CN101278003A - Metallized nanostructured chemicals as cure promoters - Google Patents
Metallized nanostructured chemicals as cure promoters Download PDFInfo
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- CN101278003A CN101278003A CNA2006800361003A CN200680036100A CN101278003A CN 101278003 A CN101278003 A CN 101278003A CN A2006800361003 A CNA2006800361003 A CN A2006800361003A CN 200680036100 A CN200680036100 A CN 200680036100A CN 101278003 A CN101278003 A CN 101278003A
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
Metallized polyhedral oligomeric silsesquioxanes and metallized polyhedral oligomeric silicates are used as cure promoters, catalysts, and alloying agents for the reinforcement of polymer microstructures, including polymer coils, domains, chains, and segments, at the molecular level. Because of their tailorable compatibility with polymers, polyhedral oligomeric metallosesquioxanes (POMS) can be readily and selectively incorporated into polymers by common mixing processes.
Description
The cross reference of related application
The application requires the right of priority of the U.S. Provisional Application sequence number No.60/722332 of submission on September 29th, 2005.
Invention field
Relate generally to of the present invention utilizes metallized nanostructured chemical to improve the method for physics, chemistry and the electrical property of polymkeric substance as curing catalyst, catalyzer and alloy addition.
Background of invention
Recognizing for a long time can be by the variable such as form, composition, thermokinetics and processing conditions, the performance of controlling polymers on high degree.The filler of known similarly various size and shape (for example lime carbonate, silicon-dioxide, carbon black etc.) can be incorporated in the polymkeric substance, the form and the gained physicals of while controlling polymers on a certain degree.In addition, known use metal comes the curing (connection) of catalytic polymer chain.Can be by character, state of cure and the curing mechanism of catalyzer, the gained physicals of controlling polymers.For example, well-known is that urethane, silicone, vinyl acetate and polydiolefin solidify by the chemically crosslinked that forms metal catalytic usually.In addition, known bismaleimides, phenols, novolac (novolacs), diolefine and vinyl polymer can be by solidifying down the auxiliary of metal catalyst.
The latest developments of nano science make and can make the lot of materials that is described as metallized nanostructured chemical best effectively by cost, this is because they have specific and the exact chemical formula, mix (inorganic-organic) chemical constitution, and with respect to the size (0.3-0.5nm) of the chemical molecular of routine and with respect to the conventional fillers of large-size (＞50nm), big physical size.The behavior that contains the nanostructured chemical of catalytically-active metals be similar to filler and catalyzer the two, promote between the polymer chain itself and with filler with surperficial and with being connected of nanostructured chemical.
Nanostructured chemical exemplifies best based on those of polyhedral oligomeric silsesquioxane (POSS) and polyhedral oligomeric silicate (POS) cheaply.Fig. 1 shows some representative example of metallized nanostructured chemical, and wherein all systems that contain silicon are called as POSS and the metallization system is called POMS.POMS (polyhedral oligomeric metal silsesquioxane) is at center cage inside of frame or the outside cage that contains one or more metal.In some cases, cage can contain greater than an atoms metal, greater than a metalloid atom or even metal alloy.
The POSS cage that contains silicon with all is the same, and (the being organic and inorganic) composition that mixes that contains POMS contains mainly by the inner frame that inorganic silicon-the oxygen key is formed, and is bonded on the cage or at one or more atoms metal (Fig. 2) of cage inside but also contain.Except metal and silicon-oxygen framework, the outside of POMS nanostructured chemicals is by reactive and the two covering of non-reacted organic functional degree (R), and this will guarantee the consistency and the modifiability (tailorabitity) of nanostructure and organic polymer.These and other performance of metallized nanostructured POSS chemical is disclosed in U.S. Patent No. 5589562.Different with metal or other particulate filler, the molecular diameter scope of these metallized nanostructured chemicals can be 0.5nm-5.0nm, have low density (but＞2.5g/ml) high dispersing in polymkeric substance and solvent, demonstrate good intrinsic flame retardant resistance, and have unique optics and electrical property.
The prior art relevant with filler, softening agent, catalyzer and polymer morphology can't be under molecular level controlling polymers chain, a ball of string and pulsating motion, state of cure or optics and electrical property fully.Therefore need be used for polymeric system suitable dimension toughener and have the diameter (nano-scale) and the distribution of control and have modifiable chemical functionality.
Summary of the invention
The invention discloses by mix metallized nanostructured chemical (being called POMS) the most commonly and prepare the method for polymer composition in the polymkeric substance.Resulting polymers itself can use, and also can combine form layers with other polymkeric substance and press body or interpenetrating(polymer)networks, and perhaps with macroscopic reinforcing agent, for example fiber, clay, glass mineral, non-metallic POSS cage, metallic particles and other filler use together.Resulting polymers especially can be used for production and has desired physical properties, for example polymkeric substance, matrix material and metallic surface, skin and hair is had binding property, the polymer composition of improved hydrophobicity and surface property.When the base of the R on POSS all was organic group, they provided the melt viscosity of water repellency, reduction, low specific inductivity, wear resistance and flame retardant resistance, biocompatibility and optical property.
The preferred composition of Ti Chuing contains the combination of two kinds of basic materials herein: the metallized nanostructured chemical that (1) is obtained by the chemical group of the polymorphic form of polyhedral oligomeric silsesquioxane, polyhedral oligomeric silicate, polyoxy metallide, carborane, borine and carbon, metallized nanostructured oligopolymer or the polymkeric substance of metallic nanostructure; (2) all crosslinkable polymeric systems, for example styrenic, amides, nitrile, olefines, aromatic oxide class, aromatics are sulfide-based, ester class, ionomer, acrylic acid or the like, carbonate (carbonates), epoxide, ethers, ester class, silicone, acid imide, amides, amino formate, phenols, cyanate, ureas, novolac, phenyl amines, fluoropolymer and synthetic and natural rubber.Polymkeric substance is included in the system that contains functional group and by in biological or natural technology deutero-hemihedral crystal, crystal, the noncrystalline or rubbery polymer.
Preferably, by blend or mixing POMS and polymkeric substance, prepolymer or monomeric mixture or oligopolymer, realize that metallized nanostructured chemical (POMS) is incorporated in the polymkeric substance.Blend and blended all types and technology, comprising melt blended, do to mix, solution blending and reactive and non-reacted blend be effective.
Except uniform mixing, can realize that the nanostructured chemical selection is incorporated in the specific region of polymkeric substance by utilizing the compatible metallized nanostructured chemical of partial potential in a certain zone in partial potential (miscible degree) and the polymkeric substance.Because their chemical property, therefore can change metallized nanostructured chemical to demonstrate consistency or the uncompatibility with nearly all polymeric system.
Its physical size also makes metallized nanostructured chemical can select to be incorporated in the plastics and control a ball of string, section, zone, pulsating kinetics and advantageously influence many physics, heat and electrical property subsequently in conjunction with its modifiable consistency.The performance that the most advantageously is improved is machinery and the thermal characteristics that depends on the time, for example thermal distortion, creep, compression set, intensity, toughness, visual appearance, sense of touch, texture, shrinking percentage, modulus, hardness, wear resistance, resistance, CTE, electric conductivity, radiation absorption, oxidative stability, hydrophobicity, biocompatibility and biological function.Except mechanical property, other physicals that advantageously is improved comprises thermal conductivity and electric conductivity, flame retardant resistance, gas barrier and ventilative and water vapour permeability and printing, coating, binding property and film properties.
The accompanying drawing summary
Fig. 1 shows the example based on the metallized nanostructured chemical of polyhedral oligomeric metal silsesquioxane (POMS).
Fig. 2 shows the structure example of metallized nanostructured chemical.
Fig. 3 shows the thermal weight loss chart of various POMS.
Fig. 4 provides the visible chart of UV-that shows the POMS absorption region.
The preferred POMS that Fig. 5 shows for catalysts for polyurethanes and curing catalyst forms.
Fig. 6 is comparison POMS and the non-POMS BMI DSC chart when beginning to solidify.
The definition of the chemical formula of nanostructured
In order to understand the purpose of chemical composition of the present invention, polyhedral oligomeric silsesquioxane (POSS) and polyhedral oligomeric silicate (POS) nanostructured chemistry formula have been made following definitions:
Polysilsesquioxane is with chemical formula [RSiO1.5]
∞Material for representative, wherein ∞ represents the mole of polymerized degree, represent organic substituent (aliphatic series of H, siloxy, ring-type or straight chain or aromatics or the group of fluoridizing with R=, described group can contain reactive functionalities, for example alcohol, ester, amine, ketone, alkene, ether or halide in addition). Polysilsesquioxane can be or equal fragment or assorted segment. All the fragment system contains only class R base, and assorted segment system contains the base greater than a class R.
POSS and POS nanostructured composition represent with following formula:
For equal slice groups compound, be [(RSiO1.5)
n]
∑#
For assorted segment composition, be [(RSiO1.5)
n(R′SiO
1.5)
m]
∑#(wherein R ≠ R ')
Assorted segment composition for functionalized is [(RSiO
1.5)
n(RXSiO
1.0)
m]
∑ #(wherein the R base can be identical or different)
For assorted functionalized assorted segment composition, be [(RSiO
1.5)
n(RSiO
1.0)
m(M)
j]
∑ #
In all were above-mentioned, R included but not limited to ONa, OLi, OK, OH, Cl, Br, I, alkoxide (OR), acetate moiety (OOCR), superoxide (OOR), amine (NR with the identical and X of above definition
2), isocyanic ester (NCO) and R.Symbol M is meant the metallic element in said composition, and it comprises high and low Z metal, comprising s and p block (block) metal, d and f block transition metal, group of the lanthanides and actinide metals.Particularly including 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, Ti and Te.Symbol m, n and j are meant the stoichiometry of composition.The symbol ∑ is meant that said composition forms nanostructure and symbol # is meant the Siliciumatom number that is included in this nanostructure.The numerical value of # is the m+n sum normally, and wherein the scope of the n scope that typically is 1-24 and m typically is 1-12.It should be noted that ∑ # should not obscure for measuring stoichiometric multiplier (multiplier), because it has only described the feature of the total nanostructure of this system (aka cage size).
Detailed Description Of The Invention
The present invention has narrated metallized nanostructured chemical is used to strengthen curable polymer as catalyzer, curing catalyst and alloy addition polymer coil, zone, chain and pulsating purposes.
Can make metallized nanostructured chemical serve as toughener under molecular level and as the key of curing catalyst be: (1) is with respect to the polymer chain size, the size that it is unique, (2) they can be compatible with polymeric system, to overcome repulsive force, described repulsive force will by polymer chain promote the incompatible of nanometer strengthener and repel and (3) they can be included in polymkeric substance, oligopolymer and the monomer and distribute catalytically-active metals atom and alloy equably.
Can by change on each cage the R base or by the association (Fig. 2) of atoms metal with the functionality that in polymkeric substance, comprises, change metallized nanostructured chemical, to demonstrate to the preferential avidity/consistency of polymer micro-structural.Meanwhile, the microstructure that can change in metallized nanostructured chemical and the same polymkeric substance is incompatible, thereby allows to select to strengthen specific polymer micro-structural.Therefore, influence the selectivity nano enhanced factor and comprise specific cage size, distribution of sizes, and in metallized nanostructured chemical and consistency between the polymeric system and difference.
Can perhaps be fixed near the atoms metal quantity on the cage or cage by the character of metal, the steric hindrance of cage and Electronic Performance, and the dispersing character of cage are controlled the catalytic activity of metallized nanostructured chemical and are solidified the promotion characteristic.Can control physicals by changing R base and POSS cage size and form.
Nanostructured chemical, metallization POMS for example shown in Figure 1 obtains with solid and two kinds of forms of oily matter.These two kinds of forms are dissolved in and are melted in polymkeric substance and the solvent, thereby have solved the long-term scattering problem relevant with curing catalyst with conventional particulate filler.In addition, because POMS is dissolved in the plastics, therefore be enough to prevent that from solvation/blended power (being free energy) cage from forming aggregation zone under molecular level, this aggregation zone will occur under the situation that adopts conventional and other functional organic filler.The gathering of particulate filler and catalyzer is the problem that perplexs compounding person, molding person and resin manufacture person routinely.
Table 1 has been listed with respect to polymer sizes and filler size, the size range of POMS.The size of POMS roughly is equivalent to the size of most polymers, thereby cage can change the motion of polymer chain effectively under molecular level.
The relative dimension of table 1 nanostructured chemical, polymer sizes and filler
| Grain type | Particle diameter |
| The non-crystalline polymer segment | 0.5-5nm |
| Seven cyclohexyl POMS | 1.5nm |
| A unregulated polymer ball of string | 5-10nm |
| Colloidal silica | 9-80nm |
| The crystallization thin slice | 1.0-9000nm |
| Filler/organic clay | 2-100,000nm |
When POSS and POMS cage are grafted on the polymer chain, their Quality Initiatives motion and promote that the ability of state of cure is especially apparent.Participate in United States Patent(USP) Nos. 5412053, U.S. Patent No. 5484867, U.S. Patent No. 5589562 and U.S. Patent No. 5047492, all are introduced by reference at this.When POMS nanostructure and polymer chain associated, they played the effect that promotes state of cure and delay chain motion, and and then improved the performance of the time that depends on, for example T widely
g, HDT, creep, modulus, hardness and set, these performances are relevant with modulus, hardness and wear resistance and the weather resistance of increase.
The present invention proved can be by mixing catalytic activity with catalyzer, curing catalyst and alloy addition form metallized nanostructured chemical in plastics, realize that significant performance improves.This has simplified prior art widely.The catalyzer of prior art does not serve as toughener in polymer morphology, do not serve as alloy addition yet.
In addition because metallization POSS nanostructured chemical is single chemical object, and has the fusing point of discrete (discontinuous), and be dissolved in the solvent, in monomer and the plastics, so they also reduce the viscosity of polymeric system effectively.The latter is similar to by softening agent being incorporated into situation about obtaining in the polymkeric substance, and additional advantage is to promote polymer cure and strengthen independent polymer chain, and this is because the nano level character of this chemical causes.Therefore, can obtain the performance and the reinforced effects of easily processing by using metallized nanostructured chemical (for example POMS), wherein prior art will require to use softening agent and these two kinds of materials of filler or POSS will be covalently bonded on the polymer chain.
Embodiment
Can be applicable to all technologic general process variables
Be typically the same with chemical technology can use many variablees to control the purity of any technology, selection rate, speed and mechanism.Metallized nanostructured chemical (for example POMS) comprises nanostructured chemical to the variable in the plastics size, polymolecularity and composition mixed in influence.Similarly, the molecular weight of polymeric system, polymolecularity and composition also must be complementary with nanostructured chemicals.At last, kinetics, thermokinetics and in the compounding process employed processing aid also be can influence by mixing load level that nanostructured chemical obtains in the polymkeric substance and the business tool that improves degree.Blending technology such as melt blended, dry blend solution mixing blend all mix effectively and the metal of alloying nanostructured chemical in plastics.
The thermostability of embodiment 1.POMS catalyzer
The thermostability of check POMS is to measure curing that whether it can keep its catalysed promoted polymkeric substance experience ability of decomposing simultaneously.Find that POMS is not subjected to low temperature effect and demonstrates thermostability (Fig. 3) under maximum 250 ℃ (480 ℉) and 550 ℃ (1022 ℉).
The ultraviolet of embodiment 2.POMS and vacuum ultraviolet (VUV) stability
The POMS cage is useful in addition in polymkeric substance, because they have the feature (Fig. 4) of absorbing radiation.The character of R base on cage and the type of atoms metal can be regulated and highly be depended on to absorbing wavelength in wide in range scope.The absorption region that combines with high thermal stability has surpassed the performance of all organic absorbents and provides new probability protection high temperature polymer, matrix material and coating to avoid UV to damage.
The curing of embodiment 3. urethane resins
POMS exists various structures or composition (Fig. 1).Many in these systems can be served as catalyzer and curing catalyst in different resin systems.The preferred compositions that is used for urethane is [(RSiO shown in Figure 5
1.5)
7(HOTiO
1.5)]
∑ 8, [(RSiO
1.5)
7(sec.-propyl OTiO
1.5)]
∑ 8[(RSiO
1.5)
7(Me
3SiO) (sec.-propyl O)
2TiO
0.5]
∑ 8POMS is possible to the activity of urethane cures in 0.001% to 50wt% POMS load range, and wherein preferred load is 0.1%-10%.
By mixing 1 minute, followed by adding POMS subsequently and mixing 2 minutes, followed by under specified temperature, solidifying, thereby contain the curing of the Bayer two component polyurethane of desmophen polyvalent alcohol 1150 (100 mass parts) and desmodur polyisocyanates N 75MPA/X (70 mass parts).Urethane is suitable on glass as coating or formula material as a whole.Although all catalyzer promoted to solidify [(RSiO in 24-72 hour
1.5)
7(Me
3SiO) (sec.-propyl O)
2TiO
0.5]
∑ 8System produces preferred smooth surface coating and transparency and minimum color.
Organometallic complex is regarded as existing catalysts for polyurethanes system, for example the feasible alternative thing of tin, amine or its mixture hardly.The major cause that organometallic complex is not widely used is their stability to hydrolysis difference and so shelf lives weak point.This is especially true for wherein usually existing more than or equal to the polyurethane foam system of 0.5wt% water.All [(RSiO
1.5)
7(HOTiO
1.5)]
∑ 8, [(RSiO
1.5)
7(sec.-propyl OTiO
1.5)]
∑ 8[(RSiO
1.5)
7(Me
3SiO) (sec.-propyl O)
2TiO
0.5] ∑
8POMS demonstrates good stability to hydrolysis.Huge and hydrophobic R base provides the atoms metal hydrophobicity to keep high-caliber catalytic activity simultaneously effectively on cage.In addition, provide POMS solubilising in resin Composition at the R base on the cage.For the aliphatic resin system, the preferred aliphatic R base on POMS, and for aromatic resin, the preferably aromatic group on POMS.The POMS derivative that contains Sn also is highly effective concerning the curing of urethane.
The curing of embodiment 4. bi-component epoxide-resins
The preferred POMS that is used for Resins, epoxy is [(RSiO as shown in Figure 5
1.5)
14(AlO
1.5)
2]
∑ 18[(RSiO
1.5)
14(MeZn)
2(ZnO
1.5)
2]
∑ 18(wherein R=Ph).POMS is possible to the activity of epoxy resin cure in the POMS of 0.001%-50wt% load range, and wherein preferred load is 0.1%-10%.
By mixing each component of suitable ratio, also thoroughly mix the POMS component followed by adding, thereby carry out curing by the Vantico bi-component epoxide-resin of araldite GY 764BD bisphenol A epoxide resin (100 parts) and araldur42 cycloaliphatic amines (23 parts).
This Resins, epoxy is suitable for twining with making coatings, material all in one piece, prepreg, VARTMable resin or long filament.Although all catalyzer promoted to solidify [(PhSiO in 24-120 hour
1.5)
14(AlO
1.5)
2]
∑ 18System produces the preferred resin with transparence and minimum color.
Huge and hydrophobic R base on cage provides the atoms metal hydrophobicity effectively, keeps high-caliber catalytic activity simultaneously.[(RSiO
1.5)
14(AlO
1.5)
2]
∑ 18POMS, wherein R=Ph demonstrates best general stability and catalytic activity.This may be owing to have high-caliber consistency between aromatics R=Ph base on cage and the aromatic bisphenols A component in the resin system.
The homopolymerization of embodiment 5. aromatic epoxy resins is solidified
Opposite with anhydride-cured or amine solidified epoxy systems, can use POMS, equal poly epoxy resin becomes to have the network polymer with the similar thermomechanical property of conventional curing system.In addition, resulting polymers contains provides the polyethers of excellent wet performance key.
Adopt [(RSiO
1.5)
14(AlO
1.5)
2]
∑ 18POMS (wherein R=Ph), in two kinds of common epoxy monomer of 150 ℃ of following homopolymerizations, diglycidylether of dihydroxyphenyl propane (DGEBA) and four glycidyl group diaminodiphenylmethane (TGDDM) 16 hours, and, compare the gained thermomechanical property with respect to resin system solidifying agent with aromatic amine.Hot mechanical data in the table 2 shows that POMS solidified system is equivalent to the performance that is obtained by amine hardener and has the hydrophobic additional advantage of improvement.These data also show improvement in performance when POMS concentration increases.This is relevant with following discovery: the POMS load level of about 0.75mol% causes the transformation efficiency of obtainable epoxy group(ing) 80%.The rate of polymerization of DGEBA is faster than TGDDM.Discovery is for DGEBA, and POMS promotes room temperature gelling in 1 hour, and TGDDM requires to heat 2 hours down to promote gelling at 110 ℃.For all systems, obtain best thermomechanical property by being heated to 150 ℃.Find that the mechanical property height depends on composition.Usually, find that the retention rate of modulus (E ') advantageously is improved under elevated temperature (240 ℃) by adopting POMS to solidify.[(PhSiO
1.5)
14(MeZn)
2(ZnO
1.5)
2]
∑ 18POMS to polymerization also be have active.
The thermomechanical property of table 2.POMS solidified DGEBA and TGDDM resin
The DGEBA resin
The homopolymerization of embodiment 6. aliphatic epoxy resins is solidified
Opposite with the anhydride-cured or the amine solidified epoxy systems of routine, [(PhSiO
1.5)
14(AlO
1.5)
2]
∑ 18POMS has great activity to the curing of cycloaliphatic epoxides.Curable all cycloaliphatic epoxy resins.Preferred composition is to contain [(epoxy group(ing) cyclohexyl ethyl SiO
1.5)
8]
∑ 8[(epoxy group(ing) cyclohexyl ethyl SiO
1.5)
10]
∑ 10, [(epoxy group(ing) cyclohexyl ethyl SiO
1.5)
12]
∑ 12[(epoxy group(ing) cyclohexyl ethyl SiO
1.5)
∞] Shell ERL4221 and Hybrid Plastics EP0408.Effectively the POMS load range is 0.01wt%-10wt%, and preferred load is 0.1%-3%.Under mixing, POMS is joined in the alicyclic resin, and promote polymerized at room temperature, obtain having outstanding thermal characteristics and wet fastness and antioxidant, for example the resin of the optical clear of steam, ozone, hydrogen peroxide and hard.Use POMS and cycloaliphatic epoxy resin for the medical device that requires to sterilize or for electronic adhesives, for example underfilling and encapsulants are ideal.[(PhSiO
1.5)
14(MeZn)
2(ZnO
1.5)
2]
∑ 18POMS also is effective in these resin systems.
The curing of embodiment 7. bimaleimide resins
Known metal energy catalysis alkene and these two kinds of reactions of Diels-Alder such as aluminium, these two kinds of reactions all take place in the BMI resin solidification.In history, use aluminium organo-metallic and mineral compound to hinder with moisture and the air-sensitive degree that catalyzer is subjected to this system as the BMI resin.[(RSiO
1.5)
14(AlO
1.5)
2]
∑ 18POMS (wherein R=Ph) demonstrates best general stability and catalytic activity in aromatics bimaleimide resin (BMI).This may be owing to having high-caliber consistency between the aromatic bisphenols A component in aromatics R=Ph base on cage and the resin system.In addition, [(PhSiO
1.5)
14(AlO
1.5)
2]
∑ 18POMS is to air and moisture stable.
With amount ranges is 0.001%-50%, and preferred load is the POMS[(PhSiO of 0.1-5%
1.5)
14(AlO
1.5)
2]
∑ 18Compounding is in Cytec BMI resin 5250-4.By stirring, POMS is joined in the BMI resin of premix, and used as single-component system, although also prediction be can be used as bicomponent system.The BMI resin that will cause having improved thermomechanical property in accordance with the standard curing process.By adding the certain benefits that POMS obtains be, catalysed promoted is solidified and resin system completely solidified more at a lower temperature, and this shows (Fig. 6) by direct scanning calorimetry.Use the feasible completely solidified resin fast, at low temperatures and more of POMS, advantageously realize lower cost processing and improved high-temperature behavior.
Although in order to set forth purpose of the present invention, show some representative embodiment and details, but for a person skilled in the art, it is evident that and under the scope of the invention situation that does not break away from the claims definition, to make various variations method and apparatus disclosed herein.
Claims (25)
1. matrix material, it comprises:
(a) be selected from metallized nanostructured chemical in the group of forming by polyhedral oligomeric metal silsesquioxane and polyhedral oligomeric metal silicate; With
(b) be selected from, ester class sulfide-based and ionomer by acrylic acid or the like, carbonate, epoxide, ester class, silicone, polyolefine, polyethers, polyester, polycarbonate-based, polyamide-based, polyurethanes, polyimide, styrenic, amides, nitrile, olefines, aromatic oxide class, aromatics or the group formed by hydrocarbon and silicone deutero-rubbery polymer in polymkeric substance
Wherein by reactive or non-reacted blend, with metallized nanostructured chemical compounding in polymkeric substance.
2. the material of claim 1, it further comprises by reactive or non-reacted blend, compounding is selected from non-metallic nanostructured chemical in the group of being made up of POSS and POS in the polymkeric substance.
3. the material of claim 1, wherein multiple metallized nanostructured chemical compounding is in polymkeric substance.
4. the material of claim 2, wherein multiple metallized nanostructured chemical compounding is in polymkeric substance.
5. the method for claim 4, wherein multiple non-metallic nanostructured chemical compounding is in polymkeric substance.
6. will be selected from metallized nanostructured chemical in the group of being made up of polyhedral oligomeric metal silsesquioxane and polyhedral oligomeric metal silicate is doped to and is selected from by acrylic acid or the like, carbonate, epoxide, the ester class, silicone, polyolefine, polyethers, polyester, polycarbonate-based, polyamide-based, polyurethanes, polyimide, styrenic, amides, nitrile, olefines, the aromatic oxide class, aromatics is sulfide-based, method in the polymkeric substance in ester class and ionomer or the group be made up of hydrocarbon and silicone deutero-rubbery polymer, this method comprise by reactive or non-reacted blend comes the step of the metallized nanostructured chemical of compounding in the polymkeric substance.
7. the method for claim 6, this method further comprise by reactive or non-reacted blend comes compounding to be selected from non-metallic nanostructured chemical in the group of being made up of POSS and POS in polymkeric substance.
8. the method for claim 6, wherein multiple metallized nanostructured chemical compounding is in polymkeric substance.
9. the method for claim 7, wherein multiple metallized nanostructured chemical compounding is in polymkeric substance.
10. the method for claim 9, wherein multiple non-metallic nanostructured chemical compounding is in polymkeric substance.
11. the method for claim 6, wherein polymkeric substance is the physical condition that is selected from the group of being made up of noncrystalline, hemihedral crystal, crystallization, elastomerics and rubber.
12. the method for claim 6, wherein polymkeric substance contains chemical sequence and relevant polymer micro-structural.
13. the method for claim 6, wherein polymkeric substance is selected from the group of being made up of polymer coil, polymer areas, polymer chain and polymer fragments.
14. the method for claim 6, wherein metallized nanostructured chemical strengthens polymkeric substance under molecular level.
15. the method for claim 6, wherein compounding right and wrong are reactive.
16. the method for claim 6, wherein compounding is reactive.
17. the method for claim 6, wherein mixing metallized nanostructured chemical is that the physicals of polymkeric substance is improved to the result in the polymkeric substance.
18. the method for claim 17, wherein physicals is selected from the group of forming by to the binding property of polymer surfaces, to the binding property of composite material surface, the binding property, water repellency, density, low-k, thermal conductivity, second-order transition temperature, viscosity, melting transition, storage modulus to the metallic surface, lax, stress transfer, wear resistance, flame retardant resistance, biocompatibility, ventilation property, porosity, optical quality and radiation shielding.
19. the method for claim 6 wherein realizes compounding by the metallized nanostructured chemical of blend in polymkeric substance.
20. the method for claim 19 wherein realizes compounding by the blending technology that is selected from the group of being made up of melt blending, dry blend solution blending.
21. the method for claim 6, wherein metallized nanostructured chemical is exercised at least a function that is selected from the group of being made up of softening agent, filler, compatilizer, antioxidant and stablizer.
22. the method for claim 7, wherein metallization and non-metallic nanostructured chemical are served as compatilizer.
23. the method for claim 6, wherein metallized nanostructured chemical selectivity compounding are in polymkeric substance, so that metallized nanostructured chemical is incorporated in the interior prospective region of polymkeric substance.
24. the method for claim 23 is wherein because metallized nanostructured chemical compounding in polymkeric substance, is improved physicals.
25. the method for claim 24, wherein performance is selected from by T
g, the group formed of HDT, modulus, creep, set and rate of permeation.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US72233205P | 2005-09-29 | 2005-09-29 | |
| US60/722,332 | 2005-09-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101278003A true CN101278003A (en) | 2008-10-01 |
Family
ID=37906742
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800361003A Pending CN101278003A (en) | 2005-09-29 | 2006-09-28 | Metallized nanostructured chemicals as cure promoters |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP1928948A4 (en) |
| JP (1) | JP2009510229A (en) |
| KR (1) | KR20080068033A (en) |
| CN (1) | CN101278003A (en) |
| RU (1) | RU2008116846A (en) |
| TW (1) | TW200738822A (en) |
| WO (1) | WO2007041344A2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702735A (en) * | 2012-01-19 | 2012-10-03 | 五行材料科技（江苏）有限公司 | Highly-filled enhanced PA 66 composite material and preparation method thereof |
| CN102781994A (en) * | 2009-12-21 | 2012-11-14 | 亨茨曼国际有限公司 | A method to form a polyurethane material |
| 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 |
| CN110709473A (en) * | 2017-04-21 | 2020-01-17 | 硝基化学阿绍有限公司 | Curable silicone rubber composition |
| CN110872437A (en) * | 2018-08-29 | 2020-03-10 | 北京化工大学 | Polyhedral oligomeric silsesquioxane containing hydroxyl metallic tin and preparation and application thereof |
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| US7612143B2 (en) * | 1999-08-04 | 2009-11-03 | Hybrid Plastics, Inc. | Metallized nanostructured chemicals alloyed into polymers |
| US7737228B2 (en) * | 2003-12-18 | 2010-06-15 | Hybrid Plastics, Inc. | Metallized polyhedral oligomeric silsesquioxanes as catalysts for polyurethanes |
| WO2009065873A2 (en) * | 2007-11-21 | 2009-05-28 | Basf Se | Polyhedral oligomeric stannasilsesquioxanes as catalyst for polyurethane curing |
| JP2009185224A (en) * | 2008-02-08 | 2009-08-20 | Kri Inc | Additive for modifying resin material optical property and method for producing the same, and optical resin composition and method for producing the same |
| US8288484B2 (en) | 2009-03-10 | 2012-10-16 | Samsung Electronics Co., Ltd. | Cross-linked product of metal-containing polyamic acid, cross-linked product of metal-containing polyimide including the cross-linked product of metal-containing polyamic acid, method of manufacturing the cross-linked product of metal-containing polyimide, and polyimide film including the cross-linked product of metal-containing polyimide |
| US9312047B2 (en) | 2012-06-22 | 2016-04-12 | Honeywell International Inc. | Method and compositions for producing polymer blends |
| EP2796493A1 (en) * | 2013-04-25 | 2014-10-29 | Huntsman International Llc | Composition comprising silylated polymers and polyhedral oligomeric metallo silsesquioxane |
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| JP3047769B2 (en) * | 1995-02-24 | 2000-06-05 | 信越化学工業株式会社 | Method for producing (poly) metallosiloxane |
| JP3008822B2 (en) * | 1995-06-27 | 2000-02-14 | 信越化学工業株式会社 | (Poly) stannosiloxane and method for producing the same |
| WO1997024344A1 (en) * | 1995-12-27 | 1997-07-10 | Shell Internationale Research Maatschappij B.V. | Preparation of oxirane compounds with titanasilsesquioxane catalysts |
| EP0967229A1 (en) * | 1998-06-26 | 1999-12-29 | Dsm N.V. | Metal complex containing one or more silsesquioxane ligands |
| US20060127583A1 (en) * | 2003-12-18 | 2006-06-15 | Lichtenhan Joseph D | Polyhedral oligomeric silsesquioxanes and polyhedral oligomeric silicates barrier materials for packaging |
| JP2001323271A (en) * | 2000-05-11 | 2001-11-22 | Kanegafuchi Chem Ind Co Ltd | Flame retardant |
| US6569932B2 (en) * | 2001-07-06 | 2003-05-27 | Benjamin S. Hsiao | Blends of organic silicon compounds with ethylene-based polymers |
| US6767930B1 (en) * | 2001-09-07 | 2004-07-27 | Steven A. Svejda | Polyhedral oligomeric silsesquioxane polyimide composites |
| JP4275907B2 (en) * | 2002-07-23 | 2009-06-10 | 旭化成ケミカルズ株式会社 | Polyphenylene ether resin composition |
| JP2004051904A (en) * | 2002-07-23 | 2004-02-19 | Asahi Kasei Chemicals Corp | Polyphenylene ether-epoxy resin composition containing silicon compound |
| JP5441084B2 (en) * | 2003-12-18 | 2014-03-12 | ハイブリッド・プラスティックス・インコーポレイテッド | Polyhedral oligomeric silsesquioxanes and metallized polyhedral oligomeric silsesquioxanes as coatings, composites and additives |
-
2006
- 2006-09-28 JP JP2008533686A patent/JP2009510229A/en active Pending
- 2006-09-28 KR KR1020087010124A patent/KR20080068033A/en not_active Application Discontinuation
- 2006-09-28 CN CNA2006800361003A patent/CN101278003A/en active Pending
- 2006-09-28 EP EP06825264A patent/EP1928948A4/en not_active Withdrawn
- 2006-09-28 RU RU2008116846/04A patent/RU2008116846A/en not_active Application Discontinuation
- 2006-09-28 WO PCT/US2006/038137 patent/WO2007041344A2/en active Application Filing
- 2006-09-28 TW TW095135999A patent/TW200738822A/en unknown
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102781994A (en) * | 2009-12-21 | 2012-11-14 | 亨茨曼国际有限公司 | A method to form a polyurethane material |
| CN102781994B (en) * | 2009-12-21 | 2014-05-07 | 亨茨曼国际有限公司 | A method to form a polyurethane material |
| CN102702735A (en) * | 2012-01-19 | 2012-10-03 | 五行材料科技（江苏）有限公司 | Highly-filled enhanced PA 66 composite material and preparation method thereof |
| 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 |
| CN105793327B (en) * | 2013-10-28 | 2019-12-17 | 亨茨曼国际有限公司 | Synthesis and use of metallized polyhedral oligomeric silsesquioxane catalyst compositions |
| CN110709473A (en) * | 2017-04-21 | 2020-01-17 | 硝基化学阿绍有限公司 | Curable silicone rubber composition |
| CN110872437A (en) * | 2018-08-29 | 2020-03-10 | 北京化工大学 | Polyhedral oligomeric silsesquioxane containing hydroxyl metallic tin and preparation and application thereof |
| CN110872437B (en) * | 2018-08-29 | 2021-02-19 | 北京化工大学 | Polyhedral oligomeric silsesquioxane containing hydroxyl metallic tin and preparation and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2009510229A (en) | 2009-03-12 |
| TW200738822A (en) | 2007-10-16 |
| EP1928948A2 (en) | 2008-06-11 |
| WO2007041344A3 (en) | 2007-12-27 |
| WO2007041344A2 (en) | 2007-04-12 |
| WO2007041344A8 (en) | 2008-05-22 |
| EP1928948A4 (en) | 2010-11-24 |
| RU2008116846A (en) | 2009-11-10 |
| KR20080068033A (en) | 2008-07-22 |
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