KR102637090B1 - Method for producing dimer acid using palm oleic acid - Google Patents
Method for producing dimer acid using palm oleic acid Download PDFInfo
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- KR102637090B1 KR102637090B1 KR1020230050944A KR20230050944A KR102637090B1 KR 102637090 B1 KR102637090 B1 KR 102637090B1 KR 1020230050944 A KR1020230050944 A KR 1020230050944A KR 20230050944 A KR20230050944 A KR 20230050944A KR 102637090 B1 KR102637090 B1 KR 102637090B1
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- Prior art keywords
- acid
- fatty acids
- dimer acid
- dimer
- fatty acid
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- 239000002253 acid Substances 0.000 title claims abstract description 95
- 239000000539 dimer Substances 0.000 title claims abstract description 83
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 title claims abstract description 42
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 title claims abstract description 41
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 title claims abstract description 41
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 title claims abstract description 41
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000005642 Oleic acid Substances 0.000 title claims abstract description 41
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 30
- 235000019482 Palm oil Nutrition 0.000 claims abstract description 34
- 239000002540 palm oil Substances 0.000 claims abstract description 34
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 30
- 150000004671 saturated fatty acids Chemical class 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 86
- 239000000194 fatty acid Substances 0.000 claims description 86
- 229930195729 fatty acid Natural products 0.000 claims description 86
- 150000004665 fatty acids Chemical class 0.000 claims description 86
- 239000002994 raw material Substances 0.000 claims description 40
- 239000003054 catalyst Substances 0.000 claims description 34
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 26
- 235000010469 Glycine max Nutrition 0.000 claims description 25
- 244000068988 Glycine max Species 0.000 claims description 21
- 235000003441 saturated fatty acids Nutrition 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000006555 catalytic reaction Methods 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 13
- 239000000376 reactant Substances 0.000 claims description 13
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 13
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 13
- 230000003301 hydrolyzing effect Effects 0.000 claims description 12
- 230000004136 fatty acid synthesis Effects 0.000 claims description 11
- 239000012535 impurity Substances 0.000 claims description 11
- 238000004821 distillation Methods 0.000 claims description 10
- 239000003549 soybean oil Substances 0.000 claims description 10
- 235000012424 soybean oil Nutrition 0.000 claims description 10
- 238000004508 fractional distillation Methods 0.000 claims description 8
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 235000020661 alpha-linolenic acid Nutrition 0.000 claims description 5
- 229960004488 linolenic acid Drugs 0.000 claims description 5
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 claims description 5
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 235000021313 oleic acid Nutrition 0.000 claims description 3
- 239000002699 waste material Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 18
- 238000000034 method Methods 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 15
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 14
- 239000003784 tall oil Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 7
- 235000021314 Palmitic acid Nutrition 0.000 description 6
- 239000004927 clay Substances 0.000 description 6
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 6
- 235000015112 vegetable and seed oil Nutrition 0.000 description 6
- 239000008158 vegetable oil Substances 0.000 description 6
- 235000021355 Stearic acid Nutrition 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000008117 stearic acid Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000007127 saponification reaction Methods 0.000 description 4
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 235000019484 Rapeseed oil Nutrition 0.000 description 2
- 235000019774 Rice Bran oil Nutrition 0.000 description 2
- 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 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000021323 fish oil Nutrition 0.000 description 2
- 235000020778 linoleic acid Nutrition 0.000 description 2
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000004006 olive oil Substances 0.000 description 2
- 235000008390 olive oil Nutrition 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000008165 rice bran oil Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- -1 soybean fatty acids) Chemical class 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 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 description 2
- 150000005671 trienes Chemical class 0.000 description 2
- CFQZKFWQLAHGSL-FNTYJUCDSA-N (3e,5e,7e,9e,11e,13e,15e,17e)-18-[(3e,5e,7e,9e,11e,13e,15e,17e)-18-[(3e,5e,7e,9e,11e,13e,15e)-octadeca-3,5,7,9,11,13,15,17-octaenoyl]oxyoctadeca-3,5,7,9,11,13,15,17-octaenoyl]oxyoctadeca-3,5,7,9,11,13,15,17-octaenoic acid Chemical compound OC(=O)C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\OC(=O)C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\OC(=O)C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\C=C CFQZKFWQLAHGSL-FNTYJUCDSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- KYXHKHDZJSDWEF-LHLOQNFPSA-N CCCCCCC1=C(CCCCCC)C(\C=C\CCCCCCCC(O)=O)C(CCCCCCCC(O)=O)CC1 Chemical compound CCCCCCC1=C(CCCCCC)C(\C=C\CCCCCCCC(O)=O)C(CCCCCCCC(O)=O)CC1 KYXHKHDZJSDWEF-LHLOQNFPSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000600039 Chromis punctipinnis Species 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 239000002285 corn oil Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000447 dimerizing effect Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
- C07C57/13—Dicarboxylic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
본 발명은 팜올레인산을 이용하여 올레인산을 단량체(monomer)로 하는 다이머산(dimer acid)의 제조방법에 관한 것으로, 팜유에 포함된 포화지방산을 저감하면서 다이머산의 합성 수율을 높이는 효과적인 방법을 고안하여 올레인산을 단량체로 하는 고품질, 고순도의 다이머산을 제조하는 방법을 제공하고자 한다.The present invention relates to a method for producing dimer acid using palm oleic acid as a monomer, by devising an effective method to increase the synthesis yield of dimer acid while reducing the saturated fatty acid contained in palm oil. The aim is to provide a method for producing high-quality, high-purity dimer acid using oleic acid as a monomer.
Description
본 발명은 팜올레인산을 이용하여 올레인산을 단량체(monomer)로 하는 다이머산(dimer acid)의 제조방법에 관한 것으로, 더욱 상세하게는 올레인산을 함유하는 팜유를 이용하여 지방산의 조성을 변화시키고 효율적인 조촉매를 사용함으로써 올레인산을 단량체로 하는 고품질, 고순도의 다이머산을 제조하는 방법에 관한 것이다.The present invention relates to a method for producing dimer acid using palm oleic acid as a monomer, and more specifically, to change the composition of fatty acids using palm oil containing oleic acid and to provide an efficient cocatalyst. It relates to a method of producing high-quality, high-purity dimer acid using oleic acid as a monomer.
페인트, 잉크 및 폴리아미드의 원료로 사용되는 다이머산의 일반적인 제조방법은 톨(tall) 지방산을 원료로 하여 열과 압력을 가하는 것이다. 다이머산의 합성은 불포화결합을 가진 불포화지방산을 이량화(二量化)하는 것으로, 그 반응식은 디엘스-알델(Diels-Alder) 축합에 의하여 생성되는 것으로서 한 분자 중에 두 개의 이중결합을 가지고 있는 분자가 보다 안정한 공액형으로 되려는 경향을 이용한 것이다.A common method for producing dimer acid, which is used as a raw material for paint, ink, and polyamide, is to use tall fatty acid as a raw material and apply heat and pressure. The synthesis of dimer acid involves dimerizing unsaturated fatty acids with unsaturated bonds. The reaction formula is Diels-Alder condensation, which is a molecule with two double bonds in one molecule. This takes advantage of the tendency of to become a more stable conjugate form.
이와 같이 디엘스-알델 축합 반응에 의한 다이머산 생산은 원료로서 톨유, 어유, 대두유, 채종유, 옥배유, 올리브유, 미강유 등 유래의 불포화지방산(unsaturated fatty acid)을 사용한다. 그 원료 중에는 포화지방산(saturated fatty acid), 트리엔산(triene acid)이 적은 것이 바람직하다. 따라서 흔히 톨유 또는 대두유 유래의 지방산이 주로 사용되고 있다.In this way, the production of dimer acid by the Diels-Aldel condensation reaction uses unsaturated fatty acids derived from tall oil, fish oil, soybean oil, rapeseed oil, corn oil, olive oil, and rice bran oil as raw materials. It is preferable that the raw materials contain less saturated fatty acid and triene acid. Therefore, fatty acids derived from tall oil or soybean oil are mainly used.
그러나 톨유에는 로진(rosin)분과 불검화분 등이 많아 이를 제거한 고품질 톨지방산이 다이머산의 주요 용도로 사용되고 있으나, 이 고품질 톨지방산은 가격이 비쌀 뿐만 아니라, 톨지방산은 소나무를 원료로 한 것이므로 임산자원 훼손면에서도 문제가 발생되며, 근래 톨지방산의 가격은 년 평균 100~200% 정도 가격이 상승되고 있다. 대두지방산(Soy fatty acid) 또한 원료인 대두(콩)의 주요 생산지 남미 기상악화에 따른 콩 국제가격 상승과, 러시아 우크라이나의 전쟁으로 인한 수급불안정으로 연 평균 10~20% 정도 가격이 상승되고 있다. However, tall oil contains a lot of rosin and ungummed pollen, so high-quality tall fatty acid that has been removed is used as the main purpose of dimer acid. However, this high-quality tall fatty acid is not only expensive, but also tall fatty acid is made from pine trees, so it is used in forestry products. Problems also arise in terms of resource damage, and recently the price of tall fatty acids has been rising by an average of 100-200% per year. The price of soy fatty acid is also rising by an average of 10-20% per year due to the rise in international prices of soybeans due to bad weather in South America, a major production area for soybeans (soybeans), a raw material, and supply and demand instability due to the war in Russia and Ukraine.
따라서 이의 대체 원료가 절실히 필요하며 다이머산의 합성에서 가장 좋은 원료를 찾기 위한 연구가 필요하다. 그 중에서도 식물유 지방산을 이용하되 경제적으로도 부담이 적은 팜유를 이용할 수 있으나, 이는 팔미틱산(palmitic acid)과 스테아릭산(stearic aicd)과 같은 포화지방산이 다량 포함되어 있어 촉매 작용에 장애가 되며 다이머산의 합성 수율이 낮다는 한계가 있다. Therefore, alternative raw materials are urgently needed, and research is needed to find the best raw materials for the synthesis of dimer acid. Among them, vegetable oil fatty acids can be used, such as palm oil, which is less economically burdensome, but it contains a large amount of saturated fatty acids such as palmitic acid and stearic acid, which hinders the catalytic action and contains dimer acid. There is a limitation in that the synthesis yield is low.
본 발명은 다이머산을 효율적으로 생산해내고자 식물유 지방산을 이용하기 위해 여러 식물을 대상으로 고찰한 결과, 다른 식물유 지방산(예: 대두 지방산)에 비해 경제적으로도 부담이 없는 팜유를 선택하였으나 이는 팔미틱산(palmitic acid)과 스테아릭산(stearic aicd)과 같은 포화지방산이 다량 포함되어 있어 촉매 작용에 장애가 되며 다이머산의 합성 수율이 낮다는 한계가 있었다. 이에 팜유에 포함된 포화지방산을 저감하면서 다이머산의 합성 수율을 높이는 효과적인 방법을 고안하여 올레인산을 단량체(monomer)로 하는 고품질, 고순도의 다이머산(dimer acid)을 제조하는 방법을 제공하고자 한다.In the present invention, as a result of examining various plants to use vegetable oil fatty acids to efficiently produce dimer acid, palm oil was selected as it is economically less burdensome compared to other vegetable oil fatty acids (e.g., soybean fatty acids), but palmitic acid ( It contained a large amount of saturated fatty acids such as palmitic acid and stearic acid, which hindered catalytic activity and had a limitation in that the synthesis yield of dimer acid was low. Accordingly, we aim to provide a method for producing high-quality, high-purity dimer acid using oleic acid as a monomer by devising an effective method to increase the synthesis yield of dimer acid while reducing the saturated fatty acids contained in palm oil.
본 발명은 올레인산을 함유하는 팜유를 가수분해하여 지방산을 얻은 후, 이를 증류하여 포화지방산을 저감시키는 단계 (a); 단계 (a)에서 얻어진 지방산에 산화 촉매와 조촉매를 첨가한 후, 물을 넣고 촉매 반응시키는 단계 (b); 단계 (b)의 반응물을 냉각하고 인산을 처리하여 지방산의 합성 반응을 종결한 후, 여과하여 촉매 및 불순물을 제거하는 단계 (c) 및; 단계 (c)의 여과된 반응물을 증류하여 다이머산을 분리하는 단계 (d);를 포함하는 것을 특징으로 하는 올레인산을 단량체(monomer)로 하는 다이머산(dimer acid)의 생산방법을 제공한다.The present invention hydrolyzes palm oil containing oleic acid to obtain fatty acids, and then distills them to reduce saturated fatty acids (a); Adding an oxidation catalyst and a cocatalyst to the fatty acid obtained in step (a), then adding water and performing a catalytic reaction (b); Step (c) of cooling the reactant of step (b) and treating it with phosphoric acid to terminate the fatty acid synthesis reaction, followed by filtering to remove the catalyst and impurities; It provides a method for producing dimer acid using oleic acid as a monomer, comprising the step (d) of distilling the filtered reaction product of step (c) to separate dimer acid.
한편, 본 발명의 생산방법에 있어서, 상기 팜유는, 바람직하게 폐 팜유인 것일 수 있다.Meanwhile, in the production method of the present invention, the palm oil may preferably be waste palm oil.
한편, 본 발명의 생산방법에 있어서, 상기 증류는, 바람직하게 분별 증류인 것이 좋다.Meanwhile, in the production method of the present invention, the distillation is preferably fractional distillation.
한편, 본 발명의 생산방법에 있어서, 상기 단계 (b)는, 바람직하게 단계 (a)에서 얻어진 지방산과 함께 대두 오일을 가수분해하여 얻은 대두 지방산을 사용하는 것일 수 있다.Meanwhile, in the production method of the present invention, step (b) may preferably use soy fatty acid obtained by hydrolyzing soybean oil together with the fatty acid obtained in step (a).
본 발명은 올레인산을 함유하는 팜유를 가공하여 효율적인 지방산 조성을 가지는 팜올레인산을 원료로 사용하고, 효율적인 조촉매를 사용하여 다이머산을 제조하는 방법을 제공함으로써 포화지방산의 함량이 다량 제거되어 높은 다이머산의 합성수율을 가지며, 고품질 및 고순도의 다이머산을 제조할 수 있다.The present invention provides a method for producing dimer acid by processing palm oil containing oleic acid, using palm oleic acid with an efficient fatty acid composition as a raw material, and using an efficient cocatalyst, thereby removing a large amount of saturated fatty acid and producing a high dimer acid. It has a high synthetic yield and can produce high quality and high purity dimer acid.
다이머산의 일반적인 제조방법은 톨(tall) 지방산을 원료로 하여 열과 압력을 가하는 것이며, 원료로서 톨유, 어유, 대두유, 채종유, 옥배유, 올리브유, 미강유 등 유래의 불포화지방산(unsaturated fatty acid)을 사용한다. 그 원료 중에는 포화지방산(saturated fatty acid), 트리엔산(triene acid)이 적은 것이 바람직함에 따라 톨유 또는 대두유가 주로 사용되고 있다. 그러나 톨유에는 로진(rosin)분과 불검화분 등이 많아 이를 제거한 고품질 톨지방산을 사용하고 있는데, 이는 고가의 가격과 자원적 한계가 있다. 또한, 대두유 역시 가격의 지속적인 상승에 따른 사용의 어려움이 있다. 따라서 원료 사용에 경제적이면서 효율적인 다이머산 생산이 가능한 대체 원료를 찾는 것이 절실히 필요한 실정이다. The general method of producing dimer acid is to use tall fatty acid as a raw material and apply heat and pressure, and unsaturated fatty acids derived from tall oil, fish oil, soybean oil, rapeseed oil, corn bran oil, olive oil, and rice bran oil are used as raw materials. . Among the raw materials, tall oil or soybean oil is mainly used as it is desirable to have less saturated fatty acid and triene acid. However, tall oil contains a lot of rosin and ungummed pollen, so high-quality tall fatty acids that have been removed are used, which is expensive and has resource limitations. In addition, soybean oil also faces difficulties in use due to the continued rise in price. Therefore, there is an urgent need to find alternative raw materials that are economical in raw material use and capable of producing dimer acid efficiently.
따라서 본 발명자들은 다이머산 생산이 가능한 대체 원료를 찾기 위해 여러 식물유 지방산을 대상으로 고찰하였으며, 그 중에서도 경제적으로도 부담이 적은 팜유를 선택하였으나 이는 팔미틱산(palmitic acid)과 스테아릭산(stearic aicd)과 같은 포화지방산이 다량 포함되어 있어 촉매 작용에 장애가 되며 다이머산의 합성 수율이 낮다는 한계가 있었다. 이에 팜유에 포함된 포화지방산을 저감하면서 다이머산의 합성 수율을 높이는 효과적인 방법을 고안하여 올레인산을 단량체(monomer)로 하는 고품질, 고순도의 다이머산(dimer acid)을 제조하는 방법을 제공하고자 한다.Therefore, the present inventors studied various vegetable oil fatty acids to find an alternative raw material capable of producing dimer acid, and among them, palm oil was selected, which is less economically burdensome, but it contains palmitic acid, stearic acid, and It contained a large amount of the same saturated fatty acid, which hindered the catalytic action and had a limitation in that the synthesis yield of dimer acid was low. Accordingly, we aim to provide a method for producing high-quality, high-purity dimer acid using oleic acid as a monomer by devising an effective method to increase the synthesis yield of dimer acid while reducing the saturated fatty acids contained in palm oil.
이에 본 발명은 올레인산을 함유하는 팜유를 가수분해하여 지방산을 얻은 후, 이를 증류하여 포화지방산을 저감시키는 단계 (a); 단계 (a)에서 얻어진 지방산에 산화 촉매와 조촉매를 첨가한 후, 물을 넣고 촉매 반응시키는 단계 (b); 단계 (b)의 반응물을 냉각하고 인산을 처리하여 지방산의 합성 반응을 종결한 후, 여과하여 촉매 및 불순물을 제거하는 단계 (c) 및; 단계 (c)의 여과된 반응물을 증류하여 다이머산을 분리하는 단계 (d);를 포함하는 것을 특징으로 하는 올레인산을 단량체(monomer)로 하는 다이머산(dimer acid)의 생산방법을 제공한다.Accordingly, the present invention hydrolyzes palm oil containing oleic acid to obtain fatty acids, and then distills them to reduce saturated fatty acids (a); Adding an oxidation catalyst and a cocatalyst to the fatty acid obtained in step (a), then adding water and performing a catalytic reaction (b); Step (c) of cooling the reactant of step (b) and treating it with phosphoric acid to terminate the fatty acid synthesis reaction, followed by filtering to remove the catalyst and impurities; It provides a method for producing dimer acid using oleic acid as a monomer, comprising the step (d) of distilling the filtered reaction product of step (c) to separate dimer acid.
상기와 같은 제조방법을 통해 포화지방산의 함량이 저감되어 높은 다이머산의 합성수율을 가지며 고품질 및 고순도의 다이머산을 제조할 수 있으며, 올레인산을 함유하는 팜유를 가공하여 효과적인 지방산 조성으로 변화시킴으로써 이를 기존의 원료들을 대체하는 원료로 사용할 수 있다. Through the above manufacturing method, the content of saturated fatty acids is reduced, resulting in a high synthesis yield of dimer acid, making it possible to produce high-quality and high-purity dimer acid. By processing palm oil containing oleic acid and changing it into an effective fatty acid composition, it is possible to produce high-quality and highly purified dimer acid. It can be used as a substitute for raw materials.
하기에서는 본 발명의 다이머산의 생산방법을 각 단계별로 세분화해서 설명하고자 한다.In the following, the production method of dimer acid of the present invention will be explained in detail in each step.
<단계 (a): 올레인산을 함유하는 팜유를 가수분해하여 지방산을 얻은 후, 이를 증류하여 포화지방산을 저감시키는 단계><Step (a): Hydrolyzing palm oil containing oleic acid to obtain fatty acids, then distilling them to reduce saturated fatty acids>
본 단계는 올레인산을 함유하는 팜유를 가수분해하여 지방산을 얻은 후, 이를 증류하여 포화지방산을 저감시키는 단계이다. This step is to hydrolyze palm oil containing oleic acid to obtain fatty acids and then distill them to reduce saturated fatty acids.
본 단계에서 상기 팜유는, 당 업계에서 사용되는 팜유라면 어느 것에든 제한되지는 않으나 바람직하게 폐 팜유를 이용하는 것일 수 있다.In this step, the palm oil is not limited to any palm oil used in the industry, but preferably waste palm oil is used.
한편, 팜유를 가수분해하여 지방산을 얻게되면 팔미트산 40~46 중량%, 미리스트산 1~3 중량%, 스테아린산 2~5중량%로 포화지방산의 총량이 최대 54 중량%로 합성 수율이 나쁘며, 촉매작용에 장애가 된다는 한계가 있다. 이에 다량으로 함유된 포화지방산을 저감하는 것이 바람직하며, 이를 위해 당 업계에 공지된 기술이라면 어느 것에든 제한되지 않으나, 바람직하게는 증류를 이용하여 불포화지방산을 포화지방산으로부터 분리하는 것이 좋다. On the other hand, when fatty acids are obtained by hydrolyzing palm oil, it contains 40-46% by weight of palmitic acid, 1-3% by weight of myristic acid, and 2-5% by weight of stearic acid, and the total amount of saturated fatty acids is up to 54% by weight, resulting in poor synthesis yield. , there is a limitation that it becomes an obstacle to catalytic action. Accordingly, it is desirable to reduce the amount of saturated fatty acids contained in large amounts, and for this purpose, there is no limitation to any technology known in the art, but preferably, the unsaturated fatty acids are separated from the saturated fatty acids using distillation.
이때, 상기 증류는 분별 증류, 수증기 증류, 진공 증류, 분해 증류, 추출 증류 등 어느 것에든 제한되지는 않으나, 바람직하게는 분별 증류하는 것이 좋다. 더욱 바람직하게는 팜유를 가수분해하여 얻은 지방산을 분별 증류하여 포화지방산과 불포화지방산으로 분리한 후, 포화지방산의 함량을 줄이고 다이머산 합성에 좋은 올레인산과 리놀레산의 함량이 증가된 지방산을 원료로 회수하여 사용하였다. 또한, 분별 증류의 조건은 당 업계에 공지된 것이라면 어느 것에든 제한되지는 않으나, 분별 증류기의 하부 온도는 216 ~ 270℃이고 상부 온도는 245 ~ 247℃이며 압력은 20 내지 30torr의 조건에서 행해지는 것이 좋으며, 이로 인해 얻어지는 불포화지방산을 결정화하여, 지방산 원료로서 얻을 수 있다.At this time, the distillation is not limited to any of fractional distillation, steam distillation, vacuum distillation, decomposition distillation, extractive distillation, etc., but fractional distillation is preferred. More preferably, the fatty acids obtained by hydrolyzing palm oil are separated into saturated and unsaturated fatty acids by fractional distillation, and then the fatty acids with reduced content of saturated fatty acids and increased content of oleic acid and linoleic acid, which are good for dimer acid synthesis, are recovered as raw materials. used. In addition, the conditions of fractional distillation are not limited to those known in the art, but the lower temperature of the fractional distiller is 216 to 270°C, the upper temperature is 245 to 247°C, and the pressure is 20 to 30 torr. It is preferable, and the unsaturated fatty acid thus obtained can be crystallized and obtained as a fatty acid raw material.
한편, 불포화지방산을 포화지방산으로부터 분리하기 위해, 상기 증류 외에, 음이온 또는 비이온 계면활성제를 선택하여 사용할 수도 있다. 이때, 상기 음이온 또는 비이온 계면활성제로는 일 예로 알킬 벤젠 설포네이트(Alkyl benzen Sulfonate : ABS), 소디움 라우릭 설포네이트(Sodium Lauric Sulfonate) 또는 폴리글리콜 에테르(Polyglycol Ether)를 사용하는 것일 수 있으며, 바람직하게는 원료지방산 100 중량부에 대하여 상기 계면활성제 0.5~5 중량부를 물에 녹인 용액(0.5~5% 용액)을 첨가하여 유화한 후, 전리제 (Na2SO4 또는 NaCl)를 원료지방산 100 중량부에 대하여 0.5~5 중량부를 첨가하고, 0~10℃까지 냉각한 후 초원심분리기에서 분리하여 이중 고체부를 제거하고 액상화된 부분을 수세하여 이를 다이머산의 제조 원료로 사용할 수 있다. 이때, 계면활성제의 첨가량이 0.5 중량부 미만, 5 중량부를 초과하는 경우에는 포화지방산의 분리가 효율적으로 이루어지지 않아 원하는 지방산 조성을 얻을 수 없어, 다소 수율이 떨어진다. 전리제의 첨가량이 0.5 중량부 미만의 경우는 전리효과가 좋지 않아 지방산의 분리가 효율적으로 일어나지 않으며, 5중량부를 초과하는 경우에도 보다 나은 효과를 나타내지 못한다.Meanwhile, in order to separate unsaturated fatty acids from saturated fatty acids, in addition to the above distillation, anionic or nonionic surfactants may be selected and used. At this time, the anionic or nonionic surfactant may be, for example, Alkyl benzene Sulfonate (ABS), Sodium Lauric Sulfonate, or Polyglycol Ether. Preferably, 0.5 to 5 parts by weight of the surfactant is added to 100 parts by weight of the raw fatty acid to emulsify it (0.5 to 5% solution) in water, and then an ionizing agent (Na 2 SO 4 or NaCl) is added to 100 parts by weight of the raw fatty acid. Add 0.5 to 5 parts by weight, cool to 0 to 10°C, separate in an ultracentrifuge, remove the double solid portion, wash the liquefied portion, and use it as a raw material for producing dimer acid. At this time, if the amount of surfactant added is less than 0.5 parts by weight but more than 5 parts by weight, the separation of saturated fatty acids is not carried out efficiently and the desired fatty acid composition cannot be obtained, resulting in a slight decrease in yield. If the amount of the ionizing agent added is less than 0.5 parts by weight, the ionizing effect is poor and fatty acid separation does not occur efficiently, and even if the amount of the ionizing agent exceeds 5 parts by weight, it does not show a better effect.
<단계 (b): 얻어진 지방산에 촉매를 첨가한 후, 물을 넣고 촉매 반응시키는 단계><Step (b): Adding a catalyst to the obtained fatty acid, then adding water and performing a catalytic reaction>
본 단계는 상기 단계 (a)에서 얻어진 지방산에 산화촉매와 조촉매를 첨가한 후, 물을 넣고 촉매 반응시키는 단계이다.In this step, an oxidation catalyst and a cocatalyst are added to the fatty acid obtained in step (a), then water is added and a catalytic reaction is performed.
본 단계에서 상기 단계 (b)는, 바람직하게 단계 (a)에서 얻어진 지방산과 함께 대두 오일을 가수분해하여 얻은 대두 지방산을 사용하는 것일 수 있다. 더욱 바람직하게는 단계 (a)에서 얻어진 지방산과 상기 대두 지방산을 1:1 혼합하여 사용하는 것이 좋으며 이를 통해 팜올레인산 및 대두지방산을 이용하여 제조된 다이머산의 중간 grade 제품에 이용가능한 중간 grade 다이머산도 제조할 수 있다.In this step, step (b) may preferably use soybean fatty acid obtained by hydrolyzing soybean oil together with the fatty acid obtained in step (a). More preferably, it is better to use a 1:1 mixture of the fatty acid obtained in step (a) and the soybean fatty acid, thereby increasing the intermediate grade dimer acid that can be used in intermediate grade products of dimer acid manufactured using palm oleic acid and soy fatty acid. It can be manufactured.
본 단계에서 상기 산화촉매는 주촉매로서, 당 업계에 공지된 산화촉매라면 어느 것에든 제한되지 않으나 바람직하게는 몬모리나이트(monmorinite)를 70%~80중량% 함유한 백토(clay)를 사용하는 것이 좋다. 또한, 상기 조촉매는 합성 수율을 높이고 산화촉매 및 산화촉매로 인한 다이머산의 변색을 막기 위하여 산화 억제제를 사용하는 것이 바람직하고, 일예로 AlCl3, SnCl2, LiCO3, CaCO3, MgO, 과산화 벤질(benzyl), 카본(Carbon) 또는 모노에탄올아민(monoethanol amine) 중 선택되는 어느 하나 이상인 것일 수 있다. 더욱 바람직하게는 LiCO3을 조촉매로 사용하는 것이 좋다. In this step, the oxidation catalyst is the main catalyst, and is not limited to any oxidation catalyst known in the art, but preferably uses clay containing 70% to 80% by weight of monmorinite. It's good. In addition, it is preferable to use an oxidation inhibitor as the cocatalyst in order to increase the synthesis yield and prevent the oxidation catalyst and discoloration of dimer acid due to the oxidation catalyst, for example AlCl 3 , SnCl 2 , LiCO 3 , CaCO 3 , MgO, peroxidation It may be one or more selected from benzyl, carbon, or monoethanol amine. More preferably, LiCO 3 is used as a cocatalyst.
한편, 상기 산화촉매는 바람직하게 원료 지방산 100 중량부에 대하여 4~10 중량부를 사용하는 것이 좋으며, 주촉매의 첨가량이 4 중량부 미만인 경우 다이머산의 합성율이 떨어지고, 10 중량부를 초과하여 사용하더라도 다이머산의 합성효율은 증대되지 않는다. 또한, 상기 조촉매는 주촉매(산화촉매) 100 중량부에 대하여 1~6중량부를 사용하는 것이 좋으며, 조촉매의 첨가량이 1 중량부 미만인 경우 생성되는 다이머산의 함량이 75중량% 이하로 낮고, 6 중량부를 초과하여 사용할 경우는 다이머산의 함량이 높아지지 않는다.Meanwhile, the oxidation catalyst is preferably used in an amount of 4 to 10 parts by weight based on 100 parts by weight of raw fatty acid. If the main catalyst addition amount is less than 4 parts by weight, the synthesis rate of dimer acid decreases, and even if used in excess of 10 parts by weight, dimer The acid synthesis efficiency is not increased. In addition, it is recommended to use 1 to 6 parts by weight of the cocatalyst per 100 parts by weight of the main catalyst (oxidation catalyst). When the amount of cocatalyst added is less than 1 part by weight, the content of dimer acid produced is as low as 75% by weight or less, and when it is used in excess of 6 parts by weight, the content of dimer acid does not increase.
본 단계에서 상기 단계 (a)에서 얻어진 지방산에 산화촉매와 조촉매를 첨가한 후, 물을 넣고 촉매 반응시킨다. 이와 같이 물을 넣음으로써, 산화반응이 잘 일어나도록 강산 환경을 완하시키며, 압력을 상승시켜 합성 반응의 속도를 증가시켜주게 된다. 이때, 바람직하게는 원료 100 중량부에 대해 물 0.5~2 중량부를 가한 상태에서 200~250℃에서 3~8시간, 압력은 6~10㎏/㎠ 내에서 유지하는 것이 좋다. 이와 같은 조건으로 촉매 반응시켜 지방산과 촉매(산화촉매 및 조촉매) 간의 촉매 반응이 원활하게 이루어져 다이머산 합성 효율을 높일 수 있다.In this step, an oxidation catalyst and a cocatalyst are added to the fatty acid obtained in step (a), then water is added and a catalytic reaction is performed. By adding water in this way, the strong acid environment is relaxed so that the oxidation reaction can occur easily, and the pressure is raised to increase the speed of the synthesis reaction. At this time, it is preferable to maintain the pressure within 6 to 10 kg/cm2 at 200 to 250°C for 3 to 8 hours with 0.5 to 2 parts by weight of water added per 100 parts by weight of the raw material. By performing a catalytic reaction under these conditions, the catalytic reaction between the fatty acid and the catalyst (oxidation catalyst and cocatalyst) can be smoothly achieved, thereby increasing the efficiency of dimer acid synthesis.
<단계 (c): 촉매 반응한 반응물을 냉각하고 인산을 처리하여 지방산의 합성 반응을 종결한 후, 여과하여 촉매 및 불순물을 제거하는 단계><Step (c): Cooling the catalyzed reactants, treating them with phosphoric acid to terminate the fatty acid synthesis reaction, and then filtering to remove the catalyst and impurities>
본 단계에서는 상기 단계 (b)의 반응물을 냉각하고 인산을 처리하여 지방산의 합성 반응을 종결한 후, 여과하여 촉매 및 불순물을 제거하는 단계이다. 이와 같이 인산을 처리함으로써 지방산의 합성 반응을 종결시키며, 여과하여 반응물에 남아있는 불순물 중 금속물을 제거하게 된다. 이때, 바람직하게는 반응물을 110~140℃로 냉각하고, 80~90% 인산을 원료 100 중량부에 대해 0.05~1 중량부를 가하여 30분~1시간 30분 반응하는 것이 좋으며, 더욱 바람직하게는 130℃로 냉각하고, 85% 인산을 원료 100 중량부에 대해 0.08~1 중량부를 가하여 1시간 반응하는 것이 좋다. In this step, the reaction product of step (b) is cooled, treated with phosphoric acid to terminate the fatty acid synthesis reaction, and then filtered to remove the catalyst and impurities. By treating the phosphoric acid in this way, the fatty acid synthesis reaction is terminated, and metals among the impurities remaining in the reactant are removed by filtration. At this time, it is preferable to cool the reactant to 110 to 140°C, add 0.05 to 1 part by weight of 80 to 90% phosphoric acid per 100 parts by weight of the raw material, and react for 30 minutes to 1 hour and 30 minutes, more preferably 130 to 1 hour. It is recommended to cool to ℃, add 0.08 to 1 part by weight of 85% phosphoric acid per 100 parts by weight of raw material, and react for 1 hour.
<단계 (d): 여과된 반응물을 증류하여 다이머산을 분리하는 단계><Step (d): Distilling the filtered reactant to separate dimer acid>
본 단계에서는 상기 단계 (c)의 여과된 반응물을 증류하여 다이머산을 분리하는 단계이다.In this step, the dimer acid is separated by distilling the filtered reactant of step (c).
본 단계에서는, 상기 단계 (c)에서 여과된 반응물 내 다이머산의 전환율이 50~70%이므로 증류하여 이중의 미반응물을 제거함으로써 다이머산을 분리하였다.In this step, since the conversion rate of dimer acid in the reactant filtered in step (c) was 50 to 70%, dimer acid was separated by distillation to remove double unreacted products.
이를 통해 제조한 다이머산은 지방산 함량을 나타내는 산가가 190 이상, 지방 함량을 나타내는 검화가가 190 이상, 색상은 가드너 넘버(number) 8이하로 바람직하며, 포화지방산의 함량이 다량 제거되고 올레산, 리놀레산, 리놀렌산의 함량이 높아 다이머산의 합성수율이 향상되었다. 또한, 점도에 있어 윤활성이 우수하고, 저온에 유연성이 좋아 페인트, 도료, 폴리아마이드수지를 제품을 제조하는 데 있어 사용이 용이하며, 트리머산 함량이 높아 열적 안정성과 마모 저항성이 우수하여 윤활제 원료로써 사용하기에도 우수하다. 이에 기존 원료로 사용되는 톨유지방산, 대두지방산과 동등 이상으로 사용될 수 있을 것으로 판단된다.The dimer acid prepared through this method preferably has an acid value of 190 or more, which represents the fatty acid content, a saponification value that represents the fat content, of 190 or more, and a color of less than Gardner number 8. A large amount of saturated fatty acid content is removed, and oleic acid, linoleic acid, and linolenic acid are preferable. Due to the high content, the synthesis yield of dimer acid was improved. In addition, it has excellent lubricity in terms of viscosity and flexibility at low temperatures, making it easy to use in manufacturing paints, paints, and polyamide resin products. It is also used as a lubricant raw material due to its high trimer acid content and excellent thermal stability and abrasion resistance. It is also excellent to use. Accordingly, it is believed that it can be used at a level equal to or greater than that of tall oil fatty acid and soybean fatty acid used as existing raw materials.
이하, 본 발명의 내용을 하기 실시예를 통해 더욱 상세히 설명하고자 한다. 다만, 본 발명의 권리범위가 하기 실시예에만 한정되는 것은 아니고, 그와 등가의 기술적 사상의 변형까지를 포함한다.Hereinafter, the contents of the present invention will be described in more detail through the following examples. However, the scope of the present invention is not limited to the following examples, but also includes modifications of the technical idea equivalent thereto.
[실시예 1: 팜올레인산을 이용한 다이머산의 제조방법][Example 1: Method for producing dimer acid using palm oleic acid]
본 실시예에서는 팜올레인산을 이용하여 다이머산을 제조하였다.In this example, dimer acid was prepared using palm oleic acid.
팜유를 가수분해하여 팜유 지방산을 회수하였으며, 이를 분별 증류하여 포화지방산을 분리한 후, 불포화지방산을 증류로 회수한 것을 원료로 하였다. 이때, 분별 증류기의 하부 온도는 216 ~ 270℃이고, 상부 온도는 245 ~ 247℃이며, 압력은 20 ~ 30torr의 조건에서 행해지며, 이로 인해 얻어지는 불포화지방산을 결정화하여, 지방산 원료로서 사용하였다.Palm oil fatty acids were recovered by hydrolyzing palm oil, and the saturated fatty acids were separated by fractional distillation, and the unsaturated fatty acids were recovered by distillation as raw materials. At this time, the lower temperature of the fractional still was 216 to 270°C, the upper temperature was 245 to 247°C, and the pressure was 20 to 30 torr, and the resulting unsaturated fatty acid was crystallized and used as a fatty acid raw material.
상기에서 분리된 지방산 1,100 g을 취하여 고온·고압 반응기에 넣고 주촉매로서 산성백토(몬모리나이트(monmorinite) 70%~80중량% 함유) 50 g과 조촉매로서 LiCO3을 3 g 첨가하고, 물 10 g을 첨가하여 240℃에서 5시간 촉매 반응시켰으며, 이때 압력은 8 kg/cm2이었다. 반응이 끝난 후 냉각하여 130℃가 될 때 85% 인산 9 g을 처리하고 1시간 반응한 후(지방산의 합성 반응이 종결됨), 필터(여과)하여 촉매 및 불순물을 제거하였다. 이후, 이중의 미반응물을 제거하기 위하여 증류하였다. 최종적으로 다이머산을 630 g 얻었다.Take 1,100 g of the fatty acid separated above, put it in a high temperature/high pressure reactor, add 50 g of acid clay (containing 70% to 80% by weight of monmorinite) as a main catalyst and 3 g of LiCO 3 as a cocatalyst, and add water. 10 g was added and catalytic reaction was performed at 240°C for 5 hours, and the pressure at this time was 8 kg/cm 2 . After the reaction was completed, the reaction mixture was cooled to 130°C, treated with 9 g of 85% phosphoric acid, reacted for 1 hour (the fatty acid synthesis reaction was completed), and then filtered to remove the catalyst and impurities. Afterwards, it was distilled to remove double unreacted substances. Finally, 630 g of dimer acid was obtained.
[실시예 2: 팜올레인산, 대두지방산을 이용한 다이머산의 제조방법][Example 2: Method for producing dimer acid using palm oleic acid and soybean fatty acid]
본 실시예에서는 팜올레인산을 이용하여 다이머산을 제조하였다.In this example, dimer acid was prepared using palm oleic acid.
팜유를 가수분해하여 팜유 지방산을 회수하였으며, 이를 분별 증류하여 포화지방산을 분리한 후, 불포화지방산을 증류로 회수한 것을 원료로 하였다. 이때, 분별 증류기의 하부 온도는 216 ~ 270℃이고, 상부 온도는 245 ~ 247℃이며, 압력은 20 ~ 30torr의 조건에서 행해지며, 이로 인해 얻어지는 불포화지방산을 결정화하여 지방산 원료로 하였다. 또한, 대두 오일을 가수분해하여 대두 지방산을 회수한 것을 원료로 하였다.Palm oil fatty acids were recovered by hydrolyzing palm oil, and the saturated fatty acids were separated by fractional distillation, and the unsaturated fatty acids were recovered by distillation as raw materials. At this time, the lower temperature of the fractional still is 216 to 270°C, the upper temperature is 245 to 247°C, and the pressure is 20 to 30 torr, and the resulting unsaturated fatty acid is crystallized and used as a fatty acid raw material. In addition, soybean fatty acids were recovered by hydrolyzing soybean oil as a raw material.
상기에서 분리된 지방산 각각 550 g씩 1,100 g을 취하여 고온·고압 반응기에 넣고 주촉매로서 산성백토(몬모리나이트(monmorinite) 70%~80중량% 함유) 50 g과 조촉매로서 LiCO3을 3 g 첨가하고, 물 10 g을 첨가하여 240℃에서 5시간 촉매 반응시켰으며, 이때 압력은 8 kg/cm2이었다. 반응이 끝난 후 냉각하여 130℃가 될 때 85% 인산 9 g을 처리하고 1시간 반응한 후(지방산의 합성 반응이 종결됨), 필터(여과)하여 촉매 및 불순물을 제거하였다. 이후, 이중의 미반응물을 제거하기 위하여 증류하였다. 최종적으로 다이머산을 630 g 얻었다.1,100 g of 550 g each of the fatty acids separated above were placed in a high-temperature/high-pressure reactor, and 50 g of acid clay (containing 70% to 80% by weight of monmorinite) as a main catalyst and 3 g of LiCO 3 as a cocatalyst were added. Then, 10 g of water was added and catalytic reaction was performed at 240°C for 5 hours, and the pressure at this time was 8 kg/cm 2 . After the reaction was completed, the reaction mixture was cooled to 130°C, treated with 9 g of 85% phosphoric acid, reacted for 1 hour (the fatty acid synthesis reaction was completed), and then filtered to remove the catalyst and impurities. Afterwards, it was distilled to remove double unreacted substances. Finally, 630 g of dimer acid was obtained.
[비교예 1: 톨유지방산을 이용한 다이머산의 제조방법][Comparative Example 1: Method for producing dimer acid using tall oil fatty acid]
본 비교예에서는 톨유지방산(Tail Oil Fatty Acid, TOFA)을 이용하여 다이머산을 제조하였다.In this comparative example, dimer acid was prepared using Tall Oil Fatty Acid (TOFA).
톨유지방산 1,100 g을 취하여 고온·고압 반응기에 넣고 주촉매로서 산성백토(몬모리나이트(monmorinite) 70%~80중량% 함유) 50 g과 조촉매로서 LiCO3을 3 g 첨가하고, 물 10 g을 첨가하여 240℃에서 5시간 촉매 반응시켰으며, 이때 압력은 8 kg/cm2이었다. 반응이 끝난 후 냉각하여 130℃가 될 때 85% 인산 9 g을 처리하고 1시간 반응한 후(지방산의 합성 반응이 종결됨), 필터(여과)하여 촉매 및 불순물을 제거하였다. 이후, 이중의 미반응물을 제거하기 위하여 증류하였다. 최종적으로 다이머산을 650 g 얻었다.Take 1,100 g of tall oil fatty acid, put it in a high temperature/high pressure reactor, add 50 g of acid clay (containing 70% to 80% by weight of monmorinite) as a main catalyst, 3 g of LiCO 3 as a cocatalyst, and add 10 g of water. was added and catalytic reaction was performed at 240°C for 5 hours, and the pressure at this time was 8 kg/cm 2 . After the reaction was completed, the reaction mixture was cooled to 130°C, treated with 9 g of 85% phosphoric acid, reacted for 1 hour (the fatty acid synthesis reaction was completed), and then filtered to remove the catalyst and impurities. Afterwards, it was distilled to remove double unreacted substances. Finally, 650 g of dimer acid was obtained.
[비교예 2: 팜유지방산을 이용한 다이머산의 제조방법][Comparative Example 2: Manufacturing method of dimer acid using palm oil fatty acid]
본 실시예에서는 팜유지방산을 이용하여 다이머산을 제조하였다.In this example, dimer acid was prepared using palm oil fatty acid.
팜유를 가수분해하여 팜유 지방산을 회수한 것을 원료로 하였다. 상기에서 분리된 팜유지방산 1,100 g을 취하여 고온·고압 반응기에 넣고 주촉매로서 산성백토(몬모리나이트(monmorinite) 70%~80중량% 함유) 50 g과 조촉매로서 LiCO3을 3 g 첨가하고, 물 10 g을 첨가하여 240℃에서 5시간 촉매 반응시켰으며, 이때 압력은 8 kg/cm2이었다. 반응이 끝난 후 냉각하여 130℃가 될 때 85% 인산 9 g을 처리하고 1시간 반응한 후(지방산의 합성 반응이 종결됨), 필터(여과)하여 촉매 및 불순물을 제거하였다. 이후, 이중의 미반응물을 제거하기 위하여 증류하였다. 최종적으로 다이머산을 530 g 얻었다.The raw material was obtained by hydrolyzing palm oil and recovering palm oil fatty acids. Take 1,100 g of the palm oil fatty acid separated above, put it in a high temperature and high pressure reactor, add 50 g of acid clay (containing 70% to 80% by weight of monmorinite) as a main catalyst and 3 g of LiCO 3 as a cocatalyst, 10 g of water was added and catalytic reaction was performed at 240°C for 5 hours, and the pressure at this time was 8 kg/cm 2 . After the reaction was completed, the reaction mixture was cooled to 130°C, treated with 9 g of 85% phosphoric acid, reacted for 1 hour (the fatty acid synthesis reaction was completed), and then filtered to remove the catalyst and impurities. Afterwards, it was distilled to remove double unreacted substances. Finally, 530 g of dimer acid was obtained.
[비교예 3: 대두지방산을 이용한 다이머산의 제조방법][Comparative Example 3: Method for producing dimer acid using soybean fatty acid]
본 실시예에서는 대두지방산을 이용하여 다이머산을 제조하였다.In this example, dimer acid was prepared using soybean fatty acid.
대두 오일을 가수분해하여 대두 지방산을 회수한 것을 원료로 하였다. 상기에서 분리된 지방산 1,100 g을 취하여 고온·고압 반응기에 넣고 주촉매로서 산성백토(몬모리나이트(monmorinite) 70%~80중량% 함유) 50 g과 조촉매로서 LiCO3을 3 g 첨가하고, 물 10 g을 첨가하여 240℃에서 5시간 촉매 반응시켰으며, 이때 압력은 8 kg/cm2이었다. 반응이 끝난 후 냉각하여 130℃가 될 때 85% 인산 9 g을 처리하고 1시간 반응한 후(지방산의 합성 반응이 종결됨), 필터(여과)하여 촉매 및 불순물을 제거하였다. 이후, 이중의 미반응물을 제거하기 위하여 증류하였다. 최종적으로 다이머산을 640 g 얻었다.Soybean fatty acids were recovered by hydrolyzing soybean oil as a raw material. Take 1,100 g of the fatty acid separated above, put it in a high temperature/high pressure reactor, add 50 g of acid clay (containing 70% to 80% by weight of monmorinite) as a main catalyst and 3 g of LiCO 3 as a cocatalyst, and add water. 10 g was added and catalytic reaction was performed at 240°C for 5 hours, and the pressure at this time was 8 kg/cm 2 . After the reaction was completed, the reaction mixture was cooled to 130°C, treated with 9 g of 85% phosphoric acid, reacted for 1 hour (the fatty acid synthesis reaction was completed), and then filtered to remove the catalyst and impurities. Afterwards, it was distilled to remove double unreacted substances. Finally, 640 g of dimer acid was obtained.
[실험예 1: 실시예 1 및 2, 비교예1 내지 3의 분석결과][Experimental Example 1: Analysis results of Examples 1 and 2 and Comparative Examples 1 to 3]
본 실험예에서는 상기 실시예 1 및 2, 비교예 1 내지 3에서 제조한 다이머산의 지방산 조성과 다이머산 조성을 분석하였다. In this experimental example, the fatty acid composition and dimer acid composition of the dimer acid prepared in Examples 1 and 2 and Comparative Examples 1 to 3 were analyzed.
(C16:0)palmitic acid
(C16:0)
(C18:0)stearic acid
(C18:0)
(C18:1)Oleic acid
(C18:1)
(C18:2)linoleic acid
(C18:2)
(C18:3)linolenic acid
(C18:3)
대두지방산
(1:1)palm oleic acid,
Soybean fatty acid
(1:1)
그 결과, 표 1과 같이 실시예 1의 팜올레인산을 이용할 시 촉매 작용에 장애가 되는 포화지방산이 다량 제거되고 올레인산과 리놀레산, 리놀렌산의 함량이 높아 다이머산의 합성을 위한 좋은 원료임을 알 수 있었다. 이는 비교예 1 내지 3의 다른 식물유 지방산을 이용할 시와 비교하여도 좋은 결과임을 확인하였고 이를 통해 기존의 톨지방산과 대두지방산의 대체 원료로 사용되기에 적합한 것을 알 수 있었다. 또한, 상기 표 1과 실시예 2의 팜올레인산, 대두지방산(1:1 혼합)을 이용할 시 촉매 작용에 장애가 되는 포화지방산이 다량 제거되고 리놀레산, 리놀렌산의 함량이 높아 다미어산의 합성을 위한 좋은 원료임을 알 수 있었다.As a result, as shown in Table 1, when using the palm oleic acid of Example 1, a large amount of saturated fatty acids, which are obstacles to catalytic action, were removed and the contents of oleic acid, linoleic acid, and linolenic acid were high, making it a good raw material for the synthesis of dimer acid. This was confirmed to be a good result compared to the use of other vegetable oil fatty acids in Comparative Examples 1 to 3, and it was confirmed that it is suitable for use as an alternative raw material to existing tall fatty acids and soybean fatty acids. In addition, when using the palm oleic acid and soybean fatty acid (1:1 mixture) of Table 1 and Example 2, a large amount of saturated fatty acids that interfere with catalysis are removed and the content of linoleic acid and linolenic acid is high, making it a good raw material for the synthesis of damialic acid. I could see that it was.
(AV)Sanga
(AV)
(SV)blacksmith
(SV)
(Monomer)monomer
(Monomer)
(Dimer)dimer
(Dimer)
(Trimer)trimmer
(Trimer)
2Example
2
대두지방산
(1:1)palm oleic acid,
Soybean fatty acid
(1:1)
한편, 표 2와 같이 다이머산의 조성을 분석하였을 때, 실시예 1의 팜올레인산을 이용하여 제조한 다이머산은 산가와 검화가, 색상이 모두 바람직한 범위임을 알 수 있었다(산가(acid value, AV): 지방산 함량으로 190 이상이어야함, 검화가(saponification value, SV): 지방 함량으로 190 이상이어야 함, 색상(가드너 넘버) 8 이하가 바람직함). 또한, 실시예 2의 팜올레인산, 대두지방산(1:1 혼합)을 이용하여 제조한 다이머산도 산가와 검화가, 색상이 모두 바람직한 범위임을 알 수 있었다. 또한, 비교예 1 및 3의 점도는 7,880~8,230 cps인 것에 비교하여 실시예 1 및 2의 7,480~7,610 cps임에 따라 점도에 있어 윤활성이 우수하고 저온에 유연성이 좋아 페인트, 도료, 폴리아마이드수지를 제품을 제조하는 데 있어 사용이 용이하다. 또한, 실시예 1 및 2는 비교예들보다 트리머산 함량이 높아 열적 안정성과 마모 저항성이 우수하여 윤활제 원료로써 사용하기에 우수함을 알 수 있었다. 특히, 실시예 2의 결과를 바탕으로 팜올레인산 및 대두지방산을 이용하여 제조된 다이머산은 필요할 시 원료를 혼합하여 제조하여 중간 grade 다이머산을 제조하는 것이 가능하다는 것을 알 수 있었다. 이와 같이 다이머산 제조에 있어서 본원발명의 팜올레인산을 이용함으로써 기존의 톨지방산과 대두지방산의 대체 원료로 사용되기에 적합한 것을 알 수 있었다.Meanwhile, when the composition of dimer acid was analyzed as shown in Table 2, it was found that the acid value, saponification, and color of the dimer acid prepared using palm oleic acid in Example 1 were all within desirable ranges (acid value (AV): fatty acid Content must be more than 190, saponification value (SV): fat content must be more than 190, color (Gardner number) 8 or less is desirable). In addition, it was found that the acid value, saponification, and color of dimer acid prepared using palm oleic acid and soybean fatty acid (1:1 mixture) in Example 2 were all within desirable ranges. In addition, the viscosity of Comparative Examples 1 and 3 was 7,880 to 8,230 cps, while that of Examples 1 and 2 was 7,480 to 7,610 cps. Therefore, the viscosity has excellent lubricity and good flexibility at low temperatures, making it suitable for use in paints, paints, and polyamide resins. It is easy to use in manufacturing products. In addition, it was found that Examples 1 and 2 had a higher trimeric acid content than the comparative examples and had excellent thermal stability and wear resistance, making them excellent for use as a lubricant raw material. In particular, based on the results of Example 2, it was found that dimer acid prepared using palm oleic acid and soy fatty acid can be produced by mixing raw materials when necessary to produce intermediate grade dimer acid. In this way, by using the palm oleic acid of the present invention in the production of dimer acid, it was found that it is suitable for use as an alternative raw material to existing tall fatty acids and soybean fatty acids.
Claims (4)
단계 (a)에서 얻어진 지방산과 함께 대두 오일을 가수분해하여 얻은 대두 지방산을 원료로 사용하고 여기에 산화 촉매와 조촉매를 첨가한 후, 물을 넣고 촉매 반응시키는 단계 (b);
단계 (b)의 반응물을 냉각하고 인산을 처리하여 지방산의 합성 반응을 종결한 후, 여과하여 촉매 및 불순물을 제거하는 단계 (c) 및;
단계 (c)의 여과된 반응물을 증류하여 다이머산을 분리하는 단계 (d);를 포함하고,
상기 원료는 불포화지방산으로 올레인산, 리놀레산 및 리놀렌산을 함유하는 것을 특징으로 하는 올레인산을 단량체(monomer)로 하는 다이머산(dimer acid)의 생산방법.
(a) hydrolyzing palm oil containing oleic acid to obtain fatty acids and then distilling them to reduce saturated fatty acids;
Using soybean fatty acid obtained by hydrolyzing soybean oil together with the fatty acid obtained in step (a) as a raw material, adding an oxidation catalyst and a cocatalyst thereto, then adding water and performing a catalytic reaction (b);
Step (c) of cooling the reactant of step (b) and treating it with phosphoric acid to terminate the fatty acid synthesis reaction, followed by filtering to remove the catalyst and impurities;
It includes a step (d) of distilling the filtered reactant of step (c) to separate dimer acid,
A method for producing dimer acid using oleic acid as a monomer, wherein the raw materials contain oleic acid, linoleic acid, and linolenic acid as unsaturated fatty acids.
상기 팜유는,
폐 팜유인 것을 특징으로 하는 올레인산을 단량체(monomer)로 하는 다이머산(dimer acid)의 생산방법.
According to paragraph 1,
The palm oil is,
A method for producing dimer acid using oleic acid as a monomer, characterized in that it is waste palm oil.
상기 증류는,
분별 증류인 것을 특징으로 하는 올레인산을 단량체(monomer)로 하는 다이머산(dimer acid)의 생산방법.
According to paragraph 1,
The distillation,
A method for producing dimer acid using oleic acid as a monomer, characterized by fractional distillation.
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| KR101334397B1 (en) | 2013-04-18 | 2013-11-29 | 대원산업 주식회사 | Preparation method of dimer acid with high purity |
| KR20210106842A (en) * | 2020-02-21 | 2021-08-31 | 에스케이에코프라임 주식회사 | Manufacturing Method of Low Viscosity Dimer Acid |
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| KR101334397B1 (en) | 2013-04-18 | 2013-11-29 | 대원산업 주식회사 | Preparation method of dimer acid with high purity |
| KR20210106842A (en) * | 2020-02-21 | 2021-08-31 | 에스케이에코프라임 주식회사 | Manufacturing Method of Low Viscosity Dimer Acid |
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