Metal-containing amino polyhedral oligomeric silsesquioxane as well as preparation method and application thereof
阅读说明：本技术 一种含金属的氨基型多面体低聚倍半硅氧烷及其制备方法和应用 (Metal-containing amino polyhedral oligomeric silsesquioxane as well as preparation method and application thereof ) 是由 徐日炜 付琪轩 包涵 徐润华 余鼎声 于 2019-04-04 设计创作，主要内容包括：本发明公开了一种含金属的氨基型多面体低聚倍半硅氧烷及其制备方法和应用。其中,所述含金属的氨基型多面体低聚倍半硅氧烷是由含氨基的多面体低聚倍半硅氧烷和金属化合物为原料,反应得到；所述方法可以将含有氨基的多面体低聚倍半硅氧烷与金属化合物在溶剂中混合反应得到；本发明的含金属的氨基型多面体低聚倍半硅氧烷中POSS为T<Sub>8</Sub>型缩合结构且结构没有受到破坏,可以降低氰酸酯树脂和苯并噁嗪树脂等材料的固化温度,具有显著的固化催化效果。本发明提供的氰酸酯树脂组合物包含氰酸酯树脂和含金属的氨基型多面体低聚倍半硅氧烷,该氰酸酯树脂组合物具有较低的固化温度。(The invention discloses a metal-containing amino polyhedral oligomeric silsesquioxane as well as a preparation method and application thereof. Wherein the metal-containing amino polyhedral oligomeric silsesquioxane is obtained by reacting amino polyhedral oligomeric silsesquioxane and a metal compound serving as raw materials; the method can be obtained by mixing and reacting polyhedral oligomeric silsesquioxane containing amino with a metal compound in a solvent; in the metal-containing amino polyhedral oligomeric silsesquioxane, POSS is T 8 The structure of the condensation type structure is not damaged, the curing temperature of materials such as cyanate resin, benzoxazine resin and the like can be reduced, and the curing catalyst has a remarkable curing catalytic effect. The cyanate ester resin composition provided by the invention comprises a cyanate ester resin and a metal-containing amino polyhedral oligomerSilsesquioxane, the cyanate ester resin composition has a lower curing temperature.)
1. The metal-containing amino polyhedral oligomeric silsesquioxane is characterized by being obtained by reacting amino polyhedral oligomeric silsesquioxane and a metal compound serving as raw materials.
2. The metal-containing amino-type polyhedral oligomeric silsesquioxane of claim 1,
the polyhedral oligomeric silsesquioxane containing amino groups is polyhedral oligomeric silsesquioxane containing amino groups and/or imino groups, preferably polyhedral oligomeric silsesquioxane containing at least one amino group and one imino group,
the metal compound is a transition metal compound, preferably one or more selected from transition metal complexes and lanthanide metal compounds.
3. The metal-containing amino-type polyhedral oligomeric silsesquioxane of claim 1 or 2, wherein the amino-containing polyhedral oligomeric silsesquioxane has a structure represented by formula (I):
wherein, in the formula (I),
R1、R2、R3、R4、R5、R6、R7each independently selected from hydrogen, alkyl, phenyl, substituted phenyl or alicyclic, preferably from alkyl, phenyl or alicyclic,
r and R' are each independently selected from-CnH2n-，-CmH2m-2-，Preferably selected from one or more of-CnH2n-，-CmH2m-2-, where n and m are integers of 0 or more.
4. The metal-containing amino-type polyhedral oligomeric silsesquioxane of claim 3, wherein R is1、R2、R3、R4、R5、R6、R7Identical and selected from alkyl, phenyl or alicyclic groups,
r and R' are each independently-CnH2nN is an integer of 0 to 8,
preferably, R1、R2、R3、R4、R5、R6、R7Identical and are each alkyl, R and R' are each independently- (CH)2)nN is an integer of 1 to 6.
5. The metal-containing amino-type polyhedral oligomeric silsesquioxane of claim 4,
the alkyl group is C1～C7Is preferably C2～C5More preferably one or more selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl; and/or
The substituted phenyl is alkyl substituted phenyl or nitro substituted phenyl, preferably one or more of p-tolyl, o-tolyl and m-tolyl; and/or
The alicyclic group is C3～C8Is preferably C3～C6The alicyclic group of (2) is more preferably one or more selected from the group consisting of a cyclopropane group, a cyclobutane group, a cyclopentane group and a cyclohexane group.
6. The metal-containing amino-type polyhedral oligomeric silsesquioxane of claim 2,
the metal in the transition metal complex is selected from one or more of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper and zinc, preferably from one or more of copper, zinc, iron, cobalt and manganese,
preferably, the transition metal complex is an acetylacetone metal complex.
7. The metal-containing amino-type polyhedral oligomeric silsesquioxane of claim 1, wherein the molar ratio of the amino-containing polyhedral oligomeric silsesquioxane to the metal compound is 1: (1-2), preferably 1: (1-1.5).
8. The metal-containing amino-type polyhedral oligomeric silsesquioxane of claim 7, wherein the reaction is performed at 10 to 60 ℃ for 4 to 30 hours, preferably at 20 to 50 ℃ for 6 to 24 hours.
9. A method for preparing the metal-containing amino-type polyhedral oligomeric silsesquioxane of any one of claims 1 to 8, comprising the steps of:
step 1, dispersing polyhedral oligomeric silsesquioxane containing amino in a solvent;
step 2, adding a metal compound for reaction;
and 3, carrying out post-treatment to obtain the metal-containing amino polyhedral oligomeric silsesquioxane.
10. Cyanate ester resin composition, characterized in that said composition comprises the metal-containing amino polyhedral oligomeric silsesquioxane of any one of claims 1 to 8, preferably wherein said transition metal-containing amino polyhedral oligomeric silsesquioxane is present in an amount of 0.1 to 15%, preferably 0.1 to 10%, more preferably 0.1 to 3%, based on 100% by weight of the composition.
Technical Field
The invention relates to the field of polyhedral oligomeric silsesquioxane, in particular to metal-containing amino polyhedral oligomeric silsesquioxane as well as a preparation method and application thereof.
Background
Polyhedral oligomeric silsesquioxane (T)8) POSS for short is a novel organic/inorganic hybrid molecule with nano scale and general formula (RSiO)1.5) n, wherein R is an organic group such as hydrogen, alkyl, alkenyl, aryl, amino, etc., and R may be further functionalized by chemical reaction. POSS is introduced into a high molecular chain in a chemical bonding mode and the like, and has potential application value on the thermal stability, the thermal oxygen stability, the mechanical property, the flame retardance and the dielectric property of a polymer.
In recent years, POSS-supported metal compounds have attracted increasing attention as a new material. The polyhedral oligomeric silsesquioxane metal complexes (POMSS) are coordination compounds which take POSS containing functional groups such as hydroxyl, amino, carboxyl, silicon hydroxyl and the like as ligands and metal atoms as coordination centers. However, POMSS in the prior art is partially condensed incomplete cage type POSS, which destroys the structure of POSS and limits the application and development of POSS. Therefore, with the development of POSS coordination chemistry, new POMSS have been continuously synthesized. The ligand structure of this new POMSS has been gradually expanded to T8POSS system and by linking various functional groups to T8-POSS, which are then coordinated to the metal by means of these side groups.
In the prior art, POSS can be used as a curing catalyst, but the curing catalyst effect is general, and the curing temperature is generally only reduced by about 50 ℃.
Thus, there is a need for metal-containing polyhedral oligomeric silsesquioxanes that can significantly reduce the curing temperature.
Disclosure of Invention
In order to overcome the above problems, the present inventors have conducted intensive studies and, as a result, found that: the metal-containing amino-type polyhedral oligomeric silsesquioxane is obtained by reacting an amino-containing polyhedral oligomeric silsesquioxane with a metal compound, wherein the metal is suspended outside POSS having a saturated structure, so that the obtained metal-containing amino-type polyhedral oligomeric silsesquioxane has a complete cage-type structure and can significantly reduce the curing temperature of materials such as isocyanate, thereby completing the present invention.
The invention aims to provide a metal-containing amino polyhedral oligomeric silsesquioxane, which is obtained by reacting an amino polyhedral oligomeric silsesquioxane and a metal compound serving as raw materials.
Wherein the polyhedral oligomeric silsesquioxane containing amino is polyhedral oligomeric silsesquioxane containing amino and/or imino, preferably polyhedral oligomeric silsesquioxane containing at least one amino and one imino,
the metal compound is a transition metal compound, preferably one or more selected from transition metal complexes and lanthanide metal compounds.
Wherein the amino group-containing polyhedral oligomeric silsesquioxane has a structure shown as a formula (I):
wherein, in the formula (I),
R1、R2、R3、R4、R5、R6、R7each independently selected from hydrogen, alkyl, phenyl, substituted phenyl or alicyclic, preferably from alkyl, phenyl or alicyclic,
r and R' are each independently selected from-CnH2n-，-CmH2m-2-，Preferably selected from one or more of-CnH2n-，-CmH2m-2-, where n, m are greater than or equal toAn integer of 0.
Preferably, R1、R2、R3、R4、R5、R6、R7Identical and selected from alkyl, phenyl or alicyclic groups,
r and R' are each independently-CnH2nN is an integer of 0 to 8,
more preferably, R1、R2、R3、R4、R5、R6、R7Are both alkyl, R and R' are each independently- (CH)2)nN is an integer of 1 to 6.
Wherein the alkyl is C1～C7Is preferably C2～C5More preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl; and/or
The substituted phenyl is alkyl substituted phenyl or nitro substituted phenyl, preferably p-tolyl, o-tolyl or m-tolyl; and/or
The alicyclic group is C3～C8Is preferably C3～C6The alicyclic group of (3) is more preferably a cyclopropane group, a cyclobutane group, a cyclopentane group or a cyclohexane group.
Wherein, the metal in the transition metal complex is selected from one or more of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper and zinc, preferably from one or more of copper, zinc, iron, cobalt and manganese,
preferably, the transition metal complex is an acetylacetone metal complex.
Wherein the molar ratio of the amino group-containing polyhedral oligomeric silsesquioxane to the metal compound is 1: (1-2), preferably (1-1.5).
Wherein the reaction is carried out at 10-60 ℃ for 4-30 h, preferably at 20-50 ℃ for 6-24 h.
Another object of the present invention is to provide a method for preparing a metal-containing amino-type polyhedral oligomeric silsesquioxane according to the first aspect of the present invention, which comprises the steps of:
step 1, dispersing polyhedral oligomeric silsesquioxane containing amino in a solvent;
step 2, adding a metal compound for reaction;
and 3, carrying out post-treatment to obtain the metal-containing amino polyhedral oligomeric silsesquioxane.
In a third aspect of the present invention, there is provided a cyanate ester resin composition comprising the metal-containing amino polyhedral oligomeric silsesquioxane described in the first aspect of the present invention and/or prepared by the method described in the second aspect of the present invention, preferably, the content of the transition metal-containing amino polyhedral oligomeric silsesquioxane in the composition is 0.1 to 15%, preferably 0.1 to 10%, more preferably 0.1 to 3%, wherein the content is 100% by weight of the composition.
The invention has the following beneficial effects:
(1) the metal-containing amino polyhedral oligomeric silsesquioxane is an amino structure taking metal as a center, wherein the metal is positioned on the outer side of POSS, and the structure of POSS is not damaged and is T8A type condensation structure;
(2) the metal-containing amino polyhedral oligomeric silsesquioxane can reduce the curing temperature of materials such as cyanate resin, benzoxazine resin and the like, and has an obvious curing and catalyzing effect;
(3) the method for preparing the metal-containing amino polyhedral oligomeric silsesquioxane is simple, high in yield and easy to implement;
(4) the cyanate ester resin composition has a lower curing temperature, and compared with pure cyanate ester resin, the curing temperature of the cyanate ester resin composition is reduced by about 120-167 ℃, for example, after 2 weight percent of metal-containing amino polyhedral oligomeric silsesquioxane is added, the curing temperature of the cyanate ester resin composition is reduced by 121.5-168.8 ℃.
Drawings
FIG. 1 shows the infrared spectra of amino group-containing heptaisobutyl polyhedral oligomeric silsesquioxane, copper acetylacetonate complex and metallic copper-containing polyhedral oligomeric silsesquioxane obtained in example 1;
FIG. 2 shows UV spectrums of copper acetylacetonate complex and metallic copper-containing polyhedral oligomeric silsesquioxane obtained in example 1;
FIG. 3 shows the IR spectra of polyhedral oligomeric silsesquioxane containing aminoheptaisobutyl, iron (III) acetylacetonate complex and metallic iron-containing polyhedral oligomeric silsesquioxane obtained in example 4;
FIG. 4 is a UV spectrum of an iron acetylacetonate complex and the metallic iron-containing polyhedral oligomeric silsesquioxane obtained in example 4;
FIG. 5 shows the IR spectra of polyhedral oligomeric silsesquioxane containing aminoheptaisobutyl, cobalt (II) acetylacetonate complex and metallic cobalt (II) -containing polyhedral oligomeric silsesquioxane obtained in example 7;
FIG. 6 shows UV spectrums of copper acetylacetonate complexes and polyhedral oligomeric silsesquioxanes containing metal cobalt (II) obtained in example 7;
FIG. 7 shows DSC plots of pure cyanate ester resin and the cyanate ester resin composition obtained in example 13;
fig. 8 shows DSC plots of the pure cyanate ester resin and the cyanate ester resin composition obtained in example 14.
Detailed Description
The invention is explained in more detail below with reference to the drawings and preferred embodiments. The features and advantages of the present invention will become more apparent from the description.
The invention provides a metal-containing amino polyhedral oligomeric silsesquioxane, which is obtained by reacting an amino polyhedral oligomeric silsesquioxane and a metal compound serving as raw materials.
According to the present invention, the amino group-containing polyhedral oligomeric silsesquioxane is a polyhedral oligomeric silsesquioxane containing an amino group and/or an imino group, preferably a polyhedral oligomeric silsesquioxane containing at least one amino group and one imino group.
According to the present invention, the amino-containing POSS has the structure shown in formula (I):
wherein, in the formula (I),
R1、R2、R3、R4、R5、R6、R7each independently selected from hydrogen, alkyl, phenyl, substituted phenyl or alicyclic, preferably from alkyl, phenyl or alicyclic.
According to the invention, alkyl is C1～C7Is preferably C2～C5More preferably one or more of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl, such as isobutyl.
According to the invention, the substituted phenyl is alkyl substituted phenyl or nitro substituted phenyl, and is preferably selected from one or more of p-tolyl, o-tolyl and m-tolyl.
According to the invention, the cycloaliphatic radical is C3～C8Is preferably C3～C6More preferably, the alicyclic group(s) of (b) is one or more selected from the group consisting of a cyclopropane group, a cyclobutane group, a cyclopentane group and a cyclohexane group.
According to the invention, R1、R2、R3、R4、R5、R6、R7And are selected from alkyl, phenyl or alicyclic groups.
According to the invention, R and R' are each independently selected from the group consisting of-CnH2n-，-CmH2m-2-，
According to the invention, R and R' are each independently-CnH2nN is an integer of 0 to 8, preferably, R and R' are each independently-(CH2)nN is an integer of 1 to 6, for example R is- (CH)2)3-, R' is- (CH)2)2-。
According to a preferred embodiment of the invention, in formula (I), R is- (CH)2)3-, R' is- (CH)2)2-, i.e. the amino group-containing polyhedral oligomeric silsesquioxane has the structure shown in formula (II):
wherein, in the formula (II), R1、R2、R3、R4、R5、R6And R7And is selected from alkyl, phenyl or substituted alkyl.
According to a particularly preferred embodiment of the present invention, the amino group-containing polyhedral oligomeric silsesquioxane has a structure as shown in formula (III):
that is, in the formula (II), R1、R2、R3、R4、R5、R6And R7Identical and are all isobutyl.
According to the present invention, the metal-containing amino polyhedral oligomeric silsesquioxane is obtained by reacting an amino-containing POSS having a structure represented by formula (I) with a metal compound as a raw material, preferably an amino-containing POSS having a structure represented by formula (II) with a metal compound as a raw material, and more preferably an amino-containing POSS having a structure represented by formula (III) with a metal compound as a raw material.
According to the invention, POSS containing amino group and having the structure shown in formula (III) and a metal compound are used as raw materials to react, two nitrogen atoms in the POSS containing amino group and having the structure shown in formula (III) are coordinated with metal atoms in the metal compound to form a ring, and the two nitrogen atoms and the two carbon atoms and the metal atoms between the two nitrogen atoms form a five-membered ring structure.
According to the present invention, the metal (M) compound is a transition metal compound, and more preferably one or more selected from the group consisting of a transition metal complex and a lanthanide metal compound.
In the present invention, the transition metal compound includes a transition metal complex and a lanthanide metal compound.
According to the invention, the metal in the transition metal complex is selected from one or more of scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu) and zinc (Zn), preferably from one or more of copper (Cu), zinc (Zn), iron (Fe), cobalt (Co) and manganese (Mn), more preferably from copper (Cu), iron (Fe) or cobalt (Co).
According to the invention, the transition metal complex is an acetylacetone metal complex.
According to the invention, acetylacetone metal complexes are described as M (acac)mM represents a metal, and M represents the valence of the metal M.
According to a preferred embodiment of the present invention, the transition metal complex is selected from iron (III) acetylacetonate complexes (Fe (acac)3) Cobalt (II) acetylacetonate complex (Co (acac)2) Copper acetylacetonate complex (Cu (acac)2) Manganese (II) acetylacetonate complex (Mn (acac)2) Cobalt (III) acetylacetonate complex (Co (acac)3) Or manganese (III) acetylacetonate (Mn (acac)3) And (3) a complex.
According to the present invention, the metal in the lanthanide metal compound is a lanthanide metal, preferably one or more selected from lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), for example, europium (Eu). Among them, since promethium (Pm) has radioactivity, more preferably, it is selected from lanthanide metals other than promethium (Pm).
According to the invention, the lanthanide metal compound is a chloride of a lanthanide metal, preferably a hydrate of a chloride of a lanthanide metal, more preferably selected from the group consisting of lanthanum (III) chloride heptahydrate (LaCl)3·7H2O), cerium (III) chloride heptahydrate (CeCl)3·7H2O), praseodymium (III) chloride hexahydrate (PrCl)3·6H2O), Neodymium chloride (III) hexahydrate (NdCl)3·6H2O), samarium (III) chloride hexahydrate (SmCl)3·6H2O), europium (III) chloride hexahydrate (EuCl)3·6H2O), gadolinium (III) chloride hexahydrate (GdCl)3·6H2O), terbium (III) chloride hexahydrate (TbCl)3·6H2O), dysprosium (III) chloride hexahydrate (DyCl)3·6H2O), holmium (III) chloride hexahydrate (HoCl)3·6H2O), erbium (III) chloride hexahydrate (ErCl)3·6H2O), thulium (III) chloride hexahydrate (TmCl)3·6H2O), ytterbium (III) chloride hexahydrate (YbCl)3·6H2O) or lutetium (III) chloride hexahydrate (LuCl)3·6H2O), for example europium (III) chloride hexahydrate (EuCl)3·6H2O)。
According to the preferred embodiment of the invention, the metal-containing amino polyhedral oligomeric silsesquioxane is obtained by reacting POSS containing amino and acetylacetone complex or lanthanide metal chloride serving as raw materials.
According to the present invention, the molar ratio of the amino group-containing POSS to the metal compound is 1: (1-2), preferably 1: (1 to 1.5), more preferably 1: (1 to 1.2), for example 1:1, wherein the molar amount of the primary amino group-containing polyhedral oligomeric silsesquioxane is the molar amount of primary ammonia therein, and the molar amount of the metal compound is the molar amount of the metal therein.
In the present invention, when the molar ratio of the amino group-containing POSS to the metal compound is relatively large or small, the metal-containing amino polyhedral oligomeric silsesquioxane cannot be obtained.
According to the invention, the reaction is carried out at 10 to 60 ℃ for 4 to 30 hours, preferably at 20 to 50 ℃ for 6 to 24 hours, more preferably at 30 to 50 ℃ for 8 to 18 hours, for example at 40 ℃ for 12 hours.
According to the invention, the reaction is carried out under an atmosphere of protective gas, preferably argon or nitrogen.
According to the invention, in the infrared spectrum of the metal-containing amino polyhedral oligomeric silsesquioxane, 1000 to E1200cm-1And the absorption peak of the stretching vibration characteristic of the Si-O bond is positioned.
According to the invention, in the infrared spectrum of the metal-containing amino polyhedral oligomeric silsesquioxane, 1575-1613 cm-1And 1515-1527 cm-1Is the characteristic absorption peak of the carbonyl group attached to the metal.
According to the invention, in the infrared spectrum of the metal-containing amino polyhedral oligomeric silsesquioxane, 510cm-1～520cm-1The vicinity is a characteristic absorption peak of a nitrogen-metal coordinate bond.
In the invention, the metal-containing amino polyhedral oligomeric silsesquioxane is formed by suspending a metal compound outside POSS, wherein the POSS structure is not damaged, and the metal is suspended outside a saturated structure of POSS.
The metal-containing amino-type POSS can be used for curing catalysis of cyanate, benzoxazine and other materials, especially for curing catalysis of cyanate resin, when the metal-containing amino-type POSS is added into the cyanate resin, the curing temperature of the cyanate resin composition is remarkably reduced, for example, after the metal-containing amino-type POSS accounting for 2 wt% of the weight of the composition is added, the curing temperature (peak curing temperature) of the cyanate resin composition can be reduced by more than 110 ℃, preferably more than 115 ℃, more preferably more than 121.5 ℃ and even more preferably 168.8 ℃. For example, after 2 weight percent of metal-containing amino polyhedral oligomeric silsesquioxane is added, the curing temperature of the obtained cyanate ester resin composition is reduced by 121.5-168.8 ℃. And, as the amount of the metal-containing amino-type POSS added increases, the curing temperature of the cyanate ester resin composition also decreases, for example, when 3% by weight of the copper-containing amino-type POSS (noted as Cu-POSS) is added, the curing temperature of the cyanate ester resin composition decreases by 160.1 ℃.
In another aspect of the present invention, there is provided a method for preparing a metal-containing amino-type polyhedral oligomeric silsesquioxane according to the first aspect of the present invention, comprising the steps of:
step 1, dispersing polyhedral oligomeric silsesquioxane containing amino in a solvent.
According to the present invention, in step 1, the amino group-containing polyhedral oligomeric silsesquioxane is as described in the first aspect of the present invention.
According to the present invention, in step 1, the solvent is a polar organic solvent, preferably dichloromethane, trichloromethane, etc.
In the present invention, a polyhedral oligomeric silsesquioxane containing an amino group is dispersed in a solvent and mixed to obtain a mixed solution.
And 2, adding a metal compound, and reacting.
According to the present invention, in step 2, the metal compound is a metal compound according to the first aspect of the present invention.
According to the present invention, in step 2, a metal compound is added to the mixed solution obtained in step 1, mixed, and reacted.
According to the invention, in step 2, the reaction is carried out under a protective gas atmosphere, preferably under an argon or nitrogen atmosphere.
According to the present invention, in step 2, the molar ratio of the amino group-containing POSS to the metal compound is 1: (1-2), preferably 1: (1 to 1.5), more preferably 1: (1 to 1.2), for example 1:1, wherein the molar amount of the primary amino group-containing polyhedral oligomeric silsesquioxane is the molar amount of the primary amino group therein, and the molar amount of the metal compound is the molar amount of the metal therein.
In the present invention, when the molar ratio of the amino group-containing POSS to the metal compound is relatively large or small, the metal-containing amino polyhedral oligomeric silsesquioxane cannot be obtained.
According to the invention, the reaction is carried out at 10 to 60 ℃ for 4 to 30 hours, preferably at 20 to 50 ℃ for 6 to 24 hours, more preferably at 30 to 50 ℃ for 8 to 18 hours, for example at 40 ℃ for 12 hours.
According to the invention, the amino-containing POSS reacts with the metal compound, two nitrogen atoms in the amino-containing POSS coordinate with the metal atoms to form a ring, the reaction temperature is too low, the metal-containing amino-type polyhedral oligomeric silsesquioxane cannot be obtained, the reaction temperature is too high, the coordination number of metal ions in the metal compound is reduced, and the metal ions cannot coordinate with the amino groups in the amino-containing POSS to form a ring.
And 3, carrying out post-treatment to obtain the metal-containing amino polyhedral oligomeric silsesquioxane.
According to the invention, in the step 3, after the reaction is finished, the product obtained in the step 2 is subjected to post-treatment to obtain a final product, wherein the post-treatment comprises rotary evaporation, precipitation, filtration and drying to obtain the transition metal-containing amino polyhedral oligomeric silsesquioxane.
According to the invention, in step 3, a rotary evaporator is adopted for rotary evaporation concentration, then precipitation and filtration are carried out, and the product obtained after rotary evaporation of the filtrate is dried.
According to the invention, in step 3, precipitation is carried out with a methanol solution, then filtration is carried out, and the filtrate is subjected to rotary evaporation.
According to the invention, the drying is carried out in a vacuum drying oven, preferably at 30-50 ℃ for 12-48 h, more preferably at 35-45 ℃ for 18-36 h, for example at 40 ℃ for 24 h.
In a third aspect of the present invention, there is provided a cyanate ester resin composition comprising the metal-containing amino-type polyhedral oligomeric silsesquioxane according to the first aspect of the present invention or prepared by the method according to the second aspect of the present invention and a cyanate ester resin.
According to the invention, the adopted metal-containing amino polyhedral oligomeric silsesquioxane has a special structure, in the structure, metal is suspended on the outer side of a POSS structure, and the Si-O-Si structure of the POSS is not damaged and is a cage (condensation) closed POSS, so that the metal-containing amino polyhedral oligomeric silsesquioxane is different from the metal-containing polyhedral oligomeric silsesquioxane in the prior art; in addition, the existing metal-containing polyhedral oligomeric silsesquioxane is generally a transition metal compound or a single lanthanide metal, and the invention synthesizes the amino polyhedral oligomeric silsesquioxane containing acetylacetone metal complexes and a plurality of lanthanide metals.
According to a preferred embodiment of the present invention, the metal-containing amino-type polyhedral oligomeric silsesquioxane is contained in the composition in an amount of 0.1% to 15%, preferably 0.1% to 10%, more preferably 0.1% to 3%, more preferably 0.5% to 3%, for example 2%, based on 100% by weight of the composition.
The composition adopts the metal-containing amino polyhedral oligomeric silsesquioxane with a special structure, so that the curing temperature of the cyanate ester resin can be remarkably reduced, and the curing temperature of the cyanate ester resin can be reduced by adding a small amount of the metal-containing amino polyhedral oligomeric silsesquioxane into the composition. Specifically, the curing temperature of the composition is reduced by about 120-167 ℃, preferably about 130-160 ℃ relative to the curing temperature of a pure cyanate ester resin. For example, after 2 weight percent of metal-containing amino polyhedral oligomeric silsesquioxane is added, the curing temperature of the obtained cyanate ester resin composition is reduced by 121.5-168.8 ℃.