CN113651945A - Glycidyl ether epoxy resin and preparation method thereof - Google Patents
Glycidyl ether epoxy resin and preparation method thereof Download PDFInfo
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- CN113651945A CN113651945A CN202110931724.8A CN202110931724A CN113651945A CN 113651945 A CN113651945 A CN 113651945A CN 202110931724 A CN202110931724 A CN 202110931724A CN 113651945 A CN113651945 A CN 113651945A
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- polyglycerol
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- molecular distillation
- epoxy resin
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 62
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 62
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 269
- 229920000223 polyglycerol Polymers 0.000 claims abstract description 151
- 238000000199 molecular distillation Methods 0.000 claims abstract description 79
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 68
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 58
- 239000002994 raw material Substances 0.000 claims abstract description 52
- 238000002156 mixing Methods 0.000 claims abstract description 30
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000011187 glycerol Nutrition 0.000 claims description 96
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 55
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 50
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- 239000003054 catalyst Substances 0.000 claims description 25
- 239000003513 alkali Substances 0.000 claims description 23
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000006297 dehydration reaction Methods 0.000 claims description 20
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 claims description 20
- AGNTUZCMJBTHOG-UHFFFAOYSA-N 3-[3-(2,3-dihydroxypropoxy)-2-hydroxypropoxy]propane-1,2-diol Chemical compound OCC(O)COCC(O)COCC(O)CO AGNTUZCMJBTHOG-UHFFFAOYSA-N 0.000 claims description 19
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 19
- 230000018044 dehydration Effects 0.000 claims description 18
- 238000004821 distillation Methods 0.000 claims description 18
- 238000004321 preservation Methods 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 16
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 16
- 239000006227 byproduct Substances 0.000 claims description 15
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 14
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 11
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- 238000000909 electrodialysis Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- 238000007790 scraping Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- JYKSTGLAIMQDRA-UHFFFAOYSA-N tetraglycerol Chemical compound OCC(O)CO.OCC(O)CO.OCC(O)CO.OCC(O)CO JYKSTGLAIMQDRA-UHFFFAOYSA-N 0.000 claims description 10
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 9
- CHQVQXZFZHACQQ-UHFFFAOYSA-M benzyl(triethyl)azanium;bromide Chemical compound [Br-].CC[N+](CC)(CC)CC1=CC=CC=C1 CHQVQXZFZHACQQ-UHFFFAOYSA-M 0.000 claims description 9
- 238000010612 desalination reaction Methods 0.000 claims description 9
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 9
- 229910015900 BF3 Inorganic materials 0.000 claims description 8
- 238000006386 neutralization reaction Methods 0.000 claims description 8
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 8
- 239000003225 biodiesel Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 5
- 229940105990 diglycerin Drugs 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- -1 triglycerin Chemical compound 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 5
- 238000011033 desalting Methods 0.000 claims 3
- 239000004593 Epoxy Substances 0.000 abstract description 24
- 238000009826 distribution Methods 0.000 abstract description 10
- 239000012535 impurity Substances 0.000 abstract description 7
- 230000007547 defect Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 26
- 239000000243 solution Substances 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 125000003700 epoxy group Chemical group 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000001476 alcoholic effect Effects 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HUXDTFZDCPYTCF-UHFFFAOYSA-N 1-chloropropane-1,1-diol Chemical compound CCC(O)(O)Cl HUXDTFZDCPYTCF-UHFFFAOYSA-N 0.000 description 2
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 2
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- RNVYQYLELCKWAN-UHFFFAOYSA-N solketal Chemical compound CC1(C)OCC(CO)O1 RNVYQYLELCKWAN-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003906 humectant Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical group ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000005406 washing Methods 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Compounds (AREA)
- Polyethers (AREA)
Abstract
The invention provides glycidyl ether epoxy resin and a preparation method thereof, wherein the preparation method comprises the following steps: sequentially rectifying and molecular distilling the raw material of the crude glycerol to obtain polyglycerol; and mixing the obtained polyglycerol and epoxy chloropropane, and then sequentially carrying out ring opening reaction and ring closing reaction to obtain the glycidyl ether epoxy resin. According to the method, the raw glycerol is firstly used as a raw material, the polyglycerol is prepared through rectification and molecular distillation, the defects of deep color, more impurities and wide molecular weight distribution in the catalytic preparation of the polyglycerol are overcome, the effects of less polyglycerol impurities and narrow molecular weight distribution are realized, the raw material is then used for preparing the glycidyl ether epoxy resin through ring-opening and ring-closing reaction with epoxy chloropropane, the market demand on the multifunctional epoxy resin is met, and the epoxy value and the epoxy functionality of the obtained epoxy resin product are higher; the method is simple and convenient to operate, high in product quality, easy for industrial production and wide in application prospect.
Description
Technical Field
The invention belongs to the technical field of fine organic chemical industry, and relates to glycidyl ether epoxy resin and a preparation method thereof.
Background
The polyglycerol is an organic compound of low molecular weight polyether polyol, can be directly used as a humectant, a thickening agent, a plasticizer, a hydrophilic modifier and the like, and has wide application in the industries of food, cosmetics, daily chemicals, medicines, detergents and the like; meanwhile, the polyglycerol can also be used as an organic intermediate for preparing multifunctional epoxy resin, wherein the multifunctional epoxy resin comprises a plurality of types, and products of the multifunctional epoxy resin comprise glycidyl ethers, glycidyl esters and other epoxy resins according to different materials reacted with the polyglycerol, so that the efficient preparation of the polyglycerol is an important step for producing the multifunctional epoxy resin.
The industrial synthesis method of the polyglycerol comprises two major methods, namely a glycerol method and a non-glycerol method, wherein the non-glycerol method comprises an allyl ether method, a glycerol acetonide method and the like, the general operation steps are more complicated, the number of byproducts is more, and multi-step purification is needed; the glycerol method comprises a glycerol self-dehydration method, a glycerol and epichlorohydrin condensation method and the like, wherein the glycerol self-dehydration method usually takes acid or alkali as a catalyst, and when the acid is taken as the catalyst, the problems of more byproducts, high requirement on equipment, wide molecular weight distribution and difficult separation of polyglycerol by molecular distillation exist; when alkali is used as a catalyst, the defects of dark product color, catalyst residue, more byproducts, wide molecular weight distribution and the like exist, so that the synthesis process of the polyglycerol needs to be improved.
CN 107235830A discloses a preparation method of polyglycerol-10, which comprises the following steps: in the presence of an acid catalyst, glycerol and glycidol are subjected to polymerization reaction to obtain a polyglycerol crude product, the product of the polymerization reaction is neutralized, the neutralized product is distilled by adopting molecular distillation equipment, and the obtained heavy component is polyglycerol-10. CN 102532515A discloses a preparation method of polyglycerol with high polymerization degree, which comprises the steps of adding reaction substrate glycerol and an alkaline catalyst with the mass of 2-4% of that of glycerol into a reactor, continuously introducing nitrogen into materials in the reaction process, taking out water generated in the reaction, heating to 260-280 ℃ while stirring, stirring at constant temperature for reaction for 1-4 h, stopping heating, and continuously introducing nitrogen until the product is cooled to 120-150 ℃, thus obtaining semisolid polyglycerol with the average polymerization degree of about 10-25. The preparation of polyglycerol in the above patent is problematic in that it uses acid or alkali as a catalyst, and does not involve a process for further preparing multifunctional propylene oxide from polyglycerol.
CN 103289057A discloses a method for preparing glycidyl ether epoxy resin by using monomers containing alcoholic hydroxyl and/or phenolic hydroxyl, which comprises the steps of adding the monomers containing alcoholic hydroxyl and/or phenolic hydroxyl and epichlorohydrin into a reactor, heating and fully dissolving; controlling the reaction temperature to be 40-80 ℃, and adding quaternary ammonium salt and solid alkali; and after the reaction is finished for 0.5-5h, removing the excessive alkali and the generated salt in the reaction by suction filtration, adding an organic solvent to dilute the product, washing the product by deionized water, separating out an organic phase, and distilling under reduced pressure to obtain the glycidyl ether epoxy resin product. In the method, the monomer raw material is directly used, the source of the monomer raw material is not clear, and according to the type of a common glycidyl ether product, the steric hindrance of the hydroxyl-containing monomer is generally larger, or the melting point is higher, so that the substitution of an epoxy group by each hydroxyl group is difficult to realize, and the requirement on multifunctional epoxy resin is difficult to meet.
In summary, for the preparation of glycidyl ether epoxy resin, especially for the step-by-step preparation process, it is necessary to ensure that the purity and other characteristics of the intermediate meet the requirements, and to select appropriate initial raw materials and control each step of process, so as to facilitate obtaining high-quality products.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide the glycidyl ether epoxy resin and the preparation method thereof, the method firstly takes crude glycerol as a raw material, and prepares the polyglycerol through rectification and molecular distillation, so that the defects of dark color, more impurities and wide molecular weight distribution in the catalytic preparation of the polyglycerol are avoided, and then the polyglycerol is taken as the raw material to prepare the glycidyl ether epoxy resin with epichlorohydrin, so that the market demand on multifunctional epoxy resin is met; the method is simple and convenient to operate, high in product quality and wide in application prospect.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the present invention provides a method for preparing glycidyl ether epoxy resin, comprising the following steps:
(1) sequentially rectifying and molecular distilling the raw material of the crude glycerol to obtain polyglycerol;
(2) and (2) mixing the polyglycerol obtained in the step (1) with epichlorohydrin, and then sequentially carrying out ring opening reaction and ring closing reaction to obtain the glycidyl ether epoxy resin.
In the invention, for the preparation of glycidyl ether epoxy resin, raw materials required by different types of glycidyl ether epoxy resin are different, wherein polyol is taken as a common raw material, crude glycerol is taken as a raw material, and a polyglycerol component is prepared by purification, so that not only can byproducts of the reaction be fully utilized, but also a path for preparing the polyglycerol by direct catalysis can be avoided, and the defects of deep color, more byproducts and wide molecular weight distribution of a product obtained by preparing the polyglycerol by catalysis are avoided; the product obtained by the method has high quality, simple and convenient operation, easy industrial production and wide application prospect.
The following technical solutions are preferred technical solutions of the present invention, but not limited to the technical solutions provided by the present invention, and technical objects and advantageous effects of the present invention can be better achieved and achieved by the following technical solutions.
As a preferred technical solution of the present invention, the raw glycerin material in step (1) is derived from any one or a combination of at least two of a by-product of epichlorohydrin preparation by direct oxidation with hydrogen peroxide, glycerin prepared by biodiesel process or glycerin prepared by propylene process, and typical but non-limiting examples of the combination are as follows: the combination of the by-product of the epichlorohydrin preparation by the hydrogen peroxide direct oxidation and the glycerin prepared by the biodiesel method, the combination of the glycerin prepared by the biodiesel method and the glycerin prepared by the propylene method, the combination of the by-product of the epichlorohydrin preparation by the hydrogen peroxide direct oxidation, the glycerin prepared by the biodiesel method and the glycerin prepared by the propylene method, and the like.
Preferably, the composition of the crude glycerin of step (1) includes glycerin, diglycerin, triglycerin, tetraglycerol, pentaglycerol, and hexaglycerol.
In the invention, the crude glycerol mainly comes from products or byproducts of related existing processes, such as byproducts of an epichlorohydrin preparation process, glycerol prepared by a biodiesel method and the like, the glycerol is easy to dehydrate and condense to form a polyglycerol component under the conditions of long-time vacuum and high temperature, and the catalytic preparation is not needed.
In the present invention, the source of the crude glycerol may be selected from allyl ether method, glycerol acetonide method, monochloropropanediol and epichlorohydrin method, glycerol and glycidol method, glycerol and epichlorohydrin condensation method, etc. to prepare crude polyglycerol product.
As the preferable technical scheme of the invention, the rectification in the step (1) is carried out under the condition of protective gas to remove the glycerol component in the crude glycerol; wherein the protective gas comprises nitrogen and/or an inert gas.
Preferably, the rectification in step (1) has a top temperature of 150 to 210 ℃, for example 150 ℃, 160 ℃, 180 ℃, 190 ℃, 200 ℃ or 210 ℃, but not limited to the recited values, and other values not recited within this range are equally applicable, preferably 160 to 190 ℃.
In the invention, when the glycerin is removed by rectification operation, the protective gas is used for protecting each component of the crude glycerin from being oxidized under the rectification temperature condition.
Preferably, the pressure for the rectification in step (1) is 0.9 to 8kPa, such as 0.9kPa, 1.5kPa, 2kPa, 3kPa, 4kPa, 5kPa, 6kPa, or 8kPa, but not limited to the recited values, and other values not recited within the range are also applicable, preferably 1 to 5 kPa.
In the invention, the rectification pressure refers to absolute pressure, namely, rectification separation is carried out under certain vacuum conditions.
Preferably, the reflux ratio of the rectification in step (1) is (1-20): 1, such as 1:1, 2:1, 4:1, 6:1, 8:1, 10:1, 12:1, 14:1, 16:1, 18:1 or 20:1, but not limited to the recited values, and other values not recited in the range of values are equally applicable, preferably (3-10): 1.
As a preferred technical scheme of the invention, the molecular distillation in the step (1) comprises primary molecular distillation and secondary molecular distillation, and the heavy-phase component of the primary molecular distillation is continuously subjected to the secondary molecular distillation.
Preferably, the molecular distillation is carried out using a wiped film molecular still.
Preferably, the temperature of the primary molecular distillation is 110 to 150 ℃, such as 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 140 ℃ or 150 ℃, but is not limited to the recited values, and other values not recited within the range of values are equally applicable, preferably 120 to 140 ℃.
Preferably, the pressure of the first molecular distillation is 100 to 500Pa, for example 100Pa, 150Pa, 200Pa, 250Pa, 300Pa, 350Pa, 400Pa or 500Pa, but not limited to the recited values, and other values within the range are also applicable, preferably 100 to 300 Pa.
Preferably, the first molecular distillation has a knifing rate of 100 to 450r/min, such as 100r/min, 150r/min, 200r/min, 250r/min, 300r/min, 350r/min, 400r/min or 450r/min, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the temperature of the secondary molecular distillation is 160 to 200 ℃, such as 160 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃ or 200 ℃, but is not limited to the recited values, and other values not recited within this range are equally applicable, preferably 170 to 190 ℃.
Preferably, the pressure of the secondary molecular distillation is 10 to 50Pa, for example, 10Pa, 15Pa, 20Pa, 25Pa, 30Pa, 35Pa, 40Pa, or 50Pa, etc., but not limited to the recited values, and other values within the range are also applicable, preferably 10 to 30 Pa.
In the invention, the pressure of the two-stage molecular distillation is also absolute pressure, and compared with the rectification pressure, the two-stage molecular distillation is carried out under stronger vacuum condition, and the separation is realized by utilizing the difference of the average free paths of different substance molecules and the difference of the evaporation rates of all components. Wherein, the primary molecular distillation mainly removes the glycerol component which is not completely removed in the rectification operation, and the secondary molecular distillation mainly separates the heavy components of the dimeric glycerol, the trimeric glycerol and the trimeric glycerol.
Preferably, the secondary molecular distillation has a knifing rate of 200 to 450r/min, such as 200r/min, 250r/min, 300r/min, 350r/min, 400r/min or 450r/min, but not limited to the recited values, and other values not recited in the range are equally applicable.
As a preferred embodiment of the present invention, the polyglycerin in of the step (1) includes diglycerin and triglycerol, and the purity thereof is 96.2 wt% or more, for example, 96.2 wt%, 96.7 wt%, 97.3 wt%, 97.8 wt%, 98.3 wt%, 98.8 wt%, 99.3 wt%, 99.7 wt%, 99.8 wt%, or 99.9 wt%, but is not limited to the exemplified values, and other values not exemplified in the range of the values are also applicable.
Preferably, the mass fraction of diglycerol in the polyglycerols is 75 to 92 wt%, such as 75 wt%, 78 wt%, 80 wt%, 82 wt%, 85 wt%, 88 wt%, 90 wt%, or 92 wt%, but not limited to the recited values, and other non-recited values within the range of values are equally applicable; the mass fraction of triglycerol is 7 to 24 wt%, for example 7 wt%, 10 wt%, 12 wt%, 15 wt%, 18 wt%, 20 wt%, or 24 wt%, but is not limited to the recited values, and other values not recited within the range of values are also applicable.
In the present invention, since the kinds of hydroxyl groups in glycerol are classified into two types, one glycerol molecule has two primary hydroxyl groups and one secondary hydroxyl group, so that the obtained diglycerol and triglycerol have various isomers according to the polymerization between different hydroxyl groups, and the polyglycerin obtained in the present invention is generally a mixture of the various isomers.
In a preferred embodiment of the present invention, the molar ratio of the number of moles of the polyglycerol in the step (2) to the epichlorohydrin is 1 (4.0 to 12.0), for example, 1:4.0, 1:5.0, 1:6.0, 1:8.0, 1:10.0 or 1:12.0, but the present invention is not limited to the above-mentioned numerical values, and other numerical values not listed in the above-mentioned numerical value range are also applicable.
Preferably, the polyglycerol of step (2) is mixed with a solvent before being mixed with epichlorohydrin.
Preferably, the solvent comprises toluene.
Preferably, the solvent is used in an amount of 2 to 3 times, for example, 2 times, 2.2 times, 2.4 times, 2.5 times, 2.7 times, 2.8 times, or 3 times, the weight of the polyglycerol, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the mixing of the polyglycerol and the epichlorohydrin in the step (2) is as follows: epichlorohydrin was added dropwise to the polyglycerol.
Preferably, the catalyst for the ring-opening reaction in step (2) comprises any one or a combination of at least two of boron trifluoride, boron trifluoride etherate, tin tetrachloride or concentrated sulfuric acid, and the combination is exemplified by, typically but not limited to: combinations of boron trifluoride etherate and tin tetrachloride, combinations of boron trifluoride and tin tetrachloride, combinations of tin tetrachloride and concentrated sulfuric acid, combinations of boron trifluoride, tin tetrachloride and concentrated sulfuric acid, and the like.
Preferably, the catalyst for the ring-opening reaction in step (2) is added in an amount of 0.1 to 3.0 wt% based on the mass of the polyglycerol, for example, 0.1 wt%, 0.4 wt%, 0.75 wt%, 1.0 wt%, 1.2 wt%, 1.5 wt%, 1.8 wt%, 2.0 wt%, 2.4 wt%, 2.7 wt%, or 3.0 wt%, but not limited to the enumerated values, and other unrecited values within the range are also applicable.
Preferably, the ring-opening reaction in step (2) is carried out at a temperature of 20 to 100 ℃, for example, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ or 100 ℃, but not limited to the recited values, and other values not recited within the range of the recited values are also applicable, preferably 50 to 80 ℃.
Preferably, the raw material dropping time of the ring-opening reaction in the step (2) is 0.5 to 6 hours, such as 0.5 hour, 1 hour, 1.5 hour, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours or 6 hours, but not limited to the enumerated values, and other unrecited values in the numerical range are also applicable; the ring-opening reaction is carried out for 1 to 6 hours, for example, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, or 6 hours, but the ring-opening reaction is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
As a preferable technical scheme of the invention, after the ring-opening reaction in the step (2) is finished, a ring-closing reaction catalyst and alkali liquor are added into a reaction system.
Preferably, the catalyst of the ring closure reaction comprises any one of or a combination of at least two of tetrabutylammonium chloride, tetrabutylammonium bromide, benzyltriethylammonium chloride, tetrabutylammonium hydrogen sulfate or benzyltriethylammonium bromide, typical but non-limiting examples of which are: combinations of tetrabutylammonium chloride and tetrabutylammonium bromide, combinations of tetrabutylammonium bromide and benzyltriethylammonium chloride, combinations of tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate and benzyltriethylammonium bromide, and the like.
Preferably, the catalyst for the ring closure reaction is added in an amount of 0.2 to 2.0 wt%, such as 0.2 wt%, 0.4 wt%, 0.6 wt%, 0.8 wt%, 1.0 wt%, 1.2 wt%, 1.4 wt%, 1.6 wt%, 1.8 wt%, or 2.0 wt%, based on the mass of the polyglycerol, but is not limited to the recited values, and other values not recited within the range of values are also applicable.
Preferably, the lye comprises a sodium hydroxide solution and/or a potassium hydroxide solution.
Preferably, the concentration of the alkali solution is 5 to 40 wt%, such as 5 wt%, 10 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt% or 40 wt%, etc., but not limited to the recited values, and other values not recited in the range of the values are also applicable, preferably 20 to 35 wt%.
Preferably, the molar ratio of base to polyglycerol in the alkaline solution is (3.9-7.0): 1, for example 3.9:1, 4.0:1, 4.1:1, 4.2:1, 4.5:1, 5.0:1, 5.5:1, 6.0:1, 6.5:1 or 7.0:1, but not limited to the recited values, and other values not recited within this range of values are equally applicable, preferably (4.0-5.5): 1.
Preferably, the addition mode of the alkali liquor is dropwise.
Preferably, the temperature of the ring closure reaction in step (2) is 30 to 70 ℃, for example 30 ℃, 40 ℃, 50 ℃, 60 ℃, 65 ℃ or 70 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable, preferably 40 to 60 ℃.
Preferably, the ring closure reaction of step (2) is performed in a raw material dropping time of 0.5 to 6 hours, such as 0.5 hour, 1 hour, 1.5 hour, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours or 6 hours, but not limited to the enumerated values, and other unrecited values in the numerical range are also applicable; the incubation time for the ring-closure reaction is 1 to 6 hours, for example, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, or 6 hours, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
According to the invention, the reaction between the polyglycerol and the epichlorohydrin is mainly carried out in two steps, as the activity of an epoxy bond on the epichlorohydrin is relatively high, an epoxy group and an alcoholic hydroxyl group in the polyglycerol generate an ether bond through a ring opening reaction, the terminal group at the moment is a hydroxyl chloride group, hydrogen chloride is removed through a ring closing reaction, an epoxy group is formed again, as the polyglycerol molecule contains a plurality of hydroxyl groups, and the hydroxyl groups partially or completely react according to the addition amount of the epichlorohydrin, so that the glycidyl ether epoxy resin is generated.
As a preferable technical scheme of the invention, after the ring-closure reaction in the step (2) is finished, the reaction product is subjected to neutralization, filtration, desalination and distillation dehydration in sequence to obtain the glycidyl ether epoxy resin.
Preferably, the desalination is electrodialysis desalination.
Preferably, the temperature of the distillation dehydration is 90 to 130 ℃, for example 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃ or 130 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable, preferably 100 to 120 ℃.
Preferably, the pressure of the distillation dehydration is-0.09 to-0.1 MPa, for example, -0.09MPa, -0.092MPa, -0.094MPa, -0.096MPa, -0.098MPa or-0.1 MPa, but not limited to the recited values, and other values not recited in the above range are also applicable.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) sequentially rectifying and molecular distilling a crude glycerol raw material, wherein the crude glycerol comprises glycerol, diglycerol, triglycerol, tetraglycerol, pentaglycerol and hexaglycerol, the rectification is carried out under the condition of protective gas to remove the glycerol component in the crude glycerol, the tower top temperature of the rectification is 150-210 ℃, the pressure of the rectification is 0.9-8 kPa, and the reflux ratio of the rectification is (1-20): 1;
the molecular distillation comprises primary molecular distillation and secondary molecular distillation, and is carried out by adopting a wiped film type molecular distiller, wherein the temperature of the primary molecular distillation is 110-150 ℃, the pressure is 100-500 Pa, and the wiped film speed is 100-450 r/min; the temperature of the secondary molecular distillation is 160-200 ℃, the pressure is 10-50 Pa, and the film scraping speed is 200-450 r/min, so that polyglycerol is obtained;
(2) mixing the polyglycerol obtained in the step (1) with a solvent, wherein the amount of the solvent is 2-3 times of the mass of the polyglycerol, then mixing the polyglycerol with epichlorohydrin, the mixing mode is that the epichlorohydrin is dripped into the polyglycerol, the molar ratio of the polyglycerol to the epichlorohydrin is 1 (4.0-12.0), then carrying out ring opening reaction and ring closing reaction in sequence, the catalyst for the ring opening reaction comprises any one or the combination of at least two of boron trifluoride, boron trifluoride diethyl etherate, stannic chloride or concentrated sulfuric acid, the amount of the catalyst is 0.1-3.0 wt% of the mass of the polyglycerol, the temperature for the ring opening reaction is 20-100 ℃, the dripping time of the raw material for the ring opening reaction is 0.5-6 hours, and the heat preservation time for the ring opening reaction is 1-6 hours;
after the ring-opening reaction is finished, adding a ring-closing reaction catalyst and alkali liquor into a reaction system, wherein the ring-closing reaction catalyst comprises one or a combination of at least two of tetrabutylammonium chloride, tetrabutylammonium bromide, benzyltriethylammonium chloride, tetrabutylammonium hydrogen sulfate and benzyltriethylammonium bromide, the dosage of the catalyst is 0.2-2.0 wt% of the mass of polyglycerol, the alkali liquor comprises a sodium hydroxide solution and/or a potassium hydroxide solution, the concentration of the alkali liquor is 5-40 wt%, the molar ratio of alkali in the alkali liquor to the polyglycerol is (3.9-7.0): 1, the ring-closing reaction temperature is 30-70 ℃, the raw material dropping time of the ring-opening reaction is 0.5-6 h, the ring-opening reaction heat preservation time is 1-6 h, and after the ring-closing reaction is finished, the reaction products are subjected to neutralization, filtration, electrodialysis desalination and distillation dehydration in sequence, the distillation dehydration temperature is 90-130 ℃, the pressure is-0.09 to-0.1 MPa, and the glycidyl ether epoxy resin is obtained.
On the other hand, the invention provides the glycidyl ether epoxy resin prepared by the method.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method comprises the steps of firstly, taking crude glycerol as a raw material, preparing the polyglycerol by rectification and molecular distillation, avoiding the defects of deep color, more impurities and wide molecular weight distribution in the catalytic preparation of the polyglycerol, realizing the effects of less polyglycerol impurities and narrow molecular weight distribution, and then, taking the polyglycerol as the raw material and epichlorohydrin to prepare the glycidyl ether epoxy resin through ring-opening and ring-closing reactions, so that the market demand on the multifunctional epoxy resin is met, the epoxy value of the obtained epoxy resin product reaches more than 0.74eq/100g, and the epoxy functionality, namely, the number of epoxy groups in each molecule on average reaches more than 2.48;
(2) the method disclosed by the invention is simple and convenient to operate, high in product quality, easy for industrial production and wide in application prospect.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. However, the following examples are only simple examples of the present invention and do not represent or limit the scope of the present invention, which is defined by the claims.
The specific embodiment of the invention provides a glycidyl ether epoxy resin and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) sequentially rectifying and molecular distilling the raw material of the crude glycerol to obtain polyglycerol;
(2) and (2) mixing the polyglycerol obtained in the step (1) with epichlorohydrin, and then sequentially carrying out ring opening reaction and ring closing reaction to obtain the glycidyl ether epoxy resin.
The following are typical but non-limiting examples of the invention:
example 1:
the embodiment provides a preparation method of glycidyl ether epoxy resin, which includes the following steps:
(1) sequentially rectifying and molecular distilling a crude glycerol raw material, wherein the crude glycerol raw material is a byproduct for preparing epoxy chloropropane by directly oxidizing hydrogen peroxide, and comprises glycerol, diglycerol, triglycerol, tetraglycerol, pentaglycerol and hexaglycerol, the rectification is carried out under the protection of nitrogen to remove glycerol components in the crude glycerol, the tower top temperature of the rectification is 177 ℃, the pressure of the rectification is 3kPa, and the reflux ratio of the rectification is 3: 1;
the molecular distillation comprises primary molecular distillation and secondary molecular distillation, and is carried out by adopting a wiped film type molecular distiller, wherein the temperature of the primary molecular distillation is 140 ℃, the pressure is 300Pa, and the wiped film speed is 100 r/min; the temperature of the secondary molecular distillation is 190 ℃, the pressure is 30Pa, and the film scraping speed is 200r/min, so that polyglycerol is obtained; wherein the content of diglycerol in the polyglycerol is 82.6 wt%, and the content of triglycerol in the polyglycerol is 16.7 wt%;
(2) uniformly mixing the polyglycerol obtained in the step (1) with toluene, wherein the amount of the toluene is 2.5 times of the mass of the polyglycerol, then mixing the polyglycerol with epichlorohydrin, dropwise adding the epichlorohydrin into the polyglycerol in a mixing mode, wherein the molar ratio of the polyglycerol to the epichlorohydrin is 1:4.2, then sequentially carrying out ring-opening reaction and ring-closing reaction, wherein the catalyst of the ring-opening reaction is boron trifluoride, the addition amount of the boron trifluoride is 0.1 wt% of the mass of the polyglycerol, the temperature of the ring-opening reaction is 100 ℃, the dropwise adding time of the raw material of the ring-opening reaction is 6 hours, and the heat preservation time is 6 hours;
after the ring-opening reaction is finished, adding a ring-closing reaction catalyst and a sodium hydroxide solution into a reaction system, wherein the ring-closing reaction catalyst is benzyltriethylammonium chloride, the addition amount of the benzyltriethylammonium chloride is 1.0 wt% of the mass of the polyglycerol, the concentration of the sodium hydroxide solution is 20 wt%, the molar ratio of sodium hydroxide to the polyglycerol is 3.9:1, the ring-closing reaction temperature is 30 ℃, the dropping time of raw materials for the ring-closing reaction is 4 hours, the heat preservation time is 4 hours, after the ring-closing reaction is finished, sequentially performing neutralization, filtration, electrodialysis desalination and distillation dehydration on reaction products, the distillation dehydration temperature is 130 ℃, and the pressure is-0.1 MPa, so as to obtain the glycidyl ether epoxy resin.
In this example, the process was used to prepare a polyglycerol and epoxy resin product in this order with an epoxy value of 0.7877eq/100g and an epoxy functionality of 2.48.
Example 2:
the embodiment provides a preparation method of glycidyl ether epoxy resin, which includes the following steps:
(1) sequentially rectifying and molecular distilling a crude glycerol raw material, wherein the crude glycerol raw material is a crude product for preparing polyglycerol by using monochloropropanediol and epichlorohydrin, the components of the crude product comprise glycerol, diglycerol, triglycerol, tetraglycerol, pentaglycerol and hexaglycerol, the rectification is carried out under the condition of argon protection to remove glycerol components in the crude glycerol, the tower top temperature of the rectification is 186 ℃, the rectification pressure is 5kPa, and the reflux ratio of the rectification is 2: 1;
the molecular distillation comprises primary molecular distillation and secondary molecular distillation, and is carried out by adopting a wiped film type molecular distiller, wherein the temperature of the primary molecular distillation is 150 ℃, the pressure is 500Pa, and the wiped film speed is 400 r/min; the temperature of the secondary molecular distillation is 200 ℃, the pressure is 50Pa, and the film scraping speed is 400r/min, so that polyglycerol is obtained; wherein the content of diglycerol in the polyglycerol is 78.5 wt%, and the content of triglycerol in the polyglycerol is 18.8 wt%;
(2) uniformly mixing the polyglycerol obtained in the step (1) with toluene, wherein the amount of the toluene is 2 times of the mass of the polyglycerol, then mixing the polyglycerol with epichlorohydrin, the mixing mode is that epichlorohydrin is dripped into the polyglycerol, the molar ratio of the polyglycerol to the epichlorohydrin is 1:6.5, then carrying out ring-opening reaction and ring-closing reaction in sequence, the catalyst of the ring-opening reaction is stannic chloride, the addition amount is 2.0 wt% of the mass of the polyglycerol, the temperature of the ring-opening reaction is 90 ℃, the dripping time of the raw material of the ring-opening reaction is 0.5h, and the heat preservation time is 1 h;
after the ring-opening reaction is finished, adding a ring-closing reaction catalyst and a potassium hydroxide solution into a reaction system, wherein the ring-closing reaction catalyst is tetrabutylammonium chloride, the addition amount of the tetrabutylammonium chloride is 1.5 wt% of the mass of the polyglycerol, the concentration of the potassium hydroxide solution is 30 wt%, the molar ratio of sodium hydroxide to the polyglycerol is 6.5:1, the ring-closing reaction temperature is 60 ℃, the dropping time of the raw materials for the ring-closing reaction is 3 hours, the heat preservation time is 3 hours, after the ring-closing reaction is finished, sequentially performing neutralization, filtration, electrodialysis desalination and distillation dehydration on the reaction products, and the distillation dehydration temperature is 100 ℃ and the pressure is-0.09 MPa to obtain the glycidyl ether epoxy resin.
In this example, the process was used to prepare a polyglycerol and epoxy resin product in this order with an epoxy value of 0.8020eq/100g and an epoxy functionality of 2.90.
Example 3:
the embodiment provides a preparation method of glycidyl ether epoxy resin, which includes the following steps:
(1) sequentially rectifying a crude glycerin raw material, namely a composition for preparing a byproduct of epichlorohydrin by directly oxidizing glycerin and hydrogen peroxide prepared by a biodiesel method to prepare a molecular distillation, wherein the crude glycerin raw material comprises glycerin, diglycerin, triglycerin, tetraglycerol, pentaglycerol and hexaglycerol, the rectification is carried out under the condition of nitrogen protection to remove glycerin components in the crude glycerin, the tower top temperature of the rectification is 154 ℃, the rectification pressure is 0.9kPa, and the reflux ratio of the rectification is 10: 1;
the molecular distillation comprises primary molecular distillation and secondary molecular distillation, and is carried out by adopting a wiped film type molecular distiller, wherein the temperature of the primary molecular distillation is 110 ℃, the pressure is 100Pa, and the wiped film speed is 300 r/min; the temperature of the secondary molecular distillation is 160 ℃, the pressure is 10Pa, and the film scraping speed is 300r/min, so that polyglycerol is obtained; wherein the content of diglycerol in the polyglycerol is 91.7 wt%, and the content of triglycerol in the polyglycerol is 8.2 wt%;
(2) uniformly mixing the polyglycerol obtained in the step (1) with toluene, wherein the amount of the toluene is 3 times of the mass of the polyglycerol, then mixing the polyglycerol with epichlorohydrin, the mixing mode is that epichlorohydrin is dripped into the polyglycerol, the molar ratio of the polyglycerol to the epichlorohydrin is 1:8.0, then carrying out ring-opening reaction and ring-closing reaction in sequence, the catalyst of the ring-opening reaction is boron trifluoride diethyl etherate, the addition amount is 1.0 wt% of the mass of the polyglycerol, the temperature of the ring-opening reaction is 40 ℃, the dripping time of the raw material of the ring-opening reaction is 4h, and the heat preservation time is 4 h;
after the ring-opening reaction is finished, adding a ring-closing reaction catalyst and a sodium hydroxide solution into a reaction system, wherein the ring-closing reaction catalyst is tetrabutylammonium bromide, the adding amount of the tetrabutylammonium bromide is 0.5 wt% of the mass of the polyglycerol, the concentration of the sodium hydroxide solution is 40 wt%, the molar ratio of sodium hydroxide to the polyglycerol is 4.1:1, the ring-closing reaction temperature is 30 ℃, the dropping time of the ring-closing reaction raw material is 5 hours, the heat preservation time is 5 hours, and after the ring-closing reaction is finished, sequentially performing neutralization, filtration, electrodialysis desalination and distillation dehydration on the reaction product, the temperature of the distillation dehydration is 105 ℃, and the pressure is-0.095 MPa to obtain the glycidyl ether epoxy resin.
In this example, the process was used to prepare a polyglycerol and epoxy resin product in this order with an epoxy value of 0.8992eq/100g and an epoxy functionality of 3.19.
Example 4:
the embodiment provides a preparation method of glycidyl ether epoxy resin, which includes the following steps:
(1) sequentially rectifying and molecular distilling a crude glycerol raw material, wherein the crude glycerol raw material is glycerol prepared by a propylene method, the components of the glycerol comprise glycerol, diglycerol, triglycerol, tetraglycerol, pentaglycerol and hexaglycerol, the rectification is carried out under the condition of nitrogen protection, the glycerol component in the crude glycerol is removed, the tower top temperature of the rectification is 163 ℃, the rectification pressure is 1kPa, and the reflux ratio of the rectification is 1: 1;
the molecular distillation comprises primary molecular distillation and secondary molecular distillation, and is carried out by adopting a wiped film type molecular distiller, wherein the temperature of the primary molecular distillation is 130 ℃, the pressure is 200Pa, and the wiped film speed is 450 r/min; the temperature of the secondary molecular distillation is 190 ℃, the pressure is 10Pa, and the film scraping speed is 450r/min, so that polyglycerol is obtained; wherein the content of diglycerol in the polyglycerol is 75.4 wt%, and the content of triglycerol in the polyglycerol is 20.8 wt%;
(2) uniformly mixing the polyglycerol obtained in the step (1) with toluene, wherein the amount of the toluene is 2.7 times of the mass of the polyglycerol, then mixing the polyglycerol with epichlorohydrin, the mixing mode is that the epichlorohydrin is dripped into the polyglycerol, the molar ratio of the polyglycerol to the epichlorohydrin is 1:5.0, then carrying out ring-opening reaction and ring-closing reaction in sequence, the catalyst of the ring-opening reaction is concentrated sulfuric acid, the addition amount is 3.0 wt% of the mass of the polyglycerol, the temperature of the ring-opening reaction is 75 ℃, the dripping time of the raw material of the ring-opening reaction is 5h, and the heat preservation time is 5 h;
after the ring-opening reaction is finished, adding a ring-closing reaction catalyst and a potassium hydroxide solution into a reaction system, wherein the ring-closing reaction catalyst is tetrabutylammonium hydrogen sulfate, the adding amount of the tetrabutylammonium hydrogen sulfate is 2.0 wt% of the mass of the polyglycerol, the concentration of the potassium hydroxide solution is 15 wt%, the molar ratio of potassium hydroxide to the polyglycerol is 7.0:1, the ring-closing reaction temperature is 70 ℃, the dropping time of the ring-closing reaction raw material is 0.5h, the heat preservation time is 1h, and after the ring-closing reaction is finished, sequentially neutralizing, filtering, removing salt by electrodialysis and distilling and dehydrating the reaction product, the temperature of the distilling and dehydrating is 90 ℃, and the pressure is-0.098 MPa to obtain the glycidyl ether epoxy resin.
In this example, the process was used to prepare a polyglycerol and epoxy resin product in this order with an epoxy value of 0.7400eq/100g and an epoxy functionality of 2.56.
Example 5:
the embodiment provides a preparation method of glycidyl ether epoxy resin, which includes the following steps:
(1) sequentially rectifying and molecular distilling a crude glycerol raw material, wherein the crude glycerol raw material is a byproduct for preparing epoxy chloropropane by directly oxidizing hydrogen peroxide, and comprises glycerol, diglycerol, triglycerol, tetraglycerol, pentaglycerol and hexaglycerol, the rectification is carried out under the protection of argon to remove glycerol components in the crude glycerol, the tower top temperature of the rectification is 195 ℃, the pressure of the rectification is 6kPa, and the reflux ratio of the rectification is 4: 1;
the molecular distillation comprises primary molecular distillation and secondary molecular distillation, and is carried out by adopting a wiped film type molecular distiller, wherein the temperature of the primary molecular distillation is 140 ℃, the pressure is 400Pa, and the wiped film speed is 200 r/min; the temperature of the secondary molecular distillation is 180 ℃, the pressure is 40Pa, and the film scraping speed is 250r/min, so that polyglycerol is obtained; wherein the content of diglycerol in the polyglycerol is 87.5 wt%, and the content of triglycerol in the polyglycerol is 12.4 wt%;
(2) uniformly mixing the polyglycerol obtained in the step (1) with toluene, wherein the amount of the toluene is 2.2 times of the mass of the polyglycerol, then mixing the polyglycerol with epichlorohydrin, dropwise adding the epichlorohydrin into the polyglycerol in a mixing mode, wherein the molar ratio of the polyglycerol to the epichlorohydrin is 1:10.0, then sequentially carrying out ring-opening reaction and ring-closing reaction, wherein the catalyst of the ring-opening reaction is boron trifluoride diethyl etherate, the adding amount of the boron trifluoride diethyl etherate is 1.5 wt% of the mass of the polyglycerol, the temperature of the ring-opening reaction is 50 ℃, the dropwise adding time of raw materials of the ring-opening reaction is 2 hours, and the heat preservation time is 3 hours;
after the ring-opening reaction is finished, adding a ring-closing reaction catalyst and a sodium hydroxide solution into a reaction system, wherein the ring-closing reaction catalyst is benzyltriethylammonium bromide, the addition amount of the benzyltriethylammonium bromide is 0.2 wt% of the mass of the polyglycerol, the concentration of the sodium hydroxide solution is 25 wt%, the molar ratio of sodium hydroxide to the polyglycerol is 5.4:1, the ring-closing reaction temperature is 40 ℃, the dropping time of the ring-closing reaction raw material is 6 hours, the heat preservation time is 6 hours, and after the ring-closing reaction is finished, the reaction product is subjected to neutralization, filtration, electrodialysis desalination and distillation dehydration in sequence, the distillation dehydration temperature is 110 ℃, and the pressure is-0.1 MPa, so that the glycidyl epoxy ether resin is obtained.
In this example, the process was used to prepare a polyglycerol and epoxy resin product in this order with an epoxy value of 0.8792eq/100g and an epoxy functionality of 3.19.
Example 6:
the embodiment provides a preparation method of glycidyl ether epoxy resin, which includes the following steps:
(1) sequentially rectifying and molecular distilling a crude glycerol raw material, wherein the crude glycerol raw material is a byproduct obtained by preparing epoxy chloropropane through direct oxidation of hydrogen peroxide, and comprises glycerol, diglycerol, triglycerol, tetraglycerol, pentaglycerol and hexaglycerol, the rectification is carried out under the protection of nitrogen to remove glycerol components in the crude glycerol, the temperature of the top of the rectification tower is 207 ℃, the pressure of the rectification is 8kPa, and the reflux ratio of the rectification is 20: 1;
the molecular distillation comprises primary molecular distillation and secondary molecular distillation, and is carried out by adopting a wiped film type molecular distiller, wherein the temperature of the primary molecular distillation is 120 ℃, the pressure is 100Pa, and the wiped film speed is 350 r/min; the temperature of the secondary molecular distillation is 170 ℃, the pressure is 20Pa, and the film scraping speed is 300r/min, so that polyglycerol is obtained; wherein the content of diglycerol in the polyglycerol is 90.3 wt%, and the content of triglycerol in the polyglycerol is 9.4 wt%;
(2) uniformly mixing the polyglycerol obtained in the step (1) with toluene, wherein the amount of the toluene is 2.5 times of the mass of the polyglycerol, then mixing the polyglycerol with epichlorohydrin, dropwise adding the epichlorohydrin into the polyglycerol in a mixing mode, wherein the molar ratio of the polyglycerol to the epichlorohydrin is 1:12.0, then sequentially carrying out ring-opening reaction and ring-closing reaction, wherein the catalyst of the ring-opening reaction is boron trifluoride diethyl etherate, the adding amount of the boron trifluoride diethyl etherate is 2.25 wt% of the mass of the polyglycerol, the temperature of the ring-opening reaction is 60 ℃, the dropwise adding time of the raw materials of the ring-opening reaction is 6 hours, and the heat preservation time is 4 hours;
after the ring-opening reaction is finished, adding a ring-closing reaction catalyst and a sodium hydroxide solution into a reaction system, wherein the ring-closing reaction catalyst is benzyltriethylammonium bromide, the adding amount of the benzyltriethylammonium bromide is 0.75 wt% of the mass of the polyglycerol, the concentration of the sodium hydroxide solution is 31 wt%, the molar ratio of sodium hydroxide to the polyglycerol is 4.5:1, the ring-closing reaction temperature is 50 ℃, the dropping time of the ring-closing reaction raw material is 2.5h, the heat preservation time is 6h, and after the ring-closing reaction is finished, sequentially neutralizing, filtering, removing salt by electrodialysis and distilling and dehydrating the reaction product, the temperature of the distilling and dehydrating is 120 ℃, and the pressure is-0.093 MPa to obtain the glycidyl ether epoxy resin.
In this example, the process was used to prepare a polyglycerol and epoxy resin product in this order with an epoxy value of 0.9475eq/100g and an epoxy functionality of 3.46.
Example 7:
this example provides a process for the preparation of glycidyl ether based epoxy resins, which is comparable to the process of example 1, except that: only primary molecular distillation is carried out after the rectification in the step (1).
In this example, since the molecular distillation is performed only in one stage, no further molecular distillation is performed at a relatively higher temperature and lower pressure, and the purification and refining effects of the crude glycerin are limited, the bottom fraction of the first-stage molecular distillation is recovered, and the components above the triglycerol are not separated from the dimeric and trimeric glycerin, which affects the purity of the polyglycerin and the quality of the epoxy resin to be prepared, and the purity of the polyglycerin is reduced to 90.4 wt%, wherein the content of the dimeric glycerin is 72.3 wt% and the content of the triglycerol is 18.1 wt%.
Example 8:
this example provides a process for the preparation of glycidyl ether based epoxy resins, which is comparable to the process of example 1, except that: the addition amount of the epoxy chloropropane in the step (2) meets the condition that the molar ratio of the polyglycerol to the epoxy chloropropane is 1: 3.6.
In this example, the epoxy value and the epoxy functionality of the epoxy resin product were reduced due to the limited extent of reaction of alcoholic hydroxyl groups on the polyglycerin caused by the relatively low amount of epichlorohydrin added, at which time the epoxy value was 0.68eq/100g and the epoxy functionality was 2.14.
It can be seen from the above examples that, according to the method of the present invention, crude glycerol is used as a raw material, and the polyglycerol is prepared through rectification and molecular distillation, such that the defects of dark color, many impurities, and wide molecular weight distribution in the catalytic preparation of the polyglycerol are avoided, the effects of few impurities and narrow molecular weight distribution of the polyglycerol are achieved, and then the raw material and epichlorohydrin are subjected to ring opening and ring closing reactions to prepare the glycidyl ether epoxy resin, such that the market demand for the multifunctional epoxy resin is satisfied, the epoxy value of the obtained epoxy resin product reaches above 0.74eq/100g, and the epoxy functionality, i.e., the number of epoxy groups in each molecule on average reaches above 2.48; the method is simple and convenient to operate, high in product quality, easy for industrial production and wide in application prospect.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It will be apparent to those skilled in the art that any modification, equivalent substitution of the process of the invention and addition of ancillary operations, selection of specific means, etc., of the present invention are within the scope and disclosure of the invention.
Claims (10)
1. The preparation method of the glycidyl ether epoxy resin is characterized by comprising the following steps:
(1) sequentially rectifying and molecular distilling the raw material of the crude glycerol to obtain polyglycerol;
(2) and (2) mixing the polyglycerol obtained in the step (1) with epichlorohydrin, and then sequentially carrying out ring opening reaction and ring closing reaction to obtain the glycidyl ether epoxy resin.
2. The preparation method according to claim 1, wherein the raw glycerol material in step (1) is derived from any one or a combination of at least two of a by-product of epichlorohydrin preparation by direct oxidation with hydrogen peroxide, glycerol prepared by a biodiesel process or glycerol prepared by a propylene process;
preferably, the composition of the crude glycerin of step (1) includes glycerin, diglycerin, triglycerin, tetraglycerol, pentaglycerol, and hexaglycerol.
3. The production method according to claim 1 or 2, wherein the rectification in the step (1) is performed under protective gas conditions to remove a glycerin component in crude glycerin;
preferably, the tower top temperature of the rectification in the step (1) is 150-210 ℃, and preferably 160-190 ℃;
preferably, the rectification pressure in the step (1) is 0.9-8 kPa, preferably 1-5 kPa;
preferably, the reflux ratio of the rectification in the step (1) is (1-20): 1, preferably (3-10): 1.
4. The production method according to any one of claims 1 to 3, wherein the molecular distillation in step (1) comprises a primary molecular distillation and a secondary molecular distillation, and the heavy phase component of the primary molecular distillation is further subjected to the secondary molecular distillation;
preferably, the molecular distillation is performed using a wiped film molecular distiller;
preferably, the temperature of the primary molecular distillation is 110-150 ℃, and preferably 120-140 ℃;
preferably, the pressure of the primary molecular distillation is 100-500 Pa, and preferably 100-300 Pa;
preferably, the film scraping speed of the primary molecular distillation is 100-450 r/min;
preferably, the temperature of the secondary molecular distillation is 160-200 ℃, and preferably 170-190 ℃;
preferably, the pressure of the secondary molecular distillation is 10-50 Pa, preferably 10-30 Pa;
preferably, the film scraping speed of the secondary molecular distillation is 200-450 r/min.
5. The production method according to any one of claims 1 to 4, wherein the purity of the polyglycerin of the step (1) is 96.2 wt% or more;
preferably, the mass fraction of the diglycerol in the polyglycerol is 75-92 wt%, and the mass fraction of the triglycerol is 7-24 wt%.
6. The production method according to any one of claims 1 to 5, wherein the molar ratio of the polyglycerol in the step (2) to the epichlorohydrin is 1 (4.0 to 12.0);
preferably, the polyglycerol in the step (2) is mixed with a solvent before being mixed with epichlorohydrin;
preferably, the solvent comprises toluene;
preferably, the using amount of the solvent is 2-3 times of the mass of the polyglycerol;
preferably, the mixing of the polyglycerol and the epichlorohydrin in the step (2) is as follows: adding epichlorohydrin dropwise to the polyglycerol;
preferably, the catalyst for the ring-opening reaction in the step (2) comprises any one or a combination of at least two of boron trifluoride, boron trifluoride diethyl etherate, stannic chloride or concentrated sulfuric acid;
preferably, the addition amount of the catalyst for the ring-opening reaction in the step (2) accounts for 0.1-3.0 wt% of the mass of the polyglycerol;
preferably, the temperature of the ring-opening reaction in the step (2) is 20-100 ℃, and preferably 50-80 ℃;
preferably, the dropping time of the raw materials of the ring-opening reaction in the step (2) is 0.5-6 h, and the heat preservation time is 1-6 h.
7. The preparation method according to any one of claims 1 to 6, wherein a ring-closing reaction catalyst and an alkali solution are added to the reaction system after the ring-opening reaction in the step (2) is completed;
preferably, the catalyst for the ring-closure reaction comprises any one or a combination of at least two of tetrabutylammonium chloride, tetrabutylammonium bromide, benzyltriethylammonium chloride, tetrabutylammonium hydrogen sulfate or benzyltriethylammonium bromide;
preferably, the addition amount of the ring-closure reaction catalyst accounts for 0.2-2.0 wt% of the mass of the polyglycerol;
preferably, the lye comprises a sodium hydroxide solution and/or a potassium hydroxide solution;
preferably, the concentration of the alkali liquor is 5-40 wt%, preferably 20-35 wt%;
preferably, the molar ratio of the alkali to the polyglycerol in the alkali liquor is (3.9-7.0): 1, preferably (4.0-5.5): 1;
preferably, the addition mode of the alkali liquor is dropwise addition;
preferably, the temperature of the ring-closure reaction in the step (2) is 30-70 ℃, and preferably 40-60 ℃;
preferably, the dripping time of the raw materials for the ring-closing reaction in the step (2) is 0.5-6 h, and the heat preservation time is 1-6 h.
8. The preparation method according to any one of claims 1 to 7, wherein after the ring-closure reaction in step (2) is completed, the reaction product is subjected to neutralization, filtration, desalting and distillation dehydration in sequence to obtain the glycidyl ether epoxy resin;
preferably, the desalting is electrodialysis desalting;
preferably, the temperature of the distillation dehydration is 90-130 ℃, and preferably 100-120 ℃;
preferably, the pressure of the distillation dehydration is-0.09 to-0.1 MPa.
9. The method of any one of claims 1 to 8, comprising the steps of:
(1) sequentially rectifying and molecular distilling a crude glycerol raw material, wherein the crude glycerol comprises glycerol, diglycerol, triglycerol, tetraglycerol, pentaglycerol and hexaglycerol, the rectification is carried out under the condition of protective gas to remove the glycerol component in the crude glycerol, the tower top temperature of the rectification is 150-210 ℃, the pressure of the rectification is 0.9-8 kPa, and the reflux ratio of the rectification is (1-20): 1;
the molecular distillation comprises primary molecular distillation and secondary molecular distillation, and is carried out by adopting a wiped film type molecular distiller, wherein the temperature of the primary molecular distillation is 110-150 ℃, the pressure is 100-500 Pa, and the wiped film speed is 100-450 r/min; the temperature of the secondary molecular distillation is 160-200 ℃, the pressure is 10-50 Pa, and the film scraping speed is 200-450 r/min, so that polyglycerol is obtained;
(2) mixing the polyglycerol obtained in the step (1) with a solvent, wherein the amount of the solvent is 2-3 times of the mass of the polyglycerol, then mixing the polyglycerol with epoxy chloropropane, the mixing mode is that epoxy chloropropane is dripped into the polyglycerol, the molar ratio of the number of moles of the polyglycerol to the number of moles of the epoxy chloropropane is 1 (4.0-12.0), then carrying out ring opening reaction and ring closing reaction in sequence, wherein a catalyst of the ring opening reaction comprises any one or the combination of at least two of boron trifluoride, boron trifluoride diethyl etherate, stannic chloride or concentrated sulfuric acid, the amount of the catalyst is 0.1-3.0 wt% of the mass of the polyglycerol, the temperature of the ring opening reaction is 20-100 ℃, the dripping time of a raw material of the ring opening reaction is 0.5-6 hours, and the heat preservation time is 1-6 hours;
after the ring-opening reaction is finished, adding a ring-closing reaction catalyst and alkali liquor into a reaction system, wherein the ring-closing reaction catalyst comprises one or a combination of at least two of tetrabutylammonium chloride, tetrabutylammonium bromide, benzyltriethylammonium chloride, tetrabutylammonium hydrogen sulfate and benzyltriethylammonium bromide, the dosage of the catalyst is 0.2-2.0 wt% of the mass of polyglycerol, the alkali liquor comprises a sodium hydroxide solution and/or a potassium hydroxide solution, the concentration of the alkali liquor is 5-40 wt%, the molar ratio of alkali in the alkali liquor to the polyglycerol is (3.9-7.0): 1, the ring-closing reaction temperature is 30-70 ℃, the dropping time of raw materials for the ring-closing reaction is 0.5-6 h, the heat preservation time is 1-6 h, and after the ring-closing reaction is finished, the reaction products are subjected to neutralization, filtration, electrodialysis desalination and distillation dehydration in sequence, the distillation dehydration temperature is 90-130 ℃, the pressure is-0.09 to-0.1 MPa, and the glycidyl ether epoxy resin is obtained.
10. A glycidyl ether type epoxy resin obtained by the production method according to any one of claims 1 to 9.
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