and the like, and the development and application of the epoxy resin are restricted, so that the flame retardant modification of the epoxy resin is a research hotspot in the field of epoxy resin and has very important significance.
The flame retardant property of the epoxy resin can be effectively improved by adding the halogen-containing flame retardant into the epoxy resin, but the halogen-containing flame retardant can release toxic gas in the combustion process, so that the environmental pollution and the health problems are caused, and therefore the halogen-free flame retardant is favored by many researchers. The halogen-free flame retardant is widely applied to polymers or high molecular materials due to the characteristics of high efficiency and low toxicity, and the epoxy resin modified by the halogen-free flame retardant is not decomposed to release toxic hydrogen halide or organic halide in the combustion process, so that the smoke generation amount and the smoke toxicity are reduced, and the possibility of people in fire escape is created. The halogen-free flame retardant modified epoxy resin can reduce or prevent the occurrence and the spread of fire in a fire scene, reduce the waste of energy and resources and the damage of ecological environment caused by the fire, and has very important practical significance for reducing the casualties and the property loss in the fire. However, with the addition of the flame retardant, the mechanical properties of the epoxy resin are reduced due to dispersion unevenness, agglomeration and the like, and the application of the epoxy resin in various fields is limited. Meanwhile, with the continuous and deep research of flame retardants and the continuous and deep understanding of human beings on problems such as environment and resource crises, the development of the flame retardants has wide raw material sources, particularly renewable resources such as biomass, simple and convenient synthesis process, no pollution, good dispersibility with epoxy resin, and the flame retardants which can endow the modified epoxy resin with excellent flame retardant performance and simultaneously have excellent thermal stability and mechanical performance are a very challenging problem.
Disclosure of Invention
The invention aims to solve the technical problem of providing a biomass flame retardant applied to epoxy resin and a preparation method thereof, wherein the flame retardant takes aldehyde compounds (vanillin and derivatives thereof) as raw materials and is a renewable biomass material, and a Si-O flexible structure is designed in a structural unit, so that the toughness of the modified epoxy resin can be improved, and the modified epoxy resin is endowed with good impact resistance; the secondary amine can participate in the curing reaction of the epoxy resin, so that the compatibility of the flame retardant and the epoxy resin is improved. Meanwhile, P, N, Si and other elements, DOPO and phenyl rigid groups in the structure can endow the modified epoxy resin with good thermal stability and flame retardant property.
The invention is realized by the following scheme: a biomass flame retardant applied to epoxy resin: the structural formula of the flame retardant is as follows:
wherein R is 3-hydroxy-4-methoxyphenyl or 3-methoxy-4-hydroxyphenyl or 3-methoxyphenyl.
A preparation method of a biomass flame retardant applied to epoxy resin comprises the following steps:
dissolving an aldehyde compound in an organic solvent, stirring at a certain temperature, slowly dropwise adding 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane, reacting for a certain time at a certain temperature after dropwise adding, distilling, washing and drying in vacuum to obtain an intermediate, wherein the reaction equation is as follows:
wherein R is 3-hydroxy-4-methoxyphenyl, 3-methoxy-4-hydroxyphenyl, 3-methoxyphenyl;
step two, dissolving the intermediate obtained in the step one in an organic solvent, stirring at a certain temperature, slowly dropwise adding a DOPO solution, reacting at a certain temperature for a certain time after dropwise adding, distilling, washing and vacuum drying to obtain the biomass flame retardant containing the silicon-oxygen bond and the DOPO structure, wherein the reaction equation is as follows:
in the first step, the molar ratio of the aldehyde compound to the 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane is 2-2.5: 1.
In the first step, the organic solvent is one or a mixture of methanol and ethanol, and the amount of the organic solvent is 6-10 times of the mass of 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane.
In the first step, 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane is dripped at the temperature of 35-50 ℃; the reaction temperature is 35-60 ℃, and the reaction time is 3-5 h.
In the second step, the molar ratio of the DOPO solution to the intermediate is 2-2.5: 1.
In the second step, the organic solvent is one or the mixture of methanol and ethanol, and the dosage of the organic solvent is 6-10 times of the mass of the DOPO solution.
In the second step, the temperature for dripping DOPO solution is 40-60 ℃; the reaction temperature is 40-65 ℃ and the reaction time is 4-6 h.
The invention has the beneficial effects that:
1. the biomass flame retardant containing the silicon-oxygen bond and the DOPO structure simultaneously contains Si-O flexible group, P, N, Si and other elements, DOPO and phenyl rigid group, and nitrogen can generate non-combustible gas during combustion to inhibit the continuous combustion of the material; phosphorus, silicon elements and benzene ring groups can promote the formation of a carbon layer, not only can prevent the overflow of decomposition products, but also can inhibit the thermal decomposition of high polymer materials, so that the flame retardant property of a matrix is improved, the existence of Si-O flexible groups and phenyl rigid groups can endow the modified epoxy resin with excellent mechanical property and thermal stability, secondary amine can participate in the curing reaction of the epoxy resin, and the compatibility of the flame retardant and the epoxy resin is improved;
2. the flame retardant of the invention takes aldehyde compounds (vanillin and derivatives thereof) as raw materials, and is a renewable biomass material.
Detailed Description
The present invention is further illustrated below, but the scope of the invention is not limited to the disclosure.
In the following description, for purposes of explanation, numerous implementation details are set forth in order to provide a thorough understanding of the present invention, and it is recognized that in the development of any such actual embodiment, the development of any such actual embodiment may be directed to a specific objective of the developer, such as changing from one implementation to another according to system-related or business-related constraints, and that such a development effort might be complex and time-consuming, but would nevertheless be a routine undertaking for those of ordinary skill in the art.
Example 1:
adding vanillin (26.4mmol) and absolute ethyl alcohol (30mL) into a three-neck flask, slowly dripping 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane (13.2mmol) into the three-neck flask at 35 ℃, reacting for 5 hours at 35 ℃ after finishing dripping, and obtaining an intermediate through distillation, washing and vacuum drying after the reaction is finished.
Adding an intermediate (7.8mmol) and absolute ethyl alcohol (10mL) into a three-neck flask, slowly dropwise adding DOPO (15.6mmol) solution dissolved in the ethyl alcohol (10mL) at 40 ℃, reacting for 6h at 40 ℃ after dropwise adding, and distilling, washing and vacuum drying after the reaction is finished to obtain the biomass flame retardant containing the silicon-oxygen bond and the DOPO structure, wherein the structural formula of the flame retardant is as follows:
wherein R is 3-methoxy-4-hydroxyphenyl.
1 H NMR spectrum: R-CH (3.9ppm), Si-CH 3 (2.6ppm)，N-CH 2 -C(3.5ppm)，Si-CH 2 -(0.5ppm)，C-CH 2 -C(1.7ppm)。
Infrared spectrum: -CH 3 (2948cm -1 )，C-P(754cm -1 )，Si-O-Si(1030cm -1 )，C-O-C(1088cm -1 )，-OH(3422cm -1 )。
The limit oxygen index of the epoxy resin modified by the product obtained in the example 1 (the added mass fraction is 10%) is 38.1%, and the UL-94 vertical combustion can reach V-0 level, so that the flame retardant effect is good; modified epoxy resin in N 2 Loss of 5% in atmosphere (T) d5 ) And 10% weight loss (T) d10 ) The corresponding temperatures are 321 ℃ and 356 ℃, the mass retention rate at 600 ℃ is 33.3%, and the thermal stability is good. The tensile strength, the bending strength and the impact strength reach 74MPa, 113MPa and 26.3kJ/m 2 42.3 percent, 37.8 percent and 165.7 percent higher than that of the unmodified epoxy resin (the tensile strength, the bending strength and the impact strength of the unmodified epoxy resin are respectively 52MPa, 82MPa and 9.9kJ/m 2 ) Has excellent mechanical property.
Example 2:
adding isovanillin (28.3mmol) and absolute ethyl alcohol (30mL) into a three-neck flask, slowly dripping 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane (13.2mmol) into the three-neck flask at 50 ℃, reacting for 3 hours at 60 ℃ after finishing dripping, and obtaining an intermediate through distillation, washing and vacuum drying after the reaction is finished.
Adding an intermediate (7.8mmol) and absolute ethyl alcohol (10mL) into a three-neck flask, slowly dropwise adding DOPO (16.2mmol) solution dissolved in the ethyl alcohol (10mL) at 60 ℃, reacting for 4 hours at 65 ℃ after dropwise adding, and distilling, washing and vacuum drying after the reaction is finished to obtain the biomass flame retardant containing the silicon-oxygen bond and the DOPO structure, wherein the structural formula of the flame retardant is as follows:
wherein R is 3-hydroxy-4-methoxyphenyl.
1 H NMR spectrum: R-CH (3.8ppm), Si-CH 3 (2.7ppm)，N-CH 2 -C(3.4ppm)，Si-CH 2 -(0.4ppm)，C-CH 2 -C(1.8ppm)。
Infrared spectrum: -CH 3 (2942cm -1 )，C-P(750cm -1 )，Si-O-Si(1032cm -1 )，C-O-C(1087cm -1 )，-OH(3328cm -1 )。
The limited oxygen index of the epoxy resin modified by the product obtained in the embodiment 2 (the added mass fraction is 8%) is 37.2%, the UL-94 vertical combustion can reach V-0 level, and the flame retardant effect is good; modified epoxy resin in N 2 Loss of 5% in atmosphere (T) d5 ) And 10% weight loss (T) d10 ) The corresponding temperatures are 320 ℃ and 353 ℃, the mass retention rate at 600 ℃ is 32.8%, and the thermal stability is good. The tensile strength, the bending strength and the impact strength reach 70MPa, 111MPa and 25.5kJ/m 2 34.6 percent, 35.4 percent and 157.6 percent higher than that of the unmodified epoxy resin (the tensile strength, the bending strength and the impact strength of the unmodified epoxy resin are respectively 52MPa, 82MPa and 9.9kJ/m 2 ) Has excellent mechanical property.
Example 3:
adding m-anisaldehyde (27.3mmol) and absolute ethyl alcohol (50mL) into a three-neck flask, slowly dripping 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane (13.2mmol) into the three-neck flask at 45 ℃, reacting for 4 hours at 50 ℃ after finishing dripping, and obtaining an intermediate after the reaction is finished and through distillation, washing and vacuum drying.
Adding an intermediate (7.8mmol) and absolute ethyl alcohol (18mL) into a three-neck flask, slowly dropwise adding DOPO (16.0mmol) solution dissolved in ethyl alcohol (20mL) at 55 ℃, reacting for 5 hours at 55 ℃, and after the reaction is finished, distilling, washing and vacuum drying to obtain the biomass flame retardant containing the silicon-oxygen bond and the DOPO structure, wherein the structural formula of the flame retardant is as follows:
wherein R is 3-methoxyphenyl.
1 H NMR spectrum: R-CH (3.9ppm), Si-CH 3 (2.7ppm)，N-CH 2 -C(3.6ppm)，Si-CH 2 -(0.6ppm)，C-CH 2 -C(1.8ppm)。
Infrared spectrum: -CH 3 (2959cm -1 )，C-P(768cm -1 )，Si-O-Si(1026cm -1 )，C-O-CH 2 -(1078cm -1 )。
The limit oxygen index of the epoxy resin modified by the product obtained in the example 3 (the added mass fraction is 15%) is 38.2%, and the UL-94 vertical combustion can reach V-0 level, so that the flame retardant effect is good; modified epoxy resin in N 2 Loss of 5% in atmosphere (T) d5 ) And 10% weight loss (T) d10 ) The corresponding temperatures are 322 ℃ and 357 ℃ respectively, the mass retention rate at 600 ℃ is 33.9 percent, and the thermal stability is good. The tensile strength, the bending strength and the impact strength reach 76MPa, 118MPa and 27.2kJ/m 2 46.1 percent, 43.9 percent and 174.7 percent higher than that of the unmodified epoxy resin (the tensile strength, the bending strength and the impact strength of the unmodified epoxy resin are respectively 52MPa, 82MPa and 9.9kJ/m 2 ) Has excellent mechanical property.
Although the invention has been described and illustrated in some detail, it should be understood that various modifications may be made to the described embodiments or equivalents may be substituted, as will be apparent to those skilled in the art, without departing from the spirit of the invention.
Claims (9)
1. The biomass flame retardant applied to the epoxy resin is characterized in that: the structural formula of the flame retardant is as follows:
2. the biomass flame retardant applied to the epoxy resin as claimed in claim 1, wherein: in the structural formula, R is 3-hydroxy-4-methoxyphenyl or 3-methoxy-4-hydroxyphenyl or 3-methoxyphenyl.
3. The preparation method of the biomass flame retardant applied to the epoxy resin, as claimed in claim 1, is characterized in that: the method comprises the following steps:
dissolving an aldehyde compound in an organic solvent, stirring at a certain temperature, slowly dropwise adding 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane, reacting for a certain time at a certain temperature after dropwise adding, and distilling, washing and vacuum drying to obtain an intermediate;
and step two, dissolving the intermediate obtained in the step one in an organic solvent, stirring at a certain temperature, slowly dropwise adding a DOPO solution, reacting at a certain temperature for a certain time after dropwise adding, and distilling, washing and vacuum drying to obtain the biomass flame retardant containing the silicon-oxygen bond and the DOPO structure.
4. The preparation method of the biomass flame retardant applied to the epoxy resin, according to claim 3, is characterized in that: in the first step, the molar ratio of the aldehyde compound to the 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane is 2-2.5: 1.
5. The preparation method of the biomass flame retardant applied to the epoxy resin, according to claim 3, is characterized in that: in the first step, the organic solvent is one or a mixture of methanol and ethanol, and the amount of the organic solvent is 6-10 times of the mass of 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane.
6. The preparation method of the biomass flame retardant applied to the epoxy resin, according to claim 3, is characterized in that: in the first step, 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane is dripped at the temperature of 35-50 ℃; the reaction temperature is 35-60 ℃, and the reaction time is 3-5 h.
7. The preparation method of the biomass flame retardant applied to the epoxy resin, according to claim 3, is characterized in that: in the second step, the molar ratio of the DOPO solution to the intermediate is 2-2.5: 1.
8. The preparation method of the biomass flame retardant applied to the epoxy resin, according to claim 3, is characterized in that: in the second step, the organic solvent is one or the mixture of methanol and ethanol, and the dosage of the organic solvent is 6-10 times of the mass of the DOPO solution.
9. The preparation method of the biomass flame retardant applied to the epoxy resin, according to claim 3, is characterized in that: in the second step, the temperature for dripping DOPO solution is 40-60 ℃; the reaction temperature is 40-65 ℃ and the reaction time is 4-6 h.
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| CN104277223A (en) * | 2013-07-12 | 2015-01-14 | 北京化工大学 | Macromolecular flame retardant containing three elements of phosphorus, nitrogen and silicon and synthesis method and application of macromolecular flame retardant |
| CN107011499A (en) * | 2017-04-18 | 2017-08-04 | 中国科学院宁波材料技术与工程研究所 | The composition epoxy resin of the phosphonium flame retardant of aldehyde radical containing vanilla and its application |
| US20180223094A1 (en) * | 2017-02-07 | 2018-08-09 | Iteq Corporation | Halogen-free epoxy resin composition having low dielectric loss |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104277223A (en) * | 2013-07-12 | 2015-01-14 | 北京化工大学 | Macromolecular flame retardant containing three elements of phosphorus, nitrogen and silicon and synthesis method and application of macromolecular flame retardant |
| US20180223094A1 (en) * | 2017-02-07 | 2018-08-09 | Iteq Corporation | Halogen-free epoxy resin composition having low dielectric loss |
| CN107011499A (en) * | 2017-04-18 | 2017-08-04 | 中国科学院宁波材料技术与工程研究所 | The composition epoxy resin of the phosphonium flame retardant of aldehyde radical containing vanilla and its application |
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