WO1994026833A1 - Process for producing colorless rosin - Google Patents
Process for producing colorless rosin Download PDFInfo
- Publication number
- WO1994026833A1 WO1994026833A1 PCT/JP1994/000792 JP9400792W WO9426833A1 WO 1994026833 A1 WO1994026833 A1 WO 1994026833A1 JP 9400792 W JP9400792 W JP 9400792W WO 9426833 A1 WO9426833 A1 WO 9426833A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- rosin
- colorless
- stability
- producing
- reaction
- Prior art date
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- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 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 title claims abstract description 48
- 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 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 7
- 230000008569 process Effects 0.000 title claims abstract description 4
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 238000005984 hydrogenation reaction Methods 0.000 claims description 27
- 239000007789 gas Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- 229910052697 platinum Inorganic materials 0.000 claims 1
- 239000003607 modifier Substances 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 6
- 239000003973 paint Substances 0.000 abstract description 6
- -1 alkali metal salt Chemical class 0.000 abstract description 4
- 230000009965 odorless effect Effects 0.000 abstract description 4
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 3
- 229920001971 elastomer Polymers 0.000 abstract description 3
- 239000003995 emulsifying agent Substances 0.000 abstract description 3
- 239000000976 ink Substances 0.000 abstract description 3
- 239000004033 plastic Substances 0.000 abstract description 3
- 229920003023 plastic Polymers 0.000 abstract description 3
- 239000005060 rubber Substances 0.000 abstract description 3
- 239000007858 starting material Substances 0.000 abstract description 3
- 229920003051 synthetic elastomer Polymers 0.000 abstract description 3
- 239000005061 synthetic rubber Substances 0.000 abstract description 3
- 239000002585 base Substances 0.000 abstract description 2
- 239000003599 detergent Substances 0.000 abstract description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 2
- 230000004907 flux Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000000049 pigment Substances 0.000 abstract description 2
- 239000004831 Hot glue Substances 0.000 abstract 1
- 235000015218 chewing gum Nutrition 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 239000000344 soap Substances 0.000 abstract 1
- 229910000679 solder Inorganic materials 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 16
- 239000011347 resin Substances 0.000 description 16
- 239000002253 acid Substances 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 6
- 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 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- QUUCYKKMFLJLFS-UHFFFAOYSA-N Dehydroabietan Natural products CC1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 QUUCYKKMFLJLFS-UHFFFAOYSA-N 0.000 description 4
- 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 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 229940118781 dehydroabietic acid Drugs 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-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 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- MXYATHGRPJZBNA-KRFUXDQASA-N isopimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@@](C=C)(C)CC2=CC1 MXYATHGRPJZBNA-KRFUXDQASA-N 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 229910052705 radium Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 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 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- MXYATHGRPJZBNA-UHFFFAOYSA-N 4-epi-isopimaric acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(C=C)(C)CC1=CC2 MXYATHGRPJZBNA-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- KGMSWPSAVZAMKR-UHFFFAOYSA-N Me ester-3, 22-Dihydroxy-29-hopanoic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(=C(C)C)C=C1CC2 KGMSWPSAVZAMKR-UHFFFAOYSA-N 0.000 description 1
- KGMSWPSAVZAMKR-ONCXSQPRSA-N Neoabietic acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CCC(=C(C)C)C=C2CC1 KGMSWPSAVZAMKR-ONCXSQPRSA-N 0.000 description 1
- 241000287463 Phalacrocorax Species 0.000 description 1
- 235000016639 Syzygium aromaticum Nutrition 0.000 description 1
- 244000223014 Syzygium aromaticum Species 0.000 description 1
- GUWKQWHKSFBVAC-UHFFFAOYSA-N [C].[Au] Chemical compound [C].[Au] GUWKQWHKSFBVAC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000001055 chewing effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000000640 hydroxylating effect Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- BQZGVMWPHXIKEQ-UHFFFAOYSA-L iron(ii) iodide Chemical compound [Fe+2].[I-].[I-] BQZGVMWPHXIKEQ-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010938 white gold Substances 0.000 description 1
- 229910000832 white gold Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
- C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
- C09F1/04—Chemical modification, e.g. esterification
Definitions
- the present invention relates to a method for producing a colorless rosin having excellent colorlessness, odorlessness, heat stability and weather resistance.
- rosin and its derivatives, rosin esters have been used in tackifiers and adhesives for tackifiers, rubbers and various plastics.
- raw materials such as modifiers for paints, resins for traffic paint, size agents for papermaking, emulsifiers for synthetic rubber, resins for inks, and resins for paints. It is used for various purposes.
- the rosin-based compound has a yellow or yellow-brown appearance, has an odor, and has thermal stability and weather resistance (hereinafter referred to as "the combined amount of both").
- Japanese Patent Publication No. 45-33771 and Japanese Patent Publication No. Sho-sho No. 1 disclose a method for disproportionating rosin or rosin-based compound with a specific organic sulfur compound. , But the disproportionated resin obtained by this method also shows color, odor and stability. Inadequate.
- any conventional rosin, uneven rosin, and hydrogenated rosin can simultaneously satisfy all the characteristics of color tone, odor, and stability. It is not. Therefore, the appearance of a colorless, odorless, and stable mouth gin is highly desired.
- An object of the present invention is to provide a novel process for producing a colorless mouth gin which further improves the color tone, odor and stability characteristics of a conventional rosin in view of the above-mentioned circumstances. It is to be.
- the present invention has been studied to improve the above characteristics by focusing on various conditions such as the type of rosin, purification operation, and dehydrogenation reaction.
- benzene as a starting material and leading it to a specific reaction step, it is a colorless, odorless, and stable colorless resin that meets the objectives of the present invention.
- the present invention provides a colorless rosin characterized in that a purified hydrogenation port is subjected to a dehydrogenation reaction in the presence of a specific reaction step, that is, a dehydrogenation catalyst.
- the present invention relates to a method for producing a gasoline, a new product that is almost colorless in appearance, and can provide a colorless mouth gin with excellent odor and stability when heated. It is about the law. .
- the colorless mouth gin obtained by the above-mentioned method has properties which are hardly considered from stereotypes formed from the characteristics of conventional rosins. is there .
- the almost colorless mouth gas that has wiped out the stereotype that has conventionally been regarded as having a yellow or tan appearance in the mouth gas is the same as the mouth Has a wide compatibility with various polymers, which are the characteristics of conventional mouth gin.
- BEST MODE FOR CARRYING OUT THE INVENTION The starting material in the present invention is a refined hydrogenation port gin, and by using this rosin, the final choice is made. The resulting rosin is colorless, odorless and has excellent stability.
- the above-mentioned purified hydrogenated rosin includes abietic acid, parastronic acid, neoabietic acid, pimaric acid, isopimaric acid, dehydrogen Partially or practically complete hydrogenation of gamlogins, pedodines, and toll oils, which are mainly composed of resin acids such as abietic acid After that, it can be further purified and obtained (hereinafter abbreviated as purified hydrogenated resin A), and gamlogins, pedodines, and Is obtained by partially or substantially completely hydrogenating the purified product after purifying a crude oil (hereinafter referred to as purified hydrogenated resin B). (Abbreviated).
- known hydrogenation reaction conditions can be appropriately selected. That is, to produce unrefined hydrogenation rosin, typically in the presence of a hydrogenation catalyst, typically 10 to 200 kg / cm 2 , preferably 5 G This is done by heating the crude oil under a hydrogen pressure of ⁇ 15 G kg / cm 2 .
- a hydrogenation catalyst typically 10 to 200 kg / cm 2 , preferably 5 G This is done by heating the crude oil under a hydrogen pressure of ⁇ 15 G kg / cm 2 .
- the hydrogenation catalyst include, for example, supported catalysts such as palladium carbon, orifice carbon, and white gold carbon, nickel, and white. It can remove metal powders such as gold, solutes such as iodine and iron iodide.
- the amount of catalyst used is relative to And usually 0.1 to 1% by weight, preferably 0.1 to 0.1% by weight, and the reaction temperature is 1 to 300, preferably 150 to 290 ° C. is there .
- the resin acid composition in the unpurified hydrogenated hydrogen obtained according to the hydrogenation reaction conditions varies depending on the amount of the hydrogenation catalyst used and the supply pressure of hydrogen gas. It varies, but usually less than 1% by weight of abietic acid, 10 to 50% by weight of tetrahydro compound, 45 to 75% by weight of dihydro compound, dehydroabietic acid 5 to 15% by weight. In particular, when the content of abietic acid is 1% by weight or more, the color tone is inferior even though the purification and dehydrogenation steps are continued. If the content of dehydroabietic acid exceeds 75% by weight, there is a disadvantage that the continuous dehydrogenation reaction does not proceed sufficiently.
- purification means that the rosin contained in the rosin before hydrogenation or the rosin after hydrogenation was included. It means to remove high molecular weight substances considered to have been generated from the oxides and the unsaponifiable substances originally contained in the rosin. Specifically, it is sufficient to perform operations such as distillation, recrystallization, and extraction. Industrially, purification by distillation is preferred from the viewpoints of workability and economy. Depending on the distillation, it is appropriately selected from the range of normal temperature of 2 QQ to 3 DQ ° C and pressure of 1 to 10 DlDlHg in consideration of the distillation time.
- the crude hydrogenated rosin is dissolved in a good solvent, and then a part of the solvent is distilled off to form a concentrated solution, and the poor solvent is added to this solution. It can be done by adding.
- Examples of good solvents include aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as chloroform, and isopro Low-grade alcohol such as pill alcohol — Toluenes, tones such as acetate, acetic acid esters such as ethyl acetate, etc., and n-hexan, as a poor solvent, n — To produce aliphatic hydrocarbons such as heptane, cyclohexane, and isooctane.
- aromatic hydrocarbons such as benzene, toluene and xylene
- halogenated hydrocarbons such as chloroform
- isopro Low-grade alcohol such as pill alcohol — Toluenes, tones such as acetate, acetic acid esters such as ethyl acetate, etc., and n-hexan, as a poor solvent, n — To produce aliphatic hydro
- the unpurified hydrogenated rosin is converted into an aqueous solution of alkali metal by using an aryl resin such as sodium hydroxide or a hydroxylating resin.
- an aryl resin such as sodium hydroxide or a hydroxylating resin.
- the aqueous layer is neutralized, and purified hydrogenated rosin A can be obtained from the aqueous layer.
- the initial fraction is removed by about 2 to 5% by weight, and the bottom is removed by about 5 to 10% by weight.
- the desired degree of purification can be obtained.
- Hydrogenation may be carried out after purifying the unpurified rosin, but the same conditions as those used in the above-mentioned fining hydrogenation port A are used for the purification conditions and hydrogenation conditions. It is.
- the initial pressure of hydrogen gas is preferably less than lQltg " 2 in a closed vessel, for example, in a pressure-resistant reactor, in the presence of a dehydrogenation catalyst.
- Ku is 5 k gZ (;.
- the reaction temperature is 100 ⁇ 300 ° C, good or to rather are not good lever be heated in the range of 2 Q 0 ⁇ ⁇ Q ° C Oh dehydrogenation reaction
- the order substantially has that hydrogen Ru Oh unnecessary, intended either et you use purified hydrogen cormorants good of the the reduction of the peracid product, less than 10 kg / cm 2 the initial pressure of hydrogen gas
- the self-pressure of the purified hydrogen Alternatively, the pressure may be adjusted by supplying a slight amount of hydrogen gas from outside the city, and the initial pressure of the hydrogen gas is preferably used for the purpose of accelerating the dehydrogenation reaction. Is less than 5 kg em 2 .
- the reaction temperature is lower than 100 ° C, the dehydrogenation reactivity tends to decrease, and when the reaction temperature exceeds 300 ° C, decomposition of rosin may occur, which is likely to occur.
- the dehydrogenation catalyst is not particularly limited, and various known ones can be used. Specifically, for example, palladium-based catalysts, rhodium-based catalysts, and white-based catalysts can be used. Examples of such catalysts include gold-based catalysts.
- the catalyst is usually used by being supported on a carrier such as silica or carbon. The amount of the catalyst used is 0.01 to 5% by weight, preferably 0.02 to 2% by weight, based on the purified hydrogenated rosin.
- the dehydrogenation reaction tends to be unsatisfactory, and if it exceeds 5% by weight, the economic efficiency decreases.
- aliphatic hydrocarbons such as cyclohexanedecalin and aromatic hydrocarbons such as toluene and xylene are used.
- Etc. can be appropriately used as a reaction solvent.
- the resin acid composition in the colorless rosin obtained by the production method of the present invention slightly varies depending on the supply pressure of hydrogen gas, but less than 1% of abietic acid, Body 1 (! ⁇ 50% by weight, dihydro body 1 (! ⁇ 40% by weight, dehydroabietic acid 2 (! ⁇ 60% by weight.
- the peroxide value of this resin is 1 or less.
- the color tone of the finally obtained rosin does not become colorless, and Dehydroabietic acid content If the amount exceeds 60% by weight, the colorless rosin can be obtained, but the crystallinity becomes stronger and the handling workability tends to be inferior.
- the method for producing the colorless mouth gas of the present invention will be described in more detail based on Comparative Examples and Comparative Examples, but the present invention is not limited to these.
- the crude hydrogenation port gas was distilled under a nitrogen sealant under a reduced pressure of 3 mmHg to obtain an acid value of 5.2, a softening point of 83 ° C, and a color tone
- the main distillate shown in Table 1 was used as the refined hydrogenation port.
- Example 1 (1) except that the palladium carbon (palladium content 5%, water content 50%) was changed to 0.7 g.
- the hydrogenation reaction is carried out in the same manner as in 1), and the acid value 169, a softening point of ° C and a color tone donor — 6 unrefined hydrogenation ports were obtained.
- the unpurified hydrogenated hydrogen was distilled under reduced pressure under the same conditions as in Example 1 (2) to obtain an acid value of ⁇ 5.5, a softening point of 85.C, and general constants of color tone guards 2 to 3.
- the main distillate shown in Table 2 was used as purified hydrogenated rosin.
- Example 1 A hydrogenation reaction was carried out on 200 g of the purified hydrogenated resin under the same conditions as in Example 1 (3), and the acid value was ⁇ 1.1, the softening point was ⁇ ° C, and the color tone was 1 or less ( The same test as in Example 1 was carried out using a colorless mouth gene of nodense color 100). The results are shown in Tables 4 and 5.
- Example 1 (1) Using the unpurified hydrogenated rosin obtained in Example 1 (1), a dehydrogenation reaction was carried out under the same conditions as in Example 1 (3) to obtain an acid value of 165 and a softening point of 75. The same test as in Example 1 was carried out at a temperature of ° C and a color tone guard of 5. The results are shown in Tables 4 and 5.
- Comparative Example 2 The rosin obtained in Comparative Example 1 was distilled under a reduced pressure of 301 mHg under a nitrogen seal to obtain an acid value, a softening point of 84 ° C, and a general constant of color tone guard 2. The same test as in Example 1 was conducted using the main berth shown in Table 3 having the number as the final mouth gin. The results are shown in Tables 4 and 5.
- a colorless mouth gin having markedly improved properties such as color tone, odor and stability as compared with the conventional rosin can be provided at a relatively low cost.
- the colorless rosin obtained by the production method of the present invention has a color tone close to almost colorless, has no odor, and has excellent stability. It has excellent properties such as stability and compatibility. Therefore, the colorless rosin can not only be suitably used as a modifier of the Shiyeo-based detergent composition, but also the alkali metal salt of the colorless rosin. Can be suitably used as an emulsifier for synthetic rubber emulsion polymerization. In addition, the colorless rosin can be hot-melted by making it esterified.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP94914627A EP0653471B1 (en) | 1993-05-18 | 1994-05-16 | Process for producing colorless rosin |
US08/373,222 US5606016A (en) | 1993-05-18 | 1994-05-16 | Process for preparing colorless rosins |
DE69427804T DE69427804T2 (de) | 1993-05-18 | 1994-05-16 | Verfahren zur herstellung farblosen kolophoniums |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP14015993A JP3371982B2 (ja) | 1993-05-18 | 1993-05-18 | 無色ロジンの製造法 |
JP5/140159 | 1993-05-18 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1994026833A1 true WO1994026833A1 (en) | 1994-11-24 |
Family
ID=15262246
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1994/000792 WO1994026833A1 (en) | 1993-05-18 | 1994-05-16 | Process for producing colorless rosin |
Country Status (5)
Country | Link |
---|---|
US (1) | US5606016A (ja) |
EP (1) | EP0653471B1 (ja) |
JP (1) | JP3371982B2 (ja) |
DE (1) | DE69427804T2 (ja) |
WO (1) | WO1994026833A1 (ja) |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE69728642T2 (de) * | 1996-08-08 | 2005-03-24 | New Japan Chemical Co., Ltd. | Molekularer kristall auf kolophonium-basis, nukleierungsmittel für polyolefinharz, polyolefinharzzusammensetzung sowie formmassen daraus |
JPH10219227A (ja) * | 1997-01-31 | 1998-08-18 | Arakawa Chem Ind Co Ltd | 粘着付与樹脂エマルジョンおよび水系粘着剤組成物 |
US7053029B2 (en) * | 2002-03-27 | 2006-05-30 | Kimberly-Clark Worldwide, Inc. | Use indicating soap |
US7960326B2 (en) * | 2002-09-05 | 2011-06-14 | Kimberly-Clark Worldwide, Inc. | Extruded cleansing product |
US20060069188A1 (en) * | 2004-09-29 | 2006-03-30 | Klosiewicz Daniel W | Processes for producing functionalized polyolefin emulsions |
US20060100356A1 (en) * | 2004-09-29 | 2006-05-11 | Klosiewicz Daniel W | Alicyclic carboxylic acid-containing functionalized polyolefins and emulsions prepared therefrom |
US20060069209A1 (en) * | 2004-09-29 | 2006-03-30 | Klosiewicz Daniel W | Heat stable functionalized polyolefin emulsions |
JP4986107B2 (ja) * | 2005-11-14 | 2012-07-25 | 花王株式会社 | トナー用ポリエステル |
JP4680040B2 (ja) * | 2005-11-14 | 2011-05-11 | 花王株式会社 | トナー |
JP4863699B2 (ja) * | 2005-11-14 | 2012-01-25 | 花王株式会社 | トナー用ポリエステル |
JP4676945B2 (ja) * | 2006-01-13 | 2011-04-27 | 日東電工株式会社 | 水性粘着剤組成物、粘着テープおよびワイヤーハーネス |
WO2007092250A2 (en) * | 2006-02-02 | 2007-08-16 | Hexion Specialty Chemicals Inc. | Rosin ester with low color and process for preparing same |
US20110034669A1 (en) * | 2006-02-02 | 2011-02-10 | Dallavia Anthony J | Rosin Ester with Low Color and Process for Preparing Same |
JP2007292792A (ja) * | 2006-04-20 | 2007-11-08 | Ricoh Co Ltd | 二成分現像剤、並びにそれを用いた画像形成方法及び画像形成装置 |
JP2009191182A (ja) * | 2008-02-15 | 2009-08-27 | Denki Kagaku Kogyo Kk | クロロプレン系重合体組成物、接着剤組成物、並びにクロロプレン系重合体組成物の製造方法 |
US20160257852A1 (en) * | 2013-10-29 | 2016-09-08 | Arakawa Chemical Industries, Ltd. | Method for manufacturing light-colored refined tall oil rosin and tall oil rosin ester, and light-colored refined tall oil rosin and tall oil rosin ester obtained via said method |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6485265A (en) * | 1987-09-26 | 1989-03-30 | Arakawa Chem Ind | Production of colorless rosin |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3313754A (en) * | 1964-12-16 | 1967-04-11 | Hercules Inc | Alloys of polyolefins and rosin derivatives |
FR1541122A (fr) * | 1967-08-25 | 1968-10-04 | Anciens Etablissements Granel | Deshydrogénation des acides résiniques |
US3664981A (en) * | 1970-06-26 | 1972-05-23 | Hercules Inc | Polyphase compositions and process for their preparation |
JPS559605A (en) * | 1978-06-23 | 1980-01-23 | Arakawa Chem Ind Co Ltd | Preparation of rosin ester having high softening point and improved stability |
US4447354A (en) * | 1983-03-21 | 1984-05-08 | Arizona Chemical Company | Method for making oxidation-stable, light-colored glycerol ester of modified rosin |
JPS6081269A (ja) * | 1983-10-12 | 1985-05-09 | Harima Kasei Kogyo Kk | ロジンエステルの製造方法 |
US4643848A (en) * | 1986-02-21 | 1987-02-17 | Westvaco Corporation | Modified rosin ester preparation |
JP2539811B2 (ja) * | 1987-01-29 | 1996-10-02 | 荒川化学工業株式会社 | ロジンエステルの製造法 |
US4906733A (en) * | 1987-01-29 | 1990-03-06 | Arakawa Kagaku Kogyo Kabushiki Kaisha | Process for preparing colorless rosin |
SE506467C2 (sv) * | 1991-06-28 | 1997-12-22 | Eka Chemicals Ab | Förfarande för framställning av stabiliserad kolofonium och dess användning som klibbgivarharts i bindemedel |
WO1993013180A1 (en) * | 1991-12-21 | 1993-07-08 | Arakawa Kagaku Kogyo Kabushiki Kaisha | Process for producing rosin ester and colorless rosin |
-
1993
- 1993-05-18 JP JP14015993A patent/JP3371982B2/ja not_active Expired - Lifetime
-
1994
- 1994-05-16 WO PCT/JP1994/000792 patent/WO1994026833A1/ja active IP Right Grant
- 1994-05-16 US US08/373,222 patent/US5606016A/en not_active Expired - Lifetime
- 1994-05-16 EP EP94914627A patent/EP0653471B1/en not_active Expired - Lifetime
- 1994-05-16 DE DE69427804T patent/DE69427804T2/de not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6485265A (en) * | 1987-09-26 | 1989-03-30 | Arakawa Chem Ind | Production of colorless rosin |
Non-Patent Citations (1)
Title |
---|
See also references of EP0653471A4 * |
Also Published As
Publication number | Publication date |
---|---|
DE69427804T2 (de) | 2001-11-08 |
DE69427804D1 (de) | 2001-08-30 |
EP0653471A1 (en) | 1995-05-17 |
EP0653471A4 (en) | 1997-08-20 |
US5606016A (en) | 1997-02-25 |
JP3371982B2 (ja) | 2003-01-27 |
EP0653471B1 (en) | 2001-07-25 |
JPH06329991A (ja) | 1994-11-29 |
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