TW200909462A - Metallized polyhedral oligomeric silsesquioxanes as catalysts for polyurethanes - Google Patents

Abstract

A method of using metallized polyhedral oligomeric silsesquioxanes as cure promoters and catalysts for polyurethanes.

Description

200909462 IX. INSTRUCTIONS: RELATED APPLICATIONS RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Patent Application Serial No. 60/931,310 (filed May 21, 2007), and is the U.S. Patent Application Serial No. 5^/ Case No. 015, 185 (17 December 2004 application, part of the continuation of the US Provisional Patent Application No. 60/531, 458 (Application of December 18, 2003)).

TECHNICAL FIELD OF THE INVENTION FIELD OF THE INVENTION The present invention generally relates to the use of metalized nanostructured chemicals as curing accelerators and catalysts to crosslink mixtures of monomers, oligomers and polymers for use as coatings. , coatings, foams, composites, and methods of applying thermosetting polyurethane resins for monolithic applications. [Prior Art 15 Background Metals are used to catalyze the curing (linkability) of polyamine phthalate chains. The polyurethane is any polymer composed of an organic unit chain bonded by a urethane chain. Polyurethanes are widely used in flexible and rigid foams, durable elastomers, high performance adhesives and sealants, fibers, 2 〇 seals, gaskets, carpet liners, and hard plastics. Components. Polyamine phthalates are a class of compounds comprising epoxides, unsaturated polyesters, and phenolic resins. The amino phthalate linkage is produced by reacting an isocyanate group, -N=C=0, with a trans group (alcohol)'-OH. The polyurethane is produced by a polyaddition of a polyisocyanate with a polyalcohol (polyol) in a catalyst and other additives 5 200909462 and in an anti-existing manner. In this case, the polyisocyanate is a molecule having two or more isocyanate functional groups, R-(N=C=C)), the polyol is a molecule having two or more hydroxyl functional groups, R, ( The product of the ketone containing urethane, -RNHCOOR,-, 5 10 15 polyurethane is commercially made by making liquid isocyanic acid gt; ''曰> The reaction of a liquid blend of a multi-opening alcohol, a catalyst, and any other additive to produce such components is referred to as a polyurethane system, or simply as a system. Isocyanates are generally referred to as hydrazine- Side, or simply called, iso |. The blend of polyol and its a addition agent is generally referred to as B-side, or 'poly. This mixture can also be called 2 tree month a or resin conjugate' The resin pusher additive may comprise a chain length, a crosslinking agent, a surfactant, a flame retardant, a blowing agent, a colorant, and a filler polymerization reaction by a tertiary amine such as dinonylcyclohexylamine. And catalyzed by an organometallic salt such as dibutyltin dilaurate. Further, the catalyst can be reacted with an amino phthalate (gelling) (such as , a diazobicyclobutene or a urea (foaming) reaction (such as bis-dimethylaminoethyl ether, or a special system of isocyanate tripolymerization (such as potassium octoate) as a reference." Catalytic action accelerates (increased rate) reaction by a substance called a catalyst (which itself is not consumed by the steroid reaction). More generally, it can sometimes be called any one that accelerates the reaction and does not itself consume or change. It is a "catalyst". Accelerator is an accelerator for catalysis, but it is not a catalyst itself. The most common catalyst for polyurethanes is dibutyltin dilaurate (DBTDL), the composition of which is C32H64〇4Sn The slightly yellow liquid, 631.6 (bp 205 °, mp 24 °). The use of DBTDL is no longer desirable for industrial use because it emits flammable and irritating toxic in fire 20 200909462 Smoke and cytotoxicity And bioaccumulation. Therefore, there is a need for a catalyst to replace DBTDL. It is highly desirable to be a non-flammable soluble solid type containing a more active atomic atom (4). Low; used at the end, and can provide a total reduction of Sn in the polyamine-based vinegar product. Recently, the development of nanoscience has now been cost-effectively manufactured in large quantities, best described as metallization. Nanostructured chemical material due to its special and precise chemical formula, mixed (inorganic-organic) chemical composition, and physical size relative to traditional chemical molecular size (0.3-0.5 nm), 10 and relative Small size of the larger size of conventional fillers (>50 nm). Nanostructured chemicals containing catalytically active metals act as fillers and catalysts to promote the polymer chains themselves, with fillers and surfaces, and with Nai Connectivity between rice structural chemicals. The best examples of metallized nanostructured chemicals are low-cost multifaceted oligosesquioxanes (P0SS) and polyhedral oligomeric phthalates (P〇s). Figure 1 illustrates some representative examples of metallized nanostructured chemicals. All 3 systems are called POSS and the metallization system is called POMS. POMS (polyhedral metal sesquioxane) is a cage containing one or more metal atoms inside or outside the intermediate cage frame. In some examples 20, the cage may contain more than one metal or metal atomic form, or even a metal alloy. Like all POS-containing POSS cages, p〇MS is a hybrid (ie, organic-inorganic) composition that contains primarily inorganic oxime-oxygen bonds but may also contain one or more combinations with cages or The internal frame of the internal metal atom is 200909462 (Fig. 2). In addition to the metal and bismuth-oxygen framework, the exterior of the p〇Ms nanostructured chemical is additionally covered by φ reactive and non-reactive organic functionality (8), which ensures compatibility of the nanostructure with the organic polymer and Can be trimmed. Unlike metal or other particulate fillers, these metallized nanostructured chemical ruthenium can have a molecular diameter ranging from 0.5 nm to 5.0 nm, and low density (>2.5 g/ml) can be highly dispersed in the polymerization. It exhibits excellent intrinsic flame retardancy and unique optical and electronic properties in materials and solvents. BRIEF DESCRIPTION OF THE INVENTION 1. The present invention describes a method and polymerization for preparing a catalyst by metallizing POSS and P〇S (nanostructured chemicals, most commonly referred to as POMS) and incorporating them into a polymer. Composition. The formed composition is used by itself or mixed with other materials to form a laminate or interpenetrating network, or with macroscopic reinforcing materials (such as 'fiber, clay, glass mineral, non-metallized p〇ss cage, metal 15 Mix the particles, and other fillers. The formed polymer is particularly useful for the improved hydrophobicity, surface properties, and reduced toxicity of the desired flexibility and rigidity of the foam, durable elastomer, high performance adhesive and sealant, fiber, Seals, gaskets, carpet liners, hard plastic parts, and skin and hair applications. 20 The preferred composition presented herein contains a mixture of two major materials: (1) polymorphs from polyhedral oligosesquioxanes, polyhedral bismuth citrates, polyoxometallates, carboronic acid, borane, and carbon. a metallized nanostructured chemical, a metalized nanostructured polymer, or a metal-containing nanostructured polymer of the chemical species; and (2) all components used in the manufacture of polyurethanes. Preferably, the metallized nanostructured chemical (POMS) is incorporated into the polymer by blending or mixing the POMS with a polymer, prepolymer, or a mixture of monomers or oligomers. All types, techniques and sequences of blending and mixing (including smelting, dry blending, solution holding, and reactivity and 5 non-reactive blending) are effective. In addition to homogenous mixing, the selective characterization of the nanostructured chemical in a particular region of the polymer can be achieved by utilizing a chemical potential (miscibility) that is compatible with the chemical potential of the region within the polymer. The metallized nanostructured chemical is completed. Because of their chemical nature, the metallized nanostructured chemical can also be trimmed to exhibit compatibility or incompatibility with nearly all polymer systems. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 illustrates a metallized nanostructured chemical mainly composed of polyhedral metal sesquioxanes (POMS). 15 Figure 2 shows an example of the general structure of a POMS catalyst. Fig. 3 is a differential scanning calorimetry diagram of [(iBuSiOu^fn-butylhSn)]^^ POMS. Figure 4 shows an ultraviolet-visible image illustrating the absorption range of p 〇 μ S . 20 [Embodiment] Definition of chemical formula of nanostructure In order to understand the chemical composition of the present invention, the following chemical formulas for polyhedral oligo-sesitene oxide (POSS) and polyhedral citrate (POS) nanostructures are used. The definition of the representative is: 9 200909462

φ聚财石夕氧系 is a material represented by the chemical formula (10) i01•▲, A represents the molar degree of polymerization, and R, an organic substituent (H, methoxy, % or linear aliphatic or aromatic steroid or A thiol group, which may additionally contain reactive luminosity, such as alcohol, brewing, amine, sulphur, smog, shout, or dentate. Polypoxy Oxygen Burn can be either coordinating or non-coordinating. The homo-coordination system contains only one R group, while the non-coordination system contains more than one R group. The POSS and p〇s nanostructures are represented by the following chemical formula: For the homogeneous coordination system [(RSi〇丨5)η]Σ# 10 For the heterogeneous coordination system [(RSi〇1 5) n(R,Si〇i 5)m(d) wherein R is R,) is a heterogeneous coordination composition for functionalization [(RSiOl.sWRXSiOi.o)!^ where the r groups may be equal or unequal) For the heterofunctionalized non-homogeneous composition system [(ί^Κ)ι·5)η(ί^ί〇ΐ.〇)ιη(Μ)]]Σ#. 15 In the above-mentioned owner, R is the same as defined above, and X includes, without limitation, ONa, OLi, OK, OH, a, Br, I, alkoxide (〇R), acetate (OOCR), Peroxide (OOR), amine (NR2), isocyanate (NCO), and R. The symbol Μ refers to the metal elements in the composition, including high and low bismuth metals, including s and ρ region metals, d and f region transitions, lanthanides, and lanthanides. These include Al, B, Ga, Gd, Ce, W, Re, Ru ' Nb, Fe, Co, Ni, Eu, Y, Zn, Mn, Os, Ir, Ta, Cd, Cu,

Ag, V, As, Tb, In, Ba, Ti, Sm, Sr, Pd, Pt, Pb, Lu,

Cs, H, Te, Sn, Zr, and Hf. The symbols m, n and j refer to the stoichiometry of the composition. The symbol Σ means that the composition forms a nanostructure, and the symbol # refers to the number of ruthenium atoms contained in the nanostructure of 200909462. The value of # is generally the sum of m+n, where the range of η is typically 丨24, and the range of (7) is typically 丨12. It should be noted that Σ# should not be confused as a multiplier for determining stoichiometry, as it only describes the overall nanostructure characteristics of the system (aka cage size). 5 DETAILED DESCRIPTION The present invention teaches the use of metallized nanostructured chemicals as catalysts for polyurethanes, curing accelerators, and blending agents. P0MS can be used as a molecular grade enhancer and as a key accelerator for curing accelerators: (1) its unique size with respect to polymer bond size, and (2) its compatibility with polymer systems to overcome repulsive 10 forces (which promotes nevus The ability of the rice fortifier to be incompatible and repelled by the polymer, and (3) its ability to uniformly accommodate and distribute the catalytically active metal atoms and alloys in the polymer, the vesicle, and the monomer. POMS provides catalytic and filler-like strengthening due to its nano nature. The metallized nanostructured chemical can be modified to exhibit preferential affinity to the 5^ microstructure by altering the 15 base on each cage or by conjugating the metal atom to the functionality contained within the polymer. /compatibility. At the same time, the metallized nanostructured chemicals can also be tailored to be incompatible with the microstructures within the same polymer, thereby selectively reinforcing specific polymer microstructures. Therefore, factors affecting selective nanofortification include specific cage size 'size 20 distributions', and compatibility and differences between metallized nanostructured chemicals and polymer systems. The catalytic activity and cure-promoting properties of metallized nanostructured chemicals can be via the nature of the metal attached to or near the cage or the number of metal atoms, the space and electronic properties of the cage, and the dispersion characteristics of the cage. And control 11 200909462

Nanostructured chemicals (such as the 丨 例 〇 ^ ^ ^ 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 Both types are soluble in molten polymers and solvents. Therefore, it solves the long-term dispersion problems associated with traditional granular fillers and curing accelerators. 5 Because P0MS is dissolved in plastics at a molecular level, it comes from the power of dissolution / = That is, the 'free energy' is sufficient to prevent the formation of cages in the coalescence of the conventional and organic bismuth-based food fillers. Agglomeration of particulate fillers and catalysts is a problem for distressed formulators, molders, and resin manufacturers. Table 1 shows the size of POMSi 10 size lnl PQMS compared to polymer size and filler size roughly approximated by most polymer sizes, so at the molecular level, the cage can effectively change the polymer chain. The movement.

Particle type particle diameter #结日日性polymer fragment 0.5 - 5 nm Seven-ring 1.5 nm Thermal gauge clad 5-10 nm Colloidal vermiculite 9 - 80 nm 矣I daily layer 1.0 - 9,000 nm Filler /Organic clay 2 - 100,000 nm —---J Table 1. Nanostructured chemicals, polymer sizes, and relative sizes of fillers POSS and POMS 茏 control chain movement and ability to promote cure It is particularly evident that it is grafted onto the polymer chain. When Pqms catalyzes the polymerization reaction, it is not consumed, and after the polymerization reaction, when the POMS nanostructure is combined with the polymer chain, it is used to slow down the chain, thus promoting the property of the financial period of time 12 15 200909462, For example, Tg, HDT, modulus, hardness, and k疋, which are associated with increased modulus, hardness, and attrition resistance, and the significant properties of the present invention promote metallization by catalytic activity. The naf made structure chemical is incorporated in the polyamine group as a catalyst, a curing accelerator, and a blending agent. In addition to this large amount of stomata (four) sex and toxicity problems, the catalyst of the conventional technology (such as bribe DL) is another day;: It is not used as a strengthening agent in the polymer form, nor as a holding agent. Furthermore, since the metallized POSS nanostructured chemical is a single chemical entity with individual refining points and is soluble in solvents, monomers and plastics, 10 can also effectively reduce the viscosity of the polymer system. The latter is similar to those produced by incorporating a plasticizer into the polymer, but has the added benefit of promoting the curing of the polymer and strengthening the individual polymeric chains due to the nano nature of the chemical. Therefore, the 'easy processing and strengthening effect can be obtained by using metallized nanostructured chemicals (for example, POMS), and the conventional art requires 15 plasticizers and fillers, or p〇ss Covalently bonded to a polymer bond. Example

The general purpose of using all methods is as follows. As is typical in chemical methods, there are several variables that can be used to control the purity, selectivity, rate and mechanism of any method. The variables affecting the method of incorporating metallized nano 20 structural chemicals (e.g., POMS) into plastics include the size and polydispersity, and composition of the nanostructured chemicals. Similarly, the molecular weight, polydispersity, and composition of the polymer system need to be consistent with those of nanostructured chemicals. Finally, the kinetics, thermodynamics, and processing aids used during the compounding process are also occupational tools that can be impacted from nanostructured chemicals and loaded into the aggregate and promoted by the polymerization. For example, your blending, dry blending, and solution blending blending methods are effective for mixing and blending metallized $m structural chemicals into plastics. EXAMPLES 1.Sn POMS 刽 刽 5 The POMS catalyst containing tin (Sn) was easily prepared by reacting dibutyltin reagent with p〇Ss sterol and POSS oxime oxide. A general example of this synthesis is provided below as proof of this method. This method is not intended to be limited. A solution of di-n-butyltin dichloride (42.8 g, 141 mmol, 1.001 eq.) in THF (90 mL) was added dropwise to a solution of ss. A solution of SS triterpenoid [(i-BuSiOuMiBi^HCOSi丨〇) 3] Σ7 (125 g, 140 mmol) and triethylamine (43.3 g, 59.6 mL, 3.05 eq.). This addition was completed after 2 hours, and the reaction was stirred at room temperature for 14 hours. The mixture was filtered and the volatiles were removed under reduced pressure to give a solid, which was dissolved in diethyl ether and filtered from activated carbon and sele. to give a waxy solid, 90% yield. A series of Sn POMS lines are shown in Table 2. These compositions are not intended to be limited, but are provided to compare the elemental composition, Sn content', and physical form of Sn POMS with respect to DBTDL. Furthermore, it should be noted that a Sn POMS composition containing a decyl group (Si(CH3)2H) is provided to indicate a secondary reaction site for forming an interpenetrating network (secondary reaction site) on the Sn POMS 20 or The ability of the nanocage to leach from the final composition. Further, this can be accomplished by using an olefin, a halide or the like containing an R group on a POSS cage. Secondary reactive groups are desirable for improving adhesives, wettability, photocuring, and biofunctional systems. 14 200909462 Table 2. Catalyst relationship between DBTDL (C32H6404Sn) and Sn POMS Catalyst structure Chemical formula Element % Physical state, ” C32H5404S11 C: 60.86, Η: oil >s, / 10.21, 0: 〆 10.13, Sn: 18.80

C64H76〇14SisSn2

C: 50.20, Η: solid 5.00, Ο: 14.63, Si: 14.67, Sn: 15.50 C25H62012Si8Sn C: 33.43, H: solid 6.96, Ο: 21.38, Si: 25.02, Sn: 13.22

C24H60〇12Si8Sll C: 32.60, Η: solid 6.84, 0: 21.72, Si: 25.41, Sn: 13.43 C32H9〇〇i3SisSn C: 37.44, Η: solid 〇np. 8.84, 〇: 52°C) 20.26, Si: 21.89 , Sn: 11.57 15 200909462

C32H90〇l2Si8Sn C: 38.04, 蜡 waxy solid 8.98, 0 (mp 19.00, Si 54 ° C) 22.24, Sn 11.75 C3iHs8〇i2Si8Sn C: 37.37, Η waxy solid 8.90, 〇19.27, Si 22.55, Sn 11.91 C67Hi46〇 12Si8Sn C: 54.11, H oil 9.89, 0 12.91, Si 15.11, Sn 7.98 C66Hi44〇12Si8Sn C: 53.81, H oil 9.85, 0 13.03, Si 15.25, Sn 8.06 Example 2. Thermal stability of POMS catalyzed ruthenium

The thermal stability of Sn POMS is tested to determine if it can maintain catalytic cure without decomposition. POMS was found to be unaffected by low temperatures and exhibited thermal stability up to 350 °C (Figure 3). 5 Example 3. Ultraviolet and vacuum UV stability of POMS POMS cages are additionally advantageous in the polymer due to their radiation absorbing properties (2009 Figure 4). The absorption wavelength can be adjusted over a wide range and is highly dependent on the nature of the R group on the cage and the type of metal atom. The absorption range combined with high heat stability exceeds the performance of all organic absorbents and provides new opportunities to protect high temperature polymers, composites and coatings from UV damage. Sn POMS is particularly desirable for absorption of 200-250 nm radiation. Ti POMS is also effective as a catalyst for polyurethanes and is effective at radiation absorption systems of 200-300 nm. f Example 4 - TIN POMS catalysis of urethane oxime POMS differs greatly in structure and composition (see, for example, Figure 10). Many of these systems are capable of acting as catalysts or cocatalysts and curing accelerators in different resin systems. The preferred composition for the curing of polyurethane is [(RSi015)8((n-butyl)2Sn)]I9 or [(RSiOMhGn-butylhSnOo.sXOSiMeJb. POMS is effective for the curing of polyamine phthalate). A range of POMS loading of 15% by weight to 50% by weight is possible, and a preferred loading amount is 0.01% by weight to 1% by weight. For example, adding 1% by weight of DBTDL to PPGDU1000 requires 2 hours of curing time' The addition of 1% by weight of Sn POMS [(iBuSiCh.AGn-butylhSn)]^9 resulted in an equalization cure over 20 minutes. Therefore, the use of Sn POMS in the use of tin provided a 7 wt% reduction, and the solidification time was 83. The reduction in % can be facilitated by the synergistic use of amines and Sn POMS catalysts. In some instances, the amine incorporation is desirable for use as a blowing agent and to control the rate of reaction. Preferred among the agents. In addition to DBTDL, the organometallic tin complex is rarely considered to be an existing polyamine 17 200909462 ruthenium acid hybrid (10), which can be implemented as an alternative. Poor hydrolytical stability and its toxicity. All Sn p〇Ms show excellent water Solubility and compatibility with the polyurethane component, because the bulky hydrophobic R group on the cage provides hydrophobicity of the metal atom while maintaining a high degree of catalytic activity. The R group on the object provides poms dissolved in the resin component. For the aliphatic resin system, the aliphatic R group on the POMS is preferred, and for the aromatic resin, the aromatic group on the POMS is preferred. The titanium and aluminum p〇Ms of a certain acid ester resin catalyze the catalysis of the POMS containing titanium (Ti) and aluminum (A1) on the amine phthalate resin 10. Generally, Ti POMS colorates polyurethanes. Coloration can be slowed by the addition of small amounts of organic peroxides which maintain the oxidation and colorless state of the butyl sulphate. Similarly, A1 POMS is effective as a polyaminocarboxylic acid. Ester catalyst. A1 POMS [(RSiObMAlOM)] is stored as a dimer in a solid state and is activated by a monomer to catalyze the reaction. This is accomplished by heating and via a diminamide synergist. Again, Tertiary amines are preferred as co-catalysts. While certain representative embodiments and details The present invention has been shown to be illustrative of the present invention. It is to be understood by those skilled in the art that the present invention may be practiced without departing from the scope of the invention as defined in the appended claims. Description of the trapped simple soap Fig. 1 illustrates a metallized nanostructured chemical mainly composed of polyhedral metal sesquix (POMS). 200909462 Fig. 2 shows a general structural example of a POMS catalyst. Fig. 3 is a differential scanning swallowing calorimetry diagram of [(iBuSiOuMb-butylhSn)]" POMS. Fig. 4 shows an ultraviolet-visible light diagram illustrating the absorption range of POMS. [Main component symbol description] (none) 19

Claims (1)

200909462 X. Patent Application Range: 1. A method for the polymerization of polyurethanes comprising the incorporation of a catalytically active material comprising a polyhedral oligometallopropenoxane (POMS) into a polyurethane system. 5. The method of claim 1, wherein the material selected from the group consisting of non-metallized POSS and non-metallized POS is incorporated into the polyurethane system. 3. The method of claim 1, wherein the POMS strengthens the polyamine phthalate at a molecular level. 10. The method of claim 1, wherein the compound is non-reactive. 5. The method of claim 1, wherein the compound is reactive. 6. The method of claim 1, wherein the compounding is accomplished by subjecting the POMS to the polyurethane system. The method of claim 6, wherein the blending method is selected from the group consisting of melt blending, dry blending, and solution blending. 8. The method of claim 1, wherein the POMS is a plasticizer. 9. The method of claim 1, wherein the POMS is used as a fill material. 10. The method of claim 1, wherein the POMS is selectively compounded into a predetermined region of the polymerized polyurethane system. 11. The method of claim 1, wherein the POMS controls molecular motion of the poly 20 200909462 urethane vinegar. 12. The method of claim 1, wherein the POMS crosslinks the polyaminocarboxylic acid S. 13. The method of claim 1, wherein the POMS is selected to have a chemical property compatible with a selected region of the polyurethane. 14. A composition comprising a polymerized polyurethane system comprising a polyhedral oligometallopropenoxane (POMS). twenty one