CN101244989A - Method for producing 1,4-dihydroxyethyl phenyl diether (HQEE) and 1,3-dihydroxyethyl phenyl diether (HER) - Google Patents
Method for producing 1,4-dihydroxyethyl phenyl diether (HQEE) and 1,3-dihydroxyethyl phenyl diether (HER) Download PDFInfo
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- CN101244989A CN101244989A CNA2008100107253A CN200810010725A CN101244989A CN 101244989 A CN101244989 A CN 101244989A CN A2008100107253 A CNA2008100107253 A CN A2008100107253A CN 200810010725 A CN200810010725 A CN 200810010725A CN 101244989 A CN101244989 A CN 101244989A
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Abstract
The invention relates to a method for manufacturing 1, 4-dihydroxyethyl benzodiazepine ether and 1, 3-dihydroxyethyl benzodiazepine ether, which includes the steps: ethylene oxide, hydroquinone or resorcinol and sodium carbonate react 8 to 10h in N2 and under 0.8 to 1.0MPa, and 60 to 100 DEG C; hydrochloride is added under 40 to 50 DEG C to lead pH value to be 5.0 to 5.5; sodium sulfite is added and reacts 30min under 60 to 80 DEG C; the temperature is reduced to 40 to 50 DEG C, and sodium carbonate is added to neutralize to lead pH value to be 7.0; 95 percent of water is steamed under 20 multiplied by 133.322Pa and 100 to 105 DEG C, and molecular sieve is added; distillation and water-removal are continued until the water content is less or equal to 0.1 percent; pressuring and filtration are taken in 110 DEG C, and a product is obtained after cooling the liquid. Compared with the prior art, the method for manufacturing the 1, 4-dihydroxyethyl benzodiazepine ether and the 1, 3-dihydroxyethyl benzodiazepine ether is reasonable in technique, high in product yield, high in purity and good in color, can cause the downstream with the product as raw material to produce various polyurethane, in particular to transparent product with better exterior quality.
Description
Technical field
The present invention relates to is the preparation method of aromatic series (polynary) alcohol, particularly uses oxirane and (polynary) phenol prepared in reaction to have the preparation method of aromatic series (polynary) alcohol of ether structure, and wherein Sauerstoffatom one end is connected with carbocyclic ring.
Background technology
The dihydroxy ethyl bis ether of aromatic hydrocarbons all has widely and uses in macromolecular materials such as urethane, polycarbonate, polyester and Synolac synthetic.Particularly 1,4-dihydroxyethylbenzenand diether (Hydroquinonebis{2-hydroxyethyl}ether, usually be called for short HQEE, down together), 1,3-dihydroxyethylbenzenand diether (Bis{2-hydroxyethyl}ether of resorcinol is called for short HER usually, down together) is in the preparation of polyurethane high molecule compound, use as linking agent, can obviously promote the physicochemical property of goods.
The linking agent that is used for urethane is divided into the compound of " amine " and " hydroxyl " two big classes usually.Although their resulting polyurethane products have their own characteristics each because used isocyanic ester () reactive behavior difference for example, TDI or MDI, the linking agent of " amine " class can not with the compatible use of MDI.Greatly faster than TDI, be applicable to " hydroxyl " compound crosslink agent of MDI based on the growth of MDI, be gesture in the ascendant.
The linking agent of " hydroxyl " compound according to structure, can be divided into fat (polynary) alcohol, fragrance (polynary) alcohol and heterocyclic (polynary) alcohol.They are mutually crosslinked with the MDI compatibility separately, obtain the different polyurethane high molecule synthetic materials of performance.
Aromatic dicarboxylic phenol---Resorcinol/Resorcinol and oxyethane carry out ethoxyl etherification, and its processing condition are at＜JP 2001-335525〉done introduction.Promptly in the aqueous solution, in the presence of basic catalyst,, remove catalyzer, get target compound through washing or neutralization with reacting ethylene oxide.Described method, in industrial production, and there is following defective in the compound quality.
(1) owing to introduce the changeable of hydroxyethyl at benzene nucleus and hydroxyl, described method inconvenience suppresses the generation of by product, and target compound purity is lower;
(2) Resorcinol/Resorcinol makes target compound in the oxidation of reaction process, and outward appearance presents (little red) color and luster, directly influences the derived product quality;
(3) target compound contained humidity directly influences the use of derived product, and described method provides the method that dewaters, and can not satisfy industrialized needs.
Summary of the invention
At the problem that above-mentioned prior art exists, the present invention provides a kind of preparation method for preparing high quality HQEE and HER through research, exploitation.And carried out industrialized checking.
As everyone knows, the superpolymer formed by soft chain segment and hard segment two class different molecular structures of urethane.Constitute and suitably adjust its segmental, will obtain the different product of performance.Chainextender (containing amino or oxy-compound) is that the key in its polyurethane preparation one of is formed, except participating in amino or hydroxyl with isocyanate reaction, the common aliphatic hydrocarbon that contains of chainextender self, virtue nuclear, heterocycle etc. also must influence the change of urethane performance.Aliphatic fourth (hot, penta etc.) dibasic alcohol is the chainextender of using always, because aliphatic hydrocarbon segment (becoming soft) limit, the desire meaning obtains the urethane of high rigidity, just must introduce segments (becoming hard) such as fragrant nuclear, realizes.HQEE/HER has aliphatic hydrocarbon segment and virtue nuclear segmental compound, and this is the preparation of urethane just,
The range of choice of broad is provided in the design between prescription and the performance.Target compound of the present invention, HQEE and HER develop for adapting to these needs.
The chemical structural formula of HQEE and HER is:
In the preparation of polyurethane product, its technology operability is an important link.According to practice in the course of the work, know very well, although the fusing point of HQEE more than 103 ℃, need be after its fusion, could with isocyanate terminated polymkeric substance (giving aggressiveness) reaction, industrial also be feasible.And seek the more low similar compound of fusing point, also be that people's institute asks.After having developed HQEE, the HER that its homologue fusing point is 89 ℃ has also developed thereupon like this.HER has been arranged, can lower the service temperature (if mix use, their eutectic point also is to be significantly less than HQEE's) of preparation urethane, the production for goods brings great convenience.
Find in the research that if with these two compounds, mix use later on according to different part by weight, the performance of the polyurethane product that obtains is used and more apparent excellence separately separately than their, producing has the complementary additive effect.These two compounds are applied to separately in the preparation of polyurethane product separately, and the performance of resulting product is very approaching.
The preparation method's of HQEE/HER of the present invention technical scheme is: Resorcinol or Resorcinol are in having the aqueous solution of catalyzer, and with reacting ethylene oxide, its chemical equation is respectively:
After as above reaction is finished, decolour, processed, remove catalyzer again, thereby obtain target compound.
The key problem in technology factor of industrial technology production method disclosed in this invention is:
1. the dihydric phenols compound that contains hydroxyl is being introduced epoxy alkane (for example oxyethane, propylene oxide), can direct addition obtains the alcohol compound (OCH of ether
2CH
2OH ,-OCH
2CH
2CH
2OH).With regard to the dihydric phenol that contains benzene nucleus, it has outside the leading product of the alcohol compound that generates ether, and epoxy alkane still can further be deepened: generate the segment of lengthening reaction, i.e. generation-OCH
2CH
2(OCH
2CH
2)
nOH ,-OCH
2CH
2CH
2(OCH
2CH
2CH
2)
nThe possibility of OH (wherein about the condition institute of the numerical value of n) because of the amount of epoxy alkane and reaction.Moreover, also exist epoxy alkane directly to enter the possibility of benzene nucleus.Like this, introduce in epoxy alkane (hydroxyethylation, hydroxypropylation) process, three class products have just been arranged, that is: the 1. alcohol compound of ether (n=0, hydroxyethyl ether, hydroxypropyl ether) at this; 2. the alcohol compound of ether (n=1 or n＞1, polyoxy ethyl-hydroxyethyl ether, polyoxy propyl group hydroxypropyl ether); 3. the compound that has hydroxyethyl, hydroxypropyl on the benzene nucleus.In aforesaid data, all showing a bit.For this reason, the generation of by product is avoided, reduced to selected preferential processing condition, is one of target compound synthetic key factor;
2. dihydric phenol is in introducing the process of epoxy alkane, need be in alkaline medium, through inducing, cause, and then react, and present method has selected a kind of alkalescence-yellow soda ash as catalyzer;
3. phenolic compound is easy to cause oxidation in above-mentioned reaction process, thereby the product that makes it to obtain darkens.Although deepening of this color and luster, can not influence (industrial goods) degree of purity of production, but it will cause the outward appearance of its derived product to deepen, especially for colourless or light-coloured transparent polyurethane product for, the outward appearance of HQEE/HER is very important, removing the color and luster (deepening) of the oxidation of phenolic compound in reaction process-occurred, is a very crucial technology.Present method discloses to adopt in acidic medium and has removed because in reaction with S-WAT---the color and luster that is produced, receive good effect;
4. common in the process of the industrialized preparation of polyurethane product, the water content of controlling employed various raw materials is very important.Distillation (or vacuum distilling) according to routine is dewatered, and desires to reach to be lower than 0.05～0.10%, comparatively difficult, present method has adopted adding molecular sieve or silica gel, carries out the method for vacuum distilling again, can guarantee that moisture content meets above-mentioned index.
Concrete scheme of the present invention is divided into reactive moieties and aftertreatment part.Reaction is to carry out in the reactor of the import and export that have chuck, agitator, condenser, various materials and temperature, pressure indicator etc.Operation steps: stir down, add entry, Resorcinol, yellow soda ash, under nitrogen protection, be lower than 50 ℃ and add oxyethane, in 0.0～2.0MPa, 60～120 ℃ of reaction 6～12h promptly finish reaction.Aftertreatment then can be with three kinds of methods: (1) is to add in reaction solution that water (water yield during for reaction amount of water 1/4～1/5) filters, washing makes reaction solution reach neutral, and be placed in the vacuum drying oven, in 90～95 ℃, be dried to water content and reach 0.20% when following.(2) be under 40～50 ℃ of stirrings, to add hydrochloric acid (concentration is 30～31%) reaction at reaction solution, the yellow soda ash of Jia Ruing makes the pH 7.0 of reaction solution then, then in vacuum (under 20 * 133.322Pa) the condition, 100～105 ℃ when water distilled out 95% left and right sides, molecular sieve is added wherein, continue distillation moisture, after treating water content≤0.1%, carry out pressure filtration in 110 ℃, remove sodium-chlor and molecular sieve in the material, the liquid HQEE cooling back of molten becomes.(3) be in 40～50 ℃ at reaction solution, under condition of stirring, adding hydrochloric acid (concentration is 30～31%) is controlled at 5.0～5.5 with the pH value of the material of reaction, add S-WAT in 60～80 ℃ of stirring reaction 30min, cool in 40～50 ℃, add the yellow soda ash pH 7.0 that neutralizes, then in vacuum (under 20 * 133.322Pa) the condition, 100～105 ℃ when water distilled out 95% left and right sides, molecular sieve is added wherein, continue distillation moisture, after treating water content≤0.1%, carry out pressure filtration in 110 ℃, remove sodium-chlor and molecular sieve in the material, the liquid HQEE cooling back of molten one-tenth.
The present invention is raw materials used to be: oxyethane, Resorcinol or Resorcinol, catalyzer carbonic acid sodium, discoloring agent S-WAT, dewatering agent molecular sieve or silica gel, and its composition of raw materials is as follows:
Oxyethane and Resorcinol or Resorcinol mol ratio are 2.0～2.5 (wherein 2.1～2.2 is the most suitable)
Water and Resorcinol or Resorcinol weight ratio are 1.0～10.0 (wherein 3～5 is the most suitable)
The mol ratio of catalyzer carbonic acid sodium and Resorcinol or Resorcinol is 0.01～0.2 (wherein 0.05～0.10 is the most suitable)
The discoloring agent S-WAT is 0.0～1.0 of Resorcinol or a Resorcinol weight
Dewatering agent and Resorcinol or Resorcinol weight ratio are 0.0～10.0% (wherein 2～3% is the most suitable)
Preparation method's processing condition are:
Temperature of reaction is 60～120 ℃ (wherein 60～100 ℃ the most suitable)
Reaction times is 6～12 hours (wherein 8～10 hours the most suitable)
Reaction pressure is 0～2MPa (wherein 0.8～1.0MPa is the most suitable)
Compared with prior art, the outstanding advantage that the present invention has is: 1. because synthetic technology, aftertreatment technology are rationally effective, and side reaction is few, and byproduct is few; Reaction obtains high yield, high purity.2. product color is good, and can make with this product is the more superior visual appearancies of product-various urethane, particularly opaque products of producing of the downstream of raw material-have.
Embodiment
Embodiment 1
In 3.0M
3Stainless steel reaction pot (subsidiary import and export that chuck, agitator, condenser, various materials are arranged and temperature, pressure indicator etc.) add entry 2000Kg, open and stir, add Resorcinol 200Kg, add yellow soda ash 9.6Kg.In nitrogen medium, add oxyethane 168Kg under 50 ℃ the situation in being lower than, again in 1.0MPa, 80～90 ℃, reaction 8h promptly finishes reaction.
Add entry 400Kg to reaction mass, be cooled to below 15 ℃, carry out filtration under diminished pressure, and wash material with water, be neutral (pH 7) to wash water.To place vacuum drying oven through the material after the washing,, carry out drying in 90～95 ℃.Reach 0.20% when following to water content, promptly can the discharging packing.Every batch can obtain outward appearance and be the HQEE 304.5Kg of baby pink pressed powder (yield 85.0%) slightly, 103.2 ℃ of fusing points, hydroxyl value 560mgKOH/g.
Embodiment 2
According to the method for embodiment 1, after reaction is finished,, under condition of stirring, add hydrochloric acid (30%) 33.2～35.2Kg in 40～50 ℃, the yellow soda ash that is added in the neutralization reaction process makes the pH of reaction (material) liquid be controlled at 7.0.(under 20 * 133.322Pa) the condition, and water is distilled fully in vacuum then in 100～105 ℃.According to practical situation, when approximately the water yield steams 95% left and right sides, the molecular sieve 3a of material total amount 2% (about 6Kg) can be added wherein, continue distillation moisture, after treating that water content is below 0.1%, carry out pressure filtration in 110 ℃ with (equipment that 15 tunic nets are arranged), remove sodium-chlor and molecular sieve in the material, after the liquid HQEE cooling of molten, can obtain the slightly solid HQEE 324.0Kg of baby pink (yield is 90.0%) of outward appearance, 102.8 ℃ of fusing points, hydroxyl value 555mgKOH/g.
Embodiment 3
Method according to embodiment 1, after reaction is finished, in 40～50 ℃, under condition of stirring, add hydrochloric acid (30%) 33.0～35.0Kg, the pH value of material of reaction is controlled at 5.0～5.5, add S-WAT 3Kg,, cool in 40～50 ℃ in 60～80 ℃ of stirring reaction 30min, add the yellow soda ash pH 7.0 that neutralizes, according to embodiment 2 methods, handle, can obtain outward appearance and be 103.0 ℃ of white solid HQEE324.3Kg (yield is 90.0%) fusing points, hydroxyl value 558mgKOH/g.
Embodiment 4
In 3.0M
3Stainless steel reaction pot (subsidiary import and export that chuck, stirring, condenser, various materials are arranged and temperature, pressure indicator etc.) add entry 2000Kg, open and stir, add Resorcinol 200Kg, add yellow soda ash 9.6Kg.In nitrogen medium, add oxyethane 168Kg under 50 ℃ the situation in being lower than, again in 1.0MPa, 80～90 ℃, reaction 8h finishes reaction.
Add entry 400Kg to reaction mass, be cooled to below 15 ℃, carry out filtration under diminished pressure, and wash material with water, be neutral pH 7 to wash water.Material after the washing is placed vacuum drying oven,, carry out drying in 70～75 ℃.Reach 0.20% when following to water content, promptly can the discharging packing.Every batch can obtain outward appearance and be the HER 308.0Kg of baby pink pressed powder (yield 85.5%) slightly, 88 ℃ of fusing points, hydroxyl value 560mgKOH/g.
Embodiment 5
According to the method for embodiment 4, after reaction is finished,, under condition of stirring, add hydrochloric acid (30%) 33.0～35.0Kg in 40～50 ℃, the yellow soda ash that is added in the neutralization reaction process makes the pH of reaction (material) liquid, is controlled at 7.0.(under 20 * 133.322Pa) the condition, and water is distilled fully in vacuum then in 100～105 ℃.According to practical situation, when approximately the water yield steams 95% left and right sides, the molecular sieve 3a of material total amount 2% (about 6Kg) can be added wherein, continue distillation moisture, treat that water content is below 0.1% after, carry out pressure filtration in 110 ℃ with (equipment that 15 tunic nets are arranged), remove sodium-chlor and molecular sieve in the material, after the liquid HER cooling of molten, can obtain the slightly solid HER 324.3Kg of baby pink (yield is 90.0%) of outward appearance, 88 ℃ of fusing points, hydroxyl value 556mgKOH/g.
Embodiment 6
According to the method for embodiment 4, after reaction is finished, in 40～50 ℃, under condition of stirring, add hydrochloric acid (30%) 33.0～35.0Kg, the pH value of the material of reaction is controlled at 5.0～5.5, add S-WAT 3Kg,, cool in 40～50 ℃ in 60～80 ℃ of stirring reaction 30min, add the yellow soda ash pH 7.0 that neutralizes, according to embodiment 5 methods, handle, can obtain outward appearance and be 88.0 ℃ of white solid HER 320.Kg (yield is 88.8%) fusing points, hydroxyl value 558mgKOH/g.
Embodiment 7
According to the method for embodiment 1, to synthesize, the water yield of its adding is reduced to 300Kg by 2000Kg, and resulting result is that yield is 87.0%, 103.0 ℃ of fusing points, hydroxyl value 558mgKOH/g.
Embodiment 8
According to the method for embodiment 1, to synthesize, the water yield of its adding is by 2000Kg, be reduced to 300Kg, (water and Resorcinol or Resorcinol weight ratio are reduced to 1.5 times by 10 times) resulting result is that yield is 87.0%, 103.0 ℃ of fusing points, hydroxyl value 558mgKOH/g.
Embodiment 9
Method according to embodiment 1, synthesize, it is that yield is 78.0% that the amount of the oxyethane of its adding increases to the resulting result of 192Kg (oxyethane and Resorcinol or Resorcinol mol ratio increase to 2.4 by 2.1) by 168kg, 98.0 ℃ of fusing points, hydroxyl value 520mgKOH
Embodiment 10
Method according to embodiment 1, synthesize, its amount that adds yellow soda ash is reduced to the resulting result of 2.0Kg (mol ratio of yellow soda ash and Resorcinol or Resorcinol is reduced to 0.01 by 0.05) by 9.6kg and is yield 82.5%), 103.0 ℃ of fusing points, hydroxyl value 560mgKOH/g.
Claims (6)
1.1,4-dihydroxyethylbenzenand diether and 1, the manufacture method of 3-dihydroxyethylbenzenand diether, be to react in the presence of basic catalyst by oxyethane, Resorcinol or Resorcinol to make, it is characterized in that raw materials usedly being: oxyethane, Resorcinol or Resorcinol, catalyzer carbonic acid sodium, discoloring agent S-WAT, dewatering agent molecular sieve or silica gel, its proportioning raw materials is:
Oxyethane and Resorcinol or Resorcinol mol ratio are 2.0～2.5;
Water and Resorcinol or Resorcinol weight ratio are 1.0～10.0;
The mol ratio of catalyzer carbonic acid sodium and Resorcinol or Resorcinol is 0.01～0.2;
The discoloring agent S-WAT is 0.0～1.0 of Resorcinol or a Resorcinol weight;
Dewatering agent molecular sieve or silica gel and Resorcinol or Resorcinol weight ratio are 0.0～10.0%; Preparation method's processing step and condition are:
(1) reaction: in the reactor of the import and export that have chuck, agitator, condenser, various materials and temperature, pressure indicator, add entry, stir and add Resorcinol, yellow soda ash down, under nitrogen protection, be lower than 50 ℃ and add oxyethane, in 0.0～2.0MPa, 60～120 ℃ of reaction 6～12h;
(2) handle: after reaction is finished,, stir down in 40～50 ℃, adding concentration is 30% hydrochloric acid, the yellow soda ash of Jia Ruing makes the pH of reaction solution reach 7.0 then, steams water in 20 * 133.322Pa, 100～105 ℃, and the water yield steamed 95% o'clock, molecular sieve is added wherein, continue distillation moisture, treat water content≤0.1% after, carry out pressure filtration in 110 ℃, remove sodium-chlor and molecular sieve in the material, promptly get product after the liquid cooling of molten.
2. described 1 according to claim 1,4-dihydroxyethylbenzenand diether and 1, the manufacture method of 3-dihydroxyethylbenzenand diether is characterized in that proportioning raw materials is:
Oxyethane and Resorcinol or Resorcinol mol ratio are 2.1～2.2;
Water and Resorcinol or Resorcinol weight ratio are 3～5;
The mol ratio of catalyzer carbonic acid sodium and Resorcinol or Resorcinol is 0.05～0.10;
The discoloring agent S-WAT is 0.5～1.0 of Resorcinol or a Resorcinol weight;
Dewatering agent and Resorcinol or Resorcinol weight ratio are 2～3%.
3. described 1 according to claim 1,4-dihydroxyethylbenzenand diether and 1, the manufacture method of 3-dihydroxyethylbenzenand diether is characterized in that temperature of reaction is 60～100 ℃ in (1) reaction of preparation method's processing step and condition; Reaction times is 8～10h; Reaction pressure is 0.8～1.0Mpa.
4. according to claim 1 described 1,4-dihydroxyethylbenzenand diether and 1, the manufacture method of 3-dihydroxyethylbenzenand diether, it is characterized in that preparation method's processing step and (2) processing of condition: after reaction is finished, in 40～50 ℃, under condition of stirring, adding concentration is 30% hydrochloric acid, and the pH value of the material of reaction is controlled at 5.0～5.5, add S-WAT, in 60～80 ℃ of stirring reaction 30min, cool in 40～50 ℃, add the yellow soda ash pH 7.0 that neutralizes, in 20 * 133.322Pa, 100～105 ℃ steam water, the water yield steamed 95% o'clock, and molecular sieve is added wherein, continued distillation moisture, after treating water content≤0.1%, carry out pressure filtration in 110 ℃, remove sodium-chlor and molecular sieve in the material, promptly get product after the liquid cooling of molten.
5. according to claim 1 described 1,4-dihydroxyethylbenzenand diether and 1, the manufacture method of 3-dihydroxyethylbenzenand diether, it is characterized in that preparation method's processing step and (2) processing of condition: add entry to reaction mass, amount of water when participating in reaction the water yield 1/4～1/5, be cooled to below 15 ℃, carry out filtration under diminished pressure, and wash material with water, be neutral pH 7 to wash water, material after the washing is placed vacuum drying oven,, be dried to water content and reach and promptly get product below 0.20% in 70～75 ℃.
6. described 1 according to claim 1,4-dihydroxyethylbenzenand diether and 1, the manufacture method of 3-dihydroxyethylbenzenand diether is characterized in that proportioning raw materials is:
Oxyethane and Resorcinol or Resorcinol mol ratio are 2.1～2.2;
Water and Resorcinol or Resorcinol weight ratio are 3～5;
The mol ratio of catalyzer carbonic acid sodium and Resorcinol or Resorcinol is 0.05～0.10;
The discoloring agent S-WAT is 0.5～1.0 of Resorcinol or a Resorcinol weight;
Dewatering agent and Resorcinol or Resorcinol weight ratio are 2～3%;
Preparation method's processing step and condition are:
(1) reaction: in the reactor of the import and export that have chuck, agitator, condenser, various materials and temperature, pressure indicator, add entry, stir and add Resorcinol, yellow soda ash down, under nitrogen protection, be lower than 50 ℃ and add oxyethane, in 0.8～1.0MPa, 60～100 ℃ of reaction 8～10h;
(2) handle: after reaction is finished, in 40～50 ℃, under condition of stirring, adding concentration is 30% hydrochloric acid, the pH value of material of reaction is controlled at 5.0～5.5, and the adding S-WAT is in 60～80 ℃ of stirring reaction 30min, cool in 40～50 ℃, add the yellow soda ash pH 7.0 that neutralizes, in 20 * 133.322Pa, 100～105 ℃ steam water, and the water yield steamed 95% o'clock, molecular sieve is added wherein, continue distillation moisture, treat water content≤0.1% after, carry out pressure filtration in 110 ℃, remove sodium-chlor and molecular sieve in the material, promptly get product after the liquid cooling of molten.
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| CN105523905A (en) * | 2016-01-14 | 2016-04-27 | 浙江皇马科技股份有限公司 | Method for synthesizing hydroquinone dihydroxyl diethyl ether |
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