CN101704803B - Method for preparing cylohexanediol diglycidyl ether - Google Patents
Method for preparing cylohexanediol diglycidyl ether Download PDFInfo
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- CN101704803B CN101704803B CN2009103087966A CN200910308796A CN101704803B CN 101704803 B CN101704803 B CN 101704803B CN 2009103087966 A CN2009103087966 A CN 2009103087966A CN 200910308796 A CN200910308796 A CN 200910308796A CN 101704803 B CN101704803 B CN 101704803B
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Abstract
The invention discloses a method for preparing cylohexanediol diglycidyl ether. The method comprises: generating cyclohexanediol through the hydration of cyclohexene oxide; synthesizing o-chlorohydrin ether through the ring-opening reaction of dehydrated cyclohexanediol and epichlorohydrin; reacting the o-chlorohydrin ether and alkali to synthesize 1,2-cylohexanediol diglycidyl ether crude products; and obtaining products by performing oil-water separation, washing and filtration on the crude products and distilling out light components, wherein catalysts for both hydration and ring-opening reaction are fluoboric acid, and the mol ratio of cyclohexene oxide to water to fluoboric acid to epichlorohydrin is 1:5-50:0.002-0.1:1.8-2.5. The method has the advantages of taking fluoboric acid as the catalysts for both hydration and ring-opening reaction, realizing the organic unity of the catalysts in a two-step process, reducing energy consumption, shortening process time, avoiding large amounts of waste water produced by repeated recrystallization during the purification of cyclohexanediol and helping to environmental protection.
Description
Technical field
The present invention relates to a kind of method for preparing cylohexanediol diglycidyl ether.
Background technology
1, the 2-cylohexanediol diglycidyl ether is a kind of epoxide additive of excellent performance.Its common method be epoxy cyclohexane hydration under the effect of hydration catalyst is generated thick 1,2-cyclohexanediol product, slough through recrystallization repeatedly thicker 1,2-cyclohexanediol product colour and impurity; And then utilize 1,2-cyclohexanediol product and epoxy chloropropane synthetic chloropharin ether under the effect of ring opening catalyst; At last that chloropharin ether and alkali reaction is synthetic 1, the thick product of 2-cylohexanediol diglycidyl ether is washed thick product neutral after-filtration and is distilled out light constituent and gets product.
The hydration catalyst of selecting for use in the above-mentioned technology often is sulfuric acid, sulfonic acid, acidic resins etc., the general oxidisability of such oxygen acid is strong, and 1,2-cyclohexanediol crude product color is darker relatively, and after reaction finishes, need neutralization, thereby recrystallization repeatedly, to improve 1, the content of 2-cyclohexanediol, improve product color, remove the influence of the salt residue of neutralization generation to quality product, total yield of products is generally 80-90%.As: CN1225918 discloses " a kind of method by cyclohexane oxidation by-product epoxy cyclohexane synthesizing cyclohexane 1 glycol ", hydration catalyst is a sulfuric acid, phosphoric acid etc., and for example: Chinese patent CN1301685 disclosed " preparation method of neopentyl glycol ", be with sulfuric acid, sulfonic acid, acidic resins etc. are hydration catalyst, their use is oxygen acid, this class oxygen acid catalyzer is because its oxidisability is strong, glycols crude product color is dark relatively, and reacted the common recrystallization that needs repeatedly in back, the process time is long, in the process of recrystallization, will produce a large amount of waste water and waste liquid dischargings.
The ring opening catalyst of selecting for use in the synthetic chloropharin ether in the above-mentioned technology often is Lewis acids such as boron trifluoride (antimony) complex compound or aluminum chloride, titanium chloride, iron(ic) chloride, perchlorate, in these catalyzer, boron trifluoride catalyst series water-absorbent is strong, meet water and cause catalyst deactivation easy the decomposition, high to the water-content requirement of reaction raw materials; And boron trifluoride (antimony) complex compound catalyst high volatility, toxicity are big, strong to equipment corrosion, have brought inconvenience to production operation.As " thermosetting resin " (2006,021 (004) disclose " triethylene glycol diglycidylether synthetic " selected the catalyzer of boron trifluoride complex for use for synthetic chloropharin ether.And lewis acid activities such as aluminum chloride, titanium chloride, iron(ic) chloride, perchlorate are low, need the well reaction of higher temperature, temperature of reaction height, product are difficult to ensure the quality of products, and therefore seldom use these catalyzer in the technology of preparation glycidyl ether.And for example Chinese patent 200610096426.7 discloses a kind of synthetic method of glycidyl allyl ether, and this method is a catalyzer with the solid acid perchlorate, is 0.05～0.5% of reactant quality at its consumption; The mole proportioning that vinyl carbinol and epoxy chloropropane feed intake is a vinyl carbinol: epoxy chloropropane=1～5: 1, and the temperature of reaction of ring-opening reaction is a synthetic chloropharin ether under 60～130 ℃ of conditions, through adding the alkali closed loop, rectifying gets the product glycidyl allyl ether again.The water-absorbent of boron trifluoride ethyl ether complex catalyzer is strong though such catalyzer has solved, high volatility, toxicity are big, to shortcomings such as equipment corrosion are strong, and the also convenient use of perchlorate catalyzer, but because catalyzer exists with solid-state, be heterogeneous reaction system, catalytic activity is low, its temperature of reaction height, be used for synthetic high boiling 1, the 2-cylohexanediol diglycidyl ether not only can increase energy consumption, but also can deepen product color, reduces product quality.
Summary of the invention
The objective of the invention is to overcome above shortcoming, a kind of new method for preparing cylohexanediol diglycidyl ether is provided.To realize the purpose of energy efficient, shortening process time, raising raw material epoxy cyclohexane utilization ratio, no a large amount of discharge of wastewater.
The present invention includes the epoxy cyclohexane hydration reaction and generate cyclohexanediol, cyclohexanediol synthesizes adjacent chloropharin ether with the epoxy chloropropane ring-opening reaction after dewatering, adjacent chloropharin ether and alkali reaction synthetic 1, the thick product of 2-cylohexanediol diglycidyl ether, thick product in oily water separation after washing, filter, distill out light constituent and obtain product, it is characterized in that, it is characterized in that, the catalyzer of described hydration reaction and the catalyzer of ring-opening reaction are fluoroboric acid, the temperature of hydration reaction is 10～95 ℃, the temperature of ring-opening reaction is 10～90 ℃, its epoxy cyclohexane: water: fluoroboric acid: the mol ratio of epoxy chloropropane=1: 1.5～30: 0.0002～0.01: 1.8～3.0.
The temperature of described hydration reaction is 30～70 ℃.
The temperature of described ring-opening reaction is 35～75 ℃.
Described epoxy cyclohexane: water: fluoroboric acid: the mol ratio of epoxy chloropropane=1: 3～15: 0.0006～0.003: 2.0～2.5.
The hydration reaction of this process using and the catalyzer of ring-opening reaction are fluoroboric acid.Therefore hydration not only can not influence follow-up synthetic quality product with fluoroboric acid, and has realized the organic unity of two step process catalyzer.This technology is because of the optimization of catalyzer; reached and not only saved energy consumption, but also shortened the process time; not only improved epoxy cyclohexane utilization ratio and target product production capacity, but also avoided producing a large amount of waste water because of carrying out recrystallization in the purification cyclohexanediol process repeatedly, help the protection of environment.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1:
Get the 1mol epoxy cyclohexane, 30mol water, 0.0002mol fluoroboric acid joins in the reactor, reaction between 75 ℃～85 ℃, after being reacted to the complete hydration of epoxy cyclohexane, add toluene 3mol dehydration, be incubated after having dewatered between 70 ℃～75 ℃, add fluoroboric acid 0.003mol again, drip epoxy chloropropane 2.5mol, 70 ℃～75 ℃ reactions 4～6 hours, reaction finished, and dripped 2.55mol NaOH solution, dropwising insulation reacted 4～5 hours between 40 ℃～50 ℃, reaction finishes and tells oil phase, and the washing oil phase arrives neutral, filters then and distill out light constituent to get product.
Embodiment 2:
Get 1.5mol water, fluoroboric acid 0.01mol joins in the reactor, keep reactor between 10 ℃～20 ℃, to drip epoxy cyclohexane 1mol, after continuing to be reacted to the complete hydration of epoxy cyclohexane after dropwising, add hexanaphthene 1.5mol distillation dehydration, dewatered back insulation between to 10 ℃～20 ℃, dripped epoxy chloropropane 2.1mol, between 10 ℃～20 ℃, reacted 9～10 hours, reaction finishes, and drips 4.15mol Na
2CO
3Solution dropwises to be incubated between 30 ℃～40 ℃ and reacted 5～6 hours, and reaction finishes and tells oil phase, and the washing oil phase arrives neutral, filters then and distill out light constituent to get product.
Embodiment 3:
Get 15mol water, 0.003mol fluoroboric acid joins in the reactor, keep reactor between 40 ℃～50 ℃, to drip epoxy cyclohexane 1mol, after continuing to be reacted to the complete hydration of epoxy cyclohexane after dropwising, add toluene 1.5mol distillation dehydration, the follow-up continuation of insurance temperature of having dewatered is between to 50 ℃～60 ℃, drip epoxy chloropropane 1.8mol, between 50 ℃～60 ℃, reacted 4～5 hours, reaction finishes, drip 1.85mol NaOH solution, dropwise to be incubated between 50 ℃～60 ℃ and reacted 3～4 hours, reaction finishes and tells oil phase, the washing oil phase arrives neutral, filters then and distill out light constituent to get product.
Embodiment 4:
Get 20mol water, the 0.0006mol fluoroboric acid joins in the reactor, keep reactor between 50 ℃～70 ℃, to drip epoxy cyclohexane 1mol, after continuing to be reacted to the complete hydration of epoxy cyclohexane after dropwising, add toluene 1.5mol distillation dehydration, the follow-up continuation of insurance of dewater is warm between to 60 ℃～70 ℃, adds fluoroboric acid 0.01mol, drip epoxy chloropropane 2.2mol again, reacted 3～4 hours between 60 ℃～70 ℃, reaction finishes, and drips 1.2mol Ca (OH)
2Solution dropwises to be incubated between 50 ℃～60 ℃ and reacted 4～5 hours, and reaction finishes and tells oil phase, and the washing oil phase arrives neutral, filters then and distill out light constituent to get product.
Embodiment 5:
Get 3mol water, 0.001mol fluoroboric acid joins in the reactor, keep reactor between 65 ℃～75 ℃, to drip epoxy cyclohexane 1mol, after continuing to be reacted to the complete hydration of epoxy cyclohexane after dropwising, add toluene 1.5mol distillation dehydration, the follow-up continuation of insurance temperature of having dewatered is between to 65 ℃～75 ℃, drip epoxy chloropropane 2.35mol again, between 65 ℃～75 ℃, reacted 6～7 hours, reaction finishes, drip 2.4mol NaOH solution, dropwise to be incubated between 30 ℃～40 ℃ and reacted 4～5 hours, reaction finishes and tells oil phase, the washing oil phase arrives neutral, filters then and distill out light constituent to get product.
Embodiment 6:
Get 5mol water, 0.01mol fluoroboric acid joins in the reactor, keep reactor between 25 ℃～35 ℃, to drip epoxy cyclohexane 1mol, after continuing to be reacted to the complete hydration of epoxy cyclohexane after dropwising, add toluene 1.5mol distillation dehydration, the follow-up continuation of insurance temperature of having dewatered is between to 35 ℃～45 ℃, drip epoxy chloropropane 1.9mol again, between 35 ℃～45 ℃, be reacted to 5～6 hours, reaction finishes, drip 2mol NaOH solution, dropwise to be incubated between 40 ℃～50 ℃ and reacted 4～5 hours, reaction finishes and tells oil phase, the washing oil phase arrives neutral, filters then and distill out light constituent to get product.
Embodiment 7:
Getting 10mol water, 0.002mol fluoroboric acid, 1mol epoxy cyclohexane joins in the reactor, reaction between 90 ℃～95 ℃,, continue to be reacted to the complete hydration of epoxy cyclohexane after dropwising after, add toluene 1.5mol distillation dehydration, the follow-up continuation of insurance temperature of having dewatered is between to 85 ℃～90 ℃, add fluoroboric acid 0.001mol, drip epoxy chloropropane 2.4mol again, between 85 ℃～90 ℃, be reacted to 7～8 hours, reaction finishes, and drips 2.45mol CaCO
3Solution dropwises to be incubated between 60 ℃～70 ℃ and reacted 4～5 hours, and reaction finishes and tells oil phase, and the washing oil phase arrives neutral, filters then and distill out light constituent to get product.
Claims (4)
1. one kind prepares 1, the method of 2-cylohexanediol diglycidyl ether, comprise that the epoxy cyclohexane hydration reaction generates cyclohexanediol, cyclohexanediol carries out ring-opening reaction with epoxy chloropropane after dewatering, again with alkali reaction synthetic 1, the thick product of 2-cylohexanediol diglycidyl ether, thick product in oily water separation after washing, filter, distill out light constituent and obtain product, it is characterized in that, the catalyzer of described hydration reaction and the catalyzer of ring-opening reaction are fluoroboric acid, the temperature of hydration reaction is 10～95 ℃, the temperature of ring-opening reaction is 10～90 ℃, its epoxy cyclohexane: water: fluoroboric acid: the mol ratio=1:1.5 of epoxy chloropropane～30:0.0002～0.01:1.8～3.0.
2. preparation 1 according to claim 1, the method for 2-cylohexanediol diglycidyl ether is characterized in that, the temperature of described hydration reaction is 30～70 ℃.
3. preparation 1 according to claim 1, the method for 2-cylohexanediol diglycidyl ether is characterized in that, the temperature of described ring-opening reaction is 35～75 ℃.
4. according to claim 1 or 2 or 3 described preparations 1, the method for 2-cylohexanediol diglycidyl ether is characterized in that, described epoxy cyclohexane: water: fluoroboric acid: the mol ratio=1:3 of epoxy chloropropane～15:0.0006～0.003:2.0～2.5.
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| CN102219762A (en) * | 2011-04-19 | 2011-10-19 | 武汉森茂精细化工有限公司 | Preparation process of 1,2-cyclohexanediol diglycidyl ether |
| CN104974112A (en) * | 2015-05-26 | 2015-10-14 | 岳阳昌德化工实业有限公司 | o-alkoxy cyclohexanol glycidyl ether and synthetic method thereof |
| CN105906585B (en) * | 2016-05-05 | 2017-12-22 | 义乌潘季涂料股份有限公司 | A kind of preparation method of dihydric alcohol diglycidyl ether |
| CN109020925A (en) * | 2018-09-19 | 2018-12-18 | 江苏三木化工股份有限公司 | The preparation method of Polyethylene Glycol Bisglycidyl Ether |
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Effective date of registration: 20181204 Address after: Room 209, 111 Yingpanling Road, Yueyang Economic and Technological Development Zone, Hunan 414000 Patentee after: Yueyang Changde Environmental Technology Co., Ltd. Address before: 414003 Yingshan Plant, Baling Branch, Sinopec Group, Wangyue Road, Yueyang City, Hunan Province Patentee before: Changde Chemical Industry Co., Ltd., Yueyang |
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Address after: 414000 room 217, No. 111, yingpanling Road, Yueyang Economic and Technological Development Zone, Yueyang City, Hunan Province Patentee after: Changde Xincai Technology Co.,Ltd. Address before: Room 209, 111 Yingpanling Road, Yueyang Economic and Technological Development Zone, Hunan 414000 Patentee before: Yueyang Changde Environmental Technology Co.,Ltd. |
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