KR102656455B1 - Tetraester compound for using eco-friendly transformer oils and and lubricants and the manufacturing method of it - Google Patents

Tetraester compound for using eco-friendly transformer oils and and lubricants and the manufacturing method of it Download PDF

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KR102656455B1
KR102656455B1 KR1020230057444A KR20230057444A KR102656455B1 KR 102656455 B1 KR102656455 B1 KR 102656455B1 KR 1020230057444 A KR1020230057444 A KR 1020230057444A KR 20230057444 A KR20230057444 A KR 20230057444A KR 102656455 B1 KR102656455 B1 KR 102656455B1
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tetraester
acid
catalyst
composite
polyhydric alcohol
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유인재
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/34—Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/604—Polycarboxylic acid esters, the acid moiety containing more than two carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/36—Esters of polycarboxylic acids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/20—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances liquids, e.g. oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/14—Electric or magnetic purposes
    • C10N2040/16—Dielectric; Insulating oil or insulators

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

본 발명은 테트라에스테르 합성물 및 그 제조방법에 대한 것으로서 더욱 상세하게는 친환경적인 전기 절연유 및 윤활유로 사용이 가능한 테트라에스테르 합성물 및 그 제조방법에 대한 것이다.
본 발명에 따른 테트라에스테르 합성물은 다가알콜(Polyhydric Alcohol)과 혼합 지방산을 1 : 4의 몰(mol) 비로 된 테트라에스테르(Tetraester) 조성물과, 상기 조성물 중 상기 다가알콜의 0.001 내지 0.02 중량%의 촉매(Catalyst)를 포함한다.
또한, 상기 테트라에스테르 합성물에 있어서, 상기 다가알콜은 펜타에리트리톨(Pentaerythritol) 또는 디펜타에리트리톨(Dipentaerythritol)인 것이 바람직하다. 그리고 상기 혼합 지방산은 C6,C8,2EHA,C10를 구비하는 것이 바람직하다.
또한, 상기 테트라에스테르 합성물에 있어서, 상기 촉매는 산촉매(Acid catalyst)나 중성 촉매(Neutral catalyst) 중 적어도 어느 하나인 것이 바람직하다.
또한, 상기 테트라에스테르 합성물에 있어서, 상기 산촉매는 염산, 인산, 황산, PTSA(Para-Toluene Sulfonic Acid) 중 적어도 어느 하나인 것이 바람직하다. 그리고 상기 중성촉매는 디에세트산디부틸(Dibutyltin diacetate) 또는 티탄산 테트라-n-부틸(Tetra-n-butyl titanate) 중 적어도 어느 하나 인 것이 바람직하다.
또한, 상기 테트라에스테르 합성물에 있어서, 상기 혼합 지방산은 C6,C8, 2EHA의 각각 몰(mol) 비가 10 ~ 60%이며, C10을 몰(mol) 비로 0 ~ 40% 더 포함하는 것이 바람직하다.The present invention relates to a tetraester composite and a method for producing the same, and more specifically, to a tetraester composite that can be used as an environmentally friendly electrical insulating oil and lubricant and a method for producing the same.
The tetraester composite according to the present invention is a tetraester composition composed of polyhydric alcohol and mixed fatty acid in a molar ratio of 1:4, and a catalyst of 0.001 to 0.02% by weight of the polyhydric alcohol in the composition. Includes (Catalyst).
Additionally, in the tetraester composite, the polyhydric alcohol is preferably Pentaerythritol or Dipentaerythritol. And the mixed fatty acids preferably include C6, C8, 2EHA, and C10.
Additionally, in the tetraester composite, the catalyst is preferably at least one of an acid catalyst or a neutral catalyst.
Additionally, in the tetraester composite, the acid catalyst is preferably at least one of hydrochloric acid, phosphoric acid, sulfuric acid, and PTSA (Para-Toluene Sulfonic Acid). And the neutral catalyst is preferably at least one of dibutyl diecetate (Dibutyltin diacetate) or tetra-n-butyl titanate (Tetra-n-butyl titanate).
In addition, in the tetraester composite, the mixed fatty acids preferably contain C6, C8, and 2EHA in molar ratios of 10 to 60%, and further contain C10 in molar ratios of 0 to 40%.

Description

친환경 전기 절연유 및 윤활유로 사용이 가능한 테트라에스테르 합성물 및 그 제조방법{Tetraester compound for using eco-friendly transformer oils and and lubricants and the manufacturing method of it}Tetraester compound for using eco-friendly transformer oils and and lubricants and the manufacturing method of it}

본 발명은 테트라에스테르 합성물 및 그 제조방법에 대한 것으로서 더욱 상세하게는 친환경적인 전기 절연유 및 윤활유로 사용이 가능한 테트라에스테르 합성물 및 그 제조방법에 대한 것이다.The present invention relates to a tetraester composite and a method for producing the same, and more specifically, to a tetraester composite that can be used as an environmentally friendly electrical insulating oil and lubricant and a method for producing the same.

전기 절연유는 열전달 유체에 의한 온도 상승을 냉각시켜주는 냉각작용과 전기적 절연 기능을 수행하며, 주로 절연유가 유입된 변압기 콘덴서, 케이블, 차단기 등에 사용된다.Electrical insulating oil performs a cooling action and electrical insulation function by cooling down the temperature rise caused by the heat transfer fluid, and is mainly used in transformer condensers, cables, and circuit breakers into which insulating oil flows.

전 세계적으로 널리 사용되는 전기 절연유는 광유계 전기 절연유(Mineral oil), 식물성 오일(Vegetable oil) 및 합성 에스테르(Synthetic ester) 등 3가지가 있다.There are three types of electrical insulating oil widely used around the world: mineral oil, vegetable oil, and synthetic ester.

광유는 1910년부터 변압기의 절연매체로 사용되고 있으며, 원류로부터 증류하여 생산된 방향족, 나프펜 혼합물로 구성된다.Mineral oil has been used as an insulating medium in transformers since 1910, and is composed of a mixture of aromatics and naphphenes produced by distillation from the source water.

식물성 오일은 자연의 씨앗 등에서 추출한 오일로 포화지방산과 불포화 지방산의 혼합물로 트리글리셀라이드 형태이다. 그리고 합성 에스테르는 발암물질을 유발하고, 환경적으로 유해한 PCBs(Polychlorodinated biphenyls) 절연유를 대체하기 위해 일정 탄소수 갖는 포화지방산과 알코올과의 합성으로 제조된 에스테르계 화합물이다.Vegetable oil is an oil extracted from natural seeds and is a mixture of saturated and unsaturated fatty acids in the form of triglycerides. Synthetic esters are ester-based compounds produced by synthesizing saturated fatty acids with a certain number of carbon atoms and alcohols to replace polychlorodinated biphenyls (PCBs) insulating oils, which cause carcinogens and are environmentally harmful.

광유계 전기 절연유는 냉각성능과 변압기 효율측면에서 우수하나, 석유계 성분으로 구성되어 생분해성이 취약하기 때문에 사용 중 누설이나 사용 후 폐기 시 제기되는 근본적인 환경문제를 안고 있다. 또한, 인화점이 낮아 변전소에서 화재발생 시 큰 피해를 입히는 요인으로 작용하고 있다.Mineral oil-based electrical insulating oil is excellent in terms of cooling performance and transformer efficiency, but because it is composed of petroleum-based components and has poor biodegradability, it has fundamental environmental problems that arise when it leaks during use or is disposed of after use. In addition, the low flash point is a factor that causes significant damage in the event of a fire in a substation.

이에 따라 생분해성과 난연 성능이 우수한 바이오 기반의 식물성 오일과 합성 에스테르의 친환경 전기 절연유 사용과 연구가 증가하고 있는 추세이다.Accordingly, the use and research of eco-friendly electrical insulating oils made of bio-based vegetable oils and synthetic esters with excellent biodegradability and flame retardant performance are increasing.

한편 전세계적으로 사용되고 있는 식물성 오일 전기 절연유는 품질 요구치를 고려하여 탄소수 C8 ~ C18 분포를 갖는 트리글리세라이드 형태로 사용되고 있다. 이러한 식물성 오일 전기 절연유는 높은 생분해성, 낮은 독성, 높은 인화점 등으로 친환경성이 높은 장점을 갖고 있으나, 구성 성분 중 불포화 지방산의 함량이 높아 산화안정성이 나쁜 단점을 가지고 있다.Meanwhile, vegetable oil electrical insulating oil used around the world is used in the form of triglycerides with a carbon number distribution of C8 to C18, considering quality requirements. This vegetable oil electrical insulating oil has the advantage of being highly environmentally friendly due to high biodegradability, low toxicity, and high flash point, but has the disadvantage of poor oxidation stability due to the high content of unsaturated fatty acids among its components.

공개특허 제10-2019-0007890호(공개일자 2019년 01월 23일)Publication Patent No. 10-2019-0007890 (publication date: January 23, 2019) 미국 특허 US9,028,727호(등록일자 2015년 5월 12일)U.S. Patent No. US9,028,727 (registration date May 12, 2015)

본 발명은 식물성 오일 전기 절연유의 단점을 극복하고 수율이 높인 합성 에스테르 전기 절연유로 사용될 수 있는 테트라에스테르 합성물을 제공하는 것을 목적으로 한다.The purpose of the present invention is to overcome the disadvantages of vegetable oil electrical insulating oil and to provide a tetraester composite that can be used as a synthetic ester electrical insulating oil with increased yield.

본 발명에 따른 테트라에스테르 합성물은 다가알콜(Polyhydric Alcohol)과 혼합 지방산을 1 : 4의 몰(mol) 비로 된 테트라에스테르(Tetraester) 조성물과, 상기 조성물 중 상기 다가알콜의 0.001 내지 0.02 중량%의 촉매(Catalyst)를 포함한다. The tetraester composite according to the present invention is a tetraester composition composed of polyhydric alcohol and mixed fatty acid in a molar ratio of 1:4, and a catalyst of 0.001 to 0.02% by weight of the polyhydric alcohol in the composition. Includes (Catalyst).

또한, 상기 테트라에스테르 합성물에 있어서, 상기 다가알콜은 펜타에리트리톨(Pentaerythritol) 또는 디펜타에리트리톨(Dipentaerythritol)인 것이 바람직하다. 그리고 상기 혼합 지방산은 탄소 수가 C6,C8, 2EHA(2-Ethylhexanoic Acid
, C8),C10를 구비하는 것이 바람직하다.Additionally, in the tetraester composite, the polyhydric alcohol is preferably Pentaerythritol or Dipentaerythritol. And the mixed fatty acid has carbon numbers C6, C8, 2EHA (2-Ethylhexanoic Acid
, C8), and C10.

또한, 상기 테트라에스테르 합성물에 있어서, 상기 촉매는 산촉매(Acid catalyst)나 중성 촉매(Neutral catalyst) 중 적어도 어느 하나인 것이 바람직하다.Additionally, in the tetraester composite, the catalyst is preferably at least one of an acid catalyst or a neutral catalyst.

또한, 상기 테트라에스테르 합성물에 있어서, 상기 산촉매는 염산, 인산, 황산, PTSA(Para-Toluene Sulfonic Acid) 중 적어도 어느 하나인 것이 바람직하다. 그리고 상기 중성촉매는 디아세트산디부틸(Dibutyltin diacetate) 또는 티탄산 테트라-n-부틸(Tetra-n-butyl titanate) 중 적어도 어느 하나 인 것이 바람직하다.Additionally, in the tetraester composite, the acid catalyst is preferably at least one of hydrochloric acid, phosphoric acid, sulfuric acid, and PTSA (Para-Toluene Sulfonic Acid). And the neutral catalyst is preferably at least one of dibutyl diacetate or tetra-n-butyl titanate.

또한, 상기 테트라에스테르 합성물에 있어서, 상기 혼합 지방산은 C6,C8, 2EHA의 각각 몰(mol) 비가 10 ~ 60%이며, 탄소 수가 C10을 몰(mol) 비로 0 ~ 40% 더 포함하는 것이 바람직하다.In addition, in the tetraester composite, the mixed fatty acids preferably have a mole ratio of C6, C8, and 2EHA of 10 to 60%, and additionally contain 0 to 40% of C10 in mole ratio. .

본 발명에 따른 테트라에스테르 합성물 제조방법은 교반단계와, 진공단계와, 환류단계와, 냉각단계를 포함한다. 상기 교반단계는 다가알콜(Polyhydric Alcohol) 1 몰(mol)과 혼합 지방산 4 ~ 6 몰(mol)의 조성물과 상기 조성물 중 상기 다가알콜의 0.001 내지 0.02 중량%의 촉매(Catalyst)가 혼합된 혼합물에 공비물(Azotroping Agent)을 상기 혼합물 100 중량부에 대해 상기 혼합물의 3 ~ 20 파트(parts)를 넣고 질소(N2) 가스를 계속 주입하면서 160 ~ 180℃까지 온도가 올라가도록 가온을 하면서 300 ~ 400rpm으로 교반한다. 상기 진공단계는 상기 교반단계 중 82 ~ 87℃에서 진공을 가한다. 상기 환류단계는 상기 진공단계 중 130 ~ 140℃ 부근에서 리플럭스(reflux)한다. 상기 냉각단계는 수산기(OHV)가 10mg/KOH이하로 되면 100℃ 이하로 냉각시킨다.The method for producing a tetraester composite according to the present invention includes a stirring step, a vacuum step, a reflux step, and a cooling step. The stirring step is a mixture of a composition of 1 mole of polyhydric alcohol and 4 to 6 moles of mixed fatty acid, and a catalyst of 0.001 to 0.02% by weight of the polyhydric alcohol in the composition. Add 3 to 20 parts of the azeotroping agent for 100 parts by weight of the mixture and continue to inject nitrogen (N2) gas while heating the mixture to raise the temperature to 160 to 180°C at 300 to 400 rpm. Stir with . In the vacuum step, a vacuum is applied at 82 to 87°C during the stirring step. The reflux step is refluxed at around 130 to 140°C during the vacuum step. In the cooling step, when the hydroxyl value (OHV) falls below 10 mg/KOH, it is cooled to below 100°C.

또한, 상기의 테트라에스테르 합성물 제작방법에 있어서, 상기 다가알콜은 펜타에리트리톨(Pentaerythritol) 또는 디펜타에리트리톨(Dipentaerythritol)인 것이 바람직하다. 그리고 상기 혼합 지방산은 C6,C8, 2EHA(2-Ethylhexanoic Acid
)가 각각 10 ~ 60%의 몰(mol) 비와, C10이 0 ~ 40%의 몰(mol)비로 혼합되는 것이 바람직하다. 그리고 상기 촉매는 염산 또는 인산 또는 황산 또는 PTSA(Para-Toluene Sulfonic Acid)의 산촉매와, 디아세트산디부틸(Dibutyltin diacetate) 또는 티탄산 테트라-n-부틸(Tetra-n-butyl titanate)의 중성 촉매 중 적어도 어느 하나인 것이 바람직하다.Additionally, in the above method of producing a tetraester composite, the polyhydric alcohol is preferably Pentaerythritol or Dipentaerythritol. And the mixed fatty acids are C6, C8, 2EHA (2-Ethylhexanoic Acid
) is preferably mixed in a mole ratio of 10 to 60%, and C10 is mixed in a mole ratio of 0 to 40%. And the catalyst is at least one of an acid catalyst of hydrochloric acid, phosphoric acid, sulfuric acid, or PTSA (Para-Toluene Sulfonic Acid), and a neutral catalyst of dibutyl diacetate or tetra-n-butyl titanate. Either one is preferable.

본 발명에 의하면, 광유 전기 절연유를 대체할 수 있으며 친환경적일 뿐만 아니라 높은 수율과 뛰어난 물성을 가진 전기 절연유 및 그리스 윤활유(lubricating oil) 등의 기제(Base oil)로 사용될 수 있는 테트라에스테르 합성물을 제공할 수 있다.According to the present invention, it is possible to provide a tetraester composite that can replace mineral oil electrical insulating oil and is not only environmentally friendly, but can be used as a base oil for electrical insulating oil and grease lubricating oil with high yield and excellent physical properties. You can.

본 발명에 따른 테트라에스테르 합성물 및 그 제조방법의 일 실시예를 설명한다.An example of the tetraester composite and its preparation method according to the present invention will be described.

본 발명에 따른 테트라에스테르 합성물은 다가알콜(Polyhydric Alcohol)과 혼합 지방산을 1 : 4의 몰(mol) 비로 된 테트라에스테르(Tetraester) 조성물과, 상기 조성물 중 상기 다가알콜의 0.001 내지 0.02 중량%의 촉매(Catalyst)를 포함한다. The tetraester composite according to the present invention is a tetraester composition composed of polyhydric alcohol and mixed fatty acid in a molar ratio of 1:4, and a catalyst of 0.001 to 0.02% by weight of the polyhydric alcohol in the composition. Includes (Catalyst).

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여기서 상기 다가알콜은 펜타에리트리톨(Pentaerythritol) 또는 디펜타에리트리톨(Dipentaerythritol)이 사용된다. Here, the polyhydric alcohol is pentaerythritol or dipentaerythritol.

그리고 상기 혼합 지방산은 탄소 수가 C6, C8, 2EHA(2-Ethylhexanoic Acid
, C8), C10을 구비하는 것이 바람직하다. 이때 C6, C8, 2EHA은 각각 몰(mol) 비가 10 ~ 60%이며, C10은 몰(mol) 비로 0 ~ 40%로 구성된다.And the mixed fatty acid has carbon numbers C6, C8, 2EHA (2-Ethylhexanoic Acid
, C8), and C10. At this time, C6, C8, and 2EHA each have a mole ratio of 10 to 60%, and C10 has a mole ratio of 0 to 40%.

상기 촉매는 산촉매(Acid catalyst)나 중성 촉매(Neutral catalyst)가 각각 단독 또는 혼합하여 사용된다.The catalyst is an acid catalyst or a neutral catalyst, used alone or in combination.

산촉매로는 염산, 인산, 황산, PTSA(Para-Toluene Sulfonic Acid) 등이 사용되고, 중성촉매로는 디아세트산디부틸(Dibutyltin diacetate) 또는 티탄산 테트라-n-부틸(Tetra-n-butyl titanate) 등이 사용된다.Hydrochloric acid, phosphoric acid, sulfuric acid, and PTSA (Para-Toluene Sulfonic Acid) are used as acid catalysts, and dibutyl diacetate or tetra-n-butyl titanate are used as neutral catalysts. It is used.

본 발명에 따른 테트라에스테르 합성물 제조방법은 교반단계와, 진공단계와, 환류단계와, 냉각단계를 포함한다. The method for producing a tetraester composite according to the present invention includes a stirring step, a vacuum step, a reflux step, and a cooling step.

상기 교반단계는 교반기와 딘스타크 트랩(Dean-Stark Trap)이 부착된 4구 플래스크(flask)에 다가알콜 1 몰(mol)에 과량의 혼합 지방산 4 ~ 6 몰(mol)의 조성물과, 상기 조성물 중 상기 다가알콜에 0.001 내지 0.02 중량%의 PTSA(촉매)로 된 혼합물에 공비물(Azotroping agent)을 상기 혼합물 100 중량부에 대해 3 ~ 20 parts 넣고 적량의 질소(N2) 가스를 계속 주입하면서 대략 160 ~ 180℃까지 온도가 올라가도록 서서히 가온하면서 300 ~ 400rpm으로 교반한다. 여기서 공비물(Azotroping agent)은 벤젠(Benzene), 톨루엔(Toluene), 크실렌(Xylene), 석유 나프타(Petroleum naphtha) 등이 사용된다. 다가알콜과 혼합 지방산은 1 : 4의 몰(mol)로 결합을 하지만 반응을 촉진시키기 위하여 혼합 지방산을 과량으로 사용한다. 그래서 본 실시예에서 다가알콜과 혼합 지방산의 몰(mol) 비가 1 : 4 ~ 6이 되도록 하였다.The stirring step is a composition of 4 to 6 moles of excess mixed fatty acid with 1 mole of polyhydric alcohol in a four-necked flask equipped with a stirrer and Dean-Stark Trap, and In the composition, 3 to 20 parts of an azotroping agent was added to a mixture of 0.001 to 0.02% by weight of PTSA (catalyst) in the polyhydric alcohol, and an appropriate amount of nitrogen (N2) gas was continuously injected for 100 parts by weight of the mixture. Slowly heat and stir at 300 to 400 rpm until the temperature rises to approximately 160 to 180°C. Here, the azotroping agent used is Benzene, Toluene, Xylene, Petroleum naphtha, etc. Polyhydric alcohols and mixed fatty acids are combined in a molar ratio of 1:4, but mixed fatty acids are used in excess to promote the reaction. Therefore, in this example, the molar ratio of polyhydric alcohol and mixed fatty acid was 1:4 to 6.

상기 진공단계는 상기 교반단계 중 82 ~ 87℃에서 진공펌프를 가동하여 진공을 시작한다. The vacuum step begins by operating a vacuum pump at 82 to 87°C during the stirring step.

상기 환류단계는 상기 진공단계 중 130 ~ 140℃ 부근에서 리플럭스(reflux)한다. 반응 시간은 10 ~ 20 시간이며, 수산기(OHV)가 10mg/KOH 이하가 될 때까지 반응을 지속한다. 이후 미 반응 산과 수분, 공비물(Azotroping agent) 등을 제거하기 위해 진공도를 5 ~ 25mgHg 까지 다운(down) 시킨다.The reflux step is refluxed at around 130 to 140°C during the vacuum step. The reaction time is 10 to 20 hours, and the reaction continues until the hydroxyl group (OHV) is below 10 mg/KOH. Afterwards, the vacuum level is lowered to 5 to 25 mgHg to remove unreacted acids, moisture, and azotroping agents.

상기 냉각단계는 수산기(OHV)가 10mg/KOH이하로 되어 반응이 완료되면 100℃이하로 냉각시킨다. In the cooling step, when the hydroxyl group (OHV) becomes less than 10 mg/KOH and the reaction is completed, the reaction is cooled to less than 100°C.

냉각한 후 통상적인 방법으로 규조토, 산화알루미늄(Al2O3), 활성탄(activated carbon) 등을 처리한 후 여과한다.After cooling, it is treated with diatomaceous earth, aluminum oxide (Al2O3), activated carbon, etc. in a conventional manner and then filtered.

아래의 표 1 및 표 2는 본 실시예를 사용하여 시험한 실험예1 및 실험예2이며, 표 3은 실험예1 및 실험예2의 시험결과이다. 표 3에 알 수 있듯이 본 실시예에 따른 테트라에스테르 합성물은 수율이 99% 이상이며 뛰어난 물성을 가진 것을 알 수 있다.Tables 1 and 2 below show Experimental Examples 1 and 2 tested using this example, and Table 3 shows the test results of Experimental Examples 1 and 2. As can be seen in Table 3, the tetraester composite according to this example has a yield of over 99% and has excellent physical properties.

원료Raw material 단위unit 실투입량Actual input amount C10 Capric acidC10 Capric acid gg 259.74(1.5 mol)259.74(1.5 mol) C6 Hexanoic acidC6 Hexanoic acid gg 174.24(1.5 mol)174.24(1.5 mol) C8 Caprylic acidC8 Caprylic acid gg 216.32(1.5 mol)216.32(1.5 mol) C8 2EHAC8 2EHA gg 216.32(1.5 mol)216.32(1.5 mol) Pentaerythritol Pentaerythritol gg 136.15(1 mol)136.15(1 mol) PTSA PTSA gg 0.0380.038 Toluene Toluene gg 6060

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원료Raw material 단위unit 실투입량Actual input amount C6 Hexanoic acidC6 Hexanoic acid gg 174.24(1.5 mol)174.24(1.5 mol) C8 Caprylic acidC8 Caprylic acid gg 324.48(2.25 mol)324.48(2.25 mol) C8 2EHAC8 2EHA gg 324.48(2.25 mol)324.48(2.25 mol) Pentaerythritol Pentaerythritol gg 136.15(1 mol)136.15(1 mol) PTSA PTSA gg 0.0380.038 Toluene Toluene gg 6060

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실험항목Experiment items 실시예1Example 1 실시예2Example 2 시험방법Test Methods 외관Exterior 투명Transparency 투명Transparency IEC 61099IEC 61099 수분(%)moisture(%) 6565 4444 IEC 60814IEC 60814 색color 5252 4949 ISO 2211ISO 2211 산가(mg/KOH)Acid value (mg/KOH) 0.010.01 0.010.01 IEC 62021-2IEC 62021-2 OH가(mg/KOH)OH value (mg/KOH) 5.045.04 3.43.4 ASTM 1899-08ASTM 1899-08 점도(cst/40℃)Viscosity (cst/40℃) 28.0728.07 27.8927.89 ISO 3104ISO 3104 유동점(℃)Pour point (℃) -57-57 -61-61 ISO 3016ISO 3016 인화점(COC)Flash point (COC) 280280 274274 ISO 2719ISO 2719 비중(20℃)Specific gravity (20℃) 0.970.97 0.960.96 ISO 3075ISO 3075 수율(%)transference number(%) 97.997.9 99.4299.42

Claims (7)

다가알콜(Polyhydric Alcohol) 1 몰(mol)과 혼합 지방산 4 ~ 6 몰(mol)의 조성물과 상기 조성물 중 상기 다가알콜의 0.001 내지 0.02 중량%의 촉매(Catalyst)가 혼합된 혼합물에 공비물(Azotroping Agent)을 상기 혼합물 100 중량부에 대해 상기 혼합물의 3 ~ 20 파트(parts)를 넣고 질소(N2) 가스를 계속 주입하면서 160 ~ 180℃까지 온도가 올라가도록 가온을 하면서 300 ~ 400rpm으로 교반하는 교반단계와,
상기 교반단계 중 82 ~ 87℃에서 진공을 가하는 진공단계와,
상기 진공단계 중 130 ~ 140℃ 부근에서 리플럭스(reflux)하는 환류단계와,
수산기(OHV)가 10mg/KOH이하로 되면 100℃이하로 냉각시키는 냉각단계를 포함하는 것을 특징으로 하는 테트라에스테르 합성물 제작방법.Azotroping is added to a mixture of 1 mole of polyhydric alcohol, 4 to 6 moles of mixed fatty acid, and 0.001 to 0.02% by weight of a catalyst of the polyhydric alcohol in the composition. Add 3 to 20 parts of the mixture for 100 parts by weight of the mixture and stir at 300 to 400 rpm while continuously injecting nitrogen (N2) gas and heating to raise the temperature to 160 to 180°C. steps,
Among the stirring steps, a vacuum step of applying vacuum at 82 to 87°C,
Among the vacuum steps, a reflux step of refluxing around 130 to 140°C;
A method of producing a tetraester composite, comprising a cooling step of cooling to 100°C or less when the hydroxyl group (OHV) becomes less than 10mg/KOH. 제1항에 있어서,
상기 다가알콜은은 펜타에리트리톨(Pentaerythritol) 또는 디펜타에리트리톨(Dipentaerythritol)이며,
상기 혼합 지방산은 C6,C8, 2EHA(2-Ethylhexanoic Acid
)가 각각 10 ~ 60%의 몰(mol) 비와, C10이 0 ~ 40%의 몰(mol)비로 혼합되며,
상기 촉매는 염산 또는 인산 또는 황산 또는 PTSA(Para-Toluene Sulfonic Acid)의 산촉매와, 디아세트산디부틸(Dibutyltin diacetate) 또는 티탄산 테트라-n-부틸(Tetra-n-butyl titanate)의 중성 촉매 중 적어도 어느 하나인 것을 특징으로 하는 테트라에스테르 합성물 제작방법.According to paragraph 1,
The polyhydric alcohol is Pentaerythritol or Dipentaerythritol,
The mixed fatty acids are C6, C8, 2EHA (2-Ethylhexanoic Acid
) is mixed in a mole ratio of 10 to 60%, and C10 is mixed in a mole ratio of 0 to 40%,
The catalyst is at least one of an acid catalyst of hydrochloric acid, phosphoric acid, sulfuric acid, or PTSA (Para-Toluene Sulfonic Acid), and a neutral catalyst of dibutyl diacetate or tetra-n-butyl titanate. A method for producing a tetraester composite, characterized in that: 제1항 또는 제2항의 방법으로 제조된 것을 특징으로 하는 테트라에스테르 합성물.A tetraester composite prepared by the method of claim 1 or 2. 삭제delete 삭제delete 삭제delete 삭제delete
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JPH05132684A (en) * 1991-11-13 1993-05-28 I C I Japan Kk Base oil for lubricating oil and lubricating oil composition for apparatus using refrigerant hfc-134a
KR20080069246A (en) * 2005-12-05 2008-07-25 교도유시 가부시끼가이샤 Grease composition and bearing
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KR20190007890A (en) 2017-07-14 2019-01-23 주식회사 피.와이.씨 Preparation of tetraester of pentaerythritol having a low acid value and a small time-lapse change of the acid value

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KR20080069246A (en) * 2005-12-05 2008-07-25 교도유시 가부시끼가이샤 Grease composition and bearing
KR101640292B1 (en) * 2010-08-24 2016-07-15 케이에이치 네오켐 가부시키가이샤 Pentaerythritol tetraester
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KR20190007890A (en) 2017-07-14 2019-01-23 주식회사 피.와이.씨 Preparation of tetraester of pentaerythritol having a low acid value and a small time-lapse change of the acid value

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