CN102492173B - Halloysite with modified surface and preparation method for halloysite - Google Patents
Halloysite with modified surface and preparation method for halloysite Download PDFInfo
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- CN102492173B CN102492173B CN 201110403428 CN201110403428A CN102492173B CN 102492173 B CN102492173 B CN 102492173B CN 201110403428 CN201110403428 CN 201110403428 CN 201110403428 A CN201110403428 A CN 201110403428A CN 102492173 B CN102492173 B CN 102492173B
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Abstract
The invention discloses halloysite with a modified surface and a preparation method for the halloysite. A modification object is hyperbranched polysiloxane containing phosphorus and an epoxy group, and the phosphorus content of the modification object is more than 14.5 weight percent. The preparation method comprises the following steps of: mixing 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, a vinyl-containing silane coupling agent, an initiator and a solvent, mixing an obtained phosphaphenanthrene silane coupling agent, a silane coupling agent containing an epoxy resin, a catalyst and a solvent, reacting to obtain hyperbranched polysiloxane containing phosphaphenanthrene and the epoxy group, and reacting activated halloysite and the hyperbranched polysiloxane in a solvent to obtain the halloysite with the modified surface. The halloysite with the modified surface has a large number of active groups and a hyperbranched topological structure, has high dispersity in resin matrixes, and has a broad application prospect in the fields of polymer modification, synthesis and preparation of novel polymer materials and multifunctionalization of nano-clay/polymer composite materials.
Description
Technical field
The present invention relates to a kind of surface modification technology of halloysite, particularly hyperbranched polyorganosiloxane is modified the method for halloysite.
Background technology
Halloysite (HNTs) is a kind of natural silicate mineral, is by kaolinite lamella curling forming under natural condition.In recent years research find (referring to document: 1. yellow will side, Jia Zhixin, Guo Baochun, the Judd people. the structure of PBT/ halloysite nanotubes matrix material and performance [J]. plastics industry, 2008,36,29 – 35. are Ning 2., N.Y.; Yin, Q.J.; Luo, F.; Zhang, Q.; Du, R.N.; Fu, Q. Crystallization behavior and mechanical properties of polypropylene/halloysite composites. Polymer 2007,48,7374-7384. 3. Jia ZX, Luo YF, Guo BC, Yang BT, Du ML, Jia DM. Reinforcing and flame-retardant effects of halloysite nanotubes on LLDPE. Polym-Plast Technol Eng 2009; 48 (6): 607-13.), as abundant, the cheap natural nano pipe of a kind of reserves, halloysite has broad application prospects at the aspects such as mechanical property, thermostability, flame retardant resistance and crystallinity that improve and improve polymer matrix composite.
Yet, take full advantage of the advantage of halloysite, its potential advantages aspect polymer modification are come true generally need to modify its surface.This is because the deployment conditions of nano inoganic particle in polymeric matrix is one of key element that determines the many performances of matrix material, and the high surface free energy that nano-inorganic substance has often makes it to be difficult to obtain good dispersiveness in polymeric matrix.Therefore, the finishing of halloysite is very important.
But the at present finishing work of halloysite mainly concentrates on how by improving the dispersiveness of halloysite in matrix, to reach the purpose that promotes composite materials property.For example, the people such as Shamsi come modification halloysite surface by the plasma polymerized coating of styrene monomer, improved the dispersiveness of halloysite in the polystyrene matrix, but because the vinylbenzene coating is non-chemically to be connected with the halloysite surface, therefore the increase rate of the storage modulus of matrix material and Young's modulus is very little (referring to document: MohtashimH Shamsi, Mohammad Luqman, Fevzihan Basarir, Joon-Seop Kim, Tae-Ho Yoona, Kurt E Geckelera, Plasma-modi ed halloysite nanocomposites:effect of plasmamodi cation on the structure and dynamicmechanical properties of halloysite – polystyrene nanocomposites. Polymer Internatonal 2010; 59:1492 – 1498).The people such as Mu Bin are by preparing bromoacrylic acid ethyl ester grafted by super branched polymer modification halloysite nanotubes from condensation vinyl polymerization and living radical transfer polymerization.Yet, rely on electrostatic force to be connected between halloysite and the bromoacrylic acid ethyl ester hyperbranched polymer, so that the thermal characteristics range of decrease of graft product is very large, and polymerizing condition is relatively harsher, the polymerization process more complicated, relatively poor (the participation document: Bin Mu of operability, Mingfei Zhao, Peng Liu. Halloysite nanotubes grafted hyperbranched (co) polymers via surface-initiated self-condensing vinyl (co) polymerization. Journal of Nanoparticle Research, 2008,10:831-838).The people such as Guo have prepared polypropylene/halloysite composite material by PP graft modification halloysite, halloysite after the modification is scattered in the polypropylene matrix with the tube bundle shape, matrix material increases before having mechanical property than the matrix material that adopts unmodified halloysite to make (referring to document: Mingliang Du, Baochun Guo, Mingxian Liu, and Demin Jia. Preparation and characterization of polypropylene grafted halloysite and their compatibility effect to polypropylene/halloysite composite. Polymer Journal, 2006; 38:1198 – 1204).
The above-mentioned importance that studies confirm that the finishing of halloysite, but the finishing that how all not to relate to by halloysite reaches halloysite to the multifunctional modification effect of polymkeric substance, comprises the improvement of giving flame retardance of polymer, toughness reinforcing, good multinomial performances such as dielectric properties.Therefore, need to seek novel modifier halloysite is carried out finishing.Hyperbranched polyorganosiloxane is a kind of highly branched thing of three-dimensional ball-like structure, have the advantages such as viscosity is low, toughness is good, Heat stability is good, can be used as novel finishing thing, have potential using value aspect the finishing of halloysite, but the bibliographical information of not being correlated with so far.Chinese invention patent (CN102199294A) discloses a kind of hyperbranched polyorganosiloxane and preparation method thereof, the preparation method of this hyperbranched polyorganosiloxane prepares first the hyperbranched polymer that contains epoxy group(ing), then the phospho hetero phenanthrene structure is interspersed around hyperbranched polymer, therefore, the phosphorus content of resulting hyperbranched polyorganosiloxane is lower, is unfavorable for obtaining under low levels good flame retarding efficiency.
In sum, providing a kind of halloysite of novel surface modification, is to improve the dispersiveness of halloysite in polymeric matrix, and gives one of its effective way with the multiple modified effect such as fire-retardant, toughness reinforcing, and tool is of great significance.
Summary of the invention
The object of the invention is to overcome the deficiency that prior art exists, a kind of good dispersity is provided, and can produce to polymkeric substance the halloysite and preparation method thereof of the finishing of multifunctional modification effect.
For realizing the object of the invention, the technical scheme that adopts provides a kind of halloysite of finishing, and its modifier is hyperbranched polyorganosiloxane, and modifier is connected with chemical bond with the halloysite surface; The structure of described hyperbranched polyorganosiloxane is:
In the described hyperbranched polyorganosiloxane, the content of phosphorus is greater than 14.5wt%.
A kind of preparation method of halloysite of finishing comprises the steps:
(1) under protection of inert gas, 0.9:1～1.1:1 mixes 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide with the silane coupling agent that contains vinyl in molar ratio, obtains mixture A;
(2) 1:50～1:100 in mass ratio mixes initiator with mixture A, obtain mixture B;
(3) 1g:3ml～1g:4ml in proportion mixes mixture B with solvent S1, be that constant temperature stirred 2～20 hours under 40～120 ℃ the condition in temperature, and after reaction finished, solvent was removed in underpressure distillation, obtains the phospho hetero phenanthrene silane coupling agent; Described solvent S1 is C
1～C
3Alcohol, acetone, acetonitrile, methylene dichloride, trichloromethane, benzene, toluene, tetrahydrofuran (THF), dimethyl formamide in a kind of, or its arbitrary combination.
(4) under argon gas or nitrogen protection, 1:1～1:3 in mass ratio, the phospho hetero phenanthrene silane coupling agent that step (3) is obtained mixes with the silane coupling agent that contains epoxy group(ing), obtains mixture C; 1:50～1:100 mixes catalyzer Ca with mixture C in mass ratio, obtains mixture D, and described catalyzer Ca is a kind of in hydrochloric acid, sulfuric acid or the nitric acid; 1g:3ml～1g:4ml mixes mixture D with solvent S2 in proportion, and described solvent S2 is deionized water, C
1～C
3Alcohol, acetone, acetonitrile, trichloromethane or its combination; Be that constant temperature stirred 0.5～8 hour under 40～100 ℃ the condition in temperature; After reaction finished, solvent was removed in underpressure distillation, obtained containing the hyperbranched polyorganosiloxane polysiloxane of phospho hetero phenanthrene and epoxy group(ing);
(5) incite somebody to action in mass ratio 1:2～1:5, halloysite is joined mix in the hydrochloric acid soln that concentration is 1～5mol/L, under 60～80 ℃ temperature condition, refluxed 2～5 hours; With the deionized water dilution, wash to neutrality after the cooling, suction filtration is dried, and obtains the halloysite of surface active;
(6) under argon gas or nitrogen protection, 1:1～1:4 in mass ratio, the halloysite that step (5) is obtained with contain amino silane coupling agent and mix, obtain mixture E; 1g:3ml～1g:5ml mixes mixture E with solvent S3 in proportion, and described solvent S3 is deionized water, C
1～C
3Alcohol, acetone, acetonitrile or its combination; Be that constant temperature stirred 0.5～8 hour under 40～120 ℃ the condition in temperature; After reaction finished, filtration, washing, drying obtained the amino halloysite of processing;
(7) 1:5～1:20 in mass ratio, the halloysite that the amino that step (6) is obtained is processed mixes with the hyperbranched polyorganosiloxane that contains phospho hetero phenanthrene and epoxy group(ing) that step (4) obtains, and obtains mixture F; 1g:1ml～1g:4ml mixes mixture F with solvent S4 in proportion, and described solvent S4 is deionized water, C
1～C
3Alcohol, acetone, acetonitrile or its combination; Be that constant temperature stirred 1～8 hour under 30～100 ℃ the condition in temperature, after reaction finished, filtration, washing, drying obtained containing the halloysite that the hyperbranched polyorganosiloxane of phospho hetero phenanthrene and epoxy group(ing) is modified.
In technical solution of the present invention:
The described silane coupling agent that contains vinyl is a kind of in vinyl-dimethyl TMOS, vinyltriethoxysilane or the γ-methacryloxypropyl trimethoxy silane.
The described silane coupling agent that contains epoxy group(ing) is shrink a kind of in oily ether oxygen base propyl trimethoxy silicane, 2-(3,4-epoxy cyclohexane base) ethyl trimethoxy silane or 2-(3, the 4-epoxy cyclohexane alkyl) ethyl triethoxysilane of 3-.It is described that to contain amino silane coupling agent be a kind of in 3-aminopropyl triethoxysilane, (2-aminoethyl)-3-aminopropyl triethoxysilane or the 3-aminoethyl aminopropyl trimethoxysilane.
Described initiator is a kind of or its combination in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo dicyclohexyl formonitrile HCN, the azo-bis-iso-dimethyl; Or a kind of or its combination in the special butyl ester of dibenzoyl peroxide, dicumyl peroxide, dilauroyl peroxide, benzoyl peroxide formic acid.
Compared with prior art, the obtained beneficial effect of the present invention is:
1, the application prepares first the tri-alkoxy silicon that contains the phospho hetero phenanthrene structure, and then self hydrolytic condensation obtains hyperbranched polyorganosiloxane, and therefore, the phosphorus content of products therefrom is high, be used for the surface modified of halloysite after, be conducive to be issued to high flame resistance at low levels.
2, compare with common halloysite, the halloysite of surface modification provided by the invention possesses multi-functional characteristic, be integrated 9, the 10-dihydro-9-oxy is assorted-good reactivity and the adhesivity of highly effective flame-retardant that the 10-phospho hetero phenanthrene-10-oxide compound (DOPO) has, phosphorus silicon cooperative flame retardant, epoxide group, and the characteristics such as the outstanding thermotolerance of hyperbranched polyorganosiloxane, toughness; These performance characteristics are so that modified halloysite disclosed in this invention has broad application prospects at the aspects such as synthetic and preparation of the multifunction of polymkeric substance and high performance, novel high polymer material.
The preparation method of the finishing halloysite that 3, provides has that suitability is wide, the simple characteristics of operating procedure.
Description of drawings
Fig. 1 is the embodiment of the invention DOPO, the phospho hetero phenanthrene silane coupling agent that provide and contains phospho hetero phenanthrene and the FT-IR spectrogram of the hyperbranched polyorganosiloxane of epoxy group(ing);
Fig. 2 is the hyperbranched polyorganosiloxane that contains phospho hetero phenanthrene and epoxy group(ing) that DOPO and the embodiment of the invention provide
31The P-NMR spectrogram;
Fig. 3 is the polysiloxane that contains phospho hetero phenanthrene and epoxy group(ing) that the DOPO embodiment of the invention provides
1The H-NMR spectrogram;
Fig. 4 is the hyperbranched polyorganosiloxane that contains phospho hetero phenanthrene and epoxy group(ing) that the embodiment of the invention provides
29The Si-NMR spectrogram;
Fig. 5 is a kind of halloysite and halloysite of activation, the infrared spectrogram of the amino halloysite of processing through the hyperbranched polyorganosiloxane finishing that the embodiment of the invention provides;
Fig. 6 is that the specific inductivity of the cyanate cured article of halloysite modification of the finishing that provides of the embodiment of the invention and ethylene rhodanate resin curing thing is with the curve comparison figure of frequency change;
Fig. 7 is that the dielectric loss of the cyanate cured article of halloysite modification of the finishing that provides of inventive embodiments and ethylene rhodanate resin curing thing is with the curve comparison figure of frequency change.
Embodiment
Below in conjunction with drawings and Examples technical solution of the present invention is further elaborated.
(1) under nitrogen protection; with 1.9g 9; the 10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10-oxide compound (DOPO), 1.9g vinyltriethoxysilane, 0.08g 2,2'-Azobis(2,4-dimethylvaleronitrile) and 10ml dimethyl formamide add flask; 120 ℃ of lower reactions 2 hours; after reaction finishes; solvent is removed in underpressure distillation, obtains the phospho hetero phenanthrene silane coupling agent.
(2) under nitrogen protection; 3g phospho hetero phenanthrene silane coupling agent, 3g glycidyl ether oxygen base propyl trimethoxy silicane, 0.1g 36wt% hydrochloric acid, 20ml deionized water and 7ml methyl alcohol are added flask; 55 ℃ of lower reactions 5 hours; after reaction finishes; solvent is removed in underpressure distillation; obtain containing the hyperbranched polyorganosiloxane of phospho hetero phenanthrene and epoxy group(ing), its molecular weight is 3020 g/mols, and phosphorus content is 14.7wt%.
(3) 20g 5mol/L hydrochloric acid soln, 10g halloysite are added flask, 60 ℃ of lower reactions 4 hours, with the deionized water dilution, wash to neutrality suction filtration, oven dry, the halloysite after obtaining activating after the cooling.Under nitrogen protection, 10g activates halloysite, and 20g aminopropyl triethoxysilane coupling agent mixes with 50ml ethanol, is under 60 ℃ the condition in temperature, and constant temperature stirred 6 hours; After reaction finished, filtration, washing, drying obtained the amino halloysite of processing.
(4) hyperbranched polyorganosiloxane, 16ml methyl alcohol and 6ml acetonitrile that halloysite, the 30g that 2g amino is processed contains phospho hetero phenanthrene and epoxy group(ing) add flask, 40 ℃ of lower reactions 8 hours, after reaction finished, filtration, washing, drying obtained containing the halloysite that the polysiloxane of phospho hetero phenanthrene and epoxy group(ing) is modified.
Referring to accompanying drawing 1, for DOPO, phospho hetero phenanthrene silane coupling agent and contain phospho hetero phenanthrene and the FT-IR spectrogram of the hyperbranched polyorganosiloxane of epoxy group(ing).As seen from the figure, DOPO is at 2438cm
-1The P-H stretching vibration at place does not occur in the infrared spectrum of phospho hetero phenanthrene silane coupling agent, show DOPO by with being incorporated on the organoalkoxysilane of the reaction success of vinyl.Contain in the FT-IR spectrogram of hyperbranched polyorganosiloxane of phospho hetero phenanthrene and epoxy group(ing) 908.43cm
-1Be the charateristic avsorption band of epoxide group, 738.71cm
-1, 1242.32cm
-1And 1482.13cm
-1Represent respectively P-O-Ph, the charateristic avsorption band of P=O and P-Ph has shown the existence of DOPO structure; 1080cm
-1~ 1145cm
-1The vibration broad peak at place shows, contains the Si-O-Si structure in the synthetic product.
The hyperbranched polyorganosiloxane that contains phospho hetero phenanthrene and epoxy group(ing) that provides for DOPO and present embodiment referring to accompanying drawing 2
31The P-NMR spectrogram.By two figure contrast as can be known, δ 14.51ppm is the peak of phosphorus atom among the DOPO; δ 10.54ppm, δ 25.50ppm and δ 27.42ppm are the peak of phosphorus atom in the DOPO epoxy group(ing) hyperbranched polyorganosiloxane, show the phospho hetero phenanthrene silane coupling agent with the silane coupling agent generation hydrolysis-condensation reaction that contains epoxy group(ing).
The hyperbranched polyorganosiloxane that contains phospho hetero phenanthrene and epoxy group(ing) that Fig. 3 provides for DOPO and present embodiment
1The H-NMR spectrogram.Contrasting two figure can find, the chemical shift of DOPO H on the δ 8.80ppm P-H of place, at DOPO epoxy group(ing) hyperbranched polyorganosiloxane
1Completely dissolve in the H-NMR spectrogram, the characteristic peak of δ 7ppm ~ δ 8ppm place benzene ring hydrogen, the two proves the existence of DOPO structure in the synthetic product jointly; δ 2.58ppm and δ 3.15ppm place are on the epoxide group-O-CH
2In the chemical shift and δ 2.78ppm place epoxide group of-upper H-and the chemical shift of the upper H of CH-O-, show that epoxide group also is present in the synthetic product.
Hyperbranched polyorganosiloxanes that contain phospho hetero phenanthrene and epoxy group(ing) that present embodiment provides referring to accompanying drawing 4
29The Si-NMR spectrogram.Therefrom can find out, three chemical shifts have appearred in δ-66.64 ppm, δ-58.15 ppm and δ-49.38 ppm place, they represent respectively the branching chain link of siloxanes, linear chain link and end-blocking chain link, proved that polymkeric substance is hyperbranched polyorganosiloxane, the degree of branching that can calculate the hyperbranched polyorganosiloxane that contains phospho hetero phenanthrene and epoxy group(ing) is 0.58.
Comprehensive accompanying drawing 1～4 as can be known, the product that synthesizes by present embodiment step (1)～(2) is the hyperbranched polyorganosiloxane that contains phospho hetero phenanthrene and epoxy group(ing).
Referring to accompanying drawing 5, the infrared spectrogram of the halloysite of the halloysite of a kind of activation that provides for present embodiment, the amino halloysite of processing and finishing.Relatively the halloysite of activation and the spectrogram of surface-treated halloysite can find that the surface-treated halloysite has occurred-CH at 2931cm-1 and 1597cm-1 place
2-and-the eigen vibration peak of N-H-; And the infrared spectrogram of the halloysite of the amino halloysite of processing of contrast and finishing as can be known, the charateristic avsorption band of P-O-Ph and Si-O-Si occurred representing.These phenomenons show that the hyperbranched polyorganosiloxane that contains phospho hetero phenanthrene and epoxy group(ing) has successfully been modified in the halloysite surface.
(1) under argon shield; with 2.4g9; the 10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10-oxide compound, 1.9g vinyltriethoxysilane, 0.08g Diisopropyl azodicarboxylate and 10ml trichloromethane add flask; 60 ℃ of lower reactions 20 hours; after reaction finishes; solvent is removed in underpressure distillation, obtains the phospho hetero phenanthrene silane coupling agent.
(2) under the protection of argon gas gas; 3g phospho hetero phenanthrene silane coupling agent, 9g glycidyl ether oxygen base propyl trimethoxy silicane, 0.1g 36wt% hydrochloric acid, 20ml deionized water and 28ml methyl alcohol are added flask; 40 ℃ of lower reactions 8 hours; after reaction finishes; solvent is removed in underpressure distillation; obtain containing the hyperbranched polyorganosiloxane of phospho hetero phenanthrene and epoxy group(ing), its molecular weight is 2820 g/mols, and phosphorus content is 14.5wt%.
(3) 50g 1mol/L hydrochloric acid soln, 10g halloysite are added flask, 80 ℃ of lower reactions 3 hours, with the deionized water dilution, wash to neutrality suction filtration, oven dry, the halloysite after obtaining activating after the cooling.Under nitrogen protection, 10g activates halloysite, and 10g aminopropyl triethoxysilane coupling agent mixes with 60ml ethanol, is under 60 ℃ the condition in temperature, and constant temperature stirred 6 hours; After reaction finished, filtration, washing, drying obtained the amino halloysite of processing.
(4) hyperbranched polyorganosiloxane, 32ml methyl alcohol and 10ml ethanol that halloysite, the 40g that 2g amino is processed contains phospho hetero phenanthrene and epoxy group(ing) add flask, 60 ℃ of lower reactions 5 hours, after reaction finished, filtration, washing, drying obtained containing the halloysite that the hyperbranched polyorganosiloxane of phospho hetero phenanthrene and epoxy group(ing) is modified.The degree of branching that calculates the hyperbranched polyorganosiloxane that contains phospho hetero phenanthrene and epoxy group(ing) is 0.42
Embodiment 3
(1) under nitrogen protection; with 2.4g 9; the 10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10-oxide compound, 1.9g vinyltriethoxysilane, 0.02g Diisopropyl azodicarboxylate, 0.02g 2,2'-Azobis(2,4-dimethylvaleronitrile) and 10ml methylene dichloride add flask; 60 ℃ of lower reactions 10 hours; after reaction finishes; solvent is removed in underpressure distillation, obtains the phospho hetero phenanthrene silane coupling agent.
(2) under the protection of nitrogen gas; 3g phospho hetero phenanthrene silane coupling agent, 9g glycidyl ether oxygen base propyl trimethoxy silicane, 0.1g 36wt% hydrochloric acid, 20ml deionized water, 14ml ethanol and 14ml propyl alcohol are added flask; 60 ℃ of lower reactions 5 hours; after reaction finishes; solvent is removed in underpressure distillation; obtain containing the hyperbranched polyorganosiloxane of phospho hetero phenanthrene and epoxy group(ing), its molecular weight is 2880 g/mols, and phosphorus content is 14.5wt%
(3) 50g 3mol/L hydrochloric acid soln, 10g halloysite are added flask, 80 ℃ of lower reactions 2 hours, with the deionized water dilution, wash to neutrality suction filtration, oven dry, the halloysite after obtaining activating after the cooling.Under nitrogen protection, 10g activates halloysite, and 15g aminopropyl triethoxysilane coupling agent mixes with the 50ml trichloromethane, is under 60 ℃ the condition in temperature, and constant temperature stirred 6 hours; After reaction finished, filtration, washing, drying obtained the amino halloysite of processing.
(4) hyperbranched polyorganosiloxane, 12ml acetonitrile that halloysite, the 10g that 2g amino is processed contains phospho hetero phenanthrene and epoxy group(ing) add flask, 90 ℃ of lower reactions 2 hours, after reaction finished, filtration, washing, drying obtained the halloysite that DOPO epoxy group(ing) hyperbranched polyorganosiloxane is modified.The degree of branching that calculates the hyperbranched polyorganosiloxane that contains phospho hetero phenanthrene and epoxy group(ing) is 0.46.
(5) take by weighing halloysite and the 100g bisphenol A cyanate ester of the finishing that the 5g above-mentioned steps obtains, they are mixed 40min under 120 ℃ temperature condition, namely obtain a kind of modified cyanic acid ester resin.Pour the modified cyanic acid ester resin that obtains into preheating and pour in the mould, in 150 ℃ of vacuum defoamations 1 hour, more respectively according to 180
0C/2h+200
0C/2h+220
0C/2h and 240
0The technique of C/4h is cured and aftertreatment, and the demoulding behind the naturally cooling namely obtains the modified cyanic acid ester resin that solidifies.
Preparation comparative example: the 100g bisphenol A cyanate ester is stirred 40min under 120 ℃ of conditions, pour the liquid cyanate that obtains into preheating and pour in the mould, in 150 ℃ of vacuum defoamations 1 hour, more respectively according to 180
0C/2h+200
0C/2h+220
0C/2h and 240
0The technique of C/4h is cured and aftertreatment, and the demoulding behind the naturally cooling namely obtains solidifying cyanate ester resin.
Referring to subordinate list 1, it is the typical performance comparison for the curing cyanate ester resin of the modified resin cured article of embodiment preparation and comparative example preparation.As can be seen from Table 1, shock strength, flexural strength and the limiting oxygen index(LOI) of the halloysite modified cyanic acid ester resin of finishing all are higher than pure cyanate ester resin, illustrate that the halloysite of the finishing of the present invention's preparation is all having unusual effect aspect raising toughness, intensity and the flame retardant resistance.
Table 1
The specific inductivity of the cyanate cured article of the halloysite modification of the finishing of solidifying cyanate ester resin and the embodiment of the invention and the providing curve comparison figure with frequency change is provided Fig. 6.By can finding out among Fig. 6, the forward and backward resin of modification is the same, all have outstanding dielectric stability, and the specific inductivity of resin is lower before the permittivity ratio modification of modified resin.
The dielectric loss of the cyanate cured article of the halloysite modification of the finishing of solidifying cyanate ester resin and the embodiment of the invention and the providing curve comparison figure with frequency change is provided Fig. 7.As can be seen from Figure 7, at low frequency (＜10
4Hz) and high frequency (〉 10
4Hz) in the scope, the resin of the resin after the modification before than modification has lower dielectric loss.
To sum up analyze, shock strength, flexural strength and the limiting oxygen index(LOI) of the halloysite modified cyanic acid ester resin of finishing all are higher than pure cyanate ester resin, and the former specific inductivity and dielectric loss all are better than the latter, show that the halloysite of the finishing that the present invention prepares can significantly improve the toughness of cyanate ester resin, intensity, flame retardant properties and dielectric properties, i.e. the halloysite of the finishing of the present invention preparation has multiple modified effect.
(1) under nitrogen protection; with 1.9g 9; the 10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10-oxide compound, 1.9g vinyltriethoxysilane, 0.08g Diisopropyl azodicarboxylate, 5ml propyl alcohol and 5ml methyl alcohol adds flask; 60 ℃ of lower reactions 6 hours; after reaction finishes; solvent is removed in underpressure distillation, obtains the phospho hetero phenanthrene silane coupling agent.
(2) under nitrogen protection; 3g phospho hetero phenanthrene silane coupling agent, 3g glycidyl ether oxygen base propyl trimethoxy silicane, 0.1g 36wt% hydrochloric acid, 20ml deionized water and 7ml propyl alcohol are added flask; 60 ℃ of lower reactions 5 hours; after reaction finishes; solvent is removed in underpressure distillation; obtain containing the hyperbranched polyorganosiloxane of phospho hetero phenanthrene and epoxy group(ing), its molecular weight is 2910 g/mols, and phosphorus content is 14.6wt%.
(3) 20g 4mol/L hydrochloric acid soln, 10g halloysite are added flask, 60 ℃ of lower reactions 5 hours, with the deionized water dilution, wash to neutrality suction filtration, oven dry, the halloysite after obtaining activating after the cooling.Under nitrogen protection, 10g activates halloysite, and 30g aminopropyl triethoxysilane coupling agent, 90ml n-propyl alcohol and 10ml acetonitrile mix, and is that constant temperature stirred 0.5 hour under 120 ℃ the condition in temperature; After reaction finished, filtration, washing, drying obtained the amino halloysite of processing.
(4) hyperbranched polyorganosiloxane, 20ml trichloromethane and 10ml acetonitrile that halloysite, the 20g that 2g amino is processed contains phospho hetero phenanthrene and epoxy group(ing) add flask, 100 ℃ of lower reactions 1 hour, after reaction finished, filtration, washing, drying obtained containing the halloysite that the hyperbranched polyorganosiloxane of phospho hetero phenanthrene and epoxy group(ing) is modified.The degree of branching that calculates the hyperbranched polyorganosiloxane that contains phospho hetero phenanthrene and epoxy group(ing) is 0.51.
Embodiment 5
(1) under argon shield; with 2.4g 9; the 10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10-oxide compound, 1.9g vinyltriethoxysilane, 0.02g dibenzoyl peroxide, 0.02 dilauroyl peroxide and 10ml toluene adds flask; 60 ℃ of lower reactions 8 hours; after reaction finishes; solvent is removed in underpressure distillation, obtains the phospho hetero phenanthrene silane coupling agent.
(2) under the protection of argon gas gas; 3g phospho hetero phenanthrene silane coupling agent, 6g glycidyl ether oxygen base propyl trimethoxy silicane, 0.1g 36wt% hydrochloric acid, 15ml deionized water and 20ml methyl alcohol are added flask; 55 ℃ of lower reactions 6 hours; after reaction finishes; solvent is removed in underpressure distillation; obtain containing the hyperbranched polyorganosiloxane of phospho hetero phenanthrene and epoxy group(ing), its molecular weight is 2920 g/mols, and phosphorus content is 14.6wt%.
(3) 30g 2mol/L hydrochloric acid soln, 10g halloysite are added flask, 60 ℃ of lower reactions 4 hours, with the deionized water dilution, wash to neutrality suction filtration, oven dry, the halloysite after obtaining activating after the cooling.Under nitrogen protection, 10g activates halloysite, and 400g aminopropyl triethoxysilane coupling agent mixes with 100ml ethanol, is under 60 ℃ the condition in temperature, and constant temperature stirred 8 hours; After reaction finished, filtration, washing, drying obtained the amino halloysite of processing.
(4) hyperbranched polyorganosiloxane, 20ml methyl alcohol and 10ml acetonitrile that halloysite, the 10g that 2g amino is processed contains phospho hetero phenanthrene and epoxy group(ing) add flask, 40 ℃ of lower reactions 8 hours, after reaction finished, filtration, washing, drying obtained containing the halloysite that the hyperbranched polyorganosiloxane of phospho hetero phenanthrene and epoxy group(ing) is modified.
The degree of branching that calculates the hyperbranched polyorganosiloxane that contains phospho hetero phenanthrene and epoxy group(ing) is 0.52.
(1) under nitrogen protection; with 1.9g 9; the 10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10-oxide compound, 1.9g vinyltriethoxysilane, 0.08g Diisopropyl azodicarboxylate and 10ml propyl alcohol add flask; 60 ℃ of lower reactions 6 hours; after reaction finishes; solvent is removed in underpressure distillation, obtains the phospho hetero phenanthrene silane coupling agent.
(2) under nitrogen protection; 3g phospho hetero phenanthrene silane coupling agent, 6g glycidyl ether oxygen base propyl trimethoxy silicane, 0.1g 36wt% hydrochloric acid, 15ml deionized water and 10ml methyl alcohol are added flask; 60 ℃ of lower reactions 4 hours; after reaction finishes; solvent is removed in underpressure distillation; obtain containing the hyperbranched polyorganosiloxane of phospho hetero phenanthrene and epoxy group(ing), its molecular weight is 3000 g/mols, and phosphorus content is 15.1wt%.
(3) 20g 3mol/L hydrochloric acid soln, 10g halloysite are added flask, 60 ℃ of lower reactions 5 hours, with the deionized water dilution, wash to neutrality suction filtration, oven dry, the halloysite after obtaining activating after the cooling.Under nitrogen protection, 10g activates halloysite, and 20g aminopropyl triethoxysilane coupling agent mixes with the 60ml n-propyl alcohol, is under 100 ℃ the condition in temperature, and constant temperature stirred 6 hours; After reaction finished, filtration, washing, drying obtained the amino halloysite of processing.
(4) hyperbranched polyorganosiloxane, 40ml acetone that halloysite, the 12g that 2g amino is processed contains phospho hetero phenanthrene and epoxy group(ing) add flask, 50 ℃ of lower reactions 4 hours, after reaction finished, filtration, washing, drying obtained containing the halloysite that the hyperbranched polyorganosiloxane of phospho hetero phenanthrene and epoxy group(ing) is modified.The degree of branching that calculates the hyperbranched polyorganosiloxane that contains phospho hetero phenanthrene and epoxy group(ing) is 0.62.
Embodiment 7
(1) under argon shield; with 2.1g 9; the 10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10-oxide compound, 1.9g vinyltriethoxysilane, 0.07g Diisopropyl azodicarboxylate and 10ml toluene adds flask; 60 ℃ of lower reactions 6 hours; after reaction finishes; solvent is removed in underpressure distillation, obtains the phospho hetero phenanthrene silane coupling agent.
(2) under the protection of argon gas gas; 3g phospho hetero phenanthrene silane coupling agent, 6g glycidyl ether oxygen base propyl trimethoxy silicane, 0.1g 36wt% hydrochloric acid, 15ml deionized water and 10ml n-propyl alcohol are added flask; 60 ℃ of lower reactions 4 hours; after reaction finishes; solvent is removed in underpressure distillation, obtains containing the hyperbranched polyorganosiloxane of phospho hetero phenanthrene and epoxy group(ing).
(3) 20g 2mol/L hydrochloric acid soln, 10g halloysite are added flask, 60 ℃ of lower reactions 5 hours, with the deionized water dilution, wash to neutrality suction filtration, oven dry, the halloysite after obtaining activating after the cooling.Under nitrogen protection, 10g activates halloysite, and 30g aminopropyl triethoxysilane coupling agent mixes with 200ml ethanol, is under 60 ℃ the condition in temperature, and constant temperature stirred 6 hours; After reaction finished, filtration, washing, drying obtained the amino halloysite of processing.
(4) hyperbranched polyorganosiloxane, 40ml acetonitrile that halloysite, the 16g that 2g amino is processed contains phospho hetero phenanthrene and epoxy group(ing) add flask, 50 ℃ of lower reactions 6 hours, after reaction finished, filtration, washing, drying obtained containing the halloysite that the hyperbranched polyorganosiloxane of phospho hetero phenanthrene and epoxy group(ing) is modified.
(1) under nitrogen protection; with 1.9g 9; the 10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10-oxide compound, 1.9g vinyltriethoxysilane, 0.08g Diisopropyl azodicarboxylate and 10ml n-propyl alcohol add flask; 100 ℃ of lower reactions 10 hours; after reaction finishes; solvent is removed in underpressure distillation, obtains the phospho hetero phenanthrene silane coupling agent.
(2) under nitrogen protection; 3g phospho hetero phenanthrene silane coupling agent, 3g glycidyl ether oxygen base propyl trimethoxy silicane, 0.1g 36wt% hydrochloric acid, 10ml deionized water and 10ml n-propyl alcohol are added flask; 80 ℃ of lower reactions 3 hours; after reaction finishes; solvent is removed in underpressure distillation, obtains containing the hyperbranched polyorganosiloxane of phospho hetero phenanthrene and epoxy group(ing).
(3) 20g 5mol/L hydrochloric acid soln, 10g halloysite are added flask, 60 ℃ of lower reactions 4 hours, with the deionized water dilution, wash to neutrality suction filtration, oven dry, the halloysite after obtaining activating after the cooling.Under nitrogen protection, 10g activates halloysite, and 15g aminopropyl triethoxysilane coupling agent and 90ml methanol mixed are that constant temperature stirred 8 hours under 40 ℃ the condition in temperature; After reaction finished, filtration, washing, drying obtained the amino halloysite of processing.
(4) hyperbranched polyorganosiloxane, 50ml acetone that halloysite, the 25g that 2g amino is processed contains phospho hetero phenanthrene and epoxy group(ing) add flask, 30 ℃ of lower reactions 8 hours, after reaction finished, filtration, washing, drying obtained containing the halloysite that the hyperbranched polyorganosiloxane of phospho hetero phenanthrene and epoxy group(ing) is modified.
Embodiment 9
(1) under argon shield; with 2.4g 9; the 10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10-oxide compound, 1.9g vinyltriethoxysilane, 0.08g dibenzoyl peroxide and 15ml methyl alcohol adds flask; 60 ℃ of lower reactions 8 hours; after reaction finishes; solvent is removed in underpressure distillation, obtains the phospho hetero phenanthrene silane coupling agent.
(2) under the protection of argon gas gas; 3g phospho hetero phenanthrene silane coupling agent, 9 g glycidyl ether oxygen base propyl trimethoxy silicanes, 0.1g 36wt% hydrochloric acid, 20ml deionized water and 10ml methyl alcohol are added flask; 60 ℃ of lower reactions 6 hours; after reaction finishes; solvent is removed in underpressure distillation, obtains containing the hyperbranched polyorganosiloxane of phospho hetero phenanthrene and epoxy group(ing).
(3) 50g 1mol/L hydrochloric acid soln, 10g halloysite are added flask, 60 ℃ of lower reactions 4 hours, with the deionized water dilution, wash to neutrality suction filtration, oven dry, the halloysite after obtaining activating after the cooling.Under nitrogen protection, 10g activates halloysite, and 25g aminopropyl triethoxysilane coupling agent mixes with 80ml ethanol, is under 60 ℃ the condition in temperature, and constant temperature stirred 4 hours; After reaction finished, filtration, washing, drying obtained the amino halloysite of processing.
(4) hyperbranched polyorganosiloxane, 50ml methyl alcohol that halloysite, the 35g that 2g amino is processed contains phospho hetero phenanthrene and epoxy group(ing) add flask, 50 ℃ of lower reactions 8 hours, after reaction finished, filtration, washing, drying obtained containing the halloysite that the hyperbranched polyorganosiloxane of phospho hetero phenanthrene and epoxy group(ing) is modified.
(1) under nitrogen protection; with 2g 9; the 10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10-oxide compound, 1.9g vinyltriethoxysilane, 0.06g Diisopropyl azodicarboxylate and 20ml methylene dichloride add flask; 60 ℃ of lower reactions 4 hours; after reaction finishes; solvent is removed in underpressure distillation, obtains the phospho hetero phenanthrene silane coupling agent.
(2) under nitrogen protection; 3g phospho hetero phenanthrene silane coupling agent, 6g glycidyl ether oxygen base propyl trimethoxy silicane, 0.1g 36wt% hydrochloric acid, 10ml deionized water and 10ml methyl alcohol are added flask; 60 ℃ of lower reactions 6 hours; after reaction finishes; solvent is removed in underpressure distillation, obtains containing the hyperbranched polyorganosiloxane of phospho hetero phenanthrene and epoxy group(ing).
(3) 20g 1mol/L hydrochloric acid soln, 10g halloysite are added flask, 80 ℃ of lower reactions 5 hours, with the deionized water dilution, wash to neutrality suction filtration, oven dry, the halloysite after obtaining activating after the cooling.Under nitrogen protection, 10g activates halloysite, and 20g aminopropyl triethoxysilane coupling agent mixes with 50ml acetone, is under 40 ℃ the condition in temperature, and constant temperature stirred 8 hours; After reaction finished, filtration, washing, drying obtained the amino halloysite of processing.
(4) the amino halloysite of processing of 2g, 40g DOPO epoxy group(ing) hyperbranched polyorganosiloxane, 100ml methyl alcohol are added flask, 60 ℃ of lower reactions 5 hours, after reaction finished, filtration, washing, drying obtained containing the halloysite that the hyperbranched polyorganosiloxane of phospho hetero phenanthrene and epoxy group(ing) is modified.
Claims (6)
1. the halloysite of a finishing, it is characterized in that: the modifier on halloysite surface is hyperbranched polyorganosiloxane, and they connect with chemical bond; The structure of described hyperbranched polyorganosiloxane is:
In the described hyperbranched polyorganosiloxane, the content of phosphorus is greater than 14.5wt%.
2. the preparation method of the halloysite of a kind of finishing as claimed in claim 1 is characterized in that comprising the steps:
(1) under protection of inert gas, 0.9:1～1.1:1 mixes 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide with the silane coupling agent that contains vinyl in molar ratio, obtains mixture A;
(2) 1:50～1:100 in mass ratio mixes initiator with mixture A, obtain mixture B;
(3) 1g:3ml～1g:4ml in proportion mixes mixture B with solvent S1, be that constant temperature stirred 2～20 hours under 40～120 ℃ the condition in temperature, and after reaction finished, solvent was removed in underpressure distillation, obtains the phospho hetero phenanthrene silane coupling agent; Described solvent S1 is C
1～C
3Alcohol, acetone, acetonitrile, methylene dichloride, trichloromethane, benzene, toluene, tetrahydrofuran (THF), dimethyl formamide in a kind of, or its arbitrary combination;
(4) under argon gas or nitrogen protection, 1:1～1:3 in mass ratio, the phospho hetero phenanthrene silane coupling agent that step (3) is obtained mixes with the silane coupling agent that contains epoxy group(ing), obtains mixture C; 1:50～1:100 mixes catalyzer Ca with mixture C in mass ratio, obtains mixture D, and described catalyzer Ca is a kind of in hydrochloric acid, sulfuric acid or the nitric acid; 1g:3ml～1g:4ml mixes mixture D with solvent S2 in proportion, and described solvent S2 is deionized water, C
1～C
3Alcohol, acetone, acetonitrile, trichloromethane or its combination; Be that constant temperature stirred 0.5～8 hour under 40～100 ℃ the condition in temperature; After reaction finished, solvent was removed in underpressure distillation, obtained containing the hyperbranched polyorganosiloxane of phospho hetero phenanthrene and epoxy group(ing);
(5) incite somebody to action in mass ratio 1:2～1:5, halloysite is joined mix in the hydrochloric acid soln that concentration is 1～5mol/L, under 60～80 ℃ temperature condition, refluxed 2～5 hours; With the deionized water dilution, wash to neutrality after the cooling, suction filtration is dried, and obtains the halloysite of surface active;
(6) under argon gas or nitrogen protection, 1:1～1:4 in mass ratio, the halloysite that step (5) is obtained with contain amino silane coupling agent and mix, obtain mixture E; 1g:3ml～1g:5ml mixes mixture E with solvent S3 in proportion, and described solvent S3 is deionized water, C
1～C
3Alcohol, acetone, acetonitrile or its combination; Be that constant temperature stirred 0.5～8 hour under 40～120 ℃ the condition in temperature; After reaction finished, filtration, washing, drying obtained the amino halloysite of processing;
(7) 1:5～1:20 in mass ratio, the halloysite that the amino that step (6) is obtained is processed mixes with the hyperbranched polyorganosiloxane that contains phospho hetero phenanthrene and epoxy group(ing) that step (4) obtains, and obtains mixture F; 1g:1ml～1g:4ml mixes mixture F with solvent S4 in proportion, and described solvent S4 is deionized water, C
1～C
3Alcohol, acetone, acetonitrile or its combination; Be that constant temperature stirred 1～8 hour under 30～100 ℃ the condition in temperature, after reaction finished, filtration, washing, drying obtained containing the halloysite that the hyperbranched polyorganosiloxane of phospho hetero phenanthrene and epoxy group(ing) is modified.
3. the preparation method of the halloysite of a kind of finishing according to claim 2 is characterized in that: the described silane coupling agent that contains vinyl is a kind of in vinyl-dimethyl TMOS, vinyltriethoxysilane or the γ-methacryloxypropyl trimethoxy silane.
4. the preparation method of the halloysite of a kind of finishing according to claim 2, it is characterized in that: the described silane coupling agent that contains epoxy group(ing) is shrink oily ether oxygen base propyl trimethoxy silicane, 2-(3 of 3-, 4-epoxy cyclohexane base) a kind of in ethyl trimethoxy silane or 2-(3, the 4-epoxy cyclohexane alkyl) ethyl triethoxysilane.
5. the preparation method of the halloysite of a kind of finishing according to claim 2 is characterized in that: described to contain amino silane coupling agent be a kind of in 3-aminopropyl triethoxysilane, (2-aminoethyl)-3-aminopropyl triethoxysilane or the 3-aminoethyl aminopropyl trimethoxysilane.
6. the preparation method of the halloysite of a kind of finishing according to claim 2, it is characterized in that: described initiator is a kind of or its combination in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo dicyclohexyl formonitrile HCN, the azo-bis-iso-dimethyl; Or a kind of or its combination in the special butyl ester of dibenzoyl peroxide, dicumyl peroxide, dilauroyl peroxide, benzoyl peroxide formic acid.
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