Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/61—Polysiloxanes
• • 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
  • C08G77/458—Block-or graft-polymers containing polysiloxane sequences containing polyurethane sequences
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions 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; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
• • 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
  • C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
  • C08G77/455—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences containing polyamide, polyesteramide or polyimide sequences

Definitions

• Organopolysiloxanes modified with organic materials include, for example, block copolymers in which organopolysiloxane blocks with organic polymer blocks (e.g. polyethers, polycarbonates, polycarbodiimides, polyurethanes; are chemically linked.
• organopolysiloxane blocks with organic polymer blocks e.g. polyethers, polycarbonates, polycarbodiimides, polyurethanes; are chemically linked.
• Such products are described, for example, in the patents US Pat. No. 3,402,192, US Pat. No. 3,701,815, US Pat. No. 3,189,662, DT-OS 2 445 220 and DT-OS 2 543 966. These products are generally manufactured using multi-stage processes.
• Modified organopolysiloxane compositions have also become known, which are formed by radical polymerization of unsaturated organic monomers in organopolysiloxanes or by mixing corresponding constituents.
• masses filled only with organic polymer particles e.g. polyolefin, polystyrene
• Such compositions and processes for their preparation are described, for example, in the patents US Pat. No. 2,965,593 and US Pat. No. 3,627,836.
• the polymers which have become known for filling or grafting result from one or more unsaturated monomers which are polymerizable, e.g. Ethylene, vinyl chloride or 1,3 butadiene.
• organic polymers usually have a low temperature resistance. They transfer this unfavorable property to the resulting hardened organopolysiloxane compositions. They also have unfavorable elastomer properties such as high compression set. The mechanical properties also deteriorate increased temperature considerably (e.g. tensile strength). The permanent heat resistance, which otherwise distinguishes the organopolysiloxanes, is lost.
• organopolysiloxane compositions which, for economic and technical reasons, also meet the condition that they can be prepared without great technical outlay and without a long reaction time, and that the compositions prepared are flowable without the use of solvents and are sufficiently stable in storage.
• the compositions After vulcanization, the compositions should cure without tack and should be distinguished from other organically modified organopolysiloxane compositions by improved mechanical properties at elevated temperature.
• the improved organopolysiloxane compositions according to the present invention can thus be regarded as polyurethane-filled organopolysiloxane mixtures which are composed of the following two phases: (i) a coherent one Phase of an organopolysiloxane liquid and (ii) a discontinuous phase of finely divided particles of a polyurethane polymer, which was obtained by polyaddition of the corresponding monomer or monomer mixture in the presence of the organopolysiloxane liquid and a catalyst accelerating the formation of polyurethane.
• the mixtures generally contain about 3 - 95 wt .-% polyurethane - based on the total mixture. Preferably about 40-80% by weight, particularly preferably 45-55% by weight.
• organopolysiloxane compositions of the present invention filled with polyurethane are produced by intensive mixing of the organopolysiloxane liquid with a di- or polyol or mixtures thereof and subsequent addition of a diisocyanate to this mixture.
• the organopolysiloxane liquids preferred for the use according to the invention are characterized by the following formula:
• R represents an optionally substituted alkyl, alkenyl, aryl or haloalkyl radical having up to 10 C atoms
• R 1 represents hydrogen, an optionally substituted alkyl, alkenyl, aryl or haloalkyl radical having up to 10 C atoms
• X is, for example, hydroxy, vinyl or methyl
• n 2 to 1000
• m 1 - 50.
• silicone resins such as are obtainable, for example, by cohydrolysis of methyltrichlorosilane and dimethyldichlorosilane, alone or in a mixture with the organopolysiloxanes mentioned.
• Suitable starting components according to the invention are aliphatic, cyclcaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates, as are described, for example, by W. Siefgen in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136, for example ethylene diisocyanate, 1,4 Tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclolzexane-1,3- and -1,4-diisocyanate and any mixtures of these isomers, 1-isocyanato-3,3, 5-trimethyl-5-isocyanatomethyl-eyclohpxan (DAS 1 202 785), 2,4- and 2,6-hoxahydrotoluenediisocyanate as well as any mixtures of these isomers, hxxahydro-1,3- and
• distillation residues containing isocyanate groups obtained in the technical production of isocyanates optionally dissolved in one or more of the aforementioned polyisocyanates. It is also possible to use any mixtures of the aforementioned polyisocyanates.
• polyisocyanates e.g. 2,4- and 2,6-tolylene diisocyanate as well as any mixtures of these isomers (“TDI”), polyphenyl-polymethylene polyisocyanates, such as those produced by aniline-formaldehyde condensation and subsequent phosgenation (“crude MDI”) and carbodiimide groups, Polyisocyanates containing urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups (“modified polyisocyanates").
• TDI polyisocyanates
• polyphenyl-polymethylene polyisocyanates such as those produced by aniline-formaldehyde condensation and subsequent phosgenation
• CAMDI aniline-formaldehyde condensation and subsequent phosgenation
• carbodiimide groups Polyisocyanates containing urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups
• Such low molecular weight polyols are, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-eutanediol, 1,6-hexanediol, 1,10-decanediol, diethylene glycol, triethylene glycol, tatraethylene glycol, dipropylene glycol , Tripropylene glycol, glycerin, trimethylolpropane and the like.
• the hydroxyl group-containing polyesters are e.g. Reaction products of polyhydric, preferably dihydric and optionally additionally trihydric alcohols with polyhydric, preferably dihydric, carboxylic acids.
• polyhydric preferably dihydric and optionally additionally trihydric alcohols
• polyhydric preferably dihydric, carboxylic acids.
• the corresponding polycarboxylic anhydrides or corresponding polycarboxylic esters of lower alcohols or mixtures thereof can also be used to produce the polyesters.
• the polycarboxylic acids can be aliphatic, cycloaliphatic, aromatic and / or heterocyclic in nature and optionally, e.g. by halogen atoms, substituted and / or unsaturated.
• the at least two, generally two to eight, preferably two to three, hydroxyl-containing polyethers which are suitable according to the invention are also of the type known per se and are obtained, for example, by polymerizing epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or Epichlorohydrin with itself, e.g. in the presence of BF 3 , or by the addition of these epoxides, optionally in a mixture or in succession, to starting components with reactive hydrogen atoms such as alcohols or amines, e.g.
• epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or Epichlorohydrin
• Sucrose polyethers such as are described, for example, in German publications 1 176 358 and 1 064 938, are also suitable according to the invention. In many cases, those polyethers are preferred which predominantly (up to 90% by weight, based on all OH groups present in the polyether) have primary OH groups.
• Polyethers modified by vinyl polymers such as those formed, for example, by polymerizing styrene or acrylonitrile in the presence of polyethers (US Pat. Nos. 3,383,351, 3,304,273, 3,523,093, 3,110,695, German Pat. No. 1,152,536) also suitable, likewise polybutadienes containing OH groups.
• Suitable polycarbonates containing hydroxyl groups are those of the type known per se, which e.g. by reacting diols such as propanediol (1,3), butanediol (1,4) and / or hexanediol + (1,5), diethylene glycol, triethylene glycol, tetraethylene glycol with diaryl carbonates, e.g. Diphenyl carbonate or phosgene can be produced.
• diols such as propanediol (1,3), butanediol (1,4) and / or hexanediol + (1,5)
• diethylene glycol triethylene glycol
• tetraethylene glycol e.g. Diphenyl carbonate or phosgene
• polyester amides and polyamides include e.g. the predominantly linear condensates obtained from polyvalent saturated and unsaturated carboxylic acids or their anhydrides and polyvalent saturated and unsaturated amino alcohols, diamines, polyamines and their mixtures.
• catalysts are often also used. Suitable catalysts to be used are those of the type known per se, e.g. tertiary amines such as triethylamine. Tributylamine, N-methylmorpholine, N-ethylmorpholine, N-cocomorpholine, N, N, N ', N'-tetramethyl-ethylenedi-ethylenediamine, 1,4-diaza-bioyclo- (2,2,2) - octane, N-methyl-N'-dimethylaminoethyl piperazine, N, N-dimethylbenzylamine, bis (N, N-diethylmyerhyl) adipate, N, N-dietyltenzylamine, pentanethyldiethylenetriamine, N, N-dimethyloyclohexylamine, N , N, N'N'-tetramethyl-1,3-butanediemine, N, N, -
• Silaamines with carbon-silimium bonds such as those e.g. in German Patent 1,229,290, in question, e.g. 2,2,4-trinetyl-2-silamorpholine, 1,3-diethylaminomethyl-tetra-methyl-disiloxane.
• the Catalystaoran are used in the ReGel in an amount between about 0.001 and 10% by weight, based on the amount of compounds with at least two isocyanate-reactive hydrogen atoms having a molecular weight of '62' to 10,000.
• the mixtures according to the invention are stable. They are suitable for the production of molding compositions curable to elastomers.
• the majority of the solid particles (greater than 80%) of the homo- or copolymer have an average diameter of about 0.3 to 10 microns, with some of the particles being less than 0.3 microns in diameter.
• the polyurethane-modified polysiloxane liquids according to the invention are advantageously prepared in such a way that an ⁇ , ⁇ -dihydroxypolysiloxane is mixed with a diol, polyol or polyetherol at room temperature or elevated temperature (up to approx. 150 ° C.), the catalyst is added, and the corresponding amount of isocyanate or isocyanate mixture is metered in uniformly and continuously within a predetermined period of time.
• the isocyanate or the isocyanate mixture is preferably added at temperatures from 60 to 120.degree.
• the rate of isocyanate addition (about 1-8 hours - depending on the batch size) is generally controlled so that the heat of reaction released can be removed and the desired reaction temperature is kept constant.
• the viscosity of the mixture increases considerably during the manufacturing process.
• the extent of the viscosity increase depends on the initial viscosity of the siloxane component used, the degree of filling by the polyurethane produced and the degree of distribution of the discontinuous phase.
• Suitable crosslinking agents are substances which are conventionally used for the production of one- or two-component systems. As such, for example, alkoxysilicon compounds, tetraalkoxysilanes, alkyl polysilicates and acyloxysilicon compounds come into question.
• One- or two-component compositions based on polyurethane-polysiloxane copolymers are prepared by mixing the polyurethane-siloxane composition with the crosslinking component and, if appropriate, the fillers and / or plasticizers in a commercially available mixer or kneader.
• a commercially available mixer or kneader for example, quartz powder, chalk or diatomaceous earth or pyrogenic Si0 2 or other finely divided metal oxides such as Ti0 2 , Fe 2 0 3 can serve as fillers.
• plasticizers can optionally be added.
• liquid inert polydiorganosiloxanes e.g. B, ⁇ , ⁇ -trimethyl-siloxy end gas-quenched polydimethylsiloxanes.
• polyurethane-modified organopolysiloxane compositions can be used both in substance and as an additional component in other polymer compositions.
• a mixture of 620 g of polydimethylsiloxane with terminal hydroxyl groups and a viscosity of 18000 centipoise (20 ° C.) and 270 g of dipropylene glycol (mixture of isomers) is heated to 80 ° C. and a mixture of 349.5 g of tolylene diisocyanate (mixture of isomers from 80 % 2,4 - and 20% 2,6-tolylene diisocyanate) and 1.8 g triethylamine evenly with stirring.
• the reaction temperature is maintained during the addition period between 80 and 90 0 C. After the addition has ended, the mixture is stirred for a further hour and then cooled.
• a white, highly viscous mass (Eta - 2.10 cP) is obtained, the further processing of which is described in Example 6.
• a mixture of 1500 g of polydimethylsiloxane from Example 1 and 804 g of dipropylene glycol is heated to 80 ° C. and a mixture of 696 g of tolylene diisocyanate from Example 1 and 3.5 g of triethylamine is added at 80 ° C. in the course of one hour with stirring.
• the molar ratio of isocyanates of tolylene diisocyanate and hydroxyl groups of dipropylene glycol is 1: 2.
• the mixture is stirred at 80 ° C. for 1 hour and then cooled.
• the yellowish-white product obtained has a viscosity of 217,000 cP (20 ° C).
• a film produced and cured from this composition in accordance with Example 1 has a Shore A hardness of 45.
• a mixture of 1500 g of polymethylsiloxane from Example 1 and 909.5 g of dipropylene glycol is heated to 80 ° C. and a mixture of 800.6 g of tolylene diisocyanate from Example 1 and 2.9 g of triethylamine is added at 80 ° C. in the course of one hour with stirring.
• the molar ratio of isocyanate groups of tolylene diisocyanate and hydroxyl groups of dipropylene glycol is 1: 2.
• the white product obtained has a viscosity of 230,000 cP (20 ° C).
• a film produced and cured from this composition in accordance with Example 1 has a Shore A hardness of 11.
• Example 3 If, analogously to Example 3, instead of a polydimethylsiloxane with a viscosity of 18,000 cP (20 ° C), one with a viscosity of 10,000 cP (20 ° C) is used, the resulting polyurethane-modified mass has a viscosity of 85,000 cP (20 ° C).
• a film produced from this in accordance with Example 1 has a Shore A hardness of 13.
• a mixture of 1200 g of the product from Example 1, 600 g of the product from Example 4 and 600 g of polydimethylsiloxane from Example 1 are mixed at 70 ° C. for 2 hours.
• the resulting white, flowable mass has a viscosity of 300,000 cP.
• the size of the diapergated particles was found to be about 1 to 2.5 microns.
• composition of a cold-curing composition and the properties of the cured product are given in Example 10, Table 1 (one-component system) and Table 2 (two-component system).
• a solution of 402 g of trimethylolpropane and 576 g of polydimethylsiloxane from Example 1 in 1150 g of dry toluene is heated from 80 ° C. and a mixture of 174 g of toluene Diisocyanate of Example 1 and 5 g of triethylemine at 80 to 100 0 C within 2 hours with stirring. After the solvent has been distilled off, a white mass is obtained which is used further in Example 8.
• This example provides an overview of the composition of some cold-curing compositions and the properties of hardened products made from them.
• a solution of 35.7 g of dipropylene glycol, 8.9 g of trimethylolpropane and 76.5 g of polymethylsiloxane from Example 1 in 150 g of dry toluene is heated to 100 ° C. and a mixture of 0.4 g of triethylamine and 31.9 within one hour g of tolylene diisocyanate added. The mixture is stirred for a further hour at 100 ° C. and then the solvent is distilled off. The residue has a viscosity of 72,000 cP (20 ° C).
• a hardened film produced therefrom according to Example 1 has a Shore A hardness of 16.
• Example 3 The experiment in Example 3 is carried out with the difference that butene (2) diol (1,4) is used instead of dipropylene glycol.
• a light brown, homogeneous and crosslinkable product with a viscosity of 145,000 cP is obtained.
• a hardened film produced therefrom according to Example 1 has the Shore A hardness 17.
• Example 3 The experiment in Example 3 is carried out with the difference that butanediol-1,4) is used instead of dipropylene glycol.
• a hardened film produced therefrom according to Example 1 has the Shore A hardness 13.
• a white crosslinkable mass with a viscosity of 182,000 cP is obtained.
• a cured film made therefrom according to Example 1 has a Shore A hardness of 13.
• a hardened film produced therefrom according to Example 1 has a Shore A hardness of 16.
• Example 3 The experiment in Example 3 is carried out with the difference that 0.06 ml of dibutyltin dilaurate is used as the catalyst instead of the triethylamine.
• a white product with a viscosity of 185,000 cP is obtained.
• a hardened film produced therefrom according to Example 1 has a Shore A hardness of 15.

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• Chemical & Material Sciences (AREA)
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• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Polyurethanes Or Polyureas (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 1977
  • 1977-07-07 DE DE19772730744 patent/DE2730744A1/de not_active Withdrawn
• 1978
  • 1978-06-21 US US05/917,717 patent/US4202807A/en not_active Expired - Lifetime
  • 1978-06-28 EP EP78100257A patent/EP0000349B1/fr not_active Expired
  • 1978-06-28 DE DE7878100257T patent/DE2861685D1/de not_active Expired
  • 1978-07-03 AU AU37720/78A patent/AU519361B2/en not_active Expired
  • 1978-07-05 IT IT50167/78A patent/IT1106603B/it active
  • 1978-07-05 CA CA000306853A patent/CA1138145A/fr not_active Expired
  • 1978-07-05 JP JP53081070A patent/JPS6019770B2/ja not_active Expired
  • 1978-07-06 ES ES471504A patent/ES471504A1/es not_active Expired
  • 1978-07-06 BR BR7804375A patent/BR7804375A/pt unknown

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