WO2008144735A1 - Metallized polyhedral oligomeric silsesquioxanes as catalysts for polyurethanes - Google Patents
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/24—Catalysts containing metal compounds of tin
- C08G18/242—Catalysts containing metal compounds of tin organometallic compounds containing tin-carbon bonds
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Abstract
A method of using metallized polyhedral ohgomeπc silsesqmoxanes as cure promoters and catalysts for polyurethanes.
Description
METALLIZED POLYHEDRAL OLIGOMERIC SILSESQUIOXANES
AS CATALYSTS FOR POLYURETHANES CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of U S Provisional Patent Application Senal No 60/931,310 filed May 21, 2007
FIELD OF INVENTION
This invention relates geneially to methods for utilizing metallized nanostructured chemicals as cure promoters and catalysts to crosslink monomeπc, ohgomeπc and polymeric mixtuies into thermosetting polyuiethane resins for application as paints, coatings, foams, composites and monoliths
BACKGROUND
Metals are used to catalyze the cure (connectivity) of polyurethane chains A polyurethane is any polymer consisting of a chain of organic units joined by urethane links Polyurethanes are widely used in flexible and πgid foams, durable elastomers, high performance adhesives and sealants, fibers, seals, gaskets, carpet underlay, and hard plastic parts.
Polyui ethanes are in the class of compounds which includes epoxies, unsaturated polyesteis, and phenolics A urethane linkage is produced by reacting an isocyanate group, -N-C=O with an hydroxyl (alcohol) group, -OH Polyurethanes are produced by the polyaddition reaction of a polyisocyanate with a polyalcohol (polyol) in the presence of a catalyst and other additives In this case, a polyisocyanate is a molecule with two or more isocyanate functional groups, R-(N=C=O)n > 2 and a polyol is a molecule with two or more
hydroxyl functional groups, R'-(OH)n > 2 The reaction product is a polymer containing the urethane linkage, -RNHCOOR'-
Polyui ethanes are produced commercially by reacting a liquid isocyanate with a liquid blend of polyols, catalyst, and any other additives These components are referred to as a polyurethane system, or simply a system The isocyanate is commonly referred to as the 'A- side' or just the 'iso' The blend of polyols and other additives is commonly referred to as the 'B-side' or as the 'poly' This mixture might also be called a 'resm' or 'resin blend' Resin blend additives may include chain extenders, cross linkers, surfactants, fire retardants, blowing agents, pigments, and fillers
The polymerization reaction is catalyzed by tertiary amines, such as dimethylcyclohexylamine, and organometallic salts, such as dibutyltindilaurate Furthermore, catalysts can be chosen based on whether they favor the urethane (gel) reaction, such as diazobicyclooctane, or the urea (blow) reaction, such as bis-dimethylammoethylether, or specifically dπve the isocyanate tπmeπzation reaction, such as potassium octoate
Catalysis is the acceleration (increase in rate) of a chemical reaction by means of a substance, called a catalyst, that is itself not consumed by the overall reaction More generally, one may at times call anything that accelerates a reaction, without itself being consumed or changed, a "catalyst" A promoter is an accelerator of catalysis, but not a catalyst by itself
The most common catalyst for polyurethanes is dibutyltin dilaurate (DBTDL) which is a yellowish liquid of composition C32H64O4Sn MW 631 6 (bp 205°, mp 24°) DBTDL usage is no longer desirable for industrial use because it is known to give off combustible and irritating toxic fumes in a fire, and is cytotoxic and bioaccumulative Therefore, a need exists
for a catalyst that replaces DBTDL Highly desirable are catalysts that contain more active Sn atoms in a nonflammable dissolvable solid form Such a catalyst could be utilized in lower concentrations and would afford an overall reduction of Sn in polyurethane products
Recent developments in nanoscience have now enabled the ability to cost effectively manufacture bulk quantities of materials that are best descπbed as metallized nanostructured chemicals due to their specific and precise chemical formula, hybπd (inorganic-organic) chemical composition, and large physical size relative to the size of traditional chemical molecules (0 3-0 5 ran) and small size relative to larger sized traditional fillers (>50 nm) Nanostructured chemicals containing catalytically active metals behave as both fillers and catalysts to promote the connectivity of polymer chains between themselves, with fillers and surfaces, and with the nanostructured chemical
Metallized nanostructured chemicals are best exemplified by those based on low-cost Polyhedral Ohgomeπc Silsesqmoxanes (POSS) and Polyhedral Ohgomeπc Silicates (POS) Figure 1 illustrates some representative examples of metallized nanostructured chemicals for which the all silicon containing systems aie known as POSS and metallized systems are known as POMS POMS (polyhedral oligomeπc metallosesquioxanes) are cages that contain one or more metal atoms mside or outside the central cage framework In certain instances cages may contain more than one metal atom or types of metal atoms, or even metal alloys
I ike the all silicon containing POSS cages, POMS are hybπd (i e organic-inorganic) compositions containing internal frameworks that are primarily compπsed of inorganic silicon-oxygen bonds but which also contain one or more metal atoms bound to or inside of the cage (Figure 2) In addition to the metal and silicon-oxygen framework, the exteπor of a POMS nanostructured chemical is covered by both reactive and nonreactive organic
functionalities (R), which ensure compatibility and tailorabihty of the nanostructure with organic polymers Unlike metal or other particulate fillers, these metallized nanostructured chemicals have molecular diameters that can range from 0 5 nm to 5 0 ran, are of low density (>2 5 g/ml), highly dispersable into polymers and soK ents, exhibit excellent inherent fire retardancy, and
electronic properties
SUMMARY OF THE INVENTION
The present invention describes methods of preparing catalyst and polymer compositions by incorporating metallized POSS and POS, nanostructured chemicals, most commonly referred to as POMS, into polymers The resulting compositions are useful by themselves or m combination with other mateπals to form laminates or interpenetrating networks or in combination with macroscopic reinforcements such as fiber, clay, glass mineral, nonmetalli/ed POSS cages, metal particulates, and other fillers The resulting polymers aie particularly useful in flexible and πgid foams, durable elastomers, high performance adhesi\es and sealants, fibers, seals, gaskets, carpet underlay, hard plastic parts, and skin and hair applications where improved hydrophobicity, surface properties, and reduced toxicity are desirable
The preferred compositions presented herein contain two primary mateπal combinations (1) metallized nanostructured chemicals, metallized nanostructured oligomers, or metal containing nanostructured polymers from the chemical classes of polyhedral oligomeπc silsesquioxanes, polyhedral oligomeπc silicates, polyoxometallates, carboranes, boranes, and polymorphs of carbon, and (2) all components for polyurethane manufacture
Piefeidbly, mcorpoiation of the metallized nanostructured chemical (POMS) into the polymers is accomplished via blending or mixing the POMS with a polymer, prepolymer or
mixture of monomers or oligomers All types, techniques, and sequences of blending, and mixing including melt blending, dry blending, solution blending, and reactive and nonreactive blending are eifective
In addition to homogeneous mixing, the selective incorporation of a nanostructured chemical into a specific region of a polymer can be accomplished by utilizing a metallized nanostructured chemical with a chemical potential (miscibihty) compatible with the chemical potential of the region within the polymer Because of their chemical nature, metallized nanoslructured chemicals can be tailored to show compatibility or incompatibility with nearly all polymer systems
BRIEF DESCRIPTION OF THE DRAWINGS
FIG 1 illustrates metallized nanostructured chemicals based upon polyhedral ohgomeric metallosilsesquioxancs (POMS)
FIG 2 shows a generic structural example of a POMS catalyst
FIG 3 is a differential scanning caloπmetry plot for [(lBuSiOi s^lXn-butyl^Sn)]^ POMS
FIG 4 shows UV- Visible plots illustrating absorption ranges of POMS
DEFINITION OF FORMULA REPRESENTA1 IONS FOR NANOSTRUCTURES
For the purposes of understanding this invention s chemical compositions the following definitions for formula representations ot Polyhedral Oligomenc Silsesquioxane (POSS) and Polyhedral Oligomenc Silicate (POS) nanostructures are made
Polysilsesquioxanes are matenals represented by the formula [RSiOi 5J00 where ∞ represents molar degree of polymerization and R = represents orgSanic substituent (H, siloxy, cyclic or linear aliphatic or aromatic, or fluoπnated groups that may additionally contain reactive functionalities such as alcohols, esters, amines, ketones, olefins, ethers or halides) Polysilsesquioxanes may be either homoleptic or heteroleptic Homoleptic systems contain only one type of R group while heteroleptic systems contain more than one type of R group
POSS and POS nanostructure compositions are represented by the formulas
[(RSiO1 5)n]∑# for homoleptic compositions
[(RSiO1 5)n(R'SiO] 5)m]∑# for heteroleptic compositions (where R ≠ R')
[(RSiO1 5Jn(RXSiO1 o)m]∑# f°r functionahzed heteroleptic compositions (where R groups can be equivalent or inequivalent)
[(RSiOi 5)n(RSiO i o)m(M)j]v# for heterofunctionalized heteroleptic compositions
In all of the above R is the same as defined above and X includes but is not limited to ONa1 OLi, OK, OH, Cl, Br, I, alkoxide (OR), acetate (OOCR), peroxide (OOR), amine (NR2) isocyanate (NCO), and R The symbol M refers to metallic elements within the composition that include high and low Z metals including s and p block metals, d and f block transition, lanthamde, and actinide metals These include Al, B, Ga, Gd, Ce, W, Re, Ru, Nb, Fe, Co, Ni, Eu, Y, Zn, Mn, Os, Ir, Td, Cd, Cu, Ag, V, As, Tb, In, Ba, Ti, Sm, Sr, Pd, Pt, Pb, Lu, Cs, Tl, Te, Sn, Zr, and Hf The symbols m, n and j refer to the stoichiometry of the composition The symbol ∑ indicates that the composition tonus a nanostructure and the symbol # refeis
to the number of silicon atoms contained within the nanostructure The value for # is usually the sum of m+n, where n ranges typically from 1 to 24 and m ranges typically from 1 to 12 It should be noted that ∑# is not to be confused as a multiplier for determining stoichiometry, as it merely descπbes the overall nanostructural characteπstics of the system (aka cage size)
DETAILED DESCRIPTION
The present invention teaches the use of metallized nanostructured chemicals as catalysts, cure promoters and alloying agents for polyurethanes The keys that enable POMS to function as molecular level reinforcing agents and as cure promoters are (1) their unique size with respect to polymer chain dimensions, (2) their ability to be compatibihzed with polymer systems to overcome repulsive forces that promote incompatibility and expulsion of the nanoreinforcing agent by the polymer chains, and (3) their ability to contain and distπbute catalytically active metal atoms and alloys homogeneously in polymers, oligomers, and monomers POMS provide both catalysis function and filler-like reinforcement because of their nanoscopic nature
Metallized nanostructured chemicals can be tailored to exhibit preferential affinity/compatibility with polymer microstructures through variation of the R groups on each cage or via association of the metal atom with functionality contained within the polymer At the same time metallized nanostructured chemicals can be tailored to be incompatible with microstructures within the same polymer, thus allowing for selective reinforcement of specific polymer microstructure Therefore, the factors to effect a selective nanoreinforcement include specific cage sizes, distributions of sizes, and compatibilities and disparities between the metallized nanostrucutured chemical and the polymer system
The catalytic activity and cure promotion attributes of metallized nanostructured chemicals can be controlled through the nature of the metal or number of metal atoms attached to or near the cage, the steπc and electronic properties of the cage and the dispersion characteristics of the cage
Nanostructured chemicals, such as the POMS illustrated in Figure 1, are available as both solids and oils Both forms dissolve in molten polymers and solvents, thus solving the long-standing dispersion problem associated with traditional particulate fillers and cure promoting agents Moreover, because POMS dissolve in plastics at the molecular level, the foices (i_e_ free eneigy) from solvation/mixing are sufficient to pi event cages from forming agglomerated domains as occurs with traditional and other organofunctionahzed fillers Agglomeration of particulate fillers and catalysts has been a problem that has plagued compounders, molders, and resin manufacturers
Table 1 lists the size range of POMS relative to polymer dimensions and filler sizes The size of POMS is roughly equivalent to that of most polymer dimensions, thus at a molecular level the cages can effectively alter the motion of polymer chains
Table 1. Relative sizes of nanostructured chemicals, polymer dimensions, and fillers
The ability of POSS and POMS cages to control chain motion and to promote extent of cuie is particularly apparent when they are grafted onto a polymer chain When POMS catalyze a polymerization they are not consumed, yet post-polymeπzation, when POMS nanostructures associate with a polymer chain, they act to retard chain motion and theieby enhance time dependent properties such as Tg, HDT, creep, modulus, hardness, and set, which correlate to increased modulus, hardness, and abrasion resistance and durability
The present invention demonstrates that significant property enhancements can be realized by the incorporation of catalytically active metallized nanostructured chemicals into polyurethanes as catalysts, cure promoters and alloying agents This greatly simplifies the prior art In addition to flammability and toxicity issues, pπor art catalysts such as DBTDL do not function as reinforcing agents nor as alloying agents within polymer morphology
Furthermoie, because metallized POSS nanostructured chemicals are single chemical entities and have discrete melting points and dissolve in solvents, monomers and plastics, they are also effective at reducing the viscosity of polymer systems The latter is similar to what is produced through the incorporation of plasticizers into polymers, yet with the added benefit of promoting the cure of polymers and reinforcement of the individual polymer chains due to the nanoscopic nature of the chemicals Thus, ease of processability and reinforcement effects are obtainable through the use of metallized nanostructured chemicals (e_g_ POMS) whereas the pπor art requires the use of both plasticizers and fillers or the covalent linking of POSS to the polymer chains
EXAMPLES
General Process Variables Applicable To AU Processes
As is typical with chemical processes there are a number of variables that can be used to control the purity, selectivity, rate and mechanism of any process Variables influencing the process for the incorpoiation of metallized nanostructured chemicals (e_g_ POMS) into plastics includes the size and polydispcrsity, and composition of the nanostructured chemical Similarly, the molecular weight, polydispersity and composition of the polymer system must also be matched with that of the nanostructured chemical Finally, the kinetics, thermodynamics, and processing aids used dunng the compounding process are also tools of the trade that can impact the loading level and degree of enhancement resulting from incorporation of nanostructured chemicals into polymers Blending processes such as melt blending, dry blending and solution mixing blending are all effective at mixing and alloying metallized nanostructured chemical into plastics
EXAMPLE 1. Sn POMS CATALYSTS
Tin (Sn) containing POMS catalysts are easily prepared through the reaction of a dibutyl tin reagents with POSS silanols and POSS siloxides A general example of such a synthesis is provided below as demonstration of the method The method is not intended to be limiting
A solution of di-n-butyltindithloπde (42 8g, 141 mmol, 1 001 eq) dissolved in THF (90 ml) was added dropwise to a solution of hepta i-butylPOSS trisilanol [(i- BuSiO, 5)4(iBu(HO)Sii 0)3]∑r (125g, 140 mmol) and tnethylamine (43 3 g, 59 6ml, 3 05 eq) in THF (500ml) The addition was completed after 2 hours and the reaction was stirred for 14 hours at room temperature The mixture was filtered and volatiles removed under reduced
U picssure to give a solid which was dissolved into diethylether and filtered through activated charcoal and celite to produce a waxy solid in 90% yield
A series of Sn POMS is shown in Table 2 These compositions are not intended to be limiting, rather they are provided to allow comparison of the elemental compositions, the Sn content, and the physical form of the Sn POMS relative to DBTDL Further, it should be noted that Sn POMS compositions containing silane groups (Si(CH3)2H) are provided to indicate the ability to incorporate a secondary reactive site on the Sn POMS for the purpose of forming an interpenetrating network, secondary reactivity site, or to mitigate leaching of the nanoscopic cage from the final composition Alternately, this can be accomplished through the use of olefin, halide, etc , containing R groups on the POSS cage Secondary reactive groups are desirable to improve adhesion, wetdbihty, photocure, and biological function
Table 2 Catalyst relationships between DBTDL (032Hs4O4Sn) and Sn POMS
Catalyst Structure Formula Elemental % Physical State
The thermal stability of Sn POMS was examined to determine if they could maintain catalytic cure while not undergoing decomposition The POMS were found to be unaffected by low temperatures and exhibited thermal stabilities up to 3500C (Figure 3)
EXAMPLE 3. ULTRAVIOLET AND VACUUM ULT RAVIOLET STABILITY OF POMS
POMS cages are additionally beneficial in polymers because of their radiation absorbing characteristics (Figure 4) The absorption wavelength is tunable over a wide range and highly dependant upon the nature of the R group on the cage and type of metal atom The absorptive range coupled with the high thermal stability exceeds the performance of wholly organic absorbers and provides a new opportunity for protection of high tempeiature polymers, composites, and coatings from UV damage Sn POMS are specifically desirable foi the absorption of radiation fiom 200-250 nm Ti POMS are also effective as polyurethane catalysts and effective at radiation absorption from 200-300 nm
EXAMPLE 4. TIN POMS CATALYSIS OF URETHANE RESINS
A large diversity in structures and compositions for POMS exists (see, e g . Figure 1) Many of these systems are capable of functioning as catalysts or co-catalysts and cure promoters in different iesin systems A pieferred composition for polyurethane cure is [(RSiO, 5)8((i>butyl)2Sn)]I9 or [(RSiO1 5)7((n-butyl)2SnOo 5)(OSiMe3)]∑9 The activity of POMS to polyurethane cure is possible over a range of POMS loading from 0 001 wt% to 50 wt%, with a preferred loading of 0 01 wt% to 1 wt%
For example, the addition of 1 wt% DBTDL to PPG DUlOOO requires a cure time of 2 hours while the addition of 1 wt% Sn POMS [(IBUSIOI 5)8((n-butyl)2Sn)]Σ9 produces equivalent cure in 20 min Thus, use of Sn POMS provides a 7 wt% reduction in tin usage and 83% reduction in cure time Additional reactivity can be promoted through the synergistic use of amines with the Sn POMS catalyst In some instances amine incorporation is desirable for use as a foaming agent and for control of reaction rate Tertiary amines are piefeπed as synergists
Organometallic tin complexes, aside from DBTDL, are rarely considered as viable alternatives to existing polyurethane catalyst systems The main reason is the poor hydrolytic stability of organo-tin complexes and their toxicity All of the Sn POMS exhibited excellent hydrolytic stability and compatibility with polyurethane components because the bulky, hydiophobic R groups on the cage effectively provide hydrophobicity to the metal atom while maintaining a high level of catalytic activity Additionally, the R groups on the cage provide for solubilization of the POMS into the resin components For aliphatic resin systems, aliphatic R groups on POMS are preferred while for aromatic resins, aromatic groups on POMS are preferred
EXAMPLE 5. TITANIUM AND ALUMINUM POMS CATALYSIS OF URETHANE RESINS
In addition to tin, POMS containing titanium (Ti) and aluminum (Al) are also effective at catalysis of urethane resins In general Ti POMS are prone to coloration of the polyurethane The coloration can be mitigated through the addition of small amounts of organoperoxide which maintains the oxidized and colorless state for Ti
Similarly Al POMS can be effective as polyurethane catalysts The Al POMS
[(RSiOi sMAlOi s)]∑8 exists as a dimer in the solid-state and must be activated as a monomer in order to catalyze reactions This is accomplished through heat and through incorporation of amine synergists, Again tertiary amines are preferred as co-catalysts
While certain representative embodiments and details have been shown for purposes of illustrating the invention, it will be apparent to those skilled in the art that vaπous changes in the methods and apparatus disclosed herein may be made without departing from the scope of the invention which is defined in the appended claims
What is claimed is
Claims
CLAIMS 1 A method oi polyurethane polymerization comprising compounding a catalytically active matcπal including a polyhedral ohgomeπc metallasilsesquioxane (POMS) into a polyurethane system 2 The method of claim 1, wherein a material selected from the group consisting of nonmetalh/ed POSS and nonmetalhzed POS is compounded into the polyurethane system 3 The method of claim 1, wherein the POMS reinforces the polyurethane at a molecular level 4 The method of claim 1 , wherein the compounding is nonreactive 5 The method of claim 1 , wherein the compounding is reactive 6 The method of claim 1 , wherein the compounding is accomplished by blending the POMS into the polyurethane system 7 The method of claim 6, wherein the blending process is selected from the group consisting of melt blending, dry blending, and solution blending 8 The method of claim 1 wherein the POMS functions as a plasticizer 9 The method of claim 1, wherein the POMS functions as a filler 10 The method of claim 1, wherein the POMS is selectively compounded into a predetermined region within the polymerized polyurethane system 11 The method of claim 1, wherein the POMS controls molecular motion of the polyurethane 12 The method of claim 1 , wherein the POMS cross-links the polyurethane 13 The method of claim 1 wherein the POMS is selected to have chemical properties compatible with a selected region of the polyurethane
14 A composition comprising a polymerized polyurethane system including a polyhedral oligomenc metallasilsesquioxane (POMS)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US93131007P | 2007-05-21 | 2007-05-21 | |
| US60/931,310 | 2007-05-21 |
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| WO2008144735A1 true WO2008144735A1 (en) | 2008-11-27 |
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| PCT/US2008/064371 WO2008144735A1 (en) | 2007-05-21 | 2008-05-21 | Metallized polyhedral oligomeric silsesquioxanes as catalysts for polyurethanes |
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| WO (1) | WO2008144735A1 (en) |
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| WO2009065873A2 (en) * | 2007-11-21 | 2009-05-28 | Basf Se | Polyhedral oligomeric stannasilsesquioxanes as catalyst for polyurethane curing |
| WO2011076570A1 (en) | 2009-12-21 | 2011-06-30 | Huntsman International Llc | A method to form a polyurethane material |
| EP2796493A1 (en) * | 2013-04-25 | 2014-10-29 | Huntsman International Llc | Composition comprising silylated polymers and polyhedral oligomeric metallo silsesquioxane |
| EP2865704A1 (en) | 2013-10-28 | 2015-04-29 | Huntsman International Llc | Synthesis and use of metallized polyhedral oligomeric silsesquioxane catalyst compositions |
| CN114729092A (en) * | 2019-03-26 | 2022-07-08 | 波利有限公司 | Selective polyurethane prepolymer synthesis |
| CN115181256A (en) * | 2022-08-01 | 2022-10-14 | 江西聚锐德新材料股份有限公司 | Cage-shaped polysilsesquioxane titanium catalyst, liquid catalyst, preparation method and application thereof |
| CN114729092B (en) * | 2019-08-12 | 2024-04-26 | 波利有限公司 | Selective polyurethane prepolymer synthesis |
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Cited By (20)
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| WO2009065873A2 (en) * | 2007-11-21 | 2009-05-28 | Basf Se | Polyhedral oligomeric stannasilsesquioxanes as catalyst for polyurethane curing |
| WO2009065873A3 (en) * | 2007-11-21 | 2009-07-16 | Basf Se | Polyhedral oligomeric stannasilsesquioxanes as catalyst for polyurethane curing |
| RU2560174C2 (en) * | 2009-12-21 | 2015-08-20 | Хантсмэн Интернэшнл Ллс | Method of producing polyurethane material |
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| CN105308109A (en) * | 2013-04-25 | 2016-02-03 | 亨茨曼国际有限公司 | Composition comprising silylated polymers |
| WO2014173638A1 (en) * | 2013-04-25 | 2014-10-30 | Huntsman International Llc | Composition comprising silylated polymers |
| EP2796493A1 (en) * | 2013-04-25 | 2014-10-29 | Huntsman International Llc | Composition comprising silylated polymers and polyhedral oligomeric metallo silsesquioxane |
| US9752013B2 (en) | 2013-04-25 | 2017-09-05 | Huntsman International Llc | Composition comprising silylated polymers |
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| EP2865704A1 (en) | 2013-10-28 | 2015-04-29 | Huntsman International Llc | Synthesis and use of metallized polyhedral oligomeric silsesquioxane catalyst compositions |
| WO2015062759A1 (en) * | 2013-10-28 | 2015-05-07 | Huntsman International Llc | Synthesis and use of metallized polyhedral oligomeric silsequioxane catalyst compositions |
| CN105793327A (en) * | 2013-10-28 | 2016-07-20 | 亨茨曼国际有限公司 | Synthesis and use of metalized polyhedral oligomeric silsequioxane catalyst compositions |
| US9822210B2 (en) | 2013-10-28 | 2017-11-21 | Huntsman International Llc | Synthesis and use of metallized polyhedral oligomeric silsesquioxane catalyst compositions |
| CN114729092A (en) * | 2019-03-26 | 2022-07-08 | 波利有限公司 | Selective polyurethane prepolymer synthesis |
| CN114729092B (en) * | 2019-08-12 | 2024-04-26 | 波利有限公司 | Selective polyurethane prepolymer synthesis |
| CN115181256A (en) * | 2022-08-01 | 2022-10-14 | 江西聚锐德新材料股份有限公司 | Cage-shaped polysilsesquioxane titanium catalyst, liquid catalyst, preparation method and application thereof |
| CN115181256B (en) * | 2022-08-01 | 2023-09-26 | 江西聚锐德新材料股份有限公司 | Cage-shaped polysilsesquioxane titanium catalyst, liquid catalyst, preparation method and application thereof |
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