CN111875778A - Method for preparing epoxy resin from triglycidyl isocyanurate production by-product - Google Patents
Method for preparing epoxy resin from triglycidyl isocyanurate production by-product Download PDFInfo
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- CN111875778A CN111875778A CN202010753111.5A CN202010753111A CN111875778A CN 111875778 A CN111875778 A CN 111875778A CN 202010753111 A CN202010753111 A CN 202010753111A CN 111875778 A CN111875778 A CN 111875778A
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- bisphenol
- epoxy resin
- triglycidyl isocyanurate
- sodium hydroxide
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- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 115
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 115
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 93
- 239000006227 byproduct Substances 0.000 title claims abstract description 91
- 238000000034 method Methods 0.000 title claims abstract description 52
- 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 claims abstract description 121
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000007787 solid Substances 0.000 claims abstract description 30
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 135
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 60
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- 239000000047 product Substances 0.000 claims description 30
- 238000006116 polymerization reaction Methods 0.000 claims description 27
- 238000007363 ring formation reaction Methods 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000004593 Epoxy Substances 0.000 claims description 22
- 239000003513 alkali Substances 0.000 claims description 22
- 239000002585 base Substances 0.000 claims description 21
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 20
- 125000003700 epoxy group Chemical group 0.000 claims description 17
- 238000004821 distillation Methods 0.000 claims description 16
- 238000001953 recrystallisation Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 14
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000007865 diluting Methods 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- 230000009471 action Effects 0.000 claims description 10
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 claims description 8
- 239000008096 xylene Substances 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229930185605 Bisphenol Natural products 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- -1 1-chloro-2-hydroxy-propyl isocyanurate Chemical compound 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 7
- 238000006068 polycondensation reaction Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 40
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000000203 mixture Substances 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 14
- 239000012452 mother liquor Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 8
- 239000012267 brine Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 7
- 239000000126 substance Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 230000006750 UV protection Effects 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- HPOKESDSMZRZLC-UHFFFAOYSA-N propan-2-one;hydrochloride Chemical compound Cl.CC(C)=O HPOKESDSMZRZLC-UHFFFAOYSA-N 0.000 description 2
- 230000004224 protection Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- OBRMNDMBJQTZHV-UHFFFAOYSA-N cresol red Chemical compound C1=C(O)C(C)=CC(C2(C3=CC=CC=C3S(=O)(=O)O2)C=2C=C(C)C(O)=CC=2)=C1 OBRMNDMBJQTZHV-UHFFFAOYSA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- PRZSXZWFJHEZBJ-UHFFFAOYSA-N thymol blue Chemical compound C1=C(O)C(C(C)C)=CC(C2(C3=CC=CC=C3S(=O)(=O)O2)C=2C(=CC(O)=C(C(C)C)C=2)C)=C1C PRZSXZWFJHEZBJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
-
- 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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
The invention provides a method for preparing epoxy resin from triglycidyl isocyanurate production byproducts, which is characterized in that the triglycidyl isocyanurate production byproducts, epichlorohydrin and bisphenol A are subjected to ring-opening polycondensation and then are subjected to ring-closing to form solid epoxy resin, so that the triglycidyl isocyanurate production byproducts can be recycled, the environmental pressure is relieved, the TGIC production cost is greatly reduced, and the prepared solid epoxy resin has excellent performance and meets the market demand.
Description
Technical Field
The invention relates to the technical field of waste treatment, in particular to a method for preparing epoxy resin from triglycidyl isocyanurate production byproducts.
Background
Epoxy resin is a general high molecular organic compound containing two or more than two epoxy groups, can form an insoluble three-dimensional reticular polymer by cross-linking reaction with various curing agents, and the cured epoxy resin has excellent mechanical property, adhesive property, electrical insulating property and chemical resistance, so the epoxy resin has common application in the industries of coatings, foods, chemical industry and anticorrosion, and the main production steps comprise: bisphenol A and epichlorohydrin generate a crude product of epoxy resin under the action of sodium hydroxide, and the crude product is washed and refined by water to obtain the commercial epoxy resin, wherein the specific reaction formula is as follows:
triglycidyl isocyanurate (1,3,5-triglycidyl isocyanurate, TGIC) is used as a functional epoxy compound, is matched with carboxyl-containing polyester resin for use, is a polyepoxy triazine heterocyclic ring-containing compound, has three epoxy functional groups, and is high in reactivity. Compared with the traditional linear bisphenol A epoxy resin, the epoxy resin is different in that the epoxy resin does not contain benzene rings and ether bonds, so that a cured coating film has excellent ultraviolet resistance and heat resistance, is mainly used for preparing powder coating with excellent weather resistance, and has the outstanding advantages of light retention, color retention, chalking resistance, heat resistance and excellent adhesive force performance to metal substrates, so that the epoxy resin occupies a large powder coating market at home and abroad.
TGIC is prepared by the ring-closure reaction of Epichlorohydrin (ECH) and cyanuric acid under the alkaline condition after the reaction, the product is desalted, the excessive ECH is distilled to obtain an initial product, the final product can be obtained after the recrystallization treatment of methanol and the centrifugation and drying, and the main by-product is in the recrystallization mother liquor generated in the recrystallization treatment of methanol.
Wherein, the main products in the TGIC synthesis process are shown as the following formula:
the TGIC methanol recrystallization mother liquor byproduct contains 20-30 wt% of methanol, and the main components of the rest substances are TGIC which is not completely crystallized and separated, a byproduct which does not have a ring closure reaction under an alkaline condition and contains two epoxy groups and one epoxy group, a part of TGIC polymer which generates epoxy ring-opening polymerization in the production process, and the like, wherein the amount of the byproduct is about 2 ten thousand tons according to the annual output of the TGIC in China at present. At present, the by-product is not reasonably utilized, and domestic TGIC manufacturers generally treat the by-product as waste, so that resource waste and environmental pollution are caused.
Therefore, there is a need to develop a recycling method of TGIC methanol recrystallization mother liquor by-products, which can improve the economic value while relieving the environmental protection pressure.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for preparing epoxy resin from TGIC production byproducts, which utilizes the ring-opening polycondensation and the ring-closing cyclization of mono-, di-and triglycidyl isocyanurates in triglycidyl isocyanurate production byproducts, epichlorohydrin and bisphenol A to form solid epoxy resin, so that the triglycidyl isocyanurate production byproducts can be recycled, the environmental pressure is relieved, the TGIC production cost is greatly reduced, and the prepared solid epoxy resin has excellent performance and meets the market demand.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing an epoxy resin from a triglycidyl isocyanurate production by-product, the method comprising: the epoxy resin is prepared from byproducts in the production of triglycidyl isocyanurate, bisphenol A and epichlorohydrin under the action of alkali.
The method for preparing the epoxy resin from the triglycidyl isocyanurate production byproduct, provided by the invention, aims at the problem that the TGIC production byproduct is directly treated as waste to cause high TGIC production cost in the prior art, and prepares the epoxy resin with bisphenol A and epoxy chloropropane under the action of alkali, so that the resource utilization of the TGIC production byproduct is well realized, components in the TGIC production byproduct can better participate in the reaction to be converted into the epoxy resin, the TGIC production cost is reduced, the environmental pressure is relieved, meanwhile, the TGIC production byproduct has a modification effect on the epoxy resin, and the prepared epoxy resin has excellent performance and higher industrial application value.
Preferably, the triglycidyl isocyanurate production by-product comprises triglycidyl isocyanurate.
The TGIC production byproduct contains triglycidyl isocyanurate, and the ultraviolet resistance and heat resistance of the epoxy resin can be improved by the triglycidyl isocyanurate participating in the preparation of the epoxy resin.
Preferably, the triglycidyl isocyanurate production byproduct further comprises any one or a combination of at least two of 2, 3-substituted ring-closed epoxypropylisocyanurate, monoglycidyl isocyanurate, diglycidyl isocyanurate, or 1-chloro-2-hydroxy-propylisocyanurate, with typical non-limiting combinations being combinations of monoglycidyl isocyanurate and diglycidyl isocyanurate, monoglycidyl isocyanurate and 1-chloro-2-hydroxy-propylisocyanurate, diglycidyl isocyanurate and 1-chloro-2-hydroxy-propylisocyanurate, and the like.
The TGIC production by-product also contains 2,3 substituted ring-closed epoxypropyl isocyanurate and other substances, and the substances can be subjected to ring-opening polycondensation with epoxy chloropropane and bisphenol A and then subjected to ring-closing to form solid epoxy resin in the reaction process, fully uses the by-product generated in the TGIC preparation process, can be recycled at one time without a complex separation process, and greatly reduces the TGIC production cost.
Preferably, the epoxy value of the triglycidyl isocyanurate production byproduct is 0.3-0.5 moL epoxy group/100 g, and may be, for example, 0.3moL epoxy group/100 g, 0.32moL epoxy group/100 g, 0.34moL epoxy group/100 g, 0.35moL epoxy group/100 g, 0.38moL epoxy group/100 g, 0.4moL epoxy group/100 g, 0.42moL epoxy group/100 g, 0.45moL epoxy group/100 g, 0.48moL epoxy group/100 g, or 0.5moL epoxy group/100 g.
Preferably, the by-product in the production of triglycidyl isocyanurate is the residue of a liquid phase distillation still or distillation still after methanol recrystallization of triglycidyl isocyanurate.
The process for the production of TGIC production by-products of the present invention comprises: raw materials of Epichlorohydrin (ECH), Cyanuric Acid (CA) and a proper amount of alkali are added into a synthesis kettle according to a certain proportion, a jacket is filled with steam and heated to 80 ℃, the synthesis reaction is carried out under normal pressure, an intermediate product of 1,3,5-tri (1' -chloro-2-hydroxy-propyl) isocyanurate is obtained, then the intermediate product and solid alkali (99 wt% NaOH) are added into a cyclization kettle, the cyclization reaction is carried out at the temperature of minus 5 ℃, a mixture containing TGIC is obtained, the mixture enters a filter-press tank for filtration, and the solid phase is solid salt containing epichlorohydrin. And standing and layering the liquid phase delayer, conveying the upper aqueous phase to an epoxy resin synthesis working section for recycling, conveying the lower organic phase to a distillation kettle, introducing hot water with the temperature of 95 ℃ into a jacket, reducing the pressure to-0.025 MPa for distillation, and recycling epoxy chloropropane to return to the synthesis kettle for use. Adding methanol into the distilled solid material, recrystallizing with a crystallization kettle to obtain TGIC, separating with a centrifuge, and drying the separated solid TGIC to remove methanol to obtain solid TGIC. Transferring the separated liquid phase to a rectifying still, introducing hot water of 80 ℃ into a jacket, rectifying at normal pressure, returning the rectified methanol solvent to the crystallizing still for reuse, and obtaining the rest of the rectifying still as a TGIC production byproduct.
Preferably, the molar ratio of the epoxy value to the bisphenol a of the triglycidyl isocyanurate production by-product is 0.01-0.2: 1, and may be, for example, 0.01:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.1:1, 0.11:1, 0.12:1, 0.14:1, 0.15:1, 0.18:1 or 0.2: 1.
Preferably, the molar ratio of the base to bisphenol a is 1.7 to 4.5:1, and may be, for example, 1.7:1, 1.8:1, 1.9:1, 2.0:1, 2.2:1, 2.5:1, 2.8:1, 3:1, 3.2:1, 3.3:1, 3.5:1, 3.8:1, 4:1, 4.2:1, or 4.5: 1.
Preferably, the method comprises the steps of:
(1') carrying out a ring-opening reaction on a triglycidyl isocyanurate production byproduct, bisphenol and epichlorohydrin under the action of a first batch of alkali to obtain a pre-polymerization solution;
(2 ') carrying out a ring-closing reaction on the pre-polymerization solution obtained in the step (1') under the action of a solvent and a second batch of alkali to prepare epoxy resin and obtain a mixed product containing the epoxy resin;
(3 ') carrying out post-treatment on the mixed product obtained in the step (2') to obtain the solid epoxy resin.
Preferably, the method comprises the steps of:
(1) carrying out ring-opening reaction on a triglycidyl isocyanurate production byproduct and bisphenol under the action of a first batch of alkali to obtain a pre-polymerization solution;
(2) carrying out a ring-closing reaction on the pre-polymerization solution, bisphenol A and epoxy chloropropane in the step (1) under the action of a second batch of alkali to prepare epoxy resin and obtain a mixed product containing the epoxy resin;
(3) and (3) carrying out post-treatment on the mixed product obtained in the step (2) to obtain the solid epoxy resin.
According to the invention, bisphenol A is preferably added in two steps, firstly, a proper amount of bisphenol A reacts with the by-product in triglycidyl isocyanurate production to realize ring-opening reaction, and then the ring-opening reaction is carried out with epichlorohydrin, so that the softening point of the epoxy resin can be improved, and the obtained epoxy resin has better performance.
Preferably, the molar ratio of the epoxy value of the triglycidyl isocyanurate production byproduct in the step (1) to the bisphenol A is 0.5-1: 1.
Preferably, the ring-opening reaction temperature is 75 ~ 85 ℃, for example can be 75 ℃, 76 ℃, 77 ℃, 78 ℃, 79 ℃, 80 ℃, 81 ℃, 82 ℃, 83 ℃, 84 ℃ or 85 ℃.
Preferably, the molar ratio of the first base to bisphenol a is 1.5-2.5: 1, for example, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2.0:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, or 2.5: 1.
Preferably, the first base comprises sodium hydroxide.
Preferably, the first base is a sodium hydroxide solution.
Preferably, the mass concentration of the sodium hydroxide solution is 35 to 50 wt%, and may be 35 wt%, 36 wt%, 38 wt%, 40 wt%, 42 wt%, 45 wt%, 50 wt%, or the like, for example.
Preferably, the sodium hydroxide solution is added dropwise.
Preferably, the dropping time is 10-20 min, for example, 10min, 12min, 13min, 14min, 15min, 16min, 17min, 18min, 19min or 20 min.
Preferably, the molar ratio of the bisphenol A in the step (2) to the bisphenol A in the step (1) is 10-16: 1, and may be, for example, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, or the like.
Preferably, the molar ratio of the sum of the aromatic hydroxyl groups and the hydroxyl groups in bisphenol a to epichlorohydrin in the prepolymerization liquid is 0.8 to 1:1, and may be, for example, 0.8:1, 0.82:1, 0.84:1, 0.85:1, 0.88:1, 0.9:1, 0.92:1, 0.95:1, 0.98:1 or 1: 1.
Preferably, the molar ratio of the second base to the epichlorohydrin is 0.2 to 2:1, for example, 0.2:1, 0.5:1, 0.7:1, 0.8:1, 1:1, 1.2:1, 1.4:1, 1.5:1, 1.6:1, 1.8:1, or 2: 1.
Preferably, the second base comprises sodium hydroxide.
Preferably, the second base is a sodium hydroxide solution.
Preferably, the mass concentration of the sodium hydroxide solution is 35 to 50 wt%, and may be 35 wt%, 36 wt%, 38 wt%, 40 wt%, 42 wt%, 45 wt%, 50 wt%, or the like, for example.
Preferably, the sodium hydroxide solution is added dropwise.
Preferably, the dropping time is 10-20 min, for example, 10min, 12min, 13min, 14min, 15min, 16min, 17min, 18min, 19min or 20 min.
Preferably, a first solvent is also added to the ring closure reaction.
Preferably, the first solvent comprises water and an organic solvent.
Preferably, the organic solvent comprises any one or a combination of at least two of benzene, toluene, xylene, ortho-dichlorobenzene, or meta-dichlorobenzene, with typical non-limiting combinations being combinations of benzene and toluene, benzene and xylene, toluene and ortho-dichlorobenzene, xylene and ortho-dichlorobenzene, ortho-dichlorobenzene and meta-dichlorobenzene, meta-dichlorobenzene and benzene, and the like.
Preferably, the molar ratio of the organic solvent in the first solvent to the bisphenol A in the step (2) is 0.5-1.1: 1, and may be, for example, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1 or 1.1: 1.
Preferably, in the ring-closing reaction, bisphenol A, epichlorohydrin, water and an organic solvent are sequentially added into the pre-polymerization solution, and then a second batch of alkali is dropwise added.
Preferably, bisphenol A, epoxy chloropropane, water and an organic solvent are sequentially added into the prepolymerization liquid at the temperature of 80-95 ℃, and then a second batch of alkali is dropwise added.
Preferably, the temperature of the ring-closure reaction in step (2) is 80 to 95 ℃, and may be, for example, 80 ℃, 81 ℃, 82 ℃, 83 ℃, 84 ℃, 85 ℃, 86 ℃, 88 ℃, 90 ℃, 92 ℃ or 95 ℃.
Preferably, the ring-closure reaction time is 2-4 h, for example, 2h, 2.2h, 2.5h, 2.8h, 3h, 3.2h, 3.3h, 3.5h, 3.8h or 4 h.
Preferably, the ring closure reaction is carried out under stirring conditions.
Preferably, the post-processing in step (3) comprises: and diluting the mixed product by using a second solvent, and sequentially carrying out solid-liquid separation, washing, solvent removal and cooling to obtain the solid epoxy resin.
Preferably, the second solvent comprises any one or a combination of at least two of benzene, toluene, xylene, ortho-dichlorobenzene, or meta-dichlorobenzene, with typical non-limiting combinations being combinations of benzene and toluene, benzene and xylene, toluene and ortho-dichlorobenzene, xylene and ortho-dichlorobenzene, ortho-dichlorobenzene and meta-dichlorobenzene, meta-dichlorobenzene and benzene, and the like.
Preferably, the means for removing the solvent comprises distillation.
The solid-liquid separation, washing and cooling methods are not particularly limited, and the steps or methods which can realize the above operations and are conventionally adopted by those skilled in the art can be adopted, or the methods can be appropriately adjusted according to actual conditions in the conventional methods, and thus, the methods are not particularly limited.
As a preferred technical scheme of the invention, the method comprises the following steps:
(1) mixing a triglycidyl isocyanurate production byproduct with bisphenol A, dripping 35-50 wt% of sodium hydroxide solution within 10-20 min at 75-85 ℃, and carrying out ring opening reaction to obtain a pre-polymerization solution;
wherein the triglycidyl isocyanurate production byproduct comprises triglycidyl isocyanurate;
the molar ratio of the epoxy value to the bisphenol A of the byproducts produced in the triglycidyl isocyanurate production is 0.5-1: 1, and the molar ratio of sodium hydroxide to the bisphenol A in the sodium hydroxide solution is 1.5-2.5: 1;
(2) sequentially adding bisphenol A, epoxy chloropropane, water and an organic solvent into the pre-polymerization liquid in the step (1) at the temperature of 80-95 ℃, dropwise adding a sodium hydroxide solution with the mass concentration of 35-50 wt%, maintaining the temperature of 80-95 ℃ and carrying out a ring-closing reaction for 2-4 h to prepare epoxy resin, so as to obtain a mixed product containing the epoxy resin;
wherein the molar ratio of the bisphenol A in the step (2) to the bisphenol A in the step (1) is 10-16: 1;
the molar ratio of the sum of aromatic hydroxyl contained in the pre-polymerization liquid and hydroxyl in the bisphenol A to the epichlorohydrin is 0.8-1: 1;
the molar ratio of the organic solvent to the bisphenol A in the step (2) is 0.5-1.1: 1;
the molar ratio of sodium hydroxide to epoxy chloropropane in the sodium hydroxide solution is 0.2-2: 1;
(3) and (3) diluting the mixed product obtained in the step (2) by using a second solvent, and then sequentially carrying out solid-liquid separation, washing, solvent removal and cooling to obtain the solid epoxy resin.
The molecular structure of the TGIC production by-product in step (1) of the present invention after prepolymerization with bisphenol A is schematically illustrated by the following formula:
in a second aspect, the present invention provides an epoxy resin obtained by the method for producing an epoxy resin from a triglycidyl isocyanurate production by-product according to the first aspect.
The epoxy resin provided by the second aspect of the invention has excellent performance, low production cost and good market application value.
The molecular structure of epoxy resin in the prior art is as follows:
the epoxy resin prepared by the byproducts in the production of triglycidyl isocyanurate has the following structure:
from the molecular structure, the method for preparing the epoxy resin from the triglycidyl isocyanurate production byproduct has a modification effect on the structure of the epoxy resin, and n in the molecular structure represents the number of the repeating units and is a natural number.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the method for preparing the epoxy resin from the triglycidyl isocyanurate production byproduct realizes resource utilization of the TGIC production byproduct, and reduces the production cost of TGIC;
(2) according to the method for preparing the epoxy resin from the triglycidyl isocyanurate production byproduct, the TGIC production byproduct is converted into the epoxy resin, the yield is more than 92 wt%, the chlorine content is less than or equal to 0.15 wt%, and the chlorine content is less than or equal to 0.08 wt% under the optimal condition, so that the environmental pressure is relieved, and the method has high environmental protection value;
(3) the method for preparing the epoxy resin from the triglycidyl isocyanurate production byproduct modifies the conventional epoxy resin through the TGIC production byproduct, the epoxy resin has a higher softening point which is not less than 65 ℃, the softening point is not less than 75 ℃ under the optimal condition, the performance is excellent, and the market demand can be better met.
Detailed Description
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
First, an embodiment
Example 1
In this embodiment, the source of the by-product in triglycidyl isocyanurate production is the residue of the distillation of TGIC recrystallization mother liquor, which specifically is: 287.5g of TGIC recrystallization mother liquor is added into a four-mouth flask, the temperature is raised to 70-75 ℃ (the heating temperature is in a fluctuation range), and methanol is removed under the normal pressure condition to obtain 35.4g of TGIC distillation kettle residue.
This example provides a method for preparing an epoxy resin from a triglycidyl isocyanurate production byproduct, comprising the steps of:
(1) to a 1.5L mechanical stirrer, thermometer, reflux condenser and dropping funnel reactor, 35g of TGIC production by-product (0.12moL epoxy value) and 27.4g of bisphenol A (0.12moL) were added and the mixture heated to 80 ℃ and the first base was added dropwise over 15min with continuous stirring: 24g of 40.0 wt.% NaOH solution (0.24moL), and keeping the reaction for 2 hours to obtain a pre-polymerization solution;
(2) keeping the temperature within the range of 80-85 ℃ (heating temperature fluctuation), sequentially adding 300g (1.314moL) of bisphenol A, 168g (1.82moL) of epichlorohydrin, 66g of water and 78g of benzene (1moL) into the pre-polymerization solution obtained in the step (1), and dropwise adding a second batch of alkali: 173g (1.725moL) of 40 wt.% NaOH solution, and keeping stirring the whole reaction system at the temperature of 80-85 ℃ for 3 hours to perform a ring-closing reaction to prepare epoxy resin, so as to obtain a mixed product containing the epoxy resin;
(3) diluting the mixed product obtained in the step (2) by 117g of benzene (1.5moL), standing for 30min, separating brine, washing the mixture subjected to standing separation twice by 200g of water at the temperature of 70-80 ℃, removing residual moisture from the washed epoxy resin azeotrope, reducing the pressure to 1.33KPa, and evaporating the solvent at the temperature of 190 ℃ to obtain 448g of solid epoxy resin.
Example 2
In this embodiment, the source of the by-product in triglycidyl isocyanurate production is the residue of the distillation of TGIC recrystallization mother liquor, which specifically is: 287.5g of TGIC recrystallization mother liquor is added into a four-mouth flask, the temperature is raised to 70-75 ℃ (the heating temperature is in a fluctuation range), and methanol is removed under the normal pressure condition to obtain 35.4g of TGIC distillation kettle residue.
This example provides a method for preparing an epoxy resin from a triglycidyl isocyanurate production byproduct, comprising the steps of:
(1) to a 1.5L mechanical stirrer, thermometer, reflux condenser and dropping funnel reactor, 35g of TGIC production by-product (epoxy value 0.12moL) was added 54.8 bisphenol A (0.24moL) and the mixture heated to 85 ℃ and the first base was added dropwise over 15min with continuous stirring: 12g of 40 wt.% NaOH (0.12moL), keeping the reaction for 4h, obtaining a pre-polymerization solution;
(2) keeping the temperature within the range of 90-95 ℃ (heating temperature fluctuation), sequentially adding 300g (1.074moL) of bisphenol A, 168g (1.82moL) of epichlorohydrin, 66g of water and 92.1g of toluene (1moL) into the pre-polymerization solution obtained in the step (1), and dropwise adding a second batch of alkali: 173g of 40 wt% NaOH solution (1.725moL), and stirring the whole reaction system at 80-85 ℃ for 3 hours to perform a ring-closing reaction to prepare epoxy resin, so as to obtain a mixed product containing the epoxy resin;
(3) diluting the mixed product obtained in the step (2) by 276g of toluene (3.0moL), standing for 30min, separating out brine, washing the mixture subjected to standing separation twice by 200g of water at the temperature of 70-80 ℃, removing residual moisture from the washed epoxy resin azeotrope, reducing the pressure to 1.33KPa, and distilling off the solvent at the temperature of 150 ℃ to obtain 432g of solid epoxy resin.
Example 3
In this embodiment, the source of the by-product in triglycidyl isocyanurate production is the residue of the distillation of TGIC recrystallization mother liquor, which specifically is: 2875g of TGIC recrystallization mother liquor is added into a four-mouth flask, the temperature is raised to 70-75 ℃ (the heating temperature fluctuates), methanol is removed under the normal pressure condition, 364g of TGIC distillation kettle residue is obtained, and the epoxy value is measured to be 0.34moL/100 g.
This example provides a method for preparing an epoxy resin from a triglycidyl isocyanurate production byproduct, comprising the steps of:
(1) to a 15L mechanical stirrer, thermometer, reflux condenser and dropping funnel reactor, 350g TGIC production by-product (1.2moL epoxy value) 274g bisphenol A (1.2moL) was added and the mixture heated to 80 ℃ dropping the first base over 15min with continuous stirring: 240g of 40 wt.% NaOH (2.4moL), maintaining the reaction for 4h to obtain a pre-polymerization solution;
(2) keeping the temperature within the range of 80-85 ℃ (heating temperature fluctuation), sequentially adding 3000g (13.14moL) of bisphenol A, 1680g (18.2moL) of epichlorohydrin, 660g of water and 921g of toluene (10moL) into the pre-polymerization solution obtained in the step (1), and dropwise adding a second batch of alkali: 1730g (17.25moL) of 40 wt.% NaOH solution, keeping stirring the whole reaction system at the temperature of 80-85 ℃ for 3 hours, and carrying out a ring-closing reaction to prepare epoxy resin to obtain a mixed product containing the epoxy resin;
(3) diluting the mixed product obtained in the step (2) by 2302g of toluene (24.98moL), standing for 30min, separating brine, washing the mixture subjected to standing separation twice by using 2kg of water at the temperature of 70-80 ℃, removing residual moisture from the washed epoxy resin azeotrope, reducing the pressure to 1.33KPa, and distilling off the solvent at the temperature of 190 ℃ to obtain 4500g of solid epoxy resin.
Example 4
In this embodiment, the source of the by-product in triglycidyl isocyanurate production is the residue of the distillation of TGIC recrystallization mother liquor, which specifically is: adding 2875g of TGIC recrystallization mother liquor into a four-mouth flask, heating to 70-75 ℃ (heating temperature fluctuation), and removing methanol under normal pressure to obtain 380g of TGIC distillation kettle residue, wherein the epoxy value is measured to be 0.34moL/100 g.
This example provides a method for preparing an epoxy resin from a triglycidyl isocyanurate production byproduct, comprising the steps of:
(1) to a 15L mechanical stirrer, thermometer, reflux condenser and dropping funnel reactor, 350g TGIC production by-product (1.2moL epoxy value) 274g bisphenol A (1.2moL) was added and the mixture heated to 80 ℃ dropping the first base over 15min with continuous stirring: 240g of 40 wt.% NaOH (2.4moL), and keeping the reaction for 3 hours to obtain a pre-polymerization solution;
(2) keeping the temperature within the range of 80-85 ℃ (heating temperature fluctuation), sequentially adding 3000g (13.14moL) of bisphenol A, 1680g (18.2moL) of epichlorohydrin, 660g of water and 921g of benzene (11.79moL) into the pre-polymerization solution obtained in the step (1), and dropwise adding a second batch of alkali: 1730g (17.25moL) of 40 wt.% NaOH solution, keeping stirring the whole reaction system at the temperature of 80-85 ℃ for 3 hours, and carrying out a ring-closing reaction to prepare epoxy resin to obtain a mixed product containing the epoxy resin;
(3) diluting the mixed product obtained in the step (2) by 1950g of benzene (24.96moL), standing for 30min, separating brine, washing the mixture subjected to standing separation twice by using 3kg of water at the temperature of 70-80 ℃, removing residual moisture from the washed epoxy resin azeotrope, reducing the pressure to 1.33KPa, and evaporating the solvent at the temperature of 190 ℃ to obtain 4480g of solid epoxy resin.
Example 5
The source of the triglycidyl isocyanurate production by-product in this example was the same as that in example 1.
This example provides a method for preparing an epoxy resin from a triglycidyl isocyanurate production byproduct, comprising the steps of:
(1) to a 15L reactor with mechanical stirrer, thermometer, reflux condenser and dropping funnel charged with 350g TGIC production by-product (1.2moL) 274g bisphenol A (1.2moL) was added and the mixture heated to 85 ℃ dropping the first base over 20min with continuous stirring: 200g of 42 wt.% NaOH (2.1moL), the reaction was maintained for 2.5h to give a prepolymerization solution;
(2) keeping the temperature within the range of 85-90 ℃ (heating temperature fluctuation), adding 3000g (13.14moL) of bisphenol A, 1680g (18.2moL) of epichlorohydrin, 660g of water and 921g of benzene (11.8moL) into the pre-polymerization solution obtained in the step (1) in sequence, and dropwise adding a second batch of alkali: 800g (9.97moL) of 50 wt.% NaOH solution, and keeping stirring the whole reaction system for 1.5h at the temperature of 85-90 ℃ (heating temperature fluctuation), and carrying out ring-closing reaction to prepare epoxy resin to obtain a mixed product containing the epoxy resin;
(3) diluting the mixed product obtained in the step (2) by 1950g of benzene (25mol), standing for 25min, separating out brine, washing the mixture by standing and separating twice with 4kg of water at the temperature of 75-85 ℃, removing residual moisture from the washed epoxy resin azeotrope, reducing the pressure to 1.2KPa, and distilling off the solvent at the temperature of 186 ℃ to obtain 4328g of solid epoxy resin.
Example 6
The source of the triglycidyl isocyanurate production by-product in this example was the same as that in example 1.
This example provides a method for preparing an epoxy resin from a triglycidyl isocyanurate production byproduct, comprising the steps of:
(1) to a 15L reactor with mechanical stirrer, thermometer, reflux condenser and dropping funnel, charged with 350g TGIC production by-product (1.2moL) was added 548g bisphenol A (2.4moL) and the mixture heated to 75 ℃ and the first base was dropped in over 12min under continuous stirring: 480g of 50 wt.% NaOH (2.5moL), and keeping the reaction for 4 hours to obtain a pre-polymerization solution;
(2) maintaining the temperature within the range of 85-90 ℃ (heating temperature fluctuation), adding 8600g (37.67moL) of bisphenol A, 5300g (57.3moL) of epoxy chloropropane, 660g of water and 4200g of benzene (53.8moL) into the pre-polymerization solution obtained in the step (1) in sequence, and dropwise adding a second batch of alkali: 1132g (9.97moL) of 50 wt.% NaOH solution, and carrying out ring-closing reaction on the whole reaction system for 1.5h under the condition that the temperature is 90-95 ℃ (heating temperature fluctuation) to prepare epoxy resin and obtain a mixed product containing the epoxy resin;
(3) diluting the mixed product obtained in the step (2) by 2090g of benzene (26.79mol), standing for 30min, separating out brine, washing, standing and separating the mixture twice by using 3.5kg of water at the temperature of 75-85 ℃, removing residual moisture from the washed epoxy resin azeotrope, reducing the pressure to 1.2KPa, and distilling off the solvent at the temperature of 186 ℃ to obtain 10745g of solid epoxy resin.
Example 7
The source of the triglycidyl isocyanurate production by-product in this example was the same as that in example 1.
This example provides a process for producing an epoxy resin from a triglycidyl isocyanurate production by-product, which is the same as in example 1 except that bisphenol A in step (2) is added as it is in step (1).
Example 8
The source of the triglycidyl isocyanurate production by-product in this example was the same as that in example 1.
This example provides a method for preparing an epoxy resin from a triglycidyl isocyanurate production byproduct, which is the same as example 1 except that bisphenol a and epichlorohydrin are added in step (1) at one time, and specifically includes the following steps:
(1) to a 1.5L mechanical stirrer, thermometer, reflux condenser and dropping funnel reactor, 35g of TGIC production by-product (0.12moL epoxy value), 327.4g of bisphenol A (1.434moL) and 168g (1.82moL) of epichlorohydrin were added to heat the mixture to 80 ℃ and the first base was added dropwise over 15min with continuous stirring: 24g of 40.0 wt% NaOH solution (0.24moL) and keeping the reaction for 2 hours to obtain a pre-polymerization solution;
(2) keeping the temperature within the range of 80-85 ℃ (heating temperature fluctuation), sequentially adding 66g of water and 78g of benzene (1moL) into the pre-polymerization solution obtained in the step (1), and dropwise adding a second batch of alkali: 173g (1.725moL) of 40 wt.% NaOH solution, and keeping stirring the whole reaction system at the temperature of 80-85 ℃ for 3 hours to perform a ring-closing reaction to prepare epoxy resin, so as to obtain a mixed product containing the epoxy resin;
(3) diluting the mixed product obtained in the step (2) by 117g of benzene (1.5moL), standing for 30min, separating brine, washing the mixture subjected to standing separation twice by 200g of water at the temperature of 70-80 ℃, removing residual moisture from the washed epoxy resin azeotrope, reducing the pressure to 1.33KPa, and evaporating the solvent at the temperature of 190 ℃ to obtain 448g of solid epoxy resin.
Third, test and results
The properties of the epoxy resins prepared by the above examples were tested, and the yield of the epoxy resin (the yield is the yield in terms of bisphenol a) was calculated from the mass of the obtained epoxy resin.
Epoxy value test method: according to the GB/T1677-2008 (hydrochloric acid-acetone method) standard for measuring the epoxy value of the plasticizer, sodium hydroxide standard solution is adopted to titrate an acetone hydrochloride solution in which an epoxy resin sample is dissolved, and a cresol red and thymol blue mixed indicator is used as an indicator.
The method for testing the chlorine content comprises the following steps: reference is made to GB/T12007.3-1989.
Method for testing softening point: according to the GB/T12007.6-1989 epoxy resin softening point determination method-ring and ball method standard, a softening point tester is adopted to determine the softening point of the resin.
The test results of the above examples and comparative examples are shown in table 1.
TABLE 1
From table 1, the following points can be seen:
(1) it can be seen from the comprehensive examples 1 to 8 that in the examples 1 to 8, the triglycidyl isocyanurate production byproduct, epichlorohydrin and bisphenol A are subjected to ring-opening polycondensation and then subjected to ring-closing to form the solid epoxy resin, so that the triglycidyl isocyanurate production byproduct can be recycled, the environmental pressure is relieved, the epoxy value of the prepared solid epoxy resin is more than 0.15g of epoxy group/100 g, the chlorine content is less than or equal to 0.15 wt%, the softening point of the solid epoxy resin is more than or equal to 65 ℃, the yield is more than 92 wt%, and the solid epoxy resin has good industrial application value;
(2) it can be seen from the comprehensive results of examples 1 and 7-8 that, in example 1, part of bisphenol a reacts with the by-product, and part of bisphenol a and epichlorohydrin are added for reaction, compared with the case that all bisphenol a is directly added in the first step in example 7, and the case that bisphenol a and epichlorohydrin are simultaneously added in the first step in example 8, the chlorine content of the solid epoxy resin prepared in example 1 is 0.08 wt%, the softening point is 75 ℃, the yield reaches 96.5 wt%, while the chlorine contents in example 7 and example 8 were 0.12 wt% and 0.118 wt%, respectively, the softening points were 65 ℃ and 68 ℃, respectively, the yields were only 92.5 wt% and 93.1 wt%, respectively, it is thus shown that the present invention improves the yield and softening point of epoxy resins and reduces the chlorine content by controlling the addition of bisphenol a in steps and limiting the addition of epichlorohydrin in the second step.
In conclusion, the method for preparing the epoxy resin from the triglycidyl isocyanurate production byproducts can recycle the byproducts, the epoxy value of the prepared solid epoxy resin is more than 0.15g of epoxy group/100 g, the chlorine content is less than or equal to 0.15 wt%, the softening point of the solid epoxy resin is more than or equal to 65 ℃, and the yield is more than 92 wt%, so that the market demand is met.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A method for producing an epoxy resin from a triglycidyl isocyanurate production byproduct, comprising: the epoxy resin is prepared from byproducts in the production of triglycidyl isocyanurate, bisphenol A and epichlorohydrin under the action of alkali.
2. The method of claim 1, wherein the triglycidyl isocyanurate production by-product comprises triglycidyl isocyanurate;
preferably, the triglycidyl isocyanurate production by-product further comprises any one or a combination of at least two of 2, 3-substituted ring-closed epoxypropyl isocyanurate, monoglycidyl isocyanurate, diglycidyl isocyanurate, or 1-chloro-2-hydroxy-propyl isocyanurate;
preferably, the epoxy value of the triglycidyl isocyanurate production byproduct is 0.3-0.5 moL of epoxy group/100 g;
preferably, the by-product in the production of triglycidyl isocyanurate is the residue of a liquid phase distillation still or distillation still after methanol recrystallization of triglycidyl isocyanurate.
3. The method according to claim 1 or 2, wherein the triglycidyl isocyanurate production by-product is prepared by mixing the epoxy value and bisphenol A in a molar ratio of 0.01-0.2: 1;
preferably, the molar ratio of the base to the bisphenol A is 1.7-4.5: 1.
4. A method according to any one of claims 1 to 3, characterized in that the method comprises the steps of:
(1) carrying out ring-opening reaction on a triglycidyl isocyanurate production byproduct and bisphenol under the action of a first batch of alkali to obtain a pre-polymerization solution;
(2) carrying out a ring-closing reaction on the pre-polymerization solution, bisphenol A and epoxy chloropropane in the step (1) under the action of a second batch of alkali to prepare epoxy resin and obtain a mixed product containing the epoxy resin;
(3) and (3) carrying out post-treatment on the mixed product obtained in the step (2) to obtain the solid epoxy resin.
5. The method according to claim 4, wherein the triglycidyl isocyanurate production byproduct in the step (1) is prepared by mixing the epoxy value and the bisphenol A in a molar ratio of 0.5-1: 1;
preferably, the temperature of the ring-opening reaction is 75-85 ℃;
preferably, the molar ratio of the first base to the bisphenol A is 1.5-2.5: 1;
preferably, the first base comprises sodium hydroxide;
preferably, the first base is a sodium hydroxide solution;
preferably, the mass concentration of the sodium hydroxide solution is 35-50 wt%;
preferably, the sodium hydroxide solution is added dropwise;
preferably, the dripping time is 10-20 min.
6. The method according to claim 4 or 5, wherein the molar ratio of the bisphenol A in step (2) to the bisphenol A in step (1) is 10-16: 1;
preferably, the molar ratio of the sum of aromatic hydroxyl groups contained in the pre-polymerization liquid and hydroxyl groups in the bisphenol A to the epichlorohydrin is 0.8-1: 1;
preferably, the molar ratio of the second base to the epichlorohydrin is 0.2-2: 1;
preferably, the second base comprises sodium hydroxide;
preferably, the second base is sodium hydroxide solution;
preferably, the mass concentration of the sodium hydroxide solution is 35-50 wt%;
preferably, the sodium hydroxide solution is added dropwise;
preferably, the dripping time is 10-20 min;
preferably, a first solvent is also added to the ring closure reaction;
preferably, the first solvent comprises water and an organic solvent;
preferably, the organic solvent comprises any one of benzene, toluene, xylene, o-dichlorobenzene or m-dichlorobenzene, or a combination of at least two thereof;
preferably, the molar ratio of the organic solvent in the first solvent to the bisphenol A in the step (2) is 0.5-1.1: 1;
preferably, in the ring-closing reaction, bisphenol A, epichlorohydrin, water and an organic solvent are sequentially added into the prepolymerization liquid, and then a second batch of alkali is dropwise added;
preferably, bisphenol A, epoxy chloropropane, water and an organic solvent are sequentially added into the prepolymerization liquid at the temperature of 80-95 ℃, and then a second batch of alkali is dropwise added.
7. The method according to any one of claims 4 to 6, wherein the temperature of the ring closure reaction in the step (2) is 80 to 95 ℃;
preferably, the ring-closure reaction time is 2-4 h;
preferably, the ring closure reaction is carried out under stirring conditions.
8. The method according to any one of claims 4 to 7, wherein the post-treatment in step (3) comprises: diluting the mixed product by a second solvent, and then sequentially carrying out solid-liquid separation, washing, solvent removal and cooling to obtain solid epoxy resin;
preferably, the second solvent comprises any one of benzene, toluene, xylene, o-dichlorobenzene or m-dichlorobenzene, or a combination of at least two thereof;
preferably, the means for removing the solvent comprises distillation.
9. A method according to any one of claims 4 to 8, characterized in that the method comprises the steps of:
(1) mixing a triglycidyl isocyanurate production byproduct with bisphenol A, dripping 35-50 wt% of sodium hydroxide solution within 10-20 min at 75-85 ℃, and carrying out ring opening reaction to obtain a pre-polymerization solution;
wherein the triglycidyl isocyanurate production byproduct comprises triglycidyl isocyanurate;
the molar ratio of the epoxy value to the bisphenol A of the byproducts produced in the triglycidyl isocyanurate production is 0.5-1: 1, and the molar ratio of sodium hydroxide to the bisphenol A in the sodium hydroxide solution is 1.5-2.5: 1;
(2) sequentially adding bisphenol A, epoxy chloropropane, water and an organic solvent into the pre-polymerization liquid in the step (1) at the temperature of 80-95 ℃, dropwise adding a sodium hydroxide solution with the mass concentration of 35-50 wt%, maintaining the temperature of 80-95 ℃ and carrying out a ring-closing reaction for 2-4 h to prepare epoxy resin, so as to obtain a mixed product containing the epoxy resin;
wherein the molar ratio of the bisphenol A in the step (2) to the bisphenol A in the step (1) is 10-16: 1;
the molar ratio of the sum of aromatic hydroxyl contained in the pre-polymerization liquid and hydroxyl in the bisphenol A to the epichlorohydrin is 0.8-1: 1;
the molar ratio of the organic solvent to the bisphenol A in the step (2) is 0.5-1.1: 1;
the molar ratio of sodium hydroxide to epoxy chloropropane in the sodium hydroxide solution is 0.2-2: 1;
(3) and (3) diluting the mixed product obtained in the step (2) by using a second solvent, and then sequentially carrying out solid-liquid separation, washing, solvent removal and cooling to obtain the solid epoxy resin.
10. An epoxy resin, wherein the epoxy resin is prepared by the method for preparing an epoxy resin from the triglycidyl isocyanurate production byproduct as claimed in any one of claims 1 to 9.
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| CN114195983A (en) * | 2021-12-20 | 2022-03-18 | 江苏扬农锦湖化工有限公司 | Method for preparing solid epoxy resin by using TGIC methanol recrystallization mother liquor by-product |
| KR20220072479A (en) * | 2020-11-25 | 2022-06-02 | 한국생산기술연구원 | Multifunctional epoxy compound having alkoxysilyl group, preparing method thereof, composition, and use thereof |
| CN116041668A (en) * | 2022-10-27 | 2023-05-02 | 江苏扬农锦湖化工有限公司 | Method for preparing epoxy resin by using bisphenol F mother liquor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20220072479A (en) * | 2020-11-25 | 2022-06-02 | 한국생산기술연구원 | Multifunctional epoxy compound having alkoxysilyl group, preparing method thereof, composition, and use thereof |
| KR102503157B1 (en) | 2020-11-25 | 2023-02-24 | 한국생산기술연구원 | Multifunctional epoxy compound having alkoxysilyl group, preparing method thereof, composition, and use thereof |
| CN114195983A (en) * | 2021-12-20 | 2022-03-18 | 江苏扬农锦湖化工有限公司 | Method for preparing solid epoxy resin by using TGIC methanol recrystallization mother liquor by-product |
| CN116041668A (en) * | 2022-10-27 | 2023-05-02 | 江苏扬农锦湖化工有限公司 | Method for preparing epoxy resin by using bisphenol F mother liquor |
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| CN111875778B (en) | 2022-12-09 |
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