CN104399533A - Homogeneous composite catalyst and application thereof in preparation of rosin ester - Google Patents
Homogeneous composite catalyst and application thereof in preparation of rosin ester Download PDFInfo
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Abstract
The invention provides a homogeneous composite catalyst and an application thereof, wherein the catalyst can be used to prepare rosin ester and is capable of reducing the product cost and simplifying the production technology. The catalyst is composed of the following components in percentage by weight: 65.1 to 90.2% of first component namely quaternary ammonium salts and 9.8 to 34.9% of second component namely zinc salts. The provided homogenous composite catalyst can be applied to the rosin ester preparation utilizing various rosins as the raw materials. The esterification time is shortened from 12 hours to 3-6 hours. Rosin ester with an acid value less than 20 mgKOH/g can be produced.
Description
Technical field
The invention belongs to chemical field, relate to a kind of homogeneous phase composite catalyst and preparing the application in rosin ester.
Background technology
Rosin ester is a kind of rosin deep processed product be obtained by reacting by rosin and alcohol, is widely used in the tackifier of pressure sensitive adhesive, PUR, fluid sealant etc., the modifier etc. of rubber and plastics.
Since the seventies, in order to the requirement making rosin ester adapt to application, large quantifier elimination is carried out to light-colored rosin esters both at home and abroad.Nearly three kinds of method: first method with U.S. US5395920 patent for representative, by disproportionated rosin or rosin refining, esterification, dehydrogenation are obtained light-colored rosin esters.Although the rosin ester produced is of light color, store with color in hot procedure without significant change, complex manufacturing, cost are higher.Second method is as US744925, US4643848 etc. select catalyst, can Reaction time shorten, improve product color and improve stability.The third method be as US5504152, US5387669 etc. in catalyst esterification process or esterification terminate after add decolorizer, obtain light color carboxylate.But catalytic effect and production cost can not reach consistent preferably.
Including the application aspect of homogeneous catalyst of quaternary ammonium salt and zinc salt, domestic more existing bibliographical informations:
Chinese patent: cis is to menthyl-3, the controlled syntheses preparation technology (CN201310082625.2) of 8-glycol discloses with the lemongrass extract citronellal of natural content 75-85% as raw material, take water as solvent, add homogeneous catalyst (quaternary ammonium salt) and acid catalysis cyclization obtains menthyl-3,8-glycol.The use amount of wherein said homogeneous catalyst is 0.1-3%; Acid catalyst addition is about 3 to be advisable for adjusting system pH.This homogeneous catalyst by acid catalyst from aqueous phase transfer in citronellal organic phase, be combined with the aldehyde radical oxygen of citronellal, aldehyde radical carbon attack double bond again, form hexatomic ring, then isopropyl carbonium ion is combined with water and sloughs proton, finally obtains menthyl-3,8-glycol, which increase the selective and yield to menthyl-3,8-diol configurations.
Chinese patent: a kind of non-noble metal homogeneous catalysis system for alcohol oxidation carbonylation and using method (CN201010201660.8) thereof disclose a kind of all homogeneous phase complex catalyst systems, this system is worked in coordination with by metal complex MXn-Lm (I), slaine the composite catalyst MNC that auxiliary agent N (II) and/or alkaline assistant C (III) combines and is formed with the solvent NS (IV) dissolving composite catalyst, and its general formula is: I+II+III+IV, I+II+IV or I+III+IV; Wherein: M is one or both in copper, zinc; X is Br
-, I
-, Cl
-, CO
3 2-, HCO
3 -, SO
4 2-, HSO
4 -, HPO
4 2-, H
2pO
4-or PO
4 3-; L is one or more in quaternary ammonium salt, quaternary alkylphosphonium salt or nitrogen-containing heterocycle compound; Ligancy m is 1 ~ 12, n is chemical valence state equilibrium number; N is one or more in IA ~ III A main group metal or the non-noble metal halide of IB ~ VIII B subgroup, carbonate, sulfate, nitrate, acetate; NS solvent is organic solvent and/or the water that the boiling point dissolving composite catalyst is greater than 150 DEG C.Also disclose this system and prepare carbonic ester and organic acid esters for alcohol oxidative carbonylation, particularly prepare the application of dimethyl carbonate and methyl acetate at methanol oxidation carbonylation.Disclosed in the document, homogeneous catalyst system is relatively complicated, and catalyst cost is quite high.
Chinese patent: the preparation method (CN01108250.X) of outdoor weathe resistance epoxy resin discloses the method preparing outdoor weathe resistance epoxy resin from rosin derivative maleopimaric anhydride, the method catalyst used includes: quaternary ammonium salt is (as tetramethyl ammonium chloride, 4 bromide, etamon chloride, tetraethylammonium bromide, tetrabutylammonium chloride, TBAB, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltriethylammoinium chloride, benzyl triethyl ammonium bromide, methyl tricapryl ammonium chloride, methyl trioctylphosphine ammonium bromide, hexadecyltrimethylammonium chloride, the tetra-alkyl-phosphonium halide ammonium salts such as softex kw), tertiary amines is (as DMA, N, N-diethylaniline, N, N-dimethyl benzylamine, N, N-diethyl benzylamine etc.), boron trifluoride based compound (as BFEE etc.), metal halide is (as zinc chloride, iron chloride, aluminium chloride, stannic chloride etc.), catalytic reaction temperature range is 50 ~ 120 DEG C, and the reaction time is more than 0.5 hour.The method catalyst amount is 0 ~ 5%, preferentially selects the quaternary ammonium salt of catalytic amount.Hydroxide ion in water and water miscible metal halide are transferred in organic phase by this quaternary ammonium salt catalyst, hydroxide ion impels maleopimaric anhydride to be hydrolyzed to maleopimaric acid, the epoxide group open loop addition of metallic halid catalyst maleopimaric acid or directly catalysis maleopimaric anhydride and epoxychloropropane, or the carboxylate of catalysis maleopimaric acid and epoxychloropropane generation nucleophilic substitution, visible the application's patent is different from the metal halide that this patent is selected.
Summary of the invention
In order to solve shortcoming in prior art with not enough, the invention provides and a kind ofly can be used for preparing rosin ester and there is good catalytic effect, Reaction time shorten, simplification production technology, reduce the homogeneous phase composite catalyst of production cost.
A kind of homogeneous phase composite catalyst, the component of this composite catalyst and weight ratio:
First component: quaternary ammonium salt 65.1 ~ 90.2%;
Second component: zinc salt 9.8% ~ 34.9%.
Above-described quaternary ammonium salt comprises DTAC, tetradecyl trimethyl ammonium chloride, tri-n-octyl methyl ammonium chloride, the mixture of one or more in benzyltriethylammoinium chloride.
Above-described zinc salt comprises zinc acetate, zinc nitrate, one or several the mixture in zinc sulfate.
The application in rosin ester prepared by above-described homogeneous phase composite catalyst, and described application comprises the following steps:
In rosin, add alcohol and described homogeneous phase composite catalyst, mix, then 240 ~ 280 DEG C of reactions 3 ~ 8 hours, be cooled to 200 ~ 220 DEG C, namely removing lower-molecular substance and water prepare described rosin ester;
The quality proportion relation adding raw material is: the addition of alcohol is 10% ~ 16% of rosin quality, and the addition of homogeneous phase composite catalyst is 0.01% ~ 4% of rosin quality.
The above alcohol comprises the mixture of one or more in ethylene glycol, glycerine, pentaerythrite.
The above prepares rosin ester is carry out under inert gas shielding, and described inert gas is nitrogen or carbon dioxide.
The above prepares in rosin ester preparation process, and rosin, alcohol add together with catalyst, stir after melting.
Above-described rosin is gum rosin, wood rosin or Starex.
The present invention has following beneficial effect:
1. the present invention use homogeneous phase composite catalyst can in reaction system dispersed catalytic active center, formed homogeneous catalysis, can catalytic active center be made full use of, thus improve catalytic efficiency, accelerate reaction rate, make the reaction time shorten to 3-6h.The shortcomings such as this to overcome in existing production rosin ester method bad dispersibility in the heterogeneous catalysis reaction systems such as zinc oxide, and catalytic efficiency is low, the reaction time long (8-12h).Such as: under 270 DEG C of reaction 6h conditions, the acid number of the rosin catalyzed pentaerythritol ester of 0.1% composite catalyst is 13 (mgKOH/g), and in 2% zinc oxide, zinc acetate and butyl stannonic acid, the acid number of any one catalyst pentalyn is all greater than 13 (mgKOH/g); Under 270 DEG C of reaction 3h conditions, the acid number of the rosin catalyzed pentaerythritol ester of 0.5% composite catalyst is respectively 19.7 (mgKOH/g).
2. the water that reaction generates can be separated by the water knockout drum used in reaction unit from reaction system, prevents reacting the water generated and suppresses esterification to be moved to the direction generating ester, promote that esterification is moved to positive reaction, be namely conducive to the generation of rosin ester.Such as: under 270 DEG C of reaction 4h and 2% zinc oxide condition, the acid number with or without water knockout drum pentalyn is respectively 23.3 and 28.5 (mgKOH/g).
3. these homogeneous phase composite catalyst wide material sources, cheap, the not advantage such as etching apparatus and contaminated environment, such as: DTAC and zinc oxide; , illustrate in 1, in its amount ratio zinc oxide, zinc acetate and butyl stannonic acid, any one catalyst pentalyn consumption all will lack meanwhile.
So homogeneous phase composite catalyst of the present invention can shorten the rosin ester production cycle, simplify production technology, reduce production cost, be applicable to large-scale industrial production, this has great importance to the energy efficiency of enterprise and China's rosin deep processing application.
Accompanying drawing explanation
Fig. 1 is the INFRARED ABSORPTION comparison diagram of rosin, pentalyn and ester gum
Fig. 2 is the thermal multigraph of composite catalyst
Fig. 3 is the thermogravimetric comparison diagram with/without ester gum during composite catalyst catalysis
Fig. 4 is ester gum gel permeation chromatography figure when having composite catalyst catalysis
Fig. 5 is without ester gum gel permeation chromatography figure during composite catalyst catalysis
Detailed description of the invention
Homogeneous phase composite catalyst embodiment 1
Tetradecyl trimethyl ammonium chloride 0.04 gram (80%), 0.01 gram of zinc acetate (20%), obtains homogeneous phase composite catalyst 1 after Homogeneous phase mixing.
Homogeneous phase composite catalyst embodiment 2
Tri-n-octyl methyl ammonium chloride 0.091 gram (72.8%), 0.034 gram of zinc sulfate (27.2%), obtains homogeneous phase composite catalyst 2 after Homogeneous phase mixing.
Homogeneous phase composite catalyst embodiment 3
DTAC 1.59 grams (79.5%), 0.41 gram of zinc nitrate (20.5%), obtains homogeneous phase composite catalyst 3 after Homogeneous phase mixing.
Homogeneous phase composite catalyst embodiment 4
Benzyltriethylammoinium chloride 1.223 grams of quaternary ammonium salts (81.5%), the zinc acetate of 0.277 gram and any part by weight mixing (18.5%) of zinc nitrate, obtain homogeneous phase composite catalyst 4 after Homogeneous phase mixing.
Homogeneous phase composite catalyst embodiment 5
The DTAC of 1.30 grams (65.1%) and tetradecyl trimethyl ammonium chloride are by any part by weight mixing, two kinds of blending ingredients Homogeneous phase mixing, by any part by weight mixing, are finally obtained homogeneous phase composite catalyst 5 by the zinc nitrate of 0.70 gram (34.9%) and zinc sulfate.
Homogeneous phase composite catalyst embodiment 6
The tetradecyl trimethyl ammonium chloride of 0.009 gram (90.2%) and tri-n-octyl methyl ammonium chloride are by any part by weight mixing, two kinds of blending ingredients Homogeneous phase mixing, by any part by weight mixing, are finally obtained homogeneous phase composite catalyst 6 by the zinc acetate of 0.0009 gram (9.8%) and zinc sulfate.
Homogeneous phase composite catalyst embodiment 7
The DTAC of 0.51 gram (85%), tetradecyl trimethyl ammonium chloride and tri-n-octyl methyl ammonium chloride are by any part by weight mixing, two kinds of blending ingredients Homogeneous phase mixing, by any part by weight mixing, are finally obtained homogeneous phase composite catalyst 7 by the good zinc sulfate of the zinc acetate of 0.09 gram (15%), zinc nitrate.
Homogeneous phase composite catalyst embodiment 8
The DTAC of 1.125 grams (75%), tetradecyl trimethyl ammonium chloride, tri-n-octyl methyl ammonium chloride and benzyltriethylammoinium chloride are by any part by weight mixing, two kinds of blending ingredients Homogeneous phase mixing, by any part by weight mixing, are finally obtained homogeneous phase composite catalyst 8 by the good zinc sulfate of the zinc acetate of 0.375 gram (25%), zinc nitrate.
The rosin that following examples are selected is superfine rosin, acid number 158 (mgKOH/g), softening point 80.1 DEG C, and being dissolved in the color and luster that toluene is made into 50% solution is 7.
The mensuration of acid number, softening point and colourity measures according to professional standard LY/T 1972-2011 " pentalyn ", standard GB/T/T 8146-2003 " Test methods of rosin " and standard GB/T/T 1722-92 " varnish, edible vegetable oil and diluent colour measurement method ".
The Application Example 9 that homogeneous phase composite catalyst is being prepared in rosin ester
Add in the reaction vessel that nitrogen inlet tube, return duct, water knockout drum, thermometer and paddle are housed 50 grams gum rosin, 6 grams of pentaerythrites, 0.05 gram of homogeneous phase composite catalyst 1, stirring reaction is slowly warming up to after 270 DEG C of meltings 6 hours in 2 hours, vacuumize 30 minutes, Temperature fall is to 220 DEG C, and namely removing lower-molecular substance and water prepare described rosin ester.
The acid number of this rosin ester after testing: 13 (mgKOH/g), softening point: 107.4 DEG C.
The Application Example 10 that homogeneous phase composite catalyst is being prepared in rosin ester
50 grams of wood rosins are added in the reaction vessel that carbon dioxide inlet tube, return duct, water knockout drum, thermometer and paddle are housed, 5 grams of glycerine, 0.125 gram of homogeneous phase composite catalyst 2, stirring reaction is slowly warming up to after 280 DEG C of meltings 3 hours in 2 hours, vacuumize 30 minutes, Temperature fall is to 200 DEG C, and namely removing lower-molecular substance and water prepare described rosin ester.
The acid number of this rosin ester after testing: 14.6 (mgKOH/g), softening point: 89.1 DEG C.
The Application Example 11 that homogeneous phase composite catalyst is being prepared in rosin ester
50 grams of Starex are added in the reaction vessel that nitrogen inlet tube, return duct, water knockout drum, thermometer and paddle are housed, 8 grams of ethylene glycol, 2 grams of homogeneous phase composite catalysts 3, stirring reaction is slowly warming up to after 240 DEG C of meltings 4 hours in 2 hours, vacuumize 30 minutes, Temperature fall is to 205 DEG C, and namely removing lower-molecular substance and water prepare described rosin ester.
The acid number of this rosin ester after testing: 18.7 (mgKOH/g), softening point: 59 DEG C.
The Application Example 12 that homogeneous phase composite catalyst is being prepared in rosin ester
50 grams of gum rosin are added in the reaction vessel that carbon dioxide inlet tube, return duct, water knockout drum, thermometer and paddle are housed, the mixture of any part by weight mixing of 5.5 grams of ethylene glycol and glycerine, 1.5 grams of homogeneous phase composite catalysts 4, stirring reaction is slowly warming up to after 250 DEG C of meltings 5 hours in 2 hours, vacuumize 30 minutes, Temperature fall is to 210 DEG C, and namely removing lower-molecular substance and water prepare described rosin ester.
The acid number of this rosin ester: 14.4-16.3 (mgKOH/g) after testing, softening point: 60.3-86 DEG C.
The Application Example 13 that homogeneous phase composite catalyst is being prepared in rosin ester
50 grams of wood rosins are added in the reaction vessel that nitrogen inlet tube, return duct, water knockout drum, thermometer and paddle are housed, 6.5 grams of glycerine and the mixing of any part by weight of pentaerythrite mixture, 2 grams of homogeneous phase composite catalysts 5, stirring reaction is slowly warming up to after 260 DEG C of meltings 7 hours in 2 hours, vacuumize 30 minutes, Temperature fall is to 215 DEG C, and namely removing lower-molecular substance and water prepare described rosin ester.
The acid number of this rosin ester: 5-13.4 (mgKOH/g) after testing, softening point: 88-107.4 DEG C.
The Application Example 14 that homogeneous phase composite catalyst is being prepared in rosin ester
50 grams of Starex are added in the reaction vessel that nitrogen inlet tube, return duct, water knockout drum, thermometer and paddle are housed, the mixture of 7 grams of ethylene glycol and any part by weight mixing of pentaerythrite), 0.01 gram of homogeneous phase composite catalyst 6, stirring reaction is slowly warming up to after 275 DEG C of meltings 8 hours in 2 hours, vacuumize 30 minutes, Temperature fall is to 220 DEG C, and namely removing lower-molecular substance and water prepare described rosin ester.
The acid number of this rosin ester: 8-18.9 (mgKOH/g) after testing, softening point: 63.1-96.8 DEG C.
The Application Example 15 that homogeneous phase composite catalyst is being prepared in rosin ester
50 grams of gum rosin are added in the reaction vessel that nitrogen inlet tube, return duct, water knockout drum, thermometer and paddle are housed, the mixture that 7.5 grams of ethylene glycol, glycerine, any part by weight of pentaerythrite three kinds mix, 0.6 gram of homogeneous phase composite catalyst 7, stirring reaction is slowly warming up to after 280 DEG C of meltings 8 hours in 2 hours, vacuumize 30 minutes, Temperature fall is to 220 DEG C, and namely removing lower-molecular substance and water prepare described rosin ester.
The acid number of this rosin ester: 4.1-11.1 (mgKOH/g) after testing, softening point: 65.2-105.1 DEG C.
The Application Example 16 that homogeneous phase composite catalyst is being prepared in rosin ester
50 grams of wood rosins are added in the reaction vessel that carbon dioxide inlet tube, return duct, water knockout drum, thermometer and paddle are housed, 8 grams of pentaerythrites, 1.5 grams of homogeneous phase composite catalysts 8, stirring reaction is slowly warming up to after 270 DEG C of meltings 3 hours in 2 hours, vacuumize 30 minutes, Temperature fall is to 220 DEG C, and namely removing lower-molecular substance and water prepare described rosin ester.The acid number of this rosin ester after testing: 17.5 (mgKOH/g), softening point: 97.3 DEG C.
Comparative example 17
Esterification catalyst is followed successively by 1 gram of zinc oxide, zinc acetate, the one in butyl stannonic acid, and without homogeneous catalyst, other conditions and consumption are with embodiment 9.
The acid number of this rosin ester is followed successively by after testing: 16.3,19.9 and 13.2 (mgKOH/g), and softening point is followed successively by: 124.6,109.1 and 115.6.
From embodiment 9 and 17, can find out that 0.05g homogeneous phase composite catalyst is than 1g zinc oxide, zinc acetate, butyl stannonic acid, in nano zine oxide, the acid number of the pentalyn of any one catalyst synthesis is all low, and its consumption is 5% of their consumptions.Illustrate that the catalytic activity of homogeneous phase composite catalyst is high, be conducive to the carrying out of esterification, significantly can reduce production cost.
With reference to Fig. 1, in the infared spectrum of rosin, 3430cm
-1for-OH stretching vibration the absworption peak in carboxyl, 1700cm
-1for the C=O stretching vibration absworption peak of carbonyl in carboxyl, compare with the infared spectrum of pentalyn and ester gum,-OH stretching vibration absworption peak in carboxyl becomes very little and slightly moves to left, in carboxyl, the C=O stretching vibration absworption peak of carbonyl slightly moves to left, become the C=O stretching vibration absworption peak of the carbonyl in ester group, meanwhile, product is at 1126cm
-1there is carbon oxygen carbon absworption peak in ester group in place, this illustrates that product pentalyn and ester gum esterification are more complete in embodiment 9 and 10.
With reference to Fig. 2, composite catalyst starts there is obvious weightlessness (10% thermal weight loss temperature) at 409 DEG C, maximum wt-lossing rates point temperature is 487 DEG C, when temperature reaches 579 DEG C, composite catalyst decomposes substantially completely, illustrates that this material has good heat resistance, can at high temperature use this composite catalyst, and there is not the change of character, namely can apply composite catalyst in embodiment 9-16.
With reference to Fig. 3, the known thermogravimetric curve basic simlarity with/without ester gum during composite catalyst catalysis, but there is the heat resistance of composite catalyst catalysate to have slight raising than the heat resistance without composite catalyst catalysate, illustrate that the ester gum heat resistance that the ester gum in embodiment 10 obtains than catalyst-free improves.
With reference to Fig. 4 and following table 1, Fig. 5 and following table 2, known when having composite catalyst catalysis the molecular weight of ester gum be greater than the molecular weight without ester gum during composite catalyst catalysis, the heat endurance further illustrating the ester gum that the ester gum in embodiment 10 obtains than catalyst-free is high, and this catalyst is conducive to the carrying out of esterification.
The molecular weight of the ester gum of table 1:0.3 composite catalyst catalysis
| M n | M w | M p | M z | M z+1 | Polydispersity | M z/M w | M z+1/M w |
| 857 | 1020 | 834 | 1326 | 1882 | 1.19 | 1.3 | 1.84 |
Table 2: without the molecular weight of the ester gum of composite catalyst catalysis
| M n | M w | M p | M z | M z+1 | Polydispersity | M z/M w | M z+1/M w |
| 804 | 942 | 776 | 1202 | 1693 | 1.17 | 1.28 | 1.8 |
Claims (8)
1. a homogeneous phase composite catalyst, is characterized in that: the component of this catalyst and weight ratio:
First component: quaternary ammonium salt 65.1 ~ 90.2%;
Second component: zinc salt 9.8% ~ 34.9%.
2. a kind of homogeneous phase composite catalyst according to claim 1, it is characterized in that: described quaternary ammonium salt comprises DTAC, tetradecyl trimethyl ammonium chloride, tri-n-octyl methyl ammonium chloride, the mixture of one or more in benzyltriethylammoinium chloride.
3. a kind of homogeneous phase composite catalyst according to claim 1 and 2, is characterized in that: described zinc salt comprises zinc acetate, zinc nitrate, one or several the mixture in zinc sulfate.
4. the application in rosin ester prepared by the homogeneous phase composite catalyst described in claim 1-3 any one, it is characterized in that: described application comprises the following steps:
In rosin, add alcohol and described homogeneous phase composite catalyst, mix, then 240 ~ 280 DEG C of reactions 3 ~ 8 hours, be cooled to 200 ~ 220 DEG C, namely removing lower-molecular substance and water prepare described rosin ester;
The quality proportion relation adding raw material is: the addition of alcohol is 10% ~ 16% of rosin quality, and the addition of homogeneous phase composite catalyst is 0.01% ~ 4% of rosin quality.
5. the application in rosin ester prepared by homogeneous phase composite catalyst according to claim 4, it is characterized in that: described alcohol comprises the mixture of one or more in ethylene glycol, glycerine, pentaerythrite.
6. the application in rosin ester prepared by the homogeneous phase composite catalyst according to claim 4 or 5, it is characterized in that: described rosin ester of preparing carries out under inert gas shielding, and described inert gas is nitrogen or carbon dioxide.
7. the application in rosin ester prepared by homogeneous phase composite catalyst according to claim 6, it is characterized in that: describedly prepare in rosin ester preparation process, and rosin, alcohol add together with catalyst, stir after melting.
8. the application in rosin ester prepared by homogeneous phase composite catalyst according to claim 7, it is characterized in that: described rosin is gum rosin, wood rosin or Starex.
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| CN106905854A (en) * | 2017-02-24 | 2017-06-30 | 青岛科技大学 | A kind of preparation method of pentalyn |
| CN106905853A (en) * | 2017-02-24 | 2017-06-30 | 青岛科技大学 | A kind of preparation method of rosin ethylene glycol ester |
| CN106928852A (en) * | 2017-02-24 | 2017-07-07 | 青岛科技大学 | A kind of preparation method of ester gum |
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