[go: up one dir, main page]

NO133404B - - Google Patents

Download PDF

Info

Publication number
NO133404B
NO133404B NO286470A NO286470A NO133404B NO 133404 B NO133404 B NO 133404B NO 286470 A NO286470 A NO 286470A NO 286470 A NO286470 A NO 286470A NO 133404 B NO133404 B NO 133404B
Authority
NO
Norway
Prior art keywords
reaction
minutes
compounds
catalyst
platinum
Prior art date
Application number
NO286470A
Other languages
Norwegian (no)
Other versions
NO133404C (en
Inventor
H-J Vahlensieck
C D Seiler
H-J Koetzsch
Original Assignee
Dynamit Nobel Ag
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 Dynamit Nobel Ag filed Critical Dynamit Nobel Ag
Publication of NO133404B publication Critical patent/NO133404B/no
Publication of NO133404C publication Critical patent/NO133404C/no

Links

Classifications

    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
    • B01J31/2234—Beta-dicarbonyl ligands, e.g. acetylacetonates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/12—Organo silicon halides
    • C07F7/14—Preparation thereof from optionally substituted halogenated silanes and hydrocarbons hydrosilylation reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
    • C07F7/1876—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-C linkages
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/828—Platinum
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2291—Olefins

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Description

hvori X betegner en alkoksy-, aryloksygruppe eller et halogen-atom, R er lik X eller betyr en alkyl-, cykloalkyl- eller arylrest og a betyr 1 eller 2 og b betyr 0 eller 1,.samt organiske forbindelser som har minst en, fortrinnsvis endeplassert alkenylrest, i nærvær av oppløste platinaforbindelser som katalysatorer. Fremgangsmåten er karakterisert ved at man som platinaforbindelser anvender et kompleks med formelen in which X denotes an alkoxy, aryloxy group or a halogen atom, R is equal to X or means an alkyl, cycloalkyl or aryl residue and a means 1 or 2 and b means 0 or 1, as well as organic compounds which have at least one, preferably terminal alkenyl residue, in the presence of dissolved platinum compounds as catalysts. The method is characterized by using a complex with the formula as platinum compounds

Ved addisjonsreaksjoner av denne type er det kjent som katalysator å anvende heksaklorplatinasyreheksahydrat. Det har imidlertid vist seg at disse omsetninger ofte selv ved skjerpede reaksjonsbetingelser stanser for tidlig, eller som In addition reactions of this type, it is known to use hexachloroplatinic acid hexahydrate as a catalyst. However, it has been shown that these turnovers often stop prematurely, or as

'følge av inntredende katalysatorforgiftninger etterhvert blir langsommere. Dessuten finner det sted ikke .ønskelige sidereaksjoner, som eksempelvis disproporsjonering av det som utgangs-material anvendte hydrogensilan eller polymerisasjon av utgangs-stoffer og addisjonsprodukter. Resultatet blir kraftige for-styrrelser i reaksjonsforløpet og utbyttenedgang. Det er derfor allerede flere ganger forsøkt istedenfor heksaklcrplatinasyre å anvende andre platinaforbindélser som katalysatorer. Således er det eksempelvis omtalt alkoholater og endolater av platina og pla-tinakompleks med oléfin-, aldehyd-, amin- og/eller fosfin-gruppeholdige, organiske forbindelser. Hovedsakelig dreier det seg derved om platinaforbindelser med to organiske rester, som 'as a result of incoming catalyst poisoning gradually becomes slower. In addition, undesirable side reactions do not take place, such as, for example, disproportionation of the hydrogen silane used as starting material or polymerization of starting substances and addition products. The result is severe disturbances in the course of the reaction and a decrease in yield. It has therefore already been attempted several times instead of hexachloroplatinic acid to use other platinum compounds as catalysts. Thus, for example, alcoholates and endolates of platinum and platinum complex with olefin, aldehyde, amine and/or phosphine group-containing organic compounds are mentioned. This mainly involves platinum compounds with two organic residues, such as

kan beskrives med den generelle formel PtABy2, hvor y er halogen og A og B er like eller forskjellige organiske ligander. Det har imidlertid vist seg at disse forbindelser bare byr på can be described by the general formula PtABy2, where y is halogen and A and B are the same or different organic ligands. However, it has been shown that these connections only offer

små fordeler sammenlignet med'heksaklorplatinasyreheksahydrat og ikke kan avhjelpe.de nevnte vanskeligheter. small advantages compared to'hexachloroplatinic acid hexahydrate and cannot remedy the aforementioned difficulties.

Det var derfor av stor interesse å finne katalysatorer for hydrosileringsreaksjonen, som ikke påvirker noen sidereaksjoner i nærvær av spesiell reaksjonsdyktigevog følsomme -funksjonelle grupper, men- som ennu er høyaktive for å kunne til-veiebringe et hurtig reaksjonsforløp. Det har nå vist seg at en katalysator med ovenfor angitt forme.l i uventet høy grad har disse egenskaper, hvilket ikke kunne forutsees. Spesielt overraskende var den høyere og' sikrere aktiviteten sammenlignet med kjente katalysatorer, som ■ gjør- det mulig heit og homogent å la også store mengder reaksjonsdeltagere reagere innen maksimalt 30 minutter og således et spesielt heldig prosessteknisk reaksjonsforløp. Den ifølge oppfinnelsen anvendte katalysatorkonsentrasjon ligger mellom It was therefore of great interest to find catalysts for the hydrosilation reaction, which do not affect any side reactions in the presence of particularly reactive and sensitive functional groups, but which are still highly active in order to provide a rapid course of reaction. It has now been shown that a catalyst of the form indicated above has these properties to an unexpectedly high degree, which could not be predicted. Particularly surprising was the higher and safer activity compared to known catalysts, which ■ makes it possible to let even large amounts of reaction participants react hot and homogeneous within a maximum of 30 minutes and thus a particularly fortunate process-technical reaction course. The catalyst concentration used according to the invention lies between

■ —2 —8 ■ -2 -8

10 og 10. millimol pr. mol substrat, dvs. pr. mol silan, fortrinnsvis mellom 10 ^ og 10~^ millimol. 10 and 10. millimol per mol of substrate, i.e. per moles of silane, preferably between 10 ^ and 10~^ millimoles.

Den i henhold til oppfinnelsen anvend-te katalysator egner seg såvel for hydrosileringer i porsjonsvis drift som for kontinuerlige metoder. Man arbeider fortrinnsvis med ekvimolare mengder, men kan imidlertid også anvende en av de to komponenter i overskudd. Ved diskontinuerlig drift kan en mindre mengde av den umettede reaksjonskomponent foreligge sammen med katalysatoroppløsninger. Man oppvarmer deretter til reaksjohstemperatur, som alt etter olefin- eller silankom-ponenten kan variere noe. Reaksjonen starter en gang med be-gynnende tilstrømning av den kalde hydrogensilankomponent og gjennomføres under egnet avkjøling og tilsetning av ytterligere kalde olefin- og hydrogensilankomponenter. Reaksjonsdeltagerne reagerer meget hurtig og på det nærmeste med kvantitativt utbytte. Overraskende nok inntrer ogs-å ved økende konsentrasjon av pro^ duktet i reaksjonskaret knapt noen forsinkning av rørsonen, hvorfor- hydrosileringsreaksjonen praktisk talt også er avsluttet når doseringen er-avsluttet. Ved kontinuerlig drift innmates blandingen av de to -reaksjonsdeltagerne og katalysatoren, The catalyst used according to the invention is suitable for hydrosilations in batch operation as well as for continuous methods. One preferably works with equimolar amounts, but one of the two components can also be used in excess. In discontinuous operation, a smaller amount of the unsaturated reaction component can be present together with catalyst solutions. It is then heated to the reaction temperature, which may vary somewhat depending on the olefin or silane component. The reaction starts once with the initial influx of the cold hydrogen silane component and is carried out during suitable cooling and the addition of further cold olefin and hydrogen silane components. The reaction participants react very quickly and immediately with quantitative yield. Surprisingly, even with an increasing concentration of the product in the reaction vessel, there is hardly any delay in the tube zone, which is why the hydrosilation reaction is practically finished when the dosing is finished. In continuous operation, the mixture of the two reaction participants and the catalyst is fed,

-oppvarmes i en- oppvarmningsanordning til reaksjonstemperatur, . -heated in a heating device to reaction temperature, .

hvorved de nødvendige oppholdstider ligger ved 1-20 minutter, fortrinnsvis 5-12 minutter, avhengig av reaksjonsdeltagerne og katalysatoren, hvorpå etterreaksjonen foregår i 2 - 10 minutter. Under etterreaks j.ons- og homogeniseringsp.erioden på 2-10 minutter opptrer ikke lenger så godt som noen varme-toning, hvilket understreker den høye katalysatoraktivitet. I forhold til dette viser såvel heksaklorplatinasyre som også eksempelvis halogenholdig platinaenolat betydelig lavere aktivitet ved at de krever lengere reaksjonstider, hvilket dessuten muliggjør sidereaksjoner og gir lavere omsetningsgrad. Denne forskjell fremgår av følgende eksempler. whereby the required residence times are 1-20 minutes, preferably 5-12 minutes, depending on the reaction participants and the catalyst, after which the post-reaction takes place for 2-10 minutes. During the post-reaction ion and homogenization period of 2-10 minutes, almost no heat fading occurs, which underlines the high catalyst activity. In relation to this, both hexachloroplatinic acid and also, for example, halogen-containing platinum enolate show significantly lower activity in that they require longer reaction times, which also enables side reactions and gives a lower degree of conversion. This difference is evident from the following examples.

De ifølge oppfinnelsen fremstilte produkter er til-strekkelig rene for de fleste anvendelsesformål, f.eks. som plast- og kunstharpikstilsetriinger, giassappreteringsmidler, impregneringsmidler for metaller, mineraler, tre tekstiler og papir samt som lim innen glassindustrien for fast forbinding mellom glass og polymer, f.eks. i glassfibertermoplast som glasstapelfiberarmert polyvinylklorid eller i glassfiberduro-mérer, som med glassfibertekstiler armerte polyester-, poly-. epoksy- eller fenolformaldehydharpikser. The products produced according to the invention are sufficiently pure for most purposes of use, e.g. as plastic and synthetic resin additives, glass dressing agents, impregnation agents for metals, minerals, wood, textiles and paper as well as as an adhesive in the glass industry for a firm connection between glass and polymer, e.g. in glass fiber thermoplastics such as glass fiber reinforced polyvinyl chloride or in glass fiber duro-meres, such as with glass fiber textiles reinforced polyester-, poly-. epoxy or phenol formaldehyde resins.

Den ifølge oppfinnelsen anvendte katalysator kan fremstilles i henhold til kjente syntesemetoder ifølge Gmelin, 68 D, side 455 - 456 (1957). Den foreligger i krystallinsk form med god stabilitet, god lagringsbestandighet og kan doseres i oppløsning med f.eks. aceton, glykoletere eller eventuelt en av de to reaksjonskomponenter ved hydrosileringsreaksjonen som oppløsnihgsmiddel uten at dens katalytiske aktivitet blir dårlig. The catalyst used according to the invention can be prepared according to known synthesis methods according to Gmelin, 68 D, pages 455 - 456 (1957). It is available in crystalline form with good stability, good storage resistance and can be dosed in solution with e.g. acetone, glycol ethers or optionally one of the two reaction components in the hydrosilation reaction as a solvent without its catalytic activity becoming poor.

Forbindelser som er hydrolyserbare ved fremgangsmåten ifølge oppfinnelsen er umettede organiske forbindelser, som alkener, eksempelvis eten, propen, 1,1,1-trifluorpropan-(2), buten-(l), buten-(2), isobuten, okten- (1) ,' deke-n- (1) , cyklo-heksen, styren, cyklopentadien osv., og alkiner som acetylen, propin, butin-(2) osv., men spesielt umettede organiske forbindelser med andre funksjonelle grupper, eksempelvis umettede etere, f.eks. divinyleter, diallyleter, etylenglykoldiallyleter, diety-lerigly-koldiallyleter, polyglykoldiallyletere, glycidallyletere, 2-allyioksymetyltetrahydrofuran, 2,2-dimetyl-4-allyloksymetyl-dibksolan, -4-allyloksymetyldioksolan-(2), 2-allyl-oksyhepta-fluorpropan, 2-allyloksy-'2H-heksafluorpropan med flere, estere og tioestere av umettede alkoholer, f.eks. vinyl- og allylestere av organiske syrer, som eddiksyre, propionsyre, tioleddiksyre, 2-etylkapronsyre, laurinsyre, isoftalsyre, tereftalsyre og halogenhydrogensyrer med flere, umettede organiske nitrogenfor-bindelser, f.eks. allylamin og allylkarbamid med flere samt umettede organiske silisiumforbindelser, f.eks. vinyltriklor-silan,. vinylmetyldiklorsilan, divinyldiklorsilan,. allyltriklor-silan, vinyltrimetoksysilan med flere. Compounds which are hydrolyzable by the method according to the invention are unsaturated organic compounds, such as alkenes, for example ethylene, propene, 1,1,1-trifluoropropane-(2), butene-(1), butene-(2), isobutene, octene- ( 1) ,' deke-n-(1) , cyclohexene, styrene, cyclopentadiene etc., and alkynes such as acetylene, propyne, butyn-(2) etc., but especially unsaturated organic compounds with other functional groups, for example unsaturated ethers , e.g. divinyl ether, diallyl ether, ethylene glycol diallyl ether, diethyleryglycol diallyl ether, polyglycol diallyl ethers, glycidallyl ethers, 2-allyloxymethyltetrahydrofuran, 2,2-dimethyl-4-allyloxymethyl dibxolane, -4-allyloxymethyldioxolane-(2), 2-allyloxyheptafluoropropane, 2 -allyloxy-'2H-hexafluoropropane with multiple, esters and thioesters of unsaturated alcohols, e.g. vinyl and allyl esters of organic acids, such as acetic acid, propionic acid, thiolacetic acid, 2-ethylcaproic acid, lauric acid, isophthalic acid, terephthalic acid and halohydrogen acids with several unsaturated organic nitrogen compounds, e.g. allylamine and allylurea with several and unsaturated organic silicon compounds, e.g. vinyltrichloro-silane,. vinylmethyldichlorosilane, divinyldichlorosilane,. allyltrichlorosilane, vinyltrimethoxysilane and more.

Egnede hydrogensilaner ér.triklorsilan, metyldi-klorsilan, dimetylklorsi-lanr etylhydrogenklorsilan, trimetoksysilan, trietoksysi-lan med flere, idet i noen tilfelle man selv-sagt må påse hvilke grupper som gjensidig utelukker hverandre, som f.eks. klorsilaner og aminogrupper. Suitable hydrogen silanes are trichlorosilane, methyldichlorosilane, dimethylchlorosilane, ethylhydrogenchlorosilane, trimethoxysilane, triethoxysilane and more, as in some cases one must of course be careful which groups are mutually exclusive, such as e.g. chlorosilanes and amino groups.

Oppfinnelsen ska! forklares nærmere ved hjelp av noen eksempler. The invention shall! is explained in more detail with the help of some examples.

Eksempel i. Example i.

I en 10 liters kolbe utstyrt med røreverk, tilbake-løpskjøler, indre termometer og to dryppetrakter-, som var fylt med- 2,85 kg allylglycideter resp. 3,05' kg trimetoksysilan ble 500 ml allylglycideter eller yglycidyloksypropyltrimetoksysilan oppvarmet til 130<G>C. Deretter ble trlsatt 1 ml av en" 0,01 molar oppløsning av mesityloksyd-platindikloridkompleks i aceton og reaksjonen forløp under hurtig- omrøring ved samtidig- tilførsel av de to reaksjonsdeltagere. i løpet av ca. 20 minutter. Ved svak ytre avkjøling og regulering av tilstrømningen ble den indre temperatur holdt mellom 130°C- og l40°Ci- Etterfølgende vakuumdestillering ga 5>4 kg av det ved kokepunkt^ 0^:8.1°C kokende y-glycidyloksypropyltr-imetoksysilan. (nn : 1,4290: ?0 In a 10 liter flask equipped with a stirrer, reflux condenser, internal thermometer and two dropping funnels, which was filled with 2.85 kg of allyl glycide resp. 3.05' kg of trimethoxysilane was heated to 130<G>C in 500 ml of allylglycidether or yglycidyloxypropyltrimethoxysilane. Then 1 ml of a 0.01 molar solution of mesityl oxide-platinum dichloride complex in acetone was added and the reaction proceeded with rapid stirring by simultaneous addition of the two reaction participants over the course of approx. 20 minutes. With slight external cooling and regulation of the inflow, the internal temperature was kept between 130°C- and 140°Ci- Subsequent vacuum distillation yielded 5>4 kg of the y-glycidyloxypropyltr-imithoxysilane boiling at boiling point^ 0^:8.1°C. (nn : 1.4290: ?0

d4 :1,073).- . d4 :1.073).- .

Eksempel 2 ( Sammenligningsforsøk). Example 2 (Comparison test).

Et sammenligningsforsøk analogt eksempel. 1 med heksaklorplatins-yre som 0,01. molar isopropanoloppløsning viste at reaksjonen forløper vesentlig langsommere. Reaksjonsdel-tagernes tilsetning krevet 2 timer. Det ble dessuten etterom-rørt i 2 timer under tilførsel av varme-. Deretter ble. det bestemt et restinnhold av 26% av .den tilsatte mengde trimetoksysilan (ved måling av det av L ml substrat med NaOH utskilte, hydrogenvol-um) . Destillasjonen ga y-gly-cidyloksypropyltri-me toks y-s i lan. i et utbytte på 66% referert til anvendt trimeto-ks-ysilan. A comparison experiment analogous example. 1 with hexachloroplatinum urea as 0.01. molar isopropanol solution showed that the reaction proceeds much more slowly. The addition of the reaction participants required 2 hours. It was also stirred again for 2 hours under the addition of heat. Then became it determined a residual content of 26% of the added amount of trimethoxysilane (by measuring the volume of hydrogen secreted by 1 ml of substrate with NaOH). The distillation gave γ-glycidyloxypropyltrimethoxy γ-s in lan. in a yield of 66% referred to the trimetho-x-ysilane used.

Eksempel 3 ( Sammenligningsforsøk). Example 3 (Comparison test).

Et ytterligere sammenligningsforsøk analogt eksempel 1 med diklorplatin-bis-acetylacetonat- som 0,01 molar acetonoppløsning ga likeledes et langsommere reaksjonsforløp. Tilsetningen av reaksjonsdeltagerne krevet likeledes- 2 timer. Etter ytterligere 2 timers omrøring og varmetilførsel ble det bestemt et restinnhold på 22$ trimetoksysilan som beskrevet i det foregående eksempel. Ved vakuumdestillasjon ble det opp-nådd et utbytte på 72% y-glycidyloksypropyltrimetoksysilan. Eksempel 4. A further comparison test analogous to example 1 with dichloroplatin bis-acetylacetonate as a 0.01 molar acetone solution likewise gave a slower course of reaction. The addition of the reaction participants also required 2 hours. After a further 2 hours of stirring and heating, a residual content of 22% trimethoxysilane was determined as described in the previous example. By vacuum distillation, a yield of 72% γ-glycidyloxypropyltrimethoxysilane was obtained. Example 4.

.Analogt eksempel 1 ble det i en 6 liters kolb.e omsatt 1,42 kg 2-allyloksymetyltetrahydrofuran (fremstilt analogt W. R. Kirner, Journal of American Chemical. Society 52 Analogously to example 1, 1.42 kg of 2-allyloxymethyltetrahydrofuran (prepared analogously to W. R. Kirner, Journal of American Chemical. Society 52) was reacted in a 6 liter flask.

(1930), side 3251-6 av allylklorid og tetrahydrofurfurylalkohol med KOH, (kokepunkt 183 - l85°C, n<20> 1,44.93) med 1,64 kg trietoksysilan på 1 ml av en 0,01 molar oppløsning av mesityl-oksydplatindiklorid i aceton. Reaksjonen krevet likeledes 20 (1930), page 3251-6 of allyl chloride and tetrahydrofurfuryl alcohol with KOH, (boiling point 183 - 185°C, n<20> 1.44.93) with 1.64 kg of triethoxysilane in 1 ml of a 0.01 molar solution of mesityl- oxideplatinum dichloride in acetone. The reaction also required 20

minutter ved 130 - l40°C.. Destillasjonen ga 3,36 kg 3-/~tetra-hydrofurfuryl-(2)-mety_l7-oksypropyl-trietoksysilan av kokepunkt2: minutes at 130 - 140°C. The distillation gave 3.36 kg of 3-[tetra-hydrofurfuryl-(2)-methyl-17-oxypropyl-triethoxysilane of boiling point 2:

127 - 129°C (nD<20>:1,4330). Elementæranalyse beregnet for C<->^<H>^O^Si (molekylvekt 306): 127 - 129°C (nD<20>:1.4330). Elemental analysis calculated for C<->^<H>^O^Si (molecular weight 306):

Molekylvektsbestemmelse: 300 (Frysepunktssenkning i benzen). Eksempel 5. Molecular weight determination: 300 (Freezing point depression in benzene). Example 5.

700 g 2-allyloksymetyltetrahydrofuran-ble fylt i en 10 liters kolbe og' oppvarmet til 130<Q>C. Det ble tilsatt 1 ml katalysator av sammensetningen fra eksempel 1. Deretter, 700 g of 2-allyloxymethyltetrahydrofuran was filled into a 10 liter flask and heated to 130°C. 1 ml of catalyst of the composition from Example 1 was added. Then,

ble reaksjonen startet ved begynnelsen av tilsetningen av tri-metoksysllan. Den startet med~ en gang, hvilket ytret seg i sterk selvoppvarming. I løpet av 20 minutter ble det tilsatt the reaction was started at the beginning of the addition of tri-methoxysilane. It started right away, which manifested itself in strong self-heating. Within 20 minutes it was added

tilsammen 4026 g trimetoks-ysilan og 4000 g 2^-all<y>loks<y>met<y> 1— tetrahydrofuran og-reaksj©nen gikk til avslutning under svak ytre avkjøling ved 130°C - l40°C. Destillasjon ga 5715 g- 3~ tetrahydrofurfuryl-(2)-metyl-bksypropyl-trimetoksysilan av kokepunkt 121°C ved 2 mm kvikksø\Lvsøy!e (nD<20>:1,43.61). Elementæranalyse beregnet for C1^H2i(O^Si: a total of 4026 g of trimethoxysilane and 4000 g of 2^-all<y>lox<y>met<y> 1-tetrahydrofuran and the reaction was completed under slight external cooling at 130°C - 140°C. Distillation gave 5715 g of 3-tetrahydrofurfuryl-(2)-methyl-boxypropyl-trimethoxysilane of boiling point 121°C at 2 mm of mercury (nD<20>: 1.43.61). Elemental analysis calculated for C1^H2i(O^Si:

2-allyloksyraetyltetrahydrofuranet ble fremstilt analogt W.R. Kirner, J.Am.Chem.Soc. 52 (1930), side 3251-6 The 2-allyloxyethyltetrahydrofuran was prepared analogously to W.R. Kirner, J. Am. Chem. Soc. 52 (1930), pp. 3251-6

av allylklorid og tetrahydrofurfurylalkohol i nærvær av et lite overskudd av konsentrert natronlut. Kokepunkt ligger ved 183 - 185°C. of allyl chloride and tetrahydrofurfuryl alcohol in the presence of a small excess of concentrated caustic soda. Boiling point is at 183 - 185°C.

Omsetningen av trimetylestere med etanol ga 3-tetrahydrofurfuryl-(2)-metyl-oksypropyl-trietoksysilan av kokepunkt 129°C ved 2 mm kvikksølvsøyle (n^0 :1, 4330 ) . Elementæranalyse beregnet' for C-^H^QOj-Si (molekylvekt 306): The reaction of trimethyl esters with ethanol gave 3-tetrahydrofurfuryl-(2)-methyl-oxypropyl-triethoxysilane of boiling point 129°C at 2 mm mercury column (n^0:1, 4330). Elemental analysis calculated' for C-^H^QOj-Si (molecular weight 306):

Molekylvektsbestemmelse: 300 (Frysepunktssenkning i benzen). Eksempel 6. Molecular weight determination: 300 (Freezing point depression in benzene). Example 6.

I en 4 liters kolbe med rører, tilbakeløpskjøler, indre termometer og to dryppetrakter som var fylt med 800 g allylacetat resp. 1,355 kg triklorsilan ble 200 ml allylacetat oppvarmet til 65°C. Deretter ble oppvarmingen fjernet, 1 ml av en 0,01 molar oppløsning av mesityloksyd-platindiklorid i allylacetat tilsatt og reaksjonen ført til avslutning under omrøring ved samtidig tilførsel av begge reaksjonsdeltagere i løpet av 8 minutter. Temperaturen økte herunder ved selvoppvarming til 105°C. Deretter kan ikke mere analytisk påvises silanhydrogen. Ved destillasjonen ble det dannet 2,28 kg 3-acetyloksypropyltriklorsilan. Kokepunkt2Q: 98 - 100°C, nD<20>:1,4359. In a 4 liter flask with stirrer, reflux condenser, internal thermometer and two dropping funnels which were filled with 800 g allyl acetate resp. 1.355 kg of trichlorosilane, 200 ml of allyl acetate were heated to 65°C. The heating was then removed, 1 ml of a 0.01 molar solution of mesityl oxide-platinum dichloride in allyl acetate was added and the reaction brought to a close with stirring by simultaneous addition of both reaction participants during 8 minutes. The temperature also increased by self-heating to 105°C. Thereafter, silane hydrogen can no longer be analytically detected. During the distillation, 2.28 kg of 3-acetyloxypropyltrichlorosilane was formed. Boiling point2Q: 98 - 100°C, nD<20>: 1.4359.

Eksempel 7. Example 7.

184 g 2-etylkapronsyreallylester (fremstilt fra 184 g of 2-ethylcaproic acid allyl ester (produced from

den fri syre og allylalkohol ved azeotrop forestring i benzen the free acid and allyl alcohol by azeotropic esterification in benzene

0 ' 20 0 ' 20

i nærvær av p-toluensulfonsyre, kokepunkt-^: 95 C, n^: 1,4298) ble.oppvarmet i en trehalset kolbe med røreverk, til-'bakeløp-skj-ø-ier, indre termometer og dryppetrakt til 75°C. Deretter ble det under -omrøring tilsatt 0,1 ml av en 0,01 molar oppløsning av mesitylo~ksydplatindikloridr>ppløsning i aceton og en mengde på 164 g trietoksysilan i løpet av 6 minutter tildosert in the presence of p-toluenesulfonic acid, boiling point -^: 95 C, n^: 1.4298) was heated in a three-necked flask with stirrer, reflux condenser, internal thermometer and dropping funnel to 75°C . Then, with stirring, 0.1 ml of a 0.01 molar solution of mesityloxideplatinum dichloride solution in acetone was added and an amount of 164 g of triethoxysilane was added over the course of 6 minutes.

fra dryppetrakten. Temperaturen økte derved til 99°C. 10 minutter etter tildrypningens avslutning kan ikke mere påvises silanhydrogen analytisk. Vakuumdestillasjonen ga 322 g 3~(2'-etylkaproyloksy)-propyl-trietoksysilan. Kokepunkt^: 134-138°C. Eksempel 8." 2 mol triklorsilan ble oppvarmet i et vanlig laboratoriums-rø-reapparat til 55°C. Det ble tilsatt 0,1 ml av en 0,01molar oppløsning av mesityloksyd-platindikloridoppløs-ning i aceton og under nitrogen i løpet av 10 minutter til-dryppet 2 mol allylmetakrylat under intens omrøring. Den indre temperatur ble herunder ved ytre avkjøling holdt under 62°C. Etter 8 minutters etteromrøring ved ca. 60°C kunne ikke mere påvises hydridhydrogen. Destillasjon ved kokepunkta ,-:.6~60'C ga 3~metakryloksypropyltriklorsilan i et utbytte av ca. 91% ved ca. 2% destillasjonsresiduum. from the drip funnel. The temperature thereby increased to 99°C. 10 minutes after the end of the drip, silane hydrogen can no longer be detected analytically. The vacuum distillation gave 322 g of 3-(2'-ethylcaproyloxy)-propyltriethoxysilane. Boiling point^: 134-138°C. Example 8." 2 moles of trichlorosilane were heated in a standard laboratory stirrer to 55°C. 0.1 ml of a 0.01 molar solution of mesityl oxide-platinum dichloride solution in acetone and under nitrogen was added during 10 minutes, 2 mol of allyl methacrylate was added drop by drop under intense stirring. The internal temperature was kept below 62°C by external cooling. After 8 minutes of stirring at approx. 60°C, hydride hydrogen could no longer be detected. Distillation at the boiling point ,-:.6~ 60'C gave 3-methacryloxypropyltrichlorosilane in a yield of about 91% at about 2% distillation residue.

Eksempel 9. Example 9.

I en gjennomstrømningsreaktor av glass med en til 64°C oppvarmet dobbeltmantel omsettes en ekvimolar blanding In a glass flow-through reactor with a double jacket heated to 64°C, an equimolar mixture is reacted

av trimetoksysilan- og allylmetakrylat som pr. mol blanding inne-holder 0,2 ml av katalysatoroppløsningen ifølge eksempel 8 ved en oppholdstid på 440 sekunder. Etter å ha forlatt reaktoren finnes det i reaksjonsprodukt ikke noe hydridhydrogen mere.. Det har den f o-r anvendelsestekniske formål nødvendige kvalitet. of trimethoxysilane and allyl methacrylate which per mol mixture contains 0.2 ml of the catalyst solution according to example 8 at a residence time of 440 seconds. After leaving the reactor, there is no more hydride hydrogen in the reaction product. It has the quality required for technical application purposes.

Claims (3)

1. Fremgangsmåte til å fremstille organosilisiumforbindelser ved addisjon av silaner med den generelle formei1. Process for preparing organosilicon compounds by addition of silanes of the general form hvori X betyr en alkoksy- eller aryloksygruppe eller et h-alogen-atom, R er lik X eller betyr alkyl-, cykloalkyl-.eller arylrest og a betegner 1 eller ,2 og b 0 eller 1, og organiske forbindelser som har minst en, fortrinnsvis endeplassert alkenylresti nærvær av oppløste platinaforbindelser som katalysatorer, kar akterisert ved at det som platinaforbindelse an-vendes et kompleks med. formelen in which X means an alkoxy or aryloxy group or an h-halogen atom, R is equal to X or means an alkyl, cycloalkyl or aryl radical and a denotes 1 or 2 and b 0 or 1, and organic compounds having at least one , preferably end-placed alkenyl residue presence of dissolved platinum compounds as catalysts, can acterized by using a complex with as platinum compound. the formula 2. Fremgangsmåte ifølge- krav 1, k a r a k t e- r i -&- e r t ved at man ved. diskontinuerlig fremgangsmåte opp-fanger en stor del av den dannede reaksjonsvarme ved tilsetning av kalde reaksjonskomponenter til reaksjonen og styrer reaksjonen ved hjelp av komponentdoseringen og bortføring av overskudd av varme. 2. Method according to claim 1, characterized in that one knows. discontinuous method captures a large part of the generated reaction heat by adding cold reaction components to the reaction and controls the reaction by means of the component dosage and removal of excess heat. 3. Fremgangsmåte ifølge krav 1, karakterisert ved at man ved kontinuerlig fremgangsmåte mater hele blandingen av de to reaksjonskomponenter og katalysatoren i oppholdstider på 1-20 minutter, fortrinnsvis 5-12 minutter, strømmende gjennom en gjennomgangsoppvarmer og deretter lar det etterreagere 2-10 minutter.3. Process according to claim 1, characterized in that, in a continuous process, the entire mixture of the two reaction components and the catalyst is fed for residence times of 1-20 minutes, preferably 5-12 minutes, flowing through a continuous heater and then allowed to react for 2-10 minutes .
NO286470A 1969-07-25 1970-07-22 NO133404C (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19691937904 DE1937904C3 (en) 1969-07-25 1969-07-25 Process for the preparation of organosilicon compounds by addition

Publications (2)

Publication Number Publication Date
NO133404B true NO133404B (en) 1976-01-19
NO133404C NO133404C (en) 1976-04-28

Family

ID=5740912

Family Applications (1)

Application Number Title Priority Date Filing Date
NO286470A NO133404C (en) 1969-07-25 1970-07-22

Country Status (11)

Country Link
JP (1) JPS4925651B1 (en)
AT (1) AT300839B (en)
BE (1) BE753898A (en)
CH (1) CH542884A (en)
DE (1) DE1937904C3 (en)
FI (1) FI51592C (en)
FR (1) FR2055613A5 (en)
GB (1) GB1292077A (en)
NL (1) NL7010996A (en)
NO (1) NO133404C (en)
SE (1) SE369723B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2159991C2 (en) * 1971-12-03 1982-10-21 Dynamit Nobel Ag, 5210 Troisdorf Silicon-containing dioxolane derivatives
EP0287659A4 (en) * 1986-10-21 1990-02-05 Inst Organicheskogo Sinteza Ak 2,6-dimethyl-3,5-dimethoxycarbonyl-4-(5'-trimethylsilyl-2'-furyl)-1,4-dihydropyridine.

Also Published As

Publication number Publication date
BE753898A (en) 1970-12-31
AT300839B (en) 1972-08-10
NO133404C (en) 1976-04-28
GB1292077A (en) 1972-10-11
NL7010996A (en) 1971-01-27
CH542884A (en) 1973-11-30
DE1937904A1 (en) 1971-02-25
DE1937904C3 (en) 1975-05-28
JPS4925651B1 (en) 1974-07-02
FI51592B (en) 1976-11-01
SE369723B (en) 1974-09-16
DE1937904B2 (en) 1974-10-10
FI51592C (en) 1977-02-10
FR2055613A5 (en) 1971-05-07

Similar Documents

Publication Publication Date Title
US3178464A (en) Production of organosilicon compounds
US2823218A (en) Process for the production of organo-silicon compounds
JP4560053B2 (en) Prescribed method for producing a silicon compound having a fluoroalkyl group by hydrosilylation
US3479392A (en) Production of unsaturated ethers and esters
EP3166952B1 (en) Process for preparation of 3-methacryloxypropyldimethylchlorosilane in continuous flow reactor
US5663400A (en) Process for preparing alkylsilanes having bulky alkyl radicals
US3576027A (en) Hydrosilation of olefins
US3950364A (en) Process for the preparation of organic silicon compounds
US4028384A (en) Process for the preparation of organic silicon compounds
NO133404B (en)
US3798252A (en) Process for the addition of silicon compounds with si-bonded hydrogen to compounds with aliphatic multiple bonds
NO761496L (en)
US6414176B2 (en) Preparation of vinylsilanes
US3933882A (en) Tube method for the preparation of olefinic siloxane compounds
Marciniec et al. Effect of substituents on silicon on cross-metathesis of vinylsilanes with 1-alkenes in the presence of ruthenium complexes
US3706777A (en) Process for the production of alkyl silanes
US4537983A (en) Method of preparing 2-phenylethylchlorosilanes
JPH09507840A (en) Method for producing fluorine-substituted olefins
US2905690A (en) Vinylation of oxazolidinones
US2424590A (en) Preparation of beta lactones
US3313837A (en) Organosilicon compounds
US3839383A (en) Hydrolysis-resistant unsaturated organic compounds containing hindered alkoxy or aryloxy groups
US3564033A (en) Tricyclohexyltin halide process
GB877050A (en) Improvements in and relating to the polymerisation of olefines, catalysts for such polymerisation, crystalline materials suitable as components of the catalysts and processes for their preparation
JPH0735388B2 (en) Process for producing alkyl orthoester of titanium, zirconium or hafnium