CN104830067A - Preparation method of a polyhedral oligomeric silsesquioxane-magnesium hydroxide composite flame-resistant material - Google Patents
Preparation method of a polyhedral oligomeric silsesquioxane-magnesium hydroxide composite flame-resistant material Download PDFInfo
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Abstract
The invention provides a preparation method of a polyhedral oligomeric silsesquioxane-magnesium hydroxide composite flame-resistant material. The preparation method comprises the following steps: step A: adding methyltrichlorosilane and acetone to a constant-temperature magnetic stirring water batch tank, heating and stirring to obtain a uniformly mixed solution, and dropwise adding distilled water into the mixed solution; step B: heating and keeping backflowing; step C: under a continuous magnetic stirring condition, dropwise adding a magnesium chloride aqueous solution to a precipitator, and meanwhile, controlling a pH value of the solution to 8-10 to obtain magnesium hydroxide sol; step D: when the backflowing reaction in the step B performs for two third of the total reaction time, slowly dropwise adding the magnesium hydroxide sol obtained in the step C to the backflow reaction solution, further carrying out the backflowing reaction for the residual one third of the total reaction time; step E: filtering the obtained mixed solution, and performing vacuum drying to obtain a composite flame-resistant material. According to the preparation of the polyhedral oligomeric silsesquioxane-magnesium hydroxide composite flame-resistant material, the synergistic effect of the polyhedral oligomeric silsesquioxane and magnesium hydroxide is put into a full play, and the flame resistance is greatly improved.
Description
Technical field
The present invention relates to the preparation method of a kind of polyhedral silsesquioxane and magnesium hydroxide composite flame retardant material.
Background technology
Polyhedral silsesquioxane (Polyhedral Oligomeric Silsesquioxanes, POSS) be by inorganic core Si-O-Si skeleton and be centered around inorganic circumnuclear organic " arm " R and form, having three-dimensional polyhedron structure, is novel organic/inorganic hybridization material and novel environmental friendly materials.Due to the special construction of POSS inorganic core Si-O-Si skeleton, thus generally all have extraordinary thermotolerance, the resistates after being heated is SiO
2,and content is very high, the thermal stability that polymer composite is excellent can be given, may be used for the flame retardant resistance improving polymkeric substance.And organic " arm " R, by the approach such as physical action and chemical bonding, the consistency between POSS and high molecular polymer can be improved, enable POSS matrix material can be dispersed in macromolecule polymer material.The structural formula of incomplete condensation seven methyl trihydroxy-seven polysilsesquioxane is:
In recent years, the macromolecular material based on plastics is widely used in the every field such as electronic apparatus, communications and transportation, building, communication cable, aerospace.But because macromolecular material is mainly made up of carbon, protium, great majority are extremely incendive.If do not consider the flame retardant resistance of macromolecular material, often cause the accident that the losses such as fire are larger, cause great loss to the property of daily life and country.In order to reduce the inflammableness of macromolecular material, prevent fire failure, also will accomplish environmental protection while reducing financial loss, so environmentally friendly fire retardant is more and more subject to people's attention, environmentally friendly fire retardant is also the inexorable trend of flame-retarded technology development simultaneously
At present, in existing conventional fire retardant, containing halogen flames such as chlorine or bromines, sizable ratio is commercially occupied.Its flame retarding efficiency is high, consumption is few, little to the performance impact of material.But research shows that the use of this based flame retardant to environment, can not meet the RoHS ban that European Union puts into effect.Along with the enhancing of people's environmental consciousness, environmentally friendly fire retardant research and development has become a large focus of flame-retarded technology.Wherein, silicon-series five-retardant is exactly one of Green Flammability agent.Polyhedral silsesquioxane is a kind of silicon-series five-retardant of novel hybrid, has the advantages such as nontoxic, high temperature resistant, corrosion-resistant, and being a kind of one-tenth cigarette type inhibitor, is again a kind of halogen-free flame retardants.Add the POSS fire retardant in macromolecular material to, " cage modle " structure of POSS when reaching certain temperature of burning starts to lose, the SiO of generation
2, the carbide such as SiOxCy, SiC has oxygen barrier insulation effect, plays good effect in suppression macromolecular material burning diffusion process.Simultaneously, because POSS monomer itself has higher thermostability, add nanometer size effect, make POSS monomer be combined tightr with macromolecular material, so just limit the motion of macromolecular material chain, thus just more improve the flame retardant properties of macromolecular material.But the complex process of POSS synthesis preparation, hydrolysis reaction is difficult to control, and production cost is high, hinders POSS large-scale industrial production and practicalization.And inorganic combustion inhibitor magnesium hydroxide (Mg (OH)
2) filler and fire retardant can be made in the plastic, it has fire-retardant, three functions of filling and eliminate smoke, and does not produce secondary pollution, has and can produce synergistic effect with many kinds of substance, non-volatile, nontoxic, corrodibility is little, the advantage such as cheap, is a kind of environment friendly flame retardant be widely used.Magnesium hydroxide can make the density loss of flammable superpolymer as stopping composition, can dehydration endotherm at 300 ~ 350 DEG C, suppresses the intensification of polymkeric substance; Meanwhile, the steam that dehydration is released can dilute the concentration of inflammable gas and oxygen, reaches further flame retardant effect; Can also can also continue to stop polymer combustion at combustiblematerials Surface Creation activated magnesia after magnesium hydroxide dehydration.At present, the POSS of domestic and international relevant report or magnesium hydroxide are applied to the fire-retardant aspect of macromolecular material and focus mostly on and add in macromolecular material at single POSS monomer, or the single magnesium hydroxide through surface modification adds in the middle of macromolecular material, POSS is become " POSS/Mg (OH) with magnesium hydroxide preparation
2composite flame-proof material " document and patent be not reported so far.
Summary of the invention
In order to solve above technical problem, the invention provides the preparation method of a kind of polyhedral silsesquioxane and magnesium hydroxide composite flame retardant material, comprising following step:
Steps A: trichloromethyl silane and acetone are joined and have in the temperature constant magnetic stirring water bath of reflux container, heated and stirred, gets a uniform mixture, and then stirs and is added dropwise in mixing solutions by distilled water;
Step B: heat up and keep backflow;
Step C: under the condition of continuous magnetic agitation, is added drop-wise in precipitation agent by magnesium chloride brine, controls pH=8 ~ 10 of solution simultaneously, after being added dropwise to complete, continuing magnetic agitation, namely obtains magnesium hydroxide colloidal sol;
Step D: step B back flow reaction to total time 2/3rds time, the magnesium hydroxide colloidal sol obtained by step C is slowly added dropwise in back flow reaction solution, continue back flow reaction residue 1/3rd time;
Step e: it is dry that the mixing solutions obtained by step D filters final vacuum, obtains polyhedral silsesquioxane and magnesium hydroxide composite flame retardant material.
Preferably, described step B obtains incomplete condensation seven methyl trihydroxy-seven polysilsesquioxane, and its structural formula is:
Preferably, in described steps A, the volume ratio of trichloromethyl silane and acetone is 1:6.5 ~ 7.5, and the volume ratio of trichloromethyl silane and distilled water is 1:4 ~ 5.
Preferably, in described steps A, whipping temp is 50 DEG C ~ 55 DEG C, and churning time is 15 ~ 30min, and distilled water time for adding is 30 ~ 40min.
Preferably, in described step B, the temperature of rising is 65 DEG C ~ 70 DEG C, and return time is 20 ~ 24h.
Preferably, in described step C, the concentration of magnesium chloride is 0.2 ~ 0.6mol/L, and precipitation agent employing mass concentration is the ammoniacal liquor dilution 4 ~ 6 times of 10% ~ 15%, and the speed of dropping is 1 ~ 3ml/min.
Preferably, in described step D, the add-on of magnesium hydroxide colloidal sol is 30 ~ 50ml.
Preferably, in described step e, vacuum drying temperature is 70 DEG C ~ 80 DEG C, and the time is 2 ~ 3h.
The preparation principle of a kind of polyhedral silsesquioxane of the present invention and magnesium hydroxide composite hybridization fire retardant material is as follows: first with trichloromethyl silane and distilled water for raw material, acetone is solvent, and hydrolysis-condensation reaction prepares incomplete condensation seven methyl trihydroxy-seven polysilsesquioxane:
When then should reach 2/3rds of total time between backflow inverse time, the magnesium hydroxide colloidal sol of 30 ~ 50ml is slowly added dropwise in back flow reaction solution, continues the time of back flow reaction residue 1/3rd.
After finally the mixing solutions that obtains being filtered under 70 DEG C ~ 80 DEG C conditions vacuum-drying 2 ~ 3h, prepare " POSS/Mg (OH)
2composite flame-proof material ".
Beneficial effect of the present invention: a kind of polyhedral silsesquioxane of proposition and magnesium hydroxide composite flame retardant material belong to halogen-free flame-retardant system, given full play to the synergy between polyhedral silsesquioxane and magnesium hydroxide, the flame retardant resistance of adding more separately polyhedral silsesquioxane or modification and unmodified magnesium hydroxide has and significantly improves.
Accompanying drawing explanation
The scanning spectra of the FTIR spectrum of Fig. 1 polyhedral silsesquioxane that to be embodiment 7 obtain through step 6 and magnesium hydroxide composite flame retardant material.
Embodiment
Below in conjunction with accompanying drawing, preferably embodiment of the present invention is described in further detail:
Embodiment 1
A kind of polyhedral silsesquioxane and hydroxide: the preparation method of magnesium composite hybridization fire retardant material carries out according to the following steps: one, in the volume ratio of trichloromethyl silane and acetone be 1:6.5 ~ 7.5, the volume ratio of trichloromethyl silane and distilled water is that the ratio of 1:4 ~ 5 takes trichloromethyl silane, acetone and distilled water; Two, the trichloromethyl silane first step one taken and acetone join to be had in the temperature constant magnetic stirring water bath of reflux container, under 50 DEG C ~ 55 DEG C conditions, magnetic agitation 15 ~ 30min, get a uniform mixture, and then under magnetic agitation condition, distilled water step one taken slowly is added dropwise in mixing solutions, and time for adding is 30 ~ 40min; Three, being warming up to temperature is that 65 DEG C ~ 70 DEG C and timing keep backflow total time to be 20 ~ 24h; Four, by magnesium chloride (MgCl
2) be made into the aqueous solution that concentration is 0.2 ~ 0.6mol/L, using the ammoniacal liquor of 10% ~ 15% dilution 4 ~ 6 times as precipitation agent, then under the condition of continuous magnetic agitation, the MgCl will configured with the speed of 1 ~ 3ml/min
2the aqueous solution is slowly added drop-wise in precipitation agent, controls the pH value of solution between 8 ~ 10 simultaneously, after being added dropwise to complete, continuing magnetic agitation 30min ~ 60min, namely obtains magnesium hydroxide (Mg (OH)
2) colloidal sol; Five, back flow reaction to total time 2/3rds time, the magnesium hydroxide colloidal sol of 30 ~ 50ml is slowly added dropwise in back flow reaction solution, continue back flow reaction residue 1/3rd time; Six, after the mixing solutions that step 5 obtained filters under 70 DEG C ~ 80 DEG C conditions vacuum-drying 2 ~ 3h, obtain polyhedral silsesquioxane and magnesium hydroxide composite flame retardant material.
Embodiment 2
The volume ratio being 1:7, trichloromethyl silane and distilled water in the volume ratio of trichloromethyl silane and acetone in step one is as different from Example 1 that the ratio of 1:4.5 takes trichloromethyl silane, acetone and distilled water.Other identical with embodiment 1.
Embodiment 3
As different from Example 2 in step 2 under 55 DEG C of water bath condition, magnetic agitation 20min, adding time of distilled water is 35min.Other identical with embodiment 2.
Embodiment 4
Be warming up to 65 DEG C in step 3 as different from Example 3, and timing keeps backflow total time to be 24h.Other identical with embodiment 3.
Embodiment 5
As different from Example 4 in step 4 by magnesium chloride (MgCl
2) be made into the aqueous solution that concentration is 0.45mol/L, the ammoniacal liquor of 10% is diluted 4.5 times as precipitation agent, then under the condition of continuous magnetic agitation, the MgCl will configured with the speed of 2ml/min
2the aqueous solution is slowly added drop-wise in precipitation agent, controls the pH=9 of solution simultaneously, after being added dropwise to complete, continuing magnetic agitation 60min, namely obtains magnesium hydroxide (Mg (OH)
2) colloidal sol.Other identical with embodiment 4.
Embodiment 6
When back flow reaction is to 16h in step 5 as different from Example 5, the magnesium hydroxide colloidal sol of 45ml is slowly added dropwise in back flow reaction solution, continues back flow reaction 8h.Other identical with embodiment 5.
Embodiment 7
After the mixing solutions that obtains in step 6 as different from Example 6 filters under 75 DEG C of conditions vacuum-drying 2h.Other are identical with embodiment 6.
The scanning spectra of the FTIR spectrum of Fig. 1 polyhedral silsesquioxane that to be embodiment 7 obtain through step 6 and magnesium hydroxide composite flame retardant material.Can find out that from collection of illustrative plates the charateristic avsorption band of the skeleton Si-O-Si of cage modle unfilled corner seven polysilsesquioxane POSS appears at 1119.01cm
-1place, 3445.7cm
-1place is the absorption peak that the hydroxyl of Si-OH and magnesium hydroxide overlaps, 2971.0cm
-1, 2924.7cm
-1two places are stretching vibration and the rocking vibration absorption peak of C-H respectively, 1270.8cm
-1place is Si-CH
3characteristic peak, 725.7cm
-1place is the charateristic avsorption band of magnesium hydroxide.So synthesized POSS/Mg (OH) from the explanation of FTIR spectrum collection of illustrative plates
2composite flame-proof material.
Embodiment 8 ~ 16:
The preparation technology of comparative example 1 and embodiment 8 ~ 16: first, the PC raw material of 100 ~ 150g is pulverized 3 ~ 5min inside micromill, then successively adds " the POSS/Mg (OH) of antioxidant butylated hydroxy anisole (BHA), not exclusively condensation seven methyl trihydroxy-seven polysilsesquioxane, magnesium hydroxide or embodiment 7 preparation according to formula (see table 1)
2composite flame-proof material " raw material; after mechanically mixing is even; the raw material mixed is joined Minitype twin-screw extrusion machine in 245 DEG C ~ 255 DEG C, plastifies the slurry extruded and be placed in miniature injection machine, go out oxygen index test sample and vertical combustion level estimate sample with corresponding mold injection.Testing standard is in table 3.
Based on POSS/Mg (OH) in comparative example 1 and embodiment 8 ~ 16
2the flame retardant properties of the PC of composite flame-proof material is as shown in table 2.Testing standard is in table 3.Embodiment 8 ~ 16 is divided into three groups, and embodiment 8 ~ 10 is one group, adds POSS, Mg (OH) that massfraction is 2% respectively
2and POSS/Mg (OH)
2composite flame-proof material; Embodiment 11 ~ 13 is one group, adds POSS, Mg (OH) that massfraction is 4% respectively
2and POSS/Mg (OH)
2composite flame-proof material; Embodiment 14 ~ 16 is one group, adds POSS, Mg (OH) that massfraction is 6% respectively
2and POSS/Mg (OH)
2composite flame-proof material.
Flame retardant properties test result shows, is adding POSS, Mg (OH) of identical amount
2and POSS/Mg (OH)
2during composite flame-proof material, POSS/Mg (OH)
2the flame retardant effect of composite flame-proof material is better, meanwhile, along with the increase of addition, and POSS/Mg (OH)
2the flame retardant properties of composite flame-proof material to PC matrix improves more more obvious, further illustrates POSS/Mg (OH)
2the flame retardant effect of composite flame-proof material is better.
Table 1 fire retardation PC formula/(weight part)
The flame retardant properties of table 2 fire retardation PC
Table 3 testing standard
| Test event | Testing standard |
| Limiting oxygen index(LOI) (LOI) | GB/T2406.2-2009 |
| Vertical combustion grade | UL-94 |
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, some simple deduction or replace can also be made, all should be considered as belonging to protection scope of the present invention.
Claims (8)
1. a preparation method for polyhedral silsesquioxane and magnesium hydroxide composite flame retardant material, is characterized in that, comprises following step:
Steps A: trichloromethyl silane and acetone are joined and have in the temperature constant magnetic stirring water bath of reflux container, heated and stirred, gets a uniform mixture, and then stirs and is added dropwise in mixing solutions by distilled water;
Step B: heat up and keep backflow;
Step C: under the condition of continuous magnetic agitation, is added drop-wise in precipitation agent by magnesium chloride brine, controls pH=8 ~ 10 of solution simultaneously, after being added dropwise to complete, continuing magnetic agitation, namely obtains magnesium hydroxide colloidal sol;
Step D: step B back flow reaction to total time 2/3rds time, the magnesium hydroxide colloidal sol obtained by step C is slowly added dropwise in back flow reaction solution, continue back flow reaction residue 1/3rd time;
Step e: it is dry that the mixing solutions obtained by step D filters final vacuum, obtains polyhedral silsesquioxane and magnesium hydroxide composite flame retardant material.
2. the method for claim 1, is characterized in that, described step B obtains incomplete condensation seven methyl trihydroxy-seven polysilsesquioxane, and its structural formula is:
3. the method for claim 1, is characterized in that, in described steps A, the volume ratio of trichloromethyl silane and acetone is 1:6.5 ~ 7.5, and the volume ratio of trichloromethyl silane and distilled water is 1:4 ~ 5.
4. the method for claim 1, is characterized in that, in described steps A, whipping temp is 50 DEG C ~ 55 DEG C, and churning time is 15 ~ 30min, and distilled water time for adding is 30 ~ 40min.
5. the method for claim 1, is characterized in that, in described step B, the temperature of rising is 65 DEG C ~ 70 DEG C, and return time is 20 ~ 24h.
6. the method for claim 1, is characterized in that, in described step C, the concentration of magnesium chloride is 0.2 ~ 0.6mol/L, and precipitation agent employing mass concentration is the ammoniacal liquor dilution 4 ~ 6 times of 10% ~ 15%, and the speed of dropping is 1 ~ 3ml/min.
7. the method for claim 1, is characterized in that, in described step D, the amount that magnesium hydroxide colloidal sol adds is 30 ~ 50ml.
8. the method for claim 1, is characterized in that, in described step e, vacuum drying temperature is 70 DEG C ~ 80 DEG C, and the time is 2 ~ 3h.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107498676A (en) * | 2017-09-27 | 2017-12-22 | 柳州隆泰竹业有限公司 | A kind of production method of anti-flaming bamboo floor |
| CN108299799A (en) * | 2018-01-27 | 2018-07-20 | 浙江大学 | The layered double hydroxide and its preparation method and application that cagelike silsesquioxane is modified |
| CN113980351A (en) * | 2021-12-08 | 2022-01-28 | 烟台艾弗尔阻燃科技有限公司 | Preparation method of modified magnesium hydroxide flame retardant and application of modified magnesium hydroxide flame retardant in low-smoke halogen-free cable material |
| CN114702749A (en) * | 2022-04-18 | 2022-07-05 | 深圳市锦昊辉实业发展有限公司 | Flame-retardant polyolefin and preparation method thereof |
| CN116120753A (en) * | 2023-01-06 | 2023-05-16 | 中科院广州化学有限公司 | Easily-ceramic flame-retardant silicone rubber and preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107498676A (en) * | 2017-09-27 | 2017-12-22 | 柳州隆泰竹业有限公司 | A kind of production method of anti-flaming bamboo floor |
| CN108299799A (en) * | 2018-01-27 | 2018-07-20 | 浙江大学 | The layered double hydroxide and its preparation method and application that cagelike silsesquioxane is modified |
| CN108299799B (en) * | 2018-01-27 | 2019-09-20 | 浙江大学 | The modified layered double hydroxide and its preparation method and application of cagelike silsesquioxane |
| CN113980351A (en) * | 2021-12-08 | 2022-01-28 | 烟台艾弗尔阻燃科技有限公司 | Preparation method of modified magnesium hydroxide flame retardant and application of modified magnesium hydroxide flame retardant in low-smoke halogen-free cable material |
| CN114702749A (en) * | 2022-04-18 | 2022-07-05 | 深圳市锦昊辉实业发展有限公司 | Flame-retardant polyolefin and preparation method thereof |
| CN116120753A (en) * | 2023-01-06 | 2023-05-16 | 中科院广州化学有限公司 | Easily-ceramic flame-retardant silicone rubber and preparation method and application thereof |
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