CN1289586C - Process for preparing regenerated cellulose / SiO2 nano composite material - Google Patents
Process for preparing regenerated cellulose / SiO2 nano composite material Download PDFInfo
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- CN1289586C CN1289586C CN 200310117767 CN200310117767A CN1289586C CN 1289586 C CN1289586 C CN 1289586C CN 200310117767 CN200310117767 CN 200310117767 CN 200310117767 A CN200310117767 A CN 200310117767A CN 1289586 C CN1289586 C CN 1289586C
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- regenerated cellulose
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- 239000004627 regenerated cellulose Substances 0.000 title claims abstract description 39
- 239000000463 material Substances 0.000 title claims abstract description 37
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title abstract 17
- 229910052681 coesite Inorganic materials 0.000 title abstract 9
- 229910052906 cristobalite Inorganic materials 0.000 title abstract 9
- 239000000377 silicon dioxide Substances 0.000 title abstract 9
- 229910052682 stishovite Inorganic materials 0.000 title abstract 9
- 229910052905 tridymite Inorganic materials 0.000 title abstract 9
- 235000012239 silicon dioxide Nutrition 0.000 title abstract 8
- 238000004519 manufacturing process Methods 0.000 title description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000835 fiber Substances 0.000 claims abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 239000011734 sodium Substances 0.000 claims abstract description 9
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 6
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012991 xanthate Substances 0.000 claims abstract description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract 3
- 229910052708 sodium Inorganic materials 0.000 claims abstract 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 37
- 229920000297 Rayon Polymers 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 23
- 235000019353 potassium silicate Nutrition 0.000 claims description 22
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 16
- 239000003292 glue Substances 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229920002678 cellulose Polymers 0.000 claims description 11
- 239000001913 cellulose Substances 0.000 claims description 11
- 238000001879 gelation Methods 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 7
- 235000011152 sodium sulphate Nutrition 0.000 claims description 7
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 7
- 229960001763 zinc sulfate Drugs 0.000 claims description 7
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 7
- 239000004111 Potassium silicate Substances 0.000 claims description 6
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 6
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 3
- 238000006424 Flood reaction Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 241001274660 Modulus Species 0.000 claims 1
- 238000012856 packing Methods 0.000 abstract description 3
- 239000002985 plastic film Substances 0.000 abstract description 2
- 229920006255 plastic film Polymers 0.000 abstract description 2
- 229920000159 gelatin Polymers 0.000 abstract 2
- 239000008273 gelatin Substances 0.000 abstract 2
- 102000005575 Cellulases Human genes 0.000 abstract 1
- 108010084185 Cellulases Proteins 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 230000000979 retarding effect Effects 0.000 abstract 1
- 235000011149 sulphuric acid Nutrition 0.000 abstract 1
- 239000003063 flame retardant Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 14
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 12
- 239000004115 Sodium Silicate Substances 0.000 description 9
- 229910052911 sodium silicate Inorganic materials 0.000 description 9
- 239000011086 glassine Substances 0.000 description 7
- 235000011121 sodium hydroxide Nutrition 0.000 description 7
- 238000011160 research Methods 0.000 description 6
- 229920003043 Cellulose fiber Polymers 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000008929 regeneration Effects 0.000 description 5
- 238000011069 regeneration method Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005304 joining Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 206010053615 Thermal burn Diseases 0.000 description 1
- 229920004935 Trevira® Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003008 phosphonic acid esters Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000013339 polymer-based nanocomposite Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Abstract
The present invention relates to preparation of a regenerated cellulose / SiO2 nanocomposite material. The inflaming retarding activity of SiO2 is enhanced by the nanometer character generation of the SiO2, and nanometer SiO2 is evenly distributed in a basal body of a regenerated cellulose. An adhesive-SiO2 predecessor solution enters a regeneration-gelatin sour bath, sodium hydratecellulose xanthate reacts with sulphuric acids in the regeneration-gelatin sour bath to generate cellulases, SiO2 predecessor silicate is gelatinized to form SiO2, and the regenerated cellulose / SiO2 nanocomposite material is obtained. According to different formation modes, the nanocomposite material is made into various plastic films, film, packing materials and fibers.
Description
Technical field
The present invention relates to a kind of matrix material of regenerated cellulose, particularly relate to a kind of by regenerated cellulose and SiO
2Polymer/inorganic thing nano composite material of forming and preparation method thereof.
Background technology
Regenerated cellulose can be used to make fiber (being commonly called as viscose fiber, artificial cotton), plastics, film, film etc.At aspects such as civilian, industrial, medical science, national defence and scientific researches purposes is widely arranged all.
The basic raw material of regenerated cellulose-cellulosic stockage is very big, and huge amount of recovery is arranged.The Nature is translated into the various plant resourceses of cellulose all at the carbon that is assimilating in 100,000,000,000,000 tons every year.As long as sunlight and water are arranged, the farm crop of trees, wild plant and various rich cellulose just can grow and constantly regeneration.And in contrast to this, synthetic materials is a basic raw material with oil, Sweet natural gas mainly, and the resource of consumption is difficult to recover, synthetic materials itself also be difficult to Recycling.Therefore, from the source of raw material, cellulosic resource is unlimited, makes full use of this rich in natural resources and develops regenerated cellulose industry, has long-range, important meaning, meets the requirement of current social sustainable development.Regenerated cellulose equally is eco-friendly with natural Mierocrystalline cellulose, and its waste can natural degradation.
The regenerated cellulose wrapping material are commonly called as " glassine paper ", are a kind of eco-friendly high-grade wrapping material, are the widely used packing and decorating materials of industry such as food, clothes, light industry, electronics, instrument.The home-made glassine paper is mainly used in outlet, and the glassine paper of domestic use also is mainly used in the packing of exported product.Glassine paper is a kind of good material that substitutes the plastic film packaging material that causes " white pollution " easily, but the manufacturing cost of glassine paper is higher than wrapping material such as polyethylene.Pass through SiO
2Compound with regenerated cellulose, not only can reduce the manufacturing cost of glassine paper and SiO
2Nano combined glassine paper also can obtain improvement to a certain degree on performance.
In filamentary material, regenerated cellulose fibre is one of the easiest incendiary fiber, and its limiting oxygen index(LOI) (LOI) has only 17%.The intensity of regenerated cellulose fibre also is minimum in the fiber, and its wet strength is generally low by about 20% than dry strength, even lower, reduces about 50% as common viscose fiber.Defectives such as the low strength of the inflammable and mechanical property of regenerated cellulose fibre, low modulus have had a strong impact on its application.
The research of fire-retardant fibre always is the important content of fiber material modification research.Though for consumption maximum, purposes trevira the most widely, its flame-retardant modified industrialization product has obtained application in a lot of fields.But existing fire-retardant polyester fibre does not change the defective of meeting the heat fusing drippage, though improved flame retardant resistance, but still can cause the person to scald because fusion adheres to.And charing only takes place in regenerated cellulose fibre chance fire burns, therefore can be used as garment material such as troop operation clothes, bunker clothing, bedclothes and old man, children, patient's clothes etc., remedies the deficiency of thermoplastic fibre.The flame-retardant modified research focus of existing regenerated cellulose fibre is to use phosphonic acid ester fire retardant and poly-silicic acid based flame retardant (as the Visil fiber of the Exolit fire retardant of Clarian company and Fire resistant viscose fiber, Kemira company etc.), this meet fire retardant non-halogen, low toxicity, press down requirement such as cigarette.But the addition of these fire retardants is bigger, and generally all at 20%-30%, this intensity to fiber has bigger influence again, and original just not high intensity is further reduced.Make flame retardant effect and fibre strength become a pair of paradox, improving flame retardant effect will be cost with the mechanical property of sacrificial fiber, and the reduction of mechanical property must influence the application of fiber.
Polymer based nanocomposites is having more research aspect the polymkeric substance such as polymeric amide, polyester and polypropylene, and the raising of its flame retardant resistance and mechanical property has obtained the confirmation of testing.When research PA66/MMT nano composite material, find, its tensile strength, tensile modulus, heat-drawn wire, thermostability and the common PA66 of flame resistivity geometric ratio are greatly improved, improve closely 50% as shock strength, and have effects such as fire-retardant, no molten drop.J.W.Giliman etc. claim that also nano composite material is to improve the method for a kind of new revolution of polymkeric substance flame retardant properties, this is a kind of structure from nano level or molecular level design consideration high polymer composite material, improves the flame retardant properties of polymkeric substance and the method for mechanical property.
Summary of the invention
Regenerated cellulose/SiO of the present invention
2Nano composite material is by making SiO
2Nanometer to improve SiO
2Flame retardant activity.And make nanometer SiO
2Be distributed in uniformly in the regenerated cellulose matrix, can reduce SiO on the one hand
2Addition, reduce influence to Mierocrystalline cellulose physics mechanical property, on the other hand, the SiO of the active nanometer of high flame retardant
2Can solve the contradiction between flame retardant resistance and the Material Physics mechanical property.
Nanometer SiO among the present invention
2Particle can be induced the cellulosic molecule crystallization as the heterogeneous nucleation agent, forms more microlitic structure, and improves cellulosic degree of crystallinity, thereby improves regenerated cellulose/SiO
2The mechanical property of nano composite material.Higher degree of crystallinity and uniform microlitic structure also can reduce the hygrometric state swollen effect of regenerated cellulose, guarantee cellulosic molecular orientation under the hygrometric state, and can prevent that Mierocrystalline cellulose from rupturing too much because of moisture absorption makes hydrogen bond, thereby improve the wet strength of material of regenerated cellulose.In addition, the improvement of physical and mechanical properties is to regenerated cellulose/SiO
2Nano composite material may be explored the approach that makes new advances in the application of aspects such as structured material such as fiber, plastics, film and wrapping material, as agricultural mulching, mess-tin, food bag etc.The degradable of cellulose materials, renewable, eco-friendly characteristics are that macromolecular materials commonly used such as other material such as polystyrene, polyethylene, polypropylene are not available.
Regenerated cellulose/SiO provided by the invention
2The preparation method of nano composite material is as follows:
1. cellulose xanthate solution (viscose glue) preparation
According to the preparation method of known viscose fiber with viscose glue: pulp (alpha-cellulose) at first floods with NaOH solution, uses CS again
2Carry out yellow and obtain cellulose xanthate, add the alkali lye dissolving at last and obtain viscose glue.The alpha-cellulose content that consists of of the viscose glue that the present invention adopts is 6～9% (quality), and sodium hydrate content is 5～6% (quality), and other compositions are water.
2. viscose glue-SiO
2The preparation of precursor solution
Silicate is as nanometer SiO
2Precursor, join in the viscose glue, thorough mixing obtains viscose glue-silicate solutions.
SiO
2Precursor can be different modulus (SiO
2: Na
2O) water glass or potassium silicate, or arbitrary proportion blended water glass and potassium silicate.The modulus of water glass can be 1-3.7, and modulus is that 1 water glass can be to contain zero water (Na
2SiO
3), five water (Na
2SiO
35H
2O) and nine water (Na
2SiO
39H
2O) water glass can directly add solid water glass or sodium silicate aqueous solution.
SiO
2The add-on of precursor (water glass or potassium silicate) is (with SiO
2Meter) be 1～50% of alpha-cellulose.The best is 3～30%.
3. regenerated cellulose/SiO
2The preparation of nano composite material
Viscose glue-SiO
2Precursor solution enters in regeneration-gelation acid bath, the generation regenerated cellulose that reacts of the sulfuric acid in cellulose xanthate and regeneration-gelation acid bath, SiO
2Precursor silicate generation gelation generates SiO
2, obtain regenerated cellulose/SiO
2Nano composite material.According to different forming modes, nano composite material can be made fiber, film etc.
Regeneration-gelation acid bath consists of: sulfuric acid 50～150 grams per liters, and the best is the 100-130 grams per liter; Sodium sulfate 0-350 grams per liter, the best are 270～340 grams per liters; Zinc sulfate 0-11 grams per liter, other compositions are water; The temperature of acid bath is 10-100 ℃, and the best is 30-50 ℃.
Embodiment
The invention will be further elaborated below by embodiment.
Embodiment 1
With 50 gram SiO
2Content is that 25% modulus is 3.5 sodium silicate aqueous solution, joining 1323.53 gram alpha-cellulose content is 8.35% (quality), sodium hydrate content is in the viscose glue of 5.8% (quality), under 18 ℃, stirred 5 minutes, sodium silicate aqueous solution is dissolved in the viscose glue fully, carries out the vacuum defoamation processing then and obtain viscose glue-sodium silicate solution.Get a little solution and paint uniform film, it is 100 grams per liters that film is put into sulfuric acid content, sodium sulfate 270 grams per liters, and zinc sulfate 15 grams per liters, temperature is in 50 ℃ the acid bath, to carry out cellulosic regeneration and SiO
2Gelation, obtain regenerated cellulose/SiO at last
2Nano composite membrane.
Embodiment 2
With 50 gram SiO
2Content is 21% water glass (Na
2SiO
39H
2O) powder, joining 2347.06 gram alpha-cellulose content is 8.35% (quality), sodium hydrate content is in the viscose glue of 5.8% (quality).Under 18 ℃, stirred 20 minutes, water glass is dissolved in the viscose glue fully, carry out the vacuum defoamation processing then and obtain viscose glue-sodium silicate solution.Get a little solution and paint uniform film, it is 50 grams per liters that film is put into sulfuric acid content, and temperature is in 50 ℃ the acid bath, to carry out cellulosic regeneration and SiO
2Gelation, obtain regenerated cellulose/SiO
2Nano composite membrane.
Embodiment 3
With 50 gram SiO
2Content is 49% water glass (Na
2SiO
3) powder, joining 1633.29 gram alpha-cellulose content is 8.35% (quality), sodium hydrate content is in the viscose glue of 5.8% (quality), under 18 ℃, stirred 20 minutes, sodium silicate aqueous solution is dissolved in the viscose glue fully, carry out the vacuum defoamation processing then and obtain viscose glue-sodium silicate solution.Get a little solution and paint uniform film, it is 130 grams per liters that film is put into sulfuric acid content, sodium sulfate 340 grams per liters, and zinc sulfate 11 grams per liters, temperature is in 50 ℃ the acid bath, to carry out cellulosic regeneration and SiO
2Gelation, obtain regenerated cellulose/SiO at last
2Nano composite membrane.
Embodiment 4
Get viscose glue-sodium silicate solution of embodiment 3, adopt the spinning processes of known common viscose fiber.It is 130 grams per liters that acid bath consists of sulfuric acid content, sodium sulfate 270 grams per liters, and zinc sulfate 11 grams per liters, temperature is 50 ℃.Viscose glue-sodium silicate solution reels off raw silk from cocoons with 80m/s speed and enters acid bath one-tenth silk, through washing, alkali cleaning, obtains regenerated cellulose/SiO again
2Nano-composite fiber.
Comparative Examples 1
As a comparison case, do not add any silicate, getting alpha-cellulose content is 8.35% (quality), and sodium hydrate content is the viscose glue of 5.8% (quality), gets a little solution and paints uniform film, it is 100 grams per liters that film is put into sulfuric acid content, sodium sulfate 270 grams per liters, zinc sulfate 15 grams per liters, temperature is in 50 ℃ the acid bath, carry out cellulosic regeneration, obtain RCF regenerated cellulose film.
Regenerated cellulose/SiO that embodiment and comparative example obtain
2The flame retardant properties of nano composite material and common RCF regenerated cellulose film relatively, and SiO in the nano composite material
2The disperse phase yardstick is listed table 1 in.
Table 1
| Project | Limiting oxygen index(LOI) (LOI) % | SiO 2Disperse phase yardstick nm |
| Embodiment 1 | 29 | 50-100 |
| Embodiment 2 | 23 | 50-100 |
| Embodiment 3 | 32 | 50-100 |
| Embodiment 4 | 30 | 50-100 |
| Comparative Examples 1 | 17 | - |
Claims (3)
1. regenerated cellulose/SiO
2The preparation method of nano composite material is characterized in that preparation process is as follows: the first step, alpha-cellulose floods with NaOH solution earlier, uses CS again
2Carry out yellow and obtain sodium cellulose xanthate, add the alkali lye dissolving at last and obtain viscose glue, the alpha-cellulose mass percentage content that consists of of viscose glue is 6～9%, and the NaOH mass percentage content is 5～6%, and other compositions are water; In second step, silicate is as nanometer SiO
2Precursor, join in the viscose glue, thorough mixing obtains viscose glue-silicate solutions, SiO
2The add-on of precursor water glass or potassium silicate is with SiO
2Count 1～50% of alpha-cellulose; The 3rd step, viscose glue-SiO
2Precursor solution enters in regeneration-gelation acid bath, and acid bath consists of: sulfuric acid 50～150 grams per liters, and sodium sulfate 0～350 grams per liter, zinc sulfate 0～11 grams per liter, other compositions are water; The temperature of acid bath is 10～100 ℃, the generation regenerated cellulose that reacts of the sulfuric acid in sodium cellulose xanthate and regeneration-gelation acid bath, SiO
2Precursor silicate generation gelation generates SiO
2, obtain regenerated cellulose/SiO
2Nano composite material, nano composite material are used to make fiber or film.
2. according to the described regenerated cellulose/SiO of claim 1
2The preparation method of nano composite material is characterized in that described SiO
2Precursor is water glass or potassium silicate or the arbitrary proportion blended water glass and the potassium silicate of different moduluses, and the modulus of water glass is 1～3.7, and modulus is that 1 water glass is the water glass that contains zero water or five water or nine water.
3. according to the described regenerated cellulose/SiO of claim 1
2The preparation method of nano composite material is characterized in that described viscose glue-SiO
2The acid bath of precursor solution regeneration-gelation consists of: sulfuric acid 100～130 grams per liters, and sodium sulfate 270～340 grams per liters, zinc sulfate 0～11 grams per liter, other compositions are water; The temperature of acid bath is 30～50 ℃.
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|---|---|---|---|
| CN 200310117767 CN1289586C (en) | 2003-12-30 | 2003-12-30 | Process for preparing regenerated cellulose / SiO2 nano composite material |
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|---|---|---|---|
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| CN1289586C true CN1289586C (en) | 2006-12-13 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101210353A (en) * | 2006-12-28 | 2008-07-02 | 山东海龙股份有限公司 | Anti-flame fusion-resisting cellulose viscose and producing method thereof |
| CN102605452B (en) * | 2012-03-13 | 2014-08-13 | 恒天海龙股份有限公司 | Flame-retardant silicate fiber, coagulation bath for producing flame-retardant silicate fiber and method for preparing flame-retardant silicate fiber |
| CN106867019B (en) * | 2017-01-06 | 2020-05-12 | 南京工业大学 | One-pot method for preparing SiO2Method for producing cellulose composite aerogel material |
| CN110028702B (en) * | 2019-04-29 | 2022-03-08 | 济南圣泉集团股份有限公司 | Nano-silica-doped nano-cellulose material and preparation method and application thereof |
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| CN1635019A (en) | 2005-07-06 |
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