CN101142332A - High use temperature nanocomposite resins - Google Patents

Abstract

A method of using olefin containing nanostructured chemicals and silanol containing nanostructured chemicals as high temperature resins is described. Vinyl containing nanostructured chemicals are particularily effective in thermosets as they control the motions of polymer chains, and segments, at the molecular level. Silanol containing nanostructured chemicals are particularily effective in thermosets containing polar groups as the silanol can enhance the reactivity of these groups. Because of their tailorable compatibility with fluorinated polymers, nanostructured chemicals can be readily and selectively incorporated into polymers by direct blending and polymerization processes. The incorporation of a nanostructured chemical into a polymer favorably impacts a multitude of polymer physical properties. Properties most favorably improved, are heat distortion and flammability characteristics, permeability, optical properties, texture, feel and durability. Other properties improved include time dependent mechanical and thermal properties such as creep, compression set, shrinkage, modulus, and hardness. In addition to mechanical properties, other physical properties are favorably improved, including lower thermal conductivity, and gas oxygen permeability. These improved properties may be useful in a number of applications, including composite materials, foams,cosmetics, and durable coatings.

Description

The nanocomposite of high use temperature

The cross reference of related application

The application requires the right of priority of the U.S. Provisional Application sequence number No.60/608582 of submission on September 10th, 2004.

Invention field

The composition of relate generally to high temperature thermosetting polymer of the present invention and fibre-reinforced matrix material and manufacture method thereof.More particularly, the present invention relates to mix and use the method for nanostructured chemical with the controlling polymers curing chemistry, described polymer cure chemistry will influence heat, machinery and the related physical performance of thermosetting polymer conversely.

The thermosetting polymer that the invention still further relates to nano level control is processed into the methods and applications of matrix material, coating, tackiness agent, sealing agent and moulded parts.The application of this resin and matrix material comprises improved compound resin, foams, fiber, paint, coating, tackiness agent and surface property, and these will cause flame retardant resistance, impressionability, biocompatibility and perviousness control, optical property and building coating.

Background of invention

Long recognized can be finely tuned polymer properties by the variable such as the mixing of polymer sequence, structure, additive and filler, composition, rheology, thermokinetics and kinetics machining control on high degree.Similarly, the filler of known various size and shape (for example, Teflon ^, lime carbonate, silicon-dioxide, carbon black etc.) can be incorporated in preformed polymkeric substance (prepolymer) or the monomer mixture, to improve the physics and the material property of gained prescription.Also concentrate on by in the middle of chain or the formation interpenetrating(polymer)networks of some or all of appearance and the crosslinked property modification that causes in the prior art aspect the thermosetting polymer.

In the prior art, required effect can reduce polymer chain and segment motion relative to each other.The chain movement that reduces finally improves physicals in conjunction with the combination of hard and heat-staple component more, for example dimensional stability, intensity and thermostability.Regrettably, the shortcoming of all prior aries is, complex process and can't control the length scale on all three-dimensional dimensions of 1-50nm level.The length scale of 1-50nm is important for polymer materials, and this is because typical polymer chain or the surface creep diameter of the crosslinked 8nm of having and the turning radius of 50nm.The present invention utilizes nanostructured chemicals to realize work simplification, and to the control of curing chemistry and speed, and nano level strengthens polymer chain under the level of 1nm.

In addition, as calculated, be reduced to when being lower than 50nm when strengthening size, they will more anti-sedimentations and polymeric system enhancing property more effectively are provided.Yet, because of lacking the actual source of granular enhancing or toughener, hindered the abundant application of this theoretical indication, the geometrical shape sharp outline of described granular enhancing or toughener and single dispersion and diameter are lower than 10 nanometer range, particularly in 1 nanometer-5 nanometer range.

The prior art relevant with thermosetting polymer, interpenetrating(polymer)networks, polymer rheology and packing technique fail under the level of 1 nanometer-10 nanometer fully the controlling polymers chain, curl and segment moves and structure.In addition, (for example, solubleness, compatibility etc.) mispairing causes high-caliber unevenness in the polymkeric substance in compounding routinely, and this unevenness is similar to and water blended oil in the partial potential between polymkeric substance and inorganic based filler and the chemical.Therefore, need have the chemical toughener of the diameter (nano-scale), distribution of control and fine-tuning chemical functionality's suitable screening, with further lifting polymer properties.

Exploitation on nano science recently makes the energy cost make the material of the merchantable quality that is described as nanostructured chemicals best effectively, this be because it have the exact chemical formula, mix the chemical constitution of (inorganic-organic), with respect to the big physical size of the chemical molecular (0.3-0.5nm) of routine with respect to the conventional fillers of large-size (＞50nm) little physical size.

Summary of the invention

The invention discloses by control its curing chemistry, structure and performance on nano level length scale, prepare the method for improved high temperature polymer thermosetting resin and composite composition.Gained nanometer polymer itself or in conjunction with other polymkeric substance or in conjunction with macroscopic reinforcing agent, for example foams, screen cloth, grid, fiber, clay, glass material and other filler and other chemical of comprising catalyzer are useful Nanoalloy fluidized polymers fully, especially can be used for producing and have desired physical properties, for example to the polymer composition of the melt viscosity of the binding property of fiber enhancer and metallic surface, water-repellancy, reduction, fire-retardant and oxidation-resistance.

The preferred composition of herein listing contains the combination of two kinds of basic materials: (1) vinyl or other olefinic R base and (2) cage or part cage (Fig. 1) of having silanol group on the POSS cage.The combination of these materials can present the form of polymkeric substance, polyhedral oligomeric silsesquioxane, polysilsesquioxane, polyhedral oligomeric silicic acid salt, polysilicate, polyoxy metallide (polyoxometallate), carborane, borine and the polymorphic carbon of the oligopolymer of nanostructure or nanostructure; Perhaps as chemical cross-linking agent or curing catalyst with nano-grade size.This linking agent again can with hydrocarbon alkene class or silane and siloxanes or phosphine, perhaps mercaptan or sulphur and multipolymer, phenoplast, novolac resin, resole, Resins, epoxy, cyanate, urethane, polyimide, bismaleimides etc. and binding substances thereof use together.

Preferably, under the situation of not using solvent,, thereby be implemented in the method for mixing nanostructured chemicals in the thermosetting resin by dissolving or blend nanostructured chemical in chemical cross-linking agent.Yet, all types of blend and technology, comprising melt blended, do to mix, solution blending, reactivity and non-reacted blend be effective.Use term thermosetting resin and " chemically crosslinked " to be because the behavior of chain entanglement between nanostructured chemicals and the polymer chain or entanglement is the same with physical crosslinking, it is similar to conventional chemically crosslinked in behavior.

The thermosetting resin of silane reaction

Have the POSS nanostructured chemical and the silane reaction of R=alkene (vinyl, allyl group, cyclopentenes, tetrahydrobenzene, norbornylene etc. and higher carbon back), make thermosetting resin demonstrate required heat, machinery, electricity and optical property.Can use the various mixtures that contain silane, siloxanes and silsesquioxane, solidify these systems (referring to people's such as Lichtenhan USP5939576) by the hydrosilylation method.What be particularly useful is three silane and cyclic silane (Fig. 2), because their auxiliary solubilising Vinylites.Available equally but unshowned in Fig. 2 be organosilanes and siloxanes.The hydrosilylation reactions process is involved on the carbon-carbon double bond oxidation addition Si-H key and does not produce by product (Fig. 3).By all known hydrosilylation catalysts with by free redical induced catalysis agent reaction.

The thioreactive thermosetting resin

Have POSS nanostructured chemical and the sulphur and the thiol reactant of R=thiazolinyl, also demonstrate outstanding heat, machinery, electricity and optical property.Can use the solidifying agent promotor and the solubilizing agent of various sulfur-bearings, solidify these systems (referring to people's such as Lichtenhan USP5939576) by sulfuration and mercaptan reaction.What be particularly useful is disulphide and epithio (Fig. 4), because their auxiliary solubilising Vinylites.Some or all sulphur can be by the sulphur donor, and for example thiuram disulfide substitutes.Promotor decision vulcanization rate, and the ratio decision curing efficiency of promotor and sulphur and determine the thermostability of gained binding substances conversely.In addition, preferred accelerators typically is 1: 5 with the ratio of sulphur, and it obtains wherein with respect to the chemical of each insertion about 20 networks that sulphur atom is crosslinked.Reaction process is involved on the carbon-carbon double bond oxidation addition S-H or S-S key and does not produce by product (Fig. 5).By all known free radicals, UV and thermal initiator catalyzed reaction.Useful especially is by zinc oxide and stearic acid activation curing process, and by adding complicated sulfenyl chemical in a small amount, typically sulfinyl amine (it not only quickens this technology, and influences the performance of resin, for example its resistance to deterioration) is with " acceleration " this technology.Can not enumerate as the employed all chemical of promotor, but more employed main groups comprise thiazole, sulfinyl amine and guanidine.

Thermosetting resin with phosphine reaction

The POSS nanostructured chemical and the phosphine reaction that have the R=thiazolinyl demonstrate outstanding heat, machinery, electricity and optical property.Can use the various mishmashes that contain phosphine, solidify these systems (referring to people's such as Lichtenhan USP5939576) by phosphorus esterification method.What be particularly useful is two and triphosphine and oligomeric phosphine (Fig. 6), because their auxiliary solubilising vinyl systems.Reaction process is involved on the carbon-carbon double bond oxidation addition P-H key and does not produce by product (Fig. 7).By all known radical initiators and UV source catalyzed reaction.

Thermosetting resin with olefine reaction

The POSS nanostructured chemical and the alkene reaction that have the R=thiazolinyl demonstrate outstanding heat, machinery, electricity and optical property.Can use the various mishmashes that contain alkene,, solidify these systems (also becoming Diels Alder usually) by 2+2 and 4+2 addition method comprising the alkynes class.What be particularly useful is straight chain and ring-type (Fig. 8), because their auxiliary solubilising vinyl systems.Reaction process is involved in the two keys of addition c-c on the carbon-carbon double bond, and does not produce by product (Fig. 9).By all known radical initiators and UV source catalyzed reaction.

The variant of thermosetting resin

Can use cited curing and the variant that has the alkene of POSS nanostructured chemical similarly.For example, can be by people such as Lichtenhan at the oxidation described in USP5942638 and 6100417 and substitution technique with by the described Heck method of people such as Laine, carry out the part derivatize of the ethylenic group that on structure shown in Figure 1, comprises.For increase binding property, under alkali or acidic conditions dissolving or in order to increase or reduce wetting ability and biological chemistry consistency, can wish one or more vinyl among derivatize Fig. 1.Vinyl system among epoxidation Fig. 1 is considered to especially can be used for improving binding property.

Reactive or the non-reacted POSS system of POSS silanol and other of mixing is useful as the toughener of olefin polymer, to comprise the end capped polyimide of bismaleimides and alkene.In addition, also can be requiredly by mixing the POSS silanol and can improving the polymkeric substance that contains non-olefinic with interactional other POSS system of one or more polymer chain, the physicals of polyimide, Resins, epoxy, urethane for example.

Silanol epoxy and cyanate thermoplastic resin

Silanol POSS nanostructured chemical can be by oxygen and the nitrogen base hydrogen bonding in polar silanes alcohol and epoxy and the cyanate ester polymer, thus with epoxy group(ing) and cyanate ester based interaction (Figure 10).The chemical structure that depends on solidifying agent and nano level object, and condition of cure can change mechanical property, from extremely flexible to high strength and hardness, and physicals, for example bond strength, chemical resistant properties, thermotolerance and electric durability.Different chemical constitutions and cure kinetics can allow the user to process and control crosslinking degree in wide temperature range.

Reported remarkable a large amount of work in the document of the properties of between about epoxide and amine, reacting.Can quicken the cure kinetics of epoxy by many factors, for example the hydroxyl that generates in the solidification process adds pure and mild Lewis acid.Especially Chun catalytic affect is admitted widely.The catalytic efficiency of alcohol can be directly proportional with its acidity approx.This is because acid or the reactivity bigger conjugate acid of electrophilic species by reversibly forming epoxide significantly quicken the addition of most of nucleophilic things.For Lewis acid, similar reaction mechanism has been proposed.Our special interest is that silanol group influences curable epoxide kinetics.Also determined the synergy between silanol and Lewis acid (complex compound of aluminium).

Because its nano level size, therefore acid POSS-silanol promotes that epoxy-amine extra in the glass transition phases of back is crosslinked, and described crosslinked mainly to be that diffusion control mechanism accounts for leading.This can be advantageously used in and use the resin extrusion process to make fibre-reinforced matrix material, wherein requires for some time to keep low viscosity, to eliminate porosity and produce the material of higher Tg under lower after fixing temperature.The nano-grade size of POSS also can be used for controlling the volume of reactive group, and this will increase the reaction tendency of the parahydrogen atom of epoxy-amine.Finally give the network that more fully forms.

Similarly association mechanism is virtuous in the cyanate system.These resins are crosslinked by ring trimerizing OCN functional group.Exist down at silanol POSS or relevant POSS system (for example, amine, Si oxide negatively charged ion etc.), POSS increases the volume of reactive group, increases the tendency of more abundant reaction subsequently.Silanol group also can addition on cyanate ester based CN triple bond, but the temperature that this auxiliary curing mechanism is had relatively high expectations, to reach complete.

Similarly association mechanism is virtuous in the polyimide system.These resins are crosslinked by generating the poly acyl amino acid intermediate, and described poly acyl amino acid intermediate hydrogen bonding and POSS consumingly can be by hydrogen bond association on it.Poly acyl amino acid by heating and loss water, changes into cyclin imide subsequently.In silanol POSS or relevant POSS system (for example, amine, Si oxide negatively charged ion etc.) exist down, POSS increases the volume of amic acid reactive group, and increases the loss speed of water by the acidity of silanol, increase the tendency of more abundant reaction subsequently, and reduce needs hot setting.

Similarly association mechanism is virtuous in Bismaleimide Resin.These resins form the ring-type cross-linking agent by the reaction of diallyl bisphenol and maleimide, thereby crosslinked.POSS hydrogen bonding consumingly increases the tendency of more abundant reaction subsequently, and reduces the needs to hot setting to diallyl bisphenol and increase the volume of reactive group.For associating by POSS and imide, the end capped polyimide of alkynes also can obtain similar mechanism.

Similarly association mechanism is virtuous in phenols, Resorcinol and novolac resin system.These resins form methylene-crosslinked network by the reaction of phenols by loss water, thereby crosslinked.POSS hydrogen bonding consumingly and increases the volume of reactive group to phenol, increase the tendency of more abundant reaction subsequently, and reduce the needs to hot setting.

Similarly association mechanism is virtuous in polyurethane system.These resins form the urethane network by condensation between alcohol or amine and the isocyanic ester and addition reaction, thereby crosslinked.POSS hydrogen bonding consumingly and increases the volume of reactive group to pure and mild isocyanic ester, increase the tendency of more abundant reaction subsequently, and reduce the needs to hot setting.

The accompanying drawing summary

Fig. 1 has set forth some representative example of the nanostructured chemical (also comprising the functionality than low vinyl) that contains polyvinyl.

Fig. 2 has set forth and has formed some different silane of available in the thermosetting resin by hydrosilylation reactions.

Fig. 3 has set forth the hydrosilanes metallization processes.

Fig. 4 has set forth some different sulfur curable agent that can be used for forming thermosetting resin.

Fig. 5 has set forth an aspect of sulfur curable technology.

Fig. 6 shows some different phosphorylated solidifying agent.

Fig. 7 shows phosphorylated technology.

Fig. 8 shows some different alkene solidifying agent.

Fig. 9 shows 2+2 alkene curing process.

Figure 10 shows the association by silanol and reactive epoxy group(ing), the formation of cross-linked network.For imide and cyanate and polyether polyols with reduced unsaturation, has similar mechanism.

The definition of the chemical formula symbol of nanostructured

In order to understand the purpose of chemical composition of the present invention, make the following definitions about the chemical formula symbol of polyhedral oligomeric silsesquioxane (POSS) and polyhedral oligomeric silicate (POS) nanostructured.

Polysilsesquioxane is with chemical formula [RSiO_1.5] _xThe material of expression, wherein x represents the mole of polymerized degree, with R=represent organic substituent (H, siloxy, can contain in addition reactive functional groups, for example alcohol, ester, amine, ketone, alkene, ether or halide or can contain ring-type or linear aliphatic or the aromatic group of fluorinated groups). Polysilsesquioxane can be or equal fragment or assorted fragment. All the fragment system contains only class R base, and assorted fragment system contains the base greater than a class R.

POSS and POS nanostructured composition represent with following formula:

For equal slice groups compound be: [(RSiO_1.5) _n] _∑#

For assorted slice groups compound be: [(RSiO_1.5) _n(R′SiO _1.5) _m] _∑#(wherein R ≠ R ')

For the functionalized heteroleptic composition be: [(RSiO_1.5) _n(RXSiO _1.0) _m] _∑#(wherein the R base can be identical or different).

In all above-mentioned chemical formulas, R is identical with above definition, and X includes, but not limited to OH, Cl, Br, I, alkoxyl (OR), acetate groups (OOCR), Si oxide (OOR), amine (NR₂), NCO (NCO) and R. Symbol m and n refer to the stoichiometry of composition. The symbol ∑ refers to that composition forms nanostructured, and symbol refers to be included in the quantity of the silicon atom in this nanostructured. The numerical value of # is the m+n sum normally, and wherein the scope of n typically is 1-24, and the scope of m typically is 1-12. Should be noted that ∑ # should not be confused with the multiplier of measuring stoichiometry, because it has only described the characteristic (aka cage size) of nanostructured total in this system.

Detailed Description Of The Invention

The present invention has instructed the chemicals of nanostructured in thermosetting resin as the purposes that strengthens the construction unit of polymer coil, zone, chain and segment under molecular level.

Can make the chemicals of nanostructured serve as the enhancing of molecular level and the key of alloying agents is: (1) is regional with respect to polymer chain, they have unique size, (2) they can be compatible with polymeric system, to overcome the repulsive force that promotes the incompatible of nanometer strengthener and repulsion because of polymer chain. That is to say, can by changing the R base on each nanostructured, finely tune the chemicals of nanostructured, to demonstrate the affinity/compatibility preferential with some polymer micro-structurals. Meanwhile, other micro-structural in the chemicals of fine-tuning nanostructured and the same polymer is incompatible, thereby is convenient to the specific polymer micro-structural of selective enhancement. Therefore, the factor of selecting nanometer to strengthen comprises the specific nano-scale of chemicals of nanostructured, the distribution of nano-scale, and in chemicals and the compatibility between the polymer chain and unbalanced of nanostructured.

The chemicals of nanostructured, for example the POSS structure of single-phase (monoscopic) size shown in Figure 1 obtains with solid and grease form. These two kinds of forms are dissolved in solvent or the co-reagent, thereby solve the long-term scattering problem relevant with conventional particulate filler or relevant with the interpenetrating networks complexity of mixing. In addition, because the POSS nanocages is dissolved in the plastics under molecular level, therefore the power (that is, free energy) from solvation/mixing is enough to prevent from adopting the conventional zone of with the functionalized filler of other organic group the POSS that occurs being condensed and forming agglomeration. The agglomeration of particulate filler becomes the problem that perplexs routinely makers-up and molding person.

The size of POSS cage is relatively as described below with respect to polymer sizes and filler diameter/length scale: amorphous segment 0.5-5nm; Eight cyclohexyl POSS 1.5nm, atactic polymer ball of string 5-10nm, pelletized silica 9-80nm, crystalline layered body 1.0-9000nm, filler/organic group clay 2-100000nm. The size of POSS roughly is equivalent to the size of most polymers, so POSS can change the motion of polymer chain effectively under molecular level.

In the time of in POSS is incorporated into polymer chain or network, the ability of POSS Quality Initiative motion is especially apparent. U.S. Patent No. 5412053 referring to people such as Lichtenhan, the people's such as Lichtenhan U.S. Patent No. 5484867, the people's such as Lichtenhan U.S. Patent No. 5589562 and the U.S. Patent No. 5047492 of Weidner, all these are specially introduced by reference at this. When the POSS nanostructured covalently bound to the polymer chain the time, they play the effect of delay chain motion and improve widely the performance of the time that depends on, for example Tg, HDT, creep and setting (set), these performances are relevant with modulus, hardness and the wearability of increase. The present invention shows and can be incorporated in the thermosetting resin by the chemicals with nanostructured, realizes that similar performance improves. This will simplify the technique of prior art widely.

In addition, because the chemicals of POSS nanostructured has spherical form (by monocrystalline X-ray diffraction studies), the sphere of similar molecule, and because their dissolvings, therefore, they also can reduce the viscosity of polymeric system effectively. This advantage is similar to the advantage that produces in the polymer by mixing plasticizer, and the advantage that adds is that nano level form because of this chemicals causes strengthening independent polymer chain. Therefore, chemicals by using nanostructured (for example, POSS, POS) can obtain to be easy to processability and strengthen effect, and prior art requires to use processing aid and filler the two and or the mixture of uncertain (illdefined) of polymer chain. Can have single chemicals of the nanostructured of cage size or polydispersion cage size (that is, polydispersity is 1) that disperses by use and realize extra advantage. For all conventional fillers, plasticizer and ipn technology, this control of relative consistency, decentralization and size is beyond example.

Embodiment

Can be applicable to all technologic general technology variablees

Chemical technology is typically, and has many variablees, wherein can utilize purity, selection rate, speed and the mechanism of any technology of described Variable Control.Influence comprises the size and the polydispersity of nanostructured chemicals with the variable that nanostructured chemical (for example, POSS/POS etc.) is incorporated into the technology in the plastics, and forms.Similarly, the molecular weight of polymeric system, polydispersity and composition also must be complementary with nanostructured chemical.At last, kinetics, thermokinetics and in the hybrid technique process employed processing aid and in the crosslinking process process employed promotor and to help solidifying agent also be can influence nanostructured chemical is incorporated into load level that causes in the polymkeric substance and the business tool that improves degree.Mixing and alloying nanostructured chemical in plastics the time, blending technology, for example melt blended, dry blend solution mixing blend all is effective.

Can supply the alternate method: the auxiliary prescription of solvent.POSS can be joined and contain in required polymkeric substance, prepolymer or the monomeric container, and be dissolved in the organic solvent (for example, hexane, toluene, methylene dichloride etc.) or fluorated solvent of capacity, to form a homogeneous phase.Then under high-shear, under the well-mixed temperature of sufficient to guarantee, stirred this mixture 30 minutes, under vacuum or use the technology of similar type,, remove volatile solvent then comprising distillation.Be noted that supercutical fluid, for example CO ₂The substitute that also can be used as flammable hydrocarbon solvents.The gained prescription can directly use or be used for processing subsequently then.

Embodiment 1-silane-cure vinyl POSS resin

Embodiment 1a

The sample of 70g vinyl POSS cage/resin compound is stirred in three dimethylsilane TMOSs of 30g phenyl.Heat this mixture to 60 ℃,, make it then at room temperature to solidify to promote dissolving.Hydrosilylation catalysts with 3ppm is stirred in this mixture then.This resin of curtain coating then, and make it at room temperature to react 8 hours is subsequently 60 ℃ of heating 4 hours and 120 ℃ of heating 2 hours down down.Take off optically transparent resin board, and find to have outstanding heat and mechanical property.

Resin	1 part
		Flexural strength under 23 ℃ of density catalyst type set time (scope) viscosity shelf-lives (w/o cat.) thermal distortions	1.20g/ml 70 ℃ of following 45-50 of platinum minutes, 80 ℃ of following 12 minutes 108cps 24-36mo＞1100  (＞600 ℃) 15000psi *

Modulus under 23 ℃ of the elongations

3.5％ 5×10 5psi *

The silane-cure of embodiment 1b-vinyl POSS and epoxy group(ing) POSS resin/cage mixture

Use is carried out the similar operation with 1a by the resin that 85% vinyl POSS and 5% epoxy group(ing) POSS form.It solidifies in the mode that is similar to 1a, and finds to have much at one machinery and thermal characteristics, and improved to timber and polar surfaces, comprising the binding property of conjugated fibre.(noticing that the vinyl of 0.1-99.9% and the scope of epoxy group(ing) are acceptable).This resin required feature in addition is its optical clarity.

The silane-cure of embodiment 1c-vinyl POSS and epoxy group(ing) POSS resin/cage mixture

Use is carried out the similar operation with 1a by the resin that 80% vinyl POSS and 20% phenyl POSS form.It solidifies in the mode that is similar to 1a, and finds to have improved flame retardant resistance (noticing that the vinyl of 0.1-99.9% and the relative scope of phenyl are acceptable).For this prescription, find that also optical clarity is required performance.

In addition, it is favourable that the tertiary mixture of vinyl, phenyl and epoxy group(ing) is found, for example determines that the vinyl POSS and the phenyl POSS of following ranges has practicality.

The final composition	ViSi(OMe) 3(mol％)	PhSi(OMe) 3(mol％)	EpCyEtSi(OMe) 3(mol％)
				PM1285-0502	80	20	0
PM1285-0502	75	20	5
				PM1285-0508	70	20	10
PM1285-0509	65	20	15
				PM1285-0510	60	20	20

Synthesizing of PM1285-0510 vinyl POSS derivative:

In being furnished with 3 liter of 3 neck round-bottomed flask of mechanical stirrer and reflux exchanger, with ViSi (OMe) ₃(184.72g, 1.246mol), PhSi (OMe) ₃(82.37g, 0.415mol) and EpCyEtSi (OMe) ₃(102.19g 0.415mol) is dissolved in MEK (1.5L) and the methyl alcohol (205ml).Under agitation, in this reaction mixture, add KOH[0.6g lentamente, be dissolved in the water (149.5ml)].Heat this reaction mixture refluxed and continued 30 hours.After reaction, interpolation HCl also stirred 30 minutes.Add 1.5kg ice/water and 400ml hexane then and stirred 30 minutes.Separate hexane/MEK layer, and in Rotary Evaporators, remove and desolvate, obtain solid PM1285 derivative.

Embodiment 2-sulfur curable

At room temperature mechanically mixed ethylene base POSS cage/resin compound (5.01g), sulphur (0.0516g), Captax (0.025g), zimate butyl ester (0.0255g) and methyl tuads (0.0254g).Solidify this mixture 24 down at 110 ℃ then, produce optically transparent resin board, find that described resin board has heat and the mechanical property that is similar to Resins, epoxy.

Embodiment 3-alkene solidifies

The sample and the cumene peroxide that thoroughly mix 50g vinyl POSS cage/resin compound, and with this mixture heating up to 100 ℃, crosslinked to promote.Find that optically transparent resinous varnish has outstanding thermal characteristics.Discovery can by add cyclopentadiene, cyclopentadiene resin, hexadiene, norbornadiene as altogether-alkene monomer reagent, the heat and the mechanical property of the fine-tuning resin that obtains by the alkene method.

Embodiment 4-epoxidized ethylene base POSS cage/resin compound

In the mixture of peracetic acid (200ml), chloroform (500ml), sodium bicarbonate (62.1g) and sodium acetate (1.1g), stir the sample and the backflow of 50g vinyl POSS cage/resin compound.After 2 hours, by the cooling termination reaction.At room temperature, add water (700ml), and stir this mixture, and make it to be separated into water layer and organic layer.Separate organic layer and, obtain the white solid epoxidation product with methyl alcohol (100ml) processing.Notice that MCPBA (chlorine peroxybenzoic acid partially) also is the acceptable oxygenant that substitutes peracetic acid.

Embodiment 5a-POSS silanol and curable epoxide

Use the epoxy monomer and the conventional amine hardener of two kinds of routines, to prove the validity of this method.The diglycidylether that under agitation mixes dihydroxyphenyl propane, (D.E.R.w 332, Dow Chemical for DGEBA, epoxy equivalent (weight) [E]: 173), with the four glycidyl group diaminodiphenylmethane, TGDDM (Aldrich Chemicals, epoxy equivalent (weight) [E]: 105.6), add the 2-methyl isophthalic acid then, 29) or the end capped poly(propylene oxide) (JeffaminewD230 of diamines 5-pentamethylene diamine (Dytek A, DuPont Chemicals, hydrogen equivalent [H]:, Huntsman Chemicals, hydrogen equivalent [H]: 57.5).Employed epoxy (E) is a stoichiometric amount with the ratio of amine (H), [E]/[H] 1/41.The interpolation scope is the phenyl three silanol POSS (POSS-triol) of 0.1-1wt% in this resin compound, heats this resin then and descends stirring 30 minutes at 50 ℃, and vacuum outgas at room temperature is 10 minutes then.This resin is poured in the mould and in the mechanical convection air oven, under the temperature of regulation, solidified 12 hours.Composition, hot machinery and machined parameters have below been provided.

POSS silanol S01458	Epoxy	Amine	Solidification value (℃)	Set time (h)	Tg(℃)	E ' under 30 ℃ (GPa)	E ' on steady section (MPa)
								0 0.4 0 0.4 0 0.2 0.6 0.8 0 0.2 0.6 0 0.4 1.0	DGEBA DGEBA TGDDM GDDM DGEBA DGEBA TGDDM TGDDM TGDDM TGDDM TGDDM TGDDM TGDDM TGDDM	Jeffamine Jeffamine Jeffamine Jeffamine DytekA DytekA DytekA DytekA DytekA DytekA DytekA DytekA DytekA DytekA	100 100 150 150 100 100 100 100 150 150 150 100 100 100	12 12 12 12 12 12 12 12 12 12 12 24 24 24	84 91 137 148 98 115 118 122 167 214 219 198 207 222	3.7 3.3 4.3 3.6 2.6 2.6 2.3 2.0 2.6 2.5 2.8 2.5 3.0 2.5	30 32 80 76 29 36 38 36 78 97 125 126 144 172

JeffamineHuntsman Chemicals，DytekA DuPont

Embodiment 5b-solidifies POSS with anhydride epoxy

The operation of 5a also can be applicable on the system of conventional epoxy and anhydride-cured.For example, the operating weight ratio is A part POSS epoxide, three parts of epoxide of B part acid anhydrides preparation of 45: 55.In this mixture, add the 3wt% imidazole catalyst, and at room temperature thoroughly mix this system.This resin is suitable for molding or dipping.Under 70 ℃, be cured 120 minutes, then before from mould, taking out, at room temperature solidify this molded parts.The POSS epoxy has following required performance: density 1.1-1.2g/ml, second-order transition temperature 110-120 ℃, viscosity (after the mixing)～10 pool, shelf-lives 24 ℃ following 12 months, tensile modulus 2.2Gpa.

Embodiment 6-POSS silanol and polyimide curing

The poly acyl amino acid (Dupont) that forms the employed routine of Kapton  film is used to prove the validity of this method.The POSS silanol is dissolved in the solution of poly acyl amino acid in nmp solvent.The solvable scope of POSS is 0.1-60wt% in this mixture, and wherein preferable range is 5-15wt%.To gather (amic acid) and POSS  solution casting film forming or the coating in NMP then, subsequently 100 ℃ of following imidizations 2 hours, then 200 ℃ following 2 hours and following 1 hour at 300 ℃.In case be exposed under oxygen gas plasma or other oxygenant; then by on the film surface, forming the protectiveness silica glass; mix POSS and will cause good optical property; the modulus of Zeng Jiaing (E ') at elevated temperatures, toughness of increase (elongation * stretching) and improved widely oxidation-resistance.

For 5%POSS  polyimide, typical machine performance at room temperature

Material	Young's modulus (KSI)	Tensile strength (KSI)	Elongation	Tg(℃)
					Polyimide 5%POSS-polyimide	346 350	9.0 10.8	5％ 7％	385℃ 385℃

Embodiment 7-POSS silanol and bismaleimides (BMI) solidify

Use commercial BMI resin, to prove the validity of this method.The POSS silanol is joined by Cytec with in the stoichiometry prescription of the BMPM/DABPA of product code 5250-4 production (BMPM=bismaleimides monomer/polymer and DABPA=diallyl bisphenol).The scope of POSS silanol can be 0.1wt%-50wt%, and wherein preferable range is 1-10wt%.At first heat DABPA to 100 ℃, dissolve the POSS silanol then, add BMPA afterwards.All mixtures of BMIPOSS are optically transparent, and this shows that the POSS silanol fully disperses.Note, can utilize other variant of BMPM according to identical operation, for example the DABPA of dimethyl ether modification (me-DABPA).By heating under 177 ℃ 1 hour, heated 1 hour down then, heated 6 hours down, solidify the gained mixture at 250 ℃ at 200 ℃.Observe the following required performance of prescription: do not need 300 ℃ of curing schedules; Viscosity under 100 ℃ is 3cps, and shelf-lives is 12 months, thermal distortion=689 , the flexural strength=15000psi under 23 ℃, the elongation=4-5% under 23 ℃, modulus=5.5 * 10 under 23 ℃ ⁵Psi (bending), the flexural strength=9000psi under 275 , the elongation=7-8% under 275 , the modulus under 275 =5.5 * 10 ⁵Psi (bending).

The POSS silanol BMI resin that dynamic mechanical analysis 0.8% is strengthened shows, with respect to the BMI contrast, and the improvement that second-order transition temperature is 60 ℃, with relative BMI contrast, the reservation of modulus (E ') at elevated temperatures.In addition, exist POSS not influence initial " low temperature " (177 ℃) round-robin kinetics.Therefore, the processibility of system obtains keeping.Although notice that BMI can realize 350 ℃ Tg separately, this also requires at 300 ℃ of following extra 2 hours after fixing.On the contrary, use lesser temps, faster with the cure cycle of simplifying (177 ℃ following 1 hour, 200 ℃ of following 2 hours and 250 ℃ are following 6 hours) under, POSS BMI provides 365 ℃ Tg.In addition, the modulus of POSS-BMI does not have the fact of remarkable deterioration that the main implementation of high temperature composite is provided under 400 ℃.

In order to estimate the composite attribute of POSS BMI, use Cytec5250-4 resin with 5wt%POSS PMI enhanced class of trade, make four layer 6 " * 6 " T650-35 carbon-fabric composition board.By carrying out short beam shear (short beam shear) test, carry out contrast, the interfacial adhesion of POSS-BMI with respect to BMI.Test 5 samples, and observe the contrast for 5250-4BMI, the average shear intensity level is 58.44MPA ± 2.68, and for 5%POSSBMI, is 59.14 ± 2.00.

Embodiment 8-POSS silanol and distant pawl polyimide curing

Synthetic being involved in of distant pawl polyimide resin (PMR) dissolved dialkyl, diamines and single alkane ester (end-capping reagent) in the lower boiling alkanol (that is methyl alcohol).Add the various weight percentage forms from 0.1 to 50wt% in this mixture, wherein preferred load range is the POSS silanol of 1-15wt%.Because POSS silanol and PMR dissolve in the alcohol, use the solution of gained viscosity, impregnation of fibers or fabric are to provide pre-impregnated article.Desolvate in case remove, then pre-impregnated article contains the uniform mixture of PMR and POSS reactant.When the temperature that is heated to 150 ℃-200 ℃, PMR experiences condensation reaction on the spot, forms end capped imide oligopolymer.The reaction conditions (temperature/pressure) that depends on employed end-capping reagent is usually at 315 ℃ of (600 ; Endo-methylene group tetrahydrophthalic acid ester is NE) to 371 ℃ of (700 ; The phenylacetylene base phthalic acid, methyl esters PEPE) carries out final curing (thermofixation) under the temperature between.Utilize commercial PMR resin,, in HFPE-II-52 PMR resin (a kind of NASA s-generation resin), add POSS silanol, for example three silanol phenyl POSS and three silanol ethyl POSS to confirm the POSS value in this system.

In case solidify, then obtain optically transparent resin.Young's modulus curve for PMR contrast and POSS PMR shows that for POSS PMR system, the retention rate of modulus increases at elevated temperatures.

In order to prove the resin with respect to PMR, this required performance of POSS PMR resin in matrix material is made 8 layers of (90/0) T650-35 carbon-fabric composition board with HFPE-II-52PMR and POSS HFPE-II PMR.Compare with the resin that does not contain POSS, the composition board that contains 7wt% and 15wt% ethyl three pure and mild phenyl triols at HFPE-II-52 CFC demonstrates good processibility.In addition, the density of POSS triol is less than HFPE PMR, and this matrix material that will cause containing POSS has lower density, and described lower density is favourable obtaining aspect " lightweight " composite structure.

Material type	Fibre content (wt%)	Density (gm/cc)	Voids content (vol%)
				HFPE-II-52	64.1	1.626	0.32
+ 15% phenyl POSS triol	64.9	1.618	0.37

In addition, this composite sample is exposed under the thermal ageing, and uses three point bending test to estimate its mechanical property.315 ℃ (600 ) down test shows flexural strength for adding the matrix material that 15wt% three silanol ethyl POSS make improve 10% and for adding the matrix material that 15wt% three silanol phenyl POSS make, flexural strength improves 15%.

Sample (～60vol%T650-35 carbon fabric)	Flexural strength * (Ksi)	Modulus in flexure * (Msi)
			HFPE-II-52 (contrast)	94.9±6	7.8±0.13
Has 7%POSS-phenyl triol	100.7±3	8.3±0.14
			Has 7%POSS-ethyl triol	95.7±8	8.5±0.16
Has 15%POSS-phenyl triol	108.2±5	8.6±0.14

Although abovely described the present invention, think that it changes and modification undoubtedly is conspicuous for a person skilled in the art with specific embodiments.Therefore following claim quasi-solution is interpreted as all this change and modifications that cover in dropping in the spirit and scope of the invention.

Claims (23)

1. the method for compounding nanostructured chemical in thermosetting polymer, this method comprise mixes nanostructured chemical and resin and a kind of step that helps the additive in solidifying agent, promotor and the catalyzer that is selected from.

2. the process of claim 1 wherein multiple nanostructured chemical compounding in polymkeric substance.

3. the process of claim 1 wherein that the thermoset mixture is a kind of physical condition that is selected from oil, amorphous, hemihedral crystal, crystal, elastomerics, rubber and cross-linked material.

4. the process of claim 1 wherein that polymkeric substance contains chemical sequence and relevant polymer micro-structural.

5. the process of claim 1 wherein that polymkeric substance is polymer coil, polymer areas, polymer chain, polymer fragments or its mixture.

6. the process of claim 1 wherein that nanostructured chemical strengthens thermosetting polymer under molecular level.

7. the process of claim 1 wherein that the compounding right and wrong are reactive.

8. the process of claim 1 wherein that compounding is reactive.

9. the process of claim 1 wherein that the compounding nanostructured chemical improved the physicals of thermosetting polymer in the polymkeric substance.

10. the method for claim 9, wherein physicals comprise the binding property that is selected from polymer surfaces, to one in the binding property of compound surface, binding property, water-repellancy, density, low specific inductivity, thermal conductivity, glass transition, viscosity, melt transform, storage modulus, lax, stress transfer, wear resistance, flame retardant resistance, biocompatibility, ventilation property and the porosity to the metallic surface.

11. the method for claim 1, this method is used the silane-cure agent.

12. the method for claim 1, this method is used the sulfur curable agent.

13. the method for claim 1, this method is used the phosphorus solidifying agent.

14. the method for claim 1, this method is used the alkene solidifying agent.

15. the process of claim 1 wherein that nanostructured chemical serves as softening agent.

16. the process of claim 1 wherein that nanostructured chemical serves as filler.

17. the process of claim 1 wherein that nanostructured chemical serves as softening agent and filler simultaneously.

18. the process of claim 1 wherein the compounding of nanostructured chemical selectivity in polymkeric substance, so that nanostructured chemical is incorporated in the prospective region in the polymkeric substance.

19. the method for the molecular motion of controlling polymers, this method comprise that the compounding nanostructured chemical is in polymkeric substance.

20. the method for claim 18, wherein compounding nanostructured chemical is that the performance that depends on the time is improved to the result in the polymkeric substance.

21. the method for claim 20, the performance that wherein depends on the time is selected from Tg, HDT, modulus, creep, deformation, perviousness, erosion resistance and wear resistance.

22. strengthen the method in the selection zone of polymkeric substance, this method comprises:

Compounding has the nanostructured chemical of the chemical property compatible with the selection zone of polymkeric substance.

23. the method for claim 1, this method is used epoxide modified vinyl component.

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