CN107513184B - Increase soft type calcium alginate/line borate hybrid inorganic-organic materials and preparation method - Google Patents
Increase soft type calcium alginate/line borate hybrid inorganic-organic materials and preparation method Download PDFInfo
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- CN107513184B CN107513184B CN201710747425.2A CN201710747425A CN107513184B CN 107513184 B CN107513184 B CN 107513184B CN 201710747425 A CN201710747425 A CN 201710747425A CN 107513184 B CN107513184 B CN 107513184B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
- C08L5/04—Alginic acid; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/14—Macromolecular materials
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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
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
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- 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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Abstract
Increase soft type calcium alginate/line borate hybrid inorganic-organic materials and preparation method the invention discloses a kind of, belongs to hybrid material preparation technical field.It first mixes sodium alginate and perborate aqueous solution, and the soft material of increasing is then added thereto and stirs to obtain reaction material liquid；Then manganese dioxide is added into reaction material liquid, stand foaming is complete at room temperature after mixing evenly；Finally, reaction material liquid is poured into molding equipment and required shape is made, subsequently into shaping in coagulating bath, until ion-exchange reactions is complete, clear water is cleaned, the soft type calcium alginate/line borate hybrid inorganic-organic materials of increasing obtained by drying.The soft type calcium alginate of the increasing that the present invention is prepared/line borate hybrid inorganic-organic materials limited oxygen index >=30 will not be thermally decomposed in 200 DEG C of holding thermal stability；And creasy recovery angle >=110 °, the mechanical properties such as damping, anti-folding are excellent, especially suitable for occasions such as the home for the aged, kindergarten, amusement, military equipments.
Description
Technical field
The present invention relates to a kind of hybrid material preparation technical fields, and in particular to and a kind of calcium alginate/line borate is organic-nothing
Machine hybrid material and preparation method thereof.
Background technique
21 century is the century of ocean, and the development and utilization of marine resources obtains world many countries, especially flourishing state
The attention of family.China coastline is very long, sea area is vast, and marine resources are abundant, attaches equal importance to marine resources development.For example, conduct
For sea-plant kelp, annual amount of regeneration is more than 15,000,000 tons.China's marine algae resource is abundant, annual output up to more than 700 ten thousand tons,
Account for more than half of Gross World Product.Wherein, China's kelp yield in 2015 reaches 1,320,000 tons, accounts for the 90% of Gross World Product
More than, there is huge resources advantage.But food is mainly directly used as to the utilization of kelp at present or extracts food addition
Agent, ton valence are thousands of members to tens of thousands of members etc..How to be converted into high value-added industries advantage using kelp resources advantage is China
One of important goal in the blue economy of starting in 2012.
Calcium alginate material is a kind of ingrain fireproofing material, becomes research hotspot due to belonging to environment-friendly material.So
And it is a kind of polysaccharide material, caramelization occurs for heat, and thermal decomposition temperature only has 150 DEG C, and heat resisting temperature low in this way is in work
The application of journey material is above very limited.Therefore, research worker always searches for improving calcium alginate material thermal resistance energy
Method, but progress is unsatisfactory at present, and heatproof is more than 200 DEG C, and there are still difficulties.
Summary of the invention
Increase soft type calcium alginate/line borate hybrid inorganic-organic materials and preparation the purpose of the present invention is to provide a kind of
Method, using the in-situ preparation line borate in sodium alginate, the soft material mixed gel of increasing, and acquisition of foaming simultaneously increases soft type seaweed
Sour calcium/line borate organic-inorganic hybrid material method.The material limited oxygen index (LOI) >=30 being prepared is kept at 200 DEG C
Thermal stability will not thermally decompose；And creasy recovery angle >=110 °.
One of task of the invention, which is to provide, a kind of increases soft type calcium alginate/line borate hybrid inorganic-organic materials
Preparation method.
A kind of preparation method increasing soft type calcium alginate/line borate hybrid inorganic-organic materials successively includes following step
It is rapid:
A, the aqueous solution that mass percent is 1~20% sodium alginate and 0.1~10% perborate is prepared；
B, it is added into mixed solution obtained by step a and increases soft material, stir evenly to obtain reaction material liquid；
C, manganese dioxide is added into reaction material liquid obtained by step b, after mixing evenly at room temperature stand foaming 10~
60min, until foaming is complete；
D, the complete feed liquid of step c foaming is added to molding equipment and required shape is made, subsequently into coagulating bath
Setting, until ion-exchange reactions is complete, clear water is cleaned, the soft type calcium alginate/line borate hybrid inorganic-organic material of increasing obtained by drying
Material.
As a preferred solution of the present invention, the perborate in step a chooses sodium perborate or potassium perborate.
Preferably, the perborate in step a chooses sodium perborate.
Preferably, described to increase soft material as carboxymethyl cellulose salt, polyacrylate or self-cross linking type aqueous polyurethane.
Preferably, in step c, the additional amount of the manganese dioxide is the 0.1%~0.3% of perborate quality.
Preferably, the solidification bath process are as follows: level-one coagulating bath is the calcium chloride solution or calcium chloride of 1~2% concentration
With the mixed solution of zinc chloride, the processing time is 0.5~3h；Second level coagulating bath be 4% calcium chloride solution or calcium chloride and
The mixed solution of zinc chloride, processing time are 0.5~5h；The mixed solution of calcium chloride and zinc chloride that three-level coagulating bath is 7%,
The processing time is 1~8h.
Preferably, bulk, plate, pelletiod, strip, silk thread shape is made in the complete feed liquid of foaming in molding equipment
Or it is membranaceous.
Another task of the invention is that providing the soft type calcium alginate/line borate of increasing that above-mentioned preparation method is prepared has
Machine-inorganic hybrid material, limited oxygen index >=30 in 200 DEG C of holding thermal stability and will not thermally decompose；Creasy recovery angle >=
110°。
Another task of the invention, which is to provide, increases soft type calcium alginate/line borate hybrid inorganic-organic materials fire-retardant
Application in ornament materials.
Advantageous effects brought by the present invention:
One, present invention in-situ preparation line borate in sodium alginate, the soft material mixed gel of increasing, and produced simultaneously by catalysis
Solid/liquid/gas reactions foaming, the reaction of gradient calcium ion-exchanged, be prepared for being able to satisfy kept at 200 DEG C thermal stability have both elasticity, damping,
Sound-absorbing, absorption, heat-insulated, thermal insulation property multifunctional flame-proof cavernosa material, and it is suitable for the home for the aged, kindergarten, public place of entertainment
Ornament materials of the occasions such as conjunction, military equipment, automobile etc. to have both damping, sound-absorbing, absorption, thermal insulation property flame-retardant sponge body material
The functional requirement of material.
Specifically, being prepared for calcium alginate/line borate organic-inorganic hybrid material by in-situ method.This is than in sodium alginate
Or directly add line borate powder in calcium alginate and not only enormously simplify technique, coupling agent, dispersing agent are eliminated, is avoided
Pollution, and obtain microcosmic homogeneous hybrid material.Because the thermal decomposition temperature of line borate is more than 900 DEG C, so that seaweed
Sour calcium thermal decomposition temperature can be increased to 200 DEG C by 150 DEG C, can not decompose in 200 DEG C of holding thermal stability.Reaction equation is as follows:
NaBO3·H2O(aq)→NaBO2(aq)+H2O2(aq)——(1)
NaBO2(aq)+Ca2+(aq)→xCaOyB2O3nH2O(s)——(2)
xCaOyB2O3nH2O(s)→CaO(s)+B2O3(s)+H2O(g)——(3)
H2O2(aq)→H2O(l)+O2(g)——(4)
NSRC (sodium alginate soluble materials plural gel)+Ca2+(aq)+Zn2+(aq)→
Ca Zn NS·RC(s)——(5)
Reaction (1) generates the BO for forming line borate crystal2 -Crystal cup；Reacting (2) is the in-situ preparation in calcium alginate gel
Water-insoluble line borate crystal xCaOyB2O3NH2O (x=1~5, Y=1~11, n=1~6)；Reacting (3) is line borate crystal
Thermally decompose the endothermic reaction；Reaction (4) is that constant temperature catalyzing decomposes air-generating reaction, gas foam in place in colloid.Reaction (5) is sea
Mosanom soluble materials plural gel passes through Na+—Ca2+Ion-exchange reactions becomes water-insoluble Ca Zn from water solubility
NSRC (alginic acid flexible material calcium zinc) increases soft type Ca Zn NSRC/xCaOyB to be formed2O3NH2O organic-inorganic
Hybrid material.
Two, the protrusion effect of perborate used is to realize quadruple purpose:
(1) sodium alginate soln belongs to polymer colloid, and the viscosity of 3% concentration is very big, so that preparation high concentration is non-
It is often difficult, since boric acid salt hydrolysis is in alkalinity, it can significantly reduce the concentration of sodium alginate soln, making it possible to be easy preparation is more than
10% sodium alginate soln, is more advantageous to the preparation processing of material, and reduces wastewater treatment, discharge amount；
(2) perborate contains dioxygen key, and molecule has good stability, evolution could be only decomposed under catalytic condition
Oxygen and make sodium alginate polymer colloid foam, and by control catalyst amount control expansion rate so that porosity
Become needing artificial control by material property with pore size.Sea is made by oxidation so as to avoid direct addition hydrogen peroxide
The fracture of mosanom macromolecular chain, the defect of the mechanical strength decline of product；It foams under alkaline condition, hydrogen peroxide oxidation is weak, also rises
The effect of oxidative degradation is avoided to protection sodium alginate macromolecular chain.
(3) it is in situ to generate BO while perborate generates gas foaming in situ2 -, it is in organic-inorganic hybrid material
The formation of line borate crystal provides crystal cup, and can be evenly distributed among alginate macromolecular colloid, so that material
Homogeneity it is good.
(4) more gap cavernous bodies are formed after foaming favorably increase elasticity, and the material economy of same volume price is more expensive
Sodium alginate, significantly reduce product cost.
Three, after macromolecular colloid is foamed, gas is gradually escaped with the time, and bubble can fade away, so as soon as possible
Bubble is shaped critically important.However, the coagulating bath ion-exchange reactions of high concentration is quickly, material can be made to form hard shell, Ca2Inwardly
Portion's infiltration migration is obstructed, internal Na+—Ca2+Ion-exchange reactions is then difficult to after material cavernous body is inhomogenous, performance uniformity
It is affected.Gradient calcium ion-exchanged reaction technology, using the three-level coagulating bath of concentration from low to high, so that ion-exchange reactions
Migration rate from outside to inside is gradually increased, and solves the above problem existing for level-one coagulating bath.
Four, the use bring advantageous effects of water soluble linear macromolecule flexible material are:
(1) linear macromolecule flexible material can effectively overcome the brittleness of calcium alginate, so that material has good elasticity
And flexibility, mechanical property requirements are able to satisfy when doing the composite materials such as weaving Tu layer and wallpaper material；But calcium alginate material itself
But it is not able to satisfy these mechanical property requirements；
(2) water soluble linear macromolecule flexible material and sodium alginate have common aqueous solvent, there is good compatibility, nothing
Emulsifier, dispersing agent etc. need to be added to generate secondary pollution, have no the chemical substance of benefit again to material itself, can ensure that material is
Green material and friendly process；
(3) water soluble linear high molecular material can effectively improve the elasticity and flexibility of calcium alginate, but finally how become
Non-aqueous materials are key technologies.Preferably carboxymethyl cellulose salt of the present invention, polyacrylate, self-crosslinkable polyurethane solution,
Reaction end, the above two can grow non-water soluble metal salt, and the latter forms the non-aqueous macromolecular of polyurethane by self-crosslinking.
Detailed description of the invention
The present invention will be further described with reference to the accompanying drawing:
Fig. 1 is the soft type calcium alginate/line borate organic-inorganic hybrid material of increasing prepared by the embodiment of the present invention 1 and pure sea
The TG curve graph of calcium alginate；
Fig. 2 is to increase the microcosmic of soft type calcium alginate/line borate organic-inorganic hybrid material prepared by the embodiment of the present invention 1
Pattern SEM picture.
Specific embodiment
Increase soft type calcium alginate/line borate hybrid inorganic-organic materials and preparation method the invention discloses a kind of, in order to
Keep advantages of the present invention, technical solution clearer, clear, the present invention will be further described combined with specific embodiments below.
Raw material needed for the present invention can be commercially available by commercial channel.
Embodiment 1:
(1) aqueous solution of the sodium alginate and 5% sodium perborate that are 10% containing mass percent is configured；
(2) it is added in the above solution and accounts for the soft material Sodium Polyacrylate (molecule of increasing that sodium alginate mass fraction is 60%
Amount >=10000) obtain reaction solution；
(3) manganese dioxide is added in above-mentioned reaction solution, after mixing evenly 10~60min of stand foaming at room temperature, until hair
It finishes complete；The additive amount of manganese dioxide is the 0.2% of sodium alginate quality；
(4) the complete reaction solution that will foam pours into molding equipment, needs to be shaped to block, plate, grain, item, silk thread, film by application
Etc. shapes, and enter in the coagulating bath of three-level gradient concentration and shape bubble, until ion-exchange reactions is complete；Clear water is cleaned, drying is
Product.
The coagulating bath of three-level gradient concentration and its technique are as follows: level-one coagulating bath is the calcium chloride solution of 1% concentration, handles the time
For 1.5h；Second level coagulating bath is the calcium chloride solution of 4% concentration, and the processing time is 2h；Three-level coagulating bath is the chlorination of 3% concentration
The zinc chloride mixed solution of calcium and 4% concentration, processing time are 4h.
The soft type calcium alginate of the increasing prepared according to the above method/line borate organic-inorganic hybrid material thermal decomposition temperature >=200
DEG C, limited oxygen index >=36, creasy recovery angle >=130 °.
In Fig. 1,1-calcium alginate, 2-increase soft type calcium alginate/line borate hybrid material.
It will be seen from figure 1 that the thermal decomposition temperature of pure calcium alginate material is 150 DEG C, and meeting fast decoupled, until 200
DEG C reach weightless peak value；And increase soft type calcium alginate/200 DEG C of line borate organic-inorganic hybrid material and just start to decompose, Er Qiere
Weight loss rate is slow, and the thermal decomposition temperature than pure calcium alginate material not only increases 50 DEG C, and thermal degradation speed is also shown
Writing reduces, and flame retardant property obtains larger raising.
Figure it is seen that calcium alginate is in layer structure, the line borate inlayed in the layered structure is 500 nanometers of left sides
Right cubic crystal.
Embodiment 2:
Difference from Example 1 is: changing 10% sodium alginate into 1%, 5% sodium perborate changes 0.1% into.
The soft type calcium alginate of the increasing prepared according to the above method/line borate organic-inorganic hybrid material thermal decomposition temperature is 170
DEG C, 20 DEG C are improved than common calcium alginate sample thermal decomposition temperature, limited oxygen index 30.1, creasy recovery angle >=117 °.
Embodiment 3:
Difference from Example 1 is: changing 10% sodium alginate into 20%, 5% sodium perborate changes 10% into, gathers
Sodium acrylate changes water-soluble self-crosslinkable polyurethane solution into, and it is 100% that mass percent, which accounts for sodium alginate mass fraction,.
The soft type calcium alginate of the increasing prepared according to the above method/line borate organic-inorganic hybrid material thermal decomposition temperature >=220
DEG C, 70 DEG C are improved than common calcium alginate sample thermal decomposition temperature, limited oxygen index >=34, creasy recovery angle >=153 °.
Embodiment 4:
Difference from Example 1 is: the manganese dioxide that sodium perborate mass fraction is 0.2% will be accounted for and change 0.1% into,
Sodium Polyacrylate changes carboxymethyl cellulose sodium salt into, and it is 50% that mass percent, which accounts for sodium alginate mass fraction,.
The soft type calcium alginate of the increasing prepared according to the above method/line borate organic-inorganic hybrid material thermal decomposition temperature is 220
DEG C, 70 DEG C are improved than common calcium alginate sample thermal decomposition temperature, limited oxygen index 43.5, creasy recovery angle >=126 °.
Embodiment 5:
Difference from Example 1 is: will account for the manganese dioxide that sodium perborate mass fraction is 0.2% and changes 0.3% into.
The soft type calcium alginate of the increasing prepared according to the above method/line borate organic-inorganic hybrid material thermal decomposition temperature is 217
DEG C, 67 DEG C are improved than common calcium alginate sample thermal decomposition temperature, limited oxygen index 37.5, creasy recovery angle >=120 °.
Embodiment 6:
Difference from Example 1 is: will stand foaming 30min at room temperature, change foaming 10min into.
The soft type calcium alginate of the increasing prepared according to the above method/line borate organic-inorganic hybrid material thermal decomposition temperature is 210
DEG C, 60 DEG C are improved than common calcium alginate sample thermal decomposition temperature, limited oxygen index 35, creasy recovery angle >=118 °.
Embodiment 7:
Difference from Example 1 is: will stand foaming 30min at room temperature, change foaming 60min into.
The soft type calcium alginate of the increasing prepared according to the above method/line borate organic-inorganic hybrid material thermal decomposition temperature is 240
DEG C, 90 DEG C are improved than common calcium alginate sample thermal decomposition temperature, limited oxygen index 52, creasy recovery angle >=125 °.
Embodiment 8:
Difference from Example 1 is: three-level gradient concentration being solidified the level-one coagulating bath in bath process and handles the time
1.5h changes 0.5h into；Second level coagulating bath processing time 2h changes 0.5h into；Three-level coagulating bath processing time 4h changes 1h into.
The soft type calcium alginate of the increasing prepared according to the above method/line borate organic-inorganic hybrid material thermal decomposition temperature is 221
DEG C, 71 DEG C are improved than common calcium alginate sample thermal decomposition temperature, limited oxygen index 38.7, creasy recovery angle >=127 °.
Embodiment 9:
Difference from Example 1 is: three-level gradient concentration being solidified the level-one coagulating bath in bath process and handles the time
1.5h changes 3h into；Second level coagulating bath processing time 2h changes 5h into；Three-level coagulating bath processing time 4h changes 8h into.
The soft type calcium alginate of the increasing prepared according to the above method/line borate organic-inorganic hybrid material thermal decomposition temperature is 218
DEG C, 68 DEG C are improved than common calcium alginate sample thermal decomposition temperature, limited oxygen index 35, creasy recovery angle >=123 °.
Embodiment 10:
Difference from Example 1 is: the calcium chloride solution that level-one coagulating bath is 1% concentration is changed to 1% concentration
The mixed solution of calcium chloride solution and the liquor zinci chloridi of 1% concentration, processing time are 1.5h；Second level coagulating bath is 4% concentration
Calcium chloride solution be changed to the mixed solution of the calcium chloride solution of 2% concentration and the liquor zinci chloridi of 3% concentration, the processing time is
2h；Three-level coagulating bath is the calcium chloride of 3% concentration and the zinc chloride mixed solution of 4% concentration, and the processing time is 4h.
The soft type calcium alginate of the increasing prepared according to the above method/line borate organic-inorganic hybrid material thermal decomposition temperature is 205
DEG C, 55 DEG C are improved than common calcium alginate sample thermal decomposition temperature, limited oxygen index 34, creasy recovery angle >=131 °.
Embodiment 11:
Difference from Example 1 is: the aqueous solution of 5% SODIUM PERCARBONATE being only substituted for the water-soluble of 5% potassium percarbonate
Liquid.
The soft type calcium alginate of the increasing prepared according to the above method/202 DEG C of line borate organic-inorganic hybrid material thermal decomposition temperature,
Limited oxygen index 36.3,137 ° of creasy recovery angle.
Comparative example 1:
(1) aqueous solution of the sodium alginate and 5% sodium perborate that are 10% containing mass percent is configured；
(2) it is added in the above solution and accounts for the manganese dioxide that sodium perborate mass fraction is 0.2%, pour into after mixing evenly
Stand foaming 30min at room temperature in equipment, until foaming is complete；
(3) the complete reaction solution that will foam pours into molding equipment, needs to be shaped to block, plate, grain, item, silk thread, film by application
Etc. shapes, and enter in the coagulating bath of three-level gradient concentration and shape bubble, until ion-exchange reactions is complete；Clear water is cleaned, drying is
Product.
The coagulating bath of three-level gradient concentration and its technique are as follows: level-one coagulating bath is the calcium chloride solution of 1% concentration, handles the time
For 1.5h；Second level coagulating bath is the calcium chloride solution of 4% concentration, and the processing time is 2h；Three-level coagulating bath is the chlorination of 7% concentration
Calcium solution, processing time are 4h.
The calcium alginate prepared according to the above method/line borate organic inorganic hybridization cavernous body thermal decomposition temperature is 250 DEG C, than
Common calcium alginate sample thermal decomposition temperature improves 100 DEG C, limited oxygen index >=60, creasy recovery angle >=33 °.
By embodiment 1-11 compared with comparative example 1, the soft type calcium alginate of the increasing that the present invention prepares/organic nothing of line borate
Machine hybrid material improves 3-4 times than calcium alginate/line borate organic inorganic hybridization cavernosa material creasy recovery angle, plays soft
Performance significantly improves.
Under the guide of above-described embodiment 1-11, other combination those skilled in the art can be obviously real
It is existing.
It should be understood that any equivalent way that those skilled in the art are made under the introduction of this specification, or
Obvious variant should all be within the scope of the present invention.
Claims (8)
1. a kind of preparation method for increasing soft type calcium alginate/line borate hybrid inorganic-organic materials, which is characterized in that successively wrap
Include following steps:
A, the aqueous solution that mass percent is 1~20% sodium alginate and 0.1~10% perborate is prepared；
B, it is added into mixed solution obtained by step a and increases soft material, stir evenly to obtain reaction material liquid；
C, manganese dioxide is added into reaction material liquid obtained by step b, after mixing evenly 10~60min of stand foaming at room temperature, until
Foaming is complete；
D, foam complete feed liquid of step c is added to molding equipment and required shape is made, subsequently into shaping in coagulating bath,
To ion-exchange reactions is complete, clear water is cleaned, the soft type calcium alginate/line borate hybrid inorganic-organic materials of increasing obtained by drying；
The solidification bath process are as follows: level-one coagulating bath is the calcium chloride solution or calcium chloride of 1~2% concentration and mixing for zinc chloride
Solution is closed, the processing time is 0.5~3h；The mixing of calcium chloride solution or calcium chloride and zinc chloride that second level coagulating bath is 4%
Solution, processing time are 0.5~5h；The mixed solution of calcium chloride and zinc chloride that three-level coagulating bath is 7%, processing time are 1
~8h.
2. the preparation method according to claim 1 for increasing soft type calcium alginate/line borate hybrid inorganic-organic materials,
Be characterized in that: the perborate in step a chooses sodium perborate or potassium perborate.
3. the preparation method according to claim 2 for increasing soft type calcium alginate/line borate hybrid inorganic-organic materials,
Be characterized in that: the perborate in step a chooses sodium perborate.
4. the preparation method according to claim 1 for increasing soft type calcium alginate/line borate hybrid inorganic-organic materials,
It is characterized in that: described to increase soft material as carboxymethyl cellulose salt, polyacrylate or self-cross linking type aqueous polyurethane.
5. the preparation method according to claim 1 for increasing soft type calcium alginate/line borate hybrid inorganic-organic materials,
Be characterized in that: in step c, the additional amount of the manganese dioxide is the 0.1%~0.3% of perborate quality.
6. the preparation method according to claim 1 for increasing soft type calcium alginate/line borate hybrid inorganic-organic materials,
Be characterized in that: bulk, plate, pelletiod, strip, silk thread shape or film is made in the complete feed liquid of foaming in molding equipment
Shape.
7. the soft type calcium alginate/line borate of the increasing that described in any item preparation methods are prepared according to claim 1~6 has
Machine-inorganic hybrid material, it is characterised in that: its limited oxygen index >=30 in 200 DEG C of holding thermal stability and will not thermally decompose；Folding
Wrinkle recovery angle >=110 °.
8. according to claim 7 increase soft type calcium alginate/line borate hybrid inorganic-organic materials in fire-retarding decorative material
In application.
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