KR930011928B1 - Process for improving the fluidity of mineral oil or mineral oil distillate - Google Patents

Process for improving the fluidity of mineral oil or mineral oil distillate Download PDF

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KR930011928B1
KR930011928B1 KR1019900006715A KR900006715A KR930011928B1 KR 930011928 B1 KR930011928 B1 KR 930011928B1 KR 1019900006715 A KR1019900006715 A KR 1019900006715A KR 900006715 A KR900006715 A KR 900006715A KR 930011928 B1 KR930011928 B1 KR 930011928B1
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vinylacetate
ethylene
mineral oil
weight
vinylpyrrolidone
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KR910001004A (en
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페이어 울프강
라이만 베르니
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훽스트 악치엔 게셀샤프트
라이첼트, 브론딘
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/146—Macromolecular compounds according to different macromolecular groups, mixtures thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
    • C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2368—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing heterocyclic compounds containing nitrogen in the ring

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Fats And Perfumes (AREA)

Abstract

The flow properties of mineral oils and mineral oil distillates are improved by addition of a mixture of an ethylene/vinyl acetate copolymer and an ethylene/vinyl acetate/N-vinylpyrrolidone terpolymer.

Description

미네랄 오일 및 미네랄 오일 증류물의 유동성 향상방법How to improve the fluidity of mineral oils and mineral oil distillates

본 발명은 에틸렌/비닐아세테이트 공중합체 및 에틸렌 비닐아세테이트/N-비닐피롤리돈 삼원공중합체의 혼합물의 참가에 의한 미네랄오일 및 미네랄오일 증류물(mimeral oil distillate)의 유동성 향상 방법에 관한 것이다.The present invention relates to a method for improving the fluidity of mineral oil and mineral oil distillate by participation of a mixture of ethylene / vinylacetate copolymer and ethylene vinylacetate / N-vinylpyrrolidone terpolymer.

출처에 따라서, 미네랄오일 및 미네랄오일 증류물은 낮은 온도에서 판상 결정체의 형태로 침전되는 여러가지 양의 파라핀을 함유하며, 여기에 오일이 여전히 흡장(occlusion)되어 있다. 이것은 미네랄오일 및 미네랄오일 증류물은 상당히 손상시킨다. 예를 들어 디젠연료의 경우에 상기로 인해 필터가 봉쇄되며, 그 결과 내연엔진 또는 제트엔진과 같은 연소 단위로의 연료공급이 불규칙하게 일어나거나 또는 완전히 정지된다. 유사하게 연소공장에서 연료 오일의 이송에 있어서 그러한 왁스 침전물이 낮은 온도로 인해 발생한다면 결함이 일어날 수 있다.Depending on the source, mineral oil and mineral oil distillate contain varying amounts of paraffin, which precipitate in the form of plate crystals at low temperatures, where the oil is still occluded. This significantly damages mineral oil and mineral oil distillate. For example, in the case of dyzen fuel, the filter is thus blocked, resulting in an irregular or completely stopped fuel supply to a combustion unit such as an internal combustion engine or a jet engine. Similarly, defects may occur if such wax deposits occur due to low temperatures in the transfer of fuel oil in a combustion plant.

비교적 긴 거리에 걸친 파이프라인을 통한 중간 증류물의 이송은 동절기에 파라핀 결정체에 의해 손상될 수 있다.Transfer of intermediate distillate through pipelines over relatively long distances can be damaged by paraffin crystals in winter.

파라핀 왁스의 침전은 통제하기 위하여, 부가제를 미네랄오일 및 미네랄오일 증류물, 특히 소위 중간 증류물에 기히는데, 이런 부가제는 파라핀 결정체의 크기 및 형상을 변경시켜 중간 증류물은 낮은 온도에서 유동성으로 남아 있다. 미레랄오일 및 미네랄오일 증류물을 위해 경제적으로 가장 중대한 유동점 강하제 및 유동향상제는 비닐알콜의 에스테르, 특별하게는 비닐아세테이트와 에틸렌 공중합체이다. 이러한 공중합체 및 그들의 용도는 예를 들어 DE-A 1,914,756 및 DE-A 2,515,805호에 기재되어 있다. 일본국 특허출원 제 58-80,386호(C.D. 99(1983) 215519)로부터 에틸렌, 비닐아세테이트 및 N-비닐-2-피롤리돈의 삼원공중합체를 유동향상제로서 사용하는 것이 공지되어 있다.In order to control the precipitation of paraffin wax, the additive is entrained in mineral oil and mineral oil distillates, especially so-called intermediate distillates, which modify the size and shape of the paraffin crystals so that the intermediate distillates are fluid at low temperatures. Remains. The most economically significant pour point depressants and flow enhancers for miraculous oil and mineral oil distillates are esters of vinyl alcohol, in particular vinyl acetate and ethylene copolymers. Such copolymers and their uses are described, for example, in DE-A 1,914,756 and DE-A 2,515,805. It is known from Japanese Patent Application No. 58-80,386 (C.D. 99 (1983) 215519) to use terpolymers of ethylene, vinyl acetate and N-vinyl-2-pyrrolidone as flow improvers.

실제로, 유동향상제로서 이들 공중합체의 효력은 그의 유동성을 향상시킬 미네랄오일 및 미네랄오일 증류물의 성질에 좌우되는 것으로 발견된다. 예를 들어, 중간 증류물의 경우에 그것은 그중에서도 n-파라핀 총함량 및 어떤 사슬 길이의 n-파라핀의 함량에 의해 영향을 받는다. 파라핀의, 함량 및 분포는 중간 증류물이 구성되는 경징, 중질(中質) 및 중질(重質) 증류물 분획에 의해서, 그리고 원유 출처에 의해서 결정된다.Indeed, the effectiveness of these copolymers as flow improvers is found to depend on the properties of mineral oils and mineral oil distillates that will improve their fluidity. For example, in the case of intermediate distillates it is influenced, among other things, by the total content of n-paraffins and the content of n-paraffins of any chain length. The content and distribution of paraffins is determined by the fraction of hard, heavy and heavy distillates from which the middle distillates are made and by the crude oil source.

따라서, 유동성을 증가시키는 그들의 탁월한 적합성에도 불구하고 에틸렌/비닐아세테이트 공중합체는 항상 바라는 효과를 보여주지 않는다. 이러한 경우에, 문제점은 그들을 다량으로 첨가하거나 또는 미네랄오일 및 미네랄오일 증류물을 저비점 탄화수소와 혼합함으로써 극복된다.Thus, despite their excellent suitability for increasing flowability, ethylene / vinylacetate copolymers do not always show the desired effect. In this case, the problem is overcome by adding them in large quantities or by mixing mineral oil and mineral oil distillate with low boiling hydrocarbons.

유동항생체의 유효성을 증가시키는 또다른 가능성은 부가재 배합물을 사용하는 것이다. 즉 DE-A-2,639,672호에는, 에틸렌 골격의 종합체와 C2- 내지 C56-올레핀의 공중합체의 혼합물이 게재되어 있는데, 이것들에 의해 동절기에 증류물 탄화수소 오일의 유동 성질이 상승적으로 향상된다.Another possibility to increase the effectiveness of flow antibiotics is to use additive formulations. That is, DE-A-2,639,672 discloses a mixture of a copolymer of an ethylene skeleton composite and a copolymer of C 2 -to C 56 -olefins, which synergistically improves the flow properties of distillate hydrocarbon oil in winter. .

US-A 3,660,057호에 따르면, 에틸렌/비닐아세테이트 공중합체와 n-파라핀이 제거된 고형 탄화수소의 혼합물을 유동 향상제로서 사용한다.According to US Pat. No. 3,660,057 a mixture of ethylene / vinylacetate copolymer and solid hydrocarbon free of n-paraffins is used as flow enhancer.

에틸렌-함유 중합체, 밀납, 지납 및/또는 장쇄 α-올레핀으로 구성된 혼합물이 US-A-4,019,878호에 원유 중간 증류물을 위한 유동항제로서 사용된다.Mixtures consisting of ethylene-containing polymers, beeswax, lead and / or long chain α-olefins are used in US Pat. No. 4,019,878 as flow agents for crude oil distillates.

비록 공지 물질이나 물질 혼합물이 많은 경우에 다양한 출저 및 조성의 미네랄 오일 및 미네랄오일 증류물의 유동성을 낮은 온도에서 향상시키고 때로는 매우 상당하게 향상시켰지만, 그럼에도 불구하고 가능한한 자유자재로 적용가능성을 가지거나 또는 상상의 경우에도 범용 적용가능성을 가지는 부가제가 필요하다.Although the known materials or mixtures of substances have improved the flowability of mineral oils and mineral oil distillates of various origins and compositions in many cases at low temperatures and sometimes very significantly, they are nevertheless freely applicable or In the case of imagination, additives with universal applicability are needed.

따라서 본 발명의 목적은 공지의 유동향상제에 비하여 매우 넓은 적용 범위를 가지는 부가제를 제공하는 것이다. 그들은 심지어 공지의 부가제가 효과를 약간만 보이거나 전혀 보이지 않는 오일들에 대해서도 유동성을 증가시켜야 한다.It is therefore an object of the present invention to provide additives having a very wide range of application compared to known flow enhancers. They should increase the flowability even for oils where known additives show little or no effect.

본 발명은 미네랄오일 및 미네랄오일 증류물의 유동성을 향상시키는 방법을 나타낸다. 그것은 에틸렌/비닐아세테이트 공중합체와 에틸렌/비닐아세테이트/N-비닐피롤리돈 삼원공중합체의 혼합물을 미네랄오일 또는 미네랄오일 증류물에 첨가하는 것으로 구성된다.The present invention represents a method for improving the fluidity of mineral oil and mineral oil distillate. It consists of adding a mixture of ethylene / vinylacetate copolymer and ethylene / vinylacetate / N-vinylpyrrolidone terpolymer to the mineral oil or mineral oil distillate.

놀랍게도, 본 발명에 따른 방법은 미네랄오일 및 미네랄오일 증류물에서 파라핀의 침점은 효과적으로 억제하며 침전되어 있을 수도 있는 파라핀 결정체를 현탁 상태로 유지함을 발견하였다. 따라서 새로운 방법에 따라 사용되는 부가제는 저하된 온도에서 탄화수소 혼합물의 점도의 증가를 방해하며 유동점을 저하시킨다. 본 발명의 방법은 미네랄오일 및 그의 증류 생성물의 유동성을 향상시키는데 그들의 점성 및 정량 조성에 무관하게 적절한 것으로 밝혀졌다. 두 개의 성분이 서로를 상승적으로 증대시키는 것이 특히 중요하다. 따라서 중합체 혼합물의 효력은 그의 성분들의 효력이 합보다 더 크다.Surprisingly, the process according to the invention has been found to effectively inhibit paraffin deposits in mineral oils and mineral oil distillates and to maintain suspended paraffin crystals which may be precipitated. The additive used according to the new method thus prevents the increase of the viscosity of the hydrocarbon mixture at lowered temperatures and lowers the pour point. The process of the present invention has been found to be suitable for improving the fluidity of mineral oils and their distillation products, regardless of their viscosity and quantitative composition. It is particularly important that the two components synergistically increase each other. Thus the potency of the polymer mixture is greater than the sum of the potents of its components.

본 발명에 따라 사용되는 에틸렌/비닐아세테이트 공중합체는 20 내지 40중량%의 비닐아세테이트를 함유한다. 25 내지 35중량%의 비닐아세테이트를 갖는 공중합체가 특히 적절한 것으로 밝혀졌다. 독일연방공화국 표준 DIN 53 019에 준하여 회전식 점도계[하이케(Haake)사에서 제조]로 140℃에서 측정된 그들의 점도는 30 내지 1000mPa.s, 특별하게는 30 내지 250mPa.s이다.The ethylene / vinylacetate copolymers used according to the invention contain 20 to 40% by weight of vinylacetate. Copolymers having 25 to 35% by weight of vinyl acetate have been found to be particularly suitable. Their viscosity measured at 140 ° C. with a rotary viscometer (manufactured by Haake) according to the Federal Republic of Germany standard DIN 53 019 is 30 to 1000 mPa · s, in particular 30 to 250 mPa · s.

100개의 CH2기에 대해서, 그들은 비닐아세테이트의 아세테이트 라디칼에서 유래하지 않은 CH3기를 측쇄에 1내지 10개, 바람직하게는 2 내지 7개를 함유한다. 여기에서 CH3기의 수의 결정은 H-NMR 분광분석으로 수행하였다.For 100 CH 2 groups they contain 1 to 10, preferably 2 to 7, CH 3 groups in the side chain not derived from the acetate radical of vinylacetate. The determination of the number of CH 3 groups here was carried out by H-NMR spectroscopy.

에틸렌/비닐아세테이트 공중합체의 제법은 공지되어 있다. 그것은 예를 들면 단량체 혼합물을 자유 라디칼을 형성시키는 개시제의 존재하에서 5 내지 15MPa의 압력에서 70 내지 150℃의 온도에서 중합반응시킴으로써 수행될 수 있다. 시용되는 반응매질은 유기용매 또는 톨루엔 같은 현탁제일 수 있다.The preparation of ethylene / vinylacetate copolymers is known. It can be carried out, for example, by polymerizing the monomer mixture at a temperature of 70 to 150 ° C. at a pressure of 5 to 15 MPa in the presence of an initiator which forms free radicals. The reaction medium applied may be an organic solvent or a suspending agent such as toluene.

유동향상제 혼합물의 두 번째 성분으로서 사용되는 에틸렌/비닐아세테이트/N-비닐피롤리돈 삼원공중합체는 15 내지 50중량%, 특별하게는 20 내지 35중량%의 비닐아세테이트 및 0.5 내지 10중량%, 특별하게는 1.0 내지 5.0중량%의 N-비닐피롤리돈을 함유한다. 그들의 점도는 에틸렌/비닐아세테이트 공중합체의 경우에서와 동일한 방식으로 측정하였으며, 100내지 5000mPa.s이고 특별하게는 150 내지 1500mPa.s이다.The ethylene / vinylacetate / N-vinylpyrrolidone terpolymer used as the second component of the rheology mixture is 15 to 50% by weight, especially 20 to 35% by weight of vinyl acetate and 0.5 to 10% by weight, special Preferably 1.0 to 5.0% by weight of N-vinylpyrrolidone. Their viscosity was measured in the same manner as in the case of ethylene / vinylacetate copolymers, 100 to 5000 mPa · s and in particular 150 to 1500 mPa · s.

에틸렌/비닐아세테이트/N-비닐프롤리돈 삼원공중합체의 제법은 공지되어 있다. 그것은 예를 들면 단량체 혼합물을 오오토클레이브 내에서 자유 라디칼을 형성시키는 개시제의 존재하에 5MPa 이상의 압력에서 60℃ 이상의 온도에서 중합반응시킴으로써 수행될 수 있다.

Figure kpo00001
5중량%의 에틸렌을 용해시키는 유기용매를 반응물질로서 사용된다. 메틴올, t-부탄올, 벤젠 및 디옥산이 적절하다[참조 : FR 1,392,353].The preparation of ethylene / vinylacetate / N-vinylprolidone terpolymers is known. It may be carried out, for example, by polymerizing the monomer mixture at a temperature of at least 60 ° C. at a pressure of at least 5 MPa in the presence of an initiator which forms free radicals in the autoclave.
Figure kpo00001
An organic solvent which dissolves 5% by weight of ethylene is used as the reactant. Methinol, t-butanol, benzene and dioxane are suitable (FR 1,392,353).

부가제 혼합물에서 두 개의 중합체의 중량비는 넓은 한계내에서 변할 수 있다. 에틸렌/비닐아세테이트 공중합체 및 에틸렌/비닐아세테이트/N-비닐피롤리돈 삼원공중합체를 1 : 1 내지 100 : 1의 중량비로 사용하는 것이 적절한 것으로 밝혀졌다. 공중합체 및 삼원공중합체를 3 : 1 내지 20 : 1의 중량비로 함유하는 혼합물이 바람직하다.The weight ratio of the two polymers in the additive mixture can vary within wide limits. It has been found suitable to use ethylene / vinylacetate copolymers and ethylene / vinylacetate / N-vinylpyrrolidone terpolymers in a weight ratio of 1: 1 to 100: 1. Preferred are mixtures containing a copolymer and terpolymer in a weight ratio of 3: 1 to 20: 1.

본 발명에 따른 방법은 미네랄오일 및 미네랄오일 증류물 둘다의 유동성을 향상시킨다. 용어 미네랄오일이란 여기서는 특별하게는 원유, 및 중질 연료오일 같은 잔류물을 의미함은 당연하다. 비점 약 150 내지 400℃의 탄화수소 분획을 미네랄오일 증류물로 표현한다. 이들로는 에를들면 페트롤륨, 경질연료오일 및 디젤연료가 있다. 연료오일 EL 및 디젤오일 같은 중간 증류물은 특히 중요하다.The process according to the invention improves the flowability of both mineral oil and mineral oil distillate. The term mineral oil is naturally meant here to mean residues, in particular crude oil, and heavy fuel oil. The hydrocarbon fraction having a boiling point of about 150 to 400 ° C. is expressed as mineral oil distillate. These include, for example, petroleum, light fuel oil and diesel fuel. Intermediate distillates such as fuel oil EL and diesel oil are particularly important.

두 중합체의 혼합물을, 용액을 기준으로 하여 20 내지 70중량%의 중합체를 함유하는 용액의 형태로, 미네랄오일 또는 미네랄오일 증류물에 가한다. 적절한 용매는 지방족 또는 방향족 탄화수호 또는 탄화수소 혼합물이며. 예를 들면 나프타 분획이다. 케로센이 특히 적절하다. 중합체의 양은 미네랄오일 또는 미네랄오일 분획을 기준으로 하여 0.001 내지 2중량%, 바람직하게는 0.005 내지 0.5중량%의 양이어야 한다.A mixture of the two polymers is added to the mineral oil or mineral oil distillate in the form of a solution containing 20 to 70% by weight of polymer, based on the solution. Suitable solvents are aliphatic or aromatic hydrocarbons or hydrocarbon mixtures. For example the naphtha fraction. Kerosene is particularly suitable. The amount of polymer should be from 0.001 to 2% by weight, preferably 0.005 to 0.5% by weight, based on mineral oil or mineral oil fraction.

중합체 혼합물은 단독으로 사용할 수 있거나, 또는 다른 부가제와 함께, 예를 들어 다른 유동점 억제제 또는 탈왁스 조제와 함께, 부식저해제, 산화방지제, 슬러지 저해제 및 클라우드 포인트 저하용 부가제와 함께 또한 사용할 수 있다.The polymer mixtures may be used alone or in combination with other additives, for example with other pour point inhibitors or dewaxing aids, as well as additives for corrosion inhibitors, antioxidants, sludge inhibitors and cloud point lowering. .

본 발명에 따른 방법은 뒤따를 실시예들에 의해 더욱 상세하게 설명한다.The method according to the invention is explained in more detail by the following examples.

실시예 1∼4는 본 발명에 따른 방법에 관한 것이다 : 실시예 5∼7은 비교시험의 결과를 재현하며, 에틸렌/비닐아세테이트 공중합체를 단독으로(실시예 5 및 6) 그리고 에틸렌/비닐아세테이트/N-비닐피롤리돈 삼원 공중합체를 단독으로(실시예 7)사용하여 얻어졌다.Examples 1 to 4 relate to the process according to the invention: Examples 5 to 7 reproduce the results of comparative tests, using ethylene / vinylacetate copolymer alone (Examples 5 and 6) and ethylene / vinylacetate It was obtained using / N-vinylpyrrolidone terpolymer alone (Example 7).

탐구된 유동성 향상 방법의 유효성은 ＂냉 필터 플러킹 테스트(CEPP 테스트)를 참조하여 설명된다. 시험은 DIN 51 428에 준하여 수행한다. 그것은 문헌[J. of the Inst. of pEtr., 52권, 1966년 6월, 173∼185면]에 또한 간행되어 있다.The effectiveness of the fluidity improvement methods explored is described with reference to the Quench Filter Flicking Test (CEPP Test). The test is carried out in accordance with DIN 51 428. It is described in J. of the Inst. of pEtr., Vol. 52, June 1966, pp. 173-185.

세가지 중간 증류물 M1,M2 및 M3을 시험용으로 사용한다. 그들은 표 1에 요약된 성질 데이터를 특징으로 한다.Three middle distillates M1, M2 and M3 are used for testing. They are characterized by the property data summarized in Table 1.

[실시예 1∼8]EXAMPLES 1-8

뒤따를 실시예에서는, 하기로 특징되는 중합체를 단독으로 또는 혼합물로서 사용한다.In the examples that follow, the polymers characterized below are used alone or as mixtures.

A : 에틸렌/비닐아세테이트 공중합체 : 30.5중량%의 비닐아세테이트 함량 및 140℃에서 30mPa.s의 점도.A: ethylene / vinylacetate copolymer: a vinylacetate content of 30.5% by weight and a viscosity of 30 mPa · s at 140 ° C.

B : 에틸렌/비닐아세테이트 공중합체 : 29 .8중량%의 비닐아세테이트 함량 및 140℃에서 80mPa.s의 점도.B: ethylene / vinylacetate copolymer: 29.8 wt% vinylacetate content and a viscosity of 80 mPa · s at 140 ° C.

C : 에틸렌/비닐아세테이트/N-비닐피롤리돈 삼원공중합체 : 23.2중량%의 비닐아세테이트 함량 및 1.4중량의 N-비닐피롤리돈 및 140℃에서 230mPa.s의 점도.C: ethylene / vinylacetate / N-vinylpyrrolidone terpolymer: 23.2 wt% vinylacetate content and 1.4 wt. N-vinylpyrrolidone and a viscosity of 230 mPa · s at 140 ° C.

중합체의 비닐아세테이트 함량은 열분해(pyrolysis)법에 의해 결정한다. 이를 위하여, 200mg의 중합체를 열분해 플라스크에서 300mg의 순수한 폴리에틸렌과 5분 동안 450℃에서 가열하고 크랙킹 기체를 250ml 둥근-바닥 플라스크에 수집한다. 형성된 아세트산을 NaI/KIO3용액과 반응시키고 방출된 요오드를 Na2S2O3용액으로 적정한다.The vinyl acetate content of the polymer is determined by pyrolysis method. To this end, 200 mg of polymer is heated in a pyrolysis flask with 300 mg of pure polyethylene at 450 ° C. for 5 minutes and the cracking gas is collected in a 250 ml round-bottom flask. The acetic acid formed is reacted with NaI / KIO 3 solution and the released iodine is titrated with Na 2 S 2 O 3 solution.

중합체의 N-비닐피롤리돈 함량은 듀마(Dumas)법에 의해 결정된 중합체의 질소 함량으로부터 계산한다.The N-vinylpyrrolidone content of the polymer is calculated from the nitrogen content of the polymer determined by the Dumas method.

표 2는 미네랄오일 및 미네랄오일 증류물의 유동성을 향상시키는 본 발명에 따른 방법의 효력에 관한 데이터를 갖는다.Table 2 has data on the effectiveness of the process according to the invention for improving the flowability of mineral oil and mineral oil distillate.

[표 1]TABLE 1

Figure kpo00002
Figure kpo00002

[표 2]TABLE 2

Figure kpo00003
Figure kpo00003

Claims (9)

에틸렌/비닐아세테이트 공중합체 및 에틸렌/비닐아세테이트/N-비닐필로리돈 삼원공중합체의 혼합물을 미네랄오일 또는 미네랄 오일 증류물에 첨가함을 특징으로 하는 미네랄오일 및 미네랄오일 증류물의 유동성 향상방법.A method of improving fluidity of mineral oil and mineral oil distillate, characterized by adding a mixture of ethylene / vinylacetate copolymer and ethylene / vinylacetate / N-vinylphyllolidon terpolymer to mineral oil or mineral oil distillate. 제1항에 있어서, 에틸렌/비닐아세테이트 공중합체는 20 내지 40중량%의 비닐아세테이트를 함유하며 140℃에서 측정된 30 내지 1000mPa.s의 점도를 가지며, 그리고 CH2기 100개에 대하여 비닐아세테이트의 아세테이트 라디칼에서 유래하지 않은 CH3기 1 내지 10개를 측쇄에 가지는 방법.The ethylene / vinylacetate copolymer according to claim 1, which contains 20 to 40% by weight of vinylacetate and has a viscosity of 30 to 1000 mPa · s measured at 140 ° C., and of vinylacetate for 100 CH 2 groups. A process having from 1 to 10 CH 3 groups not derived from an acetate radical in the side chain. 제1항에 있어서, 에틸렌/비닐아세테이트/N-비닐피롤리돈 삼원공중합체는 15 내지 50중량%의 비닐아세테이트 및 0.5 내지 10중량%의 N-비닐피롤리돈을 함유하며, 140℃에서 측정된 100 내지 500mPa.s의 점도를 가지는 방법.The ethylene / vinylacetate / N-vinylpyrrolidone terpolymer of claim 1 contains 15-50% by weight of vinylacetate and 0.5-10% by weight of N-vinylpyrrolidone, measured at 140 ° C. Having a viscosity of between 100 and 500 mPa · s. 제1항에 있어서, 에틸렌/비닐아세테이트 공중합체 및 에틸렌/비닐아세테이트/NThe ethylene / vinylacetate copolymer and ethylene / vinylacetate / N according to claim 1 -비닐피롤리돈 삼원 공중합체를 1 : 1 내지 100 : 1의 중량비로 시용하는 방법.A method in which a vinylpyrrolidone terpolymer is applied in a weight ratio of 1: 1 to 100: 1. 에틸렌/비닐아세테이트 공중합체 및 에틸렌/비닐아세테이트/N-비닐피롤리돈 삼원공중합체의 혼합물을 0.001 내지 2중량% 함유하는, 유동 거동이 향상된 미네랄오일 또는 미네랄오일 증류물.An improved flow or mineral oil or mineral oil distillate containing 0.001 to 2% by weight of a mixture of ethylene / vinylacetate copolymer and ethylene / vinylacetate / N-vinylpyrrolidone terpolymer. 제2항에 있어서, 에틸렌/비닐아세테이트 공중합체는 25 내지 35중량%의 비닐아세테이트를 포함하며, 140℃에서 측정된 30 내지 250mPa.s의 점도를 가지며, 그리고 CH2기 100개에 대하여 비닐아세테이트의 아세테이트 라디칼에서 유래하지 않은 CH3기 2 내지 7개를 측쇄에 가지는 방법.3. The ethylene / vinylacetate copolymer of claim 2 comprising 25 to 35% by weight of vinylacetate, having a viscosity of 30 to 250 mPa · s measured at 140 ° C., and vinylacetate for 100 CH 2 groups. To 2 to 7 CH 3 groups not derived from the acetate radical of 제3항에 있어서, 에틸렌/비닐아세테이트/N-비닐피롤리돈 삼원 공중합체는 20 내지 35중량%의 비닐아세테이트 및 1.0 내지 5.0중량%의 N-비닐피롤리돈을 함유하며 140℃에서 측정된 150 내지 1500mPa.s의 점도를 가지는 방법.4. The ethylene / vinylacetate / N-vinylpyrrolidone terpolymer according to claim 3 contains 20 to 35% by weight vinylacetate and 1.0 to 5.0% by weight N-vinylpyrrolidone and is measured at 140 ° C. Method having a viscosity of 150 to 1500 mPa · s. 제4항에 있어서, 에틸렌/비닐아세테이트 공중합체 및 에틸렌/비닐아세테이트/N5. The ethylene / vinylacetate copolymer and ethylene / vinylacetate / N according to claim 4 -비닐피롤리돈 삼원 중합체를 3 : 1 내지 20 : 1의 중량비로 사용하는 방법.A vinylpyrrolidone terpolymer using a weight ratio of 3: 1 to 20: 1. 제5항에 있어서, 에틸렌-비닐아세테이트 공중합체 및 에틸렌/비닐아세테이트/6. The ethylene-vinylacetate copolymer and ethylene / vinylacetate / N-비닐피롤리돈 삼원 중합체의 혼합물을 0.005 내지 0.5중량% 함유하는 유동 거동이 향상된 미네랄오일 또는 미네랄오일 증류물.Mineral oil or mineral oil distillate with improved flow behavior containing from 0.005 to 0.5% by weight of a mixture of N-vinylpyrrolidone terpolymer.
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DE59000480D1 (en) 1992-12-24
CA2020104A1 (en) 1990-12-30
ATE82587T1 (en) 1992-12-15
ES2054152T3 (en) 1994-08-01
KR910001004A (en) 1991-01-30
EP0405270A1 (en) 1991-01-02
EP0405270B1 (en) 1992-11-19
AU624965B2 (en) 1992-06-25
ZA904894B (en) 1991-04-24
JPH0339385A (en) 1991-02-20
AU5791090A (en) 1991-01-03
JPH0768505B2 (en) 1995-07-26
DE3921279A1 (en) 1991-01-03

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