CN116423600A - Vegetable oil-based flame retardant and preparation method and application thereof - Google Patents
Vegetable oil-based flame retardant and preparation method and application thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 126
- 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 120
- 235000015112 vegetable and seed oil Nutrition 0.000 title claims abstract description 88
- 239000008158 vegetable oil Substances 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000002383 tung oil Substances 0.000 claims abstract description 65
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000002023 wood Substances 0.000 claims abstract description 59
- 150000004702 methyl esters Chemical class 0.000 claims abstract description 56
- 239000003223 protective agent Substances 0.000 claims abstract description 44
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims abstract description 28
- 235000017491 Bambusa tulda Nutrition 0.000 claims abstract description 28
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims abstract description 28
- 239000011425 bamboo Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 22
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 11
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000010773 plant oil Substances 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 50
- 239000003054 catalyst Substances 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000003814 drug Substances 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 25
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 24
- 230000035484 reaction time Effects 0.000 claims description 22
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 17
- 239000004332 silver Substances 0.000 claims description 17
- 229910052709 silver Inorganic materials 0.000 claims description 17
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 238000006555 catalytic reaction Methods 0.000 claims description 13
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 9
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical group O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000009396 hybridization Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims 2
- 244000082204 Phyllostachys viridis Species 0.000 claims 1
- 241001330002 Bambuseae Species 0.000 abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000012546 transfer Methods 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 description 37
- 238000001816 cooling Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 238000007654 immersion Methods 0.000 description 8
- 238000006735 epoxidation reaction Methods 0.000 description 6
- 230000008961 swelling Effects 0.000 description 6
- 241000544043 Blyxa aubertii Species 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 150000005671 trienes Chemical group 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/34—Organic impregnating agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/02—Processes; Apparatus
- B27K3/08—Impregnating by pressure, e.g. vacuum impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
- B27K5/04—Combined bleaching or impregnating and drying of wood
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K2240/00—Purpose of the treatment
- B27K2240/30—Fireproofing
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Forests & Forestry (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
Abstract
The invention discloses a plant oil-based flame retardant, a preparation method and application thereof, wherein the plant oil-based flame retardant can be used for preparing a bamboo-wood expansion type protective agent and is prepared by the following method: (1) Reacting tung oil methyl ester with hydrogen peroxide under a catalytic condition to obtain epoxidized tung oil methyl ester; (2) The vegetable oil-based flame retardant disclosed by the invention is convenient to manufacture, relatively low in production cost, contains rich alcohol hydroxyl groups, has good compatibility with bamboo wood, and can greatly improve flame retardant efficiency; the plant oil-based intumescent flame retardant can be used for preparing the bamboo and wood intumescent protective agent, the protective agent provides a carbon source and an acid source through the plant oil-based flame retardant, and provides an air source through melamine, so that an intumescent flame retardant system is formed, oxygen, heat and substance transfer can be effectively isolated, and flame-retardant and heat-insulating protection of bamboo and wood is realized.
Description
Technical Field
The invention relates to the technical field of flame retardant materials, in particular to a plant oil-based flame retardant and a preparation method and application thereof.
Background
Bamboo is a traditional, nontoxic and harmless building material, and is widely used in house construction and interior decoration. Because the base material has combustibility, the smoke generated by combustion is often the primary cause of casualties, and has a certain adverse effect on the environment, so that great potential safety hazards are brought to the daily life of people and the fire fighting of buildings. Therefore, flame retardant and smoke suppressant treatments of wood are necessary. It is known that adding flame retardants to the interior or surface of bamboo wood is an effective way to achieve the purpose of flame retardance and smoke suppression, however, most of the conventional flame retardants use a single substance or utilize a single element to achieve flame retardance effects, such as halogen, nitrogen, phosphorus, boron and the like, and the flame retardants still have the defect of low flame retardance efficiency. Halogen-containing flame retardants can cause environmental pollution and pose a threat to human health. Among them, intumescent flame retardants are considered to be effective, economical, and environmentally friendly. Intumescent flame retardants are composed mainly of three parts, a carbon source (e.g., pentaerythritol), an acid source (e.g., phosphoric acid and organophosphates), and a gas source (e.g., urea and melamine). The intumescent flame retardant mainly comprises a plurality of compact carbon layers for preventing oxygen, heat and substances from transferring, thereby protecting wood and bamboo base materials.
The tung oil is used in China for thousands of years, is the largest world tung oil producing country, and accounts for about 80% of world tung oil yield and 60% of international trade quantity of the tung oil. The tung oil has a special conjugated triene structure and is widely applied to the field of high polymer materials as a raw material. The tung oil has the characteristics of natural sustainability, green, regeneration and the like, and the development of the bamboo wood flame retardant protective agent by using the tung oil as a raw material is rarely reported. According to the required characteristics of the intumescent flame retardant, the tung oil-based flame retardant is designed, and meanwhile, the modes of carbon source, acid source and air source addition can realize halogen-free, smoke-free, nontoxic, migration-free, lasting flame retardant performance and stable system. The carbon source contains abundant hydroxyl groups, which is very favorable for the adhesion and practical application of wood and bamboo.
Disclosure of Invention
The invention provides a plant oil-based flame retardant, a preparation method and application thereof, which are used for solving the technical problem that the existing flame retardant is poor in flame retardant efficiency.
In order to solve the technical problems, the invention adopts the following technical scheme:
a vegetable oil-based flame retardant has a molecular formula shown in a formula (1):
based on the same technical conception, the invention also provides a preparation method of the vegetable oil-based flame retardant, which comprises the following steps:
(1) Reacting tung oil methyl ester and hydrogen peroxide to be complete under the catalysis of a catalyst to obtain epoxidized tung oil methyl ester; the catalyst is a phosphotungstic acid group hybridization catalyst.
(2) And (3) reacting the epoxidized tung oil methyl ester with diethyl phosphate to be complete under the catalysis of triphenylphosphine, thus obtaining the vegetable oil-based flame retardant.
The technical scheme is characterized in that the invention adopts the phosphotung acid-based hybrid catalyst to catalyze the epoxidation reaction of tung oil methyl ester, and finally obtains the vegetable oil-based flame retardant, the epoxidation reaction is an SN1 reaction which takes super solid acid as a catalyst, and the catalyst is a heterogeneous acid catalyst, so that the catalyst has the effects of easy separation, difficult equipment corrosion and recycling, and simultaneously has high degree of fusion with a reaction system, and can promote the full contact of substrates in the reaction system, thereby improving the catalytic efficiency and the catalytic effect, and the preparation process is simple, effectively improving the yield and the preparation efficiency of the epoxidized tung oil methyl ester, and reducing the production cost and the process equipment requirements.
As a further preferable mode of the technical scheme, the molar ratio of the double bond in the tung oil methyl ester to the hydrogen peroxide in the step (1) is 1 (1.1-5); the mass of the catalyst is 3% of the mass of the tung oil methyl ester.
As a further preferable mode of the technical scheme, the reaction temperature of the tung oil methyl ester and the hydrogen peroxide in the step (1) is 40-80 ℃ and the reaction time is 3-6 hours. The invention optimizes the epoxidation process condition parameters of the tung oil methyl ester to obtain the optimal process condition.
As a further preferable mode of the technical scheme, after the tung oil methyl ester and hydrogen peroxide in the step (1) are reacted completely, cooling to 0 ℃, and centrifugally separating to obtain residual hydrogen peroxide and a catalyst.
As a further preferable mode of the above technical scheme, the catalyst in the step (1) is at least one of pyridine phosphotungstate and silver phosphotungstate; the preparation method of the catalyst comprises the following steps: 28.0g of phosphotungstic acid was weighed out and completely dissolved in 70mL of distilled water, and 30mL of 30wt% H was added 2 O 2 Uniformly mixing at room temperature to obtain a mixed solutionThe method comprises the steps of carrying out a first treatment on the surface of the Dropwise adding 0.2g of silver nitrate solution (the concentration of the solution is controlled to be 0.1M) or 0.2g of pyridine into the mixed solution, continuously stirring for 5min, keeping at 40 ℃ for 12h, filtering, and drying filter residues in a vacuum environment at 60 ℃ to obtain the catalyst.
As a further preferred aspect of the above technical solution, the molar ratio of the epoxy bond to diethyl phosphate in the epoxidized tung oil methyl ester in step (2) is 1:2; the mass of the triphenylphosphine is 0.2% of the mass of the methyl ester of the epoxidized tung oil.
As a further preferable mode of the technical scheme, the reaction temperature of the epoxidized tung oil methyl ester and the diethyl phosphate in the step (2) is 40-80 ℃ and the reaction time is 4-6 hours.
Based on the same technical conception, the invention also provides a plant oil-based flame retardant which is prepared by the preparation method of the technical scheme. The vegetable oil-based intumescent flame retardant disclosed by the invention is convenient to manufacture, relatively low in production cost, rich in alcoholic hydroxyl groups, good in compatibility with bamboo and wood, and capable of effectively improving the flame retardant efficiency of the flame retardant.
Based on the same technical conception, the invention also provides application of the vegetable oil-based flame retardant in the technical scheme, wherein the vegetable oil-based flame retardant is used for preparing a bamboo-wood expansion type protective agent, and the bamboo-wood expansion type protective agent comprises the following components in parts by mass:
50-100 parts of a vegetable oil-based flame retardant, 50-100 parts of ethanol, 50-100 parts of water and 0-30 parts of melamine.
The design idea of the technical scheme is that the plant oil-based flame retardant is utilized to provide a carbon source and an acid source, melamine is utilized to provide an air source, an intumescent flame-retardant protection system is formed, when the bamboo-wood base material is heated and encounters fire, a carbon-made multilayer structure (coke) is formed on the surface of the base material, and the generated physical barrier can effectively isolate oxygen, heat and transfer of substances, so that flame-retardant heat-insulating protection of the bamboo wood is realized.
As a further preferable mode of the technical scheme, the using method of the bamboo-wood expansion type protective agent comprises the steps of adding ethanol into a vegetable oil-based flame retardant, stirring to obtain a clear solution, adding water and melamine to form a liquid medicine, immersing bamboo-wood materials into the liquid medicine for 2 hours under pressure, taking out, and drying at 60 ℃ for 12 hours.
Compared with the prior art, the invention has the advantages that:
the vegetable oil-based flame retardant disclosed by the invention is convenient to manufacture, relatively low in production cost, rich in alcoholic hydroxyl groups and good in compatibility with bamboo wood, and can greatly improve the flame retardant efficiency; the plant oil-based intumescent flame retardant can be used for preparing the bamboo and wood intumescent protective agent, the protective agent provides a carbon source and an acid source through the plant oil-based flame retardant, and provides an air source through melamine, so that an intumescent flame retardant system is formed, oxygen, heat and substance transfer can be effectively isolated, and flame-retardant and heat-insulating protection of bamboo and wood is realized.
Drawings
FIG. 1 is a graph showing the internal element distribution of plant tissue treated with the bamboo swelling type protectant of example 1;
FIG. 2 is a graph showing the LOI comparison of a substrate treated with the bamboo swelling protectant of examples 5-7 with an untreated substrate;
FIG. 3 is a graph showing the HRR of the substrate treated with the bamboo and wood intumescent protectant of examples 5-7 versus untreated substrate;
FIG. 4 is a plot of THR comparison of substrates treated with the bamboo and wood intumescent protectants of examples 5-7 versus untreated substrates;
FIG. 5 is a graph comparing TSP of a substrate treated with the bamboo and wood intumescent protectant of examples 5-7 with an untreated substrate;
FIG. 6 is a high resolution mass spectrum of the vegetable oil-based flame retardant of example 1;
FIG. 7 is a nuclear magnetic resonance hydrogen spectrum of the vegetable oil-based flame retardant of example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Through molecular design, the method for preparing the vegetable oil-based flame retardant utilizes the reaction of tung oil crude oil and methanol to obtain tung oil methyl ester, takes the tung oil methyl ester as a raw material, takes hydrogen peroxide as an oxidant and silver phosphotungstate as a catalyst to prepare epoxidized tung oil methyl ester, takes the epoxidized tung oil methyl ester as the raw material, takes triphenylphosphine and silver phosphotungstate as the catalyst, takes toluene as a solvent and takes diethyl phosphate as a nucleophilic reagent, and carries out ring opening to obtain the vegetable oil-based flame retardant.
The specific preparation method of the phosphotungstic acid group hybridization catalyst (silver phosphotungstate and pyridine phosphotungstate) used in each example comprises the following steps: 10 parts by mass of phosphotungstic acid was weighed and completely dissolved in distilled water, and 30 parts by mass of 30wt% H was added 2 O 2 Uniformly mixing at room temperature to obtain a mixed solution; and (3) dropwise adding 30 parts by mass of silver nitrate solution or 30 parts by mass of pyridine into the mixed solution, continuously stirring for 5min, keeping at 40 ℃ for 12h, filtering, and drying filter residues in a vacuum environment at 60 ℃ to obtain the catalyst.
Example 1
The molecular formula of the vegetable oil-based flame retardant is shown in formula (1):
the results of high-resolution mass spectrum and nuclear magnetic resonance hydrogen spectrum tests on the vegetable oil-based flame retardant of this example are shown in fig. 6 and 7, and as can be seen from the nuclear magnetic resonance hydrogen spectrum of fig. 7, 4.1,5.2,3.3ppm are assigned to the specific peak of the methylene group connecting between P-O and methyl, 1-2ppm are assigned to the characteristic peak on the long-chain carbon skeleton, 3.8ppm are assigned to the characteristic peak of the carbonyl group at the carbon end and oxygen linkage, and the relative molecular mass thereof is 754.3512, which is obtained from the high-resolution mass spectrum of fig. 6, completely coincides with the theoretical relative molecular mass 754.35.
The preparation method of the vegetable oil-based flame retardant comprises the following steps:
(1) Epoxidizing 30 parts by mass of tung oil methyl ester and 60 parts by mass of hydrogen peroxide under the catalysis of 0.3 part by mass of silver phosphotungstate to obtain epoxidized tung oil methyl ester, wherein the epoxidizing temperature is 30 ℃, and the reaction time is 6 hours; cooling to 0 ℃ after the reaction is finished, and centrifugally separating hydrogen peroxide, water and a catalyst in the system;
(2) 30 parts by mass of epoxidized tung oil methyl ester is reacted with 60 parts by mass of diethyl phosphate, 0.03 part by mass of triphenylphosphine and 0.01 part by mass of silver phosphotungstate catalyst, and the vegetable oil-based flame retardant of the embodiment is obtained, wherein the reaction temperature is 60 ℃, and the reaction time is 4 hours.
The vegetable oil-based flame retardant of the embodiment can be used for preparing a bamboo-wood expansion type protective agent, and the bamboo-wood expansion type protective agent of the embodiment comprises the following components in parts by mass: 50 parts of vegetable oil-based flame retardant, 50 parts of ethanol and 50 parts of water. The application method of the bamboo-wood expansion type protective agent in the embodiment comprises the following steps: firstly, placing a vegetable oil-based flame retardant, ethanol and water in a beaker, stirring to clarify the mixture to obtain a liquid medicine, then immersing a substrate in the liquid medicine, taking out the substrate after 2h of pressurized immersion, and drying the substrate at 60 ℃ for 12h; the distribution of the elements inside the bamboo plant tissue treated with the bamboo swelling type protective agent of this example is shown in fig. 1, and it can be seen from the figure that the treated bamboo swelling type protective agent is uniformly dispersed in the bamboo plant tissue.
Example 2
The molecular formula of the vegetable oil-based flame retardant is shown in formula (1):
the preparation method of the vegetable oil-based flame retardant comprises the following steps:
(1) Epoxidizing 30 parts by mass of tung oil methyl ester and 60 parts by mass of hydrogen peroxide under the catalysis of 0.3 part by mass of pyridine phosphotungstate to obtain epoxidized tung oil methyl ester, wherein the epoxidation reaction temperature is 40 ℃, and the reaction time is 6 hours; cooling to 0 ℃ after the reaction is finished, and centrifugally separating hydrogen peroxide, water and a catalyst in the system;
(2) 30 parts by mass of epoxidized tung oil methyl ester, 60 parts by mass of diethyl phosphate, 0.03 part by mass of triphenylphosphine and 0.01 part by mass of pyridine phosphotungstate catalyst are mixed to obtain the vegetable oil-based flame retardant of the embodiment, wherein the reaction temperature is 60 ℃, and the reaction time is 4 hours.
The vegetable oil-based flame retardant of the embodiment can be used for preparing a bamboo-wood expansion type protective agent, and the bamboo-wood expansion type protective agent of the embodiment comprises the following components in parts by mass: 50 parts of vegetable oil-based flame retardant, 50 parts of ethanol and 50 parts of water. The application method of the bamboo-wood expansion type protective agent in the embodiment comprises the following steps: firstly, placing the vegetable oil-based flame retardant, ethanol and water in a beaker, stirring to clarify the mixture to obtain liquid medicine, then immersing the substrate in the liquid medicine, taking out the substrate after 2h of pressurized immersion, and drying the substrate at 60 ℃ for 12h.
Example 3
The molecular formula of the vegetable oil-based flame retardant is shown in formula (1):
the preparation method of the vegetable oil-based flame retardant comprises the following steps:
(1) Epoxidizing 30 parts by mass of tung oil methyl ester and 60 parts by mass of hydrogen peroxide under the catalysis of 0.3 part by mass of silver phosphotungstate to obtain epoxidized tung oil methyl ester, wherein the epoxidizing temperature is 50 ℃, and the reaction time is 5 hours; cooling to 0 ℃ after the reaction is finished, and centrifugally separating hydrogen peroxide, water and a catalyst in the system;
(2) 30 parts by mass of epoxidized tung oil methyl ester is reacted with 60 parts by mass of diethyl phosphate, 0.03 part by mass of triphenylphosphine and 0.01 part by mass of silver phosphotungstate catalyst to obtain the vegetable oil-based flame retardant of the embodiment, wherein the reaction temperature is 60 ℃, and the reaction time is 4 hours.
The vegetable oil-based flame retardant of the embodiment can be used for preparing a bamboo-wood expansion type protective agent, and the bamboo-wood expansion type protective agent of the embodiment comprises the following components in parts by mass: 50 parts of vegetable oil-based flame retardant, 50 parts of ethanol and 50 parts of water. The application method of the bamboo-wood expansion type protective agent in the embodiment comprises the following steps: firstly, placing the vegetable oil-based flame retardant, ethanol and water in a beaker, stirring to clarify the mixture to obtain liquid medicine, then immersing the substrate in the liquid medicine, taking out the substrate after 2h of pressurized immersion, and drying the substrate at 60 ℃ for 12h.
Example 4
The molecular formula of the vegetable oil-based flame retardant is shown in formula (1):
the preparation method of the vegetable oil-based flame retardant comprises the following steps:
(1) Epoxidizing 30 parts by mass of tung oil methyl ester and 60 parts by mass of hydrogen peroxide under the catalysis of 0.3 part by mass of silver phosphotungstate to obtain epoxidized tung oil methyl ester, wherein the epoxidizing temperature is 60 ℃, and the reaction time is 4 hours; cooling to 0 ℃ after the reaction is finished, and centrifugally separating hydrogen peroxide, water and a catalyst in the system;
(2) 30 parts by mass of epoxidized tung oil methyl ester is reacted with 60 parts by mass of diethyl phosphate, 0.03 part by mass of triphenylphosphine and 0.01 part by mass of silver phosphotungstate catalyst to obtain the vegetable oil-based flame retardant of the embodiment, wherein the reaction temperature is 60 ℃, and the reaction time is 4 hours.
The vegetable oil-based flame retardant of the embodiment can be used for preparing a bamboo-wood expansion type protective agent, and the bamboo-wood expansion type protective agent of the embodiment comprises the following components in parts by mass: 50 parts of vegetable oil-based flame retardant, 50 parts of ethanol and 50 parts of water. The application method of the bamboo-wood expansion type protective agent in the embodiment comprises the following steps: firstly, placing the vegetable oil-based flame retardant, ethanol and water in a beaker, stirring to clarify the mixture to obtain liquid medicine, then immersing the substrate in the liquid medicine, taking out the substrate after 2h of pressurized immersion, and drying the substrate at 60 ℃ for 12h.
Example 5
The molecular formula of the vegetable oil-based flame retardant is shown in formula (1):
the preparation method of the vegetable oil-based flame retardant comprises the following steps:
(1) Epoxidizing 30 parts by mass of tung oil methyl ester and 60 parts by mass of hydrogen peroxide under the catalysis of 0.3 part by mass of silver phosphotungstate to obtain epoxidized tung oil methyl ester, wherein the epoxidizing temperature is 70 ℃, and the reaction time is 3 hours; cooling to 0 ℃ after the reaction is finished, and centrifugally separating hydrogen peroxide, water and a catalyst in the system;
(2) 30 parts by mass of epoxidized tung oil methyl ester is reacted with 60 parts by mass of diethyl phosphate, 0.03 part by mass of triphenylphosphine and 0.01 part by mass of silver phosphotungstate catalyst to obtain the vegetable oil-based flame retardant of the embodiment, wherein the reaction temperature is 60 ℃, and the reaction time is 4 hours.
The vegetable oil-based flame retardant of the embodiment can be used for preparing a bamboo-wood expansion type protective agent, and the bamboo-wood expansion type protective agent of the embodiment comprises the following components in parts by mass: 50 parts of vegetable oil-based flame retardant, 50 parts of ethanol and 50 parts of water. The application method of the bamboo-wood expansion type protective agent in the embodiment comprises the following steps: firstly, placing the vegetable oil-based flame retardant, ethanol and water in a beaker, stirring to clarify the mixture to obtain liquid medicine, then immersing the substrate in the liquid medicine, taking out the substrate after 2h of pressurized immersion, and drying the substrate at 60 ℃ for 12h.
Example 6
The molecular formula of the vegetable oil-based flame retardant is shown in formula (1):
the preparation method of the vegetable oil-based flame retardant comprises the following steps:
(1) Epoxidizing 30 parts by mass of tung oil methyl ester and 60 parts by mass of hydrogen peroxide under the catalysis of 0.3 part by mass of silver phosphotungstate to obtain epoxidized tung oil methyl ester, wherein the epoxidizing temperature is 60 ℃, and the reaction time is 4 hours; cooling to 0 ℃ after the reaction is finished, and centrifugally separating hydrogen peroxide, water and a catalyst in the system;
(2) 30 parts by mass of epoxidized tung oil methyl ester is reacted with 60 parts by mass of diethyl phosphate, 0.03 part by mass of triphenylphosphine and 0.01 part by mass of silver phosphotungstate catalyst to obtain the vegetable oil-based flame retardant of the embodiment, wherein the reaction temperature is 80 ℃ and the reaction time is 4 hours.
The vegetable oil-based flame retardant of the embodiment can be used for preparing a bamboo-wood expansion type protective agent, and the bamboo-wood expansion type protective agent of the embodiment comprises the following components in parts by mass: 50 parts of vegetable oil-based flame retardant, 50 parts of ethanol and 50 parts of water. The application method of the bamboo-wood expansion type protective agent in the embodiment comprises the following steps: firstly, placing the vegetable oil-based flame retardant, ethanol and water in a beaker, stirring to clarify the mixture to obtain liquid medicine, then immersing the substrate in the liquid medicine, taking out the substrate after 2h of pressurized immersion, and drying the substrate at 60 ℃ for 12h.
Example 7
The molecular formula of the vegetable oil-based flame retardant is shown in formula (1):
the preparation method of the vegetable oil-based flame retardant comprises the following steps:
(1) Epoxidizing 30 parts by mass of tung oil methyl ester and 60 parts by mass of hydrogen peroxide under the catalysis of 0.3 part by mass of silver phosphotungstate to obtain epoxidized tung oil methyl ester, wherein the epoxidizing temperature is 60 ℃, and the reaction time is 4 hours; cooling to 0 ℃ after the reaction is finished, and centrifugally separating hydrogen peroxide, water and a catalyst in the system;
(2) 30 parts by mass of epoxidized tung oil methyl ester is reacted with 60 parts by mass of diethyl phosphate, 0.03 part by mass of triphenylphosphine and 0.01 part by mass of silver phosphotungstate catalyst to obtain the vegetable oil-based flame retardant of the embodiment, wherein the reaction temperature is 80 ℃ and the reaction time is 4 hours.
The vegetable oil-based flame retardant of the embodiment can be used for preparing a bamboo-wood expansion type protective agent, and the bamboo-wood expansion type protective agent of the embodiment comprises the following components in parts by mass: 25 parts of vegetable oil-based flame retardant, 50 parts of ethanol and 50 parts of water. The application method of the bamboo-wood expansion type protective agent in the embodiment comprises the following steps: firstly, placing the vegetable oil-based flame retardant, ethanol and water in a beaker, stirring to clarify the mixture to obtain liquid medicine, then immersing the substrate in the liquid medicine, taking out the substrate after 2h of pressurized immersion, and drying the substrate at 60 ℃ for 12h.
Example 8
The molecular formula of the vegetable oil-based flame retardant is shown in formula (1):
the preparation method of the vegetable oil-based flame retardant comprises the following steps:
(1) Epoxidizing 30 parts by mass of tung oil methyl ester and 60 parts by mass of hydrogen peroxide under the catalysis of 0.3 part by mass of pyridine phosphotungstate to obtain epoxidized tung oil methyl ester, wherein the epoxidation reaction temperature is 60 ℃, and the reaction time is 4 hours; cooling to 0 ℃ after the reaction is finished, and centrifugally separating hydrogen peroxide, water and a catalyst in the system;
(2) 30 parts by mass of epoxidized tung oil methyl ester is reacted with 60 parts by mass of diethyl phosphate, 0.03 part by mass of triphenylphosphine and 0.01 part by mass of pyridine phosphotungstic acid catalyst to obtain the vegetable oil-based flame retardant of the embodiment, wherein the reaction temperature is 80 ℃ and the reaction time is 4 hours.
The vegetable oil-based flame retardant of the embodiment can be used for preparing a bamboo-wood expansion type protective agent, and the bamboo-wood expansion type protective agent of the embodiment comprises the following components in parts by mass: 50 parts of vegetable oil-based flame retardant, 50 parts of ethanol and 50 parts of water. The application method of the bamboo-wood expansion type protective agent in the embodiment comprises the following steps: firstly, placing the vegetable oil-based flame retardant, ethanol and water in a beaker, stirring to clarify the mixture to obtain liquid medicine, then immersing the substrate in the liquid medicine, taking out the substrate after 2h of pressurized immersion, and drying the substrate at 60 ℃ for 12h.
Example 9
The molecular formula of the vegetable oil-based flame retardant is shown in formula (1):
the preparation method of the vegetable oil-based flame retardant comprises the following steps:
(1) Epoxidizing 30 parts by mass of tung oil methyl ester and 60 parts by mass of hydrogen peroxide under the catalysis of 0.3 part by mass of pyridine phosphotungstate to obtain epoxidized tung oil methyl ester, wherein the epoxidation reaction temperature is 60 ℃, and the reaction time is 4 hours; cooling to 0 ℃ after the reaction is finished, and centrifugally separating hydrogen peroxide, water and a catalyst in the system;
(2) 30 parts by mass of epoxidized tung oil methyl ester is reacted with 60 parts by mass of diethyl phosphate, 0.03 part by mass of triphenylphosphine and 0.01 part by mass of pyridine phosphotungstic acid catalyst to obtain the vegetable oil-based flame retardant of the embodiment, wherein the reaction temperature is 80 ℃ and the reaction time is 4 hours.
The vegetable oil-based flame retardant of the embodiment can be used for preparing a bamboo-wood expansion type protective agent, and the bamboo-wood expansion type protective agent of the embodiment comprises the following components in parts by mass: 50 parts of vegetable oil-based flame retardant, 50 parts of ethanol, 50 parts of water and 10 parts of melamine. The application method of the bamboo-wood expansion type protective agent in the embodiment comprises the following steps: firstly, 50 parts of vegetable oil-based flame retardant, 50 parts of ethanol and 50 parts of water are placed in a beaker, stirred to be clarified to obtain liquid medicine A, and then the substrate is immersed in the liquid medicine A for 2 hours, and is taken out after being immersed under pressure; and then placing 50 parts of melamine, 50 parts of ethanol and 50 parts of water in a beaker, stirring to clarify the mixture to obtain a liquid medicine B, placing the bamboo and wood into the liquid medicine B, transferring the liquid medicine B into an impregnating tank, pressurizing and impregnating the bamboo and wood for 2 hours, taking the bamboo and wood out, and drying the bamboo and wood at 60 ℃ for 12 hours. The distribution of the elements inside the bamboo plant tissue treated with the bamboo swelling type protective agent of this example is shown in fig. 1, and it can be seen from the figure that the treated bamboo swelling type protective agent is uniformly dispersed in the bamboo plant tissue.
The substrates treated with the bamboo and wood intumescent protective agents of examples 5-7 and the untreated substrates were subjected to a cone calorimeter, a vertical heat of combustion UL-94, and a limiting oxygen index test, and the comparison results are shown in fig. 2-5 in sequence, and the results show that the substrates treated with the vegetable oil-based flame retardant exhibit excellent thermal stability and higher, durable flame retardant properties, the flame retardant rating reaches V0, and the limiting oxygen index reaches 38.7%.
The above is only a preferred embodiment of the present invention, and the scope of the present invention is not limited to the above examples. Modifications and variations which would be obvious to those skilled in the art without departing from the spirit of the invention are also considered to be within the scope of the invention.
Claims (10)
1. The vegetable oil-based flame retardant is characterized in that the molecular formula of the vegetable oil-based flame retardant is shown as formula (1):
2. a method of preparing the vegetable oil-based flame retardant of claim 1, comprising the steps of:
(1) Reacting tung oil methyl ester and hydrogen peroxide to be complete under the catalysis of a catalyst to obtain epoxidized tung oil methyl ester; the catalyst is a phosphotungstic acid group hybridization catalyst;
(2) And (3) reacting the epoxidized tung oil methyl ester with diethyl phosphate to be complete under the catalysis of triphenylphosphine, thus obtaining the vegetable oil-based flame retardant.
3. The preparation method of the vegetable oil-based flame retardant according to claim 2, wherein the molar ratio of double bonds in the tung oil methyl ester to hydrogen peroxide in the step (1) is 1 (1.1-5); the mass of the catalyst is 1-10% of the mass of the tung oil methyl ester.
4. The method for preparing the vegetable oil-based flame retardant according to claim 2, wherein the reaction temperature of the tung oil methyl ester and the hydrogen peroxide in the step (1) is 40-80 ℃ and the reaction time is 3-6 h.
5. The method for preparing a plant oil-based flame retardant according to claim 2, wherein the tung oil methyl ester and hydrogen peroxide in the step (1) are cooled to 0 ℃ after being reacted completely, and residual hydrogen peroxide and catalyst are obtained through centrifugal separation.
6. The method for producing a vegetable oil-based flame retardant according to claim 2, wherein the catalyst in step (1) is at least one of pyridine phosphotungstate and silver phosphotungstate; the preparation method of the catalyst comprises the following steps: 10 parts by mass of phosphotungstic acid was weighed and completely dissolved in distilled water, and 30 parts by mass of 30wt% H was added 2 O 2 Uniformly mixing at room temperature to obtain a mixed solution; and (3) dropwise adding a silver nitrate solution or pyridine into the mixed solution, continuously stirring for 5min, keeping at 40 ℃ for 12h, filtering, and drying filter residues in a vacuum environment at 60 ℃ to obtain the catalyst.
7. The method for preparing a vegetable oil-based flame retardant according to claim 2, wherein the molar ratio of epoxy bond to diethyl phosphate in the epoxidized tung oil methyl ester in step (2) is 1: (1.8-2); the mass of the triphenylphosphine is 0.2% -0.4% of the mass of the methyl ester of the epoxidized tung oil.
8. The method for preparing a vegetable oil-based flame retardant according to any one of claims 2 to 7, wherein the reaction temperature of the epoxidized tung oil methyl ester and diethyl phosphate in the step (2) is 40 to 80 ℃ and the reaction time is 4 to 6 hours.
9. Use of the vegetable oil-based flame retardant according to claim 1 or the vegetable oil-based flame retardant produced by the production method according to any one of claims 2 to 7 for producing a bamboo intumescent protective agent comprising the following components in parts by mass:
50-100 parts of a vegetable oil-based flame retardant, 50-100 parts of ethanol, 50-100 parts of water and 0-30 parts of melamine.
10. The application of the vegetable oil-based flame retardant according to claim 9, wherein the bamboo-wood expansion type protective agent is used by adding ethanol solution into the vegetable oil-based flame retardant, stirring to obtain clear solution, adding water and melamine to form liquid medicine, immersing the bamboo-wood material into the liquid medicine, pressurizing and immersing for 2 hours, taking out, and drying at 60 ℃ for 12 hours; or the use method of the bamboo-wood expansion type protective agent comprises the steps of adding ethanol solution into a vegetable oil-based flame retardant, stirring to obtain a clear solution, immersing the bamboo-wood material into the clear solution for pressurized impregnation for 2 hours, taking out, immersing the bamboo-wood material into a mixed solution of melamine and ethanol for pressurized impregnation for 2 hours, taking out, and drying at 60 ℃ for 12 hours.
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