KR100196480B1 - Synthesis of fluorinated dimethyl ethers - Google Patents
Synthesis of fluorinated dimethyl ethers Download PDFInfo
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- KR100196480B1 KR100196480B1 KR1019910017334A KR910017334A KR100196480B1 KR 100196480 B1 KR100196480 B1 KR 100196480B1 KR 1019910017334 A KR1019910017334 A KR 1019910017334A KR 910017334 A KR910017334 A KR 910017334A KR 100196480 B1 KR100196480 B1 KR 100196480B1
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- C—CHEMISTRY; METALLURGY
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Abstract
본 발명은 일반식 CF2HOCC1xFyH3-(x+y)(이 식에서, x와 y는 각기 독립적으로 0, 1, 2 또는 3이고, x+y는 2또는 3)의 플루오르화 디메틸에테르를 합성하기 위한 신규 방법에 관한 것이다. 이 방법은, 메틸디플루오로메틸에테르를 염소화시켜 일반식 CH2HOCH3-ZC1Z의 화합물을 하나 이상 함유하는 염소화 반응 생성물을 형성시킨 후, 상기 화합물을 염소화 반응 생성물로부터 분리하거나 분리하지 않은 상태로 플루오르화시킴으로써, 전술한 플루오르화 디메틸에테르를 함유하는 플루오르화 반응 생성물을 수득하는 것을 포함한다.The present invention provides fluorination of the formula CF 2 HOCC1 x F y H 3- (x + y) , wherein x and y are each independently 0, 1, 2 or 3, and x + y is 2 or 3 It relates to a novel process for synthesizing dimethyl ether. This process involves chlorination of methyldifluoromethylether to form a chlorination reaction product containing at least one compound of the general formula CH 2 HOCH 3-Z C1 Z , and then the compound is separated or not separated from the chlorination reaction product. Fluorination in a state to obtain a fluorination reaction product containing the above-mentioned fluorinated dimethyl ether.
Description
본 발명은 냉매, 발포제등의 용도를 갖는 플루오르화 디메틸에테르의 제조 방법에 관한 것이다.The present invention relates to a method for producing fluorinated dimethyl ether having the use of a refrigerant, a blowing agent and the like.
종래의 비스(디플루오로메틸)에테르 제조 방법은 디메텔에테르를 염소화시킨후 분리하고 비스(디클로로메틸)에테르를 플루오르화시키는 것이었다. 상기 염소화 단계에 의하면, 그중 일부는 예컨대 증류에 대해 불안정한 염소화 디메틸에테르의 복합 혼합물이 생성되며, 이로부터 비스(디클로로메틸)에테르가 분리된다. 상기 혼합물내의 에테르중에서 클로로메틸메틸에테르 및 비스-(클로로메틸)에테르는 유력한 발암물질이다.A conventional method for preparing bis (difluoromethyl) ether was to chlorinate dimethelether and then to separate and fluorinate bis (dichloromethyl) ether. According to the chlorination step, some of these result in a complex mixture of chlorinated dimethyl ethers, for example, unstable to distillation, from which the bis (dichloromethyl) ether is separated. Among the ethers in the mixture, chloromethylmethyl ether and bis- (chloromethyl) ether are potent carcinogens.
따라서, 본 발명의 한가지 목적은 발암물질을 중간체로 생산하지 않는 플루오르화 디메틸에테르의 합성법을 제공하는 것이다.Accordingly, one object of the present invention is to provide a method for synthesizing fluorinated dimethyl ether which does not produce carcinogens as intermediates.
본 발명의 또 다른 목적은 필요한 여러 분리단계가 여러가지 중간체들의 두드려진 불안정성으로 말미암은 폭발 우험 및 수율 손실없이 증류에 의해 수행될 수 있는 플루오르화 디메틸에테르의 합성법을 제공하는 것이다.Another object of the present invention is to provide a method for the synthesis of fluorinated dimethyl ether, in which the various separation steps required can be carried out by distillation without the explosive risk and yield loss due to the tapping instability of the various intermediates.
선행기술에 따른, 일부가 발암물질인 염소화 에테르의 불안정한 복합 혼합물은 본 발명에서 메틸디플루오로메틸에테르를 출발물질로 사용함으로써 제거된다. 메텔디플루오로메틸에테르를 염소화시키면 염소화된 반응 혼합물로부터 쉽게 분리될 수 있는 CH2HOCH3-ZClZ(이 식에서, z은 1, 2 또는 3)의 식을 갖는 하나 이상의 화합물을 포함하는 염소화 반응 혼합물이 얻어진다. 메틸디플루오로메틸에테르의 염소화에 의하면 단지 세가지의 유도체, 즉 z=1, z=2 그리고 z=3 인 유도체만이 형성될 수 있다. 디클로로메틸 디플루오로메틸에테르(z=2)는 염소화된 반응 혼합물로 부터 쉽게 분리할 수 있으며, 이후 분리를 하면서 또는 분리단계 없이 플루오르화시켜서 비스(디플루오로메틸)에테르를 생성시킨다. 또한 CH2HOCH3(z=3)을 염소화 반응 생성물로부터 분리하여 플루오르화시킬 수 있다. 한가지 대안으로서, 다음과 같이 염소화 반응 생성물 그 자체를 플루오르화시킬수도 있다(사전 분리없이):According to the prior art, an unstable complex mixture of chlorinated ethers, some of which are carcinogens, is removed in the present invention by using methyldifluoromethylether as starting material. Chlorination of one or more compounds having the formula CH 2 HOCH 3-Z Cl Z , wherein z is 1, 2 or 3, can be easily separated from the chlorinated reaction mixture by chlorination of the meteldifluoromethylether The reaction mixture is obtained. Chlorination of methyldifluoromethylether can only form three derivatives, i.e. z = 1, z = 2 and z = 3. Dichloromethyl difluoromethylether (z = 2) can be easily separated from the chlorinated reaction mixture which is then fluorinated with or without a separation step to produce bis (difluoromethyl) ether. CH 2 HOCH 3 (z = 3) can also be separated from the chlorination reaction product and fluorinated. As an alternative, the chlorination reaction product itself can be fluorinated (without prior separation) as follows:
상기의 모든 물질들, 특히 (I) 모노플루오로메틸 디플루오로메틸 에테르 및 (II) 비스(디플루오로메틸)에테르는 냉매로서 사용되며, 이들 (I) 과 (II)는 각각 R-11 및 R=114 냉매에 대한 대체물로서의 가치를 갖는다.All of the above materials, in particular (I) monofluoromethyl difluoromethyl ether and (II) bis (difluoromethyl) ether, are used as refrigerants, and these (I) and (II) are each R-11 And as a replacement for the R = 114 refrigerant.
본 발명의 염소화 단계 및 플루오르화 단계는 다음과 같이 표시될 수 있다:The chlorination step and fluorination step of the present invention can be represented as follows:
본 발명의 방법을 위한 출발물질로 주목되는 메틸디플루오로메틸에테르는 Journal of the American Chemical Society 에 발표된 논문에서 Hine 과 Porter 가 보고했던 방식으로 제조될 수 있는 공지된 화합물이다. 이에 관하여 문헌(Methlene derivatives as intermediates in polar reactions. VIII. Difluoromethlene in the reaction of chiorodifluoromethane with sodium methoxide. Jack Hine and John J. Perter, J. Am. Chem. Soc. 79, 5493-6(1957))을 참고로 할 수 있다. Hine 과 Porter의 논문에는, 하기 반응식으로 표시될 수 있는 나트륨메톡시드 NaOMe와 클로로디플루오로메틴(CIF2CH)과의 반응에 의한 디플루오로메틸메틸에테르(CH3OCHF2)의 제법이 기재되어 있다.Methyldifluoromethylether, which is noted as a starting material for the process of the present invention, is a known compound that can be prepared in the manner reported by Hine and Porter in a paper published in the Journal of the American Chemical Society. In this regard, Methlene derivatives as intermediates in polar reactions.VIII.Difluoromethlene in the reaction of chiorodifluoromethane with sodium methoxide.Jack Hine and John J. Perter, J. Am. Chem. Soc. 79, 5493-6 (1957). For reference. Hine and Porter's paper describes the preparation of difluoromethylmethylether (CH 3 OCHF 2 ) by reaction of sodium methoxide NaOMe with chlorodifluoromethine (CIF 2 CH), which can be represented by the following reaction formulae. It is.
요약하자면, 이 방법에서는 나트륨메톡시드의 알코올 용액을 만들고 반응 혼합물을 통해 클로로디플루오로메탄을 천천히 발포하여, 반응 혼합물내의 잔사로서 메틸디플루오로메틸에테르를 수득하는 것이 포함된다.In summary, this method involves making an alcohol solution of sodium methoxide and slowly foaming chlorodifluoromethane through the reaction mixture to obtain methyldifluoromethylether as a residue in the reaction mixture.
출발 에테르인 CH3OCHF2는, 먼저 NaOH를 CH3OH와 반응시켜서 CH3ONa를 생성시킨 후 이를 CF2HCl과 반응시킴으로써 제조될 수도 있다. 그러나 NaOH/CH3OH 반응에서는 물도 형성되며 이러한 물이 CF2HOCH3를 형성시키기 위한 후속 반응에 어떤 영향을 미치는지에 대해 현재 알려지지 않은 상태이다.The starting ether CH 3 OCHF 2 may also be prepared by first reacting NaOH with CH 3 OH to produce CH 3 ONa and then reacting with CF 2 HCl. However, water is also formed in the NaOH / CH 3 OH reaction and it is currently unknown how this water affects subsequent reactions to form CF 2 HOCH 3 .
본 발명에 따라, 메틸디플루오로메틸에테르를 다음과 같이 염소화시킨다:According to the invention, methyldifluoromethylether is chlorinated as follows:
CF2HOCH3는 CF2HOCH3를 액화시키고 이를 염소 가스와 반응시키면서 자외선 광원을 조사함으로써 적절하게 염소화시킬 수 있다는 것이 밝혀졌다. CF2HOCH3의 염소화에 의하여 단지 세개의 유도체만이 형성될 수 있으며, 이로부터 플루오르화 단계 이전에 CF2HOCHCl2및/또는 CF2HOCHl3를 쉽게 분리하거나, 또는 반응 혼합물을 분리단계없이 플루오르화시켜 CF2HOCFCl2, CH2HOCF2Cl, CF2HOCH2F, CF2HOCFHCl 및 CF2HOCF2H 의 혼합물을 수득할 수도 있다. 모든 분리단계는 분별 증류에 의해 실시될 수 있다.CF 2 HOCH 3 has been found that the same may be suitably chlorinated by irradiating the ultraviolet light source while liquefying CF 2 HOCH 3 and it reacts with the chlorine gas. Only three derivatives can be formed by chlorination of CF 2 HOCH 3 , from which CF 2 HOCHCl 2 and / or CF 2 HOCHl 3 are easily separated before the fluorination step, or the reaction mixture is fluorinated without a separation step. To obtain a mixture of CF 2 HOCFCl 2 , CH 2 HOCF 2 Cl, CF 2 HOCH 2 F, CF 2 HOCFHCl and CF 2 HOCF 2 H. All separation steps can be carried out by fractional distillation.
염소화 반응 생성물의 플루오르화에 적합하다고 밝혀진 한가지 방법에는, 할로겐화 디메틸에테르 또는 에테르들과 트리플루오르화안티몬의 반응이 포함된다. 이 반응은 다음과 같이 표시될 수 있다.One method that has been found suitable for the fluorination of chlorination reaction products includes the reaction of halogenated dimethylether or ethers with antimony trifluoride. This reaction can be expressed as follows.
산업상 규모에서 트리플루오르화안티몬 반응은 HF를 사용하여 촉매를 연속적으로 재생시킴으로써 연속적 방식으로 실시될 수 있다. 이같은 과정은 SbF3와 염소의 혼합물을 사용하여 5개의 염인 SbF3Cl2를 형성시킴으로써 수행되거나, 혹은 소규모에서는 하기 실시예 2에서와 같이 SbF3와 SbCl5의 혼합물을 사용함으로써 수행될 수 있다. 보다 통상적으로는, 다음과 같이 펜타클로로안티몬만을 사용한다:On an industrial scale the antimony trifluoride reaction can be carried out in a continuous manner by continuously regenerating the catalyst with HF. This process can be carried out using a mixture of SbF 3 and chlorine to form five salts SbF 3 Cl 2 or, on a small scale, by using a mixture of SbF 3 and SbCl 5 as in Example 2 below. More typically, only pentachloroantimony is used as follows:
마찬가지로, HF를 첨가함으로써 혼합염 촉매를 연속적으로 재생시킬 수 있다.Similarly, the mixed salt catalyst can be continuously regenerated by adding HF.
대안적인 플루오르화 과정에서는, 염소화 반응 생성물을 무수 플루오르화수소(HF)와 반응시키며, 이를 다음과 같은 반응식으로 나타낼 수 있다:In an alternative fluorination process, the chlorination reaction product is reacted with anhydrous hydrogen fluoride (HF), which can be represented by the following scheme:
상기한 플루오르화수소의 반응을 이용하여 본 발명자는 소량의 CF2HOCFCl2와 더불어 CF2HOCH2Cl을 78%정도의 높은 수율로 수득하게 되었다. HF는 아마도 매우 높은 온도인 경우를 제외하고는 통상 염소와 같은 할로겐으로 대체되지 않고 그 대신 SbF3또는 SbF3Cl2와 같은 플루오르화제의 연속 재생에 의해 플루오르화되기 때문에 이같은 결과는 예기치않은 것이었다. 분명히 디플루오로메톡시기는 알파-탄소상의 염소를 활성화시켜 이것이 HF와 쉽게 반응할 수 있게끔 해준다.By using the above reaction of hydrogen fluoride, the present inventors obtained CF 2 HOCH 2 Cl with a small amount of CF 2 HOCFCl 2 in a high yield of about 78%. This result was unexpected because HF is not usually replaced by halogen, such as chlorine, except at very high temperatures, but instead is fluorinated by continuous regeneration of fluorinating agents such as SbF 3 or SbF 3 Cl 2 . Clearly, difluoromethoxy groups activate chlorine on the alpha-carbon, making it easier to react with HF.
본 발명을 다음과 같은 실시예에 의해 상세히 예증하고자 한다.The invention is illustrated in detail by the following examples.
[실시예 1]Example 1
[a. CF2HOCH3의 제조][a. Preparation of CF 2 HOCH 3 ]
메탄올(1000ml)을 자석 교반기, 온도계, 가스 분산관, -78℃로 냉각되고 또 역시 -78℃로 냉각된 트랩에 연결되어 있는 응축기가 구비된 3리터 용량의 가지 3개 달린 둥근바닥 플라스크에 집어넣는다. 나트륨메톡시드(2215g)을 서서히 첨가하면서 혼합물을 교반해준다. 반응 플라스크의 온도를 45 내지 55℃로 조절하고 반응중에 이 범위로 유지시킨다. 반응 혼합물을 통해 클로로디플루오로메탄(569g)을 6 1/4시간에 걸쳐 서서히 발포시킨다. 트랩으로부터 회수한 물질을 약 15분간 -26℃로 가온시켜 과량의 CHF2Cl을 제거한다. 잔류물질의 중량은 250.6g이다. 잔류 물질을 가스 크로마토그래피로 분석해보면, 이것이 85.4%의 CF2HOCH3(수율: CH3ONa 기준으로 65%)을 함유한다는 것이 밝혀진다.Methanol (1000 ml) was placed in a 3-liter three-necked round bottom flask equipped with a magnetic stirrer, thermometer, gas dispersion tube, and a condenser connected to a trap cooled to -78 ° C and also to -78 ° C. Put it in. The mixture is stirred while slowly adding sodium methoxide (2215 g). The temperature of the reaction flask is adjusted to 45-55 ° C. and maintained in this range during the reaction. Chlorodifluoromethane (569 g) was slowly bubbled through the reaction mixture over 6 1/4 hours. The material recovered from the trap is warmed to −26 ° C. for about 15 minutes to remove excess CHF 2 Cl. The weight of residue is 250.6 g. Analysis of the residual material by gas chromatography reveals that it contains 85.4% of CF 2 HOCH 3 (yield: 65% based on CH 3 ONa).
[b. CF2HOCH3의 염소화][b. Chlorination of CF 2 HOCH 3 ]
장치는 온도계, 가스 분산관, 듀와(dewar) 응축기와 나란히 연결된 공기 응축기, 냉각 트랩(-78℃) 및 HCl 세정기가 구비된 250ml 용량의 가지 3개 달린 둥근 바닥 플라스크로 구성된다.The device consists of a 250 ml three-necked round bottom flask equipped with a thermometer, a gas dispersion tube, an air condenser connected side by side with a dewar condenser, a cooling trap (-78 ° C.) and an HCl scrubber.
듀와 응축기를 드라이아이스/메탄올을 사용하여 약 -30℃로 냉각시키고, 반응 플라스크를 유사한 방식으로 -15℃까지 냉각시킨다. 장치를 15분간 질소로 세척하여 산소를 제거한다. 상기(a)에서 얻어진 바와 같은 CF2HOCH3및 CHF2Cl의 혼합물(총중량은 125.9g이고, 65%의 CF2HOCH3함유)을 플라스크속에 응축시켜넣고, 플라스크에 300와트의 태양등을 조사하면서 염소 가스(140g)을 1 3/4시간에 걸쳐 첨가한다. 냉각 트랩으로부터 회수된 물질(76g)은 90.5%의 CF2HOCHCll2를 함유한다 (수율: 37%).The dewa condenser is cooled to about −30 ° C. with dry ice / methanol and the reaction flask is cooled down to −15 ° C. in a similar manner. The device is washed with nitrogen for 15 minutes to remove oxygen. A mixture of CF 2 HOCH 3 and CHF 2 Cl (total weight is 125.9 g, containing 65% CF 2 HOCH 3 ) as obtained in (a) was condensed into the flask, and the flask was irradiated with 300 watts of solar light. While adding chlorine gas (140g) over 1 3/4 hours. The material recovered from the cold trap (76 g) contained 90.5% CF 2 HOCHCll 2 (yield 37%).
[c. CHF2OCHCl2의 플루오르화][c. Fluorination of CHF 2 OCHCl 2 ]
트리플루오르화안티몬(9.8g)과 CF2HOCHCl2(24.9g)를 온도계, 자석 교반기 및 냉각 트랩과 나란히 연결된 물 응축기가 구비된 50ml용량의 가지 3개 달린 둥근 바닥 플라스크에 집어넣는다. 혼합물을 1/2시간동안 교반한 후 15분동안 57℃로 가열한다.Antimony trifluoride (9.8 g) and CF 2 HOCHCl 2 (24.9 g) are placed in a 50 ml three-necked round bottom flask equipped with a thermometer, a magnetic stirrer and a water condenser connected side by side with a cold trap. The mixture is stirred for 1/2 hour and then heated to 57 ° C. for 15 minutes.
냉각 트랩으로부터 회수한 물질을 가스 크로마토그래피로 분석해보면, 이것이 64.2%의 CHF2OCHF2(수율: 62.5%)를 함유한다는 것이 밝혀진다. 이 반응의 또다른 생성물인 CHF2OCHCl 은 혼합 생성물의 26.5%를 차지한다.Analysis of the material recovered from the cold trap by gas chromatography reveals that it contains 64.2% CHF 2 OCHF 2 (yield: 62.5%). Another product of this reaction, CHF 2 OCHCl, accounts for 26.5% of the mixed product.
[실시예 2]Example 2
CF2HOCH3(166g) 를 실시예 1의 (b)에서와 같이 염소화시켜서, 9.4%의 CHF2OClH2, 29.1%의 CHF2OCHCl2및 51.1%의 CHF2OCCl3를 함유하는 생성물 98.8g을 얻는다. 이 혼합물의 일부분(13.6g)을 실시예 1의 (c)에 기재된 바와 유사한 장치속에서 플루오르화시킨다. SbF3(7.4g)과 SbCl5(0.75g)을 반응 플라사크에 집어넣고, 염소화 생성물을 교반 혼합물속에 서서히 첨가한다. 열을 적용하지 않으면서 반응계의 온도를 44℃로 상승시킨다. 회수된 생성물(9.2g)을 가스 크로마토그래피로 분석해보면, 이것이 CF2HOCF2H(27.0%), CF2HOCF2Cl(38.4%) 및 CF2HOCFCl2(21.89%)로 구성되어 있음이 밝혀진다.98.8 g of product containing 9.4% CHF 2 OClH 2 , 29.1% CHF 2 OCHCl 2 and 51.1% CHF 2 OCCl 3 by chlorination of CF 2 HOCH 3 (166 g) as in Example 1 (b) Get A portion (13.6 g) of this mixture is fluorinated in a device similar to that described in Example (c). SbF 3 (7.4 g) and SbCl 5 (0.75 g) are placed in the reaction plasac and the chlorinated product is slowly added into the stirred mixture. The temperature of the reaction system is raised to 44 ° C. without applying heat. Analysis of the recovered product (9.2 g) by gas chromatography reveals that it consists of CF 2 HOCF 2 H (27.0%), CF 2 HOCF 2 Cl (38.4%) and CF 2 HOCFCl 2 (21.89%). .
[실시예 3]Example 3
대안적인 플루오르화 단계Alternative Fluorination Step
50%의 CF2HOCCl3가 함유된 염소화 디플루오로메틸에테르 혼합물(25g)을, 담체 가스로 작용하는 질소를 위한 입구관, NaOH 용액(10%)을 함유하는 제2의 폴리에틸렌 플라스크로 통하는 출구관, 그 뒤에 건조관 및 드라이아이스/MeOH속에서 냉각된 트랩이 구비된 폴리에틸렌 플라스크속에 집어넣는다.Chlorinated difluoromethylether mixture (25 g) containing 50% CF 2 HOCCl 3 to the inlet tube for nitrogen acting as a carrier gas, the outlet through a second polyethylene flask containing NaOH solution (10%) The tube, followed by a drying tube, and into a polyethylene flask with a trap cooled in dry ice / MeOH.
과량의 무수 플루오르화수소를 염소화 에테르에 첨가하고, 자석 교반기를 사용하여 혼합물을 교반한다. 열은 가하지 않은채 온도를 약 20℃로 유지시킨다. 필요에 따라서는 모든 유기 물질이 반응될때까지 플루오르화수소를 혼합물에 더 첨가해준다. 냉각 트랩으로부터 수거된 물질의 중량은 9.5g이다.Excess anhydrous hydrogen fluoride is added to the chlorinated ether and the mixture is stirred using a magnetic stirrer. The temperature is maintained at about 20 ° C. without applying heat. If necessary, further hydrogen fluoride is added to the mixture until all organic material has reacted. The weight of material collected from the cold trap is 9.5 g.
회수된 생성물을 가스 크로마토그래피로 분석해보면, 이것이 84.3%의 CF2HOCF2Cl(수율 : 염소화 혼합물의 CF2HOCCl3함량을 기준으로 78%)로 구성되어 있음이 밝혀진다. 또한 소량의 CF2HOCFCl2도 존재한다.Analysis of the recovered product by gas chromatography reveals that it consists of 84.3% of CF 2 HOCF 2 Cl (yield: 78% based on the CF 2 HOCCl 3 content of the chlorination mixture). There is also a small amount of CF 2 HOCFCl 2 .
본 발명은 그의 정신이나 본질적인 특색을 벗어나지 않는 범위에서 다른 구체적 형태로 실시될 수도 있다. 그러므로 본 실시형태들은 모든 면에 있어 예시적이면서 비제한적인 것이고, 본 발명의 범주는 전술한 기재사항보다는 청구범위에 의해 표시되며, 청구범위에 상당하는 의미와 범위에 속하는 모든 변화도 본 발명에 포함된다.The invention may be embodied in other specific forms without departing from its spirit or essential features. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the claims rather than the foregoing description, and all changes that come within the meaning and range of equivalency of the claims are to be embraced therein. Included.
Claims (14)
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| US59157890A | 1990-10-02 | 1990-10-02 | |
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| AU (1) | AU641049B2 (en) |
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| US5278342A (en) * | 1992-03-25 | 1994-01-11 | Hampshire Chemical Corp. | Vapor phase chlorination of difluoromethyl methyl ether |
| US5324864A (en) * | 1992-12-18 | 1994-06-28 | Hampshire Chemical Corp. | Synthesis of fluoromethyl ether |
| AU669604B2 (en) * | 1993-03-15 | 1996-06-13 | Hampshire Chemical Corp. | Vapor phase chlorination of difluoromethyl methyl ether |
| US5543055A (en) * | 1995-06-06 | 1996-08-06 | Hampshire Chemical Corp. | Purifications of flourinated dimethyl ethers |
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| US3663715A (en) * | 1969-11-03 | 1972-05-16 | Airco Inc | Ether compounds as anesthetics |
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| ZA917855B (en) | 1993-03-31 |
| MY110269A (en) | 1998-03-31 |
| GB9120912D0 (en) | 1991-11-13 |
| GB2248617A (en) | 1992-04-15 |
| CA2052553A1 (en) | 1992-04-03 |
| GB2248617B (en) | 1994-06-22 |
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