CN1069105C - High-production low-consumption process flow for producing resin 731D - Google Patents
High-production low-consumption process flow for producing resin 731D Download PDFInfo
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- CN1069105C CN1069105C CN96122925A CN96122925A CN1069105C CN 1069105 C CN1069105 C CN 1069105C CN 96122925 A CN96122925 A CN 96122925A CN 96122925 A CN96122925 A CN 96122925A CN 1069105 C CN1069105 C CN 1069105C
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- solvent
- rosin
- reaction
- acid
- palladium
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- 238000000034 method Methods 0.000 title claims abstract description 11
- 229920005989 resin Polymers 0.000 title claims description 19
- 239000011347 resin Substances 0.000 title claims description 19
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 25
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 23
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 23
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000007323 disproportionation reaction Methods 0.000 claims abstract description 13
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 6
- ZRIHAIZYIMGOAB-UHFFFAOYSA-N butabarbital Chemical compound CCC(C)C1(CC)C(=O)NC(=O)NC1=O ZRIHAIZYIMGOAB-UHFFFAOYSA-N 0.000 claims description 18
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 7
- 150000001924 cycloalkanes Chemical class 0.000 claims description 3
- 238000005194 fractionation Methods 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 239000012188 paraffin wax Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 17
- 239000002253 acid Substances 0.000 description 15
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 9
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 9
- QUUCYKKMFLJLFS-UHFFFAOYSA-N Dehydroabietan Natural products CC1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 QUUCYKKMFLJLFS-UHFFFAOYSA-N 0.000 description 8
- NFWKVWVWBFBAOV-UHFFFAOYSA-N Dehydroabietic acid Natural products OC(=O)C1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 NFWKVWVWBFBAOV-UHFFFAOYSA-N 0.000 description 8
- NFWKVWVWBFBAOV-MISYRCLQSA-N dehydroabietic acid Chemical compound OC(=O)[C@]1(C)CCC[C@]2(C)C3=CC=C(C(C)C)C=C3CC[C@H]21 NFWKVWVWBFBAOV-MISYRCLQSA-N 0.000 description 8
- 229940118781 dehydroabietic acid Drugs 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000006356 dehydrogenation reaction Methods 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000002932 luster Substances 0.000 description 4
- MHVJRKBZMUDEEV-APQLOABGSA-N (+)-Pimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@](C=C)(C)C=C2CC1 MHVJRKBZMUDEEV-APQLOABGSA-N 0.000 description 3
- MHVJRKBZMUDEEV-UHFFFAOYSA-N (-)-ent-pimara-8(14),15-dien-19-oic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(C=C)(C)C=C1CC2 MHVJRKBZMUDEEV-UHFFFAOYSA-N 0.000 description 3
- YPGLTKHJEQHKSS-ASZLNGMRSA-N (1r,4ar,4bs,7r,8as,10ar)-1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,7,8,8a,9,10,10a-dodecahydrophenanthrene-1-carboxylic acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@@H](C(C)C)C[C@@H]2CC1 YPGLTKHJEQHKSS-ASZLNGMRSA-N 0.000 description 3
- UZZYXZWSOWQPIS-UHFFFAOYSA-N 3-fluoro-5-(trifluoromethyl)benzaldehyde Chemical compound FC1=CC(C=O)=CC(C(F)(F)F)=C1 UZZYXZWSOWQPIS-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 229920006387 Vinylite Polymers 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006114 decarboxylation reaction Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- XOKSLPVRUOBDEW-UHFFFAOYSA-N pinane Chemical compound CC1CCC2C(C)(C)C1C2 XOKSLPVRUOBDEW-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000011615 Pinus koraiensis Nutrition 0.000 description 1
- 240000007263 Pinus koraiensis Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000017858 demethylation Effects 0.000 description 1
- 238000010520 demethylation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229930006728 pinane Natural products 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229940082569 selenite Drugs 0.000 description 1
- MCAHWIHFGHIESP-UHFFFAOYSA-L selenite(2-) Chemical compound [O-][Se]([O-])=O MCAHWIHFGHIESP-UHFFFAOYSA-L 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Developing Agents For Electrophotography (AREA)
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
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 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96122925A CN1069105C (en) | 1996-10-04 | 1996-10-04 | High-production low-consumption process flow for producing resin 731D |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96122925A CN1069105C (en) | 1996-10-04 | 1996-10-04 | High-production low-consumption process flow for producing resin 731D |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1156745A CN1156745A (en) | 1997-08-13 |
| CN1069105C true CN1069105C (en) | 2001-08-01 |
Family
ID=5127498
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96122925A Expired - Fee Related CN1069105C (en) | 1996-10-04 | 1996-10-04 | High-production low-consumption process flow for producing resin 731D |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317348C (en) * | 2004-09-27 | 2007-05-23 | 广西大学 | Method for producing pale disproportionated rosin with high content dehydroabietic acid and P-camphogen simultinuously |
| CN102977789A (en) * | 2012-12-18 | 2013-03-20 | 富川瑶族自治县威龙林化有限公司 | Preparation method of pale rosin |
| CN104087176B (en) * | 2014-07-25 | 2016-03-02 | 广西众昌树脂有限公司 | The preparation method of nilox resin |
| CN104130712B (en) * | 2014-07-25 | 2015-12-30 | 广西众昌树脂有限公司 | The production method of disproportionated rosin sodium soap |
| CN109112021B (en) * | 2018-06-25 | 2021-03-30 | 广东科茂林产化工股份有限公司 | Preparation method of disproportionated rosin potassium soap |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1097448A (en) * | 1993-10-07 | 1995-01-18 | 广西大学 | Take by rosin as catalytic material hydrogenation system dihydro or tetrahydrochysene gum resin |
-
1996
- 1996-10-04 CN CN96122925A patent/CN1069105C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1097448A (en) * | 1993-10-07 | 1995-01-18 | 广西大学 | Take by rosin as catalytic material hydrogenation system dihydro or tetrahydrochysene gum resin |
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|---|---|
| CN1156745A (en) | 1997-08-13 |
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