CN101250338A - Modified inorganic nano-particle as well as preparation method and use thereof - Google Patents
Modified inorganic nano-particle as well as preparation method and use thereof Download PDFInfo
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- CN101250338A CN101250338A CNA2008101032377A CN200810103237A CN101250338A CN 101250338 A CN101250338 A CN 101250338A CN A2008101032377 A CNA2008101032377 A CN A2008101032377A CN 200810103237 A CN200810103237 A CN 200810103237A CN 101250338 A CN101250338 A CN 101250338A
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Abstract
The invention discloses modified inorganic nano particle and a preparation process and the application thereof. The modified inorganic nano particle is prepared through conducting polymerization reaction for inorganic nano particle and polyurethane prepolymer, wherein inorganic nano particle is nano calcium carbonate or nano silica dioxide. The preparation process comprises mixing inorganic nano particle and polyurethane prepolymer to react, wherein the reaction temperature is 75 DEG C to 100 DEG C, and the usage amount of polyurethane prepolymer is 3-20% of the weight of inorganic nano particle, optimally is 5-10%. Polyurethane prepolymer is obtained through reacting long-chain aliphatic alcohol and diisocyanate with mol ratio of 1:1 in 75-100 DEG C. The modified inorganic nano particle which is provided by the invention can be used as the filling of high molecular material, has excellent compatibility and dispersibility with substrate, can significantly increase the mechanical strength, abrasion resistance and heat resistance of substrate, is especially suitable to prepare polyurethane elastomer and the filling of polarity rubber, and has great industrial application prospect.
Description
Technical field
The present invention relates to modified inorganic nano-particle and preparation method thereof and application, particularly inorganic nano-particle of base polyurethane prepolymer for use as modification and preparation method thereof and application.
Background technology
The reinforcing filler of inorganic particulate (as lime carbonate, silicon-dioxide) Chang Zuowei plastics, rubber improves product performance, improves the quality of products.Along with the development of nanotechnology, can make these mineral fillers reach nano-scale.Because the particle diameter of inorganic nano-particle is little, specific surface area is big, the specific surface energy height, can effectively absorb energy, thereby reach the effect that strengthens toughening polymer, its performance has the raising of highly significant than traditional micron order inorganic particulate, and can improve other performances of polymkeric substance simultaneously, as thermotolerance, flame retardant resistance, ageing resistance etc.Yet the inorganic nano-particle particle diameter is little, easily reunites together because of huge surface energy, forms the bigger offspring of particle diameter.If this inorganic nano-particle is directly added in the polymkeric substance, in macromolecular material, can not well disperse, not only can not play the toughness reinforcing effect of polymkeric substance enhancing, material property is descended.Therefore, need carry out surface modification to improve the consistency of itself and macromolecular material.
At present, with stearic acid nano-calcium carbonate is carried out surface treatment more than industrial, with silane coupling agent nano silicon is carried out surface treatment, reduce the formation and the interaction of lime carbonate or silica aggregate network, improve dispersed, this has better effects in polyolefine and non-polar rubber, but effect is still undesirable in polar macromolecule material.
It is toughened and reinforced that Chinese patent CN 1861374A adopts liquid urethane elastomer and nano silicon that cyanate ester resin is carried out in-situ polymerization.Chinese patent CN 1927941A base polyurethane prepolymer for use as tetramethylene ether glycol-tolylene diisocyanate (PTMEG-TDI) modified manometer silicon dioxide.Chinese patent CN 1597531A makes the nano-calcium carbonate surface coat one deck Resorcinol and vulkacit H, strengthens itself and polymeric matrix bonding force.Chinese patent CN 1807519A makes the nano-calcium carbonate surface coat one deck unsaturated fatty acids and derivative thereof, strengthens the hydrophobicity on nano-calcium carbonate surface, makes it be easy to disperse in polymkeric substance.
Still exist inorganic particulate, particularly inorganic nano-particle in the above technology and the macromolecular material consistency is poor, and inorganic particulate can not be dispersed in the shortcoming in the macromolecular material, therefore still need inorganic nano-particle is carried out modification
Summary of the invention
The purpose of this invention is to provide modified inorganic nano-particle and preparation method thereof and application.
Modified inorganic nano-particle provided by the invention is formed by inorganic nano-particle and base polyurethane prepolymer for use as polyreaction; This inorganic nano-particle is nano-calcium carbonate or nano silicon.
The method of the above-mentioned modified inorganic nano-particle of preparation provided by the invention is that inorganic nano-particle is got with base polyurethane prepolymer for use as mixing afterreaction.
Among the above-mentioned preparation method, the consumption of base polyurethane prepolymer for use as is the 3-20% of described inorganic nano-particle protonatomic mass, preferred 5-10%.If the quantity not sufficient of used base polyurethane prepolymer for use as 3% is abundant inadequately to the modification of inorganic nano-particle, will cause the performance (as dispersiveness and with the consistency of macromolecule matrix etc.) of subsequent material to descend.If use the amount of base polyurethane prepolymer for use as to surpass 20%, will cause base polyurethane prepolymer for use as excessive, thereby influence modified effect, and cost can be higher.
Temperature of reaction when above-mentioned inorganic nano-particle and base polyurethane prepolymer for use as react is 75-100 ℃.
And base polyurethane prepolymer for use as be by the pure and mild vulcabond of long-chain fat with after 1: 1 mixed in molar ratio, 75-100 ℃ of reaction, an end that obtains is that chain alkyl, an end are the base polyurethane prepolymer for use as of isocyanate groups.In this reaction, various long-chain fat alcohols commonly used all are suitable for, preferred hexadecanol (C
16H
33OH), stearyl alcohol (C
18H
37OH) or eicosanol (C
20H
41The mixture of any one OH) or its arbitrary proportion; Various vulcabond commonly used all are suitable for, and are preferably tolylene diisocyanate (TDI), 4,4-diphenylmethanediisocyanate (MDI) or isophorone diisocyanate (IPDI), more preferably 4,4-diphenylmethanediisocyanate (MDI); The mol ratio of long chain aliphatic alcohol and vulcabond is 1: 1; Various organic solvents commonly used all are suitable for, as toluene, and dimethylbenzene, dimethyl formamide, dimethyl sulfoxide (DMSO), ethyl acetate etc.This reaction is carried out in inert atmosphere, and guaranteeing the selectivity of reaction, and each reactant should dewater in advance, carries out to guarantee to be reflected in the dry environment.
The method for preparing the modified Nano particle provided by the invention, be applicable to various inorganic nano-particles as packing material commonly used, as in nano-calcium carbonate, nano silicon, nanometer calcium sulfate or the nano grade carbon black any one, its particle size range only requires that the median size of nanoparticle is that Nano grade gets final product, preferred median size is 7-400nm, more preferably 20-200nm.
The possible mechanism of the present invention is as follows: because the inorganic nano-particle sub-surface contains great amount of hydroxy group, and an end contains chain alkyl, when the base polyurethane prepolymer for use as that one end contains isocyanate group (NCO group) carries out modification to inorganic nano-particle such as nano-calcium carbonate or nano silicon, the hydroxyl of this performed polymer and inorganic nano-particle sub-surface reacts, thereby the pre-polymerization physical efficiency is grafted on the inorganic nano-particle sub-surface effectively, and the inorganic nano-particle sub-surface has coated the urethane oligomer that one deck end has nonpolar fatty chain like this.This urethane oligomer because and polymkeric substance between have good consistency, and then effectively improve bonding situation between inorganic nano-particle and macromolecule matrix, and owing to it is grafted on the inorganic nano-particle sub-surface, thereby inorganic nano-particle is separated each other, and then effectively prevent its reunion.Like this, not only significantly improve the consistency between inorganic nano-particle and the macromolecule matrix, but also significantly improve the dispersiveness of inorganic nano-particle, make inorganic nano-particle evenly, stably to scatter and be bonded in the macromolecule matrix with non-aggregating state.
In addition, the modified inorganic nano-particle that utilizes above-mentioned preparation method to obtain, and the application in the filler of preparation polar macromolecule material (as polyurethane elastomer or polar rubber, especially polyurethane elastomer) also belong to protection scope of the present invention.
Modified inorganic nano-particle provided by the invention can be used as filler and joins in the macromolecular material, has good consistency and dispersiveness with macromolecule matrix, can significantly improve mechanical strength, wear resistance and the thermotolerance of macromolecule matrix.The method for preparing the modified Nano particle provided by the invention, technology is easy, easy handling, cost is lower, has favorable industrial application prospect.
Description of drawings
Fig. 1 is the infrared spectrogram of the modified nano calcium carbonate of preparation among unmodified nano-calcium carbonate and the embodiment 1.
Fig. 2 is for being filled with the electron scanning micrograph of its section under the unmodified nano-calcium carbonate situation of 1 parts by weight in the polyurethane elastomer.
Fig. 3 is the electron scanning micrograph of its section under the modified nano calcium carbonate situation that is filled with preparation among the 1 parts by weight embodiment 1 in the polyurethane elastomer.
Embodiment
The invention will be further described below in conjunction with specific embodiment, but the present invention is not limited to following examples.
The preparation of embodiment 1, modified nano calcium carbonate particle
Getting the 2.7g stearyl alcohol adds in the reactor; being warming up to 80 ℃ vacuumizes and dewaters; add 200ml toluene and 2.5g MDI successively; be warming up to 90 ℃, high-speed stirring reaction 4h adds 300ml toluene and 100g exsiccant nano-calcium carbonate then under nitrogen protection; the lime carbonate median size is 100nm; continue reaction 4h, reaction finishes the final vacuum suction filtration, and toluene wash, drying, pulverizing, sieving promptly obtains the modified nano calcium carbonate particle.
Detected as can be known by Fig. 1 infrared spectra, the modified nano calcium carbonate particle for preparing according to the method described above is at 2900cm
-1About the stretching vibration absorption peak of methylene radical is arranged, at 2240cm
-1About do not have the absorption peak of isocyanate groups, the urethane oligomer that shown the inorganic nano-particle surface grafting, and isocyanate reaction is complete, does not have residual.
The preparation of embodiment 2, modified manometer silicon dioxide particle
Getting the 2.7g stearyl alcohol adds in the reactor; being warming up to 80 ℃ vacuumizes and dewaters; add 200ml toluene and 2.5g MDI successively; be warming up to 85 ℃, high-speed stirring reaction 5h adds 800ml toluene and 50g exsiccant nano silicon then under nitrogen protection; the silicon-dioxide median size is 50nm; continue reaction 5h, reaction finishes the final vacuum suction filtration, and toluene wash, drying, pulverizing, sieving promptly obtains the modified manometer silicon dioxide particle.
The preparation of embodiment 3, modified manometer silicon dioxide particle
Getting the 2.42g hexadecanol adds in the reactor; being warming up to 80 ℃ vacuumizes and dewaters; add 200ml toluene and 1.74g TDI successively; be warming up to 90 ℃, high-speed stirring reaction 4h adds 800ml toluene and 50g exsiccant nano silicon then under nitrogen protection; the silicon-dioxide median size is 25nm; continue reaction 4h, reaction finishes the final vacuum suction filtration, and toluene wash, drying, pulverizing, sieving promptly obtains the modified manometer silicon dioxide particle.
The preparation of embodiment 4, modified nano calcium carbonate particle
Getting the 2.42g hexadecanol adds in the reactor; being warming up to 80 ℃ vacuumizes and dewaters; add 200ml toluene and 1.74g TDI successively; be warming up to 95 ℃, high-speed stirring reaction 3h adds 300ml toluene and 100g exsiccant nano-calcium carbonate then under nitrogen protection; lime carbonate median size position is 80nm; continue reaction 3h, reaction finishes the final vacuum suction filtration, and toluene wash, drying, pulverizing, sieving promptly obtains the modified nano calcium carbonate particle.
Embodiment 5, the application of modified inorganic nano-particle in the polyurethane elastomer modification
By following formulation polyurethane elastomer nano composite material, described part is mass parts:
With polyurethane elastomer and 1 part of modified nano calcium carbonate particle for preparing by embodiment 1 of 100 mass fractions, to extrude with double-screw melt blending, granulation obtains the polyurethane elastomer nano composite material.
In contrast, adopt and last identical preparation condition,, obtained adding the polyurethane elastomer of unmodified Nano particles of calcium carbonate only with 1 part of replacement of the unmodified Nano particles of calcium carbonate of 1 part of usefulness of modified nano calcium carbonate particle; With above-mentioned two kinds of polyurethane elastomers, and the polyurethane elastomer that does not add the modified Nano particle, under identical condition, above-mentioned three kinds of polyurethane elastomers being carried out performance test, gained is the result all list in the table 1.
Table 1 polyurethane elastomer/modified Nano CaCO
3The composite property test
| Tensile strength/MPa | Elongation rate of tensile failure/% | Vicat softening temperature/℃ | Aging back intensity */MPa | Akron abrasion/mm 3 | |
| TPU | 37.7 | 630 | 70.1 | 36.9 | 38 |
| The unmodified nanometer CaCO of TPU/ 3 | 32.8 | 697 | 70.2 | 36.4 | 33 |
| TPU/ modified Nano CaCO 3 | 38.5 | 660 | 75.6 | 43.1 | 32 |
*70 ℃ of hot air agings 28 days
As shown in Table 1, than polyurethane elastomer (TPU), the polyurethane elastomer nano composite material after the use modified nano calcium carbonate is particle modified, its over-all properties is significantly improved.To above-mentioned two kinds of polyurethane elastomers that be added with unmodified Nano particles of calcium carbonate and that be added with the modified nano calcium carbonate particle, do the scanning electron microscope experiment respectively.Fig. 2 and Fig. 3 are respectively the electron scanning micrograph of modified nano calcium carbonate particle in the polyurethane elastomer matrix of unmodified Nano particles of calcium carbonate and embodiment 1 preparation, inorganic nano-particle after the modification is uniformly dispersed in macromolecule matrix as can be known, and the interface is fuzzy, shows that the inorganic nano-particle of modification and macromolecule matrix consistency are good.
The application in acrylonitrile butadiene rubber modified of embodiment 6, modified inorganic nano-particle
By following formulation nitrile rubber nanocomposites, described part is mass parts:
100 parts of paracrils, the modified Nano CaCO that makes among the embodiment 4
38 parts, 2 parts of stearic acid, 4 parts in zinc oxide, 0.5 part of altax (dibenzothiazyl disulfide), 1.5 parts of accelerant CZs (N cyclohexyl 2 benzothiazole sulfenamide), anti-aging agent RD (2,2,4-trimethylammonium-1,2-dihyaroquinoline polymkeric substance) 1 part, 1.5 parts in sulphur, the compounding rubber method is mixing routinely, sulfuration obtains nitrile rubber nanocomposites.
In contrast, adopt and last identical preparation condition, only the modified nano calcium carbonate particle is replaced with unmodified Nano particles of calcium carbonate, obtained adding the polyurethane elastomer of unmodified Nano particles of calcium carbonate; With above-mentioned two kinds of polyurethane elastomers, and the polyurethane elastomer that does not add the modified Nano particle, under identical condition, above-mentioned three kinds of polyurethane elastomers being carried out performance test, gained is the result all list in the table 2.
Table 2 paracril/modified Nano CaCO
3The composite property test
| Tensile strength/MPa | Elongation rate of tensile failure/% | Vicat softening temperature/℃ | Aging back intensity */ MPa | Akron abrasion/mm 3 | |
| NBR | 24.1 | 530 | 60.2 | 19.8 | 43 |
| The unmodified nanometer CaCO of NBR/ 3 | 23.4 | 538 | 60.8 | 20.2 | 38 |
| NBR/ modified Nano CaCO 3 | 26.8 | 532 | 65.4 | 22.8 | 35 |
*70 ℃ of hot air agings 28 days
As shown in Table 2, for paracril (NBR), use modified Nano CaCO
3Nitrile rubber nanocomposites, its over-all properties is significantly improved.
Claims (13)
1. a modified inorganic nano-particle is formed by inorganic nano-particle and base polyurethane prepolymer for use as polyreaction; Described inorganic nano-particle is nano-calcium carbonate or nano silicon.
2. according to the described modified inorganic nano-particle of claim 1, it is characterized in that: the consumption of described base polyurethane prepolymer for use as is the 3-20% of described inorganic nano-particle protonatomic mass, preferred 5-10%.
3. according to the described modified inorganic nano-particle of claim 2, it is characterized in that: with 1: 1 mixed in molar ratio afterreaction, obtain an end was that chain alkyl, the other end are the base polyurethane prepolymer for use as of isocyanate groups to described base polyurethane prepolymer for use as by the pure and mild vulcabond of long-chain fat.
4. according to the described modified inorganic nano-particle of claim 3, it is characterized in that: described long chain aliphatic alcohol is any one or its arbitrary combination in hexadecanol, stearyl alcohol or the eicosanol, preferred stearyl alcohol; Described vulcabond is a tolylene diisocyanate, 4, and 4-diphenylmethanediisocyanate or isophorone diisocyanate are preferred 4, the 4-diphenylmethanediisocyanate; The temperature of reaction of described long chain aliphatic alcohol and vulcabond is 75-100 ℃.
5. according to claim 1 or 2 described modified inorganic nano-particles, it is characterized in that: the temperature that described inorganic nano-particle and base polyurethane prepolymer for use as carry out polyreaction is 75-100 ℃; The particle diameter of described inorganic nano-particle is 7-400nm, preferred 20-200nm.
6. a method for preparing the arbitrary described modified inorganic nano-particle of claim 1-5 is with inorganic nano-particle and base polyurethane prepolymer for use as mixing afterreaction, obtains described modified inorganic nano-particle; Described inorganic nano-particle is nano-calcium carbonate or nano silicon.
7. according to the described preparation method of claim 6, it is characterized in that: the consumption of described base polyurethane prepolymer for use as is the 3-20% of described inorganic nano-particle protonatomic mass, preferred 5-10%.
8. according to claim 6 or 7 described preparation methods, it is characterized in that: with 1: 1 mixed in molar ratio afterreaction, obtain an end was that chain alkyl, the other end are the base polyurethane prepolymer for use as of isocyanate groups to described base polyurethane prepolymer for use as by the pure and mild vulcabond of long-chain fat.
9. described according to Claim 8 preparation method is characterized in that: described long chain aliphatic alcohol is any one or its arbitrary combination in hexadecanol, stearyl alcohol or the eicosanol, preferred stearyl alcohol; Described vulcabond is a tolylene diisocyanate, 4, and 4-diphenylmethanediisocyanate or isophorone diisocyanate are preferred 4, the 4-diphenylmethanediisocyanate; The temperature of reaction of the pure and mild vulcabond of described long-chain fat is 75-100 ℃.
10. according to claim 6 or 7 described modified inorganic nano-particles, it is characterized in that: the temperature that described inorganic nano-particle and base polyurethane prepolymer for use as carry out polyreaction is 75-100 ℃; The particle diameter of described inorganic nano-particle is 7-400nm, preferred 20-200nm.
11. the application of the arbitrary described modified inorganic nano-particle of claim 1-5 in the filler of preparation polar macromolecule material.
12. the application of the arbitrary described modified inorganic nano-particle of claim 1-5 in the filler of preparation polyurethane elastomer or polar rubber.
13. the application of the arbitrary described modified inorganic nano-particle of claim 1-5 in the filler of preparation polyurethane elastomer.
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