CN1069105C - High-production low-consumption process flow for producing resin 731D - Google Patents

Abstract

The present invention relates to a new technological process of dissolving rosin in a solvent and carrying out catalytic disproportionation at low temperature. The solvent can be straight-chain or cyclic paraffin containing 9 to 12 carbon atoms. After the reaction, a catalyst obtained after filtration can be directly and repeatedly used, the filtered solution is distilled to remove the solvent, and the disproportionated rosin with light color, which comprises low unsaponifiable matter content, is obtained. The solvent does not take part in the disproportionation reaction, and thus, the solvent can be repeatedly used. The present invention has the advantages of high product yield up to 97% to 98.5, low consumption of palladium as the catalyst and good product quality.

Description

A kind of method for preparing nilox resin

Nilox resin is a bigger kind of output in the rosin deep processed product, and its potassium or soda soap are used for the usefulness of synthetic rubber and the polymerization of ABS synthetic resins in a large number as emulsifying agent.The rosiny disproportionation reaction needs catalyzer, existing palladium/charcoal, iodine, sulphur, metal oxide (TiO ₂, ZrO ₂) and rare earth element (Th, selenite Ce) etc. can be used as the report of this catalyzer.But for various reasons, the existing factory overwhelming majority all adopts Pd/carbon catalyst, and generally adopts and will react under 250～290 ℃ of high temperature after the rosin fusion, reaction times is about 3～4h, reacted catalyzer has not had activity, and necessary sent for calcination is reclaimed then.The reclaiming process of spent catalyst comprises calcining, reduction, dissolving, purifies and waits each step that certain loss is all arranged.And the value of 1 gram palladium metal is equivalent to the value of half gram gold.Therefore, the loss of minimizing catalyzer is exactly an importance that reduces the nilox resin cost.

In addition, under above-mentioned high temperature, carry out disproportionation reaction, also have other side reaction to produce in the lump, as decarboxylation and thermolysis (degraded) reaction.So reacted product, acid value descends 10% approximately, unsaponifiable matter content increases by 2 times than the reaction precontract, or it is higher, color and luster also deepens, and also discharges certain thermal decomposition product in the reaction process, is commonly called as " rosinol ", its amount accounts for 0.5% of raw material rosin weight, so the nilox resin productive rate has only 90～96% (wt).

Existing nilox resin preparation flow can block representation, sees Figure of description 1.

The objective of the invention is to improve productive rate, reduce the loss of palladium, improve quality product.Rosin is dissolved in the solvent and under lower temperature reacts, under same reaction times 3～4h, the yield of nilox resin is higher, the reaction after-filtration, and the gained catalyzer still has preferable activity.Can directly reuse 3～4 times, and then the calcining reclaiming, the loss of palladium just significantly reduces like this.Product color is more shallow, and unsaponifiable matter content is lower.Solvent for use can be straight chain or cyclic alkane, and its boiling point should not be low excessively, in order to avoid loss is big, also unsuitable too high when reclaiming, in order to avoid difficulty is reclaimed in distillation, promptly with C _9-12Alkane be advisable.The weight of solvent is 40～150% of rosin weight, and is advisable with 80～100% (wt), solvent more for a long time, the temperature of reaction that needs is just lower, and filters more or less freelyly, but influences the throughput of reactor unit volume.Solvent more after a little while, situation is just opposite.Because of solvent for use does not participate in disproportionation reaction, so can all reuse.

Temperature of reaction and is the best with 190～210 ℃ between 140～240 ℃.When temperature was low, product color was preferable, and productive rate is higher, but the required reaction times is longer, and temperature produces when high, and product color deepens, productive rate descends, but dehydroabietic acid content is higher in the product, and the required reaction times is shorter, the consumption of palladium is a palladium: rosin=0.008～0.02: 100 (wt), palladium consumption more for a long time, temperature of reaction can reduce, reaction times can shorten, product contains dehydroabietic acid per-cent height, but increases cost, so with 0.01～0.015: 100 is good.Rosin is a kind of mixture, and its main component is the resinous acid (molecular formula: C that accounts for rosin 90%wt ₁₉H ₂₉COOH), because the difference of structure is divided into abietic type acid and dextropimaric acid type resinous acid two big class isomerss again.The abietic type acid generates dehydroabietic acid, dihydroabietic acid and tetrahydroabietic acid through the palladium carbon catalyst effect at a certain temperature.And dextropimaric acid type resinous acid is in the presence of palladium carbon catalyst, and except that a part generated dihydropimaric acid, some were in the time of 270 ℃, and dehydrogenation, decarboxylation and demethylation carry out simultaneously, generation 1,7-dimethyl-7 ethyl-5,6,7,8 tetrahydrochysene phenanthrene (C ₁₈H ₂₂), molecular weight reduces to 238 74 by original 302.458.Also just become unsaponifiables because sloughed carboxyl.The nilox resin for preparing under 270 ℃ of temperature after we adopt chromatograph mass spectrometer to the rosin fusion carries out assay, obtain it and consist of dehydroabietic acid 45～55%wt, dihydroabietic acid 15～25%wt, tetrahydroabietic acid 0.7～1.5wt, dihydropimaric acid 6～9%wt also has decarboxylate abietene (C ₁₉H ₃₀) 4～6%wt, finding in addition has the littler DeR product of many other molecular weight, accounts for 8～10%wt of product.And (particularly temperature≤210 ℃ time) at a lower temperature, rosin is dissolved in and carries out disproportionation reaction in the solvent, and its DeR is comparatively gentle, and it is a kind of that main degradation products has only, and that takes off Vinylite acid C exactly ₁₇H ₂₇COOH (molecular weight 276.42), its amount accounts for 6～8% (wt) of product, and the less product content of other molecular weight is few.And the primary product of disproportionation reaction, dehydroabietic acid, the dihydroabietic acid, tetrahydroabietic acid all is more or less the same with traditional product, and the decarboxylate abietene also has 4～6%wt.The Vinylite acid of taking off that generates from dextropimaric acid type resinous acid contains carboxyl, be can saponified, and other degraded products is few, so unsaponifiable matter content at 3～5%wt, and does not have obvious variation before the disproportionation reaction.There is not " rosinol " to discharge in the reaction process.Thereby productive rate is higher reaches 97～98.5%.Product color is more shallow.Thereby can use secondary rosin to make one-level nilox resin (embodiment 2).

The technical process of novel method is seen Figure of description 2 with block diagram representation.

Pure abietic acid was once studied in organic solvent by the Soviet Union, in the presence of palladium carbon catalyst in 140～220 ℃ of mechanism of carrying out disproportionation reaction (CA93: 28058), but ignored the research that another important component dextrorotation Korean pine type resinous acid in the rosin (account for rosin weight 15～25%) is changed in disproportionation reaction.The raw material of Shi Yonging is pure abietic acid simultaneously, is not rosin, and what carry out is reaction mechanism (theory) research, technical process is not inquired into, and does not also mention the consumption and the repeated use problem of the height and the catalyzer of productive rate.Japanology is crossed rosin and is carried out disproportionation reaction to produce dehydroabietic acid content extra-high-speed (60～70%wt) nilox resin (JP6381181) in the alkene solvent, its ideal temperature is 220～280 ℃, productive rate is 92～96%, used solvent is an alkene, in the disproportionation reaction process, help the abietic acid dehydrogenation, thereby become alkane after quite a few olefine reaction is arranged, for keeping its dehydrogenation effect; Solvent can not recycle fully, and needs by recirculation after the fractionation.This patent purpose is in order to prepare the nilox resin of dehydroabietic acid content extra-high-speed, so that dehydroabietic acid is separated, as the intermediate of medicine and Chemicals.Whether do not mention catalyzer can directly reuse.The embodiment of the invention is as follows:

Embodiment 1:

One-level rosin (yellow 12.5, red 1.5) 550g, (main component is C to add commercially available 200# solvent oil _9～10Alkane) 450g, palladium carbon catalyst (5%Pd/c) 1.568g joins in the reactor, vacuumizing filled with nitrogen, 200 ℃ of reactions 3 hours, reactant is removed catalyzer and solvent with vacuum distilling after filtration, gets nilox resin 539g, productive rate 98%, color and luster Huang 17.2, red 2.1, acid value 171.2,78 ℃ of softening temperatures, unsaponifiables 2.9%, abietic acid 0.023%, dehydrogenation abietic acid 52.0% meets superfine nilox resin standard.

Embodiment 2:

Secondary rosin (yellow 21, red 1.8) 450g adds 200# solvent oil 370g, palladium carbon catalyst (5%Pd/c) 0.90g, join in the reactor, vacuumizing fills with nitrogen, 200 ℃ of reactions 3.5 hours, reactant was removed catalyzer and solvent with vacuum distilling after filtration, got nilox resin 438g, productive rate 97.3%, color and luster yellow 38 3, red 3.4, acid value 166,77 ℃ of softening temperatures, unsaponifiables 5.1%, abietic acid 0%, dehydrogenation abietic acid 48.15% is the one-level nilox resin.

Embodiment 3:

With one-level rosin 500 grams, pinane 600 grams, palladium carbon catalyst (5%Pd/c) 2.0 grams add in the still, vacuumizing filled with nitrogen, 173～179 ℃ of reactions 4 hours, reactant is removed catalyzer after filtration, and removes through vacuum distilling and to desolvate, and promptly get nilox resin 490 and restrains, color and luster is yellow 20, and is red 2.1, abietic acid 0.44%, dehydrogenation abietic acid 52.1%, acid value 172, unsaponifiables 4.3%, 77.3 ℃ of softening temperatures.

Claims (3)

1. a method for preparing nilox resin is characterized in that rosin is dissolved in C _9-12Straight chain or the solvent of cyclic alkane under 140-240 ℃ of temperature, carry out disproportionation reaction, use palladium carbon catalyst, its consumption is palladium: rosin=0.008-0.02: 100 (weight ratios), the resulting catalyzer of reacting liquid filtering can directly be reused 3-4 time, so reduced the loss of palladium, filtrate is by distilling to reclaim solvent, solvent does not participate in reaction, thereby also reusable, thereby avoided fractionation to reclaim loss

2. according to the method for preparing nilox resin of claim 1, it is characterized in that using solvent, solvent is C _9-12Straight chain or cyclic alkane, its consumption are rosin: solvent=100: 150-40 (wt),

3. according to the method for preparing nilox resin of claim 1, it is characterized in that temperature of reaction is lower, between 140-240 ℃.