CN105837791B - Preparation method of hydantoin epoxy resin - Google Patents
Preparation method of hydantoin epoxy resin Download PDFInfo
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- CN105837791B CN105837791B CN201610217537.2A CN201610217537A CN105837791B CN 105837791 B CN105837791 B CN 105837791B CN 201610217537 A CN201610217537 A CN 201610217537A CN 105837791 B CN105837791 B CN 105837791B
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- epoxychloropropane
- preparation
- solvent
- filtrate
- sodium hydroxide
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- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 42
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229940091173 hydantoin Drugs 0.000 title abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 110
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000463 material Substances 0.000 claims abstract description 35
- 239000000706 filtrate Substances 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 26
- 239000000047 product Substances 0.000 claims abstract description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000000967 suction filtration Methods 0.000 claims abstract description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000460 chlorine Substances 0.000 claims abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 7
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 7
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 18
- 238000007142 ring opening reaction Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 9
- 238000005185 salting out Methods 0.000 claims description 9
- 238000005292 vacuum distillation Methods 0.000 claims description 8
- 238000010612 desalination reaction Methods 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 230000006837 decompression Effects 0.000 claims description 5
- 230000009969 flowable effect Effects 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- KZDMWVBUOTWRDX-UHFFFAOYSA-J sodium cerium(3+) tetrahydroxide Chemical compound [OH-].[Na+].[Ce+3].[OH-].[OH-].[OH-] KZDMWVBUOTWRDX-UHFFFAOYSA-J 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- YWNYZQTZOONLGU-UHFFFAOYSA-N C(CC)Cl.[O] Chemical compound C(CC)Cl.[O] YWNYZQTZOONLGU-UHFFFAOYSA-N 0.000 claims description 2
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 238000012423 maintenance Methods 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical group [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 claims 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 22
- 239000011780 sodium chloride Substances 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000004821 distillation Methods 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000007809 chemical reaction catalyst Substances 0.000 abstract description 2
- YIROYDNZEPTFOL-UHFFFAOYSA-N 5,5-Dimethylhydantoin Chemical compound CC1(C)NC(=O)NC1=O YIROYDNZEPTFOL-UHFFFAOYSA-N 0.000 abstract 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 33
- 239000000243 solution Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 150000002924 oxiranes Chemical class 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000007363 ring formation reaction Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- -1 hydrogen alcohols Chemical class 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- UPBLAVFWWWKVAJ-UHFFFAOYSA-N [Cl].CCC Chemical compound [Cl].CCC UPBLAVFWWWKVAJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000002785 azepinyl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000004846 water-soluble epoxy resin Substances 0.000 description 1
- 238000009736 wetting 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
- C08G59/10—Polycondensates containing more than one epoxy group per molecule of polyamines with epihalohydrins or precursors thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/022—Polycondensates containing more than one epoxy group per molecule characterised by the preparation process or apparatus used
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)
- Epoxy Compounds (AREA)
Abstract
The invention relates to a preparation method of hydantoin epoxy resin, which takes 5, 5-dimethylhydantoin and epoxy chloropropane as raw materials, adopts quaternary ammonium salt as an open-loop catalyst, is heated and reacted under the protection of nitrogen, is cooled, takes low-grade aliphatic ketone or tetrahydrofuran as a solvent, gradually adds granular sodium hydroxide with calculated amount in batches as a closed-loop reaction catalyst, firstly carries out suction filtration on the materials under the condition of the solvent, removes partial sodium chloride particles, then transfers filtrate into a distillation device for reduced pressure distillation, reduces the volume to nearly half, transfers the product in an evaporator out when salt is separated out, carries out suction filtration and salt removal, carries out the processes of reduced pressure distillation and suction filtration for many times until no salt is separated out from the materials during the reduced pressure distillation, and then continues the reduced pressure distillation for 1-5 min until no solvent is evaporated out, so as to obtain the product. The invention has the advantages that: the preparation method of the invention can effectively remove the sodium chloride particles which are by-produced in the preparation process, reduce the content of inorganic chlorine in the product and improve the quality of the product.
Description
Technical field
The present invention relates to a kind of preparation method of low polymerization degree epoxy resin product, more particularly to a kind of glycolylurea epoxide resin
Preparation method, belong to organic chemistry raw material manufacture field.
Background technology
Glycolylurea is a kind of five member ring heterocyclic compound containing two nitrogen-atoms, is a kind of thing of the azepine ring structure of non-phenyl ring
Matter.The glycolylurea epoxide resin formed by it and epoxychloropropane etc. is nonflammable, even if having low smokiness during burning.Hydantoin epoxy
Resin has good solubility when uncured in water, and it also has excellent mechanical property, heat endurance and good work
Skill performance.It is with after acid, aldehyde, amine, the solidification of imidazoles material, and solidfied material shrinkage factor in the environment of temperature change is small, cracking resistance
Performance is good, thus with good heat resistance, weatherability.The material as made from participating in glycolylurea epoxide resin also has good resistance to molten
Agent and the performance of chemicals corrosion.The electrical insulation capability of glycolylurea epoxide resin is excellent, still has under high pressure and ultra-high pressure condition
There is excellent performance.
But good glycolylurea epoxide resin should be the viscous liquid that epoxide number is high, the degree of polymerization is small, molecular weight is low, has mobility
Body, could so there is good wetting capacity to many adherends.
Preferable glycolylurea epoxide resin has following structural formula：
Its molecular formula is C11H16N2O4.Cone ＆ Plate viscosity during 25 DEG C of high-quality glycolylurea epoxide resin should≤5 Pas,
The epoxide number of the 100g materials should be 0.70~0.80mol, content of inorganic chlorine≤0.0005mol.
Chinese invention CN 101307131A disclose a kind of synthetic method of water-soluble epoxy resin, sea used in this method
Because the mol ratio of class raw material and epoxychloropropane is 1:2~16, it is used as catalyst by the use of sodium hydroxide.Sodium hydroxide and glycolylurea rub
You are than being 1.5~2.5:1, and it is dissolved into the aqueous solution.It is known that epoxychloropropane is under the catalysis of base catalyst and water meeting
React, generate the material of glycols, thus the aqueous solution of epoxychloropropane and sodium hydroxide contact after, moreover it is possible to can not and sea
Come because two nitrogen-atoms of ring pick up, just allow very much people to suspect whether corresponding method is feasible.The invention also refers in its specification
The epoxide number for the glycolylurea epoxide resin for going out to obtain only has 0.02~0.30mol/100g.
Chinese patent ZL 200910184399.2 discloses a kind of synthetic method of flame retardant type glycolylurea epoxide resin, and 5,5-
The mol ratio of DMH and epoxychloropropane is 1:2~8, using 30% sodium hydrate aqueous solution as catalyst, hydrogen-oxygen
The mol ratio for changing sodium and epoxychloropropane is 1:1~2（It is preferred that 1:1）, 5,5- DMHs and epoxychloropropane are dissolved in
In ethanol, 0~90 DEG C is warming up in the reactor with electric mixing device, reflux condensing tube and constant pressure separatory funnel（It is excellent
Select 50~80 DEG C）, then 30% sodium hydroxide solution is slowly added drop-wise in reactor, isothermal reaction 1~8 hour is right
Reactant mixture elder generation vacuum desolvation filters to isolate solid sodium chloride, obtains lurid solid or liquid, be to constant weight
Glycolylurea epoxide resin.
ZL 200910184399.2 method have ignored in alkalescence condition because equally employing sodium hydrate aqueous solution
Down substantial amounts of water can and the fact that epichlorohydrin reaction.And the mole of the sodium hydroxide of this method is and epoxychloropropane
It is mole flux matched, it is general using relative because the price of 5,5- DMHs is higher when synthesizing glycolylurea epoxide resin
Reacted in the epoxychloropropane of 5,5- DMHs, more than 3 times moles, so in the method, added sodium hydroxide
Mole be also excessive.Excessive sodium hydrate and water finally how to remove and a troublesome thing.This method uses
For ethanol as solvent, ethanol is also a kind of alcohol containing active hydrogen, also can carry out open loop with epoxychloropropane in the basic conditions
Reaction.It is solid under normal temperature because 5,5- DMH fusing points are higher, so 5,5- DMHs and epoxychloropropane
Reaction is usually what is carried out in the case of a large amount of excess of epoxychloropropane, and this is related to will also be to the epoxychloropropane of excess
The problem of being reclaimed.In order to control the colourity of product, reaction temperature is not typically high, and the reaction time will be long.Work as epoxy
Chloropropane in the basic conditions, for a long time and have active hydrogen alcohols material contact when, it is possible to be converted into epoxychloropropane
Alcohol ethers material, cause the complexity of reaction, and cause recovery epoxychloropropane to become difficult, increase the unit consumption of production.In addition,
In the case where precipitation to constant weight, product viscosity are very big, moreover it is possible to can not by by-product, be dispersed in sodium chloride tiny in resin
Grain, which substantially filters out, also allows people to suspect very much.Even if just like described in this method, obtained after precipitation, filtering light yellow
Solid or liquid, the molecular weight of product, viscosity obtained by also illustrating are excessive, have lost the superior of glycolylurea epoxide resin
Property, it is difficult to applied well in downstream.
For in the still existing deficiency of glycolylurea epoxide resin preparation field prior art, it is necessary to which exploitation is a kind of more reasonably
Preparation method, some irrational side reactions are avoided as far as possible, reduce the consumption of raw material so that the product prepared has ring
The characteristics of oxygen value is high, viscosity is low, in flowable state, for the excellent of glycolylurea epoxide resin class material can be embodied after the product in downstream
More property.
The content of the invention
It is an object of the invention to provide a kind of preparation method of glycolylurea epoxide resin, with 5,5- DMHs and epoxy chlorine
Propane is raw material, uses ring opening catalyst of the quaternary ammonium salt for epoxychloropropane, under nitrogen protection heating response for a period of time after,
Cooling, using lower aliphatic ketone or tetrahydrofuran as solvent, the granular sodium hydroxide for being gradually added amount of calculation in batches is anti-for closed loop
The catalyst answered, sodium chloride is produced while glycolylurea epoxide resin is generated, material is first filtered in the case where there is solvent, removed
Filtrate, is then transferred in distilling apparatus, is evaporated under reduced pressure by partial oxidation sodium particle, reduction in bulk nearly half and when salting out
The transferred product in evaporator is come out, carries out suction filtration desalination, so by being repeatedly evaporated under reduced pressure and filtering process, until subtracting
Do not seen during pressure distillation in material after salting out, be further continued for vacuum distillation and be evaporated to 1~5min is solvent-free, to obtain
Liquid glycolylurea epoxide resin product with mobility.
In order to solve the above technical problems, the technical scheme is that：A kind of preparation method of glycolylurea epoxide resin, it is created
New point is：The preparation method is using mol ratio as 1:3~10 5,5- DMHs and epoxychloropropane is raw material, then is added
0.1~1% quaternary ammonium salt for entering 5,5- DMHs and epoxychloropropane quality sum is catalyzed for the open loop of epoxychloropropane
Agent, reactant is heated to 50~120 DEG C with oil bath under nitrogen protection, carries out the ring-opening reaction of epoxychloropropane, reaction 1~
After 5h, 20~40 DEG C are cooled to, using lower aliphatic ketone or tetrahydrofuran as solvent, divides 3~10 batches to be gradually added purity and is higher than
98.5% granular sodium hydroxide is the catalyst of ring-closure reaction, and pure cerium hydroxide sodium is total in all granular sodium hydroxide catalysts
Mole is 5,5, twice of-DMH mole, and sodium chloride is produced while glycolylurea epoxide resin is generated, molten having
Material is first filtered in the case of agent, part sodium chloride particle is removed, then filtrate is transferred in distilling apparatus, carries out decompression steaming
Evaporate, reduction in bulk nearly half and having comes out the transferred product in evaporator when salting out, and carries out suction filtration desalination, is then transferred to again
Continue to be evaporated under reduced pressure in distilling apparatus, so by being repeatedly evaporated under reduced pressure and filtering process, until not seeing in the product
After salting out, it is further continued for vacuum distillation and is evaporated to solvent-free in 1~5min, obtains the liquid sea with mobility
Because of epoxy resin product.
Further, the preparation method comprises the following steps that：
（1）In the reactor with electric mixing device, reflux condensing tube and thermometer boss, 5,5- dimethyl is added
Glycolylurea and epoxychloropropane so that the mol ratio of 5,5- DMHs and epoxychloropropane is 1:3~10；
（2）5,5- DMHs and 0.1~1% quaternary ammonium salt of epoxychloropropane quality sum are added in the reactor
For the ring opening catalyst of epoxychloropropane, reactor is placed into oil bath, stirring is opened, with 10~10000mL/min stream
Amount is passed through nitrogen, and reactant is heated into 50~120 DEG C in 1~5 hour, carries out the ring-opening reaction of epoxychloropropane；
（3）Stop the heating of oil bath, maintain stirring, reaction solution is cooled to 20~40 DEG C, then stop logical nitrogen；
（4）The low of 0.8~4 times of quality of 5,5- DMHs and epoxychloropropane quality sum is added in the reactor
Level aliphatic ketone or tetrahydrofuran stir 10~30min, are well mixed reaction solution and solvent as solvent；
（5）With twice of mole as pure cerium hydroxide sodium of 5,5- DMHs mole used, then by pure hydrogen-oxygen
The mole for changing sodium is converted into mass number of the purity more than 98.5% needed for granular sodium hydroxide, weighs the hydrogen of respective quality number
Sodium oxide molybdena, is divided into 3~10 batches, and the temperature of material is 15~50 DEG C in maintenance reaction device, adds granular sodium hydroxide by batch, often
Add a collection of sodium hydroxide and maintain 1~3h of stirring, dissolve the sodium hydroxide of addition, while closed loop can have been observed, neutralized
The muddy generation of sodium chloride arrived, makes the material in reactor be creamy white；
（6）The sodium hydroxide of all batches is added, and after being stirred for 1~3h, the material in reactor is transferred into suction filtration dress
In putting, filter, obtained clear filtrate is transferred in distilling apparatus, is evaporated under reduced pressure；
（7）After when the reduction in bulk 40~60% of filtrate is just looked in the material of concentration and salting out, by concentration
Material is transferred in Suction filtration device, carries out suction filtration desalination, and the concentration filtrate clarified；
（8）Filtrate after concentration is then transferred in distilling apparatus, is evaporated under reduced pressure；
（9）Repeat step（7）~（8）, until obtained concentration filtrate is no longer seen in subsequent vacuum distillation
To salting out；
（10）This is distilled within 1~5min times in concentration process there is no the filtrate decompression salted out and observed
Less than untill thering is solvent to be distilled out of；
（11）Collect, merge the solvent being collected into still-process and the epoxychloropropane of excess, after rectification and purification,
The preparation of follow-up glycolylurea epoxide resin can be back to；
（12）Flowable liquids in vacuum distillation apparatus are transferred in container, obtain glycolylurea epoxide resin product.
Further, the quaternary ammonium salt is 4 bromide, tetramethyl chloride or combinations thereof.
Further, the lower aliphatic ketone is acetone, butanone or combinations thereof.
The advantage of the invention is that：
（1）, can control ring well using different catalyst come the open loop and ring-closure reaction of Epichlorohydrin
The open loop degree of oxygen chloropropane so that the viscosity of the glycolylurea epoxide resin being synthesized is as small as possible, epoxide number is as high as possible, carries
The quality of glycolylurea epoxide resin is risen, is advantageous to the application of downstream industry.
（2）Whole preparation process by the use of alkaline aqueous solution as catalyst, will not cause active epoxychloropropane to exist
Ring-opening reaction occurs with the water added under alkalescence condition, corresponding side reaction will not be caused.
（3）Using will not be with lower boiling the low-carbon aliphatic ketone or tetrahydrofuran of epichlorohydrin reaction as ring-closure reaction
Catalyst, without as solvent, the pair of alcohols and epoxychloropropane can be effectively prevented from using the alcohols with active hydrogen
Reaction, is advantageous to the recovery of solvent and excess epoxy chloropropane, reduces the raw material consumption of production process, reduces production cost, subtracts
Few " three wastes " amount.
（4）Ring-closure reaction is catalyzed using the method for reinforcing body alkali in batches, concentration of the alkali in reaction mass can be controlled,
It is unlikely to make reaction excessively violent, causes the temperature of material to raise, the colourity of product is deepened.
（5）Under conditions of having solvent, the viscosity of material is not very high, concentration crystallization and filtering, Ke Yiyou is conducted batch-wise
Effect ground removes the sodium chloride particle of by-product in preparation process, reduces the content of inorganic chlorine in product, lifts the quality of product.
Embodiment
The following examples can make professional and technical personnel that the present invention be more fully understood, but therefore not send out this
It is bright to be limited among described scope of embodiments.
Embodiment 1
A kind of preparation method of glycolylurea epoxide resin, step include：
（1）In the nature of glass four-hole boiling flask of the 500mL with electric mixing device, reflux condensing tube and thermometer boss
In, add 0.3mol（38.4g）5,5- DMHs and 1.8mol（166.5g）Epoxychloropropane so that 5,5- dimethyl sea
Cause and the mol ratio of epoxychloropropane are 1:6；
（2）The 0.48% of 5,5- DMHs and epoxychloropropane quality sum 204.9g is added in flask（1g）'s
4 bromide is the ring opening catalyst of epoxychloropropane, and reactor is placed into oil bath, stirring is opened, with 20mL/min
Flow be passed through nitrogen, be stepped up the temperature of oil bath, reactant be heated to 115 DEG C with 3 hours, carries out epoxychloropropane
Ring-opening reaction；
（3）After reaction 3 hours, stop the heating of oil bath, maintain stirring, reaction solution is cooled to 30 DEG C, Ran Houting
Only lead to nitrogen；
（4）0.93 times of 5,5- DMHs and epoxychloropropane quality sum 204.9g is added in flask
（190.2g）The acetone of quality stirs 20min, is well mixed reaction solution and solvent as solvent；
（5）Twice of mole for calculating sodium hydroxide according to 5,5- DMHs mole used is 0.6mol,
That is the mass number of the granular sodium hydroxide that purity is 100% is 24g, then is converted into needed for the granular sodium hydroxide that purity is 99.1%
Mass number be 24.22g, then weigh the granular sodium hydroxides of 24.22g, be divided into 6 batches, the temperature for maintaining material in flask is
20~40 DEG C, granular sodium hydroxide is added by batch, a collection of sodium hydroxide is often added and maintains stirring 2h, make the sodium hydroxide of addition molten
Solution, while the muddy generation of sodium chloride that closed loop, neutralization obtain can be observed, the material in flask is creamy white；
（6）The sodium hydroxide of 6 batches adds, stir 2h after, by the material in reactor be transferred to place mat have it is fixed at a slow speed
In the Buchner funnel for measuring filter paper, filter, obtained clear filtrate is transferred in rotary evaporator, is evaporated under reduced pressure；
（7）Reduction in bulk 50% when filtrate, after just look in the material of concentration and salt out, by the material of concentration
It is transferred in Suction filtration device, carries out suction filtration desalination, and the concentration filtrate clarified；
（8）Filtrate after concentration is then transferred in rotary evaporator, is evaporated under reduced pressure；
（9）Repeat step（7）~（8）, until obtained concentration filtrate is no longer seen in subsequent vacuum distillation
To salting out；
（10）This is distilled within the 2min times in concentration process there is no the filtrate decompression salted out and not observed
Have untill solvent is distilled out of；
（11）Collect, merge the solvent being collected into still-process and the epoxychloropropane of excess, after rectification and purification,
The preparation of follow-up glycolylurea epoxide resin can be back to；
（12）Flowable liquids in cucurbit are transferred in the reagent bottle with ground, obtain glycolylurea epoxide resin product.
The glycolylurea epoxide resin that above-described embodiment obtains is detected, the epoxide number for measuring product is 0.76mol/
100g, content of inorganic chlorine 0.0004mol/100g, Cone ＆ Plate viscosity at 25 DEG C is 1.6Pas, has reached high-quality hydantoin epoxy
The requirement of resin.
Embodiment 2
A kind of preparation method of glycolylurea epoxide resin, step include：
（1）In the nature of glass four-hole boiling flask of the 500mL with electric mixing device, reflux condensing tube and thermometer boss
In, add 0.3mol（38.4g）5,5- DMHs and 1.5mol（138.8g）Epoxychloropropane so that 5,5- dimethyl sea
Cause and the mol ratio of epoxychloropropane are 1:6；
（2）The 0.28% of 5,5- DMHs and epoxychloropropane quality sum 177.2g is added in flask（0.5g）
Tetramethyl ammonium chloride be epoxychloropropane ring opening catalyst, reactor is placed into oil bath, open stirring, with 15mL/
Min flow is passed through nitrogen, is stepped up the temperature of oil bath, and reactant is heated into 116 DEG C with 3.5 hours, carries out epoxy chlorine
The ring-opening reaction of propane；
（3）After reaction 3.5 hours, stop the heating of oil bath, maintain stirring, reaction solution is cooled to 28 DEG C, then
Stop logical nitrogen；
（4）1.08 times of 5,5- DMHs and epoxychloropropane quality sum 177.2g are added in flask
（190.7g）The tetrahydrofuran of quality stirs 15min, is well mixed reaction solution and solvent as solvent；
（5）Twice of mole for calculating sodium hydroxide according to 5,5- DMHs mole used is 0.6mol,
That is the mass number of the granular sodium hydroxide that purity is 100% is 24g, then is converted into needed for the granular sodium hydroxide that purity is 99.1%
Mass number be 24.22g, then weigh 24.22g sodium hydroxides, be divided into 6 batches, maintain the temperature of material in flask for 20~
40 DEG C, granular sodium hydroxide is added by batch, a collection of sodium hydroxide is often added and maintains stirring 2h, dissolve the sodium hydroxide of addition,
The muddy generation of sodium chloride that closed loop, cancellation, neutralization obtain can be observed simultaneously, the material in flask is creamy white；
（6）The sodium hydroxide of 6 batches adds, stir 2h after, by the material in reactor be transferred to place mat have it is fixed at a slow speed
In the Buchner funnel for measuring filter paper, filter, obtained clear filtrate is transferred in rotary evaporator, is evaporated under reduced pressure；
（7）Reduction in bulk 50% when filtrate, after just look in the material of concentration and salt out, by the material of concentration
It is transferred in Suction filtration device, carries out suction filtration desalination, and the concentration filtrate clarified；
（8）Filtrate after concentration is then transferred in rotary evaporator, is evaporated under reduced pressure；
（9）Repeat step（7）~（8）, until obtained concentration filtrate is no longer seen in subsequent vacuum distillation
To salting out；
（10）This is distilled within the 3min times in concentration process there is no the filtrate decompression salted out and not observed
Have untill solvent is distilled out of；
（11）Collect, merge the solvent being collected into still-process and the epoxychloropropane of excess, after rectification and purification,
The preparation of follow-up glycolylurea epoxide resin can be back to；
（12）Flowable liquids in cucurbit are transferred in the reagent bottle with ground, obtain glycolylurea epoxide resin product.
The glycolylurea epoxide resin that above-described embodiment obtains is detected, the epoxide number for measuring product is 0.73mol/
100g, content of inorganic chlorine 0.0002mol/100g, Cone ＆ Plate viscosity at 25 DEG C is 1.26Pas, has reached high-quality glycolylurea ring
The requirement of oxygen tree fat.
The general principle and principal character and advantages of the present invention of the present invention has been shown and described above.The skill of the industry
For art personnel it should be appreciated that the present invention is not limited to the above embodiments, described in above-described embodiment and specification is explanation
The principle of the present invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these
Changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and
Its equivalent thereof.
Claims (3)
- A kind of 1. preparation method of glycolylurea epoxide resin, it is characterised in that：The preparation method comprises the following steps that：（1）In the reactor with electric mixing device, reflux condensing tube and thermometer boss, 5,5- DMHs are added And epoxychloropropane so that the mol ratio of 5,5- DMHs and epoxychloropropane is 1:3~10；（2）It is ring to add 5,5- DMHs and 0.1 ~ 1% quaternary ammonium salt of epoxychloropropane quality sum in the reactor The ring opening catalyst of oxygen chloropropane, reactor is placed into oil bath, is opened stirring, is passed through with 10 ~ 10000mL/min flow Nitrogen, reactant is heated to 50 ~ 120 DEG C in 1 ~ 5 hour, carries out the ring-opening reaction of epoxychloropropane；（3）Stop the heating of oil bath, maintain stirring, reaction solution is cooled to 20 ~ 40 DEG C, then stop logical nitrogen；（4）The rudimentary fat of 0.8 ~ 4 times of quality of 5,5- DMHs and epoxychloropropane quality sum is added in the reactor Fat ketone or tetrahydrofuran stir 10 ~ 30min, are well mixed reaction solution and solvent as solvent；（5）With twice of mole as pure cerium hydroxide sodium of 5,5- DMHs mole used, then by pure cerium hydroxide sodium Mole be converted into mass number of the purity more than 98.5% needed for granular sodium hydroxide, weigh the hydroxide of respective quality number Sodium, is divided into 3~10 batches, and the temperature of material is 15~50 DEG C in maintenance reaction device, adds granular sodium hydroxide by batch, often adds A collection of sodium hydroxide maintains 1 ~ 3h of stirring, dissolves the sodium hydroxide of addition, while can observe the chlorine that closed loop, neutralization obtain Change the muddy generation of sodium, the material in reactor is creamy white；（6）The sodium hydroxide of all batches is added, and after being stirred for 1 ~ 3h, the material in reactor is transferred in Suction filtration device, Filter, obtained clear filtrate is transferred in distilling apparatus, is evaporated under reduced pressure；（7）After when the reduction in bulk 40~60% of filtrate is just looked in the material of concentration and salting out, by the material of concentration It is transferred in Suction filtration device, carries out suction filtration desalination, and the concentration filtrate clarified；（8）Filtrate after concentration is then transferred in distilling apparatus, is evaporated under reduced pressure；（9）Repeat step（7）~（8）, until obtained concentration filtrate has no longer seen salt in subsequent vacuum distillation Separate out；（10）This is distilled to not observing within 1 ~ 5min times in concentration process there is no the filtrate decompression salted out has Untill solvent is distilled out of；（11）Collect, merge the solvent being collected into still-process and the epoxychloropropane of excess, after rectification and purification, can return Preparation for follow-up glycolylurea epoxide resin；（12）Flowable liquids in vacuum distillation apparatus are transferred in container, obtain glycolylurea epoxide resin product.
- 2. the preparation method of glycolylurea epoxide resin according to claim 1, it is characterised in that：The quaternary ammonium salt is tetramethyl Ammonium bromide, tetramethyl ammonium chloride or combinations thereof.
- 3. the preparation method of glycolylurea epoxide resin according to claim 1, it is characterised in that：The lower aliphatic ketone is third Ketone, butanone or combinations thereof.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101307131A (en) * | 2008-07-11 | 2008-11-19 | 马承银 | Synthetic method for water-solubility hydantoin epoxy resins |
| CN101624439A (en) * | 2009-08-04 | 2010-01-13 | 无锡美华化工有限公司 | Synthesizing method for flame retardant type glycolylurea epoxide resin |
| CN102485764A (en) * | 2010-12-03 | 2012-06-06 | 黄振庭 | Synthesis process for epoxy resin |
| CN103030785A (en) * | 2011-10-08 | 2013-04-10 | 黄芷若 | Synthesis process of epoxy resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101307131A (en) * | 2008-07-11 | 2008-11-19 | 马承银 | Synthetic method for water-solubility hydantoin epoxy resins |
| CN101624439A (en) * | 2009-08-04 | 2010-01-13 | 无锡美华化工有限公司 | Synthesizing method for flame retardant type glycolylurea epoxide resin |
| CN102485764A (en) * | 2010-12-03 | 2012-06-06 | 黄振庭 | Synthesis process for epoxy resin |
| CN103030785A (en) * | 2011-10-08 | 2013-04-10 | 黄芷若 | Synthesis process of epoxy resin |
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