CN107353909B - CaO·4B2O3·2H2O/SiO2Composite nanometer flame retardant and preparation method thereof - Google Patents

CaO·4B2O3·2H2O/SiO2Composite nanometer flame retardant and preparation method thereof Download PDF

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CN107353909B
CN107353909B CN201710546937.2A CN201710546937A CN107353909B CN 107353909 B CN107353909 B CN 107353909B CN 201710546937 A CN201710546937 A CN 201710546937A CN 107353909 B CN107353909 B CN 107353909B
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cao4b
sio
flame retardant
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retardant
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CN107353909A (en
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刘志宏
闫红红
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Shaanxi Normal University
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Shaanxi Normal University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/16—Inorganic impregnating agents
    • B27K3/32—Mixtures of different inorganic impregnating agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K2240/00—Purpose of the treatment
    • B27K2240/30—Fireproofing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Forests & Forestry (AREA)
  • Silicon Compounds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Fireproofing Substances (AREA)

Abstract

The invention discloses a kind of CaO4B2O3·2H2O/SiO2Teos hydrolysis is first obtained silicon dioxide colloid, CaCl is then added into silicon dioxide colloid by composite nanometer flame retardant and preparation method thereof2、H3BO3, in confined conditions 140~240 DEG C of progress solvent thermal reactions to get arrive CaO4B2O3·2H2O/SiO2Composite nanometer flame retardant.Ball shaped nano SiO in composite flame-retardant agent of the present invention2Equably it is supported on CaO4B2O3·2H2The surface of O nanometer sheet, CaO4B2O3·2H2O nanometer sheet and ball shaped nano SiO2The contact surface of fire retardant and material can be increased to improve compatibility, both in addition good thermal stability, the two is compound to have cooperative flame retardant effect, keeps the flame retardant effect of fire retardant more preferable, while reducing the dosage of fire retardant.CaO4B of the present invention2O3·2H2O/SiO2Composite nanometer flame retardant preparation method is simple, has good anti-flammability to polypropylene and wood powder, has vast potential for future development.

Description

CaO·4B2O3·2H2O/SiO2Composite nanometer flame retardant and preparation method thereof
Technical field
The invention belongs to fire proofing technical fields, and in particular to a kind of CaO4B2O3·2H2O/SiO2Nano combined resistance Fire agent and preparation method thereof.
Background technique
Line borate is a kind of effective and inexpensive inorganic fire retardants, suppression cigarette, combustion product good, nontoxic with thermal stability The advantages that small toxicity, is widely used in various fibers, resin, rubber product, electrical apparatus insulation material, electric wire, cable, timber and prevents Rust paint etc. it is fire-retardant.However, the borate partial size usually prepared is larger, it is not easy to disperse in the polymer, also reduces height The mechanical performance of Molecularly Imprinted Polymer, limits its application.If borate fire retardant is prepared into nanoscale, it is likely that both may be used Increase the contact surface of fire retardant and host material and improve compatibility, and the dosage of fire retardant can be reduced.Also, if by nanometer Borate fire retardant and other fire retardants are prepared into nanocomposite, can both play in this way borate fire retardant advantage or The advantage of other fire retardants can be played.
Silicon-series five-retardant is divided into organic and inorganic silicon-series five-retardant.Silicone flame retardant such as polysiloxanes, silicone resin, silicon Rubber and a variety of silane copolymers etc., at present in terms of the research of organic Gui flame retardant is concentrated mainly on plastic flame.Nothing Machine silicon-series five-retardant such as silica, silicate (such as montmorillonite), silica gel, talcum powder, there is fire-retardant answer in Wood-plastic material With.Wherein, inorganic silicon based compound has good dispersibility and efficient anti-flammability in the composite.
Inventor has found many preparation reports in relation to being hydrated line borate nanostructure, such as Lihong in R&D process Bao et al. proposes to prepare line borate 2CaOB using hydro-thermal method2O3·H2O nanobelt, this seminar also once reported ellipsoid, Silkworm chrysalis shape 4CaO5B2O3·7H2The preparation of O nanostructure, phase inversion prepare sheet, ellipsoid, cauliflower-shaped CaO 3B2O3·4H2O nanostructure.But not it is proposed that becoming CaO4B about group2O3·2H2The nano material and its nanometer of O The relevant report of compound product preparation.So carrying out line borate nano material and its and SiO2The system of composite nanometer flame retardant Standby and flame retardant property research has important practical significance.
Summary of the invention
Technical problem to be solved by the present invention lies in providing, a kind of preparation method is simple, have good flame retardant property and The CaO4B of smoke suppressing2O3·2H2O/SiO2The preparation method of composite nanometer flame retardant and the composite flame-retardant agent.
Solve CaO4B used by above-mentioned technical problem2O3·2H2O/SiO2Composite nanometer flame retardant is by following methods Be prepared: by deionized water, dehydrated alcohol mix, with ammonium hydroxide adjust pH to 8~9, be then heated to 60~80 DEG C, dropwise plus Enter ethyl orthosilicate, constant temperature stirs 3~6 hours, obtains white colloidal；CaCl is added into white colloidal2、H3BO3, mixing is It after even, reacts 8~20 hours for 140~240 DEG C in confined conditions, cooled to room temperature, filters, washing, drying, obtain CaO·4B2O3·2H2O/SiO2Composite nanometer flame retardant；
Above-mentioned ethyl orthosilicate is 1:(0.5~1.2 with deionized water, the volume ratio of dehydrated alcohol): (5~20), it is excellent Selecting ethyl orthosilicate and deionized water, the volume ratio of dehydrated alcohol is 1:(0.8~1): (10~15).
Above-mentioned ethyl orthosilicate and CaCl2H3BO3Molar ratio be 1:7:(45~55), preferably ethyl orthosilicate with CaCl2、H3BO3Molar ratio be 1:7:(46~53).
In above-mentioned preparation method, preferably in confined conditions 150~200 DEG C are reacted 8~12 hours.
Beneficial effects of the present invention are as follows:
1, the present invention passes through solvent-thermal method fabricated in situ CaO4B2O3·2H2O/SiO2Composite nanometer flame retardant, it is multiple at this It closes in fire retardant, ball shaped nano SiO2Equably it is supported on CaO4B2O3·2H2The surface of O nanometer sheet.Wherein CaO 4B2O3·2H2O nanometer sheet and ball shaped nano SiO2The contact surface of fire retardant and material can be increased to improve compatibility, in addition two Person's good thermal stability, the two is compound to have cooperative flame retardant effect, moreover it is possible to which the mechanical property for more effectively improving blend composition makes to hinder The flame retardant effect for firing agent is more preferable, reduces the dosage of fire retardant.
2, CaO4B of the present invention2O3·2H2O/SiO2Composite nanometer flame retardant has good resistance to polypropylene and wood powder Combustion property, can inhibit polyacrylic cracking, reduce polyacrylic heat release rate, reduce the risk of polypropylene in a fire, And the firmness of polypropylene carbon-coating can be improved, the expansion carbon-coating of formation can be effectively heat-insulated, oxygen barrier；Wood powder can effectively be slowed down Burning velocity, improve the flame retardant property of wood powder.
3, CaO4B of the present invention2O3·2H2O/SiO2Composite nanometer flame retardant has flame retarding efficiency high, easy to process, low The advantages that poison, small pollution, there is vast potential for future development.
Detailed description of the invention
Fig. 1 is CaO4B prepared by embodiment 12O3·2H2O/SiO2The XRD diagram of composite nanometer flame retardant.
Fig. 2 is CaO4B prepared by embodiment 12O3·2H2O/SiO2The SEM of composite nanometer flame retardant schemes.
Fig. 3 is the enlarged drawing of Fig. 2.
Fig. 4 is CaO4B prepared by embodiment 12O3·2H2O/SiO2The EDS map of composite nanometer flame retardant.
Fig. 5 is CaO4B prepared by embodiment 22O3·2H2O/SiO2The XRD diagram of composite nanometer flame retardant.
Fig. 6 is CaO4B prepared by embodiment 22O3·2H2O/SiO2The SEM of composite nanometer flame retardant schemes.
Fig. 7 is that polypropylene (adds the CaO4B of 5% comparative example 1 respectively in curve a), polypropylene2O3·2H2O fire retardant (the CaO4B of curve b) and embodiment 12O3·2H2O/SiO2Composite nanometer flame retardant (the TG curve of curve c).
Fig. 8 is that pure wood powder (adds the CaO4B of 20% comparative example 1 respectively in curve a), wood powder2O3·2H2O fire retardant (the CaO4B of curve b) and embodiment 12O3·2H2O/SiO2Composite nanometer flame retardant (the TG curve of curve c).
Fig. 9 is the CaO4B for adding 5% comparative example 1 in polypropylene (a) and polypropylene respectively2O3·2H2O fire retardant (the CaO4B of curve b) and embodiment 12O3·2H2O/SiO2Composite nanometer flame retardant (the oxygen index value figure of curve c).
Specific embodiment
The present invention is described in more detail with reference to the accompanying drawings and examples, but protection scope of the present invention is not limited only to These embodiments.
Embodiment 1
10mL dehydrated alcohol, 0.8mL deionized water are added in three-necked flask, and the ammonium hydroxide tune of 1mL 4.2mol/L are added PH to 8 is saved, 70 DEG C is then heated to, 1mL (4.3mmol) ethyl orthosilicate is added dropwise into three-necked flask, it is permanent at 70 DEG C Temperature stirring 4 hours, obtains white colloidal；3.3294g (30mmol) CaCl is added to white colloidal2、12.3592g (200mmol)H3BO3, the stainless steel cauldron for being uniformly then transferred to that volume is 100mL polytetrafluoroethyllining lining is stirred at room temperature It is interior, reaction kettle is placed in baking oven and is kept for 10 hours for 150 DEG C, reaction kettle is taken out, in air cooled to room temperature, gained Product filtered, the washing of 80 DEG C of second distillation water washing, dehydrated alcohol, 60 DEG C drying 12 hours, obtain CaO4B2O3· 2H2O/SiO2Composite nanometer flame retardant.
Comparative example 1
By 2.7745g (25mmol) CaCl2、10.2985g(166.6mmol)H3BO3It is stirred at room temperature uniformly, is then transferred to appearance Product is that reaction kettle is placed in baking oven and is kept for 10 hours for 200 DEG C in the stainless steel cauldron of 100mL polytetrafluoroethyllining lining, will Reaction kettle takes out, in air cooled to room temperature, and products therefrom is through suction filtration, 80 DEG C of second distillation water washing, anhydrous second Alcohol washing, 60 DEG C drying 12 hours, obtain CaO4B2O3·2H2O fire retardant.
Embodiment 2
5mL dehydrated alcohol, 0.4mL deionized water are added in three-necked flask, and the ammonium hydroxide of 0.5mL 4.2mol/L are added PH to 8 is adjusted, 70 DEG C is then heated to, 0.5mL (2.15mmol) ethyl orthosilicate is added dropwise into three-necked flask, 70 Constant temperature stirs 4 hours at DEG C, obtains white colloidal；1.6647g (15mmol) CaCl is added to white colloidal2、6.1796g (100mmol)H3BO3, the stainless steel cauldron for being uniformly then transferred to that volume is 100mL polytetrafluoroethyllining lining is stirred at room temperature It is interior, reaction kettle is placed in baking oven and is kept for 10 hours for 200 DEG C, reaction kettle is taken out, in air cooled to room temperature, gained Product filtered, the washing of 80 DEG C of second distillation water washing, dehydrated alcohol, 60 DEG C drying 12 hours, obtain CaO4B2O3· 2H2O/SiO2Composite nanometer flame retardant.
Inventor is using x-ray diffractometer, scanning electron microscope and energy spectrum analysis to sample obtained by Examples 1 and 2 It is characterized, the result is shown in Figure 1~6.By the XRD characterization result of Fig. 1 and 5 as it can be seen that sample goes out peak position and CaO4B2O3· 2H2The peak position out of O is consistent, and the EDS characterization result of Fig. 4 also indicates that, line borate and SiO are contained in sample2Each member Element illustrates that CaO4B has been prepared2O3·2H2O and SiO2Compound.By Fig. 2,3,6 as it can be seen that ball shaped nano SiO2Uniformly Ground is supported on CaO4B2O3·2H2The surface of O nanometer sheet, CaO4B2O3·2H2O nanometer sheet with a thickness of 100nm, SiO2's Diameter is 100nm or so.
Embodiment 3
15mL dehydrated alcohol, 1mL deionized water are added in three-necked flask, and the ammonium hydroxide that 1mL 4.2mol/L is added is adjusted PH to 9, is then heated to 70 DEG C, and 1mL (4.3mmol) ethyl orthosilicate, the constant temperature at 70 DEG C are added dropwise into three-necked flask Stirring 4 hours, obtains white colloidal；3.3294g (30mmol) CaCl is added to white colloidal2、13.2861g(215mmol) H3BO3, it is stirred at room temperature and is uniformly then transferred in the stainless steel cauldron that volume is 100mL polytetrafluoroethyllining lining, by reaction kettle It is placed in baking oven 240 DEG C to be kept for 8 hours, reaction kettle be taken out, in air cooled to room temperature, products therefrom filtered, 80 DEG C of second distillation water washing, dehydrated alcohol washing, 60 DEG C drying 12 hours, obtain CaO4B2O3·2H2O/SiO2Nanometer Composite flame-retardant agent.
In order to prove beneficial effects of the present invention, inventor adds CaO prepared by 5% comparative example 1 to polypropylene respectively 4B2O3·2H2CaO4B prepared by O fire retardant and embodiment 12O3·2H2O/SiO2Composite nanometer flame retardant is added to wood powder The CaO4B of 20% comparative example 1 preparation2O3·2H2CaO4B prepared by O fire retardant and embodiment 12O3·2H2O/SiO2It receives Rice composite flame-retardant agent carries out thermogravimetric analysis (N using thermal analyzer2Atmosphere), as a result see Fig. 7 and 8.And it is surveyed using JF-3 oxygen index (OI) Determine instrument (the bright thunder experimental instruments and equipment limited in Nanjing provides) and carried out flame retardant property test, as a result sees Fig. 9.
From figure 7 it can be seen that CaO4B in doping comparative example 12O3·2H2The polypropylene weight loss ratio of O fire retardant is not mixed Miscellaneous polypropylene weight loss is few, and adulterates CaO4B in 5% embodiment 12O3·2H2O/SiO2Poly- the third of composite nanometer flame retardant Alkene weight loss is less；As can be seen from Figure 9, oxygen index value is sequentially increased by (a) to (c).These results indicate that 5% embodiment 1 of doping Middle CaO4B2O3·2H2O/SiO2The Flame Retardant of composite nanometer flame retardant > doping 5%CaO4B2O3·2H2O resistance Fire Flame Retardant > polyacrylic flame retardant property of agent.
From figure 8, it is seen that weight loss is sequentially reduced by (a) to (c), this shows to adulterate CaO in 5% embodiment 1 4B2O3·2H2O/SiO2The wood powder flame retardant property of composite nanometer flame retardant > 5% CaO4B of doping2O3·2H2The wood of O fire retardant Powder flame retardant property > pure wood powder flame retardant property.

Claims (5)

1. a kind of CaO4B2O3·2H2O/SiO2The preparation method of composite nanometer flame retardant, it is characterised in that: by deionized water, Dehydrated alcohol mixing adjusts pH to 8~9 with ammonium hydroxide, is then heated to 60~80 DEG C, ethyl orthosilicate is added dropwise, constant temperature stirs It mixes 3~6 hours, obtains white colloidal；CaCl is added into white colloidal2、H3BO3, after mixing, in confined conditions 140 ~240 DEG C are reacted 8~20 hours, cooled to room temperature, are filtered, washing, drying, are obtained CaO4B2O3·2H2O/SiO2It receives Rice composite flame-retardant agent；
Above-mentioned ethyl orthosilicate is 1:(0.5~1.2 with deionized water, the volume ratio of dehydrated alcohol): (5~20), positive silicic acid Ethyl ester and CaCl2、H3BO3Molar ratio be 1:7:(45~55).
2. CaO4B according to claim 12O3·2H2O/SiO2The preparation method of composite nanometer flame retardant, feature exist In: the ethyl orthosilicate is 1:(0.8~1 with deionized water, the volume ratio of dehydrated alcohol): (10~15).
3. CaO4B according to claim 12O3·2H2O/SiO2The preparation method of composite nanometer flame retardant, feature exist In: the ethyl orthosilicate and CaCl2、H3BO3Molar ratio be 1:7:(46~53).
4. CaO4B according to any one of claims 1 to 32O3·2H2O/SiO2The preparation side of composite nanometer flame retardant Method, it is characterised in that: react 8~12 hours for 150~200 DEG C in confined conditions.
5. the CaO4B of method of claim 1 preparation2O3·2H2O/SiO2Composite nanometer flame retardant.
CN201710546937.2A 2017-07-06 2017-07-06 CaO·4B2O3·2H2O/SiO2Composite nanometer flame retardant and preparation method thereof Expired - Fee Related CN107353909B (en)

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