WO2014163414A1 - Procédé de préparation d'un polysilane - Google Patents

Procédé de préparation d'un polysilane Download PDF

Info

Publication number
WO2014163414A1
WO2014163414A1 PCT/KR2014/002890 KR2014002890W WO2014163414A1 WO 2014163414 A1 WO2014163414 A1 WO 2014163414A1 KR 2014002890 W KR2014002890 W KR 2014002890W WO 2014163414 A1 WO2014163414 A1 WO 2014163414A1
Authority
WO
WIPO (PCT)
Prior art keywords
polysilane
chlorine
chloride
reaction product
tin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2014/002890
Other languages
English (en)
Korean (ko)
Inventor
서진석
강경훈
고태호
노영수
전문규
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
KCC Corp
Original Assignee
KCC Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by KCC Corp filed Critical KCC Corp
Publication of WO2014163414A1 publication Critical patent/WO2014163414A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/08—Compounds containing halogen
    • C01B33/107—Halogenated silanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/08—Halides
    • B01J27/10—Chlorides

Definitions

  • the present invention relates to a method for producing polysilane, and more particularly, to a method for producing a polysilane comprising disilane chloride by reacting silicon powder with a chlorine-containing gas in the presence of a catalyst.
  • Chlorinesilanes and methylchloridesilanes are the basic raw materials for the production of silicone chemicals.
  • High-value chemicals used in the production of polysilicon which is a raw material for semiconductor manufacturing gases or solar cells, as precursors for producing silicon carbide single crystals or thin films, and as raw materials for various other chemical products.
  • polysilanes such as polysilanes and polymethylsilanes having a large number of bonds between silicones of silane chloride and methyl chloride silane are chemically unstable compared to monomolecular silanes, and thus are difficult to manufacture and high in purity.
  • the reduction temperature to silicon is low and it has a great advantage in the manufacture of semiconductors, polysilicon and silicon carbide.
  • US Pat. No. 4,861,574 proposes a reaction composition for the production of polychlorosilane having a low amount of by-product metal chloride using metal silicon powder and a copper catalyst, but the selectivity of dichlorosilane is low (less than 60%). It is not suitable for commercialization in reactor operation and reaction efficiency by using a fixed bed reactor in which chlorine, a reaction source gas, is introduced in a top-down manner.
  • US Patent US 6846473 B2 proposed a method for recovering the polychlorinated silane as a by-product from the waste gas flowing out of the Siemens reactor for the production of polysilicon using trichlorosilane, but the amount of polychlorinated silane contained in the waste gas is small and additional chlorine is added. It is very inefficient in the recovery of polychlorosilane, such as through a multi-stage distillation plant.
  • European Patent EP 2415712 A1 proposes a process for recovering polychlorinated chlorosilanes from the high fertilizers generated as a by-product of a facility for converting tetrachloride silanes into trichlorides during the polysilicon manufacturing process. High costs are expected to operate the facility to recover the wastewater.
  • the present invention provides a production method capable of commercially mass-producing a polysilane comprising a high purity disilane silane.
  • Polysilane production method the step of preparing a reaction product by adding a silicon powder, a catalyst, and a chlorine-containing gas to the reactor and proceeding the reaction; Liquefying the reaction product prepared; First distillation to remove impurities having a lower boiling point than the final product in the liquefied reaction product; A second distillation to remove impurities having a boiling point higher than that of the final product in the first distilled reaction product; And removing metal impurities from the second distilled reaction product using an adsorption column.
  • the production step of the reaction product may be made by adding silicon powder, a catalyst, a chlorine-containing gas and an inert gas to the reactor. If there is a cooling device inside and outside the reactor to be superior to the cooling effect of the inert gas may not include an inert gas, otherwise it is preferred to perform the reaction by the simultaneous inert gas.
  • the reactor internal cooling device is a cooling coil inside the reactor and the refrigerant contains oil and water or an inert gas.
  • the reactor external cooling device is a cooling jacket, and the refrigerant includes oil and water or an inert gas, and may be naturally cooled by mounting several rings to increase the cooling surface area on the outside.
  • the inert gas may include one or more selected from the group consisting of nitrogen, argon, helium and hydrogen.
  • the inert gas is not only able to assist fluidization but also very important in controlling the reaction temperature and reactivity, so that the use of the inert gas is important.
  • the amount of the inert gas may be 1 to 90%, and more preferably 1 to 70% based on the total volume of the chlorine-containing gas and the inert gas. If the amount of use is less than 1%, there is a concern that the selectivity is reduced by increasing the reaction temperature. If the amount is more than 90%, the reactor productivity and selectivity may be rapidly decreased.
  • the reactor used in the polysilane production method may be a fluidized bed reactor.
  • the reaction heat generated during the polysilane synthesis reaction can be effectively removed to maintain a uniform reaction temperature, and the mixing of the reactants can be promoted, thereby improving production efficiency.
  • the ratio of the flow rate (U) of the chlorine-containing gas and the inert gas and the minimum fluidization rate (Umf) of the silicon powder is 0.5 to 20 (U / Umf).
  • a silicon powder which can be used at low cost without using a silicon alloy as an initial reactant was used.
  • Purity of the silicon powder is preferably 10 ⁇ 99.999999999 wt%, more preferably 90 ⁇ 99.99 wt%.
  • the silicon powder contains metals such as Fe, Ca, Al, Ti, Mn, Cr, Ni, Cu, and Zn as impurities. These metals may react with chlorine contained in the reaction gas to form a metal chlorine compound.
  • metal chlorine compounds include materials similar to the boiling points of polysilanes, in particular dihexachloride, which may make it difficult to separate and purify polysilanes. Therefore, it may be desirable to have a low content of metal impurities present in the raw silicon powder.
  • the concentration of titanium and aluminum contained in the silicon powder is preferably 5,000 ppm or less, more preferably 1,000 ppm or less.
  • the silicon powder may have a particle diameter of 1 to 2,000 ⁇ m, more preferably, a particle having a particle size distribution of 10 to 1,000 ⁇ m and an average particle diameter of 50 to 500 ⁇ m. It is suitable for use in a fluidized bed reactor when the size of the particle diameter is in this range. That is, if the particle diameter is less than 1 ⁇ m, the silicon powder is easily released out of the reactor due to fluidization in the reactor, and if it exceeds 2,000 ⁇ m, the effective fluidization is not performed. Therefore, the heat of reaction generated by the chlorine-containing gas is effectively dispersed. It can be difficult to make.
  • Tin (Sn), copper (Cu), zinc (Zn), etc. may be used as the catalyst, but zinc (Zn), zinc chloride, zinc oxide, or zinc alloy may be used rather than the main catalyst of copper.
  • Catalysts made of (zinc alloy) and catalysts made of tin (Sn), tin chloride, tin oxide or tin alloy may be preferred. More preferably tin alloy or tin oxide can be used.
  • Tin alloys include tin-copper (SnCu), tin-lead (SnPb), tin-bismuth (SnBi) and other alloys. Among them, it is preferable to use a highly active tin-copper alloy.
  • the tin-copper alloy may be composed of 0.10 to 50% by weight of tin and 50 to 99.9% by weight of copper.
  • the content of the catalyst may be 0.1 to 20% by weight, more preferably 1 to 10% by weight based on the total solid reactants.
  • the role of the catalyst decreases, so that the reactivity and selectivity are difficult to sustain.
  • the catalyst content exceeds 20%, the catalyst may accumulate in the reactor and the Si content may decrease in the reactor, thereby reducing the reactivity. It is not desirable to go out of range significantly.
  • the chlorine-containing gas may include one or more selected from the group consisting of chlorine, hydrogen chloride and methyl chloride. Considering that the polysilane prepared may easily react with water, it may be preferable to use anhydrous chlorine, anhydrous hydrochloric acid, and anhydrous methyl chloride gas with a minimum amount of water in the reaction gas.
  • the step of preparing the reaction product may be carried out at 120 ⁇ 350 °C and more preferably may be carried out at 150 ⁇ 300 °C. If the reaction temperature is less than 120 ° C., the reaction does not proceed smoothly, and if it exceeds 350 ° C., there is a fear that the selectivity is sharply reduced.
  • reaction raw material since the amount of the reaction raw material decreases as the reaction proceeds, the reaction raw material may be additionally added periodically to maintain a constant amount of the reaction raw material.
  • Polysilane prepared according to an embodiment of the present invention may be represented by the following formula (1).
  • the polysilane may contain a large amount of disilane silane.
  • Apparatus a is a fluidized bed reactor that fills a solid reactant and adds reactant gas to produce polysilane
  • device b is a solid waste catalyst, waste silicon, and solids contained as impurities in the gas (reaction product) flowing out of the fluidized bed reactor (a).
  • Device c is a cooling device for condensing the effluent gas (reaction product) from which impurities are removed
  • device d is a reservoir for storing the condensed reaction product (polysilane mixture)
  • device e has a low boiling point (lower boiling point than the final product).
  • Distillation column for removing impurities in the apparatus apparatus f is a purification column for separating impurities having high boiling point (boiling point higher than the final product) separated from column (e), and apparatus g is an adsorption column for removing metal impurities. to be.
  • Solid reactants such as silicon powder, catalyst and the like filled in the fluidized bed reactor (a) may be filled to a height of 0.5 to 8 times the diameter of the reactor for contact time with the reaction gas and proper fluidization, and preferably 0.5 to It can be filled up to six times the height.
  • the inert gas and the chlorine-containing gas 1 for fluidization are introduced into the bottom of the fluidized bed reactor a, and may be introduced into the reactor through a dispersion plate to support the reactants and evenly introduce the gas.
  • the reactant packed in the reactor may allow the reaction to proceed in the range of 120 to 350 ° C, more preferably 150 to 300 ° C. Since the amount of reactants decreases as the reaction proceeds, the reactant 2, which is a mixture of silicon powder and catalyst, may be added periodically to maintain a constant amount of reactants.
  • the gas (reaction product, 3) flowing out of the fluidized bed reactor (a) may be accompanied by an inert gas, unreacted chlorine containing gas, synthesized polysilanes, spent catalyst, waste silicon powder, and metal chlorides.
  • the filter (b) may be passed to remove solid impurities among them.
  • the filter (b) may be used in parallel with a microfiltration device such as a cyclone as a device for removing solid impurities, and may also include adsorption reaction devices for removing some metal chlorides.
  • the impurities 4 removed from the filter b are corrosive and reactive, so that they can be neutralized and safely disposed of.
  • the effluent gas (reaction product) from which impurities are removed may be liquefied while passing through the condenser (c).
  • the liquefaction 6 may be transferred to the reservoir d.
  • the inert gas and the unreacted chlorine-containing gas 7 which are not liquefied in the condenser may be recovered and reused or transferred to a scrubber for safe neutralization and discharged.
  • the liquefaction 6 may be a mixture in which the content of silane tetrachloride and dichlorochloride is 95% by weight or more based on the total weight, and among these, the hexachloride may be a mixture containing as little as 20% or more and as much as 80% or more. .
  • the liquefaction 6 can be transferred to the distillation column e to separate impurities having a lower boiling point (low boiling point) than disilane silane.
  • Impurities flowing to the top of the distillation column (e) may include a silane chloride composed mostly of monosilicon atoms such as silane tetrachloride, and may include trace amounts of siloxane and unreacted chlorine-containing gas, some low boiling metal chlorides, and the like.
  • Low boiling metal chlorides may include titanium chloride and tin chloride.
  • the distillate 10 flowing out to the bottom of the distillation column (e) may include mostly dihexachloride, more polysilanes and high boiling metal chlorides.
  • the high boiling point metal chloride may include aluminum chloride, iron chloride, copper chloride, and the like, and some chloride may be present as a solid dispersed in a solution. Distillate 10 may be sent to distillation column f to remove these high boiling metal chlorides.
  • the upper distillate (11) of the column (f) may be discharged by removing polysilane containing high purity dichlorochloride and the lower distillate (12) having higher boiling point than the polysilane and high boiling metal chloride. have.
  • column (f) may be composed of one or more distillation columns according to the type of polysilane to be distilled.
  • the polysilane 11 including disilane silane may be introduced into the adsorption column (g).
  • adsorption column g
  • metal impurities contained in polysilanes such as disilane chlorochloride it is important to select an appropriate adsorbent.
  • adsorbents include polymers having molecular sieve structures such as activated carbon, zeolite, silica, and alumina, and polymers. Adsorption resin, resin, etc. which were formed.
  • the polysilane 13 containing the highly purified dichlorosilane through the adsorption column is transferred to the corresponding reservoir, and the polysilane 14 including the impurities removed from the adsorption column may be neutralized and disposed of.
  • the adsorption column (g) may be subjected to a regeneration process for reuse.
  • polysilane especially dichlorochloride, which is useful as a raw material for amorphous silicon thin films, optical glass substrates, and the like.
  • FIG. 1 illustrates a polysilane manufacturing process according to an embodiment of the present invention.
  • the chlorine (Cl 2 ) gas was slowly increased to adjust to 2 of the flow rate ratio (U / Umf).
  • the reaction product was filtered to remove solid impurities and condensed at 25 ° C. for 8 hours in a cooler to prepare a liquefaction (polysilane mixture). Then, the unliquefied nitrogen and unreacted chlorine gas were removed and stored in a storage tank, which was taken as a sample and analyzed for the composition of each component by gas chromatography.
  • Example 4 As shown in Table 1, the yield of disilane silane was the highest in Example 4 using the tin-copper alloy as a catalyst.
  • the weight ratio of the catalyst is 1% by weight, 3% by weight, 10% by weight, and 15% by weight, and the other conditions are the same as in Example 4.
  • the sample was prepared and its composition was confirmed by gas chromatogram.
  • Example 8 As shown in Table 2, the yield of disilane hexachloride was the highest in Example 8 using the catalyst content of 10% by weight.
  • the temperature in the fluidized bed reactor was 240 °C, 280 °C, 300 °C and the other conditions were the same as in Example 4 to prepare a sample and the composition was confirmed by gas chromatogram, The ratios were compared based on Example 4 (yield hexachloride 64% by weight).
  • Example 10 As shown in Table 3, the yield of disilane silane was the highest in Example 10 maintained the reaction temperature at 240 °C.
  • the yield of dichlorosilane in the case of using the reaction gas as chlorine and hydrogen chloride was 64% by weight and 43% by weight, respectively.
  • the yield of polysilane when the reaction gas was used as chlorine and when the mixed gas of chlorine / methane chloride was used was 64% by weight and 53% by weight, respectively.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Silicon Compounds (AREA)

Abstract

La présente invention concerne un procédé de préparation d'un polysilane et, plus précisément, un procédé de préparation d'un polysilane pouvant être l'hexachlorodisilane, ledit procédé impliquant de faire réagir une poudre de silicium avec un gaz chloré en présence d'un catalyseur. Selon un mode de réalisation de la présente invention, il est possible d'augmenter le rendement en polysilane, en particulier en hexachlorodisilane, lequel peut être utilisé en tant que matière première dans une couche mince de silicium polycristallin amorphe, un substrat de verre pour fibre optique, etc. En outre, grâce à l'utilisation d'un réacteur à lit fluidisé, la chaleur réactionnelle générée lors de la synthèse du polysilane, tel que l'hexachlorodisilane, peut être éliminée efficacement, ce qui permet de maintenir une température réactionnelle uniforme, et un réactif peut être mélangé de façon plus homogène, ce qui permet donc d'améliorer l'efficacité de préparation du polysilane. Il est également possible de préparer un polysilane très pur grâce à une technique consistant à séparer et purifier successivement un mélange de polysilanes.
PCT/KR2014/002890 2013-04-03 2014-04-03 Procédé de préparation d'un polysilane Ceased WO2014163414A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2013-0036343 2013-04-03
KR1020130036343A KR20140120507A (ko) 2013-04-03 2013-04-03 폴리실란 제조방법

Publications (1)

Publication Number Publication Date
WO2014163414A1 true WO2014163414A1 (fr) 2014-10-09

Family

ID=51658635

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2014/002890 Ceased WO2014163414A1 (fr) 2013-04-03 2014-04-03 Procédé de préparation d'un polysilane

Country Status (2)

Country Link
KR (1) KR20140120507A (fr)
WO (1) WO2014163414A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109881305A (zh) * 2019-04-03 2019-06-14 中国恩菲工程技术有限公司 一种连续制备硅纳米纤维的气相纺丝方法及装置
CN115215729A (zh) * 2021-04-14 2022-10-21 中国石油化工股份有限公司 一种聚酯级煤基乙二醇的制法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090057367A (ko) * 2006-07-20 2009-06-05 레브 리뉴어블 에너지 벤쳐스 아게 폴리실란의 가공 및 용도
KR20100091573A (ko) * 2009-02-11 2010-08-19 코아텍주식회사 촉매와 반응열을 이용한 삼염화실란의 제조방법 및 장치
KR101134230B1 (ko) * 2011-06-24 2012-04-09 웅진폴리실리콘주식회사 염화실란 정제 방법 및 시스템, 그리고 금속계 불순물 정제용 흡착제
JP2012091960A (ja) * 2010-10-27 2012-05-17 Shin-Etsu Chemical Co Ltd クロロシラン類の精製方法
KR20120089195A (ko) * 2011-02-01 2012-08-09 와커 헤미 아게 증류에 의한 클로로실란의 정제 방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090057367A (ko) * 2006-07-20 2009-06-05 레브 리뉴어블 에너지 벤쳐스 아게 폴리실란의 가공 및 용도
KR20100091573A (ko) * 2009-02-11 2010-08-19 코아텍주식회사 촉매와 반응열을 이용한 삼염화실란의 제조방법 및 장치
JP2012091960A (ja) * 2010-10-27 2012-05-17 Shin-Etsu Chemical Co Ltd クロロシラン類の精製方法
KR20120089195A (ko) * 2011-02-01 2012-08-09 와커 헤미 아게 증류에 의한 클로로실란의 정제 방법
KR101134230B1 (ko) * 2011-06-24 2012-04-09 웅진폴리실리콘주식회사 염화실란 정제 방법 및 시스템, 그리고 금속계 불순물 정제용 흡착제

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109881305A (zh) * 2019-04-03 2019-06-14 中国恩菲工程技术有限公司 一种连续制备硅纳米纤维的气相纺丝方法及装置
CN109881305B (zh) * 2019-04-03 2023-08-22 中国恩菲工程技术有限公司 一种连续制备硅纳米纤维的气相纺丝方法及装置
CN115215729A (zh) * 2021-04-14 2022-10-21 中国石油化工股份有限公司 一种聚酯级煤基乙二醇的制法

Also Published As

Publication number Publication date
KR20140120507A (ko) 2014-10-14

Similar Documents

Publication Publication Date Title
CN102753478B (zh) 三氯硅烷的制造方法
JP5442780B2 (ja) クロロシランの蒸留による精製方法
JP5311014B2 (ja) 転換反応ガスの分離回収方法。
EP2036858B1 (fr) Procédé de purification de chlorosilanes
RU2368568C2 (ru) Способ получения кремния
EP2634142A1 (fr) Procédé pour la purification de chlorosilanes
US11242253B2 (en) Method for producing polycrystalline silicon
JP5339948B2 (ja) 高純度多結晶シリコン製造方法
JP6179246B2 (ja) 多結晶シリコン製造方法及び製造装置
EP1882675B1 (fr) Procede de production de silicium
US8404205B2 (en) Apparatus and method for producing polycrystalline silicon having a reduced amount of boron compounds by forming phosphorus-boron compounds
WO2011024257A1 (fr) Purification du chlorosilane à l'aide d'un composé d'amine
JP2014034474A (ja) 多結晶シリコンの製造方法
KR20140120507A (ko) 폴리실란 제조방법
JP6446163B2 (ja) 多結晶シリコンの製造方法
KR20160096655A (ko) 트리클로로실란의 제조 방법
JPH02196014A (ja) 高純度ジクロロシランの製造方法
KR20170091623A (ko) 공정 배출가스 흐름 내에 함유된 클로로실란 혼합물로부터 헥사클로로디실란의 회수 방법
US20130121908A1 (en) Method for producing trichlorosilane with reduced boron compound impurities
TWI726508B (zh) 用於降低含鹵矽烷的組合物中之硼化合物含量的方法
CN112645976B (zh) 一种利用氯基CVD晶体薄膜生长制程尾气FTrPSA制备甲基氯硅烷类有机硅方法
CN117263141A (zh) 一种提纯多晶硅生产中循环氢气的方法
CN115974907A (zh) 一种电子级四甲基硅烷的制备方法
JP2007269679A (ja) 高純度アルキルシランの製造方法
CN121044586B (zh) 一种六氯乙硅烷的回收方法及回收装置

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14779872

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14779872

Country of ref document: EP

Kind code of ref document: A1