KR20040051775A - Process for preparing dichloroiodoperfluorobutane by low temperature radical initiator - Google Patents
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- 239000003999 initiator Substances 0.000 title claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 89
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 11
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical group CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 claims description 15
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 claims description 2
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000376 reactant Substances 0.000 abstract description 10
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 15
- 239000011737 fluorine Substances 0.000 description 7
- 229910052731 fluorine Inorganic materials 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
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- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- 229960003328 benzoyl peroxide Drugs 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
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- 101100492795 Aspergillus flavus atmG gene Proteins 0.000 description 1
- 108010017842 Telomerase Proteins 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 208000018459 dissociative disease Diseases 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
- C07C17/269—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions of only halogenated hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C19/00—Acyclic saturated compounds containing halogen atoms
- C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
- C07C19/16—Acyclic saturated compounds containing halogen atoms containing fluorine and iodine
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
본 발명은 저온 라디칼개시제를 이용한 디클로로아이오도퍼플루오로부탄의 제조방법에 관한 것으로, 더욱 상세하게는 디클로로아이오도퍼플루오로에탄(DCIPFE)과 테트라플루오로에틸렌(TFE)의 텔로머라이제이션 반응에, 기존에 사용되어온 고온 라디칼개시제를 대신하여 -10 ℃ 이하의 낮은 온도에서 1 ∼ 15 시간 정도의 일정한 반감기를 갖고 해리되는 저온 라디칼 개시제의 선택 사용으로 저온 조건에서도 텔로머라이제이션 반응이 가능하고 또한 저온 반응 온도 유지에 따른 증기압을 감소시킬수 있음으로서, 장치비를 감소시키고 공정의 안정성을 개선하였으며, 특히 반응물과 라디칼개시제의 양의 조절로 전환율과 생성물의 비율을 높게 개선시킨 디클로로아이오도퍼플루오로부탄(DCIPFB)의 제조방법에 관한 것이다.The present invention relates to a method for producing dichloroiodoperfluorobutane using a low temperature radical initiator, and more particularly, to the telomerization reaction of dichloroiodoperfluoroethane (DCIPFE) and tetrafluoroethylene (TFE). In addition to the existing high temperature radical initiator, the use of a low temperature radical initiator that dissociates with a constant half-life of about 1 to 15 hours at a low temperature of -10 ° C. or lower allows the telomerization reaction even at low temperature conditions. It is possible to reduce the vapor pressure with maintaining the reaction temperature, thereby reducing the equipment cost and improving the stability of the process, and in particular, by controlling the amount of the reactants and radical initiators, dichloroiodoperfluorobutane which has improved the conversion rate and the product ratio It relates to a method for producing DCIPFB).
Description
본 발명은 저온 라디칼개시제를 이용한 디클로로아이오도퍼플루오로부탄의 제조방법에 관한 것으로, 더욱 상세하게는 디클로로아이오도퍼플루오로에탄(DCIPFE)과 테트라플루오로에틸렌(TFE)의 텔로머라이제이션 반응에, 기존에 사용되어온 고온 라디칼개시제를 대신하여 -10 ℃ 이하의 낮은 온도에서 1 ∼ 15 시간 정도의 일정한 반감기를 갖고 해리되는 저온 라디칼 개시제의 선택 사용으로 저온 조건에서도 텔로머라이제이션 반응이 가능하고 또한 저온 반응 온도 유지에 따른 증기압을 감소시킬수 있음으로서, 장치비를 감소시키고 공정의 안정성을 개선하였으며, 특히 반응물과 라디칼개시제의 양의 조절로 전환율과 생성물의 비율을 높게 개선시킨 디클로로아이오도퍼플루오로부탄(DCIPFB)의 제조방법에 관한 것이다.The present invention relates to a method for producing dichloroiodoperfluorobutane using a low temperature radical initiator, and more particularly, to the telomerization reaction of dichloroiodoperfluoroethane (DCIPFE) and tetrafluoroethylene (TFE). In addition to the existing high temperature radical initiator, the use of a low temperature radical initiator that dissociates with a constant half-life of about 1 to 15 hours at a low temperature of -10 ° C. or lower allows the telomerization reaction even at low temperature conditions. It is possible to reduce the vapor pressure with maintaining the reaction temperature, thereby reducing the equipment cost and improving the stability of the process, and in particular, by controlling the amount of the reactants and radical initiators, dichloroiodoperfluorobutane which has improved the conversion rate and the product ratio It relates to a method for producing DCIPFB).
불소계 텔로머는 다음 표 1에서 보는 바와 같이 계면활성제, 분리막, 섬유가공제, 금속, 유리, 가죽, 마이크로에멀젼, 불소실리콘, 내열성의 불소오일, 불소계폴리에스터, 표면개질제에 사용되는 불소계우레탄 등의 응용분야를 갖는 불소소재의 중간체이다. 또한 부분적으로 염소기를 갖는 불소계 텔로머는 광전자 및 전불소계 투광성 고분자를 제조하기 위한 중간체로서 그 응용분야가 넓다.Fluorinated telomers are used in surfactants, separators, fiber processing agents, metals, glass, leather, microemulsions, fluorine silicon, heat resistant fluorine oils, fluorine polyesters, and surface modifiers, as shown in Table 1 below. It is an intermediate of fluorine material with application field. In addition, the fluorine-based telomer partially having a chlorine group has a wide application field as an intermediate for preparing optoelectronic and all-fluorine-based light transmitting polymers.
불소계 텔로머중 디클로로아이오도퍼플루오로부탄(DCIPFB)의 일반적인 제조방법에서는 디클로로아이오도퍼플루오로에탄(DCIPFE)과 테트라플루오로에틸렌(TFE)를 라디칼 개시제와 함께 일정비율로 혼합하여 텔로머라이제이션 반응에 의해 제조한다. 상기 텔로머라이제이션 반응의 압력은 상온 이상에서 기상을 보이는 TFE 및 DCIPFE의 증기압에 따라 결정되며, 반응의 진행에 필요한 개시제의 해리온도 및 반감기에 따라 반응온도, 반응시간 및 반응압력이 결정된다. 이러한 반응은 전형적인 회분식 반응[미국특허 5,260,492]에 따라 진행된다.In a general method for preparing dichloroiodoperfluorobutane (DCIPFB) in fluorine-based telomers, telomerization is achieved by mixing dichloroiodoperfluoroethane (DCIPFE) and tetrafluoroethylene (TFE) in a ratio with a radical initiator. Prepared by the reaction. The pressure of the telomerization reaction is determined according to the vapor pressures of TFE and DCIPFE exhibiting a gas phase at room temperature or higher, and the reaction temperature, reaction time and reaction pressure are determined according to the dissociation temperature and the half-life of the initiator necessary for the progress of the reaction. This reaction proceeds according to a typical batch reaction [US Pat. No. 5,260,492].
기존의 DCIPFB 제조법에서는 고온에서 해리되는 라디칼개시제를 사용하였다. 고온의 라디칼개시제를 사용할 경우 반응온도가 높아지므로 반응압력을 결정하는 원료인 DCIPFE와 TFE의 증기압이 약 20 기압 이상으로 매우 높다. 이때 TFE는 온도 증가에 따라 증기압이 급격히 증가하므로 기존의 고온의 라디칼개시제를 사용하는 방법에 따라 DCIPFB를 제조하는 경우 고온/고압 반응기가 필요할 뿐만아니라, TFE를 공급하기 위한 부대장치도 역시 고압의 저장조로 이루어진 것이 필요하다.TFE는 매우 폭발성이 강한 가스이므로, 약 7 ∼ 8 기압 이상 압축하는 것이 매우 어려울 뿐만 아니라, 고압으로 압축할 수록 공정의 위험도가 급격히 증가하는 문제점이 있다. 또한 개시제의 반감기는 온도가 상승할수록 급격히 감소하므로 반응온도가 고온일 수록 급격한 발열 해리반응으로 고압에 의한 폭발 위험성이 있으며, 규모가 큰 반응의 경우 반응 온도 유지를 위한 냉각장치를 필요로 한다.Conventional DCIPFB manufacturing method used a radical initiator that dissociates at high temperature. When the high temperature radical initiator is used, the reaction temperature is high, so the vapor pressures of DCIPFE and TFE, which are the raw materials for determining the reaction pressure, are very high, about 20 atm. At this time, since TFE rapidly increases the vapor pressure with increasing temperature, a high temperature / high pressure reactor is required when manufacturing DCIPFB according to the method of using a high temperature radical initiator, and an auxiliary device for supplying TFE is also a high pressure storage tank. Since TFE is a highly explosive gas, it is very difficult to compress at least about 7 to 8 atm, and there is a problem that the risk of the process is rapidly increased as it is compressed at a high pressure. In addition, since the half-life of the initiator decreases rapidly as the temperature increases, there is a risk of explosion due to a high exothermic dissociation reaction as the reaction temperature increases, and a large scale reaction requires a cooling device for maintaining the reaction temperature.
따라서 고온 라디칼개시제를 사용하여 DCIPFB를 제조하는 경우 고압에 의한 폭발 위험성과 반응온도 유지 외에도 원료인 TFE의 자체중합으로 부반응 물의 생성가능성이 높으므로 반응온도 및 압력의 개선이 반드시 필요하다.Therefore, in the case of manufacturing DCIPFB using a high temperature radical initiator, it is necessary to improve the reaction temperature and pressure because the possibility of generation of side reactions is high due to the self-polymerization of TFE as a raw material in addition to the explosion risk due to the high pressure and the reaction temperature.
본 발명자는 고온, 고압 반응조건에서의 DCIPFB의 제조방법상의 문제점을 개선하기 위해 수년간 연구 검토한 결과, 텔로머라이제이션 반응에서 낮은 온도조건에서 일정한 반감기를 갖는 저온의 라디칼개시제를 사용하는 것에 주목하였다. 상기의 라디칼개시제는 낮은 온도조건을 가능하게 하므로, 온도에 따른 급격한 증기압의 증가를 보이는 반응물의 반응압력을 감소시킬수 있는 특성을 가지는 저온 라디칼개시제를 선택 사용하므로써 본 발명을 완성하게 되었다. 따라서 본 발명은 기존의 고온 라디칼개시제 사용시 문제점인 반응온도를 낮추고, 반응의 압력을 결정하는 DCIPFE와 TFE의 증기압을 낮추어 전체 반응압력을 낮추므로 고압에 의한 폭발 위험성을 줄이고, 고온에서 온도 상승에 따른 라디칼개시제의 급속한 발열 해리반응으로 인한 반응 온도의 증가를 방지하며, 자체중합과 부반응 생성 가능성을 감소시킬 수 있으며, 또한 원료비와 개시제의 양을 조절하므로 생성물의 전환율을 기존의 합성결과에 비해 높일 수 있는 DCIPFB 제조방법을 제공하는데 그 목적이 있다.The present inventors have studied and studied for several years to improve the problems of the manufacturing method of DCIPFB under high temperature and high pressure reaction conditions, and noticed the use of a low temperature radical initiator having a constant half-life at low temperature conditions in the telomerization reaction. Since the radical initiator enables a low temperature condition, the present invention has been completed by selecting and using a low-temperature radical initiator having a property capable of reducing the reaction pressure of a reactant exhibiting a rapid increase in vapor pressure with temperature. Therefore, the present invention lowers the reaction temperature which is a problem when using the existing high temperature radical initiator, and lowers the overall reaction pressure by lowering the vapor pressure of DCIPFE and TFE to determine the pressure of the reaction, thereby reducing the risk of explosion due to high pressure, It can prevent the increase of reaction temperature due to the rapid exothermic dissociation of radical initiator, reduce the possibility of self-polymerization and side reaction formation, and control the raw material cost and the amount of initiator to increase the conversion of the product compared with the existing synthesis results. The purpose of the present invention is to provide a manufacturing method of DCIPFB.
본 발명은 디클로로아이오도퍼플루오로에탄(DCIPFE)과 테트라플루오로에틸렌(TFE)을 라디칼개시제와 함께 일정비율로 혼합하여 텔로머라이제이션 반응시켜 디클로로아이오도퍼플루오로부탄(DCIPFB)의 제조방법에 있어서, -10 ℃ 이하에서 반감기가 1 ∼ 15 시간인 라디칼개시제를 사용하여 35 ∼ 80 ℃ 와 7 ∼ 10 atm의 반응조건에서 텔로머라이제이션 반응시키켜 디클로로아이오도퍼플루오로부탄(DCIPFB)을 제조하는 방법에 그 특징이 있다.The present invention is a method for producing dichloroiodoperfluorobutane (DCIPFB) by mixing dichloroiodoperfluoroethane (DCIPFE) and tetrafluoroethylene (TFE) with a radical initiator in a certain ratio and telomerization reaction. And dichloroiodoperfluorobutane (DCIPFB) by telomerization reaction at a reaction condition of 35 to 80 DEG C and 7 to 10 atm using a radical initiator having a half-life of 1 to 15 hours at -10 DEG C or less. How to do that is characteristic.
이와 같은 발명을 더욱 상세히 설명하면 다음과 같다.When explaining the invention in more detail as follows.
일반적인 방법으로 디클로로아이오도퍼플루오로에탄(DCIPFE)과 테트라플루오로에틸렌(TFE)을 라디칼개시제를 사용하여 텔로머라이제이션 반응시켜 디클로로아이오도퍼플루오로부탄(DCIPFB)을 제조하는 방법에 있어서, 일반적으로 고온의 라디칼개시제 예를들면 벤조일퍼옥사이드를 사용하였는 바[Appled chemistry Vol.6, No 1, 170 ∼ 173], 이들 고온 라디칼개시제는 70 ∼ 100 ℃의 고온에서 0.693/kd 정도의 반감기를 갖는다. 상기한 특징을 가지는 고온 라디칼개시제로 텔로머라이제이션 반응을 시킬 경우 반응 온도가 높아져 온도에 따른 급격한 증기압의 증가를 보이는 반응물의 반응압력이 증가되므로 반응 공정 안정성의 문제가 제기되었다.In a general method, a dichloroiodoperfluorobutane (DCIPFB) is prepared by telomerizing a dichloroiodoperfluoroethane (DCIPFE) with tetrafluoroethylene (TFE) using a radical initiator. As a high temperature radical initiator such as benzoyl peroxide was used [Appled chemistry Vol. 6, No. 1, 170-173], these high temperature radical initiators have a half-life of about 0.693 / kd at a high temperature of 70 to 100 ° C. . In the case of the telomerization reaction with the high temperature radical initiator having the above characteristics, the reaction temperature is increased, and the reaction pressure of the reactant exhibiting a sudden increase in vapor pressure increases with temperature, thereby raising the problem of reaction process stability.
따라서 본 발명자는 이러한 상기 문제점을 극복하기 위하여 저온의 라디칼개시제를 도입하게 되었다. 그러나 모든 저온 라디칼개시제가 상기 문제점 극복에 해당되지는 않았으며, 본 발명에서 사용된 -10 ℃ 이하의 저온에서 1 ∼ 15 시간의 일정한 반감기를 갖는 저온 라디칼개시제를 텔로머라이제이션 반응에 도입한 경우에만 상기의 문제점을 극복한 효과적인 결과를 얻을 수 있다.Therefore, the present inventors have introduced a low-temperature radical initiator to overcome this problem. However, not all low temperature radical initiators have overcome the above problems, and only when a low temperature radical initiator having a constant half-life of 1 to 15 hours is used in the telomerization reaction at a low temperature of -10 ° C. or lower used in the present invention. An effective result that overcomes the above problems can be obtained.
본 발명은 DCIPFE와 TFE에 저온 라디칼개시제를 혼합하여 텔로머라이제이션 반응시켜 DCIPFB를 제조하는 것으로 원료의 몰비, 반응온도, 촉매를 반응변수로 하는 텔로머라이제이션 반응에서 저온의 라디칼개시제 사용으로 반응온도를 낮추므로, 반응온도와 압력을 낮춰서 반응조건을 개선하고 원료비와 개시제의 양을 조절하여 DCIPFB의 전환율을 최대로 얻을 수 있는 DCIPFB의 제조방법에 관한 것이다. 즉, 본 발명은 저온 라디칼개시제의 선택 사용에 그 특징이 있는 바, 본 발명이 사용한 라디칼개시제는 낮은 온도에서 일정한 반감기를 갖고 해리되어, 저온의 반응 온도를 가능하게 하므로 텔로머라이제이션 반응에서 온도에 따른 급격한 증기압의 증가를 보이는 반응물의 반응압력을 감소시킬수 있게 하므로써 저온 저압의 유지로 원활한 반응 수행이 가능하다.The present invention is to prepare a DCIPFB by mixing a low-temperature radical initiator with DCIPFE and TFE to produce a telomerization reaction, the reaction temperature by using a low-temperature radical initiator in the telomerization reaction using the molar ratio of the raw material, the reaction temperature, the catalyst as a reaction variable Therefore, the present invention relates to a method for preparing DCIPFB which can obtain a maximum conversion rate of DCIPFB by improving the reaction conditions by reducing the reaction temperature and pressure, and adjusting the raw material cost and the amount of the initiator. That is, the present invention is characterized by the selective use of low-temperature radical initiators. The radical initiators used in the present invention dissociate with a constant half-life at low temperatures, thus allowing a low-temperature reaction temperature, and thus the temperature of the radical initiators in the telomerization reaction. It is possible to reduce the reaction pressure of the reactants showing a sudden increase in the vapor pressure, it is possible to perform a smooth reaction by maintaining a low temperature low pressure.
본 발명에서 사용하는 라디칼개시제는 -10 ℃ 이하의 저온에서 1 ∼ 15 시간의 일정한 반감기를 갖는 것으로, 디이소프로필퍼옥시디카보네이트(DIPPDC), t-부틸퍼옥시피발레이트(HPO-PV)및 t-부틸퍼옥시-2-에틸헥사노에이트(HOP-O)이 포함된다.The radical initiator used in the present invention has a constant half-life of 1 to 15 hours at a low temperature of −10 ° C. or less, and isopropyl peroxydicarbonate (DIPPDC), t-butylperoxy pivalate (HPO-PV) and t -Butyl peroxy-2-ethylhexanoate (HOP-O).
상기한 라디칼개시제를 반응물인 DCIPFE에 대하여 0.01 ∼ 10 몰% 범위로 사용하며, 그 사용량이 0.01 몰% 미만인 경우에는 반응물에 포함된 미량의 불순물의 영향을 받아 반응이 거의 진행되지 않아 전환율이 매우 낮으며, 10 몰% 초과할 경우는 TFE의 자체 중합에 의한 불순물과 원활한 종결반응(chain-transfer)이 일어나지 않아 개시제와 반응물의 반응에 의한 불순물이 다량 생성되어 수율 및 선택도가 나빠지는 문제점이 있다.The radical initiator is used in the range of 0.01 to 10 mol% with respect to the reactant DCIPFE. When the amount of the radical initiator is less than 0.01 mol%, the reaction is hardly progressed due to the small amount of impurities included in the reactant, so the conversion rate is very low. If it exceeds 10 mol%, impurities due to self-polymerization of TFE and a smooth chain-transfer do not occur, and a large amount of impurities are generated by the reaction between the initiator and the reactant, resulting in poor yield and selectivity. .
본 발명의 반응 메카니즘은 다음과 같다.The reaction mechanism of the present invention is as follows.
(1) DIPPDC → DIPPDCI·(1) DIPPDC → DIPPDCI
(2) DIPPDC· + CClF2CClFI → CClF2CClF·(2) DIPPDC + CClF 2 CClFI → CClF 2 CClF
(3) CClF2CClF· + nCF2=CF2→ CClF2CClF(CF2CF2)n=1,2,3·(3) CClF 2 CClF · + nCF 2 = CF 2 → CClF 2 CClF (CF 2 CF 2 ) n = 1,2,3
(4) CClF2CClF(CF2CF2)n=1,2,3· + CClF2CClFI → CClF2CClF(CF2CF2)n=1,2,3I(4) CClF 2 CClF (CF 2 CF 2 ) n = 1,2,3 · + CClF 2 CClFI → CClF 2 CClF (CF 2 CF 2 ) n = 1,2,3 I
+ CClF2CClF·+ CClF 2 CClF
(5) DIPPDC· + mCF2=CF2→ DIPPDC(CF2CF2)m=1,2,3,4,...·(5) DIPPDC · + mCF 2 = CF 2 → DIPPDC (CF 2 CF 2 ) m = 1,2,3,4, ...
(6) DIPPDC· + CClF2CClFI → DIPPDFClCCClF2 (6) DIPPDC + CClF 2 CClFI → DIPPDFClCCClF 2
본 발명에서 DCIPFB를 제조하기 위해 사용된 반응물 DCIPFE와 TFE의 몰비([DCIPFE]/[TFE])는 50/1 ∼ 1/5 범위로 유지하도록 하며, 더욱 바람직하기로는 5/1 ∼ 1/5 범위를 유지한다. 상기 DCIPFE와 TFE의 몰비([DCIPFE]/[TFE])가 50/1 미만이면 TFE의 공급의 부족으로 DCIPFB로의 전환이 이루어지지 않으며, 1/5초과시에는 반응기 안에 TFE가 과량으로 존재하게 되므로 자체 중합이나 2 몰 이상의 TFE 단량체가 DCIPFE로 텔로머라이제이션 되어 목표로 하는 DCIPFB로의 전환율이 감소하는 문제가 발생한다.In the present invention, the molar ratio ([DCIPFE] / [TFE]) of the reactants DCIPFE and TFE used to prepare DCIPFB is maintained in the range of 50/1 to 1/5, more preferably 5/1 to 1/5. Maintain the range. If the DCIPFE and TFE molar ratio ([DCIPFE] / [TFE]) is less than 50/1, there is no conversion of DCIPFB due to the lack of TFE supply, and when 1/5 is exceeded, the TFE is excessively present in the reactor. There arises a problem that polymerization or more than 2 moles of TFE monomers are telomerized to DCIPFE to reduce the conversion to the target DCIPFB.
또한 본 발명은 저온의 라디칼개시제 DIPPDC으로 텔로머라이제이션 반응을 수행하여, 기존의 고온의 개시제를 사용한 경우보다 비교적 낮은 온도인 35 ∼ 80 ℃ 범위, 7 ∼ 10 atm에서 수행 가능하며, TFE의 연속 주입이 가능하므로 회분식(batch) 및 반-회분식(semi-batch)의 반응이 가능하다. 상기 반응온도가 35 ℃ 미만인 경우 라디칼 개시제의 분해 속도가 느리므로 반응이 매우 늦어 생산성이 나쁘며, 반응온도가 80 ℃ 초과할 경우 반응용액중 TFE의 증기압이 높아 반응의 위험성이 크게 증가하여 반응을 위한 장치비가 급격히 증가하는 문제가 있다. 상기 반응으로 DCIPFB 외에도, 디클로로아이오도퍼플루오로헥산(DCIPFH), 디클로로아이오도퍼플루오로옥탄(DCIPFO) 그리고 기타 불순물 등의 반응 생성물을 얻는다.In addition, the present invention can be carried out by the telomerization reaction with a low-temperature radical initiator DIPPDC, it can be carried out at a relatively low temperature range of 35 ~ 80 ℃, 7 ~ 10 atm, and continuous injection of TFE than using a conventional high temperature initiator This allows for batch and semi-batch reactions. When the reaction temperature is less than 35 ℃, the decomposition rate of the radical initiator is slow, so the reaction is very late, the productivity is bad, and when the reaction temperature exceeds 80 ℃, the vapor pressure of the TFE in the reaction solution is high, the risk of the reaction increases greatly for the reaction There is a problem that the equipment cost increases rapidly. In addition to DCIPFB, the reaction yields reaction products such as dichloroiodoperfluorohexane (DCIPFH), dichloroiodoperfluorooctane (DCIPFO) and other impurities.
이하, 본 발명을 다음의 실시예에 의하여 더욱 상세하게 설명하겠는 바, 본 발명이 실시예에 의하여 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples, which are not intended to limit the present invention.
실시예 1Example 1
온도와 압력 게이지가 장착된 150 ㎖ 용량의 오토클레이브(sus 316)에 디클로로아이오도퍼플루오로에탄(DCIPFE) 40 g (0.14 mol), 디이소프로필퍼옥시디카보네이트(DIPPDC) 0.32 g (0.0015 mol)을 투입하고, 질소 및테트라플루오로에틸렌(TFE)으로 치환한 후에, 액체질소를 사용하여 반응기를 냉각하고 TFE 14 g (0.14 mol)을 주입하여 DCIPFB, DCIPFH, DCIPFO를 얻었다. 반응시 승온한 온도는 50 ℃이고, 반응시간은 4.5 시간, 반응 최대 압력은 10 atm 이었다.40 g (0.14 mol) of dichloroiodoperfluoroethane (DCIPFE) and 0.32 g (0.0015 mol) of diisopropylperoxydicarbonate (DIPPDC) in a 150 ml capacity autoclave (sus 316) equipped with a temperature and pressure gauge Was added, and after substituting with nitrogen and tetrafluoroethylene (TFE), the reactor was cooled using liquid nitrogen and 14 g (0.14 mol) of TFE was injected to obtain DCIPFB, DCIPFH, and DCIPFO. The temperature which heated up at the time of reaction was 50 degreeC, reaction time was 4.5 hours, and reaction maximum pressure was 10 atm.
실시예 2Example 2
실시예 1과 동일방법으로 실시하되, DIPPDC 0.64 g (0.0030 mol)을 사용하여DCIPFB, DCIPFH, DCIPFO를 얻었다. 반응시 승온한 온도는 50 ℃이고, 반응시간은 4.5 시간, 반응 최대 압력은 9 atm 이었다.In the same manner as in Example 1, using DIPPDC 0.64 g (0.0030 mol) to obtain DCIPFB, DCIPFH, DCIPFO. The temperature which heated up at the time of reaction was 50 degreeC, reaction time was 4.5 hours, and reaction maximum pressure was 9 atm.
실시예 3Example 3
실시예 1과 동일 방법으로 실시하되, TFE 28 g (0.28 mol)을 사용하여 DCIPFB, DCIPFH, DCIPFO를 얻었다. 반응시 승온한 온도는 60 ℃이고, 반응시간은 4.5 시간, 반응 최대 압력은 12 atm 이었다.The same procedure as in Example 1 was carried out to obtain DCIPFB, DCIPFH, DCIPFO using 28 g (0.28 mol) of TFE. The temperature which heated up at the time of reaction was 60 degreeC, reaction time was 4.5 hours, and reaction maximum pressure was 12 atm.
실시예 4Example 4
온도와 압력 게이지가 장착된 150 mL 오토클레이브(sus316)에 DCIPFE 40 g (0.14 mol), DIPPDC 0.32 g (0.0015 mol)을 투입하고, 질소 및 TFE 로 치환한 후에, 반응기 온도를 55 ℃로 유지하며 7 atmG로 압축된 TFE 14 g (0.14 mol)를 연속적으로 주입하여 DCIPFB, DCIPFH, DCIPFO를 얻었다. 반응시간은 4.5 시간, 반응중 반응기 내의 압력 변화는 없었다.DCIPFE 40 g (0.14 mol), DIPPDC 0.32 g (0.0015 mol) were added to a 150 mL autoclave (sus316) equipped with a temperature and pressure gauge, and the reactor temperature was maintained at 55 ° C. after replacement with nitrogen and TFE. 14 g (0.14 mol) of TFE compressed to 7 atmG were continuously injected to obtain DCIPFB, DCIPFH, and DCIPFO. The reaction time was 4.5 hours and there was no pressure change in the reactor during the reaction.
비교예 1Comparative Example 1
상기 실시예 1과 동일한 방법에 의해 텔로머라이제이션을 실시하되 라디칼 개시제로 고온개시제인 벤조일퍼옥사이드(benzoylperoxide) 0.34 g (0.0014 mol)를 사용하여 DCIPFB, DCIPFH, DCIPFO를 얻었다. 반응시 승온한 온도는 105 ℃이고, 반응시간은 4 시간, 반응 최대 압력은 20 atm 이었다.Telomerization was carried out in the same manner as in Example 1, but DCIPFB, DCIPFH, and DCIPFO were obtained using 0.34 g (0.0014 mol) of benzoylperoxide, a high-temperature initiator, as a radical initiator. The temperature which heated up at the time of reaction was 105 degreeC, reaction time was 4 hours, and reaction maximum pressure was 20 atm.
비교예 2Comparative Example 2
실시예 1과 동일방법으로 실시하되, DIPPDC 0.16 g (0.0007 mol)을 사용하 여 DCIPFB, DCIPFH, DCIPFO를 얻었다. 반응시 승온한 온도는 50 ℃이고, 반응시간은 4.5 시간, 반응 최대 압력은 15 atm 이었다.The same procedure as in Example 1 was carried out, except that DCIPFB, DCIPFH, and DCIPFO were obtained using DIPPDC 0.16 g (0.0007 mol). The temperature which heated up at the time of reaction was 50 degreeC, reaction time was 4.5 hours, and reaction maximum pressure was 15 atm.
상기 저온 개시제를 사용한 실시예 1은 고온의 라디칼개시제를 사용한 비교예 1에 비하여 반응온도는 50 ℃정도로 극히 낮아졌고, 반응 최대 압력도 20 atm이상에서 7 ∼ 10 atm 내외의 극히 부드러운 조건으로 낮출 수 있었다. 또한 가스크로마토그래피(DONAM INSTRUMENT INC., DONAM DS 62000)로 전환율과 생성물을 분석하여 나타낸 표 1을 살펴보면 생성물의 DCIPFB의 조성도 향상되었다.In Example 1 using the low-temperature initiator, the reaction temperature was extremely low, as compared to Comparative Example 1 using a high temperature radical initiator, about 50 ℃, the reaction maximum pressure can be lowered to extremely soft conditions of about 7 to 10 atm above 20 atm. there was. In addition, the gas chromatography (DONAM INSTRUMENT INC., DONAM DS 62000) analyzed the conversion rate and the product.
본 발명은 디클로로아이오도퍼플루오로에탄(DCIPFE)와 테트라플루오로에틸렌(TFE)을 35 ∼ 80 ℃ 반응온도와 7 ∼ 10 atm 반응압력의 조건에서 저온 라디칼개시제와 함께 일정비율로 혼합하여 텔로머라이제이션 반응시켜 디클로로아이오도퍼플루오로부탄(DCIPFB)을 제조함으로써, 저온·저압으로 반응조건을 개선하여 장치비를 감소시키고 공정의 안정성을 개선하였으며, 상기의 반응물과 저온 라디칼개시제의 양의 조절로 전환율과 생성물의 비율을 높게 개선시키는데 효과가 있다.The present invention is a telomerase by mixing dichloroiodoperfluoroethane (DCIPFE) and tetrafluoroethylene (TFE) with a low temperature radical initiator at a constant ratio at a reaction temperature of 35 ~ 80 ℃ and 7 ~ 10 atm reaction pressure By producing the dichloroiodoperfluorobutane (DCIPFB) by the reaction reaction, by improving the reaction conditions at low temperature and low pressure, to reduce the equipment cost and to improve the stability of the process, the conversion rate by controlling the amount of the reactant and the low temperature radical initiator It is effective in improving the ratio of and products.
Claims (5)
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| KR20040051775A true KR20040051775A (en) | 2004-06-19 |
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| Application Number | Title | Priority Date | Filing Date |
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| KR1020020079440A Ceased KR20040051775A (en) | 2002-12-13 | 2002-12-13 | Process for preparing dichloroiodoperfluorobutane by low temperature radical initiator |
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| Country | Link |
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| KR (1) | KR20040051775A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH035434A (en) * | 1989-05-13 | 1991-01-11 | Hoechst Ag | Production of telomer alcohol |
| US5260492A (en) * | 1992-12-21 | 1993-11-09 | E. I. Du Pont De Nemours And Company | Fluorinated monomers and polymers |
| US5326917A (en) * | 1992-12-21 | 1994-07-05 | E. I. Du Pont De Nemours And Company | Fluorinated monomers and polymers |
-
2002
- 2002-12-13 KR KR1020020079440A patent/KR20040051775A/en not_active Ceased
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH035434A (en) * | 1989-05-13 | 1991-01-11 | Hoechst Ag | Production of telomer alcohol |
| US5260492A (en) * | 1992-12-21 | 1993-11-09 | E. I. Du Pont De Nemours And Company | Fluorinated monomers and polymers |
| US5326917A (en) * | 1992-12-21 | 1994-07-05 | E. I. Du Pont De Nemours And Company | Fluorinated monomers and polymers |
| US5350821A (en) * | 1992-12-21 | 1994-09-27 | E. I. Du Pont De Nemours And Company | Fluorinated monomers and polymers |
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