CN108373484A - A kind of phosphorous anacardol polyglycidyl ether and preparation method thereof - Google Patents
A kind of phosphorous anacardol polyglycidyl ether and preparation method thereof Download PDFInfo
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- CN108373484A CN108373484A CN201810157861.9A CN201810157861A CN108373484A CN 108373484 A CN108373484 A CN 108373484A CN 201810157861 A CN201810157861 A CN 201810157861A CN 108373484 A CN108373484 A CN 108373484A
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- anacardol
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- polyglycidyl ether
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 50
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 244000226021 Anacardium occidentale Species 0.000 claims abstract description 10
- 235000020226 cashew nut Nutrition 0.000 claims abstract description 10
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 7
- 235000021317 phosphate Nutrition 0.000 claims abstract description 7
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims abstract description 7
- 239000004593 Epoxy Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 4
- 239000011574 phosphorus Substances 0.000 claims abstract description 4
- HSRJKNPTNIJEKV-UHFFFAOYSA-N Guaifenesin Chemical compound COC1=CC=CC=C1OCC(O)CO HSRJKNPTNIJEKV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims description 25
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- CUXQLKLUPGTTKL-UHFFFAOYSA-M microcosmic salt Chemical compound [NH4+].[Na+].OP([O-])([O-])=O CUXQLKLUPGTTKL-UHFFFAOYSA-M 0.000 claims description 6
- 208000012287 Prolapse Diseases 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000006467 substitution reaction Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- -1 Alkyl imidazole Chemical compound 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 238000006114 decarboxylation reaction Methods 0.000 claims description 3
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 claims description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 2
- 150000004941 2-phenylimidazoles Chemical class 0.000 claims description 2
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical group OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims description 2
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- LULAYUGMBFYYEX-UHFFFAOYSA-N metachloroperbenzoic acid Natural products OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims 2
- 150000002924 oxiranes Chemical class 0.000 claims 2
- 125000003944 tolyl group Chemical group 0.000 claims 2
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims 1
- 239000003822 epoxy resin Substances 0.000 abstract description 9
- 229920000647 polyepoxide Polymers 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 150000002118 epoxides Chemical class 0.000 abstract description 4
- 239000003063 flame retardant Substances 0.000 abstract description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 150000001412 amines Chemical class 0.000 abstract description 2
- 239000003085 diluting agent Substances 0.000 abstract description 2
- 125000003700 epoxy group Chemical group 0.000 abstract 1
- 150000002170 ethers Chemical class 0.000 abstract 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 abstract 1
- 239000010452 phosphate Substances 0.000 abstract 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 abstract 1
- 239000000463 material Substances 0.000 description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 239000005711 Benzoic acid Substances 0.000 description 3
- 235000010233 benzoic acid Nutrition 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical class CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000009967 tasteless effect Effects 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
- C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
- C07F9/65502—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a three-membered ring
- C07F9/65505—Phosphonic acids containing oxirane groups; esters thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Epoxy Resins (AREA)
Abstract
The present invention relates to a kind of phosphorous anacardol polyglycidyl ethers and preparation method thereof with flame retardant effect and toughening effect.Anacardol and phosphorus oxychloride reaction are prepared three cashew nut phosphates by the present invention by nucleophilic substitution reaction, and the unsaturated hydro carbons on this phosphate is then carried out peroxidization, epoxy group is oxidized to, prepares phosphorous anacardol polyglycidyl ether.Glycerin ether prepared by the present invention have many advantages, such as it is at low cost, environmentally friendly, renewable, while generate phosphorous anacardol polyglycidyl ether have polyepoxy, the characteristic containing ignition-proof element phosphorus.The polyglycidyl ether that the present invention synthesizes, due to the alkyl chain with multiple length, to have good toughness.On the one hand the phosphorous anacardol polyglycidyl ether that the present invention synthesizes can be used as epoxide diluent, still further aspect can be used for modified epoxy amine curing agent, and both methods can improve the toughness of epoxy resin.
Description
Technical field
Extract-cardanol glycidyl ether in a kind of plant of present invention design, and in particular to a kind of phosphorous more shrinks are sweet
The preparation method of oily ether.
Background technology
Anacardol is the natural phenolic compound obtained from natural cashew nut shell liquid, is that cashew nut shell liquid passes through at high temperature decarboxylation
What reason obtained.Anacardol as the natural phenolic compound of the long carbon alkyl containing 0-3 degree of unsaturation, not only with fragrance
The chemical property of compounds of group and unsaturated aliphatic hydrocarbon, the also feature with phenolic compound, its unique chemical constitution assign
Its special chemical property, and abundance, it is cheap, non-toxic and tasteless, there is huge application prospect and research and development valence
Value.
The long chain hydrocarbon groups structure of anacardol side chain can provide good toughness, particularly this crisp to epoxy resin for system
Property material, have good toughening effect.The currently reported use about anacardol toughening or modified epoxy
In method, on the one hand added with physics based on, but easily cause the migration of anacardol in solidfied material, another invention is with anacardol
Reaction prepares epoxy resin together with phenol, bisphenol-A etc., and preparation process is more complex, and often lead to the anacardol introduced compared with
Few, ideal effect is not achieved in toughening effect.
At fire-retardant aspect, it is considered that there is relatively good effect with phosphorus-the fire-retardant of nitrogen collaboration, and about phosphorous anacardol
Polyglycidyl ether is rarely reported.Therefore the present invention attempts the toughness of anacardol and P elements being concomitantly introduced by chemical mode
Into structure, the anti-flammability of epoxy resin is also improved while improving epoxy resin roughening.
Invention content
The present invention be to solve the above-mentioned problems and provide solution
The present invention provides that a kind of epoxide equivalent is relatively low, viscosity is relatively low, anacardol polyglycidyl ether containing ignition-proof element phosphorus
Method, while the glycidol ether has good toughness.
The purpose of the present invention is what is be accomplished by the following way：
A kind of phosphorous anacardol polyglycidyl ether preparation method, including following following steps：
(1) substitution reaction
It is added in reaction kettle with anacardol, after suitable solvent is then added, catalyst is added, then reduces the temperature of system
To 0 DEG C or so, phosphorus oxychloride is added dropwise, keeps the reaction temperature of system to be less than 10 DEG C, after reacting 3-6 hours, is washed, extracted
It takes, prolapse solvent, prepares three cashew nut base phosphates.
The each component additive amount is that the molar ratio of anacardol and phosphorus oxychloride is 1:（3-5）, catalyst loading is
The 0.5-1% of total amount weight, solvent are selected as the 30-70% of total amount mass fraction.
The anacardol is that natural cashew nut shell liquid is obtained by high temperature decarboxylation, and anacardol content is 95% or more
The phosphorus oxychloride is industrial goods, precision>99%
The solvent be selected from toluene, benzene, dimethylbenzene, tetrahydrofuran, dioxane, isobutanol, acetone, dichloromethane, chloroform,
At least one of propyl alcohol etc., required solvent are anhydrous.
The catalyst is selected from triethylamine, tri-n-butylamine, benzyldimethylamine, 2,4,2,4,6- tri- (dimethylaminomethyl) benzene
Phenol, the tertiary amines such as N methyl piperazine and its esters；2-methylimidazole, 2- phenylimidazoles, 2- undecyl imidazoles, 2- ethyls -4-
Methylimidazole；Tetraphenyl microcosmic salt, methyl tributyl microcosmic salt, methyl tricyanoethyl microcosmic salt, at least one of tetrabutyl microcosmic salt
（2）Oxidation reaction
It will（1）The substance of middle preparation is added in reaction kettle, and solvent is then added, and is then added and is accounted for（1）The substance weight of middle preparation
The oxidant that score is 1-5% is measured, between reaction temperature is 40-50 DEG C, the reaction time is 4-8 hours, after the completion of reaction, is removed
After solvent, it is washed with water, it is dry, prepare phosphorous anacardol polyglycidyl ether.
The solvent be selected from toluene, benzene, dimethylbenzene, tetrahydrofuran, dioxane, isobutanol, acetone, dichloromethane,
At least one of propyl alcohol.
The oxidant is selected from metachloroperbenzoic acid.
The material source of the present invention has many advantages, such as phosphorous waist that is at low cost, environmentally friendly, renewable, while generating in plant
Fruit phenol polyglycidyl ether has polyepoxy, the characteristic containing ignition-proof element phosphorus.The polyglycidyl ether that the present invention synthesizes, by
In the alkyl chain with multiple length, to have good toughness.The phosphorous anacardol polyglycidyl ether one that the present invention synthesizes
Aspect can be used as epoxide diluent, and still further aspect can be used for modified epoxy amine curing agent, both sides
Method can improve the toughness of epoxy resin.
Specific implementation mode
For a further understanding of the present invention, the present invention is illustrated below in conjunction with specific example：
Embodiment 1
(1) substitution reaction
It is added in reaction kettle with 305g anacardols, after 300g dichloromethane solvents then are added, 5g Triethylamine catalysts is added,
Then the temperature of system is reduced to 0 DEG C or so, 450g phosphorus oxychloride is added dropwise, and keeps the reaction temperature of system to be less than 10 DEG C, reaction 3
It after hour, is washed, is extracted, prolapse solvent, prepare three cashew nut base phosphates.
（2）Oxidation reaction
By 500g（1）The substance of middle preparation is added in reaction kettle, and 400g chloroforms are then added, and 10g m-chloro peroxides are then added
Benzoic acid oxidant, between reaction temperature is 40 DEG C, the reaction time is 5 hours, after the completion of reaction, after removing solvent, is washed with water
It washs, it is dry, prepare phosphorous anacardol polyglycidyl ether.
The performance prepared is shown in Table 1
Embodiment 2
(1) substitution reaction
It is added in reaction kettle with 305g anacardols, after 300g dichloromethane solvents then are added, the catalysis of 10g triethylamines is added
Then agent reduces the temperature of system to 0 DEG C or so, 600g phosphorus oxychloride is added dropwise, keep the reaction temperature of system to be less than 10 DEG C, instead
It after answering 4 hours, is washed, is extracted, prolapse solvent, prepare three cashew nut base phosphates.
（2）Oxidation reaction
By 500g（1）The substance of middle preparation is added in reaction kettle, and 400g chloroforms are then added, and 30g m-chloro peroxides are then added
Benzoic acid oxidant, between reaction temperature is 40 DEG C, the reaction time is 6 hours, after the completion of reaction, after removing solvent, is washed with water
It washs, it is dry, prepare phosphorous anacardol polyglycidyl ether.
The performance prepared is shown in Table 1
Embodiment 3
(1) substitution reaction
It is added in reaction kettle with 305g anacardols, after 300g dichloromethane solvents then are added, the catalysis of 15g triethylamines is added
Then agent reduces the temperature of system to 0 DEG C or so, 750g phosphorus oxychloride is added dropwise, keep the reaction temperature of system to be less than 10 DEG C, instead
It after answering 6 hours, is washed, is extracted, prolapse solvent, prepare three cashew nut base phosphates.
（2）Oxidation reaction
By 500g（1）The substance of middle preparation is added in reaction kettle, and 400g chloroforms are then added, and 45g m-chloro peroxides are then added
Benzoic acid oxidant, between reaction temperature is 40 DEG C, the reaction time is 8 hours, after the completion of reaction, after removing solvent, is washed with water
It washs, it is dry, prepare phosphorous anacardol polyglycidyl ether.
The performance prepared is shown in Table 1
Embodiment 4
The cure test of phosphorous anacardol polyglycidyl ether and curing agent
The present embodiment uses the glycerin ether prepared in embodiment 2, and it is mixed with epoxy resin E51 to test different glycidol ethers respectively
The factors such as viscosity, the Solidified enzyme of conjunction, used curing mode are room temperature curing seven days.Specific performance is shown in Table 2
Table 1
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Appearance | Weak yellow liquid | Weak yellow liquid | Weak yellow liquid |
| Viscosity mPa.s | 100-160 | 140-190 | 170-230 |
| Epoxide equivalent g/eq | 780 | 560 | 420 |
Table 2
| Project | 1 | 2 | 3 | 4 |
| Epoxy resin E51 | 100 | 100 | 100 | 100 |
| The phosphorous more glycidols of anacardol Ether | 5 | 10 | 15 | 0 |
| Polyamide 6 50 | 90 | 90 | 90 | 90 |
| The viscosity Pa.s of mixture | 8-10 | 5-7 | 2-4 | 12-14 |
| Solidfied material hardness（Shore D） | 89 | 85 | 75 | 90 |
| Toughness | Brittleness improves, and has tough Property | Toughness is moderate, and hardness reduces not Greatly | Good toughness, hardness drop It is low | Brittleness is big, is easily broken off |
| Oxygen index (OI) | 21 | 23 | 25 | 18 |
From Table 2, it can be seen that with the increase of phosphorous anacardol polyglycidyl ether ratio, there is the toughness of solidfied material after solidification
Increased, hardness decreases, and when additive amount is 10 parts, solidfied material has good toughness and hardness；Simultaneously in solidfied material
P elements are introduced, the oxygen index (OI) of solidfied material is improved, improves the flame retardant property of epoxy resin.
Claims (9)
1. the present invention provides, a kind of epoxide equivalent is relatively low, viscosity is relatively low, the anacardol polyglycidyl ether containing ignition-proof element phosphorus
Method, while the glycidol ether have good toughness, the purpose of the present invention is what is be accomplished by the following way：
(1) substitution reaction
It is added in reaction kettle with anacardol, after suitable solvent is then added, catalyst is added, then reduces the temperature of system
To 0 DEG C or so, phosphorus oxychloride is added dropwise, keeps the reaction temperature of system to be less than 10 DEG C, after reacting 3-6 hours, is washed, extracted
It takes, prolapse solvent, prepares three cashew nut base phosphates；
(2) oxidation reaction
It will（1）The substance of middle preparation is added in reaction kettle, and solvent is then added, and is then added and is accounted for（1）The substance weight of middle preparation
The oxidant that score is 1-5% is measured, between reaction temperature is 40-50 DEG C, the reaction time is 4-8 hours, after the completion of reaction, is removed
After solvent, it is washed with water, it is dry, prepare phosphorous anacardol polyglycidyl ether
。
2. according to claim 1（1）The each component additive amount is that the molar ratio of anacardol and phosphorus oxychloride is 1:（3-
5）, catalyst loading is the 0.5-1% of total amount weight, and solvent is selected as the 30-70% of total amount mass fraction.
3. according to claim 1（1）The anacardol is that natural cashew nut shell liquid is obtained by high temperature decarboxylation, anacardol content
95% or more.
4. according to claim 1（1）The phosphorus oxychloride is industrial goods, precision>99%.
5. according to claim 1（1）The solvent is selected from toluene, benzene, dimethylbenzene, tetrahydrofuran, dioxane, isobutyl
At least one of alcohol, acetone, dichloromethane, chloroform, propyl alcohol etc., required solvent are anhydrous.
6. according to claim 1（1）The catalyst is selected from triethylamine, tri-n-butylamine, benzyldimethylamine, 2,4,2,4,6- tri-
(dimethylaminomethyl) phenol, the tertiary amines such as N methyl piperazine and its esters；2-methylimidazole, 2- phenylimidazoles, 2- 11
Alkyl imidazole, 2-ethyl-4-methylimidazole；Tetraphenyl microcosmic salt, methyl tributyl microcosmic salt, methyl tricyanoethyl microcosmic salt, four fourths
At least one of base microcosmic salt.
7. according to claim 1（2）The solvent is selected from toluene, benzene, dimethylbenzene, tetrahydrofuran, dioxane, isobutyl
At least one of alcohol, acetone, dichloromethane, propyl alcohol.
8. claim 1（1）The oxidant is selected from metachloroperbenzoic acid.
9. according to claim 1-8, prepare phosphorous anacardol polyglycidyl ether, the glycerin ether have epoxide equivalent it is relatively low,
Viscosity is relatively low, also can provide anti-flammability to epoxy while flexibilizing epoxy.
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