CN108360286A - A kind of preparation method of recessed native fire retardant papers - Google Patents
A kind of preparation method of recessed native fire retardant papers Download PDFInfo
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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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
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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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
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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
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to nitrogen
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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
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
- C08L1/04—Oxycellulose; Hydrocellulose, e.g. microcrystalline cellulose
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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
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/24—Homopolymers or copolymers of amides or imides
- C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
-
- 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
- D21H17/28—Starch
- D21H17/29—Starch cationic
-
- 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
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/69—Water-insoluble compounds, e.g. fillers, pigments modified, e.g. by association with other compositions prior to incorporation in the pulp or paper
-
- 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
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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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
- C08K2003/3081—Aluminum sulfate
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Abstract
The invention belongs to paper industry preparing technical fields, disclose a kind of preparation method of recessed native fire retardant papers, aluminum sulfate, microcrystalline cellulose, recessed soil, three phosphonitrile of N hexamethylol amino ring and ethylene glycol are added to the water 70 75 DEG C of stirrings jointly；Then sodium hydroxide solution high-speed stirred is added；Acrylamide and polyoxyethylene sorbitan monoleate are added in complex sol and are uniformly mixed；Then initiator is added, it is dry；It will be stirred evenly in the addition paper pulp for obtaining composite flame-proof filler, fire retardant papers obtained after manufacturing paper with pulp.The present invention adds recessed soil in the production process, recessed soil is the rare clay mineral of zeopan containing Shuifu County of layer chain structure, it is added in paper pulp simultaneously with other additive in paper technology copy paper process, fire retardant papers can be become, there is certain flame retardant effect when encountering open fire.
Description
Technical field
The invention belongs to paper industry preparing technical field more particularly to a kind of preparation methods of recessed native fire retardant papers.
Background technology
Currently, the prior art commonly used in the trade is such：
It is primary raw material that current paper, which mostly uses greatly plant fiber, by slurrying, and --- copy paper --- coating --- is processed
Etc. processes finally at paper, but this paper meets open fire and easily burns.
It is well known that paper and paper products are usually made of being manufactured paper with pulp by plant fiber.The inflammability of plant fiber determines
The inflammability of paper product, thus the use of paper often causes fire.As people are to the pay attention to day by day of fire safety evaluating, to certain paper
And the flame-retardancy requirements of board grades are also growing day by day.Therefore, preparation fire retardant papers also become more and more important, and [Li Chao, Hui Lanfeng, Liu Zhong hinder
The Development Status and trend [J] China paper industry of combustion paper, 2010,23:62-66.].
Fire retardant papers belong to the scope of speciality paper, refer to (disappearing certainly with flame with inhibition propagation of flame performance when catching fire
Property) paper.The anti-flammability of paper is only carbonized and burns without open fire that is in flame, and resistance is generated to the expansion of flame
Hinder effect.[Liu Jiao paper packages the pre-test of product fire protection flame retarding [J] China that fire retardant papers are realized generally by addition fire retardant
Packaging industry, 2002, (7):38-39；Huang Fanghui, Rayleigh honor Fire Retardant Honeycomb Paperboards [J] paper and papermaking, 2008,27 (1):46-
47.].The various types of fire retardant, but it is fire-retardant and few suitable for paper.It includes metallic hydrogen to be usually used in the fire retardant of paper at present
Oxide, metal oxide and halogen system, phosphorus system, boron system and nitrogenated flame retardant etc..Metal hydroxides, metal oxide-type are fire-retardant
Although agent and its compound have certain flame retardant effect and suppression cigarette ability, but flame retarding efficiency is low, to obtain good flame retardant effect,
Additive amount is generally 50% or more, so that the processing performance and physical property of paper are remarkably decreased [Zhao Qiang, Deng Guilin fire retardants
Application [J] China paper industry in paper industry, 2006,06:58-61.].In addition, this based flame retardant majority is hydrophily object
Matter, and most of fiber surface is hydroxyl, disturbs the formation of intermolecular hydrogen bonding between fiber, it is fire-retardant to limit such
Additive amount [the fire-retardant Annual Conference meeting of the flat halogen-free flame retardants current situation of Wang Hu, Liu Ji and trend [A] .2011 China of agent
Fire-retardant association of collection of thesis [C] China, 2011:5.].Common halogenated flame retardant mainly has organohalogen compounds, halogen ammonia in papermaking
Class hydrochlorate and halogen macromolecule etc., and mostly chlorine system and bromide fire retardant.Its advantage protruded is with high fire-retardance effect, the limit
Oxygen index (OI) is high, and oxygen index (OI) can reach 40% or more when exclusive use, the disadvantage is that releasing dense smoke after meeting combustion and corrosivity is toxic
Substance, during fire-retardant there may be the toxicants such as bioxin, furans [Christopher M, Preston L,
Amarasinghe G, et al.Evaluation of polar ethylene copolymers as fire retardant
Nanocomposite matrices [J] .Polymer Degradation and Stability, 2004,84：533-
544.], expiratory dyspnea, asphyxia are made one, or even is got lost, affects escape adversely, and problem of environmental pollution is serious.It is fire-retardant for paper
Phosphorus flame retardant mainly have phosphate, ammonium polyphosphate and phosphate etc..Phosphate ester flame retardants are that the fire-retardant middle comparison of paper is normal
, typical kind is tricresyl phosphate.Phosphorus flame retardant mainly passes through dilution effect and blanketing effect [Zhang Guanghua
The Beijing papermaking chemical product [M]:Sinopec publishing house, 2000:261-262] it is fire-retardant to be carried out to paper.Phosphorus flame retardant is gone through
History is longer, it not only overcomes, and halogen containing flame-retardant combustion fumes are big, release toxic and corrosive gas defect, while overcoming again
Inorganic combustion inhibitor high additive amount, has a high flame retardant at the shortcomings that seriously affecting the physical mechanical property of material, low cigarette, low toxicity,
The advantages that non-corrosive gas generates.But the use of phosphate flame retardant is mainly at present micromolecular compound, most of is liquid,
Have the shortcomings that volatility height, poor heat resistance.In order to overcome these disadvantages, from now on by give priority to macromolecule compound and
Copolymer [Ma Yongsheng Flame Retardant in Paper [J] southwest papermaking, 2006,03:47-49.].Boron system used in paper is fire-retardant is fire-retardant
Agent has zinc borate, barium metaborate, borax, ammonium borate etc..Incombustible is generated when borate compounds are heated is coated on paper surface, every
Exhausted contact of the paper with air, promotes carbonization.In addition, the crystallization water or thermally decomposed in conjunction with water that borate compounds contain,
Also flame retardant effect is enhanced to a certain extent.At present, boride as fire retardant still based on inorganic borate and boric acid, and
Organoboron flame-retardant is limited it and is used [the brave fire retardants of Wang Shu to a certain extent due to factors such as its stability difference and price height
With the Taiyuan flame-retarded technology [J] science and technology, 1995 (6):23].The nitrogenated flame retardant fire-retardant for paper be mainly melamine and its
Derivative, dicyandiamide salt, amine salt etc., they are also mainly by dilution effect and blanketing effect come fire retardant papers and paper products.Nitrogen
Flame retardant have many advantages, such as it is less toxic, corrosion-free, to heat and UV stable, inexpensive, but flame retardant effect poor [public affairs when being used alone
Dimension light, progress [J] papermaking chemical products of high jade outstanding person's papermaking fire retardants, 2002,03:26-28.].Phosphorus, nitrogenated flame retardant
It is generally applied in combination, because the two has synergistic function, [the fire retardants such as Pan Quanli, Xu Chengcheng, Liu Mingyou are in papermaking
Using with the papermaking of development [J] China, 2006, (5):39-42.].Melamine phosphate because simultaneously contain higher phosphorus, nitrogen, and
To the flame retardant effect of timber and paper, preferably [Wu Shengen, Liu Cuiying, Wang Xiong shake application [J] Hangzhou of the fire retardants in papermaking
Chemical industry, 2010,02:23-26；Progress [J] New Chemical Materials of Li Qiaoling, Wang Ya elder brother's halogen-free flame retardants, 1999,27
(5):14]。
As a whole, at present there are some disadvantages in the fire-retardant fire retardant of paper, and paper flame-retarded technology has been enter into one
New developing stage, the fire-retardant of the following paper base material are developed towards efficient, economic, environmentally friendly direction.
Phosphonitrile is that one kind is alternately arranged with phosphorus, nitrogen, has the compound of stable phosphorus nitrogen skeleton structure.Phosphonitrile
Unique phosphorus, aza structure and high phosphorus, nitrogen content are with good thermal stability and anti-flammability.Phosphonitrile has nothing
Smoke amount is few, flame retarding efficiency is high, does not generate the advantages that toxic and corrosive gas and is considered as before most having development when halogen, burning
One based flame retardant on way, has broad application prospects, and is developing direction [the flat phosphonitriles class of Bao Dongmei, Liu Ji of fire retardant from now on
Application study progress China of the compound in fire proofing is fire-retardant, and 2011, (3)：15-19；The current phosphorous flame-retardants of Qian Lijun
The researching and developing status China of agent is fire-retardant, and 2011, (3)：2-4；Allen,C.W.The use of phosphazenes as
fire resistant material s.J.Fire Sci.1993,11,320-328；Cai Zhe, Zhang Hong, He Hong force organophosphors
Fire retardant New research progress [J] fine-chemical intermediates, 2010,40 (4)：6-13.].
Three phosphonitrile of N- hexamethylol amino ring is one of the phosphonitrile fire retardant having been commercialized few in number.Document report,
The fire retardant not only has good flame retardant effect, but also washable [Hebesh A., WalyA., Abou-Okeil to textile
A.M..Flame retardant cotton[J].
Fire and aterials,1999,23(3):117-123；Kubota Shizuo, Fireproofing
method of fibers by aminophosphazene derivatives [P],JP0104074A2,1989-2-10；
Allen,C.W.The use of phosphazenes as fire resistant materials.J.Fire
Sci.1993,11,320-328；Higher-dimension is complete, Tang Shujuan, the synthesis of three phosphazene derivative fire retardant of the hydroxyls such as Sun De ring and performance
Study [J] dyeing and finishing techniques, 2008,30 (9)：11-14].Similitude based on paper products and textile fiber composition, this is fire-retardant
Agent should also have good flame retardant effect to paper and paper products, but yet there are no document report.
The method of production fire retardant papers mainly has the method that fire retardant is added in infusion process, surface rubbing method and slurry.Infusion process
Fire retardant papers are prepared by the way that paper is impregnated absorption fire retardant, this method need to adsorb a large amount of fire retardant, to performance shadow of paper itself
It rings greatly, such as moisture absorption is strong, deformation is big, intensity is low.Surface rubbing method is that fire retardant papers are made in the surface of fire retardant coating paper, is led to
It is often used a large amount of organic binder, flame retardant effect is not ideal enough, and is only suitable for the paper that need to be coated with, narrow application range.Slurry
Interior addition fire retardant is then the fire retardant that water-insoluble is added in slurry, and mixing is copied into fire retardant papers.This method is simple, is applicable in model
It encloses extensively, there is larger potentiality to be exploited and market value.
Aluminium hydroxide is a kind of common inorganic fire-retarded filler of papermaking, has suppression cigarette, low corrosion, cheap spy
Point, moreover it is possible to play the role of wear-resisting, enhancing, there is unique advantage.But the addition of a large amount of filling aluminium hydrates can be to body paper
Physical property has an adverse effect, and additive amount is few to influence flame retardant effect again.Therefore, filling aluminium hydrate how is reduced to paper
The adverse effect of physical property becomes important research topic.
In conclusion problem of the existing technology is：
(1) to the flame retardant effect of three phosphonitrile of N- hexamethylol amino ring, not specific foundation in evaluation；
(2) method that fire retardant is added in existing infusion process, surface rubbing method and slurry obtains the poor performance of product；
(3) existing preparation method pollution is big, not environmentally.
Solve the difficulty and meaning of above-mentioned technical problem：
Fire retardation of three phosphonitrile of N- hexamethylol amino ring to paper.As a result, it has been found that this fire retardant has very paper
Good flame retardant effect.When its dosage is the 5% of fire proofing gross mass, by TAPPI T461OS-79 (1.3mm) standard method
Experiment, vertical combustion have reached Eligibility requirements.When the dosage of the fire retardant is the 5.5% of fire proofing gross mass, the resistance of paper
Combustion grade has reached level-one, i.e. char length is less than 30mm, and ember is less than 0.5s, is not present after dust 0.5min.
Invention content
In view of the problems of the existing technology, the present invention provides a kind of preparation methods of recessed native fire retardant papers.
The invention is realized in this way a kind of preparation method of recessed native fire retardant papers, the preparation method of the recessed native fire retardant papers
Including：
1) by 10-15 parts sulfuric acids aluminium, 10-15 parts by weight microcrystalline cellulose, recessed soil 5-10 parts by weight, N- hexamethylols
70-75 DEG C of stirring in 60-100 parts by weight water is added in three phosphonitrile 3-8 parts by weight of amino ring and 0.5-1 parts by weight polyethylene glycol jointly
1-1.5h；
2) then be added 100-180 parts by weight mass fractions be 2-3% sodium hydroxide solution in 35-45 DEG C of high-speed stirred
20-25min obtains complex sol after cooling；
3) 100-120 parts by weight steps 1) are added in 2-4 parts by weight propylene amide and 0.5-1 parts by weight Tween-80s
It is uniformly mixed in obtained complex sol and pH is adjusted to 7-8；
4) and then 0.1-0.2 parts by weight initiators are added, 3-5h are stirred to react in 75-85 DEG C under argon gas protective condition,
It dries and grinds uniformly, obtain composite flame-proof filler；
5) it will be stirred evenly in the addition paper pulp for obtaining composite flame-proof filler, fire retardant papers, the compound resistance obtained after manufacturing paper with pulp
The absolute dry mass ratio for firing filler and paper pulp is (1-1.5)：8.
Further, it is coated again after fire retardant papers are obtained after manufacturing paper with pulp, finally carries out being cut into paper.
Further, the additive amount of three phosphonitrile of N- hexamethylols amino ring is 5 parts by weight.
Further, chemical addition agent, the absolute dry mass ratio of the chemical addition agent and paper pulp are also added in the paper pulp
For (0.1-0.2)：8.
Further, the chemical addition agent is cationic starch.
Further, the initiator is ammonium superphosphate.
Another object of the present invention is to provide a kind of preparation method of recessed native fire retardant papers,
Including：
1) by 10 parts sulfuric acid aluminium, 10 parts by weight microcrystalline celluloses, recessed native 5 parts by weight, N- hexamethylol amino ring three
70 DEG C of stirring 1h in 60 parts by weight water are added in 3 parts by weight of phosphonitrile and 0.5 parts by weight polyethylene glycol jointly；
2) and then sodium hydroxide solution that 100 parts by weight mass fractions are 2% is added in 35 DEG C of high-speed stirred 20min, it is cold
But complex sol is obtained afterwards；
3) it is answered what 2 parts by weight propylene amides and 0.5 parts by weight Tween-80 addition, 100 parts by weight steps 1) obtained
It closes and is uniformly mixed in colloidal sol and pH is adjusted to 7；
4) and then 0.1 parts by weight initiator is added, is stirred to react 3h in 75 DEG C under argon gas protective condition, drying is simultaneously ground
Uniformly, composite flame-proof filler is obtained；
5) it will be stirred evenly in the addition paper pulp for obtaining composite flame-proof filler, fire retardant papers, the compound resistance obtained after manufacturing paper with pulp
The absolute dry mass ratio for firing filler and paper pulp is 1：8.
Another object of the present invention is to provide a kind of preparation method of recessed native fire retardant papers,
Including：
1) by 15 parts sulfuric acid aluminium, 15 parts by weight microcrystalline celluloses, recessed native 10 parts by weight, N- hexamethylol amino ring three
75 DEG C of stirring 1.5h in 100 parts by weight water are added in 8 parts by weight of phosphonitrile and 1 parts by weight polyethylene glycol jointly；
2) and then sodium hydroxide solution that 180 parts by weight mass fractions are 3% is added in 45 DEG C of high-speed stirred 25min, it is cold
But complex sol is obtained afterwards；
3) 4 parts by weight propylene amides and 1 parts by weight Tween-80 addition, 120 parts by weight steps 1) are obtained compound
It is uniformly mixed in colloidal sol and pH is adjusted to 8；
4) and then 0.2 parts by weight initiator is added, is stirred to react 5h in 85 DEG C under argon gas protective condition, drying is simultaneously ground
Uniformly, composite flame-proof filler is obtained；
5) it will be stirred evenly in the addition paper pulp for obtaining composite flame-proof filler, fire retardant papers, the compound resistance obtained after manufacturing paper with pulp
The absolute dry mass ratio for firing filler and paper pulp is 1.5：8.
Another object of the present invention is to provide the preparation methods of the recessed native fire retardant papers
Including：
1) by 12 parts sulfuric acid aluminium, 12 parts by weight microcrystalline celluloses, recessed native 7 parts by weight, N- hexamethylol amino ring three
72 DEG C of stirring 1.2h in 80 parts by weight water are added in 6 parts by weight of phosphonitrile and 0.75 parts by weight polyethylene glycol jointly；
2) and then the sodium hydroxide solution that 150 parts by weight mass fractions are 2.5% is added in 40 DEG C of high-speed stirred 23min,
Complex sol is obtained after cooling；
3) it is answered what 3 parts by weight propylene amides and 0.75 parts by weight Tween-80 addition, 110 parts by weight steps 1) obtained
It closes and is uniformly mixed in colloidal sol and pH is adjusted to 7.5；
4) and then 0.15 parts by weight initiator is added, is stirred to react 4h in 80 DEG C under argon gas protective condition, drying is simultaneously ground
Mill is uniform, obtains composite flame-proof filler；
5) it will be stirred evenly in the addition paper pulp for obtaining composite flame-proof filler, fire retardant papers, the compound resistance obtained after manufacturing paper with pulp
The absolute dry mass ratio for firing filler and paper pulp is 1.2：8.
In conclusion advantages of the present invention and good effect are：
The present invention adds recessed soil in the production process, and recessed soil is the rare clay of zeopan containing Shuifu County of layer chain structure
Mineral, crystal shape are rodlike, needle-shaped, fibrous length 0.5~5um, wide 0.05~0.15um, are 2:1 clay mineral, i.e., two layers
Oxygen-octahedron, one layer of alumina octahedral determine that it is a kind of natural anti-flammability substance by its ingredient and construction, are making
It is added in paper pulp simultaneously with other additive in paper technique copy paper process, fire retardant papers can be become, had when encountering open fire certain
Flame retardant effect.
Three phosphonitrile of N- hexamethylol amino ring not only to the flame retarding efficiency of paper height, has with its fire-retardant paper and meets fiery carbonization face
Product is small, without residual flame, do not glow the advantages that, and easy to use, the intensity of fire retardant papers is still more satisfactory.
First aluminum sulfate is blended in water with microcrystalline cellulose by the present invention, then uses neutralisation in-situ preparation in the solution
Aluminium hydroxide, to obtain aluminium hydroxide-microcrystalline cellulose Inorganic-Organic Hybrid Material, then graft acrylamide obtains again
Composite flame-proof filler mixes with paper pulp and obtains fire retardant papers after manufacturing paper with pulp.
The preparation method of the present invention first pass through by aluminium hydroxide with microcrystalline cellulose is compound obtains inorganic-organic hybridization material
Material, on the one hand improves the binding ability of fire-retardant filler and paper fibre, the introducing of another aspect microcrystalline cellulose makes paper
Toughness be enhanced, to reduce adverse effect of the filler to paper physical property, meanwhile, acrylamide further connects
The modified binding ability for enhancing fire-retardant filler and paper once more of branch and the retention in paper, make fire-retardant filler in paper
Additive amount be increased, the efficient hardening physical property and flame retardant effect of fire retardant papers is highly practical.
The preparation method of the present invention is very environmentally friendly, and waste water used may be recovered, and can continue cycling through profit after processing
With.
Description of the drawings
Fig. 1 is the preparation method flow chart of recessed native fire retardant papers provided in an embodiment of the present invention.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
The prior art is to the flame retardant effect of three phosphonitrile of N- hexamethylol amino ring, not specific foundation in evaluation；
The method of addition fire retardant obtains the poor performance of product in existing infusion process, surface rubbing method and slurry；
Existing preparation method pollution is big, not environmentally.
Fig. 1, the preparation method of recessed native fire retardant papers provided in an embodiment of the present invention, including：
S101：By 10-15 parts sulfuric acids aluminium, 10-15 parts by weight microcrystalline cellulose, recessed soil 5-10 parts by weight, six hydroxyls of N-
Three phosphonitrile 3-8 parts by weight of methylamino ring and 0.5-1 parts by weight polyethylene glycol are added in 60-100 parts by weight water 70-75 DEG C jointly
Stir 1-1.5h；
S102：Then addition 100-180 parts by weight mass fractions are the sodium hydroxide solution of 2-3% in 35-45 DEG C of high speed
20-25min is stirred, complex sol is obtained after cooling；
S103：100-120 parts by weight steps are added in 2-4 parts by weight propylene amide and 0.5-1 parts by weight Tween-80s
It is uniformly mixed in the complex sol that S101 is obtained and pH is adjusted to 7-8；
S104：Then 0.1-0.2 parts by weight initiators are added, 3- is stirred to react in 75-85 DEG C under argon gas protective condition
5h, drying are simultaneously ground uniformly, and composite flame-proof filler is obtained；
S105：It will be stirred evenly in the addition paper pulp for obtaining composite flame-proof filler, fire retardant papers obtained after manufacturing paper with pulp, it is described compound
The absolute dry mass of fire-retardant filler and paper pulp ratio is (1-1.5)：8.
S106：It is coated again after obtaining fire retardant papers after manufacturing paper with pulp, finally carries out being cut into paper.
The additive amount of three phosphonitrile of N- hexamethylol amino ring is 5 parts by weight.
Chemical addition agent is also added in the paper pulp, the absolute dry mass ratio of the chemical addition agent and paper pulp is (0.1-
0.2)：8.
The chemical addition agent is cationic starch.
The initiator is ammonium superphosphate.
With reference to specific embodiment, the invention will be further described.
Embodiment 1
Another object of the present invention is to provide a kind of preparation method of recessed native fire retardant papers,
Including：
1) by 10 parts sulfuric acid aluminium, 10 parts by weight microcrystalline celluloses, recessed native 5 parts by weight, N- hexamethylol amino ring three
70 DEG C of stirring 1h in 60 parts by weight water are added in 3 parts by weight of phosphonitrile and 0.5 parts by weight polyethylene glycol jointly；
2) and then sodium hydroxide solution that 100 parts by weight mass fractions are 2% is added in 35 DEG C of high-speed stirred 20min, it is cold
But complex sol is obtained afterwards；
3) it is answered what 2 parts by weight propylene amides and 0.5 parts by weight Tween-80 addition, 100 parts by weight steps 1) obtained
It closes and is uniformly mixed in colloidal sol and pH is adjusted to 7；
4) and then 0.1 parts by weight initiator is added, is stirred to react 3h in 75 DEG C under argon gas protective condition, drying is simultaneously ground
Uniformly, composite flame-proof filler is obtained；
5) it will be stirred evenly in the addition paper pulp for obtaining composite flame-proof filler, fire retardant papers, the compound resistance obtained after manufacturing paper with pulp
The absolute dry mass ratio for firing filler and paper pulp is 1：8.
Embodiment 2
Another object of the present invention is to provide a kind of preparation method of recessed native fire retardant papers,
Including：
1) by 15 parts sulfuric acid aluminium, 15 parts by weight microcrystalline celluloses, recessed native 10 parts by weight, N- hexamethylol amino ring three
75 DEG C of stirring 1.5h in 100 parts by weight water are added in 8 parts by weight of phosphonitrile and 1 parts by weight polyethylene glycol jointly；
2) and then sodium hydroxide solution that 180 parts by weight mass fractions are 3% is added in 45 DEG C of high-speed stirred 25min, it is cold
But complex sol is obtained afterwards；
3) 4 parts by weight propylene amides and 1 parts by weight Tween-80 addition, 120 parts by weight steps 1) are obtained compound
It is uniformly mixed in colloidal sol and pH is adjusted to 8；
4) and then 0.2 parts by weight initiator is added, is stirred to react 5h in 85 DEG C under argon gas protective condition, drying is simultaneously ground
Uniformly, composite flame-proof filler is obtained；
5) it will be stirred evenly in the addition paper pulp for obtaining composite flame-proof filler, fire retardant papers, the compound resistance obtained after manufacturing paper with pulp
The absolute dry mass ratio for firing filler and paper pulp is 1.5：8.
Embodiment 3
Another object of the present invention is to provide the preparation methods of the recessed native fire retardant papers
Including：
1) by 12 parts sulfuric acid aluminium, 12 parts by weight microcrystalline celluloses, recessed native 7 parts by weight, N- hexamethylol amino ring three
72 DEG C of stirring 1.2h in 80 parts by weight water are added in 6 parts by weight of phosphonitrile and 0.75 parts by weight polyethylene glycol jointly；
2) and then the sodium hydroxide solution that 150 parts by weight mass fractions are 2.5% is added in 40 DEG C of high-speed stirred 23min,
Complex sol is obtained after cooling；
3) it is answered what 3 parts by weight propylene amides and 0.75 parts by weight Tween-80 addition, 110 parts by weight steps 1) obtained
It closes and is uniformly mixed in colloidal sol and pH is adjusted to 7.5；
4) and then 0.15 parts by weight initiator is added, is stirred to react 4h in 80 DEG C under argon gas protective condition, drying is simultaneously ground
Mill is uniform, obtains composite flame-proof filler；
5) it will be stirred evenly in the addition paper pulp for obtaining composite flame-proof filler, fire retardant papers, the compound resistance obtained after manufacturing paper with pulp
The absolute dry mass ratio for firing filler and paper pulp is 1.2：8.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement etc., should all be included in the protection scope of the present invention made by within refreshing and principle.
Claims (9)
1. a kind of preparation method of recessed native fire retardant papers, which is characterized in that the preparation method of the recessed native fire retardant papers includes：
1) by 10-15 parts sulfuric acids aluminium, 10-15 parts by weight microcrystalline cellulose, recessed soil 5-10 parts by weight, N- hexamethylol amino
70-75 DEG C of stirring 1- in 60-100 parts by weight water is added in three phosphonitrile 3-8 parts by weight of ring and 0.5-1 parts by weight polyethylene glycol jointly
1.5h；
2) then be added 100-180 parts by weight mass fractions be 2-3% sodium hydroxide solution in 35-45 DEG C of high-speed stirred 20-
25min obtains complex sol after cooling；
3) 100-120 parts by weight steps 1) are added in 2-4 parts by weight propylene amide and 0.5-1 parts by weight Tween-80s to obtain
Complex sol in be uniformly mixed and pH is adjusted to 7-8；
4) and then 0.1-0.2 parts by weight initiators are added, 3-5h is stirred to react in 75-85 DEG C under argon gas protective condition, it is dry
And grind uniformly, obtain composite flame-proof filler；
5) it will be stirred evenly in the addition paper pulp for obtaining composite flame-proof filler, fire retardant papers obtained after manufacturing paper with pulp, the composite flame-proof is filled out
The absolute dry mass ratio of material and paper pulp is (1-1.5)：8.
2. the preparation method of recessed native fire retardant papers as described in claim 1, which is characterized in that obtained after manufacturing paper with pulp after fire retardant papers again into
Row coating, finally carries out being cut into paper.
3. the preparation method of recessed native fire retardant papers as described in claim 1, which is characterized in that
The additive amount of three phosphonitrile of N- hexamethylol amino ring is 5 parts by weight.
4. the preparation method of recessed native fire retardant papers as described in claim 1, which is characterized in that be also added with chemistry in the paper pulp
The absolute dry mass ratio of additive, the chemical addition agent and paper pulp is (0.1-0.2)：8.
5. the preparation method of recessed native fire retardant papers as claimed in claim 4, which is characterized in that the chemical addition agent is cation
Starch.
6. the preparation method of recessed native fire retardant papers as described in claim 1, which is characterized in that the initiator is ammonium superphosphate.
7. a kind of preparation method of recessed native fire retardant papers, which is characterized in that the preparation method of the recessed native fire retardant papers includes：
1) by 10 parts sulfuric acid aluminium, 10 parts by weight microcrystalline celluloses, recessed native 5 parts by weight, three phosphonitrile 3 of N- hexamethylol amino ring
70 DEG C of stirring 1h in 60 parts by weight water are added in parts by weight and 0.5 parts by weight polyethylene glycol jointly；
2) and then the sodium hydroxide solution that 100 parts by weight mass fractions are 2% is added in 35 DEG C of high-speed stirred 20min, after cooling
Obtain complex sol；
3) 2 parts by weight propylene amides and 0.5 parts by weight Tween-80 addition, 100 parts by weight steps 1) are obtained compound molten
It is uniformly mixed in glue and pH is adjusted to 7；
4) and then 0.1 parts by weight initiator is added, is stirred to react 3h in 75 DEG C under argon gas protective condition, drying is simultaneously ground
It is even, obtain composite flame-proof filler；
5) it will be stirred evenly in the addition paper pulp for obtaining composite flame-proof filler, fire retardant papers obtained after manufacturing paper with pulp, the composite flame-proof is filled out
The absolute dry mass ratio of material and paper pulp is 1：8.
8. a kind of preparation method of recessed native fire retardant papers, which is characterized in that the preparation method of the recessed native fire retardant papers includes：
1) by 15 parts sulfuric acid aluminium, 15 parts by weight microcrystalline celluloses, recessed native 10 parts by weight, three phosphonitrile of N- hexamethylol amino ring
75 DEG C of stirring 1.5h in 100 parts by weight water are added in 8 parts by weight and 1 parts by weight polyethylene glycol jointly；
2) and then the sodium hydroxide solution that 180 parts by weight mass fractions are 3% is added in 45 DEG C of high-speed stirred 25min, after cooling
Obtain complex sol；
3) complex sol that 120 parts by weight steps 1) obtain is added in 4 parts by weight propylene amides and 1 parts by weight Tween-80
In be uniformly mixed and pH is adjusted to 8；
4) and then 0.2 parts by weight initiator is added, is stirred to react 5h in 85 DEG C under argon gas protective condition, drying is simultaneously ground
It is even, obtain composite flame-proof filler；
5) it will be stirred evenly in the addition paper pulp for obtaining composite flame-proof filler, fire retardant papers obtained after manufacturing paper with pulp, the composite flame-proof is filled out
The absolute dry mass ratio of material and paper pulp is 1.5：8.
9. a kind of preparation method of recessed native fire retardant papers, which is characterized in that the preparation method of the recessed native fire retardant papers includes：
1) by 12 parts sulfuric acid aluminium, 12 parts by weight microcrystalline celluloses, recessed native 7 parts by weight, three phosphonitrile 6 of N- hexamethylol amino ring
72 DEG C of stirring 1.2h in 80 parts by weight water are added in parts by weight and 0.75 parts by weight polyethylene glycol jointly；
2) and then the sodium hydroxide solution that 150 parts by weight mass fractions are 2.5% is added in 40 DEG C of high-speed stirred 23min, it is cooling
Complex sol is obtained afterwards；
3) 3 parts by weight propylene amides and 0.75 parts by weight Tween-80 addition, 110 parts by weight steps 1) are obtained compound molten
It is uniformly mixed in glue and pH is adjusted to 7.5；
4) and then 0.15 parts by weight initiator is added, is stirred to react 4h in 80 DEG C under argon gas protective condition, drying is simultaneously ground
It is even, obtain composite flame-proof filler；
5) it will be stirred evenly in the addition paper pulp for obtaining composite flame-proof filler, fire retardant papers obtained after manufacturing paper with pulp, the composite flame-proof is filled out
The absolute dry mass ratio of material and paper pulp is 1.2：8.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101117780A (en) * | 2007-08-16 | 2008-02-06 | 淮阴工学院 | Preparation method of modified attapulgite powder for paper making filler |
| CN103866648A (en) * | 2014-04-02 | 2014-06-18 | 青岛科技大学 | Preparation method of flame-resistant paper |
| CN103938487A (en) * | 2014-03-10 | 2014-07-23 | 王兆进 | Attapulgite clay fire retardation paper preparation method |
| CN105968414A (en) * | 2016-05-13 | 2016-09-28 | 江苏艾特克阻燃材料有限公司 | Attapulgite-synergetic hydroxide flame retardant |
| CN107059476A (en) * | 2017-03-30 | 2017-08-18 | 天长市天达纸箱纸品厂 | A kind of preparation method of fire retardant papers |
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2018
- 2018-01-25 CN CN201810073171.5A patent/CN108360286A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101117780A (en) * | 2007-08-16 | 2008-02-06 | 淮阴工学院 | Preparation method of modified attapulgite powder for paper making filler |
| CN103938487A (en) * | 2014-03-10 | 2014-07-23 | 王兆进 | Attapulgite clay fire retardation paper preparation method |
| CN103866648A (en) * | 2014-04-02 | 2014-06-18 | 青岛科技大学 | Preparation method of flame-resistant paper |
| CN105968414A (en) * | 2016-05-13 | 2016-09-28 | 江苏艾特克阻燃材料有限公司 | Attapulgite-synergetic hydroxide flame retardant |
| CN107059476A (en) * | 2017-03-30 | 2017-08-18 | 天长市天达纸箱纸品厂 | A kind of preparation method of fire retardant papers |
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