CN109516965A - A kind of synthetic method of TGDDM epoxy resin - Google Patents
A kind of synthetic method of TGDDM epoxy resin Download PDFInfo
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- CN109516965A CN109516965A CN201811399513.9A CN201811399513A CN109516965A CN 109516965 A CN109516965 A CN 109516965A CN 201811399513 A CN201811399513 A CN 201811399513A CN 109516965 A CN109516965 A CN 109516965A
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- Prior art keywords
- epoxy resin
- tgddm
- epoxychloropropane
- synthetic method
- temperature
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- FAUAZXVRLVIARB-UHFFFAOYSA-N 4-[[4-[bis(oxiran-2-ylmethyl)amino]phenyl]methyl]-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC(CC=2C=CC(=CC=2)N(CC2OC2)CC2OC2)=CC=1)CC1CO1 FAUAZXVRLVIARB-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 108
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 108
- 238000010189 synthetic method Methods 0.000 title claims abstract description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 83
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- 238000005406 washing Methods 0.000 claims abstract description 56
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000002002 slurry Substances 0.000 claims abstract description 37
- -1 amino chloropropyl alcohol Chemical compound 0.000 claims abstract description 33
- 238000000605 extraction Methods 0.000 claims abstract description 31
- 239000003085 diluting agent Substances 0.000 claims abstract description 28
- 238000000926 separation method Methods 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 26
- 230000018044 dehydration Effects 0.000 claims abstract description 22
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 19
- 239000012074 organic phase Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims abstract description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 115
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 74
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 63
- 235000019441 ethanol Nutrition 0.000 claims description 60
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 47
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 47
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 42
- 239000012071 phase Substances 0.000 claims description 41
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 39
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 29
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 28
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 28
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 28
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims description 28
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 28
- BVWCFOXBDSMXEP-UHFFFAOYSA-N 1-(5-acetyl-2-methoxyphenyl)-3-methylbutan-1-one Chemical compound COC1=CC=C(C(C)=O)C=C1C(=O)CC(C)C BVWCFOXBDSMXEP-UHFFFAOYSA-N 0.000 claims description 26
- 238000002360 preparation method Methods 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 22
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 21
- 239000003960 organic solvent Substances 0.000 claims description 21
- 238000004821 distillation Methods 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 239000011521 glass Substances 0.000 claims description 17
- ZXUCBXRTRRIBSO-UHFFFAOYSA-L tetrabutylazanium;sulfate Chemical compound [O-]S([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC ZXUCBXRTRRIBSO-UHFFFAOYSA-L 0.000 claims description 15
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 14
- 235000011187 glycerol Nutrition 0.000 claims description 14
- ARRNBPCNZJXHRJ-UHFFFAOYSA-M hydron;tetrabutylazanium;phosphate Chemical compound OP(O)([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC ARRNBPCNZJXHRJ-UHFFFAOYSA-M 0.000 claims description 14
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 14
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims description 14
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 13
- AJSHDAOMUKXVDC-UHFFFAOYSA-N butan-1-amine;sulfuric acid Chemical compound CCCC[NH3+].OS([O-])(=O)=O AJSHDAOMUKXVDC-UHFFFAOYSA-N 0.000 claims description 11
- CFYRHPJXXCHEFX-UHFFFAOYSA-L hydrogen phosphate;tetrabutylazanium Chemical compound OP([O-])([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC CFYRHPJXXCHEFX-UHFFFAOYSA-L 0.000 claims description 11
- 239000008346 aqueous phase Substances 0.000 claims description 8
- 239000008096 xylene Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 4
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 238000007086 side reaction Methods 0.000 abstract description 8
- 230000035484 reaction time Effects 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 19
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 11
- 239000000460 chlorine Substances 0.000 description 11
- 229910052801 chlorine Inorganic materials 0.000 description 11
- 150000002924 oxiranes Chemical class 0.000 description 10
- 238000010792 warming Methods 0.000 description 9
- 238000009833 condensation Methods 0.000 description 7
- 230000005494 condensation Effects 0.000 description 7
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 description 3
- 239000010426 asphalt Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- ICXXXLGATNSZAV-UHFFFAOYSA-N butylazanium;chloride Chemical compound [Cl-].CCCC[NH3+] ICXXXLGATNSZAV-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001335 demethylating effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000006166 lysate Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- WSGCRAOTEDLMFQ-UHFFFAOYSA-N nonan-5-one Chemical compound CCCCC(=O)CCCC WSGCRAOTEDLMFQ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/24—Synthesis of the oxirane ring by splitting off HAL—Y from compounds containing the radical HAL—C—C—OY
- C07D301/26—Y being hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/36—Compounds containing oxirane rings with hydrocarbon radicals, substituted by nitrogen atoms
-
- 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
- C08G59/20—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 epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3227—Compounds containing acyclic nitrogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a kind of synthetic method of TGDDM epoxy resin, this method comprises: one, 4,4'- diaminodiphenylmethane mixed into obtain material liquid with organic diluent, epoxychloropropane；Two, droplets of feed is added in epoxychloropropane, catalyst and auxiliary agent and reacts to obtain the slurry containing amino chloropropyl alcohol；Three, sodium hydroxide solution is added drop-wise to dehydration closed-loop reaction in the slurry containing amino chloropropyl alcohol must be containing the slurry of TGDDM epoxy resin；Four, the slurry containing TGDDM epoxy resin is carried out extracting to obtain extraction organic phase；Five, extraction organic phase is washed into obtain washing organic phase；Six, washing organic phase is distilled into obtain TGDDM epoxy resin.The present invention shortens the reaction time using catalyst and auxiliary agent, reduces the generation of side reaction, by using short-path evaporator Separation of Organic and product, avoids TGDDM epoxy resin self-curing at high temperature, improve the quality of product.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to a kind of synthetic method of TGDDM epoxy resin.
Background technique
N, N, N', N'- four glycidyl group -4,4'- diaminodiphenylmethane (TGDDM) have biggish rigidity and reaction
Activity can be used as the resin matrix of high-performance composite materials, be widely used in space flight and aviation, medical instrument, electronic package material
And the fields such as solar panel.Its structural formula is as follows:
The current universal synthesis method of TGDDM epoxy resin be 4,4 '-diaminodiphenylmethane solids at a certain temperature
It is added in epoxychloropropane and carries out ring-opening reaction, after reacting a period of time, add acetone, the reaction was continued a period of time, so
Sodium hydroxide solution is added afterwards and carries out ring-closure reaction, after reaction, toluene is added and extracts TGDDM epoxy resin, obtained first
Benzene layer is distilled to obtain TGDDM epoxy resin at not less than 120 DEG C after washing.Since the reaction is that violent heat release is anti-
It answers, a large amount of 4 is once added into epoxychloropropane, 4 '-diaminodiphenylmethane will lead to reaction temperature and rise rapidly and send out
It is raw sudden and violent poly-, it can also make intermediate product chloropharin and 4, the amino polycondensation of 4 '-diamino hexichol first generates macromolecule product, influences to produce
Article matter；Acetone energy lysate TGDDM epoxy resin, causes product yield to decline；It is higher to be evaporated under reduced pressure piptonychia benzene temperature, produces
Object may self-curing.
CN103819653 discloses a kind of deceleration distillating method of solvent in removal synthetic epoxy resin, and this method is by one
4, the 4'- diaminodiphenylmethane of quantitative proportioning is put into flask, and epoxychloropropane and toluene is added, lower anti-at 60 DEG C or so
It answers 6 hours, 30 DEG C or so is cooled to after having reacted, in two steps plus lye, add within 2 hours.Standing divides water after reaching reaction end,
It is warming up to 110 DEG C of recycling epoxychloropropane.It adds a large amount of methyl-isobutyls (first) ketone and water is extracted, again through washing, mistake
Filter obtains crude product.When crude product is warming up to 100 DEG C or so, solvent is largely vaporized, and opens vacuum pump at this time, most of molten
Agent is condensed to form condensate liquid, enters the spherical part of buffer by the condensation of the first weight condensing unit；?
Filter latter stage be warming up to 150 DEG C or so, in crude product residual solvent can directly by first weight condensing unit condense out to be formed it is cold
Lime set obtains qualified product so that reach solvent sufficiently eliminates separation.The inventive step is cumbersome, and water rinses are easy to produce
Raw emulsion, product impurity content is high, and waste liquid amount is big, and post processing cost is high.
That there are processing steps is cumbersome for TGDDM epoxy resin synthetic method at present, and by-product is more, and the waste liquid amount generated
Greatly, the disadvantages of post processing cost is high.
Summary of the invention
Technical problem to be solved by the present invention lies in view of the above shortcomings of the prior art, provide a kind of TGDDM ring
The synthetic method of oxygen resin.This method shortens the time being stirred to react with dehydration closed-loop reaction using catalyst and auxiliary agent, from
And the generation of side reaction is effectively controlled and reduces, the quality of product is improved, and use short-path evaporator Separation of Organic
With TGDDM epoxy resin, the high-temperature residence time of TGDDM epoxy resin is substantially reduced, avoids TGDDM epoxy resin in height
The lower self-curing of temperature, further improves the quality of TGDDM epoxy resin, solves that the reaction time existing in the prior art is long, produces
The problem that object epoxide equivalent is big, impurity content is high.
In order to solve the above technical problems, the technical solution adopted by the present invention is that: a kind of synthesis side of TGDDM epoxy resin
Method, which is characterized in that method includes the following steps:
Step 1: the preparation of material liquid: under conditions of normal pressure and temperature are 20 DEG C~35 DEG C, by 4,4'- diamino two
Phenylmethane is uniformly mixed with organic diluent, epoxychloropropane, obtains material liquid；
Step 2: the preparation of amino chloropropyl alcohol:, will in 1h~5h under conditions of normal pressure and temperature are 35 DEG C~75 DEG C
Droplets of feed obtained in step 1 is added in the double-layer glass reaction kettle for being contained with epoxychloropropane, catalyst and auxiliary agent and stirs
5h~20h is reacted, the slurry containing amino chloropropyl alcohol is obtained；It is described be stirred to react during when reaction system becomes viscous to being not easy
When stirring, into reaction system be added organic diluent be diluted, the organic diluent with it is organic dilute described in step 1
It is identical to release agent；
Step 3: the dehydration closed-loop of amino chloropropyl alcohol: under conditions of normal pressure and temperature are 35 DEG C~80 DEG C, by quality hundred
The sodium hydroxide solution that point concentration is 20%~40% is added drop-wise in 0.5h~3h contains amino chlorine third obtained in step 2
In the slurry of alcohol, then dehydration closed-loop reaction 0.5h~4h under the conditions of 35 DEG C~80 DEG C of temperature, is obtained containing TGDDM epoxy
The slurry of resin；
Step 4: extraction: organic solvent is added into the slurry containing TGDDM epoxy resin obtained in step 3, so
Afterwards under conditions of normal pressure and temperature are 50 DEG C~90 DEG C using the speed of 100r/min~260r/min stir 10min~
30min, then be layered after standing 10min~40min, extraction organic phase and aqueous phase extracted are respectively obtained after separation；
Step 5: washing: deionized water is added into extraction organic phase obtained in step 4, is then 50 DEG C in temperature
10min~30min is stirred using the speed of 100r/min~260r/min under conditions of~90 DEG C, then stands 10min~40min
After be layered, respectively obtain after separation washing organic phase and washing water phase；
Step 6: distillation: to obtained in step 5 washing organic phase repeat step 5 in plus water, stirring, layering and
Separating technology obtains the washing organic phase of the epoxy resin containing TGDDM until washing water phase is neutrality, is then evaporated using short distance
The washing organic phase of the epoxy resin containing TGDDM is carried out distillation and sloughs organic solvent by device, obtains amber TGDDM asphalt mixtures modified by epoxy resin
Rouge.
First material liquid is made in the dissolution of 4,4'- diaminodiphenylmethane by the present invention, is added drop-wise to containing catalyst and auxiliary agent
It is stirred to react in epoxychloropropane, obtains the slurry containing amino chloropropyl alcohol, sodium hydroxide solution is then added dropwise and is taken off
Water ring-closure reaction successively after extraction and washing, then uses short-path evaporator to be distilled, obtains amber TGDDM epoxy
Resin, due to shortening the time being stirred to react with dehydration closed-loop reaction using catalyst and auxiliary agent, to effectively control and subtract
The generation for having lacked side reaction improves the quality of product, and uses short-path evaporator Separation of Organic and TGDDM asphalt mixtures modified by epoxy resin
Rouge substantially reduces the high-temperature residence time of TGDDM epoxy resin, avoids TGDDM epoxy resin self-curing at high temperature, into
One step improves the quality of TGDDM epoxy resin.
Chemical reaction process of the invention is as follows:
The synthetic method of above-mentioned a kind of TGDDM epoxy resin, which is characterized in that organic diluent described in step 1 is
The mixture of one or more of methanol, ethyl alcohol, isopropanol, acetone, methyl iso-butyl ketone (MIBK) and espeleton, it is described to have
The volume of machine diluent be epoxychloropropane total volume described in epoxychloropropane and step 2 described in step 1 20%~
30%.Organic diluent described in step 1 is preferably the mixture of one or more of methanol, ethyl alcohol or acetone.Step
The concentration for preferably reducing reactants and products in reaction system is played in rapid one using above-mentioned diluent, slows down ring-opening reaction speed
Degree, while reaction system viscosity is reduced, increase heat transfer rate, avoids the effect for leading to implode due to very exothermic；In step 1
In it is too small without using the amount of diluent or diluent, will lead to 4,4'- diaminodiphenylmethane and epoxychloropropane mixed process
It is middle that violent exothermic reaction occurs, but dilution dosage is too big, and reactant concentration reduces, and the reaction that will lead to step 2 cannot be complete
It carries out, so that being easily saponified chlorinity increase in final product, epoxide number is reduced, therefore both using the organic diluent of above-mentioned volume
It is avoided that violent exothermic reaction, in turn ensures going on smoothly for the reaction of step 2.
A kind of synthetic method of above-mentioned TGDDM epoxy resin, which is characterized in that epoxychloropropane described in step 1
Volume is 40%~80% of epoxychloropropane total volume described in epoxychloropropane described in step 1 and step 2, step 1
Described in epoxychloropropane described in epoxychloropropane and step 2 total material amount and step 1 described in 4,4'- diamino
The ratio between amount of substance of diphenyl-methane is (4~5): 1.Reasonable distribution is added to the volume of the epoxychloropropane in material liquid, with
And reaction raw materials epoxychloropropane and 4, the additional amount ratio of 4'- diaminodiphenylmethane effectively control material liquid and prepared
Rate of heat release in journey, avoids raw material implode and intermediate product chloropharin and 4 caused by reaction temperature rises rapidly, and 4 '-two
The by-product that the amino polycondensation of aminodiphenyl first generates, further improves the quality of product TGDDM epoxy resin.
The synthetic method of above-mentioned a kind of TGDDM epoxy resin, which is characterized in that catalyst described in step 2 is four fourths
Base ammonium bromide, tetrabutylammonium iodide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, tetrabutyl ammonium hydrogen phosphate, tetrabutyl ammonium sulfate
With one or more kinds of mixtures of tetrabutyl ammonium phosphate, the quality of the catalyst is 4,4'- bis- described in step 1
The 0.2%~2% of diaminodiphenylmethane quality.The preferred tetrabutylammonium chloride of catalyst described in step 2, tetrabutyl hydrogen sulfate
The mixture of one or more of ammonium and tetrabutyl ammonium sulfate.Be conducive to shorten the reaction time using above-mentioned catalyst,
The generation for reducing side reaction improves the epoxide number of product to reduce the quality of impurity in product TGDDM epoxy resin.
The synthetic method of above-mentioned a kind of TGDDM epoxy resin, which is characterized in that auxiliary agent described in step 2 is second two
The mixture of one or more of alcohol, propylene glycol, glycerine and pentaerythrite, the quality of the auxiliary agent are in step 1
The 5%~20% of the 4,4'- diaminodiphenylmethane quality.The auxiliary agent is preferably ethylene glycol and/or glycerine.Using alcohol
Analog assistant effectively inhibits the hydrolysis of epoxychloropropane, reduces the generation of side reaction, is conducive to improve product TGDDM asphalt mixtures modified by epoxy resin
The epoxide number of rouge, to reduce the content of the inorganic chlorine and easily saponification chlorine in product.
A kind of synthetic method of above-mentioned TGDDM epoxy resin, which is characterized in that organic diluent described in step 2
Volume is 20%~80% of epoxychloropropane total volume described in epoxychloropropane described in step 1 and step 2.Stirring is anti-
Answer process that the organic diluent of above-mentioned volume is added, reduce the viscosity of reaction system, facilitate mass transfer in reaction process and
Heat transfer is conducive to going on smoothly for reaction.
A kind of synthetic method of above-mentioned TGDDM epoxy resin, which is characterized in that sodium hydroxide solution described in step 3
The total material of epoxychloropropane described in epoxychloropropane described in the amount and step 1 of the substance of middle sodium hydroxide and step 2
The ratio between amount be (1.0~1.5): 1.The amount of sodium hydroxide is added by control, to control the degree of dehydration closed-loop reaction, makes anti-
It answers the main reaction in system to carry out towards the direction of dehydration closed-loop reaction, reduces the generation of side reaction, be conducive to improve product
The quality of TGDDM epoxy resin.
The synthetic method of above-mentioned a kind of TGDDM epoxy resin, which is characterized in that organic solvent described in step 4 is second
The mixture of one or more of acetoacetic ester, dioxane, benzene,toluene,xylene and hexone, it is described
The volume of organic solvent is 1~4 times of epoxychloropropane total volume described in epoxychloropropane described in step 1 and step 2.
The organic solvent is preferably benzene, toluene or dimethylbenzene.Above-mentioned organic solvent not only has product TGDDM epoxy resin good
Dissolubility, and polarity is smaller, is easily separated from water, and is conducive to the progress of extraction separation process；Due to organic in extraction process
Solvent usage is too small to will lead to organic phase difficulty separated from the water, and consumption of organic solvent is excessive to will increase separation costs, therefore selects
The efficiency of extraction and separation can be improved with the organic solvent of above-mentioned volume, reduce separation costs.
The synthetic method of above-mentioned a kind of TGDDM epoxy resin, which is characterized in that deionized water described in step 5 and step
The volume ratio of organic solvent described in rapid four is (0.2~0.6): 1.The deionized water of above-mentioned volume, which can effectively remove extraction, to be had
Water-soluble impurity in machine phase, further improves the quality of product TGDDM epoxy resin, and is conducive to subsequent distillation process
Go on smoothly.
The synthetic method of above-mentioned a kind of TGDDM epoxy resin, which is characterized in that the temperature of distillation described in step 6 is
110 DEG C~180 DEG C, pressure is 0.01MPa~0.03MPa.Solvent and TGDDM ring are conducive to using above-mentioned distillation technique parameter
The separation of oxygen resin, while the high-temperature residence time of TGDDM epoxy resin is also shortened, TGDDM epoxy resin is avoided in height
The lower self-curing of temperature, further improves the quality of TGDDM epoxy resin.
Compared with the prior art, the present invention has the following advantages:
1, the present invention shortens the time being stirred to react with dehydration closed-loop reaction using catalyst and auxiliary agent, to effectively control
The generation for making and reducing side reaction improves the quality of product, and uses short-path evaporator Separation of Organic and TGDDM ring
Oxygen resin substantially reduces the high-temperature residence time of TGDDM epoxy resin, avoids TGDDM epoxy resin at high temperature from solid
Change, further improve the quality of TGDDM epoxy resin, solves that reaction time existing in the prior art is long, product epoxy is worked as
The problem that amount is big, impurity content is high.
2, the present invention using alcohols organic diluent preparation raw material liquid and is diluted reaction system, reduces side reaction
Generation, effectively reduce the content of inorganic chlorine in product and easily saponification chlorine, solve machine chlorine in product TGDDM epoxy resin,
The high problem of content of organic chloride.
3, the deionized water in synthesis process of the present invention, extractant, diluent can be recycled, to reduce place
Cost is managed, greatly reduces waste material liquid measure, and entire synthesis process is almost pollution-free to environment.
4, present invention short-path evaporator Separation of Organic and product TGDDM epoxy resin, improves organic solvent
The rate of recovery, reduces the discharge of synthesis waste liquid, while improving production efficiency, reduces the energy consumption in production process.
Technical solution of the present invention is described in further detail below by embodiment.
Specific embodiment
Embodiment 1
The preparation method of the present embodiment the following steps are included:
Step 1: the preparation of material liquid: under conditions of normal pressure and temperature are 20 DEG C, by 4, the 4'- diamino of 594.8g
Diphenyl-methane is uniformly mixed with 282mL ethyl alcohol, 376mL epoxychloropropane, obtains material liquid；
Step 2: the preparation of amino chloropropyl alcohol: in the double-layer glass reaction kettle that condensation reflux unit and agitating device are housed
Middle addition 565mL epoxychloropropane and 1.2g tetrabutylammonium chloride simultaneously open agitating device, and 29.74g is added after being warming up to 75 DEG C
Droplets of feed obtained in step 1 is added to bilayer in 1h then under conditions of normal pressure and temperature are 75 DEG C by glycerine
In glass reaction kettle, it is stirred to react 2h under conditions of 75 DEG C, when reaction system becomes viscous to when being not easy to stir, to reaction system
Middle addition 753mL ethyl alcohol is diluted, then is stirred to react 3h under conditions of 75 DEG C, obtains the slurry containing amino chloropropyl alcohol；
Step 3: the dehydration closed-loop of amino chloropropyl alcohol: under conditions of normal pressure and temperature are 80 DEG C, by mass percentage concentration
It is added drop-wise in 0.5h in the slurry containing amino chloropropyl alcohol obtained in step 2 for 20% sodium hydroxide solution, then exists
Dehydration closed-loop reaction 0.5h under the conditions of 80 DEG C of temperature, obtains the slurry containing TGDDM epoxy resin；The sodium hydroxide solution
It is dissolved in 1920mL deionized water by 480g sodium hydroxide and prepares and obtain；
Step 4: extraction: it is different that 941mL methyl being added into the slurry containing TGDDM epoxy resin obtained in step 3
Butyl ketone, then normal pressure and it is at a temperature of 90 °C under the conditions of 10min stirred using the speed of 100r/min, then stand
It is layered after 10min, respectively obtains extraction hexone phase and aqueous phase extracted after separation；
Step 5: washing: 565mL deionized water is added into extraction hexone phase obtained in step 4,
Then 10min is stirred using the speed of 100r/min under the conditions of at a temperature of 90 °C, then is layered after standing 10min, through separating
After respectively obtain washing hexone phase and washing water phase；
Step 6: distillation: mutually repeating in step 5 plus water to washing hexone obtained in step 5, stir
It mixes, be layered and separating technology, until washing water phase is neutrality, obtain the washing hexone of the epoxy resin containing TGDDM
Then phase uses short-path evaporator in temperature for 110 DEG C, pressure washes epoxy resin containing TGDDM under conditions of being 0.01MPa
It washs hexone and mutually carries out distillation demethylating isobutyl ketone, obtain amber TGDDM epoxy resin.
Through detecting, the quality for the TGDDM epoxy resin that the present embodiment is prepared is 1152g, yield 91%, TGDDM
The epoxide equivalent of epoxy resin is 132, content of inorganic chlorine 13.3ppm, and being easily saponified chlorinity is 486ppm, and viscosity (50 DEG C) is
3429mPa·S。
The organic diluent of the present embodiment can also be in methanol, isopropanol, acetone, methyl iso-butyl ketone (MIBK) and espeleton
Two or more mixtures in one kind or methanol, ethyl alcohol, isopropanol, acetone, methyl iso-butyl ketone (MIBK) and espeleton.
The catalyst of the present embodiment can also be tetrabutylammonium bromide, tetrabutylammonium iodide, 4-butyl ammonium hydrogen sulfate, four fourths
One of base ammonium hydrogen phosphate, tetrabutyl ammonium sulfate and tetrabutyl ammonium phosphate or tetrabutylammonium bromide, tetrabutylammonium iodide,
Two kinds in tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, tetrabutyl ammonium hydrogen phosphate, tetrabutyl ammonium sulfate and tetrabutyl ammonium phosphate
Above mixture.
The auxiliary agent of the present embodiment can also be one of ethylene glycol, propylene glycol and pentaerythrite or ethylene glycol, the third two
Alcohol, glycerine, the two or more mixtures in pentaerythrite.
The organic solvent of the present embodiment can also one of for ethyl acetate, dioxane, benzene, dimethylbenzene and toluene,
Or the two or more mixtures in ethyl acetate, dioxane, benzene,toluene,xylene and hexone.
Embodiment 2
The preparation method of the present embodiment the following steps are included:
Step 1: the preparation of material liquid: under conditions of normal pressure and temperature are 35 DEG C, by 4, the 4'- diamino of 594.8g
Diphenyl-methane is uniformly mixed with 198mL methanol, 790mL epoxychloropropane, obtains material liquid；
Step 2: the preparation of amino chloropropyl alcohol: in the double-layer glass reaction kettle that condensation reflux unit and agitating device are housed
Middle addition 198mL epoxychloropropane and 5.95g tetrabutyl ammonium sulfate simultaneously open agitating device, and 59.5g is added after being warming up to 35 DEG C
Droplets of feed obtained in step 1 is added to bilayer in 5h then under conditions of normal pressure and temperature are 35 DEG C by glycerine
In glass reaction kettle, it is stirred to react 6h under conditions of 35 DEG C, when reaction system becomes viscous to when being not easy to stir, to reaction system
Middle addition 593mL methanol is diluted, then is stirred to react 14h under conditions of 35 DEG C, obtains the slurry containing amino chloropropyl alcohol；
Step 3: the dehydration closed-loop of amino chloropropyl alcohol: under conditions of normal pressure and temperature are 35 DEG C, by mass percentage concentration
It is added drop-wise in 0.5h in the slurry containing amino chloropropyl alcohol obtained in step 2 for 40% sodium hydroxide solution, then exists
Dehydration closed-loop reaction 4h under the conditions of 35 DEG C of temperature, obtains the slurry containing TGDDM epoxy resin；The sodium hydroxide solution by
756g sodium hydroxide is dissolved in 1134mL deionized water and prepares and obtain；
Step 4: extraction: 3952mL benzene being added into the slurry containing TGDDM epoxy resin obtained in step 3, so
30min is stirred using the speed of 260r/min under conditions of normal pressure and temperature are 50 DEG C afterwards, then is layered after standing 40min, is passed through
Benzene extraction phase and aqueous phase extracted are respectively obtained after separation；
Step 5: washing: 1186mL deionized water being added into benzene extraction phase obtained in step 4, is then in temperature
30min is stirred using the speed of 260r/min under conditions of 50 DEG C, then is layered after standing 40min, respectively obtains wash after separation
Wash benzene phase and washing water phase；
Step 6: distillation: mutually repeating in step 5 plus water, stirring, layering to washing benzene obtained in step 5 and divide
Separating process obtains the washing benzene phase of the epoxy resin containing TGDDM until washing water phase is neutrality, is then existed using short-path evaporator
Temperature is 180 DEG C, and pressure mutually carries out distillation to the washing benzene of the epoxy resin containing TGDDM under conditions of being 0.03MPa and sloughs benzene, is obtained
To amber TGDDM epoxy resin.
Through detecting, the quality for the TGDDM epoxy resin that the present embodiment is prepared is 1132g, yield 89%, TGDDM
The epoxide equivalent of epoxy resin is 128, content of inorganic chlorine 10.5ppm, and being easily saponified chlorinity is 385ppm, and viscosity (50 DEG C) is
3350mPa·S。
The organic diluent of the present embodiment can also be in ethyl alcohol, isopropanol, acetone, methyl iso-butyl ketone (MIBK) and espeleton
Two or more mixtures in one kind or methanol, ethyl alcohol, isopropanol, acetone, methyl iso-butyl ketone (MIBK) and espeleton.
The catalyst of the present embodiment can also be tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium chloride, the tetrabutyl
One of ammonium hydrogen sulfate, tetrabutyl ammonium hydrogen phosphate and tetrabutyl ammonium phosphate or tetrabutylammonium bromide, tetrabutylammonium iodide,
In tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, tetrabutyl ammonium hydrogen phosphate, tetrabutyl ammonium sulfate and tetrabutyl ammonium phosphate two kinds with
On mixture.
The auxiliary agent of the present embodiment can also be one of ethylene glycol, propylene glycol and pentaerythrite or ethylene glycol, the third two
Alcohol, glycerine, the two or more mixtures in pentaerythrite.
The organic solvent of the present embodiment can also be in ethyl acetate, dioxane, toluene and hexone
Two or more mixing in one kind or ethyl acetate, dioxane, benzene,toluene,xylene and hexone
Object.
Embodiment 3
The preparation method of the present embodiment the following steps are included:
Step 1: the preparation of material liquid: under conditions of normal pressure and temperature are 25 DEG C, by 4, the 4'- diamino of 594.8g
Diphenyl-methane is uniformly mixed with 265mL acetone, 635mL epoxychloropropane, obtains material liquid；
Step 2: the preparation of amino chloropropyl alcohol: in the double-layer glass reaction kettle that condensation reflux unit and agitating device are housed
Middle addition 423mL epoxychloropropane and 11.9g 4-butyl ammonium hydrogen sulfate simultaneously open agitating device, and 119g second is added after being warming up to 60 DEG C
Droplets of feed obtained in step 1 is added to bilayer in 2.5h then under conditions of normal pressure and temperature are 60 DEG C by glycol
In glass reaction kettle, it is stirred to react 3h under conditions of 60 DEG C, when reaction system becomes viscous to when being not easy to stir, to reaction system
Middle addition 423mL acetone is diluted, then is stirred to react 12h under conditions of 60 DEG C, obtains the slurry containing amino chloropropyl alcohol；
Step 3: the dehydration closed-loop of amino chloropropyl alcohol: under conditions of normal pressure and temperature are 60 DEG C, by mass percentage concentration
It is added drop-wise in 0.5h in the slurry containing amino chloropropyl alcohol obtained in step 2 for 40% sodium hydroxide solution, then exists
Dehydration closed-loop reaction 1h under the conditions of 60 DEG C of temperature, obtains the slurry containing TGDDM epoxy resin；The sodium hydroxide solution by
648g sodium hydroxide is dissolved in 972mL deionized water and prepares and obtain；
Step 4: extraction: 3174mL toluene is added into the slurry containing TGDDM epoxy resin obtained in step 3,
Then 20min is stirred using the speed of 200r/min under conditions of normal pressure and temperature are 60 DEG C, then is layered after standing 40min,
Extraction toluene phase and aqueous phase extracted are respectively obtained after separation；
Step 5: washing: 1587mL deionized water being added into extraction toluene phase obtained in step 4, then in temperature
20min is stirred using the speed of 200r/min under conditions of being 60 DEG C, then is layered after standing 40min, is respectively obtained after separation
Wash toluene phase and washing water phase；
Step 6: distillation: to obtained in step 5 washing toluene mutually repeat step 5 in plus water, stirring, layering and
Separating technology obtains the washing toluene phase of the epoxy resin containing TGDDM until washing water phase is neutrality, is then evaporated using short distance
Device is 140 DEG C in temperature, and it is de- that pressure mutually carries out distillation to the washing toluene of the epoxy resin containing TGDDM under conditions of being 0.02MPa
Toluene is removed, amber TGDDM epoxy resin is obtained.
Through detecting, the quality for the TGDDM epoxy resin that the present embodiment is prepared is 1127g, yield 89%, TGDDM
The epoxide equivalent of epoxy resin is 119, content of inorganic chlorine 9.5ppm, and being easily saponified chlorinity is 305ppm, and viscosity (50 DEG C) is
4120mPa·S。
The organic diluent of the present embodiment can also be in methanol, ethyl alcohol, isopropanol, methyl iso-butyl ketone (MIBK) and espeleton
It is two or more in one kind or methanol, ethyl alcohol, isopropanol, acetone, methyl iso-butyl ketone (MIBK) and espeleton.
The catalyst of the present embodiment can also be tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium chloride, the tetrabutyl
One of ammonium hydrogen phosphate, tetrabutyl ammonium sulfate and tetrabutyl ammonium phosphate or tetrabutylammonium bromide, tetrabutylammonium iodide, four
Butyl ammonium chloride, 4-butyl ammonium hydrogen sulfate, tetrabutyl ammonium hydrogen phosphate, tetrabutyl ammonium sulfate and tetrabutyl ammonium phosphate it is two or more
Mixture.
The auxiliary agent of the present embodiment can also be one of glycerine, propylene glycol and pentaerythrite or ethylene glycol, the third two
Alcohol, glycerine, the two or more mixtures in pentaerythrite.
The organic solvent of the present embodiment can also be ethyl acetate, dioxane, benzene, dimethylbenzene and hexone
One of or ethyl acetate, dioxane, benzene,toluene,xylene and hexone in it is two or more mixed
Close object.
Embodiment 4
The preparation method of the present embodiment the following steps are included:
Step 1: the preparation of material liquid: under conditions of normal pressure and temperature are 25 DEG C, by 4, the 4'- diamino of 594.8g
Diphenyl-methane is uniformly mixed with 176mL ethyl alcohol, 176mL acetone, 588mL epoxychloropropane, obtains material liquid；
Step 2: the preparation of amino chloropropyl alcohol: in the double-layer glass reaction kettle that condensation reflux unit and agitating device are housed
Middle addition 588mL epoxychloropropane and 3.0g tetrabutylammonium bromide simultaneously open agitating device, and 59.5g second is added after being warming up to 65 DEG C
Droplets of feed obtained in step 1 is added to the double-deck glass in 3h then under conditions of normal pressure and temperature are 65 DEG C by glycol
In glass reaction kettle, it is stirred to react 3h under conditions of 65 DEG C, when reaction system becomes viscous to when being not easy to stir, into reaction system
294mL methanol is added to be diluted with 294mL acetone, then is stirred to react 10h under conditions of 65 DEG C, obtains containing amino chlorine third
The slurry of alcohol；
Step 3: the dehydration closed-loop of amino chloropropyl alcohol: under conditions of normal pressure and temperature are 55 DEG C, by mass percentage concentration
It is added drop-wise in 1.5h in the slurry containing amino chloropropyl alcohol obtained in step 2 for 35% sodium hydroxide solution, then exists
Dehydration closed-loop reaction 2h under the conditions of 55 DEG C of temperature, obtains the slurry containing TGDDM epoxy resin；The sodium hydroxide solution by
720g sodium hydroxide is dissolved in 1337mL deionized water and prepares and obtain；
Step 4: extraction: 3528mL diformazan being added into the slurry containing TGDDM epoxy resin obtained in step 3
Then benzene stirs 20min using the speed of 200r/min under conditions of normal pressure and temperature are 80 DEG C, then divide after standing 20min
Layer respectively obtains extraction dimethylbenzene phase and aqueous phase extracted after separation；
Step 5: washing: 833mL deionized water being added into extraction dimethylbenzene phase obtained in step 4, then in temperature
Degree uses the speed of 200r/min to stir 20min under conditions of being 80 DEG C, then is layered after standing 20min, after separation respectively
To washing dimethylbenzene phase and washing water phase；
Step 6: distillation: mutually repeating in step 5 plus water to washing first dimethylbenzene obtained in step 5, stirring, divide
Layer and separating technology obtain the washing dimethylbenzene phase of the epoxy resin containing TGDDM until washing water phase is neutrality, then using short
Journey evaporator is 160 DEG C in temperature, pressure be 0.01MPa under conditions of to the washing dimethylbenzene of the epoxy resin containing TGDDM mutually into
Dimethylbenzene is sloughed in row distillation, obtains amber TGDDM epoxy resin.
Through detecting, the quality of the TGDDM epoxy resin that the present embodiment is prepared is 1183g, yield 93.3%,
The epoxide equivalent of TGDDM epoxy resin is 117, content of inorganic chlorine 3.2ppm, and being easily saponified chlorinity is 204ppm, viscosity (50
DEG C) it is 3633mPaS.
The organic diluent of the present embodiment can also be methanol, ethyl alcohol, isopropanol, acetone, methyl iso-butyl ketone (MIBK) and methyl fourth
Two or more (ethyl alcohol in one of ketone or methanol, ethyl alcohol, isopropanol, acetone, methyl iso-butyl ketone (MIBK) and espeleton
Except the combination of acetone).
The catalyst of the present embodiment can also be tetrabutylammonium chloride, tetrabutylammonium iodide, 4-butyl ammonium hydrogen sulfate, four fourths
One of base ammonium hydrogen phosphate, tetrabutyl ammonium sulfate and tetrabutyl ammonium phosphate or tetrabutylammonium bromide, tetrabutylammonium iodide,
Tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, tetrabutyl ammonium hydrogen phosphate, two kinds of tetrabutyl ammonium sulfate and tetrabutyl ammonium phosphate with
On mixture.
The auxiliary agent of the present embodiment can also be one of glycerine, propylene glycol and pentaerythrite or ethylene glycol, the third two
Alcohol, glycerine, the two or more mixtures in pentaerythrite.
The organic solvent of the present embodiment can also be in ethyl acetate, dioxane, benzene, toluene and hexone
One kind or ethyl acetate, dioxane, benzene,toluene,xylene and hexone in two or more mixing
Object.
Embodiment 5
The preparation method of the present embodiment the following steps are included:
Step 1: the preparation of material liquid: under conditions of normal pressure and temperature are 30 DEG C, by 4, the 4'- diamino of 594.8g
Diphenyl-methane is uniformly mixed with 282mL methanol, 790mL epoxychloropropane, obtains material liquid；
Step 2: the preparation of amino chloropropyl alcohol: in the double-layer glass reaction kettle that condensation reflux unit and agitating device are housed
Middle addition 339mL epoxychloropropane and 8.92g tetrabutyl ammonium phosphate simultaneously open agitating device, and 89g third is added after being warming up to 70 DEG C
Droplets of feed obtained in step 1 is added to the double-deck glass in 5h then under conditions of normal pressure and temperature are 70 DEG C by triol
In glass reaction kettle, it is stirred to react 2.5h under conditions of 70 DEG C, when reaction system becomes viscous to when being not easy to stir, to reaction system
Middle addition 226mL methanol is diluted, then is stirred to react 7.5h under conditions of 70 DEG C, obtains the material containing amino chloropropyl alcohol
Slurry；
Step 3: the dehydration closed-loop of amino chloropropyl alcohol: under conditions of normal pressure and temperature are 70 DEG C, by mass percentage concentration
It is added drop-wise in 3h in the slurry containing amino chloropropyl alcohol obtained in step 2 for 40% sodium hydroxide solution, then 70
DEG C temperature under the conditions of dehydration closed-loop reaction 2h, obtain the slurry containing TGDDM epoxy resin；The sodium hydroxide solution by
634g sodium hydroxide is dissolved in 951mL deionized water and prepares and obtain；
Step 4: extraction: 2260mL toluene is added into the slurry containing TGDDM epoxy resin obtained in step 3,
Then 15min is stirred using the speed of 160r/min under conditions of normal pressure and temperature are 80 DEG C, then is layered after standing 20min,
Extraction toluene phase and aqueous phase extracted are respectively obtained after separation；
Step 5: washing: 1355mL deionized water being added into extraction toluene phase obtained in step 4, then in temperature
20min is stirred using the speed of 200r/min under conditions of being 80 DEG C, then is layered after standing 30min, is respectively obtained after separation
Wash toluene phase and washing water phase；
Step 6: distillation: to obtained in step 5 washing toluene mutually repeat step 5 in plus water, stirring, layering and
Separating technology obtains the washing toluene phase of the epoxy resin containing TGDDM until washing water phase is neutrality, is then evaporated using short distance
Device is 150 DEG C in temperature, and it is de- that pressure mutually carries out distillation to the washing toluene of the epoxy resin containing TGDDM under conditions of being 0.015MPa
Toluene is removed, amber TGDDM epoxy resin is obtained.
Through detecting, the quality of the TGDDM epoxy resin that the present embodiment is prepared is 1147g, yield 90.5%,
The epoxide equivalent of TGDDM epoxy resin is 112, content of inorganic chlorine 8.2ppm, and being easily saponified chlorinity is 217ppm, viscosity (50
DEG C) it is 3250mPaS.
The organic diluent of the present embodiment can also be in ethyl alcohol, isopropanol, acetone, methyl iso-butyl ketone (MIBK) and espeleton
It is two or more in one kind or methanol, ethyl alcohol, isopropanol, acetone, methyl iso-butyl ketone (MIBK) and espeleton.
The catalyst of the present embodiment can also be tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, the tetrabutyl
One of ammonium hydrogen sulfate, tetrabutyl ammonium hydrogen phosphate and tetrabutyl ammonium sulfate or tetrabutylammonium bromide, tetrabutylammonium iodide,
Tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, tetrabutyl ammonium hydrogen phosphate, two kinds of tetrabutyl ammonium sulfate and tetrabutyl ammonium phosphate with
On mixture.
The auxiliary agent of the present embodiment can also be one of ethylene glycol, propylene glycol and pentaerythrite or ethylene glycol, the third two
Alcohol, glycerine, the two or more mixtures in pentaerythrite.
The organic solvent of the present embodiment can also be ethyl acetate, dioxane, benzene, dimethylbenzene and hexone
One of or ethyl acetate, dioxane, benzene,toluene,xylene and hexone in it is two or more mixed
Close object.
Embodiment 6
The preparation method of the present embodiment the following steps are included:
Step 1: the preparation of material liquid: under conditions of normal pressure and temperature are 35 DEG C, by 4, the 4'- diamino of 594.8g
Diphenyl-methane is uniformly mixed with 221mL ethyl alcohol, 664mL epoxychloropropane, obtains material liquid；
Step 2: the preparation of amino chloropropyl alcohol: in the double-layer glass reaction kettle that condensation reflux unit and agitating device are housed
Middle addition 442mL epoxychloropropane and 3.0g tetrabutyl ammonium sulfate simultaneously open agitating device, and 119g third is added after being warming up to 65 DEG C
Droplets of feed obtained in step 1 is added to the double-deck glass in 4h then under conditions of normal pressure and temperature are 65 DEG C by glycol
In glass reaction kettle, it is stirred to react 3h under conditions of 65 DEG C, when reaction system becomes viscous to when being not easy to stir, into reaction system
442mL ethyl alcohol is added to be diluted, then is stirred to react 10h under conditions of 65 DEG C, obtains the slurry containing amino chloropropyl alcohol；
Step 3: the dehydration closed-loop of amino chloropropyl alcohol: under conditions of normal pressure and temperature are 45 DEG C, by mass percentage concentration
It is added drop-wise in 1.5h in the slurry containing amino chloropropyl alcohol obtained in step 2 for 30% sodium hydroxide solution, then exists
Dehydration closed-loop reaction 1h under the conditions of 45 DEG C of temperature, obtains the slurry containing TGDDM epoxy resin；The sodium hydroxide solution by
620g sodium hydroxide is dissolved in 1447mL deionized water and prepares and obtain；
Step 4: extraction: 2765mL toluene is added into the slurry containing TGDDM epoxy resin obtained in step 3,
Then 15min is stirred using the speed of 200r/min under conditions of normal pressure and temperature are 80 DEG C, then is layered after standing 20min,
Extraction toluene phase and aqueous phase extracted are respectively obtained after separation；
Step 5: washing: 1000mL deionized water being added into extraction toluene phase obtained in step 4, then in temperature
15min is stirred using the speed of 260r/min under conditions of being 80 DEG C, then is layered after standing 20min, is respectively obtained after separation
Wash toluene phase and washing water phase；
Step 6: distillation: to obtained in step 5 washing toluene mutually repeat step 5 in plus water, stirring, layering and
Separating technology obtains the washing toluene phase of the epoxy resin containing TGDDM until washing water phase is neutrality, is then evaporated using short distance
Device is 160 DEG C in temperature, and it is de- that pressure mutually carries out distillation to the washing toluene of the epoxy resin containing TGDDM under conditions of being 0.02MPa
Toluene is removed, amber TGDDM epoxy resin is obtained.
Through detecting, the quality for the TGDDM epoxy resin that the present embodiment is prepared is 1216g, yield 96%, TGDDM
The epoxide equivalent of epoxy resin is 112, content of inorganic chlorine 3.0ppm, and being easily saponified chlorinity is 134ppm, and viscosity (50 DEG C) is
3960mPa·S。
The organic diluent of the present embodiment can also be in methanol, isopropanol, acetone, methyl iso-butyl ketone (MIBK) and espeleton
It is two or more in one kind or methanol, ethyl alcohol, isopropanol, acetone, methyl iso-butyl ketone (MIBK) and espeleton.
The catalyst of the present embodiment can also be tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium chloride, the tetrabutyl
One of ammonium hydrogen sulfate, tetrabutyl ammonium hydrogen phosphate and tetrabutyl ammonium phosphate or tetrabutylammonium bromide, tetrabutylammonium iodide,
Tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, tetrabutyl ammonium hydrogen phosphate, two kinds of tetrabutyl ammonium sulfate and tetrabutyl ammonium phosphate with
On mixture.
The auxiliary agent of the present embodiment can also be one of ethylene glycol, glycerine and pentaerythrite or ethylene glycol, the third two
Alcohol, glycerine, the two or more mixtures in pentaerythrite.
The organic solvent of the present embodiment can also be ethyl acetate, dioxane, benzene, dimethylbenzene and hexone
One of or ethyl acetate, dioxane, benzene, toluene and hexone in two or more mixtures.
The above is only presently preferred embodiments of the present invention, is not intended to limit the invention in any way.It is all according to invention skill
Art any simple modification, change and equivalence change substantially to the above embodiments, still fall within technical solution of the present invention
Protection scope.
Claims (10)
1. a kind of synthetic method of TGDDM epoxy resin, which is characterized in that method includes the following steps:
Step 1: the preparation of material liquid: under conditions of normal pressure and temperature are 20 DEG C~35 DEG C, by 4,4'- diamino hexichol first
Alkane is uniformly mixed with organic diluent, epoxychloropropane, obtains material liquid；
Step 2: the preparation of amino chloropropyl alcohol: under conditions of normal pressure and temperature are 35 DEG C~75 DEG C, by step in 1h~5h
Droplets of feed obtained in one is added in the double-layer glass reaction kettle for being contained with epoxychloropropane, catalyst and auxiliary agent and is stirred to react
5h~20h obtains the slurry containing amino chloropropyl alcohol；It is described be stirred to react during when reaction system becomes viscous to being not easy to stir
When, organic diluent is added into reaction system and is diluted, organic diluent described in the organic diluent and step 1
It is identical；
Step 3: the dehydration closed-loop of amino chloropropyl alcohol: under conditions of normal pressure and temperature are 35 DEG C~80 DEG C, quality percentage is dense
Degree is added drop-wise to obtained in step 2 containing amino chloropropyl alcohol for 20%~40% sodium hydroxide solution in 0.5h~3h
In slurry, then dehydration closed-loop reaction 0.5h~4h under the conditions of 35 DEG C~80 DEG C of temperature, is obtained containing TGDDM epoxy resin
Slurry；
Step 4: extraction: organic solvent is added into the slurry containing TGDDM epoxy resin obtained in step 3, then exists
Normal pressure and temperature use the speed of 100r/min~260r/min to stir 10min~30min under conditions of being 50 DEG C~90 DEG C, then
It is layered after standing 10min~40min, respectively obtains extraction organic phase and aqueous phase extracted after separation；
Step 5: washing: deionized water is added into extraction organic phase obtained in step 4, is then 50 DEG C~90 in temperature
10min~30min is stirred using the speed of 100r/min~260r/min under conditions of DEG C, then is divided after standing 10min~40min
Layer respectively obtains washing organic phase and washing water phase after separation；
Step 6: distillation: repeating in step 5 plus water, stirring, layering and separation to washing organic phase obtained in step 5
Technique obtains the washing organic phase of the epoxy resin containing TGDDM until washing water phase is neutrality, then will using short-path evaporator
The washing organic phase of the epoxy resin containing TGDDM carries out distillation and sloughs organic solvent, obtains amber TGDDM epoxy resin.
2. a kind of synthetic method of TGDDM epoxy resin according to claim 1, which is characterized in that described in step 1
Organic diluent is one or more of methanol, ethyl alcohol, isopropanol, acetone, methyl iso-butyl ketone (MIBK) and espeleton
Mixture, the volume of the organic diluent are that epoxychloropropane described in epoxychloropropane described in step 1 and step 2 is total
The 20%~30% of volume.
3. a kind of synthetic method of TGDDM epoxy resin according to claim 1, which is characterized in that described in step 1
The volume of epoxychloropropane is 40% of epoxychloropropane total volume described in epoxychloropropane described in step 1 and step 2
~80%, institute in the amount and step 1 of the total material of epoxychloropropane described in epoxychloropropane described in step 1 and step 2
Stating the ratio between amount of substance of 4,4'- diaminodiphenylmethane is (4~5): 1.
4. a kind of synthetic method of TGDDM epoxy resin according to claim 1, which is characterized in that described in step 2
Catalyst be tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, tetrabutyl ammonium hydrogen phosphate,
One or more kinds of mixtures of tetrabutyl ammonium sulfate and tetrabutyl ammonium phosphate, the quality of the catalyst are in step 1
The 0.2%~2% of the 4,4'- diaminodiphenylmethane quality.
5. a kind of synthetic method of TGDDM epoxy resin according to claim 1, which is characterized in that described in step 2
Auxiliary agent is the mixture of one or more of ethylene glycol, propylene glycol, glycerine and pentaerythrite, the quality of the auxiliary agent
It is the 5%~20% of the quality of 4,4'- diaminodiphenylmethane described in step 1.
6. a kind of synthetic method of TGDDM epoxy resin according to claim 1, which is characterized in that described in step 2
The volume of organic diluent is 20% of epoxychloropropane total volume described in epoxychloropropane described in step 1 and step 2
~80%.
7. a kind of synthetic method of TGDDM epoxy resin according to claim 1, which is characterized in that described in step 3
The total material of epoxychloropropane described in epoxychloropropane described in the amount and step 1 of the substance of sodium hydroxide and step 2
The ratio between amount is (1.0~1.5): 1.
8. a kind of synthetic method of TGDDM epoxy resin according to claim 1, which is characterized in that described in step 4
Organic solvent is one or more of ethyl acetate, dioxane, benzene,toluene,xylene and hexone
Mixture, the volume of the organic solvent is that epoxychloropropane described in epoxychloropropane described in step 1 and step 2 is total
1~4 times of volume.
9. a kind of synthetic method of TGDDM epoxy resin according to claim 1, which is characterized in that described in step 5
The volume ratio of organic solvent described in deionized water and step 4 is (0.2~0.6): 1.
10. a kind of synthetic method of TGDDM epoxy resin according to claim 1, which is characterized in that described in step 6
The temperature of distillation is 110 DEG C~180 DEG C, and pressure is 0.01MPa~0.03MPa.
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| CN112724106A (en) * | 2020-12-30 | 2021-04-30 | 西安元创化工科技股份有限公司 | Synthetic method of high-purity TGDDM epoxy resin |
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