DE1220615B - Process for the preparation of organopolysiloxane polyalkylene oxide block copolymers - Google Patents
Process for the preparation of organopolysiloxane polyalkylene oxide block copolymersInfo
- Publication number
- DE1220615B DE1220615B DED39518A DED0039518A DE1220615B DE 1220615 B DE1220615 B DE 1220615B DE D39518 A DED39518 A DE D39518A DE D0039518 A DED0039518 A DE D0039518A DE 1220615 B DE1220615 B DE 1220615B
- Authority
- DE
- Germany
- Prior art keywords
- general formula
- formula
- atoms
- units
- block copolymers
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 20
- 229920000233 poly(alkylene oxides) Polymers 0.000 title claims description 14
- 229920001296 polysiloxane Polymers 0.000 title claims description 14
- 229920001400 block copolymer Polymers 0.000 title claims description 8
- 238000002360 preparation method Methods 0.000 title description 2
- -1 dimethylsiloxane units Chemical group 0.000 claims description 41
- 238000004519 manufacturing process Methods 0.000 claims description 9
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 125000004429 atom Chemical group 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 150000001340 alkali metals Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000005375 organosiloxane group Chemical group 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 239000006260 foam Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 229920005830 Polyurethane Foam Polymers 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000011496 polyurethane foam Substances 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 3
- 238000011067 equilibration Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- UXTFKIJKRJJXNV-UHFFFAOYSA-N 1-$l^{1}-oxidanylethanone Chemical compound CC([O])=O UXTFKIJKRJJXNV-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- YGHUUVGIRWMJGE-UHFFFAOYSA-N chlorodimethylsilane Chemical compound C[SiH](C)Cl YGHUUVGIRWMJGE-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000005048 methyldichlorosilane Substances 0.000 description 2
- 125000005702 oxyalkylene group Chemical group 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N trimethylsilyl-trifluoromethansulfonate Natural products C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001266 acyl halides Chemical class 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000004651 carbonic acid esters Chemical group 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Silicon Polymers (AREA)
- Polyurethanes Or Polyureas (AREA)
Description
Verfahren zur Herstellung von Organopolysiloxanpolyalkylenoxydblockmischpolymeren Die Verwendung von Mischpolymeren, bestehend aus Polyalkylenoxydblöcken, die an Organopolysiloxanblöcke durch SiOC-Bindung gebunden sind, als oberflächenaktive Mittel zur Schaumregelung bei der Herstellung von Polyurethanschaumstoffen ist bekannt.Process for the preparation of organopolysiloxane polyalkylene oxide block copolymers The use of copolymers, consisting of polyalkylene oxide blocks, which at Organopolysiloxane blocks are bound by SiOC bonds, as surface-active Means for regulating foam in the production of polyurethane foams are known.
Ferner wurde bereits die Verwendung von Mischpolymeren, bestehend aus miteinander durch Si=C-Bindung verbundenen Polyalkylenoxyd- und linearen Organopolysiloxanblöcken, für den gleichen Zweck vorgeschlagen. Furthermore, the use of copolymers has already been made from polyalkylene oxide and linear organopolysiloxane blocks connected to one another by Si = C bonds, proposed for the same purpose.
Die letztere Art von Mischpolymeren besitzt gegenüber der ersteren Art den beträchtlichen Vorteil, daß sie beständig gegen Wasser und andere Verbindungen mit reaktionsfähigen Hydroxylgruppen ist und somit auch unter feuchten Bedingungen oder im Gemisch mit Hydroxylgruppen enthaltenden Polyäthern oder Polyestern vor dem Verschäumen gelagert werden kann. The latter kind of interpolymers has over the former Kind have the considerable advantage of being resistant to water and other compounds with reactive hydroxyl groups and therefore also under humid conditions or in a mixture with polyethers or polyesters containing hydroxyl groups can be stored after foaming.
Die unter Verwendung der bisher bekannten Mischpolymeren aus durch Silicium-Kohlenstoff-Bindungen miteinander verbundenen Polyoxyalkylen-und Organopolysiloxanblöcken im Einstufenverfahren hergestellten biegsamen Schaumstoffe weisen jedoch den Nachteil auf, daß sie den sogenannten pneumatischen Effekt zeigen, d. h., daß sie nach dem Zusammendrücken und dem Aufheben des Druckes nicht sofort ihre ursprüngliche Form annehmen. Dies ist besonders nachteilig, wenn die Schaumstoffe als Polster verwendet werden. Using the previously known copolymers from by Silicon-carbon bonds interconnected polyoxyalkylene and organopolysiloxane blocks However, flexible foams produced by the one-step process have the disadvantage on that they show the so-called pneumatic effect, d. that is, after the Squeezing and releasing the pressure does not immediately return to their original shape accept. This is particularly disadvantageous when the foams are used as a cushion will.
Der pneumatische Effekt kann zwar durch mechanische Behandlung der Schaumstoffe unter Zerreißung der geschlossenen Zellen beseitigt werden. The pneumatic effect can be achieved by mechanical treatment of the Foams are eliminated with rupture of the closed cells.
Dies bedeutet jedoch einen zusätzlichen Arbeitsgang.However, this means an additional operation.
Es ist ferner bekannt, daß durch Mitverwendung von Organopolysiloxanölen, die keine Polyalkylenoxydblöcke enthalten, der Gehalt an offenen Zellen gesteigert werden kann. Wegen der geringen Löslichkeit der unmodifizierten Organopolysiloxanöle im Reaktionsgemisch entfalten diese Ole jedoch zu früh ihre Wirkung, so daß die Zellen zu klein und zu unregelmäßig ausfallen. It is also known that by using organopolysiloxane oils, which do not contain any polyalkylene oxide blocks, the content of open cells is increased can be. Because of the low solubility of the unmodified organopolysiloxane oils In the reaction mixture, however, these oils develop their effect too early, so that the Cells are too small and too irregular.
Beansprucht ist ein Verfahren zur Herstellung von Organopolysiloxanpolyalkylenoxydblockmischpolymeren durch Umsetzung von Organopolysiloxanen mit Polyalkylenoxyden, das dadurch gekennzeichnet ist, daß man solche Organopolysiloxane verwendet, die je Molekül durchschnittlich 6 bis 30 Dimethylsiloxaneinheiten sowie 3 oder 4 Organosiloxaneinheiten mit einem oder zwei Si-gebundenen Methylrest(en) und je einem an das Si-Atom gebundenen Wasserstoffatom oder je einer Gruppe der allgemeinen Formel (CH2)3X (X = Halogenatom), gegebenenfalls neben Siloxaneinheiten der allgemeinen Formel RaSi04-a 2 (R = von aliphatischen Mehrfachbindungen freier Kohlenwasserstoffrest mit 1 bis 10 C-Atomen; a = 0 oder 1), oder Trimethylsiloxyeinheiten enthalten, und als Polyalkylenoxyde Allyläther der allgemeinen Formel CH2 = CHCH2(0R")mA oder Alkoholate der allgemeinen Formel Me(OR"),A (R" = Athylen-, Propylen- und/oder Butylenrest; Verhältnis der Athylenreste zu den gesamten anderen Alkylenresten und Verhältnis der Kohlenstoffatome zu den Sauerstoffatomen = 2,3 :1 bis 2,8 :1; m = 25 bis 80; A = Rest der Formel - OR', - OOCR' und/oder R' = von aliphatischen Mehrfachbindungen freier, gegebenenfalls durch Athersauerstoffatome unter- brochener Kohlenwasserstoffrest, der außer den Wasserstoffatomen nicht mehr als 10 Atome aufweist; Me = Alkalimetall) verwendet.What is claimed is a process for the production of organopolysiloxane polyalkylene oxide block copolymers by reacting organopolysiloxanes with polyalkylene oxides, which is characterized in that organopolysiloxanes are used which contain an average of 6 to 30 dimethylsiloxane units and 3 or 4 organosiloxane units with one or two Si-bonded methyl radical (s) per molecule. and one hydrogen atom bonded to the Si atom or one group of the general formula (CH2) 3X (X = halogen atom), optionally in addition to siloxane units of the general formula RaSi04-a 2 (R = hydrocarbon radical with 1 to 10 C free of aliphatic multiple bonds Atoms; a = 0 or 1), or contain trimethylsiloxy units, and as polyalkylene oxides, allyl ethers of the general formula CH2 = CHCH2 (0R ") mA or alcoholates of the general formula Me (OR"), A (R "= ethylene, propylene and / or butylene radicals; ratio of the ethylene radicals to all of the other alkylene radicals and ratio de r carbon atoms to the oxygen atoms = 2.3: 1 to 2.8: 1; m = 25 to 80; A = remainder of the formula - OR ', - OOCR' and / or R '= hydrocarbon radical free of aliphatic multiple bonds, possibly interrupted by ether oxygen atoms, which apart from the hydrogen atoms has no more than 10 atoms; Me = alkali metal) is used.
Die erfindungsgemäß hergestellten Organopolysiloxanpolyalkylenoxydblockmischpolymeren eignen sich besonders zur Schaumregulierung bei der Herstellung von Polyurethanschaumstoffen, ohne daß der oben geschilderte Nachteil eines pneumatischen Effektes auftritt. The organopolysiloxane polyalkylene oxide block copolymers prepared in accordance with the invention are particularly suitable for foam regulation in the production of polyurethane foams, without the above-described disadvantage of a pneumatic effect occurring.
Die beanspruchte Umsetzung wird nach an sich bekannten Verfahren durchgeführt. Ausführungs- formen dieser bekannten Verfahren, die zu Organosilciumverbindungen mit porenregelnder Wirkung bei der Herstellung von Polyurethanschaumstoffen führen, sind jedoch bisher nicht bekanntgeworden, sondern sind nur Gegenstand bisher . unveröffentlichter Vorschläge. The claimed implementation is carried out according to processes known per se carried out. Execution form these known processes, which lead to organosilicon compounds with a pore-regulating effect in the production of polyurethane foams, however, have not yet become known, but have only been the subject matter so far. unpublished Suggestions.
Nach dem beanspruchten Verfahren herzustellende und bei der hier nicht beanspruchten Polyurethanschaumstoffherstellung bevorzugt zu verwendende Organopolysiloxan-Polyalkylenoxyd-Blockmischpolymere sind solche der allgemeinen Formeln In diesen Formeln haben R, R', R", A und m die angegebene Bedeutung, n ist durchschnittlich 6 bis 30, a 0 oder 1, b 1 oder 2 und c 3 oder 4. Zweckmäßig enthalten die Mischpolymeren mindestens 13 Gewichtsprozent (CH3)2SiO-Einheiten.Organopolysiloxane-polyalkylene oxide block copolymers to be produced by the claimed process and preferably used in the polyurethane foam production not claimed here are those of the general formulas In these formulas, R, R ', R ", A and m have the meanings given, n is on average 6 to 30, a 0 or 1, b 1 or 2 and c 3 or 4. The copolymers expediently contain at least 13 percent by weight (CH3 ) 2SiO units.
Es sei darauf hingewiesen, daß die angegebenen Formeln der durchschnittlichen molekularen Zusammensetzung der nach dem beanspruchten Verfahren herzustellenden Polymeren entsprechen, d. h., daß die Länge der Dimethylsiloxyblöcke und/oder der Oxyalkylenblöcke in den Mischpolymeren keineswegs einheitlich sein muß, sondern beträchtlichen Schwankungen unterworfen sein kann, solange die Durchschnittswerte von n und m in den angegebenen Bereichen liegen. Außerdem müssen die Siliciumatome, an die Oxyalkylenblöcke gebunden sind, nicht gleichmäßig entlang der Siloxankette verteilt sein. It should be noted that the formulas given are the average molecular composition of the to be produced by the claimed method Correspond to polymers, d. That is, the length of the dimethylsiloxy blocks and / or the Oxyalkylene blocks in the copolymers by no means have to be uniform, but rather can be subject to considerable fluctuations as long as the averages of n and m are in the specified ranges. In addition, the silicon atoms bound to the oxyalkylene blocks, not evenly along the siloxane chain be distributed.
Beispiele für Reste R sind Methyl, Äthyl, Isopropyl, Phenyl, Benzyl, Cyclohexyl, beta-Phenylpropyl, beta-Phenyläthyl, Hexyl, Methylcyclohexyl, Decyl, Tolyl und Xylyl. Examples of radicals R are methyl, ethyl, isopropyl, phenyl, benzyl, Cyclohexyl, beta-phenylpropyl, beta-phenylethyl, hexyl, methylcyclohexyl, decyl, Tolyl and xylyl.
Die nach dem beanspruchten Verfahren zu verwendenden Polyalkylenoxyde können jeweils aus Äthylenoxyd und Propylenoxyd oder Äthylenoxyd und Butylenoxyd oder aus allen drei Alkylenoxyden aufgebaut sein. The polyalkylene oxides to be used according to the claimed process can each from ethylene oxide and propylene oxide or ethylene oxide and butylene oxide or be built up from all three alkylene oxides.
Beispiele für Kohlenwasserstoffreste R' sind Methyl, Äthyl, Isopropyl, Cyclohexyl, Phenyl, Benzyl, Butyl, Tolyl und Xenyl. Examples of hydrocarbon radicals R 'are methyl, ethyl, isopropyl, Cyclohexyl, phenyl, benzyl, butyl, tolyl and xenyl.
Als Beispiel eines durch Äthersauerstoffatome unterbrochenen Kohlenwasserstoffrestes R' sei der Rest der Formel - 0CH(CH20CH3)2 genannt. As an example of a hydrocarbon residue interrupted by ether oxygen atoms R 'is the remainder of the formula - OCH (CH20CH3) 2.
Bei der beanspruchten Herstellung werden die erfindungsgemäß verwendeten Reaktionsteilnehmer in bekannter Weise in Gegenwart eines geeigneten Katalysators, z. B. von auf einem inerten Träger feinverteiltem Platin oder einer Platinverbindung, wie Chlorplatinsäure, auf 100 bis 200"C erhitzt. In the production claimed, those used according to the invention are used Reactants in a known manner in the presence of a suitable catalyst, z. B. of platinum finely divided on an inert carrier or a platinum compound, like chloroplatinic acid, heated to 100 to 200 "C.
Bevorzugt werden erfindungsgemäß als SiH-Gruppen enthaltende Siloxane Verbindungen folgender Formeln verwendet: und/oder Gemäß einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens ist R der Methylrest und A der Acetoxyrest, und ein Teil der Reste R" besteht aus Äthylenresten, während die übrigen Reste R" Butylenreste sind.According to the invention, compounds of the following formulas are preferably used as siloxanes containing SiH groups: and or According to a preferred embodiment of the process according to the invention, R is the methyl radical and A is the acetoxy radical, and some of the radicals R ″ consist of ethylene radicals, while the remaining radicals R ″ are butylene radicals.
Wenn R der Methylrest und A der Acetoxyrest ist, gehören zu den besonders bevorzugt nach dem beanspruchten Verfahren herzustellenden Verbindungen solche der allgemeinen Formel worin n und m die oben angegebene Bedeutung besitzen und a' 1 oder 2 ist.If R is the methyl radical and A is the acetoxy radical, the compounds of the general formula which are particularly preferably to be prepared by the claimed process include those of the general formula where n and m have the meanings given above and a 'is 1 or 2.
Die SiH-Gruppen enthaltenden Siloxane (1) werden nach hier nicht beanspruchtem Verfahren zweckmäßig durch Mischhydrolyse von 1 Mol des Silans der Formel RaSiX4-a mit n Mol Dimethyldichlorsilan und mindestens 4 -- a Mol Dimethylmonochlorsilan und anschließende Aquilibrierung des Mischhydrolysats mit einem sauren Katalysator, wie H2S04, hergestellt. The siloxanes (1) containing SiH groups are not used here claimed process expediently by mixed hydrolysis of 1 mol of the silane Formula RaSiX4-a with n mol of dimethyldichlorosilane and at least 4 - a mol of dimethylmonochlorosilane and subsequent equilibration of the mixed hydrolyzate with an acidic catalyst, like H2S04.
Die SiH-Gruppen enthaltenden Siloxane (2) werden nach hier nicht beanspruchtem Verfahren zweckmäßig durch Mischhydrolyse von n Mol Dimethyldichlorsilan mit 2 Mol Dimethylmonochlorsilan und 1 oder 2 Mol Methyldichlorsilan und anschließende Äquilibrierung mit H2S04 hergestellt. The siloxanes (2) containing SiH groups are not used here claimed process expediently by mixed hydrolysis of n moles of dimethyldichlorosilane with 2 moles of dimethylmonochlorosilane and 1 or 2 moles of methyldichlorosilane and then Equilibration with H2S04 established.
Die SiH-Gruppen enthaltenden Siloxane (3) werden nach hier nicht beanspruchtem Verfahren zweckmäßig durch Mischhydrolyse von n Mol Dimethyldichlorsilan mit 2 Mol Trimethylmonochlorsilan und 3 oder 4 Mol Methyldichlorsilan und anschließende Äquilibrierung hergestellt. The siloxanes (3) containing SiH groups are not used here claimed process expediently by mixed hydrolysis of n moles of dimethyldichlorosilane with 2 moles of trimethylmonochlorosilane and 3 or 4 moles of methyldichlorosilane and then Equilibration established.
Die Allyläther der allgemeinen Formel CH2 = CH - CH2(0R")mA werden nach hier nicht beanspruchtem Verfahren zweckmäßig durch Endblockierung von Polyalkylen- glykolmonoallyläthern mit den Äther-, Acyl- oder Kohlensäureestergruppen hergestellt. So kann man z. B. das Alkalimetallsalz des Monoallyläthers mit einem Alkylchlorid um setzen, wobei eine OR'-Gruppe entsteht, oder den Monoallyläther mit einem Acylhalogenid oder Säureanhydrid umsetzen, wobei eine OOCR'-Gruppe entsteht, oder den Monoallyläther mit einem Chlorameisensäurealkylester zur Einführung der OCOOR-Gruppe umsetzen. The allyl ethers of the general formula CH2 = CH - CH2 (OR ") mA are according to the method not claimed here, expediently by end blocking polyalkylene glycol monoallyl ethers made with the ether, acyl or carbonic acid ester groups. So you can z. B. put the alkali metal salt of monoallyl ether with an alkyl chloride, wherein an OR 'group is formed, or the monoallyl ether with an acyl halide or acid anhydride react, whereby an OOCR 'group is formed, or the monoallyl ether with an alkyl chloroformate to implement the OCOOR group.
Die beanspruchte Herstellung der Blockmischpolymeren aus Verbindungen der allgemeinen Formel Me(OR")mA mit den entsprechenden Siloxanen, die an Stelle von SiH-Gruppen Gruppen der Formel Si(CH2)3X enthalten, erfolgt zweckmäßig oberhalb 50"C in Gegenwart von polaren Lösungsmitteln, wie N,N-Dialkylamiden, aliphatischen Nitrilen, tertiären Aminen oder Athern. The claimed production of the block copolymers from compounds the general formula Me (OR ") mA with the corresponding siloxanes in place of SiH groups containing groups of the formula Si (CH2) 3X is advantageously carried out above 50 "C in the presence of polar solvents such as N, N-dialkylamides, aliphatic Nitriles, tertiary amines or ethers.
Die nach dem beanspruchten Verfahren hergestellten Blockmischpolymeren eignen sich als Emulgiermittel zur Regelung der Schaumbildung bei der hier nicht beanspruchten Herstellung jeder Art von Polyurethanen, z. B. solcher auf Grundlage von Polyestern oder von Polyäthern. Aufbau und Hydroxylierungsgrad des Polyesters sind ohne Einfluß auf die Wirksamkeit der Emulgiermittel. The block copolymers produced by the claimed process are not suitable as emulsifiers for regulating foam formation here claimed production of any type of polyurethanes, e.g. B. based on of polyesters or of polyethers. Structure and degree of hydroxylation of the polyester have no effect on the effectiveness of the emulsifying agents.
Beispiel 1 130,8 g des Allyläthers der Formel CH2 = CHCH2 - O-tC2H4 - ( C3Hs - On6,7 0CCH3 wurden mit 204 g Xylol, 43,2 g des Siloxans der Formel und 2 g Aluminiumoxyd, auf dem 10/o seines Gewichtes an Platin dispergiert wurde, vermischt und 24 Stunden auf 141 0C erhitzt. Nach dem Abdestillieren der bis zu 200"C/1,2 mm Hg siedenden Bestandteile hinterblieb eine wasserlösliche Flüssigkeit mit einem Brechungsindex von 1,4460/25"C, einer Viskosität von 1368 cSt/25°C und folgender Durchschnittsformel: Beispiel 2 Ein Gemisch aus 163,7 g des Allyläthers der Formel CH2 = CHCH2 -O -(C2H4 - O) 27,5 -( C3H6 -O)20,9 OCCH3 54.9 o des Siloxans der Formel 125 g Toluol und 0,2 g einer 1 Gewichtsprozent Platin enthaltenden Lösung von Chlorplatinsäure in Dimethylphthalat wurde 24 Stunden auf 122°C erhitzt. Nach dem Abdampfen des Lösungsmittels verblieb ein Produkt mit einer Viskosität von 2655 cSt/25°C, einem Brechungsindex von 1,4450/25°C und der Durchschnittsformel Beispiel 3 Nach der im Beispiel 2 beschriebenen Arbeitsweise wurden 130,8 g des Allyläthers der Formel CH2 CHCH2#(OC2H4)35,4 #(OC4H8)14,4 OOCCH3 mit 42,6 g des Siloxans der Formel in Xylol bei 146°C umgesetzt.Example 1 130.8 g of the allyl ether of the formula CH2 = CHCH2 - O-tC2H4 - (C3Hs - On6.7 0CCH3 were combined with 204 g of xylene, 43.2 g of the siloxane of the formula and 2 g of aluminum oxide on which 10 / o of its weight was dispersed in platinum, mixed and heated to 141 ° C. for 24 hours. After the components boiling up to 200 "C / 1.2 mm Hg had been distilled off, a water-soluble liquid remained with a refractive index of 1.4460 / 25" C, a viscosity of 1368 cSt / 25 ° C and the following average formula: Example 2 A mixture of 163.7 g of the allyl ether of the formula CH2 = CHCH2 -O - (C2H4 - O) 27.5 - (C3H6 -O) 20.9 OCCH3 54.9 o of the siloxane of the formula 125 g of toluene and 0.2 g of a solution of chloroplatinic acid in dimethyl phthalate containing 1 percent by weight of platinum were heated to 122 ° C. for 24 hours. After evaporation of the solvent, a product remained with a viscosity of 2655 cSt / 25 ° C, a refractive index of 1.4450 / 25 ° C and the average formula Example 3 According to the procedure described in Example 2, 130.8 g of the allyl ether of the formula CH2 CHCH2 # (OC2H4) 35.4 # (OC4H8) 14.4 OOCCH3 with 42.6 g of the siloxane of the formula reacted in xylene at 146 ° C.
Es wurde eine Flüssigkeit mit einer Viskosität von 4405 cSt/25°C, einem Brechungsindex von 1,4490/25°C und der Durchschnittsformel erhalten. Beispiel 4 168,5 g des Allyläthers der Formel CH2= CHCH2-(OC2H4)28,1 #OC4H8)9,24 OOCCH3 wurden nach der im Beispiel 2 beschriebenen Arbeitsweise mit 53,8 g des Siloxans der Formel in 252,3 g Xylol bei 144°C umgesetzt. Es wurde ein sol mit einer Viskosität von 1950 cSt/25°C, einem Brechungsindex von 1.4480/25°C und der Durchschnittsformel erhalten. A liquid with a viscosity of 4405 cSt / 25 ° C, a refractive index of 1.4490 / 25 ° C and the average formula was obtained obtain. Example 4 168.5 g of the allyl ether of the formula CH2 = CHCH2- (OC2H4) 28.1 # OC4H8) 9.24 OOCCH3 were prepared using the procedure described in Example 2 with 53.8 g of the siloxane of the formula reacted in 252.3 g of xylene at 144 ° C. A sol with a viscosity of 1950 cSt / 25 ° C, a refractive index of 1.4480 / 25 ° C and the average formula was obtained.
Beispiel 5 120,3 g des Allyläthers der Formel CH2= CHCH2-#OC2H4)22,5 ( OC3H)17,1 OOCCH3 wurden nach der im Beispiel 2 beschriebenen Arbeitsweise mit 45,5 g des Siloxans der Formel in 195,8 g Xylol umgesetzt. Es wurde ein Ol mit einer Viskosität von 2175 cSt/25°C, einem Brechungsindex von 1,4425/25"C und der Durchschnittsformel erhalten.Example 5 120.3 g of the allyl ether of the formula CH2 = CHCH2- # OC2H4) 22.5 (OC3H) 17.1 OOCCH3 were prepared using the procedure described in Example 2 with 45.5 g of the siloxane of the formula reacted in 195.8 g of xylene. An oil with a viscosity of 2175 cSt / 25 ° C, a refractive index of 1.4425 / 25 "C and the average formula was obtained obtain.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12784361A | 1961-07-31 | 1961-07-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1220615B true DE1220615B (en) | 1966-07-07 |
Family
ID=93333509
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DED39518A Pending DE1220615B (en) | 1961-07-31 | 1962-07-31 | Process for the preparation of organopolysiloxane polyalkylene oxide block copolymers |
Country Status (5)
| Country | Link |
|---|---|
| BE (1) | BE620800A (en) |
| CH (1) | CH455295A (en) |
| DE (1) | DE1220615B (en) |
| GB (1) | GB955916A (en) |
| NL (1) | NL129134C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6166098A (en) * | 1999-02-20 | 2000-12-26 | Goldschmidt Ag | Use of organofunctionally modified polysiloxanes in the production of polyurethane foam |
| US6506810B2 (en) | 2000-11-28 | 2003-01-14 | Goldschmidt Ag | Use of mixtures of organofunctionally modified polysiloxanes with branched alcohols in the production of flexible polyurethane foams |
| DE102013217395A1 (en) | 2013-09-02 | 2015-03-05 | Evonik Industries Ag | Use of mixtures of organofunctionally modified polysiloxanes with amides in the production of flexible polyurethane foams |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA695633A (en) * | 1961-07-31 | 1964-10-06 | A. Haluska Loren | Siloxane glycol branch copolymers |
| GB1143205A (en) * | 1965-02-08 | 1969-02-19 | Union Carbide Corp | Improvements in the formation of polyurethane foams |
| NL130315C (en) * | 1966-01-17 | 1900-01-01 | ||
| US3505377A (en) * | 1966-08-12 | 1970-04-07 | Union Carbide Corp | Siloxane-oxyalkylene copolymer foam stabilizers |
| US3427271A (en) * | 1966-11-04 | 1969-02-11 | Dow Corning | Novel organosilicon compositions |
| US3507923A (en) * | 1967-01-06 | 1970-04-21 | Union Carbide Corp | Method of capping allyl endblocked oxyalkylene polymers |
| US3654195A (en) * | 1970-05-27 | 1972-04-04 | Gen Electric | Process for the preparation of polyurethane foams in the presence of an organopolysiloxane copolymer surfactant |
| US4094690A (en) | 1972-08-07 | 1978-06-13 | Imperial Chemical Industries Limited | Liquid composition |
| US4724248A (en) * | 1986-07-02 | 1988-02-09 | Ciba-Geigy Corporation | Voltage stabilizing esters and urethanes |
| JPH03264512A (en) * | 1990-03-15 | 1991-11-25 | Kao Corp | Ester-modified silicone derivative and cosmetic containing the same |
| WO2018074257A1 (en) | 2016-10-18 | 2018-04-26 | 東レ・ダウコーニング株式会社 | Polyether-modified silicone composition, surfactant, foam stabilizer, polyurethane foam forming composition, and cosmetic preparation including said composition, and method for producing said composition |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE594065A (en) * | ||||
| DE1091324B (en) * | 1957-09-25 | 1960-10-20 | Union Carbide Corp | Process for the production of polyurethane foams |
| DE1096033B (en) * | 1959-12-31 | 1960-12-29 | Bayer Ag | Process for the production of foams containing urethane groups |
| US2970150A (en) * | 1957-12-17 | 1961-01-31 | Union Carbide Corp | Processes for the reaction of silanic hydrogen-bonded siloxanes with unsaturated organic compounds with a platinum catalyst |
-
1962
- 1962-03-23 NL NL276311A patent/NL129134C/en active
- 1962-03-23 CH CH347062A patent/CH455295A/en unknown
- 1962-07-20 GB GB28050/62A patent/GB955916A/en not_active Expired
- 1962-07-30 BE BE620800A patent/BE620800A/fr unknown
- 1962-07-31 DE DED39518A patent/DE1220615B/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE594065A (en) * | ||||
| DE1091324B (en) * | 1957-09-25 | 1960-10-20 | Union Carbide Corp | Process for the production of polyurethane foams |
| US2970150A (en) * | 1957-12-17 | 1961-01-31 | Union Carbide Corp | Processes for the reaction of silanic hydrogen-bonded siloxanes with unsaturated organic compounds with a platinum catalyst |
| DE1096033B (en) * | 1959-12-31 | 1960-12-29 | Bayer Ag | Process for the production of foams containing urethane groups |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6166098A (en) * | 1999-02-20 | 2000-12-26 | Goldschmidt Ag | Use of organofunctionally modified polysiloxanes in the production of polyurethane foam |
| US6506810B2 (en) | 2000-11-28 | 2003-01-14 | Goldschmidt Ag | Use of mixtures of organofunctionally modified polysiloxanes with branched alcohols in the production of flexible polyurethane foams |
| DE102013217395A1 (en) | 2013-09-02 | 2015-03-05 | Evonik Industries Ag | Use of mixtures of organofunctionally modified polysiloxanes with amides in the production of flexible polyurethane foams |
Also Published As
| Publication number | Publication date |
|---|---|
| GB955916A (en) | 1964-04-22 |
| NL129134C (en) | 1970-02-16 |
| NL276311A (en) | 1964-10-26 |
| CH455295A (en) | 1968-06-28 |
| BE620800A (en) | 1963-01-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE1770523C3 (en) | Organosiloxane-oxyalkylene copolymers | |
| DE69827083T2 (en) | Vacuum process for the preparation of siloxane-oxyalkylene copolymers | |
| DE3133869C1 (en) | Process for the addition of organic silicon compounds with SiH groups to compounds with olefinic double bonds | |
| DE1220615B (en) | Process for the preparation of organopolysiloxane polyalkylene oxide block copolymers | |
| DE1262271B (en) | Process for the preparation of organosilicon compounds | |
| DE1445347B2 (en) | PROCESS FOR THE PRODUCTION OF ORGANOSILANES AND ORGANOPOLYSILO XANES CONTAINING CARBON-BONDED HYDROXYL GROUPS | |
| DE1570686A1 (en) | Process for the production of organosilicon compounds | |
| DE3616575C2 (en) | Polish | |
| DE1595248A1 (en) | Process for the preparation of siloxane-polyoxyalkylene copolymers | |
| DE4440499A1 (en) | Antiperspirant compositions | |
| EP0670342B1 (en) | Polysiloxane-polyoxyalkylene block copolymers and their use as cosmetic additive for hair | |
| DE102010028182A1 (en) | Hydrophilic polyorganosiloxanes | |
| DE1115927B (en) | Process for the preparation of organopolysiloxanes | |
| WO1999013151A1 (en) | Aminosiloxane polyether polymers | |
| DE2637383A1 (en) | ORGANOSILICIUM COMPOUNDS AND PROCESS FOR THEIR PRODUCTION | |
| DE1792046B2 (en) | Ointment BASE AND SKIN PROTECTION AND SKIN CARE PRODUCTS | |
| DE69608413T2 (en) | HYDROSILYLATION IN ESTERS WITHOUT HYDROXYL GROUPS | |
| DE1570719A1 (en) | Process for the production of organosilicon polymers | |
| EP0849352B1 (en) | Use of silicone polyether copolymers for defoaming diesel fuel | |
| DE1040251B (en) | Process for the preparation of polysiloxane-polyoxyalkylene copolymers | |
| DE2629137A1 (en) | SULFOLANYLOXYALKYL ORGANOPOLYSILOXANES | |
| DE1266496B (en) | Organopolysiloxane emulsions | |
| DE19726653A1 (en) | Organofunctionally modified polysiloxanes | |
| DE1795557A1 (en) | Process for the production of polyalkyl silicic acid esters with a polymer distribution which approximates the statistical equilibrium | |
| DE1694366B1 (en) | Process for the production of polyurethane foams from polyethers |