CN106904628A - The preparation method of hollow rod-shape Firebrake ZB - Google Patents

The preparation method of hollow rod-shape Firebrake ZB Download PDF

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CN106904628A
CN106904628A CN201710324359.8A CN201710324359A CN106904628A CN 106904628 A CN106904628 A CN 106904628A CN 201710324359 A CN201710324359 A CN 201710324359A CN 106904628 A CN106904628 A CN 106904628A
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firebrake
shape
hollow rod
preparation
deionized water
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CN106904628B (en
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王春锋
韩志东
王继华
王永亮
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Harbin University of Science and Technology
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Abstract

The preparation method of hollow rod-shape Firebrake ZB, it is related to a kind of preparation method of Firebrake ZB.The invention aims to solve the existing complex process for preparing Firebrake ZB, time-consuming and the problem of poor flame retardant properties with ageing for reaction.Preparation method：First, boric acid, zinc oxide and deionized water are well mixed, obtain mixed solution；2nd, mixed solution is put into hydrothermal reaction kettle, then carries out hydro-thermal reaction under agitation, then cleaned, dried, obtain hollow rod-shape Firebrake ZB.Firebrake ZB prepared by the present invention is because with hollow rod-shape structure, when being used as inorganic combustion inhibitor, Firebrake ZB can be improved with fire retardant and the contact area of fire proofing, the Firebrake ZB that in fire retardant prepared by the present invention of addition 1%~5%, both the fire resistance of bittern-free flame-proof material can have been effectively improved, i.e. oxygen index (OI) improves 1~4 unit, is more suitable for the exploitation and application of bittern-free flame-proof material.The present invention can obtain hollow rod-shape Firebrake ZB.

Description

The preparation method of hollow rod-shape Firebrake ZB
Technical field
The present invention relates to a kind of preparation method of Firebrake ZB.
Background technology
Firebrake ZB as a kind of inorganic combustion inhibitor, with excellent nontoxic, fire-retardant, the suppression characteristic such as cigarette and anti-molten drop.Boric acid Zinc is mainly made up of Zn, B, O element, and structure is more complicated, at present, with determine molecular formula Firebrake ZB structure such as, 2ZnO·3B2O3·7H2O、2ZnO·3B2O3·3H2O、3ZnO·5B2O3·14H2O、3ZnO·3B2O3·3.5H2O、6ZnO· 5B2O3·3H2O and ZnO5B2O3·4H2O etc..2ZnO3B is successfully prepared from Nies in 19722O3·3.5H2O simultaneously proves it After with fire retardation, by the development 2ZnO3B of more than 30 years2O3·3.5H2The application of O gradually widely approved and As a kind of wide variety of commodity.
Firebrake ZB as fire retardant application mainly has 2ZnO3B2O3·3.5H2O and 4ZnOB2O3·H2Two kinds of O, this The dehydration temperature of two kinds of Firebrake ZBs is respectively 290 DEG C and 410 DEG C, and the former can apply in most of general-purpose plastics, such as PVC Deng the latter is then commonly applied in processing temperature engineering plastics higher.With other inorganic combustion inhibitors such as magnesium hydroxide, aluminium hydroxide Etc. comparing, Firebrake ZB while fire retardation is played, also with other functions.Istanbul technology university of Turkey Basar Yildiz researchs find that Firebrake ZB also improves the uvioresistant of polyurethane while polyurethane against oxidative performance is improved Line stabilization performance.The Stina of KTH of SwedenResearch finds that Firebrake ZB can strengthen the anti-of silicon rubber Bacterium performance, suppresses growth of the bacterium in silastic surface.
At present, the preparation method of Firebrake ZB mainly uses two kinds of material systems, and one kind is zinc oxide and boric acid, and another kind is Borax and zinc salt.According to the research of Eltepe etc., when reaction temperature is less than 80 DEG C, the product prepared is 2ZnO3B2O3· 7H2O rather than 2ZnO3B2O3·3.5H2O.Therefore, 2ZnO3B is prepared2O3·3.5H2The reaction temperature of O is generally greater than 80 DEG C, It is general more than 4 hours the time required to reaction.Patent of invention CN 103964455B disclose one kind and prepare 2ZnO3B2O3· 3.5H2The method of O, reaction temperature is 85 DEG C~95 DEG C, and the reaction time is 5h~7h.
Firebrake ZB with anisotropy pattern advantageously accounts for the agglomeration traits of Firebrake ZB, and raising Firebrake ZB is in resin Dispersion, therefore suffer from concern.In recent years, the preparation method of several Firebrake ZBs with many patterns is disclosed.Chinese invention is special Sharp CN 1789735B disclose a kind of hydrothermal preparing process of the low-hydrate zinc borate powder of morphology controllable, can synthesis particle shape, pin The zinc borate power of shape and bar-shaped three kinds of patterns.Chinese invention patent CN 102417189B disclose a kind of columnar zinc borate Synthetic method.Both the above method is required to prolonged reaction and ageing process.The Firebrake ZB of hollow structure can improve While dispersive property, increase contact of the Firebrake ZB with flame retardance element and promote interaction, it is expected to improve fire resistance, so far There is no the report of the Firebrake ZB of associated hollow structure.
The content of the invention
The invention aims to solve the existing complex process for preparing Firebrake ZB, time-consuming and anti-flammability with ageing for reaction The problem of energy difference, and the preparation method of hollow rod-shape Firebrake ZB is provided.
The preparation method of hollow rod-shape Firebrake ZB, is specifically realized by the following steps：
First, boric acid, zinc oxide and deionized water are well mixed, obtain mixed solution；
The amount of the material of the boric acid described in step one is (3mol~5mol) with the volume ratio of deionized water:(400mL~ 700mL)；
The amount of the material of the zinc oxide described in step one is 1mol with the volume ratio of deionized water:(400mL~ 700mL)；
2nd, mixed solution is put into hydrothermal reaction kettle, then hydrothermal reaction kettle is warming up to 100 DEG C~160 DEG C, then in temperature It is that 100 DEG C~160 DEG C and mixing speed are magnetic agitation reaction 0.5h~4h under 30r/min~60r/min to spend, and is reacted Liquid；Hydrothermal reaction kettle is quickly cooled to room temperature again, reaction solution is removed, then is filtered, obtain reactant；Use distilled water pair Reactant carries out washing 3 times~5 times, then the reactant after washing is dried into 4h~8h in the case where temperature is for 90 DEG C~120 DEG C, obtains Hollow rod-shape Firebrake ZB.
The present invention has advantages below compared with prior art：
First, in initial reaction solution, the consumption of boric acid exceedes its solubility, once feeds intake, it is easy to control；
2nd, magnetic agitation technique is used in hydrothermal reaction process, is conducive to accelerating reaction speed, shorten the reaction time, water The thermal response time is only 0.5h~4h, and compared with prior art, the reaction time reduces more than 1h；
3rd, the inventive method building-up process is simple, without ageing process；
4th, hollow rod-shape Firebrake ZB morphology controllable prepared by the present invention, prepared Firebrake ZB has hollow structure, endoporus Footpath is 0.8 μm~1.2 μm, and external diameter is 1.6 μm~2.5 μm, a length of 4 μm~6 μm of rod；
5th, the present invention prepare Firebrake ZB because have hollow rod-shape structure, when being used as inorganic combustion inhibitor, it is possible to increase Firebrake ZB and fire retardant and the contact area of fire proofing, add Firebrake ZB prepared by 1%~5% present invention in fire retardant, Both the fire resistance of bittern-free flame-proof material, i.e. oxygen index (OI) can have been effectively improved and had improve 1~4 unit, be more suitable for halogen-free flameproof material The exploitation of material and application.
The present invention can obtain hollow rod-shape Firebrake ZB.
Brief description of the drawings
Fig. 1 is the XRD spectrum of hollow rod-shape Firebrake ZB prepared by embodiment one；
Fig. 2 is the SEM figures of hollow rod-shape Firebrake ZB prepared by embodiment one.
Specific embodiment
Specific embodiment one：Present embodiment is the preparation method of hollow rod-shape Firebrake ZB, specifically according to the following steps Complete：
First, boric acid, zinc oxide and deionized water are well mixed, obtain mixed solution；
The amount of the material of the boric acid described in step one is (3mol~5mol) with the volume ratio of deionized water:(400mL~ 700mL)；
The amount of the material of the zinc oxide described in step one is 1mol with the volume ratio of deionized water:(400mL~ 700mL)；
2nd, mixed solution is put into hydrothermal reaction kettle, then hydrothermal reaction kettle is warming up to 100 DEG C~160 DEG C, then in temperature It is that 100 DEG C~160 DEG C and mixing speed are magnetic agitation reaction 0.5h~4h under 30r/min~60r/min to spend, and is reacted Liquid；Hydrothermal reaction kettle is quickly cooled to room temperature again, reaction solution is removed, then is filtered, obtain reactant；Use distilled water pair Reactant carries out washing 3 times~5 times, then the reactant after washing is dried into 4h~8h in the case where temperature is for 90 DEG C~120 DEG C, obtains Hollow rod-shape Firebrake ZB.
Present embodiment has advantages below compared with prior art：
First, in initial reaction solution, the consumption of boric acid exceedes its solubility, once feeds intake, it is easy to control；
2nd, magnetic agitation technique is used in hydrothermal reaction process, is conducive to accelerating reaction speed, shorten the reaction time, water The thermal response time is only 0.5h~4h, and compared with prior art, the reaction time reduces more than 1h；
3rd, present embodiment method building-up process is simple, without ageing process；
4th, hollow rod-shape Firebrake ZB morphology controllable prepared by present embodiment, prepared Firebrake ZB has hollow structure, Internal orifice dimension is 0.8 μm~1.2 μm, and external diameter is 1.6 μm~2.5 μm, a length of 4 μm~6 μm of rod；
5th, present embodiment prepare Firebrake ZB because have hollow rod-shape structure, when being used as inorganic combustion inhibitor, can Firebrake ZB and fire retardant and the contact area of fire proofing are improved, adds prepared by 1%~5% present embodiment in fire retardant Firebrake ZB, can both effectively improve the fire resistance of bittern-free flame-proof material, i.e. oxygen index (OI) and improve 1~4 unit, be more suitable for Halogen The exploitation of fire proofing and application.
Present embodiment can obtain hollow rod-shape Firebrake ZB.
Specific embodiment two：Present embodiment is with the difference of specific embodiment one：By hydro-thermal reaction in step 2 Kettle is quickly cooled to during hydrothermal reaction kettle is put into room-temperature water bath by room temperature and is cooled down.Other steps and specific embodiment party Formula one is identical.
Specific embodiment three：One of present embodiment and specific embodiment one or two difference is：Institute in step one The amount of the material of the boric acid stated is 3.5mol with the volume ratio of deionized water:(420mL~700mL).Other steps and specific reality Apply mode one or two identical.
Specific embodiment four：One of present embodiment and specific embodiment one to three difference is：Institute in step one The amount of the material of the boric acid stated is (3mol~4mol) with the volume ratio of deionized water:(400mL~500mL).Other steps with Specific embodiment one to three is identical.
Specific embodiment five：One of present embodiment and specific embodiment one to four difference is：Institute in step one The amount of the material of the boric acid stated is (3mol~4.5mol) with the volume ratio of deionized water:(400mL~580mL).Other steps It is identical with specific embodiment one to four.
Specific embodiment six：One of present embodiment and specific embodiment one to five difference is：Institute in step one The amount of the material of the boric acid stated is 5mol with the volume ratio of deionized water:(400mL~620mL).Other steps and specific implementation Mode one to five is identical.
Specific embodiment seven：One of present embodiment and specific embodiment one to six difference is：Institute in step one The amount of the material of the zinc oxide stated is 1mol with the volume ratio of deionized water:(420mL~500mL).Other steps and specific reality Apply mode one to six identical.
Specific embodiment eight：One of present embodiment and specific embodiment one to seven difference is：Institute in step one The amount of the material of the zinc oxide stated is 1mol with the volume ratio of deionized water:(580mL~620mL).Other steps and specific reality Apply mode one to seven identical.
Specific embodiment nine：One of present embodiment and specific embodiment one to eight difference is：Will in step 2 Mixed solution is put into hydrothermal reaction kettle, then hydrothermal reaction kettle is warming up into 150 DEG C, then is 150 DEG C and mixing speed in temperature It is magnetic agitation reaction 1h under 50r/min, obtains reaction solution；Hydrothermal reaction kettle is quickly cooled to room temperature again, reaction solution is removed, Filtered again, obtained reactant；Washing 4 times is carried out to reactant using distilled water, then by the reactant after washing in temperature To dry 6h at 100 DEG C, hollow rod-shape Firebrake ZB is obtained.Other steps are identical with specific embodiment one to eight.
Specific embodiment ten：One of present embodiment and specific embodiment one to nine difference is：Will in step 2 Mixed solution is put into hydrothermal reaction kettle, then hydrothermal reaction kettle is warming up into 120 DEG C~140 DEG C, then temperature be 120 DEG C~ 140 DEG C is magnetic agitation reaction 2h~2.5h under 30r/min~60r/min with mixing speed, obtains reaction solution；It is again that hydro-thermal is anti- Answer kettle to be quickly cooled to room temperature, remove reaction solution, then filtered, obtain reactant；Reactant is washed using distilled water Wash 3 times~5 times, then the reactant after washing is dried into 4h~6h in the case where temperature is for 90 DEG C~100 DEG C, obtain hollow rod-shape boric acid Zinc.Other steps are identical with specific embodiment one to nine.
Beneficial effects of the present invention are verified using following examples：
Embodiment one：The preparation method of hollow rod-shape Firebrake ZB, is specifically realized by the following steps：
First, boric acid, zinc oxide and deionized water are well mixed, obtain mixed solution；
The amount of the material of the boric acid described in step one is 3.5mol with the volume ratio of deionized water:420mL；
The amount of the material of the zinc oxide described in step one is 1mol with the volume ratio of deionized water:420mL；
2nd, mixed solution is put into hydrothermal reaction kettle, then hydrothermal reaction kettle is warming up to 100 DEG C, then be 100 in temperature DEG C and mixing speed be 30r/min under magnetic agitation reaction 4h, obtain reaction solution；Hydrothermal reaction kettle is quickly cooled to room again Temperature, removes reaction solution, then is filtered, and obtains reactant；Washing 3 times is carried out to reactant using distilled water, then by after washing Reactant temperature be 90 DEG C at dry 8h, obtain hollow rod-shape Firebrake ZB.
Embodiment two：The preparation method of hollow rod-shape Firebrake ZB, is specifically realized by the following steps：
First, boric acid, zinc oxide and deionized water are well mixed, obtain mixed solution；
The amount of the material of the boric acid described in step one is 4mol with the volume ratio of deionized water:500mL；
The amount of the material of the zinc oxide described in step one is 1mol with the volume ratio of deionized water:500mL；
2nd, mixed solution is put into hydrothermal reaction kettle, then hydrothermal reaction kettle is warming up to 120 DEG C, then be 120 in temperature DEG C and mixing speed be 40r/min under magnetic agitation reaction 2.5h, obtain reaction solution；Hydrothermal reaction kettle is quickly cooled to room again Temperature, removes reaction solution, then is filtered, and obtains reactant；Washing 3 times is carried out to reactant using distilled water, then by after washing Reactant temperature be 100 DEG C at dry 6h, obtain hollow rod-shape Firebrake ZB.
Embodiment three：The preparation method of hollow rod-shape Firebrake ZB, is specifically realized by the following steps：
First, boric acid, zinc oxide and deionized water are well mixed, obtain mixed solution；
The amount of the material of the boric acid described in step one is 4.5mol with the volume ratio of deionized water:580mL；
The amount of the material of the zinc oxide described in step one is 1mol with the volume ratio of deionized water:580mL；
2nd, mixed solution is put into hydrothermal reaction kettle, then hydrothermal reaction kettle is warming up to 140 DEG C, then be 140 in temperature DEG C and mixing speed be 50r/min under magnetic agitation reaction 2h, obtain reaction solution；Hydrothermal reaction kettle is quickly cooled to room again Temperature, removes reaction solution, then is filtered, and obtains reactant；Washing 3 times is carried out to reactant using distilled water, then by after washing Reactant temperature be 120 DEG C at dry 4h, obtain hollow rod-shape Firebrake ZB.
Example IV：The preparation method of hollow rod-shape Firebrake ZB, is specifically realized by the following steps：
First, boric acid, zinc oxide and deionized water are well mixed, obtain mixed solution；
The amount of the material of the boric acid described in step one is 5mol with the volume ratio of deionized water:620mL；
The amount of the material of the zinc oxide described in step one is 1mol with the volume ratio of deionized water:620mL；
2nd, mixed solution is put into hydrothermal reaction kettle, then hydrothermal reaction kettle is warming up to 150 DEG C, then be 150 in temperature DEG C and mixing speed be 50r/min under magnetic agitation reaction 1h, obtain reaction solution；Hydrothermal reaction kettle is quickly cooled to room again Temperature, removes reaction solution, then is filtered, and obtains reactant；Washing 3 times is carried out to reactant using distilled water, then by after washing Reactant temperature be 100 DEG C at dry 6h, obtain hollow rod-shape Firebrake ZB.
Fig. 1 is the XRD spectrum of hollow rod-shape Firebrake ZB prepared by embodiment one；
From fig. 1, it can be seen that Firebrake ZB prepared by embodiment one is 2ZnO3B2O3·3.5H2O。
Fig. 2 is the SEM figures of hollow rod-shape Firebrake ZB prepared by embodiment one.
As can be seen from Figure 2, the boric acid zinc particles that prepared by embodiment one have stub shape, a diameter of 100~300nm, length It is 500~700nm, stub particle ordered arrangement forms the zinc borate power with hollow rod-shape structure, internal orifice dimension is 0.8 μm~ 1.2 μm, external diameter is 1.6 μm~2.5 μm, a length of 4 μm~6 μm of rod.
Hollow rod-shape Firebrake ZB prepared by embodiment one is used for halogen-free anti-flaming polyolefin as inorganic combustion inhibitor, and formula is such as Shown in table 1；
The halogen-free anti-flaming polyolefin of table 1
Hollow rod-shape Firebrake ZB prepared by embodiment one is used for halogen-free anti-flaming polyolefin elastomer as inorganic combustion inhibitor, Formula is as shown in table 2；
The halogen-free flameproof POE of table 2
Hollow rod-shape Firebrake ZB prepared by embodiment one is used for halogen-free flame-retardant thermoplastic elastomer as inorganic combustion inhibitor, Formula is as shown in table 3；
The halogen-free flameproof TPE of table 3
Hollow rod-shape Firebrake ZB prepared by embodiment one is used for halogen-free flame-retardant thermoplastic elastomer as inorganic combustion inhibitor, Formula is as shown in table 4；
The halogen-free polypropylene flame redardant of table 4
The oxygen index (OI) of each formula as shown in table 5, as can be seen from Table 5, adds hollow rod-shape boric acid prepared by embodiment one Zinc powder body is conducive to improving the fire resistance of bittern-free flame-proof material, and its main cause is：Hollow rod-shape structure increased thermal degradation During Firebrake ZB response area, meanwhile, hollow rod-shape zinc borate power structure can improve the dispersity of Firebrake ZB, this Outward, the nanostructured of boric acid zinc particles more can effectively play its fire retardation.Therefore, when same recipe compares, with commercialization boron Sour zinc is compared, and the oxygen index (OI) of the bittern-free flame-proof material of Firebrake ZB prepared by addition embodiment one increased 1.5~4.0 units. The fire resistance of the halogen-free anti-flaming polyolefin of table 5
Formula Formula 1 Formula 2 Formula 3 Formula 4 Formula 5 Formula 6 Formula 7 Formula 8
Oxygen index (OI) 33.0 29.0 32.5 29.5 31.5 28.0 30.0 28.5

Claims (10)

1. the preparation method of hollow rod-shape Firebrake ZB, it is characterised in that the preparation method of hollow rod-shape Firebrake ZB is specifically by following What step was completed：
First, boric acid, zinc oxide and deionized water are well mixed, obtain mixed solution；
The amount of the material of the boric acid described in step one is (3mol~5mol) with the volume ratio of deionized water:(400mL~ 700mL)；
The amount of the material of the zinc oxide described in step one is 1mol with the volume ratio of deionized water:(400mL~700mL)；
2nd, mixed solution is put into hydrothermal reaction kettle, then hydrothermal reaction kettle is warming up to 100 DEG C~160 DEG C, then be in temperature 100 DEG C~160 DEG C is magnetic agitation reaction 0.5h~4h under 30r/min~60r/min with mixing speed, obtains reaction solution；Again Hydrothermal reaction kettle is quickly cooled to room temperature, reaction solution is removed, then is filtered, obtain reactant；Using distilled water to reaction Thing carries out washing 3 times~5 times, then the reactant after washing is dried into 4h~8h in the case where temperature is for 90 DEG C~120 DEG C, obtains hollow Bar-shaped Firebrake ZB.
2. the preparation method of hollow rod-shape Firebrake ZB according to claim 1, it is characterised in that in step 2 that hydro-thermal is anti- Answer kettle to be quickly cooled to during hydrothermal reaction kettle is put into room-temperature water bath by room temperature to be cooled down.
3. the preparation method of hollow rod-shape Firebrake ZB according to claim 1, it is characterised in that the boron described in step one The amount of the material of acid is 3.5mol with the volume ratio of deionized water:(420mL~700mL).
4. the preparation method of hollow rod-shape Firebrake ZB according to claim 1, it is characterised in that the boron described in step one The amount of the material of acid is (3mol~4mol) with the volume ratio of deionized water:(400mL~500mL).
5. the preparation method of hollow rod-shape Firebrake ZB according to claim 1, it is characterised in that the boron described in step one The amount of the material of acid is (3mol~4.5mol) with the volume ratio of deionized water:(400mL~580mL).
6. the preparation method of hollow rod-shape Firebrake ZB according to claim 1, it is characterised in that the boron described in step one The amount of the material of acid is 5mol with the volume ratio of deionized water:(400mL~620mL).
7. the preparation method of hollow rod-shape Firebrake ZB according to claim 1, it is characterised in that the oxygen described in step one The amount of material and the volume ratio of deionized water for changing zinc are 1mol:(420mL~500mL).
8. the preparation method of hollow rod-shape Firebrake ZB according to claim 1, it is characterised in that the oxygen described in step one The amount of material and the volume ratio of deionized water for changing zinc are 1mol:(580mL~620mL).
9. the preparation method of hollow rod-shape Firebrake ZB according to claim 1, it is characterised in that will mix in step 2 molten Liquid is put into hydrothermal reaction kettle, then hydrothermal reaction kettle is warming up into 150 DEG C, then it is 50r/ with mixing speed to be 150 DEG C in temperature Magnetic agitation reaction 1h, obtains reaction solution under min；Hydrothermal reaction kettle is quickly cooled to room temperature again, reaction solution is removed, then carry out Filtering, obtains reactant；Using distilled water to reactant carry out washing 4 times, then by the reactant after washing temperature be 100 DEG C Lower drying 6h, obtains hollow rod-shape Firebrake ZB.
10. the preparation method of hollow rod-shape Firebrake ZB according to claim 1, it is characterised in that will mix in step 2 molten Liquid is put into hydrothermal reaction kettle, then hydrothermal reaction kettle is warming up into 120 DEG C~140 DEG C, then temperature be 120 DEG C~140 DEG C and Mixing speed is magnetic agitation reaction 2h~2.5h under 30r/min~60r/min, obtains reaction solution；It is again that hydrothermal reaction kettle is fast Speed is cooled to room temperature, removes reaction solution, then is filtered, and obtains reactant；Using distilled water to reactant carry out washing 3 times~ 5 times, then the reactant after washing is dried into 4h~6h in the case where temperature is for 90 DEG C~100 DEG C, obtain hollow rod-shape Firebrake ZB.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1789135A (en) * 2005-12-12 2006-06-21 中国科学院青海盐湖研究所 Hydrothermal method for preparation of shape-controllable low-hydrate zinc borate powder
CN101254927A (en) * 2008-03-28 2008-09-03 江南大学 Method for preparing active zinc borate by one-step proccess
CN101508444A (en) * 2009-03-30 2009-08-19 梁宝忠 Process for producing dewatering nano-sheet zinc borate power

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1789135A (en) * 2005-12-12 2006-06-21 中国科学院青海盐湖研究所 Hydrothermal method for preparation of shape-controllable low-hydrate zinc borate powder
CN101254927A (en) * 2008-03-28 2008-09-03 江南大学 Method for preparing active zinc borate by one-step proccess
CN101508444A (en) * 2009-03-30 2009-08-19 梁宝忠 Process for producing dewatering nano-sheet zinc borate power

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