CN116103955A - Water-insoluble green environment-friendly flame retardant and preparation method and application thereof - Google Patents
Water-insoluble green environment-friendly flame retardant and preparation method and application thereof Download PDFInfo
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- CN116103955A CN116103955A CN202111319861.2A CN202111319861A CN116103955A CN 116103955 A CN116103955 A CN 116103955A CN 202111319861 A CN202111319861 A CN 202111319861A CN 116103955 A CN116103955 A CN 116103955A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 112
- 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 title claims abstract description 107
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000004114 Ammonium polyphosphate Substances 0.000 claims abstract description 58
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims abstract description 58
- 229920001276 ammonium polyphosphate Polymers 0.000 claims abstract description 58
- 239000002121 nanofiber Substances 0.000 claims abstract description 55
- 239000002245 particle Substances 0.000 claims abstract description 7
- 238000000498 ball milling Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 229940057499 anhydrous zinc acetate Drugs 0.000 claims description 7
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 5
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229920002488 Hemicellulose Polymers 0.000 claims description 2
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 2
- 229920005610 lignin Polymers 0.000 claims description 2
- 239000011667 zinc carbonate Substances 0.000 claims description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 2
- 235000004416 zinc carbonate Nutrition 0.000 claims description 2
- 229920001131 Pulp (paper) Polymers 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- 230000002411 adverse Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 22
- 238000012360 testing method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
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- 239000010902 straw Substances 0.000 description 8
- 235000014676 Phragmites communis Nutrition 0.000 description 7
- 239000000779 smoke Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 4
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- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 230000001629 suppression Effects 0.000 description 3
- 241000662429 Fenerbahce Species 0.000 description 2
- 239000002154 agricultural waste Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 239000012796 inorganic flame retardant Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
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- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010016654 Fibrosis Diseases 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000004761 fibrosis Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
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- 239000002699 waste material Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 229960000314 zinc acetate Drugs 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Images
Classifications
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/34—Ignifugeants
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/25—Cellulose
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/65—Acid compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
- D21H17/74—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic and inorganic material
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/50—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by form
- D21H21/52—Additives of definite length or shape
Abstract
The invention discloses a water-insoluble green environment-friendly flame retardant, which comprises lignocellulose nanofibers and ammonium polyphosphate loaded on the lignocellulose nanofibers; wherein the diameter of the lignocellulose nanofiber is 2-5nm, and the length is 10-40 mu m; the particle size of the ammonium polyphosphate is 5-600nm, and the thickness is 5-600nm. The ammonium polyphosphate with larger specific surface area in the flame retardant is uniformly and stably loaded on lignocellulose nanofibers with large length-diameter ratio, has good compatibility with paper pulp, is not easy to separate out when being used for preparing paper, can be uniformly dispersed in the paper, and can not have adverse effect on the paper performance while endowing the paper with flame retardant performance. Meanwhile, the flame retardant has the advantages of wide raw material sources, environmental protection, simple preparation, good compatibility with paper-based materials and wide application prospect.
Description
Technical Field
The invention relates to the technical field of flame-retardant paper. More particularly, relates to a water-insoluble green environment-friendly flame retardant, and a preparation method and application thereof.
Background
Paper is widely used in all aspects of daily life, however paper is a flammable material, which is often the ignition material of a fire, and its flammable nature brings great hidden fire hazards and great economic losses to society. Therefore, flame retardant treatment of paper is a necessary requirement for removing fire threat from paper, and research on flame retardance of paper will promote application of paper in a wider field.
The traditional water-soluble flame retardant is fixed on the surface of paper by a soaking method, and paper wrinkles are easily caused by soaking, so that the performance of the paper is damaged. However, the existing water-insoluble flame retardants are mainly inorganic flame retardants, and when the flame retardants are added to paper, the flame retardants are easily precipitated on the surface of the paper due to the problems of incompatibility with paper-based materials, high density, large dosage, poor water resistance, high migration and the like, so that the flame retardant performance of the paper is reduced, the strength is reduced, the plasticity is deteriorated and the like.
Accordingly, it is desirable to provide a flame retardant that imparts flame retardant properties to paper without adversely affecting other properties of the paper.
Disclosure of Invention
The invention aims to provide a water-insoluble green environment-friendly flame retardant, wherein ammonium polyphosphate with larger specific surface area in raw materials is loaded on lignocellulose nanofibers with large length-diameter ratio, and the flame retardant has good flame retardance and good compatibility with paper fibers, so that excellent mechanical properties of flame retardant paper are ensured.
The invention further aims at providing a preparation method of the water-insoluble green environment-friendly flame retardant.
The invention also aims to provide flame retardant paper, which comprises the water-insoluble green environment-friendly flame retardant.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a non-water-soluble green environmental-friendly flame retardant, which comprises lignocellulose nano-fibers and ammonium polyphosphate loaded on the lignocellulose nano-fibers;
wherein the diameter of the lignocellulose nanofiber is 2-5nm, and the length is 10-40 mu m;
the particle size of the ammonium polyphosphate is 5-600nm, and the thickness is 5-600nm.
The traditional water-insoluble flame retardants are mainly inorganic flame retardants, and when the flame retardants are added into paper, the flame retardants are easy to precipitate on the surface of the paper due to incompatibility with paper-based materials, high density, large dosage, poor water resistance, high migration and the like, so that the strength of the paper is reduced, the plasticity is poor and the like.
According to the invention, the micro-nano lignocellulose with good compatibility with paper-based materials and large length-diameter ratio is combined with the ammonium polyphosphate with large specific surface area, so that the ammonium polyphosphate is uniformly loaded on the lignocellulose nanofiber, and the water-insoluble green environment-friendly flame retardant is obtained. The modified flame retardant paper is used for preparing flame retardant paper, has good compatibility with paper pulp, can be uniformly dispersed in the paper, and does not have adverse effect on the performance of the paper.
Preferably, the mass ratio of the lignocellulose nano fiber to the ammonium polyphosphate is 1 (1-8).
For example, the mass ratio of lignocellulosic nanofibers to ammonium polyphosphate includes, but is not limited to, 1:2, 1:3, 1:4, 1:5, 1:6, or 1:7.
Preferably, the lignocellulosic nanofibres are composed of full component lignocellulose, comprising 12 to 15wt% lignin, 29 to 40wt% cellulose and 24 to 28wt% hemicellulose. The preparation process simplifies the bleaching and purifying process of the traditional cellulose, greatly reduces the processing technology and reduces the cost; and the lignocellulose sources are wide, can be easily obtained by discarding reed straw, corn straw and the like, and can be reused for agricultural wastes, so that the environmental hazard caused by the combustion of the agricultural wastes is reduced.
Preferably, the environment-friendly flame retardant further comprises a transition metal ion compound, so that the flame retardant has a smoke suppression function.
Preferably, the transition metal ion compound comprises anhydrous zinc acetate or/and zinc carbonate.
Preferably, the mass ratio of the lignocellulose nano fiber to the ammonium polyphosphate to the transition metal ion compound is 1 (1-8): 1-4.
For example, the mass ratio of lignocellulosic nanofibers, ammonium polyphosphate, and transition metal ion compound includes, but is not limited to, 1:6:1, 1:4:1, 1:2:1, 1:6:2, 1:6:3, 1:4:2, 1:4:3, 1:2:2, or 1:2:3, etc.
The second aspect of the invention provides a preparation method of the water-insoluble green environment-friendly flame retardant.
When the flame retardant does not contain a transition metal ion compound, the preparation method comprises the following steps:
mixing lignocellulose nanofiber with solid content of 0.8-1.4 wt% with ammonium polyphosphate, ball milling to obtain the water-insoluble green environment-friendly flame retardant.
When the flame retardant contains a transition metal ion compound, the preparation steps are as follows:
mixing and ball milling lignocellulose nanofiber with the solid content of 0.8-1.4 wt%, ammonium polyphosphate and a transition metal ion compound to obtain the water-insoluble green environment-friendly flame retardant.
The preparation process of the flame retardant is simple, and only raw materials are mixed together for ball milling. In the ball milling process, the degree of fibrosis of the lignocellulose nanofiber is increased, the specific surface area of ammonium polyphosphate is increased, the contact area of the lignocellulose nanofiber and the ammonium polyphosphate is increased, the ammonium polyphosphate can be more uniformly loaded on the nanofiber, and the binding force is stronger. When the flame retardant is used for preparing paper, ammonium polyphosphate loaded on the nanofibers cannot be separated out, and the mechanical properties, flexibility and the like of the paper cannot be adversely affected while the flame retardance of the paper is endowed.
The technological parameters of the ball milling process have important influence on the performance of the flame retardant, if the ball milling rotating speed is too high, the time is too long, the degradation of lignocellulose nanofibers can be caused, and the length is shortened; too low ball milling speed and too short time can cause too large ammonium polyphosphate particles to be combined with lignocellulose nanofibers and not uniformly dispersed on lignocellulose nanofibers. In a preferred example, the ball milling is performed at a rate of 100 to 300rpm for a time of 0.5 to 6 hours. Further preferably, the ball milling time is 0.5 to 6 hours, preferably 4 hours.
The invention takes reed straw powder as an example, and provides a possible lignocellulose nanofiber preparation process:
crushing the reed straw which is harvested naturally, sieving the crushed reed straw with a 60-mesh sieve to obtain reed straw powder, soaking the reed straw powder in a 1% sodium hydroxide solution for ball milling, and performing ultrasonic treatment after washing. Wherein the ball milling time is 0.5-6 h, preferably 3h; the ultrasonic time is 0.5-3 h, preferably 2h.
The third aspect of the invention provides a flame retardant paper, which comprises the water-insoluble green environment-friendly flame retardant;
in the process of preparing the flame-retardant paper, a proper amount of flame retardant is added into pulp such as bamboo pulp board, wood pulp board, waste newspaper or printing paper, and the like, mixed and stirred, and then the paper is filtered and made. Preferably, the flame retardant is incorporated in the flame retardant paper in an amount of 10 to 30wt%, more preferably 20wt%.
The paper containing the flame retardant has flame retardant property and smoke suppression property, and also has excellent paper mechanical property, and has wide application prospect.
The beneficial effects of the invention are as follows:
the invention provides a non-water-soluble green environment-friendly flame retardant, wherein ammonium polyphosphate with larger specific surface area is uniformly and stably loaded on lignocellulose nanofibers with large length-diameter ratio, and when the flame retardant is used for preparing paper, the flame retardant is good in compatibility with paper pulp, not easy to separate out, can be uniformly dispersed in the paper, and can not have adverse effect on the paper performance while endowing the paper with flame retardant performance. Meanwhile, the flame retardant has the advantages of wide raw material sources, environmental protection, simple preparation, good compatibility with paper-based materials and wide application prospect.
Drawings
The following describes the embodiments of the present invention in further detail with reference to the drawings.
In FIG. 1 a) shows an SEM image of lignocellulose nanofibers before ball milling, b) shows an SEM image of ammonium polyphosphate before ball milling, c) shows flame retardant A in example 1 8 SEM image of LC, d) shows a 8 Phosphorous EDS map in LC.
Fig. 2 shows the results of the burning test of the paper in example 1.
Fig. 3 shows the results of the burning test of the paper sheets in example 2 and example 3.
Fig. 4 shows the results of the burning test of the paper sheets in comparative example 1 and comparative example 2.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments and the accompanying drawings. Like parts in the drawings are denoted by the same reference numerals. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
Example 1
The preparation process of the lignocellulose nanofiber/ammonium polyphosphate flame retardant comprises the following steps:
(1) Soaking reed straw powder particles in a 1% sodium hydroxide solution, then ball-milling for 3 hours at a rotating speed of 300rpm, washing a ball-milled product to be neutral, and then obtaining lignocellulose nanofiber by ultrasonic treatment;
(2) Adding lignocellulose nanofiber and ammonium polyphosphate (Aldammars reagent) into a ball milling tank according to the mass ratio of 1:8, and ball milling in an aqueous system for 3 hours at the rotating speed of 300rpm to obtain a No. 1 flame retardant A 8 LC (liquid crystal). As shown in FIG. 1, A in c) 8 The SEM image of LC shows that the flocculent ammonium polyphosphate is loaded among the nanofibers, wherein the diameter of the lignocellulose nanofibers is 2-5nm, and the length is 10-40 μm; the grain diameter of the ammonium polyphosphate is 50-300nm, and the thickness is 50-300nm; whereas the distribution of nanofibers before ball milling in a) is clearer; d) Shown A 8 The phosphorus element EDS map in LC shows that the ammonium polyphosphate is shown in A 8 The distribution in LC coincides with the distribution position of the nano fiber in c), namely the ammonium polyphosphate after ball milling is distributed on the nano fiber; it can also be seen that the ammonium polyphosphate before ball milling in b) is in the form of a block and has a size which is much larger than that of the ammonium polyphosphate in c).
The flame retardant No. 1 obtained in the embodiment is mixed with paper pulp for suction filtration, and the flame retardant paper is obtained after drying. Wherein the weight ratio of the flame retardant is 10wt%, 20wt% and 30wt%, respectively, corresponding toThe paper is recorded as 10A 8 LC、20A 8 LC and 30A 8 LC (liquid crystal). The paper to which the flame retardant was not added was designated as "control paper". The paper was subjected to a burn test, the results of which are shown in fig. 2. It can be seen that the paper without flame retardant burns rapidly and eventually forms soot, after 9s the fire is completely extinguished; and 10A 8 The LC paper rapidly forms coke, the fire is completely extinguished after 5 seconds, the burning time is shortened, and the LC paper has certain flame retardance; when the flame retardant is added by more than 20%, the flame retardant has the effect of non-continuous combustion, wherein 20A 8 LC and 30A 8 LC flame has extinguished at 3s and 1s respectively, and most of the paper remains uncombusted.
Example 2
The preparation process of the lignocellulose nanofiber/ammonium polyphosphate flame retardant in example 2 is exactly the same as that of example 1, and the difference from example 1 is that the mass ratio of lignocellulose nanofiber and ammonium polyphosphate (adamas reagent) is 1:2 to obtain the No. 2 flame retardant.
And mixing the No. 2 flame retardant obtained in the embodiment with paper pulp, performing suction filtration, and drying to obtain the flame-retardant paper. Wherein the weight ratio of the flame retardant is 30wt%, and the corresponding paper is 30A 2 LC (liquid crystal). The paper was subjected to a burn test, the results of which are shown in fig. 3. It can be seen that the paper has a certain flame retardance, becomes coke after burning, and can self-extinguish.
Example 3
The preparation process of the lignocellulose nanofiber/ammonium polyphosphate flame retardant in example 3 is exactly the same as that of example 1, and the difference from example 1 is that the mass ratio of lignocellulose nanofiber to ammonium polyphosphate (adamas reagent) is 1:4, so as to obtain a 3# flame retardant.
And mixing the 3# flame retardant obtained in the embodiment with paper pulp, performing suction filtration, and drying to obtain the flame retardant paper. Wherein the weight ratio of the flame retardant is 30wt%, and the corresponding paper is 30A 4 LC (liquid crystal). The paper was subjected to a burn test, the results of which are shown in fig. 3. It can be seen that the paper has a rapid char formation effect, self-extinguishes after a period of combustion process, leaving a longer residual carbon content. And 30A in example 2 2 LC comparison, with the same flame retardant addition, with flame retardantThe proportion of the lignocellulose nanofiber to the ammonium polyphosphate is reduced, namely the relative content of the ammonium polyphosphate in the flame retardant is increased, and the flame retardant effect of the paper is gradually increased.
Example 4
The preparation process of the lignocellulose nanofiber/ammonium polyphosphate/anhydrous zinc acetate flame retardant is different from that of the embodiment 1, anhydrous zinc acetate (Ala Ding Shiji) is added in the ball milling process of the step (2), wherein the mass ratio of the lignocellulose nanofiber to the ammonium polyphosphate (Ala Mars reagent) to the anhydrous zinc acetate (Ala Ding Shiji) is 1:8:1 and 1:8:1.5, and ball milling is carried out in an aqueous system for 3 hours at the rotating speed of 300rpm, so that the No. 4 flame retardant and No. 5 flame retardant are obtained.
The flame retardant No. 4 and the flame retardant No. 5 obtained in the embodiment are respectively mixed with paper pulp for suction filtration, and the flame retardant paper is obtained after drying, and the corresponding paper is marked as 20A 8 LCZn 1 And 20A 8 LCZn 1.5 . Wherein the weight ratio of the flame retardant is 20wt%. To a paper "control paper" to which no flame retardant was added, a flame retardant paper 20A containing no anhydrous zinc acetate was added 8 LC and paper 20A 8 LCZn 1 And 20A 8 LCZn 1.5 Cone calorimetric tests were performed to determine the time required for ignition (TTI), maximum heat release rate (pHRR), total Heat Release (THR), average weight loss rate (AMLR) and Smoke Release (SR). The results are shown in Table 1.
Table 1 results of cone calorimetric test of paper
Due to the existence of ammonium polyphosphate, the smoke generation amount of the paper in the combustion process is greatly improved, and the smoke amount is reduced after zinc acetate is added. The data of highest heat release rate, total heat release amount, average weight loss rate and the like show that when the mass ratio of lignocellulose nanofiber to ammonium polyphosphate (Aldammars reagent) to anhydrous zinc acetate is 1:8:1 or 1:8:1.5, the flame retardant ensures the flame retardant characteristics, and the smoke amount is 20A at the same time 8 LC is reduced, indicating that the flame retardant isBetter smoke suppression effect.
Comparative example 1
In comparison to example 1, ammonium polyphosphate was added directly to the pulp as follows:
mixing ammonium polyphosphate particles with paper pulp according to a dry weight ratio of 3:7, filtering, and drying to obtain the flame-retardant paper in the comparative example 1. Wherein the grain diameter of the ammonium polyphosphate is 2-40 μm and the thickness is 2-40 μm.
The flame retardant obtained in the comparative example 1 is mixed with paper pulp, filtered and dried to obtain flame retardant paper, and the corresponding paper is marked as 30APP. The paper was subjected to a burning test, the results of which are shown in fig. 4. It can be seen that at the same amount of flame retardant added, when ammonium polyphosphate is directly added, the paper cannot self-extinguish because of the loss in the paper making process due to incompatibility of ammonium polyphosphate and paper pulp and precipitation on the surface of the paper, resulting in a decrease in flame retardant effect.
Comparative example 2
In comparison with example 1, comparative example 2 was prepared by mixing lignocellulose nanofibers with ammonium polyphosphate and using the mixture as a flame retardant without performing a ball milling process.
And directly stirring and mixing lignocellulose nanofiber with the solid content of 1% and ammonium polyphosphate according to the mass ratio of 1:8, mixing with paper pulp according to the dry weight ratio of 3:7, carrying out suction filtration, and drying to obtain the flame-retardant paper in comparative example 2. Wherein the diameter of the lignocellulose nanofiber is 2-5nm, and the length is 10-40 mu m; the grain diameter of the ammonium polyphosphate is 2-40 mu m, and the thickness is 2-40 mu m.
The flame retardant obtained in comparative example 2 was mixed with pulp, suction filtered and dried to obtain flame retardant paper, the corresponding paper was designated 30A8LC-unBM. The paper was subjected to a burning test, the results of which are shown in fig. 4. Therefore, under the condition that the same flame retardant additive amount is adopted, when lignocellulose nanofibers and ammonium polyphosphate are directly stirred and mixed for papermaking, paper cannot be self-quenched, because the ammonium polyphosphate cannot be combined with the lignocellulose nanofibers under the action of mechanical external force without ball milling to uniformly disperse the ammonium polyphosphate on the lignocellulose nanofibers, the ammonium polyphosphate still exists in large particles independently, the incompatibility of the ammonium polyphosphate and paper pulp leads to loss in the papermaking process and precipitation on the surface of the paper, and the flame retardant effect is reduced.
It should be understood that the foregoing examples of the present invention are provided merely for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention, and that various other changes and modifications may be made therein by one skilled in the art without departing from the spirit and scope of the present invention as defined by the appended claims.
Claims (10)
1. The water-insoluble green environment-friendly flame retardant is characterized by comprising lignocellulose nanofibers and ammonium polyphosphate loaded on the lignocellulose nanofibers;
wherein the diameter of the lignocellulose nanofiber is 2-5nm, and the length is 10-40 mu m;
the particle size of the ammonium polyphosphate is 5-600nm, and the thickness is 5-600nm.
2. The flame retardant according to claim 1, wherein the mass ratio of the lignocellulose nanofibers to the ammonium polyphosphate is 1 (1-8).
3. The flame retardant of claim 1, wherein the lignocellulosic nanofiber comprises 12wt% to 15wt% lignin, 29wt% to 40wt% cellulose, and 24wt% to 28wt% hemicellulose.
4. The flame retardant of claim 1, wherein the environmentally friendly flame retardant further comprises a transition metal ion compound.
5. The flame retardant of claim 4, wherein the transition metal ion compound comprises anhydrous zinc acetate or/and zinc carbonate.
6. The flame retardant according to claim 4, wherein the mass ratio of the lignocellulose nanofibers, ammonium polyphosphate and transition metal ion compound is 1 (1-8): 1-4.
7. A method for preparing the water-insoluble green environmental-friendly flame retardant according to any one of claims 1 to 3, comprising the following steps:
mixing and ball milling lignocellulose nano fiber with solid content of 0.8-1.4 wt% and ammonium polyphosphate to obtain the water-insoluble green environment-friendly flame retardant.
8. A method for preparing the water-insoluble green environmental-friendly flame retardant according to any one of claims 4 to 6, comprising the following steps:
mixing and ball milling lignocellulose nanofiber with the solid content of 0.8-1.4 wt%, ammonium polyphosphate and a transition metal ion compound to obtain the water-insoluble green environment-friendly flame retardant.
9. The method according to claim 7 or 8, wherein the ball milling is performed at a rate of 100 to 300rpm for 0.5 to 6 hours.
10. A flame retardant paper comprising the water insoluble green flame retardant according to any one of claims 1 to 6;
preferably, the flame retardant is incorporated in the flame retardant paper in an amount of 10 to 30wt%.
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Cited By (1)
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| CN116875129A (en) * | 2023-07-19 | 2023-10-13 | 安徽畅宇泵阀制造有限公司 | Preparation method of refractory coating for centrifugal pump |
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