CN106478953A - A kind of metal hybrid POSS complex and its preparation method and application - Google Patents
A kind of metal hybrid POSS complex and its preparation method and application Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C08L2201/02—Flame or fire retardant/resistant
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
The invention discloses a kind of metal hybrid POSS complex and its preparation method and application.This preparation method is in the presence of water and inorganic base, and phenyl siloxane occurs hydrolytic condensation in organic solvent, then reacts, with containing silicane hydroxide, the POSS being obtained containing two silicon hydrogen groups；Subsequently successively be there are hydrosilylation and hydrolysis with acrylate in prepared POSS, obtain mono carboxylic POSS；Last mono carboxylic POSS and metal acetate salt occur displacement reaction that metal hybrid POSS complex is obtained.Compared with prior art, the features such as metal hybrid POSS complex prepared by the present invention has excellent heat stability with becoming charcoal and rubber compatibility is good.Only a small amount of metal hybrid POSS complex need to be added in silicone rubber, you can prepare that heat stability is good, excellent fireproof performance silastic material, can be widely applied to the fields such as space flight and aviation, Nuclear Power Industry, electronic apparatus and medical apparatus and instruments.
Description
Technical field
The present invention relates to the synthesis of metal complex and application, in more detail a kind of metal hybrid POSS complex
And its preparation method and application.
Background technology
In recent years, with silastic material in opening up of the application such as electronic apparatus and space flight and aviation wide, high performance silicon rubber
The demand of glue material increasingly increases, simultaneously this also the heat stability to add-on type liquid silicon rubber and fire resistance propose higher
Requirement.
At present, improving add-on type liquid silicon rubber heat stability and the main method of fire resistance is to add heat resistant inorganic to fill out
Material.Wherein, variable valency metal ionses such as Cu, Fe etc. with Organic substance formed complex when, because quantivalence is susceptible to possibility of reversal
Change, there is radical-scavenging function, and can promote matrix that porcelain altogether occurs in the combustion process of silicone rubber, thus improving its resistance
Combustion performance (impact to silicon rubber heat-resisting for the transition metal oxide. China Synthetic Rubber Industry, 1997,20:296-299).Additionally,
Because most metals hydroxide has the advantages that cheap, asepsis environment-protecting and flame-retardant smoke inhibition, it is also widely used for silicon
In rubber.Fang etc. adds 60 parts of magnesium salt whiskers in silicone rubber so as to LOI rises to 39.5% from 24%, has passed through to hang down
Direct combustion burns UL-94V-0 level (Mechanical properties, fire performance and thermal stability
of magnesium hydroxide sulfate hydrate whiskers flame retardant silicone
rubber.Journal of materials science,2008,43(3):1057-1062).But this quasi-tradition is fire-retardant
The heat stability of agent is relatively low, and the thermal stability of matrix can be made after being added to silicone rubber to decline, and limits silicone rubber in high-temperature field
In application；And its flame retarding efficiency is relatively low, a large amount of interpolation is needed to can be only achieved ideal effect；Further, since itself
Poor with rubber compatibility, mechanical property and the processing characteristics of silicone rubber can be deteriorated.Therefore need exploitation excellent heat stability, resistance badly
Combustion efficiency high, and the BACN good with the matrix compatibility is applied to silicon rubber flame-retardant.
Caged silsesquioxane (polyhedral oligomeric silsesquioxane, POSS) has structure because of it
Designability, is easily reacted and is modified, excellent heat stability and be widely used in the heat-resisting research of polymer.Chen Fan etc.
Vinyl seven phenyl POSS is grafted to containing hydrogen silicone oil, and prepares addition-type silicon rubber as cross-linking agent.Research finds,
The addition of POSS effectively increase silicone rubber heat stability (preparation of the Methyl Hydrogen Polysiloxane Fluid of side base containing POSS and application performance.
Bonding, 2015,36 (10):37-41).But, because phenyl POSS is poor with the compatibility of silicone rubber, lead to POSS in silicon rubber
Poor dispersion in glue, is susceptible to reunite, and makes silicone rubber cannot form the protective layer of densification during becoming charcoal it is difficult to carry
The fire resistance of high silicone rubber.
Content of the invention
Present invention aims to the defect that prior art exists, provide a kind of metal hybrid POSS complex, should
Compound has the advantages that excellent heat stability with to become charcoal good with rubber compatibility, adds small amount and can prepare tool
There is the silastic material of excellent heat stability energy and fire resistance.
Another object of the present invention is to providing the synthetic method of described metal hybrid POSS complex.
Further object of the present invention is to provide application in add-on type liquid silicon rubber for the described complex.
Complex prepared by the present invention is the caged silsesquioxane containing si-h bond, its Si-O-Si inner core with
The add-on type liquid silicon rubber compatibility is good, and the si-h bond containing can make complex pass through hydrosilylation in sulfidation
It is grafted on silicone rubber side chain, contribute to complex dispersed in the base with molecular level.The present invention can be by preparation gold
Belong to the complex of hydridization POSS, the radical-scavenging function of the high thermal stability of POSS and metal complex is combined, and
It is applied in silicone rubber, effectively improve thermal stability and the fire resistance of silicone rubber.
The purpose of the present invention is achieved through the following technical solutions：
A kind of metal hybrid POSS complex：This metal hybrid POSS complex is the caged times of hydrosilyl group-containing group and carboxyl
The compound of half siloxanes and metallic element complexation, its general molecular formula is：
Wherein, R1=CH3、CH2CH3Or CH2CH2CH3, R2=H, CH3Or OCH3, M=Cu, Fe, Ce or La.
The preparation method of described metal hybrid POSS complex, comprises the steps：
(1) synthesis of phenyl caged silsesquioxane tetrol alkali metal salt：Phenyl siloxane is dissolved in organic solvent, plus
Enter sodium hydroxide and deionized water, back flow reaction 3～5h at 60～70 DEG C；At 20～30 DEG C, subsequently react 10～15h, instead
Should after the completion of, remove solvent through sucking filtration and obtain white filter cake, then with isopropanol to Cake Wash sucking filtration 3 times, the white filter obtaining
Cake is phenyl caged silsesquioxane tetrol alkali metal salt.Described phenyl siloxane is phenyltrimethoxysila,e or phenyl three
One or more of Ethoxysilane；Described inorganic base is one or more of Lithium hydrate or sodium hydroxide；Described
Organic solvent be one or more of isopropanol or oxolane (THF)；
(2) contain the synthesis of the POSS of two silicon hydrogen groups：Described alkali metal salt and hydrogeneous oxosilane are dissolved in anhydrous THF
In, add tertiary amine catalyst, react 2～3h at 0～10 DEG C；At 20～30 DEG C, subsequently react 10～15h；Reaction completes
Afterwards, obtain filtrate through sucking filtration, vacuum distillation 30～60min at 40～50 DEG C, the white solid obtaining methanol washs three times,
Obtain the POSS that white powder contains two silicon hydrogen groups.Described hydrogeneous oxosilane is one or more of following structural formula：
Wherein n is 0～2；
Described tertiary amine catalyst is one or more of triethylamine, triethylenediamine or dimethyl benzylamine；
(3) synthesis of monoesters base POSS：POSS containing two silicon hydrogen groups and platinum catalyst are dissolved in toluene, 90～
It is slowly added dropwise the toluene solution of acrylate, back flow reaction 24～36h at 110 DEG C；After the completion of reaction, by solution temperature 60～
Vacuum distillation 30～60min at 70 DEG C, the white solid obtaining methanol washs three times, and obtaining white powder is monoesters base POSS.
Described acrylate is acrylic acid methyl ester., methyl methacrylate, Tert-butyl Methacrylate and 3- methoxy acrylic acid first
One or more of ester；Described platinum catalyst is one or more of chloroplatinic acid or this special platinum catalyst of karr；
(4) synthesis of mono carboxylic POSS：Monoesters base POSS is dissolved in anhydrous tetrahydro furan, adds organic acid catalysis
Agent, flow back at 60～80 DEG C 8～10h；After the completion of reaction, by solution at 40～50 DEG C of temperature vacuum distillation 30～60min；
The white powder of precipitation is dissolved in chloroform, deionized water wash solution three times in separatory funnel, finally by organic faciess
Vacuum distillation 30～60min at 40～50 DEG C of temperature, obtains white powder i.e. only carboxyl POSS.Described organic acid is
One or more of methanesulfonic acid or p-methyl benzenesulfonic acid；
(5) synthesis of metal hybrid POSS complex：Add only carboxyl POSS and oxolane in a kettle., at the uniform velocity
Stir；Metal acetate salt is dissolved in methanol, is added dropwise in 30～40min in described reactor, after being added dropwise to complete
Continue reaction 8～10h at 20～30 DEG C；After the completion of reaction by solution at 40～50 DEG C of temperature vacuum distillation 30～60min,
The solid obtaining chloroform dissolution filter；And by filtrate at 40～50 DEG C of temperature vacuum distillation 30～60min, the solid of precipitation
Washed with methanol three times, obtain metal hybrid POSS complex.Described metal acetate salt is Schweinfurt green, Ferrous acetate, acetic acid
One or more of cerium or lanthanum acetate.
Preferably, inorganic base described in step (1) and the mol ratio of phenyl siloxane are 1:0.49～1:0.53.
Preferably, deionized water described in step (1) and the mol ratio of phenyl siloxane are 1:1.05～1:1.20.
Preferably, described phenyl caged silsesquioxane tetrol alkali metal salt and the mol ratio of hydrogeneous oxosilane are 1:2～
1:3.
Preferably, described phenyl caged silsesquioxane tetrol alkali metal salt and the mol ratio of tertiary amine catalyst are 1:1
～1:2.
Preferably, described in step (3), the POSS containing two silicon hydrogen groups with the mol ratio of Tert-butyl Methacrylate is
1:1～1:1.2.
Preferably, the consumption (in terms of platinum) of the platinum catalyst described in step (3) accounts for the POSS matter containing two silicon hydrogen groups
5～30ppm of amount.
Preferably, the consumption of the organic acid described in step (4) is the 0.5%～2% of monoesters base POSS mass.
Preferably, the metal acetate salt described in step (4) and the mol ratio of mono carboxylic POSS are 1:2～1:2.5
Application in add-on type liquid silicon rubber for the described metal hybrid POSS complex：By 100 mass parts vinyls
Silicone oil, 2～3 mass parts high-vinyl silicone oil, the metal hybrid POSS complex of 2～3 mass parts, containing hydrogen silicone oil, 0.004～
0.03 mass parts 1- acetenyl -1- Hexalin, 0.00001～0.00004 mass parts platinum catalyst, mix homogeneously at room temperature,
Vulcanize 10～12min molding under the conditions of 100～150 DEG C, 7～8Mpa；Si-h bond and vinyl silicone oil in described containing hydrogen silicone oil,
In high-vinyl silicone oil and fire retardant, the mol ratio of carbon-carbon double bond summation is 1:1～1.7:1.
Compared with prior art, the invention has the advantages that：
1st, the metal hybrid POSS complex heat stability prepared by the present invention is good, and flame retarding efficiency is high, can pass through phenyl
The radical-scavenging function of the thermostability of POSS and metal ion significantly improves heat stability and the resistance of add-on type liquid silicon rubber
Combustion performance, adds the complex of small amount (≤2 mass parts) in add-on type liquid silicon rubber, and vertical combustion can reach UL-
94V-0 level.
2nd, the complex prepared by the present invention is the caged silsesquioxane containing si-h bond, its Si-O-Si inner core
Good with the add-on type liquid silicon rubber compatibility, and the si-h bond containing can make complex anti-by Si-H addition reaction in sulfidation
Should be grafted on silicone rubber side chain, contribute to complex dispersed in the base with molecular level.
3rd, the add-on type liquid silicon rubber of present invention preparation has the advantages that excellent thermal stability and fire resistance, can
It is widely used in the fields such as space flight and aviation, Nuclear Power Industry, electronic apparatus and medical apparatus and instruments.
Brief description
Fig. 1 is the infrared spectrum of the complex synthesized by embodiment 1.
Fig. 2 is the nuclear magnetic spectrogram of the complex synthesized by embodiment 1.
Fig. 3 is the TG figure of the complex synthesized by embodiment 1.
Specific embodiment
Below in conjunction with drawings and Examples, the present invention is described in detail.It is important to point out that, illustrated embodiment
Simply the present invention is further illustrated, be not limiting the scope of the invention.
Embodiment of the present invention detection method relevant with comparative example is as follows：
1) Fourier descriptors (FT-IR)
Sample is obtained through pressing potassium bromide troche, carries out test analysis using fourier-transform infrared spectrometer：Precision is 4cm-1, sweep
Retouching scope is 4000-500cm-1.
2) nuclear magnetic resonance, NMR silicon spectrum (29Si-NMR)
Prepared POSS is composed with its silicon of nmr determination, and with deuterochloroform as solvent, tetramethylsilane is internal standard.
3) thermogravimetric analysiss (TGA)
Using thermogravimetric analyzer, in air atmosphere, 5-10mg sample is taken to be tested, analysis temperature scope：30-900
DEG C, heating rate：20℃/min.
Embodiment 1
(1) sequentially add 360mL in being equipped with the 500mL single necked round bottom flask of condensing reflux pipe and magnetic stir bar different
Propanol, 71.38g phenyltrimethoxysila,e, 7.45g deionized water and 9.50g sodium hydroxide.Flask is placed in oil bath pan,
It is made to be stirred at reflux 4h at 70 DEG C；Then it is cooled to room temperature, continue stirring 15h.After the completion of reaction, remove solvent through sucking filtration and obtain
White filter cake, then with isopropanol to Cake Wash sucking filtration 3 times, the white filter cake obtaining is phenyl caged silsesquioxane tetrol
Sodium salt.
(2) 57.80g phenyl caged silsesquioxane four sodium alkoxide, 15.18g triethylamine are added in 500mL four-hole boiling flask
(TEA) and the anhydrous THF of 300mL, ice bath stirs 0.5h.Under nitrogen protection, inject 21.16g dimethyl dichlorosilane (DMCS), in ice bath bar
React 3h under part, then rise to 25 DEG C and continue reaction 15h.After reaction terminates, remove insoluble reaction thing through sucking filtration, by solution in temperature
Vacuum distillation 30min at 40 DEG C of degree, again with methanol, to the solid washing and filtering three times separating out, obtains white solid and contains two silicon
The POSS of hydrogen group.
(3) 23.04g is added to contain POSS, 100mL toluene and the 0.17g card of two silicon hydrogen groups in 500mL four-hole boiling flask
Er Site platinum catalyst, temperature rises to 95 DEG C.3.13g Tert-butyl Methacrylate is dissolved in 100mL toluene, in nitrogen
Under protection, solution is slowly dropped in above-mentioned flask.It is added dropwise to complete rear back flow reaction 36h.After the completion of reaction, by solution in temperature
Vacuum distillation 30min at 65 DEG C of degree, the white solid of precipitation is washed with methanol three times, and obtaining white solid is monoesters base POSS.
(4) add the anhydrous THF of 20g monoesters base POSS and 200mL in 500mL four-hole boiling flask, be warming up to 75 DEG C and stir back
After stream 0.5h, add 0.4g to benzene methanesulfonic acid, and Deca 2 is dripped, keep solution to flow back at 75 DEG C 8h.After the completion of reaction, will
Solution vacuum distillation 30min at 40 DEG C of temperature；The white powder of precipitation is dissolved in 30mL chloroform, uses 50mL deionized water
Wash solution three times in separatory funnel, finally by organic faciess at 40 DEG C of temperature vacuum distillation 30min, obtaining white powder is
Only carboxyl POSS.
(5) add 7.2g mono carboxylic POSS and 100mL THF in 500mL four-hole boiling flask, stir.Then will
0.53g Schweinfurt green ultrasonic dissolution is in 150mL methanol, and is slowly dropped in four-hole boiling flask.It is added dropwise to complete temperature and be maintained at 20 DEG C,
Continue reaction 10h.After the completion of reaction by solution at 40 DEG C of temperature vacuum distillation 30min, the solid obtaining is molten with 50mL chloroform
Solution filters；And by filtrate at 40 DEG C of temperature vacuum distillation 30min, the solids with methanol of precipitation washs three times, obtains light green color
Powder is metal hybrid POSS complex 1.
As shown in figure 1, by infrared spectrum as can be seen that metal hybrid POSS complex 1 mainly has following characteristics peak：3073
And 3051cm-1(υAr-H), 2960 and 2927cm-1(υC-H)、2167cm-1(υSi-H), 1709 and 1569cm-1(υC=o), 1200～
1000cm-1(υSi-O-Si).As shown in Fig. 2 the nuclear magnetic resonance, NMR silicon spectrum of metal hybrid POSS complex 1 can be seen that：(1) δ=-
18.4 belong to the Si connecting carboxylate radical；(2) δ=- 63.0 belong to 2 Si near carboxylate radical；(3) δ=- 64.8 belong to
2 Si near silicon hydrogen group；(4) δ=- 69.4 belong to the Si of silicon hydrogen group；(5) δ=- 79.0 belong to POSS caged knot
In the middle of structure 4 Si.And this five unimodal integral area ratios are about 1:2:2:1:4, illustrate to successfully synthesize metal miscellaneous
Change POSS complex 1.
From TGA and DTG spectrogram (Fig. 3) under air atmosphere for the complex 1, the mass loss rate of complex 1 is
Temperature (T during 5wt%5) and mass loss rate be 10wt% when temperature (T10) it is respectively 293.3 DEG C and 481.0 DEG C, maximum
Thermal weight loss temperature (Tmax) it is 580.5 DEG C, and the quality residual volume at 800 DEG C has reached 51.0wt%, and metal hybrid POSS is described
Complex 1 has excellent heat stability and becomes charcoal.
By 100 mass parts vinyl silicone oils, (viscosity at 25 DEG C is 25200mPa s, and contents of ethylene is
0.09115wt%), (viscosity at 25 DEG C is 2095mPa s to 2 mass parts high-vinyl silicone oil, and contents of ethylene is
3.15wt%), 3 mass parts metal hybrid POSS complex 1,1.18 mass parts containing hydrogen silicone oils (hydrogen content be 0.75wt%),
1- acetenyl -1- the Hexalin of 0.06 mass parts and 0.00001～0.00004 mass parts platinum catalyst, are stirred at room temperature all
Even, it is molded 10min at 120 DEG C, after finally carrying out post-cure 60min in 150 DEG C of drying baker, take piece to carry out thermogravimetric analysiss
Test, test result is shown in Table 1.
Can see from table 1, in comparative example 1, be not added with the T of the add-on type liquid silicon rubber of complex5And T10It is respectively
363.1 DEG C and 405.6 DEG C, at 504.1 DEG C, maximum heat degradation peak occurs, and only have 20.4wt% in 800 DEG C of residual volumes；Burning is surveyed
Examination display, LOI only has 24.5%, and vertical combustion performance cannot pass through UL-94 grade.And add the metal hybrid of 3 mass parts
After POSS complex 1, the T of silicone rubber5And T1019.9 DEG C and 22.9 DEG C have been respectively increased it, TmaxAlso improve 20.7 DEG C, 800
DEG C residual volume has reached 35.7wt%, and the silicone rubber being relatively not added with complex improves 15.3wt%；And LOI is from 24.5% rising
To 28.0%, vertical combustion performance passes through UL-94V-0 grade；Show that fire retardant 1 can significantly increase add-on type liquid silicon rubber
The heat stability of glue and fire resistance, this is preferable mainly due to the phenyl of aryl POSS and the thermostability of caged kernel, and network
Metal copper ion in compound can change the heat ageing course of silicone rubber in silicone rubber by electron transfer, simultaneously with silicone rubber
There is porcelainization effect altogether, effectively increase heat stability and the fire resistance of silicone rubber.
Embodiment 2
The present embodiment difference from Example 1 is：In step (2), dimethyl dichlorosilane (DMCS) replaces with ethyl dichloro silicon
Alkane, and its consumption is 23.23g；Catalyst of triethylamine replaces with triethylenediamine, and its consumption is 20.19g；React at 3 DEG C
2.5h, then reacts 10h at 30 DEG C；Synthesizing the structural formula of metal hybrid POSS complex 2 obtaining is：
The add-on type liquid silicon rubber preparation technology difference from Example 1 of the present embodiment is：By in embodiment 1
Metal hybrid POSS complex 1 is changed into metal hybrid POSS complex 2.The performance of sample as shown in Table 1 and Table 2 it can be seen that
The T of complex 25And T10It is respectively 290.2 DEG C and 473.5 DEG C, TmaxFor 576.4 DEG C, and the quality residual volume at 800 DEG C reaches
50.6wt%, illustrates that metal hybrid POSS complex 2 has excellent heat stability and becomes charcoal.Relatively complex 2 and network
The thermal stability of compound 1, the latter has and somewhat declines compared with the former, and this is possibly due to the alkyl of metal hybrid POSS complex 2
Group is active compared with complex 1, is susceptible to fracture oxidation.After adding the metal hybrid POSS complex 2 of 3 mass parts, silicone rubber
Heat stability and fire resistance effectively improve, wherein T5And T10It is respectively 390.4 DEG C and 429.6 DEG C, go out at 531.2 DEG C
Existing maximum heat degradation peak, has reached 34.9wt% in 800 DEG C of residual volumes；Combustion testing shows, LOI is 28.5%, vertical combustion
Property remain to by UL-94V-0 grade, illustrate the interpolation of metal hybrid POSS complex 2 also can effectively improve silicone rubber heat steady
Qualitative and fire resistance.
Embodiment 3
The present embodiment difference from Example 1 is：In step (2), dimethyl dichlorosilane (DMCS) replaces with propyl group dichloro silicon
Alkane, and its consumption is 25.74g；Catalyst of triethylamine replaces with dimethyl benzylamine, and its consumption is 24.34g；React at 5 DEG C
2h, then reacts 10h at 30 DEG C；Synthesizing the structural formula of metal hybrid POSS complex 3 obtaining is：
The add-on type liquid silicon rubber preparation technology difference from Example 1 of the present embodiment is：By in embodiment 1
Metal hybrid POSS complex 1 is changed into metal hybrid POSS complex 3, and the consumption of corresponding containing hydrogen silicone oil is reduced to 1.16 mass
Part.The performance of sample is as shown in Table 1 and Table 2 it can be seen that the T of metal hybrid POSS complex 35And T10It is respectively 288.3 DEG C
With 470.4 DEG C, TmaxFor 575.5 DEG C, and the quality residual volume at 800 DEG C has reached 50.5wt%, and metal hybrid POSS network is described
Compound 3 has excellent heat stability and becomes charcoal.After adding the metal hybrid POSS complex 3 of 3 mass parts, the T of silicone rubber5
And T10It is respectively 388.7 DEG C and 426.4 DEG C, at 527.5 DEG C, maximum heat degradation peak occurs, reach in 800 DEG C of residual volumes
32.4wt%；Combustion testing shows, LOI is 28.2%, and vertical burn flammability remains to, by UL-94V-0 grade, metal hybrid is described
The interpolation of POSS complex 3 effectively increases heat stability and the fire resistance of silicone rubber.
Embodiment 4
The present embodiment difference from Example 1 is：In step (3), Tert-butyl Methacrylate replaces with acrylic acid first
Ester, and its consumption is 1.49g；React 24h at 100 DEG C；Synthesizing the structural formula of metal hybrid POSS complex 4 obtaining is：
The add-on type liquid silicon rubber preparation technology difference from Example 1 of the present embodiment is：By in embodiment 1
Metal hybrid POSS complex 1 is changed into metal hybrid POSS complex 4, and the consumption of corresponding containing hydrogen silicone oil increases as 1.19 mass
Part.The performance of sample is as shown in Table 1 and Table 2 it can be seen that the T of metal hybrid POSS complex 45And T10It is respectively 297.8 DEG C
With 487.1 DEG C, TmaxFor 588.4 DEG C, and the quality residual volume at 800 DEG C has reached 52.7wt%, illustrates compared to complex 1,
Metal hybrid POSS complex 4 heat stability is with to become charcoal more preferable.After adding the metal hybrid POSS complex 4 of 3 mass parts, silicon
The T of rubber5And T10It is respectively 398.5 DEG C and 435.1 DEG C, at 540.7 DEG C, maximum heat degradation peak occurs, reach in 800 DEG C of residual volumes
Arrive 37.9wt%；Combustion testing shows, LOI is 29.2%, and vertical burn flammability remains to, by UL-94V-0 grade, metal is described
The interpolation of hydridization POSS complex 4 effectively increases heat stability and the fire resistance of silicone rubber.
Embodiment 5
The present embodiment difference from Example 1 is：In step (3), Tert-butyl Methacrylate replaces with 3- methoxyl group
Acrylic acid methyl ester., and its consumption is 2.55g；React 36h at 90 DEG C；Synthesize the structure of the metal hybrid POSS complex 5 obtaining
Formula is：
The add-on type liquid silicon rubber preparation technology difference from Example 1 of the present embodiment is：By in embodiment 1
Metal hybrid POSS complex 1 is changed into metal hybrid POSS complex 5, and the consumption of corresponding containing hydrogen silicone oil is reduced to 1.15 mass
Part.The performance of sample is as shown in Table 1 and Table 2 it can be seen that the T of metal hybrid POSS complex 55And T10It is respectively 286.7 DEG C
With 480.1 DEG C, TmaxFor 574.9 DEG C, and the quality residual volume at 800 DEG C has reached 49.7wt%, and metal hybrid POSS network is described
Compound 5 has excellent heat stability and becomes charcoal.After adding the metal hybrid POSS complex 5 of 3 mass parts, the T of silicone rubber5
And T10It is respectively 400.3 DEG C and 437.8 DEG C, at 544.6 DEG C, maximum heat degradation peak occurs, reach in 800 DEG C of residual volumes
38.2wt%；Combustion testing shows, LOI is 28.6%, and vertical burn flammability remains to, by UL-94V-0 grade, metal hybrid is described
The interpolation of POSS complex 5 effectively increases heat stability and the fire resistance of silicone rubber.
Embodiment 6
The present embodiment difference from Example 1 is：In step (5), Schweinfurt green replaces with lanthanum acetate, and its consumption is
0.83g；React 8h at 30 DEG C；Synthesizing the structural formula of complex 6 obtaining is：
The add-on type liquid silicon rubber preparation technology difference from Example 1 of the present embodiment is：By in embodiment 1
Complex 1 is changed into metal hybrid POSS complex 6, and the consumption of corresponding containing hydrogen silicone oil increases as 1.20 mass parts.The property of sample
Can be as shown in Table 1 and Table 2 it can be seen that the T of metal hybrid POSS complex 65And T10It is respectively 272.1 DEG C and 468.4 DEG C,
TmaxFor 558.3 DEG C, and the quality residual volume at 800 DEG C has reached 45.9wt%, illustrates that metal hybrid POSS complex 5 has
Excellent heat stability with become charcoal.After adding the metal hybrid POSS complex 6 of 3 mass parts, the T of silicone rubber5And T10Respectively
For 385.6 DEG C and 428.1 DEG C, at 540.6 DEG C, maximum heat degradation peak occurs, reached 29.7wt% in 800 DEG C of residual volumes；Burning
Test display, LOI is 27.7%, and vertical burn flammability remains to by UL-94V-1 grade, and metal hybrid POSS complex 6 is described
Add heat stability and the fire resistance effectively increasing silicone rubber.
Embodiment 7
The present embodiment difference from Example 1 is：In step (5), Schweinfurt green replaces with Ferrous acetate, and its consumption
For 0.46g；React 8h at 30 DEG C；Synthesizing the structural formula of complex 7 obtaining is：
The add-on type liquid silicon rubber preparation technology difference from Example 1 of the present embodiment is：By in embodiment 1
Complex 1 is changed into metal hybrid POSS complex 7.The performance of sample is as shown in Table 1 and Table 2 it can be seen that metal hybrid POSS
The T of complex 75And T10It is respectively 300.4 DEG C and 493.5 DEG C, TmaxFor 598.4 DEG C, and the quality residual volume at 800 DEG C reaches
62.3wt%, illustrates that metal hybrid POSS complex 7 has excellent heat stability and becomes charcoal.Add the gold of 3 mass parts
After belonging to hydridization POSS complex 7, the T of silicone rubber5And T10It is respectively 407.7 DEG C and 435.4 DEG C, at 552.8 DEG C, maximum heat occurs
Degradation peak, has reached 41.5wt% in 800 DEG C of residual volumes；Combustion testing shows, LOI is 29.6%, and vertical burn flammability remains to lead to
Cross UL-94V-0 grade, illustrate that the interpolation of metal hybrid POSS complex 7 effectively increases the heat stability of silicone rubber and fire-retardant
Performance.
Embodiment 8
The present embodiment difference from Example 1 is：The consumption of complex 1 in embodiment 1 is reduced to 2 mass parts,
The consumption of corresponding containing hydrogen silicone oil increases as 1.20 mass parts.The performance of sample is as shown in Table 1 and Table 2.As shown in Table 2, add 1
The metal hybrid POSS complex 1 of mass parts, the T of add-on type liquid silicon rubber5And T10It is respectively 386.1 DEG C and 423.9 DEG C,
529.7 DEG C maximum heat degradation peak, and the quality residual volume at 800 DEG C has reached 30.2wt%；Combustion testing shows, LOI
For 27.1%, vertical burn flammability remains to by UL-94V-1 grade, shows to add metal hybrid POSS complexation within the specific limits
Thing 1, silicone rubber all has good heat stability and fire resistance.
Embodiment 9
The present embodiment difference from Example 1 is：Vinyl silicone oil in embodiment 1 is changed into contents of ethylene is
0.23wt%, viscosity are the vinyl silicone oil of 2000mPa s (25 DEG C), and the consumption of corresponding containing hydrogen silicone oil increases to 1.56 matter
Amount part.The performance of sample is as shown in table 2.As shown in Table 2, compared with comparative example 2, the T of the silicone rubber of the present embodiment5And T10Respectively
Improve 23.6 DEG C and 24.4 DEG C, maximum heat degradation peak occurs in 10.3 DEG C, reach in 800 DEG C of quality residual volumes
28.7wt%；Combustion testing shows, LOI is 27.5%, and vertical burn flammability remains to, by UL-94V-0 grade, show for difference
The vinyl silicone oil system of molecular weight, adds metal hybrid POSS complex 1, add-on type liquid silicon rubber equally has good
Heat stability and fire resistance.
Comparative example 1
By 100 mass parts vinyl silicone oils, (viscosity at 25 DEG C is 20000mPa s, and contents of ethylene is
0.12wt%), 2 mass parts vinyl silicone oils (viscosity at 25 DEG C be 2095mPa s, contents of ethylene be 3.15wt%),
1.29 mass parts containing hydrogen silicone oils (hydrogen content be 0.75wt%), the 1- acetenyl -1- Hexalin of 0.01 mass parts and 0.00001～
0.00004 mass parts platinum catalyst, is stirred at room temperature uniformly, is molded 10min, at 120 DEG C finally in 150 DEG C of drying baker
Piece is taken to carry out thermogravimetric analysiss test after carrying out post-cure 60min.The performance of sample is as shown in table 2.
Comparative example 2
By 100 mass parts vinyl silicone oils, (viscosity at 25 DEG C is 2000mPa s, and contents of ethylene is
0.23wt%), 2.46 mass parts containing hydrogen silicone oils (hydrogen content is 0.75wt%), the 1- acetenyl -1- Hexalin of 0.01 mass parts
With 0.00001～0.00004 mass parts platinum catalyst, it is stirred at room temperature uniformly, is molded 10min at 120 DEG C, finally exists
Piece is taken to carry out thermogravimetric analysiss test after carrying out post-cure 60min in 150 DEG C of drying baker.The performance of sample is as shown in table 2.
The thermogravimetric test result of table 1 complex
The thermogravimetric test result of table 2 add-on type liquid silicon rubber
Claims (10)
1. a kind of metal hybrid POSS complex it is characterised in that：This metal hybrid POSS complex is silicon-hydrogen bond containing and carboxyl
Caged silsesquioxane and metallic element complexation compound, its general molecular formula is：
Wherein, R1=CH3、CH2CH3Or CH2CH2CH3, R2=H, CH3Or OCH3, M=Cu, Fe, Ce or La.
2. the preparation method of the metal hybrid POSS complex described in claim 1 is it is characterised in that comprise the following steps：
(1) synthesis of phenyl caged silsesquioxane tetrol alkali metal salt：Phenyl siloxane is dissolved in organic solvent, adds no
Machine alkali and deionized water, back flow reaction 3～5h at 60～70 DEG C；At 20～30 DEG C, subsequently react 10～15h, reaction completes
Afterwards, remove solvent through sucking filtration and obtain filter cake, to Cake Wash sucking filtration, obtain phenyl caged silsesquioxane tetrol alkali metal salt；
(2) contain the synthesis of the POSS of two silicon hydrogen groups：By phenyl caged silsesquioxane tetrol alkali metal salt and Silicon Containing Hydrogen chlorine
Alkane is dissolved in anhydrous THF, adds tertiary amine catalyst, reacts 2～3h at 0～10 DEG C；Subsequently react at 20～30 DEG C
10～15h；After the completion of reaction, obtain filtrate, vacuum distillation, washing through sucking filtration, obtain the POSS containing two silicon hydrogen groups；Described uncle
Amines catalyst is one or more of triethylamine, triethylenediamine and dimethyl benzylamine；Described hydrogeneous oxosilane is
One or more of following structural formula：
Wherein n is 0～2；
(3) synthesis of monoesters base POSS：POSS containing two silicon hydrogen groups and platinum catalyst are dissolved in toluene, 90～110
It is slowly added dropwise the toluene solution of acrylate, back flow reaction 24～36h at DEG C；After the completion of reaction, vacuum distillation, washing, obtain list
Ester group POSS；
(4) synthesis of mono carboxylic POSS：Monoesters base POSS is dissolved in anhydrous tetrahydro furan, adds organic acid catalyst,
Flow back at 60～80 DEG C 8～10h；After the completion of reaction, purification, obtain mono carboxylic POSS；Described organic acid is methanesulfonic acid
One or more of or p-methyl benzenesulfonic acid；
(5) synthesis of metal hybrid POSS complex：Add mono carboxylic POSS and oxolane in a kettle., at the uniform velocity stir all
Even；Metal acetate salt is dissolved in methanol, is added dropwise in reactor, continue at 20～30 DEG C after being added dropwise to complete reaction 8～
10h；Purification obtains metal hybrid POSS complex；Described metal acetate salt is Schweinfurt green, Ferrous acetate, cerous acetate or acetic acid
One or more of lanthanum.
3. preparation method according to claim 2 it is characterised in that：Inorganic base and phenyl siloxane described in step (1)
Mol ratio be 1:0.49～1:0.53；Deionized water is 1 with the mol ratio of phenyl siloxane:1.05～1:1.20.
4. preparation method according to claim 2 it is characterised in that：In step (1), described phenyl siloxane is phenyl
One or more of trimethoxy silane or phenyl triethoxysilane；Described inorganic base is Lithium hydrate or sodium hydroxide
One or more of；Described organic solvent is one or more of isopropanol or oxolane；Described to Cake Wash
Sucking filtration is to Cake Wash sucking filtration at least 1 time with isopropanol.
5. preparation method according to claim 2 it is characterised in that：Phenyl caged silsesquioxane described in step (2)
Tetrol alkali metal salt is 1 with the mol ratio of hydrogeneous oxosilane:2～1:3；Described phenyl caged silsesquioxane tetrol alkali metal salt
Mol ratio with tertiary amine catalyst is 1:1～1:2.
6. preparation method according to claim 2 it is characterised in that：In step (3), described contain two silicon hydrogen groups
POSS is 1 with the mol ratio of Tert-butyl Methacrylate:1～1:1.2；In terms of platinum, the consumption of described platinum catalyst is containing two
5～30ppm of the POSS mass of individual silicon hydrogen group；Described acrylate is acrylic acid methyl ester., methyl methacrylate, methyl
One or more of tert-butyl acrylate and 3- methoxy-methyl acrylate；Described platinum catalyst be chloroplatinic acid or karr this
One or more of special platinum catalyst.
7. preparation method according to claim 2 it is characterised in that：In step (3), described vacuum distillation is that solution exists
Vacuum distillation 30～60min at 60～70 DEG C of temperature；Described washing is to wash at least one times by the white solid obtaining with methanol,
Obtain white powder monoesters base POSS.
8. preparation method according to claim 2 it is characterised in that：In step (4), the consumption of described organic acid is
The 0.5%～2% of monoesters base POSS mass；Described purification be by resulting solution at 40～50 DEG C of temperature vacuum distillation 30～
60min；The white powder of precipitation is dissolved in chloroform, deionized water wash solution three times in separatory funnel, finally will
Organic faciess vacuum distillation 30～60min at 40～50 DEG C of temperature；
In step (5), described metal acetate salt is 1 with the mol ratio of mono carboxylic POSS:2～1:2.5；Described it is added dropwise to reaction
Time in kettle is 30～40min；Described purify for after the completion of reaction by solution at 40～50 DEG C of temperature vacuum distillation 30～
60min, the solid obtaining chloroform dissolution filter；And by filtrate at 40～50 DEG C of temperature vacuum distillation 30～60min, separate out
Solids with methanol at least washed once.
9. application in add-on type liquid silicon rubber for the metal hybrid POSS complex described in claim 1.
10. application in add-on type liquid silicon rubber for the metal hybrid POSS complex according to claim 9, its feature
It is：By 100 mass parts vinyl silicone oils, 2～3 mass parts high-vinyl silicone oil, 2～3 mass parts metal hybrid POSS network
Compound, containing hydrogen silicone oil, 0.004～0.03 mass parts 1- acetenyl -1- Hexalin, 0.00001～0.00004 mass parts platinum catalysis
Agent, mix homogeneously at room temperature, vulcanize 10～12min molding under the conditions of 100～150 DEG C, 7～8Mpa；Described containing hydrogen silicone oil
Middle si-h bond with the mol ratio of carbon-carbon double bond summation in vinyl silicone oil, high-vinyl silicone oil and metal hybrid POSS complex is
1:1～1.7:1.
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