KR970003956B1 - Preparation of refrigerator oil compatible with r-134a - Google Patents
Preparation of refrigerator oil compatible with r-134a Download PDFInfo
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- KR970003956B1 KR970003956B1 KR1019930010165A KR930010165A KR970003956B1 KR 970003956 B1 KR970003956 B1 KR 970003956B1 KR 1019930010165 A KR1019930010165 A KR 1019930010165A KR 930010165 A KR930010165 A KR 930010165A KR 970003956 B1 KR970003956 B1 KR 970003956B1
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- 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
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
- C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
- C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
- C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
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- 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
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
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- 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
- C10N2040/30—Refrigerators lubricants or compressors lubricants
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- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Lubricants (AREA)
Abstract
Description
본 발명은 새로운 대체냉매인 R-134a(1,1,1,2-테트라플루오르에탄)을 냉매로 사용한 가정용 냉장고용 냉도기유의 제조방법에 관한 것이다.The present invention relates to a method for producing cold air oil for a domestic refrigerator using a new alternative refrigerant R-134a (1,1,1,2-tetrafluoroethane) as a refrigerant.
종래의 냉매로 사용되어오던 R-12후레온 냉매는 오존층 파괴로 인하여 사용의 규제를 받고 있으며 이에 대응하기 위하여 새로운 냉매로 R-134a가 개발되었다. 그러나 R-134a는 종래의 R-12냉매에 비해 극성이 크므로 기존의 냉동기유로 사용되어 오던 나프텐계 광유나 알킬벤젠계 합성유등에 녹지않는 문제점을 갖고 있다. 따라서 미국, 일본, 영국등의 기술 선진국에서는 R-134a와 상용성이 있는 새로운 구조의 냉동기유 개발에 박차를 가하고 있으며 여러종류의 냉동기유가 보고되고 있다. 이미 보고된 R-134a용 냉동기유의 구조는 1~6개의 히드록시기를 갖는 네오펜틸글리콜, 트리메틸올프로판, 펜타에리스리톨, 디펜타에리스리톨등의 다가 알콜과 탄소수 2~9개의 모노지방산, 탄소수 2~10개의 2가 지방산으로 합성된 에스테르 화합물중 100℃에서 동점도가 1~100cSt인 화합물이 냉동기유로 쓰인다는 것이 알려져 있다.R-12freon refrigerant, which has been used as a conventional refrigerant, is regulated due to the destruction of the ozone layer. To cope with this, a new refrigerant, R-134a, has been developed. However, R-134a has a problem in that it is insoluble in naphthenic mineral oil or alkylbenzene synthetic oil, which has been used as a conventional refrigeration oil because of its greater polarity than conventional R-12 refrigerants. Therefore, the developed countries such as the United States, Japan, and the United Kingdom are spurring the development of a new structure of refrigeration oil compatible with R-134a, and various types of refrigeration oil have been reported. The structure of the refrigerator oil for R-134a that has been reported is polyhydric alcohols such as neopentylglycol, trimethylolpropane, pentaerythritol, dipentaerythritol having 1 to 6 hydroxy groups, monohydric acid having 2 to 9 carbon atoms and 2 to 10 carbon atoms. It is known that a compound having a kinematic viscosity of 1 to 100 cSt at 100 ° C. is used as a refrigeration oil among ester compounds synthesized with a divalent fatty acid.
그런데 상기의 에스테르 화합물들을 합성하기 위해서는 HCI, H2SO4, ρ-톨루엔-설폰산등의 산촉매 또는 IR-120, IR-210등과 같은 레진촉매를 용매와 함께 사용하게 된다. 그러나 산촉매를 사용하는 경우에는 이촉매들에 의해서 최종생성물에 산도(acidity)가 혼합되어 반응후에 산도를 제거하기 위한 추출공정을 추가로 설치해야하는 문제점이 있으며 또한 레진촉매를 사용하는 경우에는 반응물에 산도가 혼입되지는 않으나 수율이 80% 정도 내외로써 제조원가의 절감에 매우 불리하다는 문제점이 있다. 따라서 종래에는 이 문제를 해결하기 위하여 상기의 촉매 및 용매등을 전혀 사용하지 않는 무촉매 열반응에 의해 200℃ 이상의 고온에서 장시간 동안 반응시키므로써 상기의 에스테르 화합물들을 합성하여 반응물에 산도가 혼입되지 않도록하고 수율도 95% 이상으로 얻을 수 있었다. 그러나 무촉매, 열반응의 경우에는 용매를 사용하지 않기 때문에 반응물인 다가알콜과 지방산이 쉽게 용해되지 않으므로 반응이 완결되려면 적어도 12~16시간 정도의 반응시간이 소요되어 열손실이 매우 클 뿐만 아니라 고온에서 유기물들이 산화되어 최종생성물이 변색되는등의 문제점이 있다.However, in order to synthesize the ester compounds, an acid catalyst such as HCI, H 2 SO 4, ρ-toluene-sulfonic acid, or a resin catalyst such as IR-120 or IR-210 may be used together with a solvent. However, in the case of using an acid catalyst, acidity is mixed in the final product by these catalysts, and there is a problem in that an extraction process for removing acidity after the reaction has to be additionally installed. Although not mixed, there is a problem that the yield is about 80%, which is very disadvantageous in the reduction of manufacturing cost. Therefore, in order to solve this problem conventionally, by reacting for a long time at a high temperature of 200 ℃ or more by a non-catalytic thermal reaction that does not use any of the above catalysts and solvents to synthesize the ester compounds so that acidity is not mixed in the reactants. Yield was also obtained in more than 95%. However, in the case of non-catalyst and thermal reaction, since the solvent is not used, the reactant polyhydric alcohol and fatty acid are not easily dissolved. Therefore, the reaction takes at least 12 to 16 hours to complete the reaction. There is a problem in that the organic matter is oxidized in the final product discoloration.
본 발명에서는 이와같은 문제점을 해결하기 위하여 반응생성물인 상기의 에스테르 화합물들을 다음 반응에 용매로 사용하여 고체인 다가 알콜들과 지방산이 쉽게 용해될 수 있도록 하여 반응시간을 6~10시간으로 단축하므로써 열손실을 최소화하여 제조원가를 절감할 수 있도록 하였고, 이와 더불어 최종생성물이 변색되는 문제도 동시에 해결하는 새로운 제조방법을 발견했다.In the present invention, in order to solve such a problem, the above ester compound as a reaction product is used as a solvent in the next reaction so that the solid polyhydric alcohols and fatty acids can be easily dissolved, thereby reducing the reaction time to 6 to 10 hours. In addition to minimizing losses, manufacturing costs have been reduced, and new manufacturing methods have been found to solve the problem of discoloration of the final product.
본 발명을 상세히 설명하면 펜타에리스리톨 1몰에 대하여 탄소수 5~9개의 모노지방산 5~6몰을 넣고 200~250℃의 온도에서 장시간 반응시키면서 GC 크로마토그래피를 이용하여 반응의 진행상황을 조사하였다. 상기의 반응시 완결되기까지는 12~16시간의 반응시 소요되며 반응 완결후 미반응 모노지방산을 증류하여 제거하면 100℃에서 동점도가 15~32cSt인 냉동기유가 얻어진다. 얻어진 냉동기유의 ASTM색을 측정하고 반응시간을 결정하여 본 발명에 의한 제조방법과 비교하였다.When the present invention is described in detail, the progress of the reaction was investigated using GC chromatography while adding 5 to 6 moles of mono-fatty acid having 5 to 9 carbon atoms to 1 mole of pentaerythritol and reacting for a long time at a temperature of 200 to 250 ° C. It takes 12 to 16 hours to complete the reaction, and when the unreacted monofatty acid is removed by distillation, the refrigerator oil having a kinematic viscosity of 15 to 32 cSt at 100 ° C. is obtained. ASTM color of the obtained refrigeration oil was measured and the reaction time was determined and compared with the production method according to the present invention.
한편 본 발명에서는 펜타에리스리톨 1몰에 대하여 탄소수 5~9개의 모노지방산 5~6몰을 넣고 여기에 상기의 방법에 의해 합성된 냉동기유를 용매로 사용하여 고체인 다가알콜과 지방산이 쉽게 용해될 수 있도록 한다. 이 때 용매의 사용량은 전체 반응물의 5~20%가 되도록 첨가하고 200~250℃의 온도까지 반응시키면서 GC 크로마토그래피를 이용하여 반응 진행상황을 조사하였다. 본 반응이 완결되기까지는 6~10시간이 소요되며 반응완결후 미반응 모노지방산을 증류하여 제거하면 100℃에서 동점도가 15~32cSt인 냉동기유가 얻어진다. 제조된 냉동기유의 ASTM색과 반응시간을 위의 제조방법과 비교하므로써 반응시간을 단축시켜 열손실을 최소화하고 최종생성물이 변색되지 않도록 하여 제품의 부가가치를 높일 수 있다는 실험결과를 얻었다.Meanwhile, in the present invention, 5-6 mol of mono fatty acids having 5 to 9 carbon atoms are added to 1 mol of pentaerythritol, and solid polyhydric alcohol and fatty acid can be easily dissolved by using the refrigeration oil synthesized by the above method as a solvent. Make sure At this time, the amount of the solvent was added to 5 to 20% of the total reactants and the reaction progress was investigated by using GC chromatography while reacting to a temperature of 200 to 250 ° C. It takes 6 ~ 10 hours to complete the reaction. After completion of the reaction, unreacted monofatty acid is distilled off to obtain a refrigeration oil having a kinematic viscosity of 15 to 32 cSt at 100 ° C. By comparing the ASTM color and reaction time of the prepared refrigeration oil with the above manufacturing method, an experimental result was obtained that the reaction time can be shortened to minimize heat loss and the final product is not discolored to increase the added value of the product.
본 발명의 상세한 설명을 실시예를 들어 설명하면 다음과 같다.The detailed description of the present invention will be described below with reference to Examples.
실시예 1Example 1
교반기, 환류냉각기, 딘스타크장치, 온도계등이 장치된 4ℓ 케틀형 반응기에 펜타에리스리톨 408.6g(3몰), 2-에틸헥실산 1038.3g(7.2몰, 2-메틸헥실산 1405.1g(10.8몰)을 넣고 230℃에서 반응시키면서 2시간마다 시료를 채취하여 GC 크로마토그래피로 반응의 진행 상황을 관찰하였다. 또한 채취된 시료 각각의 ASTM색을 측정하여 그 결과를 표 1에 나타내었다.408.6 g (3 mol) of pentaerythritol, 1038.3 g of 2-ethylhexyl acid (7.2 mol, 1405.1 g of 2-methylhexyl acid (10.8 mol) The sample was taken every 2 hours while the reaction was carried out at 230 ° C. and the progress of the reaction was observed by GC chromatography, and the ASTM color of each sample was measured and the results are shown in Table 1.
[표 1] 반응진척도 및 ASTM-색Table 1 Reaction Progress and ASTM-Color
* 전화율(%) : 과량의 지방산을 제외한 모든 반응생성물의 GC넓이 %* Conversion rate (%):% GC area of all reaction products except excess fatty acid
** 수율(%) : 최종생성물의 GC넓이 %** Yield (%): GC area% of final product
*** ASTM D 1500-82에 의해 측정함*** Measured by ASTM D 1500-82
실시예 2Example 2
실시예 1과 동일한 반응기에 펜타에리스리톨 334.6g(2.46몰), 2-에틸헥실산 851.2g(5.91몰), 2-메틸헥실산 1152.2g(8.9몰)을 넣고, 여기에 용매로 실시예 1에 의해 합성된 최종생성물을 460ml 첨가하여 230℃에서 반응시키면서 2시간 마다 시료를 채취하여 GC 크로마토그래피로 반응의 진행상황을 관찰하였다. 또한 채취된 시료의 각각의 ASTM색을 측정하여 실시예 1의 경우와 비교하였다. 측정된 결과를 표2에 나타내었다.Into the same reactor as in Example 1, 334.6 g (2.46 mol) of pentaerythritol, 851.2 g (5.91 mol) of 2-ethylhexyl acid, and 1152.2 g (8.9 mol) of 2-methylhexyl acid were added to Example 1 as a solvent. 460ml of the final product synthesized was added, and samples were taken every 2 hours while reacting at 230 ° C., and the progress of the reaction was observed by GC chromatography. In addition, the respective ASTM colors of the collected samples were measured and compared with the case of Example 1. The measured results are shown in Table 2.
* 전화율(%) : 과량의 지방산을 제외한 모든 반응생성물의 GC넓이 %* Conversion rate (%):% GC area of all reaction products except excess fatty acid
** 수율(%) : 최종생성물의 GC넓이 %** Yield (%): GC area% of final product
*** ASTM D 1500-82에 의해 측정함*** Measured by ASTM D 1500-82
상기의 실시예에서 보여준 바와같이 종래의 합성방법에 의하면 반응이 완결되기까지 반응시간이 15시간정도 소요되나 본 발명에 의한 합성방법인 냉동기유를 용매로 사용하는 합성법에 의하면 반응시간이 9시간정도로 단축시킬 수 있고 따라서 열손실을 최소화하여 제조원가를 절감할 수 있을 뿐만 아니라 최종생성물이 변색되지 않아서 제품의 부가가치를 높일 수 있는 등의 우수한 작용효과가 있다.As shown in the above embodiment, according to the conventional synthesis method, the reaction time takes about 15 hours until the reaction is completed, but according to the synthesis method using the refrigerator oil, which is the synthesis method according to the present invention, as a solvent, the reaction time is about 9 hours. It can reduce the manufacturing cost by minimizing the heat loss, thus minimizing the heat loss, and there is an excellent effect, such as to increase the added value of the product because the final product is not discolored.
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| KR1019930010165A KR970003956B1 (en) | 1993-06-05 | 1993-06-05 | Preparation of refrigerator oil compatible with r-134a |
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| KR1019930010165A KR970003956B1 (en) | 1993-06-05 | 1993-06-05 | Preparation of refrigerator oil compatible with r-134a |
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