CN104211989B - Preparation method of organic acid-doped hydrophobic zinc borate 411 - Google Patents
Preparation method of organic acid-doped hydrophobic zinc borate 411 Download PDFInfo
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- CN104211989B CN104211989B CN201410459162.1A CN201410459162A CN104211989B CN 104211989 B CN104211989 B CN 104211989B CN 201410459162 A CN201410459162 A CN 201410459162A CN 104211989 B CN104211989 B CN 104211989B
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Abstract
The invention discloses a preparation method of organic acid-doped hydrophobic zinc borate 411, belonging to the field of inorganic materials. The preparation method is characterized in that organic acid, a boron source and a zinc source are mixed through a direct solvothermal one-step method, so that the organic acid is doped into zinc borate 411; or organic acid, a boron source and a zinc source are mixed through a hydrothermal and chemical precipitation combined two-step method, so that the organic acid is doped into zinc borate 411. By using the method, a zinc borate inorganic-organic hybrid material having favorable hydrophobicity can be conveniently prepared, and the prepared product is high in activity, regular in shape and favorable in dispersivity.
Description
Technical field
The invention belongs to field of inorganic materials, and in particular to a kind of organic acid doped hydrophobic 4ZnOB2O3·H2O boric acid
The preparation method of zinc, obtains a kind of Inorganic-Organic Hybrid Material with good hydrophobic performance.
Background technology
Firebrake ZB can be added in the materials such as polyvinyl chloride (PVC), polyolefin, polyamide, polyurethane, as effective
Fire retardant, rush coking agent, anti-dripping agent and smoke suppressant.By putting into practice for many years, people have prepared the hydration boron of various different compositions
Sour zinc such as 2ZnO3B2O3·3H2O、2ZnO·3B2O3·3.5H2O、2ZnO·3B2O3·7H2O and 4ZnOB2O3·H2O
Deng, and their fire resistance is studied in detail.
Because boric acid zinc surface carries electric charge, with stronger hydrophily, the deployment conditions when being blended with macromolecular material
Difference, is easily caused the mechanical properties decrease of macromolecular material.People are typically using by Firebrake ZB building-up process at this stage
The method for adding organic formwork agent, is modified to Firebrake ZB particle surface.
With other several hydration zinc borate compound phase ratios, 411 type (4ZnOB2O3·H2O) Firebrake ZB dehydration temperaturre 415
DEG C, it is that heat endurance is good, nontoxic, inexpensive, one of superior flame retardant property halogen-free flame retardants.Using PEG-300 as template,
Hydro-thermal method can prepare the 4ZnOB of the bar-shaped of different-shape, wire, stratiform and nano-micrometer rod microspheroidal structure2O3·H2It is O-shaped
Firebrake ZB, wherein, the addition of template PEG-300 serves vital effect for the formation of specific morphology Firebrake ZB.
There is document report with phosphate as soft template, Na2B4O7·10H2O and Zn (NO3)2·6H2O is raw material, is precipitated by a step
Reaction is prepared for 4ZnOB2O3·H2O nano whiskers, it can improve its heat endurance in being added to polyvinyl chloride.People survey
4ZnOB is tried2O3·H2The fire resistance of O nano-clusters and nanobelt, finds there is nanostructured 4ZnO by combustion experiment
B2O3·H2O-shaped Firebrake ZB has better flame resistance than non-nano structure sample.But numerous results of study show：Large scale
Nanometer boron after Firebrake ZB is difficult to be doped in the middle of polymer, and its fire resistance is surfactant-modified not as good as PEG etc.
Sour zinc fiber, whisker, nanosphere etc..Therefore, carry out organic molecule to boric acid zinc surface to be modified, improve inorganic boric acid zinc impregnation and close
The compatibility of thing and polymeric material, tool is of great significance.
The content of the invention
Present invention aim at a kind of preparation method of organic acid doped hydrophobic 411 type Firebrake ZB is provided, by more
Easy method prepares the Firebrake ZB Inorganic-Organic Hybrid Material with good hydrophobic performance, and products obtained therefrom activity is high, pattern
Rule, good dispersion.
The present invention for reach technical scheme that above-mentioned purpose used for：
A kind of preparation method of organic acid doped hydrophobic 411 type Firebrake ZB, the one-step method using direct solvent heat will have
Machine acid, boron source and the mixing of zinc source, by organic acid doped in 411 type Firebrake ZBs, or are mutually tied using hydro-thermal method with chemical precipitation method
By organic acid, boron source and zinc source mix the two step method of conjunction, by organic acid doped in 411 type Firebrake ZBs.
The preparation method of described a kind of organic acid doped hydrophobic 411 type Firebrake ZB, the one-step method tool of the solvent heat
Body is to take during zinc source, boron source and organic acid are dissolved in the mixed liquor of 6mL deionized waters and 1mL ethanol to be modulated into suspension；By gained
Suspension be transferred in closed synthesis reaction vessel, after solvent thermal reaction 8-24h is carried out at 100-180 DEG C, cooling, filtering,
Washing, drying.Described organic acid is that solid organic acid includes ethanedioic acid, malonic acid, succinic acid, glutaric acid, adipic acid, heptan two
Acid, tartaric acid, malic acid, n-capric acid, laurate, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignin acid, wax
Acid, montanic acid, beeswax acid.It is zinc oxide or zinc nitrate in the zinc source, the boron source is boric acid or borax, and the zinc source contains
Zinc amount is 1 with the boron content of boron source and the ratio of organic acid：1~4：0.1~1.
The preparation method of described a kind of organic acid doped hydrophobic 411 type Firebrake ZB, the hydro-thermal method and chemical precipitation
The two step method that method is combined be specially take zinc source and boron source be dissolved in the mixed liquor of 6mL deionized waters and 1mL ethanol be modulated into it is outstanding
Turbid liquid；The suspension of gained is transferred in closed hydrothermal synthesis reaction kettle, after hydro-thermal reaction 8-24h is carried out at 100-180 DEG C,
Take out, cooling, filtering, washing obtains 411 type Firebrake ZBs after drying；It is 3 that 411 type Firebrake ZBs are added into volume ratio：1 distilled water
In the mixed liquor of absolute ethyl alcohol, then to organic acid is added dropwise in mixed liquor, it is heated to reflux through 80 DEG C, after stirring 5h, cooling, mistake
Filter, washing, drying.Described organic acid is that liquid organic acid includes propionic acid, n-butyric acie, positive valeric acid, n-caproic acid, positive enanthic acid, just
Octanoic acid, acrylic acid, oleic acid, linoleic acid, linolenic acid.The zinc source is zinc oxide or zinc nitrate.The boron source is boric acid or boron
Sand.The zinc content in the zinc source is 1 with the ratio of the boron content of boron source and organic acid：1~4：0.1~1.
Using a kind of above-mentioned organic acid doped hydrophobic 411 type Firebrake ZB preparation method prepare Firebrake ZB in macromolecule
Used as additive in polymer.
The high molecular polymer is polymethyl methacrylate, polystyrene, and the Firebrake ZB is in polymethylacrylic acid
Addition usage amount in the high molecular polymers such as methyl esters, polystyrene is 25%-35%.
The beneficial effects of the invention are as follows：
Organic acid doped hydrophobic 411 type Firebrake ZB prepared by the present invention, due to organic acid doped in zinc borate products,
There are polarity carboxyl and apolar organic chains in organic acid molecule, products molecule has certain oleophilic drainage characteristic simultaneously, while
Also there is certain coordinate bonding capability, the compatibility at interface between inorganic Firebrake ZB and polymer molecule is enhanced.Obtained with this
What is obtained is high through organic acid doped Firebrake ZB activity, can be evenly dispersed in polymer, improves the mechanical property of polymer
And product appearance, for relatively purely inorganic Firebrake ZB, the organic acid doped Firebrake ZB additive as polymer preferably
Use.
Present invention process is easily controllable, simple to operate, short preparation period, low production cost, good product quality, can pass through
Control reaction condition obtains the organic acid doped Firebrake ZB of not jljl phase.
Brief description of the drawings
Fig. 1 is organic acid doped hydrophobic 411 type Firebrake ZB and the contrast of the gained of embodiment 11,12,14,8 in the present invention
The scanning electron microscope (SEM) photograph of 411 type Firebrake ZBs of non-organic acid doping in experiment.
In figure, a：411 type Firebrake ZBs of non-organic acid doping in contrast experiment；b：It is hydrophobic that the malonic acid of embodiment 11 adulterates
411 type Firebrake ZBs；c：The hydrophobic 411 type Firebrake ZB of the succinic acid of embodiment 12 doping；d：It is hydrophobic that the adipic acid of embodiment 14 adulterates
411 type Firebrake ZBs；e：The hydrophobic 411 type Firebrake ZB of the oleic acid of embodiment 8 doping.
Fig. 2 has for non-in the hydrophobic 411 type Firebrake ZB of the adipic acid doping of the gained of the embodiment of the present invention 14 and contrast experiment
The infrared spectrogram of 411 type Firebrake ZBs of machine acid doping.
In figure, a：411 type Firebrake ZBs of non-organic acid doping in contrast experiment；b：It is hydrophobic that the adipic acid of embodiment 14 adulterates
411 type Firebrake ZBs.
Fig. 3 is organic acid doped hydrophobic 411 type Firebrake ZB and the contrast of the gained of embodiment 6,12,13,14 in the present invention
411 type Firebrake ZB X-ray powder diffraction patterns of non-organic acid doping in experiment.
In figure, a：411 type Firebrake ZBs of non-organic acid doping in contrast experiment；b：It is hydrophobic that the glutaric acid of embodiment 13 adulterates
411 type Firebrake ZBs；c：The hydrophobic 411 type Firebrake ZB of the succinic acid of embodiment 12 doping；d：It is hydrophobic that the adipic acid of embodiment 14 adulterates
411 type Firebrake ZBs；e：The hydrophobic type Firebrake ZB of the n-caproic acid of embodiment 6 doping.
Fig. 4 is non-organic acid in the hydrophobic 411 type Firebrake ZB that the oleic acid obtained by the embodiment of the present invention 8 adulterates and contrast experiment
The contact angle photo of 411 type Firebrake ZBs of doping.
In figure, a：411 type Firebrake ZBs of non-organic acid doping in contrast experiment；b：Hydrophobic 411 type of the oleic acid of embodiment 8 doping
Firebrake ZB.
Fig. 5 is the oil in the hydrophobic 411 type Firebrake ZB and embodiment 8 of the oleic acid doping in polystyrene microsphere, embodiment 8
The hydrophobic 411 type Firebrake ZB of acid doping and the INFRARED SPECTRUM of polystyrene microsphere compound.
A is the infrared spectrum of the hydrophobic 411 type Firebrake ZB of the oleic acid doping in embodiment 8 in figure；B is polystyrene microsphere
Infrared spectrum；The hydrophobic 411 type Firebrake ZB of the oleic acid doping in c embodiments 8 and the infrared light of polystyrene microsphere compound
Spectrum.
Fig. 6 is the thermogravimetric test result of polymer and compound.
1 is the thermogravimetric of the hydrophobic 411 type Firebrake ZB with polystyrene microsphere compound of the oleic acid doping in embodiment 8 in figure
Test result；2 is the thermogravimetric test result of polystyrene microsphere in figure.
Fig. 7 is the sem test photo of polymer and compound.
A is the sem test photo of polystyrene microsphere in figure；B is dredging for the oleic acid doping in embodiment 8 in figure
The sem test photo of the type Firebrake ZB of water 411 and polystyrene microsphere compound.
Specific embodiment
With reference to embodiments, the present invention is further described in detail, but is not limited to this.Adopted in the following example
Chemicals is all commercial chemicals.
A kind of organic acid doped hydrophobic 4ZnOB of embodiment 12O3·H2The preparation method of O Firebrake ZBs
1) weigh 0.16g (0.002mol) zinc oxide respectively and 0.12g (0.002mol) boric acid be dissolved in 6mL deionized waters and
In 1mL ethanol, suspension is modulated into.
2) gained suspension is transferred in closed hydrothermal synthesis reaction kettle, is reacted 8 hours in 100 DEG C, take out reactor
Room temperature is cooled to, product is filtered out, washed, dry to obtain 4ZnOB2O3·H2O-shaped Firebrake ZB.
3) 4ZnOB of a certain amount of hydro-thermal method synthesis is added in round-bottomed flask2O3·H2O Firebrake ZBs, solvent steams for 30ml
Distilled water and 10ml absolute ethyl alcohols (volume ratio 3:1) mixed liquor, is added dropwise 0.0015g (0.0002mol) propionic acid thereto, and 80 DEG C add
Heat, stirring, backflow, the reaction time is 5h.Reaction is finished and is cooled to room temperature, is filtered, washing, drying, obtains final product dredging for propionic acid doping
The type Firebrake ZB of water 411.
A kind of organic acid doped hydrophobic 4ZnOB of embodiment 22O3·H2The preparation method of O Firebrake ZBs
1) weigh 0.16g (0.002mol) zinc oxide respectively and 0.37g (0.006mol) boric acid be dissolved in 6mL deionized waters and
In 1mL ethanol, suspension is modulated into.
2) resulting solution is transferred in closed hydrothermal synthesis reaction kettle, is reacted 15 hours in 100 DEG C, take out reactor cold
But to room temperature, product is filtered out, is washed, dry to obtain 4ZnOB2O3·H2O-shaped Firebrake ZB.
3) 4ZnOB of a certain amount of hydro-thermal method synthesis is added in round-bottomed flask2O3·H2O Firebrake ZBs, solvent steams for 30ml
Distilled water and 10ml absolute ethyl alcohols (volume ratio 3:1) mixed liquor, is added dropwise 0.037g (0.0005mol) propionic acid thereto, and 80 DEG C are heated,
Stirring, backflow, the reaction time is 5h.Reaction is finished and is cooled to room temperature, is filtered, washing, drying, obtains final product the hydrophobic of propionic acid doping
411 type Firebrake ZBs.
A kind of organic acid doped hydrophobic 4ZnOB of embodiment 32O3·H2The preparation method of O Firebrake ZBs
1) weigh 0.59g (0.002mol) zinc nitrates respectively and 0.76g (0.002mol) borax be dissolved in 6mL deionized waters and
In 1mL ethanol, suspension is modulated into.
2) resulting solution is transferred in closed hydrothermal synthesis reaction kettle, is reacted 15 hours in 140 DEG C, take out reactor cold
But to room temperature, product is filtered out, is washed, dry to obtain 4ZnOB2O3·H2O-shaped Firebrake ZB.
3) 4ZnOB of a certain amount of hydro-thermal method synthesis is added in round-bottomed flask2O3·H2O Firebrake ZBs, solvent steams for 30ml
Distilled water and 10ml absolute ethyl alcohols (volume ratio 3:1) mixed liquor, is added dropwise 0.05g (0.0007mol) propionic acid thereto, and 80 DEG C are heated,
Stirring, backflow, the reaction time is 5h.Reaction is finished and is cooled to room temperature, is filtered, washing, drying, obtains final product the hydrophobic of propionic acid doping
411 type Firebrake ZBs.
A kind of organic acid doped hydrophobic 4ZnOB of embodiment 42O3·H2The preparation method of O Firebrake ZBs
1) weigh 0.59g (0.002mol) zinc nitrates respectively and 0.76g (0.002mol) borax be dissolved in 6mL deionized waters and
In 1mL ethanol, suspension is modulated into.
2) resulting solution is transferred in closed hydrothermal synthesis reaction kettle, is reacted 24 hours in 180 DEG C, take out reactor cold
But to room temperature, product is filtered out, is washed, dry to obtain 4ZnOB2O3·H2O-shaped Firebrake ZB.
3) 4ZnOB of a certain amount of hydro-thermal method synthesis is added in round-bottomed flask2O3·H2O Firebrake ZBs, solvent steams for 30ml
Distilled water and 10ml absolute ethyl alcohols (volume ratio 3:1) mixed liquor, is added dropwise 0.07g (0.001mol) propionic acid thereto, and 80 DEG C of heating are stirred
Mix, flow back, the reaction time is 5h.Reaction is finished and is cooled to room temperature, is filtered, washing, drying, obtains final product hydrophobic the 411 of propionic acid doping
Type Firebrake ZB.
A kind of organic acid doped hydrophobic 4ZnOB of embodiment 52O3·H2The preparation method of O Firebrake ZBs
1) weigh 0.59g (0.002mol) zinc nitrates respectively and 0.76g (0.002mol) borax be dissolved in 6mL deionized waters and
In 1mL ethanol, suspension is modulated into.
2) resulting solution is transferred in closed hydrothermal synthesis reaction kettle, is reacted 24 hours in 180 DEG C, take out reactor cold
But to room temperature, product is filtered out, is washed, dry to obtain 4ZnOB2O3·H2O-shaped Firebrake ZB.
3) 4ZnOB of a certain amount of hydro-thermal method synthesis is added in round-bottomed flask2O3·H2O Firebrake ZBs, solvent steams for 30ml
Distilled water and 10ml absolute ethyl alcohols (volume ratio 3:1) mixed liquor, is added dropwise 0.176g (0.002mol) n-butyric acie thereto, and 80 DEG C add
Heat, stirring, backflow, the reaction time is 5h.Reaction is finished and is cooled to room temperature, is filtered, washing, drying, obtains final product n-butyric acie doping
Hydrophobic 411 type Firebrake ZB.
A kind of organic acid doped hydrophobic 4ZnOB of embodiment 62O3·H2The preparation method of O Firebrake ZBs
1) weigh 0.59g (0.002mol) zinc nitrates respectively and 0.76g (0.002mol) borax be dissolved in 6mL deionized waters and
In 1mL ethanol, suspension is modulated into.
2) resulting solution is transferred in closed hydrothermal synthesis reaction kettle, is reacted 24 hours in 180 DEG C, take out reactor cold
But to room temperature, product is filtered out, is washed, dry to obtain 4ZnOB2O3·H2O-shaped Firebrake ZB.
3) 4ZnOB of a certain amount of hydro-thermal method synthesis is added in round-bottomed flask2O3·H2O Firebrake ZBs, solvent steams for 30ml
Distilled water 10ml absolute ethyl alcohol (volume ratios 3:1) mixed liquor, is added dropwise 0.116g (0.001mol) n-caproic acid thereto, and 80 DEG C are heated,
Stirring, backflow, the reaction time is 5h.Reaction is finished and is cooled to room temperature, is filtered, washing, drying, obtains final product the hydrophobic of n-caproic acid doping
411 type Firebrake ZBs.
A kind of organic acid doped hydrophobic 4ZnOB of embodiment 72O3·H2The preparation method of O Firebrake ZBs
1) weigh 0.59g (0.002mol) zinc nitrates respectively and 0.76g (0.002mol) borax be dissolved in 6mL deionized waters and
In 1mL ethanol, suspension is modulated into,
2) resulting solution is transferred in closed hydrothermal synthesis reaction kettle, is reacted 24 hours in 180 DEG C, take out reactor cold
But to room temperature, product is filtered out, is washed, dry to obtain 4ZnOB2O3·H2O-shaped Firebrake ZB.
3) 4ZnOB of a certain amount of hydro-thermal method synthesis is added in round-bottomed flask2O3·H2O Firebrake ZBs, solvent steams for 30ml
Distilled water and 10ml absolute ethyl alcohols (volume ratio 3:1) mixed liquor, is added dropwise 0.072g (0.001mol) acrylic acid thereto, and 80 DEG C add
Heat, stirring, backflow, the reaction time is 5h.Reaction is finished and is cooled to room temperature, is filtered, washing, and drying obtains final product propylene acid doping
Hydrophobic 411 type Firebrake ZB.
A kind of organic acid doped hydrophobic 4ZnOB of embodiment 82O3·H2The preparation method of O Firebrake ZBs
1) weigh 0.59g (0.002mol) zinc nitrates respectively and 0.76g (0.002mol) borax be dissolved in 6mL deionized waters and
In 1mL ethanol, suspension is modulated into,
2) resulting solution is transferred in closed hydrothermal synthesis reaction kettle, is reacted 24 hours in 180 DEG C, take out reactor cold
But to room temperature, product is filtered out, is washed, dry to obtain 4ZnOB2O3·H2O-shaped Firebrake ZB.
3) 4ZnOB of a certain amount of hydro-thermal method synthesis is added in round-bottomed flask2O3·H2O Firebrake ZBs, solvent steams for 30ml
Distilled water and 10ml absolute ethyl alcohols (volume ratio 3:1) mixed liquor, is added dropwise 0.28g (0.001mol) oleic acid thereto, and 80 DEG C of heating are stirred
Mix, flow back, the reaction time is 5h.Reaction is finished and is cooled to room temperature, is filtered, washing, drying, obtains final product hydrophobic the 411 of oleic acid doping
Type Firebrake ZB.
A kind of organic acid doped hydrophobic 4ZnOB of embodiment 92O3·H2The preparation method of O Firebrake ZBs
1) 0.59g (0.002mol) zinc nitrate, 0.76g (0.002mol) boraxs and 0.04g (0.0004mol) are weighed respectively
Malonic acid is dissolved in 6mL deionized waters and 1mL ethanol, is modulated into suspension,
2) resulting solution is transferred in closed synthesis reaction vessel and is reacted 8 hours in 120 DEG C, taken out reactor and be cooled to room
Temperature, filters out product, washing, and drying obtains final product the hydrophobic 411 type Firebrake ZB of malonic acid doping.
A kind of organic acid doped hydrophobic 4ZnOB of embodiment 102O3·H2The preparation method of O Firebrake ZBs
1) 0.16g (0.002mol) zinc oxide and 0.25g (0.004mol) boric acid and 0.083g are weighed respectively
(0.0008mol) malonic acid is dissolved in 6mL deionized waters and 1mL ethanol, is modulated into suspension.
2) resulting solution is transferred in closed synthesis reaction vessel and is reacted 20 hours in 140 DEG C, taken out reactor and be cooled to
Room temperature, filters out product, washing, and drying obtains final product the hydrophobic 411 type Firebrake ZB of malonic acid doping.
A kind of organic acid doped hydrophobic 4ZnOB of embodiment 112O3·H2The preparation method of O Firebrake ZBs
1) 0.16g (0.002mol) zinc oxide and 0.37g (0.006mol) boric acid and 0.10g (0.001mol) are weighed respectively
Malonic acid is dissolved in 6mL deionized waters and 1mL ethanol, is modulated into suspension.
2) resulting solution is transferred in closed synthesis reaction vessel and is reacted 24 hours in 180 DEG C, taken out reactor and be cooled to
Room temperature, filters out product, washing, and drying obtains final product the hydrophobic 411 type Firebrake ZB of malonic acid doping.
A kind of organic acid doped hydrophobic 4ZnOB of embodiment 122O3·H2The preparation method of O Firebrake ZBs
1) 0.16g (0.002mol) zinc oxide and 0.37g (0.006mol) boric acid and 0.12g (0.001mol) are weighed respectively
Succinic acid is dissolved in 6mL deionized waters and 1mL ethanol, is modulated into suspension.
2) resulting solution is transferred in closed synthesis reaction vessel and is reacted 24 hours in 180 DEG C, taken out reactor and be cooled to
Room temperature, filters out product, washing, and drying obtains final product the hydrophobic 411 type Firebrake ZB of succinic acid doping.
A kind of organic acid doped hydrophobic 4ZnOB of embodiment 132O3·H2The preparation method of O Firebrake ZBs
1) 0.16g (0.002mol) zinc oxide and 0.37g (0.006mol) boric acid and 0.13g are weighed respectively
(0.001mmol) glutaric acid is dissolved in 6mL deionized waters and 1mL ethanol, is modulated into suspension.
2) resulting solution is transferred in closed synthesis reaction vessel and is reacted 24 hours in 180 DEG C, taken out reactor and be cooled to
Room temperature, filters out product, washing, and drying obtains final product the hydrophobic 411 type Firebrake ZB of glutaric acid doping.
A kind of organic acid doped hydrophobic 4ZnOB of embodiment 142O3·H2The preparation method of O Firebrake ZBs
1) 0.16g (0.002mol) zinc oxide and 0.37g (0.006mol) boric acid and 0.15g are weighed respectively
(0.001mmol) adipic acid is dissolved in 6mL deionized waters and 1mL ethanol, is modulated into suspension.
2) resulting solution is transferred in closed synthesis reaction vessel and is reacted 24 hours in 180 DEG C, taken out reactor and be cooled to
Room temperature, filters out product, washing, and drying obtains final product the hydrophobic 411 type Firebrake ZB of adipic acid doping.
A kind of organic acid doped hydrophobic 4ZnOB of embodiment 152O3·H2The preparation method of O Firebrake ZBs
1) 0.16g (0.002mol) zinc oxide and 0.37g (0.006mol) boric acid and 0.51g are weighed respectively
(0.002mmol) palmitic acid is dissolved in 6mL deionized waters and 1mL ethanol, is modulated into suspension.
2) resulting solution is transferred in closed synthesis reaction vessel and is reacted 24 hours in 180 DEG C, taken out reactor and be cooled to
Room temperature, filters out product, washing, and drying obtains final product the hydrophobic 411 type Firebrake ZB of palmitin acid doping
Contrast experiment 1
1) weigh 0.59g (0.002mol) zinc nitrates respectively and 0.76g (0.002mol) borax be dissolved in 6mL deionized waters and
In 1mL ethanol, suspension is modulated into,
2) resulting solution is transferred in closed hydrothermal synthesis reaction kettle and is reacted 24 hours in 180 DEG C, take out reactor cold
But to room temperature, product is filtered out, is washed, dry to obtain 411 type Firebrake ZBs.
Test result
1. the 411 organic acid doped type Firebrake ZBs that pair the inventive method embodiment 11,12,14,8 is prepared (divide
Not through malonic acid, succinic acid, hexanedioic acid and oleic acid adulterate Firebrake ZB) and contrast experiment in non-organic acid doping 4ZnO
B2O3·H2O Firebrake ZBs are scanned electron microscope (SEM) test respectively, and test result is as shown in Figure 1.
Fig. 1-a are the 4ZnOB of non-organic acid doping2O3·H2O Firebrake ZBs, compound pattern is bar-shaped.Fig. 1-b, c, d,
E difference malonic acid, succinic acid, adipic acid, the 4ZnOB of oleic acid doping2O3·H2O Firebrake ZBs.It can be seen that doping is organic
After acid, there are some changes in compound pattern, and without substantially reunion, dispersiveness is preferably.Compound after malonic acid, succinic acid doping
Pattern is changed into flake, and compound is changed into bar-shaped and granular mixing pattern after adipic acid doping.Change after being adulterated through oleic acid
Compound pattern is changed into relatively regular palpus shape.
2. the hydrophobic 4ZnOB of the target product adipic acid doping that pair the inventive method embodiment 14 is prepared2O3·
H2The 4ZnOB of the non-organic acid doping prepared in O Firebrake ZBs and contrast experiment2O3·H2O Firebrake ZBs carry out infrared respectively
Spectrogram (IR) is tested, and as shown in Figure 2, Fig. 2-a are non-organic acid doping 4ZnOB in contrast experiment to test result2O3·H2O
The infrared spectrum of Firebrake ZB, Fig. 2-b are the 4ZnOB of adipic acid doping2O3·H2The infrared spectrum of O Firebrake ZBs.
Characteristic absorption wave number ownership to them is as follows：3363cm-1, 3402cm-1The strong absworption peak in vicinity is [O-H]
The stretching vibration of key；959~1419cm-1Place's absworption peak is respectively three-fold coordination boron oxygen key [B(3)- O] stretching vibration；1244cm-1
Vicinity absworption peak is attributed to the in-plane bending vibration of [B-O-H] key；716cm-1Vicinity absworption peak is attributed to [B(3)- O] key
Out-of-plane bending vibration；530cm-1Place's absworption peak is attributed to [B(3)- O] key flexural vibrations.These results explanation gained Firebrake ZB knot
Structure is 4ZnOB2O3·H2O.1545cm in Fig. 2-b-1、900cm-1The stretching vibration that vicinity absworption peak is attributed to carboxyl absorbs
Peak.2932cm-1Vicinity absworption peak is attributed to the flexural vibrations of alkyl chain.Illustrate to contain organic acid chemical combination in the Firebrake ZB of synthesis
Thing.Successfully organic acid doped zinc borate compound is synthesized.
3rd, the organic acid doped 4ZnOB prepared to the inventive method embodiment 6,12,13,142O3·H2O boric acid
What is prepared in zinc (Firebrake ZB for being adulterated through n-caproic acid, succinic acid, glutaric acid and hexanedioic acid respectively) and contrast experiment is non-
Organic acid doped 4ZnOB2O3·H2O Firebrake ZBs carry out X-ray powder diffraction (XRD) test respectively, and test result is such as
Shown in accompanying drawing 3.
Fig. 3-a are non-organic acid doping 4ZnOB in contrast experiment2O3·H2The XRD of O Firebrake ZBs, in figure(2θ/°)
It is 4.71 (18.8), 2.82 (31.6), 4.04 (21.98), 1.55 (59.75), 2.64 (33.80), 3.98 (22.40), 3.13
(28.47), 2.46 (36.76), 2.39 (37.66) is 4ZnOB2O3·H2The diffraction maximum of O.Fig. 3-b are the boron of glutaric acid doping
The XRD of sour zinc,(2 θ/°) it is 6.90 (12.75), 3.87 (22.99), 4.77 (18.64), 4.35 (20.38), 3.32
(26.87), 2.80 (31.84), 2.31 (38.89), 2.08 (43.45) is consistent with the diffraction maximum of glutaric acid.Fig. 3-c are succinic acid
The XRD of the Firebrake ZB of doping,For 5.87 (15.07), 4.56 (19.51), 2.75 (32.55), 3.30 (26.92),
3.57 (24.84), 2.31 (39.07) is consistent with the diffraction maximum of succinic acid.Fig. 3-d are the Firebrake ZB XRDs of adipic acid doping,(2 θ/°) it is 8.06 (11.01), 4.12 (21.54), 3.52 (25.28), 3.08 (28.95), 2.69 (33.23), 2.27
(39.64) it is the diffraction maximum of adipic acid.Fig. 3-e be n-caproic acid doping Firebrake ZB XRD, 2 θ/° for 31.6 °, 34.4 °,
36.2 °, 56.5 °, 59.8 °, 62.8 °, 67.9 °, 69 ° of diffraction maximum belong to the diffraction maximum of n-caproic acid.
4th, contact angle analysis：The oleic acid doping 4ZnOB prepared to the inventive method embodiment 82O3·H2O boric acid
The 4ZnOB of the non-organic acid doping prepared in zinc and contrast experiment2O3·H2O Firebrake ZBs carry out contact angle analysis respectively,
Result as shown in Figure 4, contrasts the contact angle of the Firebrake ZB of oleic acid doping and non-acid doping, and after doping oleic acid, contact angle shows
Increase is write, is 128 ° 6, hydrophobicity enhancing.
Using a kind of organic acid doped hydrophobic 411 type Firebrake ZB preparation method prepare Firebrake ZB in high molecular polymerization
Used as additive in thing
Firebrake ZB prepared by a kind of preparation method of the organic acid doped hydrophobic 411 type Firebrake ZB of embodiment 16 is in polyphenyl second
Addition in alkene microballoon.
Claim 0.3g polystyrene microspheres in round-bottomed flask, add deionized water, 90 DEG C of heating-up temperature to stir and flow back
1h, adds the hydrophobic 411 type Firebrake ZB of the oleic acid doping in the embodiment 8 of polymer microsphere quality 30%, maintains this temperature
Degree continues to stir 3d, stops heating, and filtration washing is simultaneously dried.
Test result
1st, during Fig. 5 is hydrophobic 411 type Firebrake ZB, polystyrene microsphere and the embodiment 8 of the oleic acid doping in embodiment 8
The hydrophobic 411 type Firebrake ZB of oleic acid doping and the INFRARED SPECTRUM of polystyrene microsphere compound, a is the oleic acid in embodiment 8 in figure
The infrared spectrum of the hydrophobic 411 type Firebrake ZB of doping；B is the infrared spectrum of polystyrene microsphere；Oleic acid in c embodiments 8 is mixed
Miscellaneous hydrophobic 411 type Firebrake ZB and the infrared spectrum of polystyrene microsphere compound.As shown in Figure 5, the infrared spectrum of compound
In there are the characteristic absorption peak of boric acid modification zinc and polystyrene microsphere simultaneously.
2nd, Fig. 6 is the thermogravimetric test result of polymer and compound, and 1 is the hydrophobic of the oleic acid doping in embodiment 8 in figure
The thermogravimetric test result of 411 type Firebrake ZBs and polystyrene microsphere compound；2 is the thermogravimetric test knot of polystyrene microsphere in figure
Really.As can be seen that compound is weightless until 420 DEG C since 300 DEG C, it is 30% to lose mass fraction；And polystyrene microsphere
Until 430 DEG C, it is 35% to lose quality to weightlessness since 280 DEG C, it can be seen that, the better heat stability of compound.
3rd, Fig. 7 is the sem test photo of polymer and compound, and a is the oleic acid doping in embodiment 8 in figure
The sem test photo of hydrophobic 411 type Firebrake ZB and polystyrene microsphere compound；B sweeping for polystyrene microsphere in figure
Retouch Electronic Speculum test photo.As can be seen that polymer microballoon diameter is significantly increased, and it is swelling after polymer microballoon surface become compared with
For coarse, preferably combined with reference to the data such as infrared spectrum, thermogravimetric analysis and X-ray powder diffraction explanation Firebrake ZB sample
In polystyrene microsphere.
Claims (5)
1. a kind of preparation method of organic acid doped hydrophobic 411 type Firebrake ZB, it is characterised in that heavy using hydro-thermal method and chemistry
By organic acid, boron source and zinc source mix the two step method that shallow lake method is combined, by organic acid doped in 411 type Firebrake ZBs；Specially
Take zinc source and be modulated into suspension during boron source is dissolved in the mixed liquor of 6mL deionized waters and 1mL ethanol；The suspension of gained is transferred to
In closed hydrothermal synthesis reaction kettle, after hydro-thermal reaction 8-24h is carried out at 100-180 DEG C, take out, cooling, filtering, washing is dried
411 type Firebrake ZBs are obtained after dry；It is 3 that 411 type Firebrake ZBs are added into volume ratio：In 1 distilled water and the mixed liquor of absolute ethyl alcohol, then
To organic acid is added dropwise in mixed liquor, it is heated to reflux through 80 DEG C, after stirring 5h, cooling, filtering, washing, drying；The zinc source contains
Zinc amount is 1 with the boron content of boron source and the ratio of organic acid：1~4：0.1~1.
2. the preparation method of a kind of organic acid doped hydrophobic 411 type Firebrake ZB according to claim 1, it is characterised in that
Described organic acid is that liquid organic acid includes propionic acid, n-butyric acie, positive valeric acid, n-caproic acid, positive enanthic acid, caprylic acid, acrylic acid, oil
Acid, linoleic acid, linolenic acid.
3. the preparation method of a kind of organic acid doped hydrophobic 411 type Firebrake ZB according to claim any one of 1-2, its
It is characterised by that the zinc source is zinc oxide or zinc nitrate.
4. the preparation method of a kind of organic acid doped hydrophobic 411 type Firebrake ZB according to claim any one of 1-2, its
It is characterised by that the boron source is boric acid or borax.
5. using the preparation method system of a kind of organic acid doped hydrophobic 411 type Firebrake ZB described in claim any one of 1-2
Standby Firebrake ZB is used in high molecular polymer as additive, it is characterised in that the high molecular polymer is poly- methyl
Methyl acrylate, polystyrene, addition of the Firebrake ZB in polymethyl methacrylate, polystyrene polymeric polymer
Amount usage amount is 25%-35%.
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| CN102226299A (en) * | 2011-05-30 | 2011-10-26 | 中国科学院青海盐湖研究所 | New hydrothermal synthesis method of zinc borate whisker |
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| CN102226299A (en) * | 2011-05-30 | 2011-10-26 | 中国科学院青海盐湖研究所 | New hydrothermal synthesis method of zinc borate whisker |
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