EP0000350B1 - Organopolysiloxanes modifiés par des polycarbodiimides, procédé pour leur préparation et leur application - Google Patents

Organopolysiloxanes modifiés par des polycarbodiimides, procédé pour leur préparation et leur application Download PDF

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Publication number
EP0000350B1
EP0000350B1 EP78100258A EP78100258A EP0000350B1 EP 0000350 B1 EP0000350 B1 EP 0000350B1 EP 78100258 A EP78100258 A EP 78100258A EP 78100258 A EP78100258 A EP 78100258A EP 0000350 B1 EP0000350 B1 EP 0000350B1
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polycarbodiimide
mixture
polydimethylsiloxane
mpa
hours
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EP0000350A1 (fr
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Hans-Heinrich Dr. Moretto
Helmut Dr. Steinberger
Ingrid Larking
Hans Dr. Sattlegger
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Bayer AG
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    • 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 organo
  • Organopolysiloxanes modified with organic materials include e.g. Block copolymers in which organopolysiloxane blocks are chemically linked to organic polymer blocks (e.g. polyethers, polyesters, polycarbonates, polycarbodiimides).
  • organic polymer blocks e.g. polyethers, polyesters, polycarbonates, polycarbodiimides.
  • Such products are e.g. in U.S. Patent 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 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, e.g. high compression set. Furthermore, the mechanical properties deteriorate considerably at elevated temperatures (e.g. tensile strength). The permanent heat resistance, which otherwise distinguishes the organopolysiloxanes, is lost.
  • the present invention relates to ⁇ , ⁇ -dihydroxypolysiloxanes modified with polycarbodiimide, which are characterized in that the ⁇ , ⁇ -dihydroxypolysiloxane and polycarbodiimide are present as distinguishable phases.
  • the improved organopolysiloxane compositions according to the present invention are thus polycarbodiimide-filled ⁇ , ⁇ -dihydroxypolysiloxane mixtures which are composed of the following two phases: (i) a continuous phase of an organopolysiloxane liquid and (ii) a non-continuous phase of finely divided Particles of a carbodiimide polymer obtained by polycondensation of the corresponding monomer or monomer mixture in the presence of the (Y, w-dihydroxypolysiloxane and a carbodiimidation catalyst.
  • the polycarbodiimide-filled organopolysiloxane compositions of the present invention are prepared by intensively mixing the ( Y , (o-dihydroxypolysiloxane 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 prepared in situ and known per se.
  • the polymer mixture consists of 3-80% by weight, preferably 5-70% 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.
  • Such starting components to be used according to the invention are aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates, such as those e.g. 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, cyclohexane-1,3- and -1,4-diisocyanate and any mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (DAS 1,202,785), 2,4- and 2, 6-hexahydrotoluenediisocyanate and any mixtures of these isomers, hexahydro-1,3- and
  • German Patent Specification 1,157,601 describes polyisocyanates containing carbodiimide groups, as described in German Patent 1,092,007, diisocyanates as described in American Patent 3,492,330, polyisocyanates containing allophanate groups, such as those e.g. in the British patent specification 994 890, the Belgian patent specification 761 626 and the published Dutch patent application 7 102 524, polyisocyanates containing isocyanurate groups, e.g. in German patents 1 022 789, 1 222 067 and 1 027 394 and in German laid-open publications 1 929 034 and 2 004 048, polyisocyanates containing urethane groups, such as those e.g.
  • 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 polyisocyanates
  • polyphenyl-polymethylene polyisocyanates such as those produced by aniline-formaldehyde condensation and subsequent phosgenation ("crude MDI") and carbodiimide groups, urethane groups
  • Polyisocyanates containing alllophanate groups isocyanurate groups, urea groups or biuret groups
  • 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 bringing the isocyanate component (s) together 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 pm, with some of the particles being less than 0.3 ⁇ m in diameter.
  • the carbodiimide-modified polysiloxanes according to the invention are advantageously prepared in such a way that an ⁇ , ⁇ -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 di- 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 preparing 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 of time.
  • the isocyanate or the isocyanate mixture is preferably added 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 which occurs 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 polycarbodiimide-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 also contain fillers and plasticizers.
  • quartz powder, chalk or diatomaceous earth or pyrogenic Si0 2 or other finely divided metal oxides can serve as fillers.
  • liquid inert polydiorganosiloxanes e.g. ⁇ , ⁇ -trimethylsiloxy end-stopped polydimethylsiloxanes.
  • the water required for the vulcanization of 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 which have hardened to elastomers at room temperature show excellent, moisture-resistant adhesion to concrete substrates, which is achieved without the use of so-called primer substances.
  • the polycarbodiimide-modified organopolysiloxane compositions as an additional component to, for example, silicone hot vulcanizate mixtures, improve their water vapor resistance.
  • This example illustrates the preparation of a dispersion of 24% polycarbodiimide based on tolylene diisocyanate and 76% of a, w-dihydroxypolydimethylsiloxane.
  • a mixture of 1750 g of polydimethylsiloxane with terminal hydroxyl groups and a viscosity of 18000 mPa ⁇ s (at 20 ° C.) and 750 g of an isomer mixture of 80% 2,4- and 20% 2,6-tolylene diisocyanate are added for 4 hours with an anchor stirrer Stirred at 25 ° C. 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 having a viscosity of about 68500 mPa ⁇ s 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 mPa ⁇ s 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 13300 mPa ⁇ s (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 approx. 800,000 mPa.s. 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.
  • 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 of 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 mPa ⁇ s and an NCO 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 complete hydroxyl groups and a viscosity of 10000 mPa.s (at 20 ° C) are heated in a vessel to 80 ° C 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 mPa.s.
  • 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 mPa.s (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 in a sealed tube with 50 mg of H Z O / 20 cm 3 carried out in air at 236 ° 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 mPa.s) and 250 g of polydimethylsiloxane from Example 2 (1000 mPa.s) 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 mPa ⁇ s and is cross-linkable.
  • the product is yellowish and homogeneous and has a viscosity of 56,400 mPa.s.
  • 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 polydimethylsiloxane with terminal silanol groups and a visco 50,000 mPa ⁇ s (20 ° C) and 1 kg of a polycarbodiimide powder based on 4,4'-diisocyanatodiphenylmethane (1.8% NCO) are mixed for 4 hours at room temperature in a planetary mixer with 80 U / Min. mixed.
  • a white, homogeneous, non-flowable, crosslinkable paste is obtained.
  • 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, 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.
  • This example illustrates the preparation of a dispersion of 43% toluene diisocyanate-based polycarbodiimide and 57% vinyl end group polydimethylsiloxane.
  • 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.

Claims (3)

1. α,ω-dihydroxypolysiloxannes modifiés par un polycarbodiimide, caractérisés en ce que l'α,ω-dihydroxypolysiloxanne et le polycarbodiimide sont présents sous forme de phases distinctes.
2. Procédé pour la préparation d'α,ω-dihydroxypolysiloxannes modifiés par un polycarbodiimide selon la revendication 1, caractérisé en ce que le polycarbodiimide est produit par réaction d'isocyanates de formule générale
Figure imgb0014
dans laquelle R' représente un reste alkylène ou arylène, de préférence jusqu'en C24, éventuellement substitué aussi par des groupes NCO, en présence d'un catalyseur de carbodiimidisation connu in situ dans l'α,ω-dihydroxypolysiloxanne.
3. Utilisation des α,ω-dihdyroxypolysiloxannes modifiés par un polycarbodiimide pour la 5 préparation de systèmes à un ou à deux composants durcissables sous l'influence de l'humidité.
EP78100258A 1977-07-07 1978-06-28 Organopolysiloxanes modifiés par des polycarbodiimides, procédé pour leur préparation et leur application Expired EP0000350B1 (fr)

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DE19772730743 DE2730743A1 (de) 1977-07-07 1977-07-07 Mit polycarbodiimid modifizierte organopolysiloxane
DE2730743 1977-07-07

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EP0000350B1 true EP0000350B1 (fr) 1982-01-20

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JP (1) JPS5833893B2 (fr)
AU (1) AU518879B2 (fr)
BR (1) BR7804340A (fr)
CA (1) CA1133165A (fr)
DE (2) DE2730743A1 (fr)
ES (1) ES471505A1 (fr)
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DE102007060791A1 (de) * 2007-12-18 2009-06-25 Bayer Materialscience Ag Verfahren zur Herstellung monomerenarmer organischer Polyisocyanate
TW201434882A (zh) * 2013-03-13 2014-09-16 Momentive Performance Mat Inc 可濕氣固化之有機聚矽氧烷組成物

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Publication number Publication date
AU3772178A (en) 1980-01-10
IT1106604B (it) 1985-11-11
JPS5417961A (en) 1979-02-09
AU518879B2 (en) 1981-10-22
JPS5833893B2 (ja) 1983-07-22
ES471505A1 (es) 1979-01-16
IT7850166A0 (it) 1978-07-05
DE2730743A1 (de) 1979-01-25
CA1133165A (fr) 1982-10-05
DE2861542D1 (en) 1982-03-04
EP0000350A1 (fr) 1979-01-24
US4214066A (en) 1980-07-22
BR7804340A (pt) 1979-03-20

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