CN1034582C - Process for preparing cyclohexanone resin using rectification residue of cyclohexanol and cyclohexanone - Google Patents
Process for preparing cyclohexanone resin using rectification residue of cyclohexanol and cyclohexanone Download PDFInfo
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- CN1034582C CN1034582C CN 93110699 CN93110699A CN1034582C CN 1034582 C CN1034582 C CN 1034582C CN 93110699 CN93110699 CN 93110699 CN 93110699 A CN93110699 A CN 93110699A CN 1034582 C CN1034582 C CN 1034582C
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Abstract
The present invention discloses a method for preparing cyclohexanone resin by using the rectification residues of cyclohexanone and cyclohexanol. The present invention solves the problem that the cyclohexanone resin prepared from the rectification residues has the disadvantages of low softening point, poor physical and mechanical properties, poor property of heat resistance, etc. The rectification residues react with aldehyde according to the w eight ratio of 1.2 to 4.3: 1 in the presence of 3.0 to 5.8% (by weight) of acidic catalyst and 0.2 to 3.0% (by weight) of A-01 cocatalyst at the temperature of 95 to 110 DEG C. Next, after the dewatering process by layers, a condensation reaction in a vacuum dehydration mode, etc. are carried out, the cyclohexanone resin whose the softening point is from 100 to 125 DEG C and the relative viscosity is from1.10 to 1.40 is prepared. The cyclohexanone resin can be used for the technical fields of coating, adhesives, printing ink, etc.
Description
The present invention relates to a kind of method of utilizing pimelinketone and the pure rectification residue of ring (being X oil) to prepare cyclohexanone resin.
As everyone knows, being in the technological process of raw material production pimelinketone with the petroleum benzene, can produce a large amount of hexalin and cyclohexanone distillation residue.In these residues, contain a spot of hexalin and pimelinketone, also have multiple esters such as hexanodioic acid cyclohexyl, diketone, cyclopentanol and other materials such as cyclohexene ring hexanone, meter accounts for the about 40-50% of residue total amount.In addition, other undetermined component, polycondensate and impurity etc. are still arranged.Because the generation of above-mentioned substance, the Cyclohexanone Production cost is improved and result in hand cramps.Therefore, must adopt appropriate means, the residue of said components complexity is effectively handled and utilized, with the cost that reduces Cyclohexanone Production and improve production environment.
In the prior art, existingly utilize pimelinketone and rectification residue of cyclohexanol to prepare the method for cyclohexanone resin.The SU690029 patented technology discloses a kind of method for preparing cyclohexanone resin, make raw material with X oil with Paraformaldehyde 96, in the presence of the 1-2% hydrochloric acid catalyst, synthesize softening temperature and be 52-70 ℃ resin, the used Paraformaldehyde 96 price of this method is expensive, and the softening temperature of resin is low, and physical and mechanical properties is poor; In the patented technology of SU897784, utilize X oil and gaseous formaldehyde reaction, in the presence of the phosphoric acid catalyst of 6.99-7.4%, make softening temperature and be 79-100 ℃ cyclohexanone resin, though improved the softening temperature and the corresponding physical and mechanical properties and the water tolerance of having improved resin of product, but its reaction is difficult to control, poor operability.In addition, the method that other synthesizing cyclohexane 1 ketone resin is still arranged uses sulfuric acid or the hydrochloric acid of 1-2% to make catalyzer as the SU979385 patented technology, under 96-99 ℃ temperature, X oil with formaldehyde reaction 10-16 hour, make softening temperature and be 75-96 ℃ dark cassia bark chromoresin; The SU1344758 patented technology uses the sulfuric acid of 1-2.6% to make catalyzer, and under 96-106 ℃ of temperature, X oil reaches more than 14 hours with formaldehyde reaction, can make softening temperature and be 92-125 ℃ cyclohexanone resin.The weak point of aforesaid method be or the reaction times longer, or the softening temperature of product is on the low side, or reaction is difficult to control, and the product acid number is higher, color and luster dark, curing performance is poor, physical and mechanical properties and resistance toheat are also relatively poor.
The object of the present invention is to provide a kind of method of utilizing pimelinketone and rectification residue of cyclohexanol synthesizing cyclohexane 1 ketone resin, shorten the reaction times, reduce the acid number of product, improve more than its softening temperature to 100 ℃, its physical and mechanical properties of corresponding raising and resistance toheat make X oil reach better utilised.
The objective of the invention is to realize by the following technical solutions: with X oil and aldehyde synthesizing cyclohexane 1 ketone resin, in that acid catalyst and promotor are arranged is to react in the presence of the A-01 series promotor, with product through cooling, washing, layering with dewater, then resin is carried out dehydration condensation under vacuum state, promptly get the cyclohexanone resin that relative viscosity is 1.10-1.40.
The present invention uses formaldehyde and X oil to carry out building-up reactions, the ratio 1.2-4.3 of X oil and formaldehyde: 1 (weight), and the add-on of formaldehyde is not too high or too low, when the consumption of formaldehyde is too high, not only cause the formaldehyde waste, improve production cost, also be unfavorable for improving the softening temperature of resin product; The consumption of formaldehyde is crossed when hanging down, and the resin color and luster of generation deepens, and the softening temperature that improves product is brought disadvantageous effect equally.The aldehyde that uses can be formaldehyde, acetaldehyde or other aldehydes, but the most handy formaldehyde, because the chemical property of formaldehyde is comparatively active, and cost of material is cheap, is easy to buy.
The used acid catalyst consumption of the present invention is the 3-5.8% (weight) of X oil and formaldehyde total amount sum, when the acid amount less than 3% the time, sluggish and long reaction time, the loss of formaldehyde is bigger, when the acid catalyst consumption is higher than 5.8%, reaction is relatively fiercer, and needing increases operation steps, and serious to equipment corrosion.The acid catalyst that reacts used can be one or more of sulfuric acid, phosphoric acid, hydrochloric acid, oxalic acid or other acid, but sulfuric acid preferably, because very fast with sulfuric acid reaction speed, sulfuric acid is difficult for decomposing and non-volatility, not only consumption is little and easy handling.
The promotor that the present invention is used, promptly A-01 series promotor contains one or several identical or different-NH
2,-N=C=O ,-OH ,-CN ,-CON,
I.e. one or more of the aliphatics of amino, isocyanate group, hydroxyl, cyano group, amide group, acid anhydride base, cycloalkyl groups or aromatics or derivatives thereof.The consumption of above-mentioned promotor is the 0.2-3.0% (weight) of X oil and formaldehyde total amount, and consumption is not too high or too low.The A-01 that adds in reaction series promotor can very improve the physical and mechanical properties and the thermotolerance of resin effectively, and when its consumption was less than 0.2%, the softening temperature of resin was lower, and is not obvious to its physical and mechanical properties and stable on heating improvement; When its consumption was higher than 3%, the resin dissolves performance reduced, and technological operation is wayward.The optimum amount of A-01 series promotor is the 0.8-1.5% (weight) of X oil and formaldehyde total amount.
In the resin building-up process of the present invention, by proportioning and the acid catalyst of aforesaid X oil with formaldehyde, A-01 series promotor consumption, and temperature of reaction is controlled at 95-110 ℃ scope internal reaction 7-9 hour, make the resin of generation and the water can layering, and when the aldehyde of water layer was equal to or less than 10% (weight), reaction can be ended.Similarly, temperature of reaction is not crossed low or too high, and temperature is crossed low then sluggish, and the too high then reaction of temperature is fierce, and the formaldehyde loss amount is big, and reactor will be with press operation.
The water that before the dehydration condensation of the present invention, the synthetic resin should be cooled off, leave standstill, the upper strata is gone in layering, suction, resin layer is inhaled the water that goes to the upper strata more again through washing, standing demix.Dehydration condensation carries out under the temperature of 43-73 kPa of vacuum tightness and 140-160 ℃, and moisture content distillates gradually in this process, and the molecular weight of resin constantly increases, when the relative viscosity of resin reaches 1.10-1.40, and the stopped reaction of can lowering the temperature.In implementation process, also can wait and judge whether reaction can stop according to the quantity of distillate or stir current value.For example: when the amount of steaming of overhead product seldom the time, the termination dehydration condensation of generally can lowering the temperature.In the dehydrating condensation process, must suitably control its vacuum tightness and temperature, temperature is too high, may cause boiling to dash material, temperature is crossed low then dehydration and condensation reaction speed reduces, even termination reaction, under aforesaid vacuum tightness, dehydration condensation temperature of the present invention should be controlled between 140-160 ℃.
Compared with prior art, the present invention has following tangible advantage:
1, the present invention has used acid catalyst and A-01 series promotor, makes the reaction times from foreshortening to 7-9 hour more than 14 hours, and the acid number of resin is reduced to below 10 milligrams of KOH/ grams, and the softening temperature of resin correspondingly is increased to 100-125 ℃;
2, the present invention has adopted A-01 series promotor, introduced the functional group of promotor, improved the molecular weight of resin, reduced hydroxy radical content, not only improve the curing performance of resin, improved its thermotolerance simultaneously, improved its physical mechanical strength, widened the range of application of resin, made it can be widely used for fields such as coating, tackiness agent, printing-ink, waterproof board, printed wiring.This resin adds 5% in the epoxy quick-drying primer, its performance comparison such as table 1.
Table 1: add 5% resin property contrast table of the present invention in the epoxy sharp paint
| Project | Index | A | B |
| Paint film appearance and color | It is smooth smooth to meet model | With a left side | With a left side |
| Viscosity S (is coated with 4 #Cup) | 25-40 | 35 | 36 |
| Fineness (low-light) is not more than | 60 | 55 | 55 |
| Surface drying (25 ± 1 ℃) is not more than | 5 | 5 | 5 |
| Doing solid work (25 ± 1 ℃) is not more than | 10 | 10 | 10 |
| The snappiness level is not more than | 2 | 1 | 1 |
| Shock strength (Newton meter) is not less than | 4.9 | 4.9 | 4.9 |
| Hardness is no less than | 0.4 | 0.55 | 0.59 |
| Water tolerance, hour | 72 | 168 | 240* |
| Resistance to salt water (25 ℃, 3%NaCL solution) hour | 72 | 96 | 144 |
* do not proceed test after 240 hours
A is an iron oxide red epoxy sharp paint in the table 1, and B is the iron oxide red epoxy sharp paint that contains 5% resin of the present invention, and as can be seen from the table: water tolerance and the resistance to salt water of B all improve a lot.In addition, add 5% this resin in pure acidic group baking enamel, water tolerance exceeds index more than 4 times, and oil-proofness exceeds 3 times, and petrol-resistance exceeds 2 times.
Below by specific embodiment the present invention is carried out more detailed description.
Example 1: having splash bar, thermometer, add X oil 750 grams in the there-necked flask of condenser, concentration is 36% formaldehyde solution 500 grams, 98% sulfuric acid, 45 grams, dimethylolpropionic urea 2.5 grams, back flow reaction is 7 hours 40 minutes under 98-102 ℃ temperature, containing aldehyde 8.8% to water layer lowers the temperature, stopped reaction also leaves standstill, 300 milliliters of upper waters are removed in suction, resin layer is again through washing, layering, upper water is removed in suction, then 43-72 kPa vacuum tightness, carry out dehydration condensation under 150-160 ℃ the temperature, to relative viscosity be 1.18 (pressing the GB1632-79 standard, as follows), when acid number is 8.73 milligrams of KOH/ grams, cooling also stops to vacuumize, and the vacuum overhead product is 350 milliliters, wherein contains 76 milliliters of organism oil.The softening temperature of this resin is 102 ℃.
Example 2:X oil and reaction process add X oil 750 grams all with example 1, and concentration is formaldehyde 1700 grams of 36 %%, 98% sulfuric acid 78 grams, 2,4-toluene di-isocyanate (T fat 16.5 grams, temperature of reaction 95-98 ℃, in 8 hours reaction times, the reaction back is inhaled and is removed 762 milliliters of upper waters, and the water layer aldehyde is 9.3%.After washing forever under the temperature of the vacuum tightness of 0.43-0.6 crust and 143-155 ℃ dehydrating condensation, 592 ml waters of rushing wherein divide fuel-displaced 48 milliliters, the relative viscosity of this resin is 1.38, acid number is 9.87 milligrams of KOH/ grams, softening temperature is 123 ℃.
Example 3:X oil and reaction process are all with example 1, and X oil 759 restrains, and concentration is 36% formaldehyde solution 1040 grams, 98% phosphatase 24 0 gram, triglycidyl group isocyanurate 12 grams, temperature of reaction 96-102 ℃, 7 hours reaction times, divide 780 milliliters of water outlets, the water layer aldehyde is 9.7%.The vacuum tightness of dehydrating condensation is 44-51 kPa, and temperature is 152-160 ℃, and 350 milliliters in the water of rushing wherein divides fuel-displaced 50 milliliters, and the relative viscosity of this resin is 1.26, and acid number is 7.23 milligrams of KOH/ grams, and softening temperature is 105 ℃.
Example 4:X oil and reaction process are carried out in the pilot plant of 200 liters all with example 1.In reactor, drop into 65 kilograms of X oil, concentration is 90 kilograms in 36% formaldehyde, concentration is 6.7 kilograms of 30% hydrochloric acid, and concentration is 1 kilogram of 100% oxalic acid, add 2.8 kilograms of phthalic anhydrides, reacted 9 hours down in 100-108 ℃, 21.2 kilograms of water outlets are divided in the reaction back, the water layer aldehyde is 8.1%, and the vacuum tightness of fat water condensation is that 43-67 kPa of temperature is 141-155 ℃, 65.8 kilograms of vacuum water outlets, fuel-displaced 6.2 kilograms, the relative viscosity of this resin is 1.28, and acid number is 7.05 milligrams of KOH/ grams, and softening temperature is 115 ℃.
Example 5: device and operating process add 40 kilograms of X oil with example 4, and concentration is 85 kilograms of 36% formaldehyde solutions, 3.0 kilograms in 98% sulfuric acid, dintrile is 2 kilograms, reacts 8.5 hours down at 98-105 ℃, 54 kilograms of water outlets are divided in the reaction back, the aldehyde of water layer is 7.6%, and the vacuum tightness of dehydrating condensation is 43-72 kPa, and temperature is 70 kilograms of 150-160 ℃ of vacuum water outlets, wherein oil-containing is 5.5 kilograms, the relative viscosity of this resin is 1.27, and acid number is 4.8 milligrams of KOH/ grams, and softening temperature is 108 ℃.
Proportioning raw materials, processing condition and the resin quality of routine 1-5 are summarized in table 2.
Table 2: the processing parameter of routine 1-5 and resin quality summary sheet
Claims (2)
1. method of utilizing pimelinketone and rectification residue of cyclohexanol to prepare cyclohexanone resin by the resin building-up reactions, the cooling layering dewaters and washing, condensation process of vacuum dehydration, the invention is characterized in:
(1) carries out building-up reactions with pimelinketone and rectification residue of cyclohexanol and aldehyde, residue is 1.2-4.3 with the ratio of aldehyde: 1 (weight), one or several the identical or different amino that contains at the acid catalyst of the 3.0-5.8% of residue and aldehyde total amount (weight) and 0.2-3.0% (weight), isocyanate group, the acid anhydride base, hydroxyl, epoxy group(ing), cyano group, one or more promotors of the aliphatics of amide group group or aromatics exist down, reaction is 7-9 hour under 95-110 ℃ temperature, to resultant of reaction energy and water stratification, the aldehyde of water-yielding stratum is equal to or less than 10% (weight), then
(2) through cooling, layering, dewater, and with resin layer washing, layering and dewatering again, then
(3) under the temperature of 43-73 kPa vacuum tightness and 140-160 ℃, carry out dehydration condensation, to relative viscosity be 1.10-1.40, be softening temperature and be 100-125 ℃ cyclohexanone resin.
2. the method for preparing cyclohexanone resin according to claim 1, the consumption that it is characterized in that promotor are the 0.8-1.5% (weight) of residue and aldehyde total amount.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93110699 CN1034582C (en) | 1993-05-13 | 1993-05-13 | Process for preparing cyclohexanone resin using rectification residue of cyclohexanol and cyclohexanone |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93110699 CN1034582C (en) | 1993-05-13 | 1993-05-13 | Process for preparing cyclohexanone resin using rectification residue of cyclohexanol and cyclohexanone |
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| Publication Number | Publication Date |
|---|---|
| CN1077720A CN1077720A (en) | 1993-10-27 |
| CN1034582C true CN1034582C (en) | 1997-04-16 |
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| CN 93110699 Expired - Fee Related CN1034582C (en) | 1993-05-13 | 1993-05-13 | Process for preparing cyclohexanone resin using rectification residue of cyclohexanol and cyclohexanone |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100383169C (en) * | 2006-04-21 | 2008-04-23 | 华南理工大学 | Process for preparing cyclohexanone-formaldehyde resin |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186565B (en) * | 2007-12-14 | 2010-06-02 | 岳阳昌德化工实业有限公司 | Dimeric cyclohexanone condensation compound and its preparation method and use |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100383169C (en) * | 2006-04-21 | 2008-04-23 | 华南理工大学 | Process for preparing cyclohexanone-formaldehyde resin |
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