Classifications

• • 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
• • 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
  • C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
  • C08G18/025—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing carbodiimide groups
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
  • C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
• • 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 inorganic and organic materials are known per se. So with inorganic fillers such as Silicon dioxide aerogels, diatomaceous earth, magnesium oxide and / or iron oxide mixed organopolysiloxanes or organopolysiloxane mixtures with additional crosslinking agents and processing aids are used in many areas. This includes e.g. the use of so-called one or two-component systems which cure under the action of moisture, the curing by the reaction of OH-functional siloxanes with crosslinking and curing catalysts, e.g. Alkyl silicates or alkyl triacyloxysilanes and water is brought about. Other known crosslinking systems are based on the reaction of Si-H-containing siloxanes with unsaturated compounds in the presence of catalytically active metal compounds or the crosslinking by organic peroxides.
• inorganic fillers such as Silicon dioxide aerogels, diatomaceous earth, magnesium oxide and / or iron oxide mixed organopol
• Organopolysiloxanes modified with organic materials include, for example, block copolymers in which Organopolysiloxane blocks are chemically linked to organic polymer blocks (for example polyethers, polyesters, polycarbonates, polycarbodiimides). Products of this type are described, for example, in US Pat. Nos. 3,402,192, 3,701,815 and 3,189,662. These products are manufactured using multi-stage processes and are therefore usually difficult to manufacture and, in comparison to their properties, are generally less favorable than organopolysiloxane compositions modified with inorganic fillers.
• Modified organopolysiloxane compositions have also become known, which are formed by free-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 elasto properties such as high compression set. Furthermore, the mechanical properties deteriorate considerably at elevated temperatures (eg tensile strength). The permanent heat resistance, which otherwise distinguishes the organopolysiloxanes, is lost.
• the present invention relates to polysiloxanes modified with polycarbodiimide, which are characterized in that polysiloxane and polycarbodiimide are distinguishable phases, optionally with a partial chemical and / or physical bond to one another.
• the improved organopolysiloxane compositions according to the present invention are thus polycarbodiimide-filled organopolysiloxane mixtures which are composed of the following two phases: (i) a continuous phase of an organopolysiloxane liquid and (ii) a non-continuous phase composed of finely divided particles of a carbodiimide Polymer obtained by polycondensing the corresponding monomer or monomer mixture in the presence of the organopolysiloxane liquid and a carbodiimidation catalyst.
• the polycarbodiimide-filled organopolysiloxane compositions of the present invention are produced by intensive mixing of the organopolysiloxane liquid with di- or polyisocyanates or mixtures thereof in the presence of a catalyst which accelerates the formation of carbodiimide, or by mixing the organopolysiloxane liquid with polycarbodiimides which are prepared in situ and are known per se.
• the polymer mixture consists of 3 to 80% by weight, preferably 5 to 70% by weight, of polycarbodiimide (based on the total mixture).
• silicone resins such as are obtainable, for example, by cohydrolysis of methyltrichlorosilane and dimethyldichlorosilane, alone or in a mixture with the organopolysiloxane liquids mentioned (see, for example, US Pat. No. 2,587,295, US Pat. No. 2,384,340 , U.S. Patent 2,584,341, U.S. Patent 2,584,342, U.S. Patent 2,584,343, U.S. Patent 2,584,344 and U.S. Patent 2,686,739).
• Suitable di- or polyisocyanates are those of the general formula into question, where R 'is an alkyl or aryl radical which is optionally also substituted with isocyanate groups and preferably has up to 24 C atoms.
• distillation residues containing isocyanate groups obtained in industrial tsocyanate production optionally dissolved in one or more of the aforementioned polyisocyanates. It is also possible to use any mixtures of the aforementioned polyisocyanates.
• polycarbodiimides are used directly, the substances known per se, such as those e.g. described in DT-OS 2 318 406 in question.
• the isocyanates used are carbodiimidized in a manner known per se by combining the isocyanate component (s) with a suitable amount of a catalyst which accelerates the carbodiimidization reaction.
• a catalyst which accelerates the carbodiimidization reaction.
• the majority of the solid particles of the homopolymer or copolymer have an average diameter of less than about 0.4-10 microns, with some of the particles being less than 0.3 microns in diameter.
• the carbodiimide-modified polysiloxanes according to the invention are advantageously prepared in such a way that an a, ⁇ -dihydroxypolysiloxane with 5 to 80% by weight (preferably 10-60% by weight) at room temperature or elevated temperature (up to approx. 160 ° C.) , based on the polymer mixture) of a difunctional and / or polyfunctional isocyanate or a mixture of several isocyanates mixed with stirring (possibly in a mixer or kneader) and then the carbodiimidization reaction with stirring by adding catalytic amounts (0.01-2%) of phospholine oxide carries out.
• the CO 2 formed in the reaction is removed from the mass at a slightly elevated temperature and, if appropriate, under vacuum.
• a modified process for the preparation of the masses has proven to be particularly advantageous, in which the required amount of ⁇ , ⁇ -dihydroxypolysiloxane is initially introduced and stirred together with the carbodiimidization catalyst and the corresponding amount of isocyanate or isocyanate mixture is metered in uniformly and continuously within a predetermined period.
• the addition of the isocyanate or isocyanate mixture is preferably carried out at temperatures from 25 ° to 140 ° C, preferably from 50 to 110 ° C.
• the rate of isocyanate addition is generally controlled in such a way that the CO 2 evolution occurring still permits a homogeneous distribution of the carbodiimide formed and excessive swelling of the mass is avoided. This will generally be the case within about 1 to about 8 hours, depending on the batch size.
• the fine particle size of the carbodiimide phase distributed in the organosiloxane phase depends on the stirring speed, the temperature during the mixing process and the viscosity of the organosiloxane phase.
• the viscosity of the system obtained increases considerably and is dependent on the initial viscosity of the siloxane component used, on the degree of filling by the polycarbodiimide produced or incorporated and on the degree of distribution of the closed phase (see, for example, P.Sherman, Research (London) 8, 396 (1955 ).
• the carbodiimide-modified polysiloxanes obtained are white, mostly non-transparent, flowable and crosslinkable compositions with medium to high viscosity, which can be cured with many of the customary catalysts which are suitable for silanol condensation.
• crosslinking agents can be used which are conventionally used for the production of one- or two-component systems.
• alkoxysilicon compounds, tetraalkoxysilanes, alkyl polysilicates and acyloxysilicon compounds come into question.
• the one- or two-component compositions based on the polycarboditmide-polysiloxane copolymers according to the invention are produced by mixing the polycarbodiimide-siloxane composition with the crosslinking component and, if appropriate, the fillers and / or plasticizers in a commercially available mixer or kneader.
• the compositions mentioned can in addition to crosslinking agents and curing catalysts also contain fillers and plasticizers.
• quartz powder, chalk or diatomaceous earth or pyrogenic SiO 2 or other finely divided metal oxides can serve as fillers.
• liquid inert polydiorganosiloxanes are used, e.g. ⁇ , ⁇ -trimethylsiloxy end-stopped polydimethylsiloxanes.
• the water required to vulcanize the copolymers can be added to the curable copolymer compositions by atmospheric moisture or by direct mixing.
• polycarbodiimide-modified organopolysiloxane compositions can be used on their own as well as an additional component in other polymer compositions.
• polycarbodiimide-modified organopolysiloxane compositions that harden at room temperature to give elastomers show an excellent, moisture-resistant adhesion to concrete substrates, which is achieved without the use of so-called primer substances.
• polycarbodiimide-modified organopolysiloxane compositions as an additional component to, for example, silicone home vulcanization mixtures, improve their water vapor resistance.
• silicone home vulcanization mixtures improve their water vapor resistance.
• the invention is explained in more detail below with the aid of examples. The percentages given below mean percentages by weight, unless expressly stated otherwise.
• This example illustrates the preparation of a dispersion of 24% polycarbodiimide based on tolylene diisocyanate and 76% of an L, ⁇ -dihydroxypolydimethylsiloxane.
• a mixture of 1750 g of polydimethylsiloxane with terminal hydroxyl groups and a viscosity of 18000 centipoise (at 20 ° C) and 750 g of an isomer mixture of 80% 2,4- and 20% 2,6-tolylene diisocyanate are 4 hours with an anchor at 25 ° C stirred. 1.25 g of 1-methylphospholine oxide is added, whereupon gas evolution begins for a short time. The mixture is subsequently stirred at 25 ° C. for 3 hours and then at 50 ° C. for 2.5 hours.
• a white, flowable dispersion with a viscosity of approximately 68500 centipoise is obtained.
• the average grain size of the dispersed polycarbodiimide is about 3 microns.
• composition of a cold-curing one-component system produced from the composition and the properties of the cured product are shown in Example 8, Table I.
• a white, homogeneous dispersion having a viscosity of 53,600 cP at 20 ° C. and an NCO content of 0.2% is obtained.
• Example 8 The composition of a cold-curing composition and the properties of the cured product are given in Example 8, Table 1.
• the adhesion of a sample applied to concrete is good after 4 weeks of storage under water.
• a white, flowable dispersion with a viscosity of 133000 cP (20 ° C.) is obtained.
• the average grain size of the distributed carbodiimide phase is 1-2 microns.
• Example 8 The composition of a cold-curing composition and the properties of the cured product are given in Example 8, Table 1 (one-component system) or in Example 9 (two-component system).
• the product obtained is white and homogeneous and has a viscosity of approximately 800,000 cP. His NCO group content was determined to be 1.6%.
• Example 8 The composition of a cold curing composition and the properties of the cured product are shown in Example 8, Table 1.
• a white, homogeneous and flowable product with a viscosity of 200,000 cP is obtained.
• the NCO group content determined by titration is 3.1%.
• Example 8 The composition of a cold-curing composition and the properties of the cured product are shown in Example 8, Table 1.
• 1500 g of polydimethylsiloxane from Example 1 are heated to 80 ° C. in a vessel and 1.5 g of phospholine oxide are added. With stirring, 1500 g of tolylene diisocyanate from Example 1 are metered in at a constant rate over a period of 2 hours at a constant temperature. When the addition is complete, the mixture is stirred at 80 ° C. for 1 hour and the mixture is cooled to room temperature.
• the dispersion obtained has a viscosity of approximately 700,000 cP and an NCO group content of 1.6%.
• Example 8 The composition of a cold-curing composition and the properties of the cured product are shown in Example 8, Table 1.
• Example 10 The product obtained was used as a stabilizing additive against hydrolytic degradation of hot-vulcanizable silicone rubber. The results obtained are illustrated in Example 10 , Table 3.
• 500 g of polydimethylsiloxane with terminal hydroxyl groups and a viscosity of 10000 cP (at 20 ° C) are heated to 80 ° C in a vessel and mixed with 0.5 g of phospholine oxide.
• 500 g of tolylene diisocyanate from Example 1 are metered in over the course of 2 hours.
• the product is cooled to room temperature with stirring.
• a slightly yellowish homogeneous dispersion with a viscosity of 130,000 cP is obtained.
• Example 8 The composition of a cold-curing mixture and the properties of the cured product are given in Example 8, Table 1.
• this example shows the compositions as one-component systems (in% by weight) of the cold-curing organosiloxane compositions of Examples 1 to 7 and the properties of the products cured after 7 days at room temperature.
• compositions were prepared from a pure polydimethylsiloxane with terminal hydroxyl groups and a viscosity of 50,000 cP (at 20 °) (composition and properties in Table 1).
• Cured products A and B will last less than a week when applied to concrete and stored under water.
• the example illustrates the production of a cold-curing mass (two-component system) and the hardened product from it.
• Example 3 95 parts of the dispersion of Example 3 and 5 parts of a crosslinking agent consisting of 97% ethyl silicate and 3% dibutyltin dilaurate are mixed. The mixture is allowed to harden at room temperature for a few hours and then at 65 ° C. for 5 hours.
• a crosslinking agent consisting of 97% ethyl silicate and 3% dibutyltin dilaurate
• the hydrolysis was carried out in the sealed tube with 50 mg H 2 0/2 0 cm 3 air at 236 0 C.
• test products A and B The composition in parts by weight of test products A and B is listed in Table 2.
• Product A contained 100 parts by weight of a hot-vulcanizable silicone rubber, 0.6 part by weight of dicumyl peroxide and had a density of 1.229 g / cm 3 .
• Product B had the same composition, but additionally contained 1.0 part by weight of the dispersion according to Example 6 (resulting density 1.225).
• a white, homogeneous, crosslinkable, non-flowing mixture is obtained.
• 250 g of polydimethylsiloxane from Example 1 (18,000 cP) and 250 g of polydimethylsiloxane from Example 2 (1000 cP) are heated to 80 ° C. together with 0.5 g of phospholine oxide.
• 500 g of tolylene diisocyanate from Example 1 are metered into the mixture at 80 ° C. in the course of 2 hours. After the addition, the mixture is stirred at 80 ° C. for 1 hour.
• the cream-colored product has a viscosity of 100,000 cP and is cross-linkable.
• the product is yellowish and homogeneous and has a viscosity of 56,400 cP.
• Example 1 100 g of polydimethylsiloxane from Example 1 are dissolved in 200 ml of dry toluene and 100 g of tolylene diisocyanate from Example 1 are added. The mixture is stirred at 110 ° C. for 2 hours. The mixture is cooled to 50 ° C. and 0.1 g of phospholine oxide is added to the mixture. The mixture is stirred for a further hour at 50.degree. C., heated to 110.degree. C. and left at this temperature until the evolution of CO 2 has ended.
• the polycarbodiimide was used in powder form.
• a mixture of 1.5 kg of polydimethylsiloxane with terminal silanol groups and a viscosity of 50,000 cP (20 ° C.) and 1 kg of a polycarbodiimide powder based on 4,1'-diisocyanatodiphenylmethane (1.8% NCO) are mixed for 4 hours at room temperature in a planetary mixer at 80 rpm. mixed.
• M an receives a white, homogeneous, non-flowable, crosslinkable paste.
• 750 g of polydimethylsiloxane from Example 1 are heated to 80 ° C. and 0.75 ml of phospholine oxide are added.
• 750 g of 4,4'-diisocyanatodiphenylmethane are metered in at 80 ° C. in the course of 2 hours with constant stirring and, after the addition has ended, the mixture is stirred at 80 ° C. for 1 hour.
• a white, homogeneous, crosslinkable product with a viscosity of 336,000 cP is obtained.
• a white, tough and crosslinkable product is obtained.
• 600 g of polydimethylsiloxane from Example 1 are heated to 80 ° C. and 0.6 ml of phospholine oxide are added.
• 600 g of a mixture of tolylene diisocyanate from Example 1 and 4,4'-diisocyanatodiphenylmethane (weight distribution 1: 1) are metered in uniformly at 80 ° C. in the course of 2 hours and then stirred at the same temperature for 1 hour.
• a white, homogeneous and crosslinkable dispersion with a viscosity of 178,000 cP is obtained.
• This example illustrates the preparation of a dispersion of 43% toluylene diisocyanate-based polyoarbodiimide and 57% vinyl end group polydimethylsiloxane.
• M an receives a yellowish dispersion with a viscosity of 15 390 cP.
• This example illustrates the preparation of a dispersion of 24% polycarbodiimide based on tolylene diisocyanate, 43 of an ⁇ , ⁇ -dihydroxypolydimethylsiloxane and 33% of a silicone resin.
• 300 g of tolylene diisocyanate from Example 1 are sudosized at 80 ° C. in the course of 2 hours, with stirring, and the mixture is subsequently stirred at the same temperature for one hour.

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Citations (3)

• 1977
  • 1977-07-07 DE DE19772730743 patent/DE2730743A1/de not_active Withdrawn
• 1978
  • 1978-06-22 US US05/918,128 patent/US4214066A/en not_active Expired - Lifetime
  • 1978-06-28 DE DE7878100258T patent/DE2861542D1/de not_active Expired
  • 1978-06-28 EP EP78100258A patent/EP0000350B1/fr not_active Expired
  • 1978-07-03 AU AU37721/78A patent/AU518879B2/en not_active Expired
  • 1978-07-05 IT IT50166/78A patent/IT1106604B/it active
  • 1978-07-05 CA CA306,852A patent/CA1133165A/fr not_active Expired
  • 1978-07-05 JP JP53081069A patent/JPS5833893B2/ja not_active Expired
  • 1978-07-06 ES ES471505A patent/ES471505A1/es not_active Expired
  • 1978-07-06 BR BR7804340A patent/BR7804340A/pt unknown

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