CN1915985A - Method for producing maleic anhydride of hydriding terpene - Google Patents
Method for producing maleic anhydride of hydriding terpene Download PDFInfo
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- CN1915985A CN1915985A CN 200610086156 CN200610086156A CN1915985A CN 1915985 A CN1915985 A CN 1915985A CN 200610086156 CN200610086156 CN 200610086156 CN 200610086156 A CN200610086156 A CN 200610086156A CN 1915985 A CN1915985 A CN 1915985A
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- maleic anhydride
- terpinene maleic
- hydrogenation
- terpinene
- hydrogenated
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Abstract
This invention discloses a method for preparing hydrogenated terpinene maleic anhydride. The comprises: (1) dissolving 1 part of terpinene maleic anhydride in 0.2-5 parts of toluene solvent, and adding 0.04-0.08 part of Pd-C catalyst; (2) heating to 120-180 deg.C, stirring under 50-120 kg/cm2 hydrogen atmosphere, and reacting for 2-8 h to obtain a mixture containing hydrogenated terpinene maleic anhydride; (3) filtering to remove Pd-C catalyst, and vacuum-distilling to remove toluene and obtain hydrogenated terpinene maleic anhydride. The method has such advantages as high catalytic selectivity, high conversion rate, short reaction time, light product color and no side reactions such as condensation, hydrogenolysis and crosslinking.
Description
Technical field
The present invention relates to a kind of manufacture method of epoxy curing agent, relate in particular to a kind of manufacture method of hydrogenated terpinene maleic anhydride.
Background technology
Terpinene maleic anhydride is a kind of important epoxy curing agent.It is compared with present widely used methyl tetrahydro phthalic anhydride solidifying agent, has that cheap, excellent storage stability, water absorbability are little, an advantage such as thermal value is low when long service life, curing.Can be used for the casting of epoxy resin-based paint, sqtructural adhesive, matrix material and electric insulation goods, simultaneously also is the intermediate of important fine chemicals such as pesticide synergistic agent.But owing to contain carbon-carbon double bond in the molecular structure of terpinene maleic anhydride, thereby have yellow or tawny in appearance, and thermostability, weather resistance are had bigger influence.
Summary of the invention
The invention provides a kind of method of making hydrogenated terpinene maleic anhydride, this method has advantages such as the catalyzed reaction selectivity is good, transformation efficiency is high, the reaction times is short, product lighter color.
The present invention adopts following technical scheme:
A kind of manufacture method of hydrogenated terpinene maleic anhydride is that raw material directly carries out hydrogenation manufacturing hydrogenated terpinene maleic anhydride with the terpinene maleic anhydride, and this method realizes as follows:
The first step is dissolved in terpinene maleic anhydride in the benzene kind solvent, adds the palladium catalyst charcoal, form the hybrid reaction objects system, wherein, the quality of benzene kind solvent is 0.2 times-5 times of terpinene maleic anhydride quality, and the quality of palladium catalyst charcoal is the 4%-8% of terpinene maleic anhydride quality;
Second step with the airtight formation enclosed system of above-mentioned mixed reactant, was heated to 120-180 ℃, fed hydrogen in above-mentioned enclosed system, and made hydrogen atmosphere pressure remain on 50-120kg/cm
2, stir above-mentioned mixed reactant simultaneously, reacted 2-8 hour, obtain containing the mixture of hydrogenation terpinene maleic anhydride.
Wherein said benzene kind solvent is one or more the mixture in benzene, toluene and the dimethylbenzene, and the benzene kind solvent optimum quantum of utilization is 1 times of terpinene maleic anhydride quality.
The hydrogenation top condition is: in the first step, palladium catalyst charcoal consumption is the 4%-6% of raw material terpinene maleic anhydride quality, and the benzene kind solvent optimum quantum of utilization is 1 times of terpinene maleic anhydride quality; In second step, Heating temperature 150-160 ℃, hydrogen pressure 80-100kg/cm
2Reaction times is 4-6 hour.
In the technical program, the mixture secondary hydrogenation that contains the hydrogenation terpinene maleic anhydride that second step can be obtained, in secondary hydrogenation process and condition and the claim 1 be with the terpinene maleic anhydride raw material hydrogenation identical.
In the technical program, also comprise the step that the mixture that contains the hydrogenation terpinene maleic anhydride is purified: filter, remove the palladium catalyst charcoal, solvent toluene is removed in underpressure distillation, obtains hydrogenated terpinene maleic anhydride.
Beneficial effect of the present invention is:
1. the present invention has advantages such as the catalyzed reaction selectivity is good, transformation efficiency is high, the reaction times is short, product lighter color, no acid anhydrides condensation in the hydriding process, hydrogenolysis, side reaction such as crosslinked.
2. by gas-chromatography and gas chromatograph-mass spectrometer chemical constitution thing analysis on Content to material before and after the hydrogenation, terpinene maleic anhydride select to adopt palladium carbon catalyst under above-mentioned optimum reaction condition through catalytic hydrogenation reaction, gas-chromatography Central Plains mass spectrum molecular ion peak (M
+) be that 234 terpinene maleic anhydride chromatographic peak disappears, generate mass spectrum molecular ion peak (M
+) be 236 hydrogenated terpinene maleic anhydride chromatographic peak, and do not have other mass spectrum molecular ion peak (M
+) occur greater than 236 compound, reaction preference is 100%, reaction conversion ratio reaches 93%-96%; Through the secondary hydrogenation, reaction preference is 100%, and transformation efficiency reaches more than 98%, and the hydrogenated terpinene maleic anhydride that obtains is a colourless liquid, acid number 430-445mgKOH/g, acid anhydride base content 27-29%, iodine number＜10gI
2/ 100g.Spectrum Analysis IR (v, cm
-1): 2960,1860,1776,1460,1385,1371,1214,923; MS (m/z): 236 (M
+).Spectrogram is seen accompanying drawing 1～2.
With terpinene maleic anhydride by shortening, eliminate the carbon-carbon double bond in the molecular structure, can obtain color and luster near colourless, Heat stability is good, hydrogenated terpinene maleic anhydride that anti-uv-ray is strong.
4. for the hydrogenation of terpinene maleic anhydride, require the alkene C=C unsaturated double-bond in the selective hydration molecular structure, and carbonyl C=O unsaturated double-bond keeps, must adopt reaction preference, active high catalyzer.Nickel system and palladium series catalyst all can be used for the hydrogenation of terpinene maleic anhydride.Be used for the relatively discovery of terpinene maleic anhydride shortening effect by two kinds of catalyzer, aspect catalytic hydrogenation selectivity and reaction conversion ratio, the Raney nickel catalyst is far below palladium carbon catalyst.
5. adopting the Pd/C catalyzer that the terpinene maleic anhydride catalytic hydrogenation is prepared hydrogenated terpinene maleic anhydride, is that 150-160 ℃, the consumption of palladium carbon catalyst are that the 4%-6% of terpinene maleic anhydride quality, hydrogen pressure are 80-100kg/cm in temperature of reaction
2, the reaction times is that reaction preference reaches 100%, transformation efficiency 93%-96% under 4-6 hour the condition.Through the secondary hydrogenation, reaction preference is 100%, and transformation efficiency reaches more than 98%, and the hydrogenated terpinene maleic anhydride that obtains is a colourless liquid.This method has advantages such as the catalyzed reaction selectivity is good, transformation efficiency is high, the reaction times is short, product lighter color, no acid anhydrides condensation in the hydriding process, hydrogenolysis, side reaction such as crosslinked.
Description of drawings
The mass spectrum of Fig. 1 hydrogenated terpinene maleic anhydride (HTMA).
Infrared (IR) spectrogram of Fig. 2 hydrogenated terpinene maleic anhydride (HTMA).
Embodiment
Embodiment 1
A kind of manufacture method of hydrogenated terpinene maleic anhydride is that the direct hydrogenation of raw material is made hydrogenated terpinene maleic anhydride with the terpinene maleic anhydride, and this method realizes as follows:
The first step is dissolved in terpinene maleic anhydride in the benzene kind solvent, adds the palladium catalyst charcoal, form the hybrid reaction objects system, wherein, described benzene kind solvent is one or more the mixture in benzene, toluene and the dimethylbenzene, the proportioning of mixture can be any proportioning, the quality of benzene kind solvent is 0.2 times-5 times of terpinene maleic anhydride quality, for example can be chosen for 0.3 times, 0.5 times, 1 times, 1.5 doubly, 1.8 times, 2.1 times, 2.5 doubly, 3 times, 3.4 times, 3.8 times, 4 times, 4.3 doubly, 4.7 times, the benzene kind solvent optimum quantum of utilization is 1 times of terpinene maleic anhydride quality; The quality of palladium catalyst charcoal is the 4%-8% of terpinene maleic anhydride quality, for example can be chosen for 4.2%, 4.5%, 5.1%, 5.4%, 5.9%, 6.3%, 6.6%, 6.9%, 7.2%, 7.8%, 7.9%;
Second step with the airtight formation enclosed system of above-mentioned mixed reactant, was heated to 120-180 ℃, for example can be chosen for 125 ℃, 130 ℃, 145 ℃, 150 ℃, 162 ℃, 170 ℃, feed hydrogen in above-mentioned enclosed system, and to make it be in pressure was 50-120kg/cm
2Hydrogen atmosphere under, pressure can be chosen for: 60kg/cm
2, 70kg/cm
2, 85kg/cm
2, 90kg/cm
2, 95kg/cm
2, 105kg/cm
2, 112kg/cm
2, stir above-mentioned mixed reactant simultaneously, reacted 2-8 hour, reaction times can be chosen for: 2.5 hours, and 3 hours, 3.8 hours, 4.5 hour, 5.7 hours, 6.5 hours, 7.2 hour, 7.9 hours, obtain containing the mixture of hydrogenation terpinene maleic anhydride, at this moment, general transformation efficiency does not all reach 100%, thereby often needs secondary hydrogenation, to improve transformation efficiency;
Also comprise the step that the mixture that contains the hydrogenation terpinene maleic anhydride is purified in the present embodiment: filter, remove the palladium catalyst charcoal, solvent toluene is removed in underpressure distillation, obtains hydrogenated terpinene maleic anhydride.
In the present embodiment, the hydrogenation top condition is: in the first step, palladium catalyst charcoal consumption is the 4%-6% of raw material terpinene maleic anhydride quality, and the benzene kind solvent optimum quantum of utilization is 1 times of terpinene maleic anhydride quality; In second step, Heating temperature 150-160 ℃, hydrogen pressure 80-100kg/cm
2Reaction times is 4-6 hour.
The mixture secondary hydrogenation that contains the hydrogenation terpinene maleic anhydride that second step can be obtained in the present embodiment, the secondary hydrogenation process is identical with the hydrogenation of condition and claim 1.
Among the present invention the mixture that contains the hydrogenation terpinene maleic anhydride purified and adopt to filter and distillating method, concrete grammar is: adopt water-circulating pump suction filtration reaction product to remove catalyzer, adopt vacuum oil pump underpressure distillation reaction product and collect 182 ℃ of-183 ℃ of cuts under 5-10mmHg mercury column vacuum tightness.
Embodiment 2
A kind of manufacture method of hydrogenated terpinene maleic anhydride is that the direct hydrogenation of raw material is made hydrogenated terpinene maleic anhydride with the terpinene maleic anhydride, and this method realizes as follows:
The first step is dissolved in terpinene maleic anhydride in the benzene kind solvent, adds hydrogenation catalyst, and it is airtight to be placed on reactor, wherein, the quality of benzene kind solvent is 0.2 times-5 times of terpinene maleic anhydride quality, and the quality of hydrogenation catalyst is the 4%-8% of terpinene maleic anhydride quality;
Second step was heated to 120-180 ℃, fed hydrogen, made hydrogen pressure at 50-120kg/cm
2Between, reacted 2-8 hour, obtain hydrogenated terpinene maleic anhydride; At last, hydrogenated terpinene maleic anhydride is purified.
Wherein said solvent is one or more the mixture in benzene, toluene and the dimethylbenzene, and optimum amount is 1 times of terpinene maleic anhydride quality.Wherein said hydrogenation catalyst is the palladium charcoal, and the optimum reaction condition of wherein said hydrogenation reaction is: Heating temperature 150-160 ℃; The palladium carbon catalyst consumption is the 4%-6% of raw material terpinene maleic anhydride quality; Hydrogen pressure 80-100kg/cm
2In the toluene of 1 times of raw material terpinene maleic anhydride quality reaction times 4-6 hour, terpinene maleic anhydride adopted palladium carbon catalyst through a shortening, reaction preference 100%, and reaction conversion ratio reaches 93%-96%; Through the quadric catalysis hydrogenation, reaction preference 100%, transformation efficiency reach more than 98%, and the hydrogenated terpinene maleic anhydride that obtains is a colourless liquid, acid number 430-445mgKOH/g, acid anhydride base content 27-29%, iodine number＜10gI
2/ 100g.Wherein said method of purification comprises filters and underpressure distillation.Adopt water-circulating pump suction filtration reaction product to remove catalyzer, adopt vacuum oil pump underpressure distillation reaction product and collect 182 ℃ of-183 ℃ of cuts under 5-10mmHg mercury column vacuum tightness.
Embodiment 3
Toluene 100g, terpinene maleic anhydride 100g and 5% palladium carbon catalyst 5g are joined in the fast open form stainless steel cauldron of 1L, with reaction kettle for vacuumizing, replace (each pressure 5kg/cm repeatedly three times with hydrogen and nitrogen again with vacuum pump
2), keep hydrogen pressure 50kg/cm at last
2Start autoclave agitator and heating unit then, keep certain rotating speed 200rpm.When temperature of reaction rises to 140 ℃, improve agitator speed to 800rpm, and maintain the temperature at 160 ℃.Constantly feed hydrogen in the reaction process, keep still internal pressure 70kg/cm
2React and finish reaction when hydrogen pressure remains unchanged substantially to still.After the cooling, the palladium catalyst charcoal is removed and reclaimed to suction filtration, and solvent toluene is removed and reclaimed in underpressure distillation again, obtains light hydrogenated terpinene maleic anhydride, and reaction conversion ratio is 87.2%.
Embodiment 4
Toluene 100g, terpinene maleic anhydride 100g and 5% palladium carbon catalyst 4.5g are joined in the fast open form stainless steel cauldron of 1L, with reaction kettle for vacuumizing, replace (each pressure 5kg/cm repeatedly three times with hydrogen and nitrogen again with vacuum pump
2), keep hydrogen pressure 50kg/cm at last
2Start autoclave agitator and heating unit then, keep certain rotating speed 600rpm.When temperature of reaction rises to 120 ℃, improve agitator speed to 800rpm, and maintain the temperature at 180 ℃.Constantly feed hydrogen in the reaction process, keep still internal pressure 60kg/cm
2, react and finish reaction when hydrogen pressure remains unchanged substantially to still.After the cooling, the palladium catalyst charcoal is removed and reclaimed to suction filtration, and solvent toluene is removed and reclaimed in underpressure distillation then, obtains light hydrogenated terpinene maleic anhydride, and reaction conversion ratio is 96.1%.
Embodiment 5
Toluene 100g, terpinene maleic anhydride 100g and 5% palladium carbon catalyst 4g are joined in the fast open form stainless steel cauldron of 1L, with reaction kettle for vacuumizing, replace (each pressure 5kg/cm repeatedly three times with hydrogen and nitrogen again with vacuum pump
2), keep hydrogen pressure 70kg/cm at last
2Start autoclave agitator and heating unit then, keep certain rotating speed 600rpm.When temperature of reaction rises to 120 ℃, improve agitator speed to 800rpm, and maintain the temperature at 160 ℃.Constantly feed hydrogen in the reaction process, keep still internal pressure 90kg/cm
2, react and finish reaction when hydrogen pressure remains unchanged substantially to still.After the cooling, the palladium catalyst charcoal is removed and reclaimed to suction filtration, and solvent toluene is removed and reclaimed in underpressure distillation then, obtains light hydrogenated terpinene maleic anhydride, and reaction conversion ratio is 95.7%.
Embodiment 6
Toluene 100g, terpinene maleic anhydride 50g and 5% palladium carbon catalyst 3g are joined in the fast open form stainless steel cauldron of 1L, with reaction kettle for vacuumizing, replace (each pressure 5kg/cm repeatedly three times with hydrogen and nitrogen again with vacuum pump
2), keep hydrogen pressure 70kg/cm at last
2Start autoclave agitator and heating unit then, keep certain rotating speed 600rpm.When temperature of reaction rises to 120 ℃, improve agitator speed to 800rpm, and maintain the temperature at 150 ℃.Constantly feed hydrogen in the reaction process, keep still internal pressure 90kg/cm
2, react and finish reaction when hydrogen pressure remains unchanged substantially to still.After the cooling, the palladium catalyst charcoal is removed and reclaimed to suction filtration, and solvent toluene is removed and reclaimed in underpressure distillation then, obtains light hydrogenated terpinene maleic anhydride, and reaction conversion ratio is 93.1%.
Embodiment 7
Toluene 100g, terpinene maleic anhydride 100g and 5% palladium carbon catalyst 4g are joined in the fast open form stainless steel cauldron of 1L, use hydrogen exchange again, three times repeatedly (each pressure 5kg/cm
2), keep hydrogen pressure 50kg/cm at last
2Start autoclave agitator and heating unit then, keep certain rotating speed 200rpm.When temperature of reaction rises to 100 ℃, improve agitator speed to 800rpm, and maintain the temperature at 150 ℃.Constantly feed hydrogen in the reaction, keep the reaction pressure that sets, react and finish reaction when hydrogen pressure remains unchanged substantially to still.After the cooling, suction filtration is removed palladium carbon catalyst, obtains containing the hydrogenated terpinene maleic anhydride of toluene.
The secondary hydrogenation process: will join in the fast open form stainless steel cauldron of 1L through the product 100g (containing toluene solvant) and the 5% palladium carbon catalyst 3g of aforesaid method hydrogenation, remove air after, keep hydrogen pressure 80kg/cm
2Start autoclave agitator and heating unit then, keep certain rotating speed 600rpm.When temperature of reaction rises to 140 ℃, improve agitator speed to 800rpm, and maintain the temperature at 160 ℃.Constantly feed hydrogen in the reaction process, keep the reaction pressure that sets, reacted 5 hours.Reaction is removed palladium carbon catalyst by suction filtration after finishing, and toluene is removed in underpressure distillation then, obtains colourless hydrogenated terpinene maleic anhydride, and reaction conversion ratio is 98.6%.
Terpinene maleic anhydride adopts palladium carbon catalyst through a shortening, reaction preference 100%, and reaction conversion ratio reaches 93%-96%; Through the quadric catalysis hydrogenation, reaction preference 100%, transformation efficiency reach more than 98%, and the hydrogenated terpinene maleic anhydride that obtains is a colourless liquid, acid number 430-445mgKOH/g, acid anhydride base content 27-29%, iodine number＜10gI
2/ 100g.
Claims (5)
1, a kind of manufacture method of hydrogenated terpinene maleic anhydride is characterized in that, is that raw material directly carries out hydrogenation manufacturing hydrogenated terpinene maleic anhydride with the terpinene maleic anhydride, and this method realizes as follows:
The first step is dissolved in terpinene maleic anhydride in the benzene kind solvent, adds the palladium catalyst charcoal, form the hybrid reaction objects system, wherein, the quality of benzene kind solvent is 0.2 times-5 times of terpinene maleic anhydride quality, and the quality of palladium catalyst charcoal is the 4%-8% of terpinene maleic anhydride quality;
Second step with the airtight formation enclosed system of above-mentioned mixed reactant, was heated to 120-180 ℃, fed hydrogen in above-mentioned enclosed system, and made hydrogen atmosphere pressure remain on 50-120kg/cm
2, stir above-mentioned mixed reactant simultaneously, reacted 2-8 hour, obtain containing the mixture of hydrogenation terpinene maleic anhydride.
2. the manufacture method of hydrogenated terpinene maleic anhydride according to claim 1, it is characterized in that also comprising the step that the mixture that contains the hydrogenation terpinene maleic anhydride is purified: filter, remove the palladium catalyst charcoal, solvent toluene is removed in underpressure distillation, obtains hydrogenated terpinene maleic anhydride.
3. the manufacture method of hydrogenated terpinene maleic anhydride according to claim 1, it is characterized in that wherein said benzene kind solvent is one or more the mixture in benzene, toluene and the dimethylbenzene, the benzene kind solvent optimum quantum of utilization is 1 times of terpinene maleic anhydride quality.
4. the manufacture method of hydrogenated terpinene maleic anhydride according to claim 1, it is characterized in that the hydrogenation top condition is: in the first step, palladium catalyst charcoal consumption is the 4%-6% of raw material terpinene maleic anhydride quality, and the benzene kind solvent optimum quantum of utilization is 1 times of terpinene maleic anhydride quality; In second step, Heating temperature 150-160 ℃, hydrogen pressure 80-100kg/cm
2Reaction times is 4-6 hour.
5. the manufacture method of hydrogenated terpinene maleic anhydride according to claim 1 and 2, it is characterized in that the mixture secondary hydrogenation that contains the hydrogenation terpinene maleic anhydride that second step was obtained, in secondary hydrogenation process and condition and the claim 1 be with the terpinene maleic anhydride raw material hydrogenation identical.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100861561A CN100463905C (en) | 2006-09-05 | 2006-09-05 | Method for producing maleic anhydride of hydriding terpene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100861561A CN100463905C (en) | 2006-09-05 | 2006-09-05 | Method for producing maleic anhydride of hydriding terpene |
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| Publication Number | Publication Date |
|---|---|
| CN1915985A true CN1915985A (en) | 2007-02-21 |
| CN100463905C CN100463905C (en) | 2009-02-25 |
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