CN109777138A - The method that fire protection flame retarding, ultralight high-strength paper pulp foam are prepared using lignocellulose raw material - Google Patents
The method that fire protection flame retarding, ultralight high-strength paper pulp foam are prepared using lignocellulose raw material Download PDFInfo
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Abstract
The present invention provides provide the formula and preparation method of a kind of fire protection flame retarding, ultralight high-strength paper pulp foam.The formula are as follows: according to parts by weight, composed of the following components: 100 parts by weight of natural wooden fiber's raw material, cross-linking aid 0.5-10 parts by weight of preventing fires；Inorganic filler 1-20 parts by weight, chitosan 0-20 parts by weight；Foaming agent 0.5-10 parts by weight；Several parts by weight of water；Wherein, the weight fraction of natural wooden fiber's raw material in water is 0.5-5wt%.The method are as follows: natural wooden fiber's raw material after mechanical crushing is added in fire prevention cross-linking aid solution, cross-linking reaction is carried out under the conditions of heating and stirring；Continue to add inorganic filler and appropriate chitosan, continues stirring to end of reaction；Then foaming agent, mechanical stirring foaming are added；Remove extra moisture and foam, drying and moulding is to get arriving paper pulp foam.For the present invention using beneficial reciprocation between additive compound and different component, the paper pulp foaming properties being prepared are excellent, have wide industrialization prospect and it can be expected that economic benefit.
Description
Technical field
The invention belongs to Material Fields, are related to green fiber material and environment-friendly materials field, and in particular to a kind of ultralight height
Bullet and the paper pulp foam and preparation method thereof with fire prevention water resistance.
Background technique
Foamed material is a kind of high porous material of lightweight that can reach certain particular characteristic indexs.In recent years, porous
Foamed material due to its Ultralight, permeable, high porosity, high accessible surface product the features such as, be increasingly becoming new material and grind
The hot spot studied carefully.Currently, foam of polymers is mainly to be prepared by nondegradable petroleum based material, to resource and environment band
To threaten, therefore, has developed and used renewable resource to substitute the trend that conventional fossil resource becomes inevitable.Cellulose is the earth
The natural polymer of upper rich reserves, is primarily present in the cell wall of higher plant.Cellulose not only has source
Extensively, the advantages that nontoxic, good biocompatibility, biodegradability, and since a large amount of hydroxyl is contained on surface, it is easily modified,
It can also be used to prepare multifunctional material.Cellulose energy fictitious hosts valuableness, not biodegradable synthetic material are (such as: poly-
Urethane), the material of new generation referred to as great potential.
Currently, using cellulose preparation lightweight, high porosity porous material there are two main classes method: (1) by natural fiber material
Material dissolution forms homogeneous liquid and gel, captures gas in homogeneous liquid by surface tension, forms subsphaeroidal bubble；
Then curing molding and drying are carried out in certain circumstances, obtain solid foam.However, homogeneous cellulose solution is obtained,
Usually require cellulose solvent costly；And cellulose solvent is difficult to recycle under normal circumstances, i.e., can recycle, cost
Also extremely expensive.(2) in a liquid by nano-cellulose dispersion, gel is formed with modes such as solvent displacements by being crosslinked, finally
Freeze-dried/casting or the dry porous articles obtained of supercritical carbon dioxide.These porous materials are loosely referred to as cellulose
Foamed material, wherein internal can also be referred to as aeroge there are nano size voids.And obtain uniform nano-cellulose point
Dispersion liquid, first step are to prepare nano-cellulose, usually either logical by TEMPO oxidation, high-pressure homogeneous sour water solution
It crosses natural wooden fiber's raw material dissolution in low temperature and then regenerates acquisition；Chemical reagent used in the process is expensive, is not only produced into
This height, and have certain harm to environment.
To solve the above problems, researcher is dedicated to developing the preparation work of more environmentally friendly and inexpensive cellulose sponge
Skill.Patent of invention CN103131038A discloses " a kind of preparation method of lignocellulose foam material ".Described in the invention
Preparation method mainly comprises the steps that (1) crushes lignocellulosic to obtain the wood powder of 20~200 mesh；(2) wood powder is added
Grinding distribution 30min~48h is carried out into water, obtains lignocellulosic aqueous dispersions；(3) to lignocellulosic aqueous dispersions into
Row freeze-drying process to get arrive lignocellulose foam material.Preparation method described in the invention is simple, and cost of material is low
It is honest and clean, reduce preparation cost；And pure green environmental protection.Application for a patent for invention CN107915860A discloses a kind of " nanofiber
The preparation method of plain microcellular foam ".The application for a patent for invention is first with concentrated sulfuric acid hydrolyzing microcrystalline cellulose, ultrasound centrifugation system
Standby nano-cellulose, then with polylactic acid (PLA) it is composite foamed after uniform foam cell obtained by supercritical drying drying method
PLA/NCC composite foam material.Preparation method described in this application, it is simple easily operated, save raw material.It is freeze-dried and super
Critical drying is traditional method for preparing porous material.Wherein, it is dry can also to change freezing by distillation dehydration for frozen product
Dry condition and medium adjust the network state and density of aeroge.The principle of supercritical drying is in the supercritical state, no
There are liquid-vapor interfaces, capillarity are also just not present, therefore will not cause the contraction and structural damage of gelinite, final
There is the material of nano-pore structure to gassy.However, both methods all deposits method length experimental period, equipment high production cost
And the problem of complex process, it is difficult to form large-scale production.
In conclusion foam fabrication process remains the production and application that many problems restrict its scale, such as:
In drying process, foam generates biggish cavity, to influence the performance of foam, the treatment process period is long, not green, chemical drugs
The problems such as product are expensive and are difficult to recycle, and preparation cost is higher.In addition, conventional method preparation paper pulp foamy body and fire prevention,
Heat-proof quality is poor, is not easy to be commercialized.To be modified, need to carry out complicated, the disagreeableness subsequent place of at high cost or environment
Reason.Therefore, it is necessary to develop a kind of efficient, sustainable, inexpensive and environment amenable method to prepare high-performance paper pulp foam,
Method involved in the present invention can satisfy these urgent demands just.
Summary of the invention
Aiming at the problem that in the presence of the preparation of foam in the prior art, the present invention provides provide a kind of fire protection flame retarding, super
The preparation method of light high-strength paper pulp foam.Not only process is simple, low in cost for method of the present invention, and is not related to holding high
Expensive chemical reagent and process equipment；Furthermore the present invention utilizes the beneficial reciprocation between additive compound and different component, system
Standby obtained paper pulp foaming properties are excellent, have wide industrialization prospect and it can be expected that economic benefit.
Technical solution of the present invention: the method that fire protection flame retarding, ultralight high-strength paper pulp foam are prepared using lignocellulose raw material,
The following steps are included:
(1) according to weight ratio 1:(20-200), natural wooden fiber's raw material after mechanical crushing is added to fire prevention cross-linking aid
In solution, cross-linking reaction is carried out under the conditions of heating and stirring, obtains pulp fiber suspension.The fire prevention cross-linking aid is
Borate, boric acid or metaboric acid, the borate are sodium borate decahydrate, kodalk, more Boratexes, dipotassium tetraborate or inclined
Potassium borate；The concentration of the fire proofing additive solution is 0.1-0.6M.The temperature of the cross-linking reaction is 35-60 DEG C, reaction
Time is 0.5-6 h, and mixing speed is 100-2000 rpm.Boron element is the element of plant health growth, and in minute quantity
The mechanical tenacity of plant can be dramatically increased in the presence of boron element, present invention utilizes bio-imitability can increase paper pulp foam
Intensity, so that the intensity of foam has obtained significantly improving.In addition, boron-containing compound or environmentally protective fire retardant.
Wherein, natural wooden fiber's raw material is market pulp, waste paper, straw-stalk type cultural waste, cotton and cotton
The mixing of one or more of short flannel；The market pulp is bleaching needle-point leaf pulp, bleached hardwood pulp, dissolving pulp or does not float
Paper pulp.
(2) it remains temperature-resistant, inorganic filler is added in the pulp fiber suspension obtained to step (1) and appropriate shell is poly-
Sugar continues stirring to end of reaction, obtains uniform paper pulp fiber mixed material.The inorganic filler is nanometer titanium dioxide
Silicon, montmorillonite, flyash, sepiolite, expanded perlite and hollow glass micropearl are one or more of；The dosage of the inorganic filler
For the 1-20wt% of natural wooden fiber's raw material.The dosage of the chitosan is the 1-20wt% of natural wooden fiber's raw material.It is described
Mixing speed is 100-2000 rpm, and mixing time is 0.5-6 h.Not only intensity is more for the paper pulp foam for preparing after addition chitosan
It is good, and have water resistance, it can be stable not defeated and dispersed in water.The transmitting that inorganic filler is not only able to retardance heat is added, drops significantly
Compressive strength is also promoted to original 3 times or more by the thermal conductive property of low paper pulp foam.This is because Boratex and chitosan
It can play the role of crosslinking, retention, enhancing, more inorganic fillers can be made to pass through the modes such as charge effect, covalent linkage
It keeps, increases the binding force of inorganic filler and fiber.
(3) foaming agent, mechanical stirring foaming are added in the paper pulp fiber mixed material obtained to step (2)；Then it removes
Extra moisture and foam, the paper pulp foam isolated.The foaming agent be lauryl sodium sulfate, octylame, decyl amine,
Dodecyl p-methyl benzenesulfonic acid receives, one or more of sodium sulfate of polyethenoxy ether of fatty alcohol；The dosage of the foaming agent is
The 0.5-10wt% of natural wooden fiber's raw material.
(4) molding is dried in the paper pulp foam that step (3) obtains to get the fire prevention, wet-strong paper pulp foam is arrived.
After the method for the drying and moulding is natural air drying 2-10h, vacuum drying or convection drying are carried out.The vacuum drying temperature
It is 30-60 DEG C, the vacuum drying time is 1-8 h；The temperature of the convection drying is 25-90 DEG C, and the time of convection drying is
10-24h。
The formula of fire protection flame retarding, ultralight high-strength paper pulp foam is prepared using lignocellulose raw material, according to parts by weight, by with
The following group is grouped as: 100 parts by weight of natural wooden fiber's raw material of crushing, cross-linking aid 0.5-10 parts by weight of preventing fires；Inorganic filler
1-20 parts by weight, chitosan 0-20 parts by weight；Foaming agent 0.5-10 parts by weight；Several parts by weight of water；Wherein, the natural wood
The weight fraction of fibrous raw material in water is 0.5-5wt%.Natural wooden fiber's raw material is market pulp, waste paper, stalk
The mixing of one or more of class agricultural wastes, cotton and cotton linter；The market pulp is bleaching needle-point leaf pulp, bleaching
Hardwood pulp, dissolving pulp do not float paper pulp.The fire prevention cross-linking aid is borate, boric acid or metaboric acid, and the borate is
Sodium borate decahydrate, kodalk, more Boratexes, dipotassium tetraborate or potassium metaborate；The inorganic filler is nanometer titanium dioxide
Silicon, montmorillonite, flyash, sepiolite, expanded perlite and hollow glass micropearl are one or more of；The foaming agent is dodecane
Base sodium sulphate, octylame, decyl amine, dodecyl p-methyl benzenesulfonic acid receive, one or more of sodium sulfate of polyethenoxy ether of fatty alcohol.
The application of the fire protection flame retarding, ultralight high-strength paper pulp foam, the thermal insulating material as outdoor architecture and interior decoration
Material.The thermal insulation material has both water-fast, sound-absorbing/sound insulation performance of preventing fires.
The advantages of the present invention are as follows:
1. one step of preparation method of the present invention utilizes the collaboration crosslinked action of boron ion, cellulose and chitosan, not only mention
The machinery and fire protecting performance of product have been risen, and has effectively increased the retention of inorganic filler and natural fiber, has improved product
Production efficiency；Meanwhile the increase that inorganic filler is kept reduces expanding with heat and contract with cold for foamed material, the size for improving foam is steady
It is qualitative, and then the reliability and service life of final paper pulp foam can be improved.
2. preparation method of the present invention uses cheap natural wooden fiber for raw material, " one kettle way " is utilized simultaneously
Realize the purpose of cellulose chemistry crosslinking and foaming；Not only raw material sources are extensive, renewable, cheap；And it prepared
Journey is simple, and temperature is lower, can carry out under normal pressure, and low energy consumption, low for equipment requirements, to substantially increase industrialization production
Feasibility.
3. the used chemicals of preparation method of the present invention is at low cost, and produced waste liquid can be recycled,
Whole process is sustainable, environmentally friendly；Further improve the prospect of the marketization.
4. the density of paper pulp foam prepared by the present invention is down to 20 mg/cm3；After compression 30 times, foam shape is still
Certain physical strength and original form are so kept, greatest compressive strength is up to 500 KPa；Limit oxygen index is up to 39, thermally conductive
Coefficient, can be with self-extinguishment down to 15 mW/ (mK), and fire protecting performance is excellent.
Detailed description of the invention
Fig. 1 is pictorial diagram of the paper pulp foam of the preparation of the embodiment of the present invention 1 at the top of dandelion.
Fig. 2 is that the state diagram after paper pulp foam combustion is made in comparative example 2.
Fig. 3 is the state diagram after the paper pulp foam combustion prepared in the embodiment of the present invention 2.
Fig. 4 is the state diagram after the burning of the paper pulp foam prepared in the embodiment of the present invention 5.
Fig. 5 is the stress-strain curve of the paper pulp foam prepared in the embodiment of the present invention 4.
Fig. 6 is the paper pulp foam for preparing stable diagram in water in the embodiment of the present invention 5.
Fig. 7 is the infrared thermal imaging figure after the paper pulp foam bottom end heating prepared in the embodiment of the present invention 4.
Fig. 8 is the infrared thermal imaging figure being made after the heating of paper pulp foam bottom end in comparative example 2.
Specific embodiment
The present invention will be further explained with reference to the examples below.
Following embodiment is only used as the example of embodiment of the present invention to enumerate, and does not limit the present invention in any way,
It will be appreciated by those skilled in the art that the modification or expansion in the range of without departing from essence and design of the invention each fall within this
The protection scope of invention.
Embodiment 1: preparing paper pulp foam by raw material of commodity bleaching needle-point leaf pulp plate, according to the following steps:
(1) bleaching needle-point leaf pulp plate is broken up with pulverizer, the raw material for then taking 3 g to break up is placed in reaction vessel, is added 197
The sodium borate decahydrate solution of 0.1 M of mL stirs 2 h at 35 DEG C, and adjusting mixing speed is 100 rpm；Nothing is added later
10 wt%(of machine filler sepiolite is relative to natural fiber raw material) and 20 wt%(of chitosan relative to natural fiber raw material), after
Continuous stirring 0.5h, mixing speed are 1000 rpm；Finally addition 5 wt%(of foaming agent lauryl sodium sulfate is relative to natural fibre
Dimension raw material) continue to stir 2 h, mixing speed is 2000 rpm, is cooled to room temperature after reaction.
(2) extra foam and liquid are removed by way of vacuum filtration, the paper pulp foam of acquisition is at ambient temperature
Dry 2h, the then dry 14 h molding under 60 DEG C of oven conditions, obtains paper pulp foam.
The density of the paper pulp foam is 20 mg/cm3；Compressive strength is 280.1 KPa, after compressing 30 times, is kept original
85 % of height；Thermal coefficient is 35 mW/ (mK)；Limit oxygen index is 28.The paper pulp foam can be placed on dandelion
Top (Fig. 1), intuitively illustrates the characteristic that its density is low, ultralight.
Embodiment 2: preparing paper pulp foam by raw material of commodity bleached hardwood pulp plate, according to the following steps:
(1) it then takes 3 g above-mentioned raw materials to be placed in reaction kettle bleached hardwood pulp plate mechanical dispersion with pulverizer, is added 197
More dobell's solutions of 0.1 M of mL react 1 h at 45 DEG C, and adjusting mixing speed is 2000 rpm；Inorganic fill out is added later
Expect nano silica 1wt% (relative to natural fiber raw material) and chitosan 5wt%(relative to natural fiber raw material), continue
1 h is stirred, mixing speed is 1500 rpm.Finally addition foaming agent octylame 0.5wt%(is relative to natural fiber raw material) continue to stir
2 h, 1000 rpm of mixing speed, are cooled to room temperature after reaction.
(2) extra foam and liquid are removed by way of vacuum filtration.The paper pulp foam of acquisition is at ambient temperature
Dry 4 h, the then dry 8 h molding under 30 DEG C of vacuum conditions, obtain paper pulp foam.
The density of the paper pulp foam is 20.5 mg/cm3；Compressive strength is 398.5 KPa, after compressing 30 times, keeps former
The 88% of beginning height；Thermal coefficient is 25.7 mW/ (mK), limit oxygen index 33.
Embodiment 3: preparing paper pulp foam by raw material of old newsprint, according to the following steps:
(1) old newsprint is broken up with pulverizer, 3 g above-mentioned raw materials is then taken to be placed in reaction vessel, 397 mL, 0.1 M is added
Sodium borate decahydrate solution.Then 0.5 h is stirred to react at 90 DEG C, adjusting mixing speed is 1000 rpm, Zhi Houjia
Enter 20 wt% of inorganic filler nano zeolite (relative to wastepaper as raw material) and chitosan 15wt%(relative to wastepaper as raw material), continue
3h is stirred, mixing speed is 1200 rpm.Finally addition 10 wt%(of foaming agent dodecyl p-methyl benzenesulfonic acid sodium is relative to useless
Paper material) continue to stir 0.5h, mixing speed is 1500 rpm, is cooled to room temperature after reaction.
(2) extra foam and liquid are removed by way of vacuum filtration.The paper pulp foam of acquisition is at ambient temperature
Dry 4h, then drying forms for 24 hours under 25 DEG C of natural conditions, obtains paper pulp foam.
The density of the paper pulp foam is 19 mg/cm3；Compressive strength is 387.2KPa, after compression 30 times, is kept original
The 90% of height；Thermal coefficient is 18.7 mW/ (mK), limit oxygen index 31.
Embodiment 4: being that raw material prepares paper pulp foam by commodity bleaching wheat-straw pulp, according to the following steps:
(1) wheat-straw pulp is broken up with pulverizer, the raw material for taking 3 g to break up is placed in reaction vessel, and the ten of 197 mL0.1M are added
It is hydrated sodium tetraborate solution, 5 h are then stirred to react at 60 DEG C, adjusting mixing speed is 500 rpm.It is added later inorganic
5 wt% of filler nanometer montmorillonite (relative to natural fiber raw material) and 20 wt%(of chitosan are relative to natural fiber raw material),
Continue to stir 2 h, mixing speed is 800 rpm.Finally addition foaming agent lauryl sodium sulfate 7wt%(is relative to natural fiber
Raw material) continue to stir 1 h, mixing speed is 800 rpm, is cooled to room temperature after reaction.
(2) extra foam and liquid are removed by way of vacuum filtration.The paper pulp foam of acquisition is at ambient temperature
Dry 2 h, the then dry 20 h molding under 45 DEG C of oven conditions, obtain paper pulp foam.
The density of the paper pulp foam is 20.1 mg/cm3；Compressive strength is up to 500.0 KPa(Fig. 5), after compressing 30 times,
It keeps 83 % of original height；Thermal coefficient is 20.6 mW/ (mK), limit oxygen index 36.Fig. 7 is the present embodiment system
The infrared thermal imaging figure of standby paper pulp foam.As seen from Figure 7, sample is placed on 70oIn C heating plate after 3 hours, sample top
End temperature only has 15oC, and the temperature of sample middle-end only has about 18oC, heat-proof quality are good.Its compressive strength is up to 500 kPa
Embodiment 5: preparing paper pulp foam by raw material of cotton, according to the following steps:
(1) cotton is crushed to 2-10 mm long with pulverizer, 3 g above-mentioned raw materials is then taken to be placed in reaction vessel, be added 197
The metaboric acid solution of 0.2 M of mL；Then 1.5 h are stirred to react at 90 DEG C, adjusting mixing speed is 800 rpm.It is added later
15 wt% of inorganic filler nano montmorillonite (relative to natural fiber raw material) and chitosan 8wt%(is relative to natural fiber original
Material), continue to stir 0.5h, mixing speed is 500 rpm.Finally add 3 wt% of foaming agent sodium sulfate of polyethenoxy ether of fatty alcohol
(relative to natural fiber raw material) continues to stir 4 h, and mixing speed is 500 rpm, is cooled to room temperature after reaction.
(2) extra foam and liquid are removed by way of vacuum filtration.The paper pulp foam of acquisition is at ambient temperature
Dry 4 h, the then dry 6 h molding under 90 DEG C of oven conditions, obtain paper pulp foam.
The density of the paper pulp foam is 19.7 mg/cm3；Compressive strength is 335.1 KPa, after compressing 30 times, keeps former
The 78% of beginning height；Thermal coefficient is 24.8 mW/ (mK), limit oxygen index 35.The paper pulp foamed material is immersed in water
In, it is able to maintain that original foam form (Fig. 6)；In the case where lighting, there is self-extinguishment phenomenon, and remains to tie up after fray-out of flame
Hold original physical aspect (Fig. 4).
Embodiment 6: preparing paper pulp foam by not floating leaf wood paddle board, according to the following steps:
(1) commodity needlebush paddle board is broken up with pulverizer, 3 g above-mentioned raw materials is then taken to be placed in reaction vessel, be added 197
In the dipotassium tetraborate solution of 0.4 M of ml；Then 3h is stirred at 75 DEG C, adjusting mixing speed is 1500 rpm.It is added later
Inorganic filler flyash 8wt% (relative to natural wooden fiber's raw material) and chitosan 10wt%(is relative to natural wooden fiber's original
Material), continue to stir 4h, mixing speed is 2000 rpm.Finally addition foaming agent lauryl sodium sulfate 8wt%(is relative to natural
Fibrous raw material), continue to stir 6h, mixing speed is 500 rpm, is cooled to room temperature after reaction.
(2) extra foam and liquid are removed by way of vacuum filtration.The paper pulp foam of acquisition is at ambient temperature
Dry 10 h, the then dry 1h molding under 60 DEG C of vacuum conditions, obtain paper pulp foam.
The density of the paper pulp foam is 20.3 mg/cm3；Compressive strength is 365.3 KPa, after compressing 30 times, is kept
87 % of original height；Thermal coefficient is 32.3 mW/ (mK), limit oxygen index 28.
Embodiment 7: preparing paper pulp foam by commodity softwood pulp, according to the following steps:
(1) pulpboard is broken up with pulverizer, 3 g needlebush paddle boards is taken to be placed in reaction vessel, ten water of 597 mL 0.6M are added
Close sodium tetraborate solution；Then 4 h are stirred to react at 60 DEG C, adjusting mixing speed is 1200 rpm.Inorganic fill out is added later
Expect 20 wt% of nano montmorillonite (relative to natural fiber raw material), continues to stir 6h, mixing speed is 100 rpm.Finally add
2 wt%(of foaming agent octylame is relative to natural fiber raw material) continue to stir 2 h, adjusting mixing speed is 1000 rpm, reaction knot
It is cooled to room temperature after beam.
(2) extra foam and liquid are removed by way of vacuum filtration.The paper pulp foam of acquisition is at ambient temperature
Dry 6 h, the then dry 3 h molding under 45 DEG C of vacuum conditions, obtain paper pulp foam.
The density of the paper pulp foam is 21 mg/cm3；Compressive strength is 180.6 KPa, after compressing 30 times, keeps former
The 80% of beginning height；Thermal coefficient is 30.6 mW/ (mK), limit oxygen index 29.
Comparative example 1: preparing paper pulp foam by raw material of cotton, according to the following steps:
(1) cotton is crushed to 2-10 mm long with pulverizer, then takes 3 g above-mentioned raw materials to be placed in reaction vessel, does not add boron
Sour sodium and chitosan, are then stirred to react 1.5 h at 90 DEG C, and adjusting mixing speed is 800 rpm.Inorganic filler is added later
15 wt% of nano montmorillonite (relative to natural fiber raw material) continues to stir 0.5h, and mixing speed is 500 rpm.Finally add
3 wt%(of foaming agent sodium sulfate of polyethenoxy ether of fatty alcohol is relative to natural fiber raw material) continue to stir 4 h, mixing speed is
500 rpm, are cooled to room temperature after reaction.
(2) extra foam and liquid are removed by way of really filtering.The paper pulp foam of acquisition is done at ambient temperature
Dry 4 h, the then dry 6 h molding under 90 DEG C of oven conditions, obtains paper pulp foam.
The compressive strength of the paper pulp foam is 72.8 KPa；After compression 30 times, it is only able to maintain the 42.5% of original height；It leads
Hot coefficient is 52.8 mW/ (mK), limit oxygen index 29.Paper pulp foam (the compressive strength 335.1 prepared with embodiment 5
KPa after compressing 30 times, keeps the 78% of original height；Thermal coefficient is 24.8 mW/ (mK), limit oxygen index 35) phase
Than it is found that the compressive strength of the paper pulp foam substantially reduces, thermal coefficient is greatly increased.This is because not adding sodium tetraborate
Lack effective interaction between the paper pulp foamed fibre of chitosan, while also resulting in inorganic filler in the process of suction filtration
In be largely lost, cause compressive strength and elasticity decline to a great extent.
Comparative example 2: being that raw material prepares paper pulp foam by commodity bleaching wheat-straw pulp, according to the following steps:
(1) pulpboard is broken up with pulverizer, 3 g straws is taken to be placed in reaction vessel, ten four boron of hydration of 197 mL0.1M are added
Acid sodium solution, is then stirred to react 5 h at 60 DEG C, and adjusting mixing speed is 500 rpm.It is added without any inorganic fill out later
Material, is directly added into 20 wt%(of chitosan relative to natural wooden fiber's raw material), continue to stir 2 h, mixing speed 800
rpm.Finally addition foaming agent lauryl sodium sulfate 7wt%(is relative to natural wooden fiber's raw material) continue to stir 1 h, stirring
Speed is 800 rpm, is cooled to room temperature after reaction.
(2) extra foam and liquid are removed by way of vacuum filtration.The paper pulp foam of acquisition is at ambient temperature
Dry 2 h, the then dry 20 h molding under 45 DEG C of oven conditions, obtain paper pulp foam.
The compressive strength of the paper pulp foam is 132.0 KPa, after compressing 30 times, keeps 82.1 % of original height；It leads
Hot coefficient is 60.6 mW/ (mK), limit oxygen index 36.The embodiment 4(compressive strength more similar with preparation process be
500.0 KPa after compressing 30 times, keep 83 % of original height；Thermal coefficient is 20.6 mW/ (mK), limit oxygen index
36) to compare, inorganic filler is not added, the Flexible change of product is little, but compressive strength decline is obvious, and thermal coefficient is big
It is big to increase.
Fig. 8 is the infrared thermal imaging figure that sample is made in the present embodiment.As shown in Figure 8, add at 70 DEG C of bottom end temperature of heating plate
For heat under conditions of three hours, the tip temperature of the sample is 18 DEG C, and middle-end temperature is 23 DEG C.Illustrate, this comparative example system
Standby sample still has certain heat-proof quality, but compared with the sample of addition inorganic filler (compared with Fig. 7 of embodiment 4),
Heat-proof quality has a degree of decline.
Comparative example 3: preparing common paper pulp foam as raw material using cotton, according to the following steps:
(1) cotton is crushed to 2-10 mm long with pulverizer, then takes 3 g above-mentioned raw materials to be placed in reaction vessel, does not add boron
Sour sodium and chitosan, are then stirred to react 1.5 h at 90 DEG C, and adjusting mixing speed is 800 rpm.Foaming agent rouge is added later
3 wt%(of fat alcohol polyethenoxy ether sodium sulfate is relative to natural fiber raw material) continue to stir 4 h, mixing speed is 500 rpm, instead
It is cooled to room temperature after answering.
(2) extra foam and liquid are removed by way of vacuum filtration.The paper pulp foam of acquisition is at ambient temperature
Dry 4 h, the then dry 6 h molding under 90 DEG C of oven conditions, obtain paper pulp foam.
The intensity of the paper pulp foam only has 1.3KPa, and shape is collapsed rapidly in water, becomes original paper pulp form.And
In the state of lighting, burning becomes ashes rapidly, is unable to maintain that original foam form.
In summary, the density of paper pulp foam of the present invention is down to 20 mg/cm3；After compression 30 times, foam shape
Shape still maintains certain physical strength and original form, and greatest compressive strength is up to 500 KPa；Limit oxygen index is up to 39,
Thermal coefficient, can be with self-extinguishment down to 15 mW/ (mK), and fire protecting performance is excellent.This is because the present invention utilizes boron ion, fiber
The collaboration crosslinked action of element and chitosan, not only improves the machinery and fire protecting performance of product, but also effectively increase inorganic fill out
The retention of material and natural fiber, and then expanding with heat and contract with cold for foamed material is reduced, improve the dimensional stability of foamed material.
Claims (10)
1. the method for preparing fire protection flame retarding, ultralight high-strength paper pulp foam using lignocellulose raw material；It is characterized by comprising following
Step:
(1) according to weight ratio 1:(20-200), natural wooden fiber's raw material after mechanical crushing is added to fire prevention cross-linking aid
In solution, cross-linking reaction is carried out under the conditions of heating and stirring, obtains pulp fiber suspension；
(2) it remains temperature-resistant, inorganic filler and appropriate chitosan is added in the pulp fiber suspension obtained to step (1),
Continue stirring to end of reaction, obtains uniform paper pulp fiber mixed material；The dosage of the inorganic filler is that natural wood is fine
Tie up the 1-20wt% of raw material；
(3) foaming agent, mechanical stirring foaming are added in the paper pulp fiber mixed material obtained to step (2)；Then it is extra to remove
Moisture and foam, the paper pulp foam isolated；
(4) molding is dried in the paper pulp foam that step (3) obtains to get the fire prevention, wet-strong paper pulp foam is arrived.
2. the method according to claim 1 that fire protection flame retarding, ultralight high-strength paper pulp foam are prepared using lignocellulose raw material,
It is characterized by: fire prevention cross-linking aid described in step (1) is borate, boric acid or metaboric acid, the borate is ten hydrations
Sodium tetraborate, kodalk, more Boratexes, dipotassium tetraborate or potassium metaborate；The concentration of the fire proofing additive solution is 0.1-
0.6M；Inorganic filler described in step (2) is nano silica, montmorillonite, flyash, sepiolite, expanded perlite and sky
Heart glass microballoon is one or more of.
3. the method according to claim 2 that fire protection flame retarding, ultralight high-strength paper pulp foam are prepared using lignocellulose raw material,
It is characterized by: the temperature of cross-linking reaction described in step (1) is 35-90 DEG C, the time of reaction is 0.5-6 h, mixing speed
For 100-2000 rpm.
4. the method according to claim 2 that fire protection flame retarding, ultralight high-strength paper pulp foam are prepared using lignocellulose raw material,
It is characterized by: the dosage of chitosan described in step (2) is the 0-20wt% of natural wooden fiber's raw material；The mixing speed
For 100-2000 rpm, mixing time is 0.5-6 h.
5. the method according to claim 2 that fire protection flame retarding, ultralight high-strength paper pulp foam are prepared using lignocellulose raw material,
It is characterized by: foaming agent described in step (3) is lauryl sodium sulfate, octylame, decyl amine, dodecyl p-methyl benzenesulfonic acid
It receives, one or more of sodium sulfate of polyethenoxy ether of fatty alcohol；The dosage of the foaming agent is natural wooden fiber's raw material
0.5-10wt%；The mixing speed is 100-2000 rpm, and mixing time is 0.5-6 h.
6. the method according to claim 2 that fire protection flame retarding, ultralight high-strength paper pulp foam are prepared using lignocellulose raw material,
It is characterized by: carrying out vacuum drying or convection drying after the method for step (4) described drying and moulding is natural air drying 2-10h；
The vacuum drying temperature is 30-60 DEG C, and the vacuum drying time is 1-8 h；The temperature of the convection drying is 25-90
DEG C, the time of convection drying is 10-24h.
7. preparing fire protection flame retarding, ultralight high-strength paper pulp using lignocellulose raw material described in -6 any one according to claim 1
The method of foam, it is characterised in that: natural wooden fiber's raw material described in step (1) is market pulp, waste paper, straw-stalk type cultural
The mixing of one or more of waste, cotton and cotton linter；The market pulp is bleaching needle-point leaf pulp, bleaching leaf wood
Slurry, dissolving pulp do not float paper pulp；Go the method for moisture removal and foam for vacuum filtration described in step (2).
8. preparing the formula of fire protection flame retarding, ultralight high-strength paper pulp foam using lignocellulose raw material, it is characterised in that: by weight
Number meter, composed of the following components: 100 parts by weight of natural wooden fiber's raw material of crushing, cross-linking aid 0.5-10 parts by weight of preventing fires,
Inorganic filler 1-20 parts by weight, chitosan 0-20 parts by weight；Foaming agent 0.5-10 parts by weight；Several parts by weight of water；Wherein, described
The weight fraction of natural wooden fiber's raw material in water is 0.5-5wt%.
9. the formula according to claim 8 that fire protection flame retarding, ultralight high-strength paper pulp foam are prepared using lignocellulose raw material,
It is characterized by: natural wooden fiber's raw material is that market pulp, waste paper, straw-stalk type cultural waste, cotton and cotton are short
The mixing of one or more of suede, the market pulp are bleaching needle-point leaf pulp, bleached hardwood pulp, dissolving pulp or do not float paper
Slurry；The fire prevention cross-linking aid be borate, boric acid or metaboric acid, the borate be sodium borate decahydrate, kodalk,
More Boratexes, dipotassium tetraborate or potassium metaborate；The inorganic filler be nano silica, montmorillonite, flyash, sepiolite,
Expanded perlite and hollow glass micropearl are one or more of；The foaming agent is lauryl sodium sulfate, octylame, decyl amine, 12
Alkyl p-methyl benzenesulfonic acid receives, one or more of sodium sulfate of polyethenoxy ether of fatty alcohol.
10. power 1-7 as described in fire protection flame retarding, ultralight high-strength paper pulp foam application, it is characterised in that: be used as outdoor architecture and
The thermal insulation material of interior decoration；The thermal insulation material has both water-fast, sound absorption qualities of preventing fires.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114012858A (en) * | 2021-11-08 | 2022-02-08 | 河南佳诺威木业有限公司 | Production process of light high-strength PB plate |
| CN114230868A (en) * | 2022-01-14 | 2022-03-25 | 宋金华 | Light heat-insulating flame-retardant composite natural polymer foam material and preparation method and application thereof |
| CN116063730A (en) * | 2023-02-22 | 2023-05-05 | 国际竹藤中心 | Natural flame-retardant bamboo pulp foam material and preparation method and application thereof |
| CN116903921A (en) * | 2023-09-13 | 2023-10-20 | 山东科迈生物制浆有限公司 | Pulp foam material and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1386122A (en) * | 2000-07-28 | 2002-12-18 | 大日本油墨化学工业株式会社 | Water-absorbing material and absorbent article employing the same |
| CN103131035A (en) * | 2011-12-05 | 2013-06-05 | 江南大学 | Environment-friendly paper fiber foaming material and preparation method thereof |
| WO2015066806A1 (en) * | 2013-11-05 | 2015-05-14 | Fpinnovations | Method of producing ultra-low density fiber composite materials |
| CN107057391A (en) * | 2017-04-19 | 2017-08-18 | 广西大学 | A kind of non-migratory antibacterial cellulose base foam and preparation method thereof |
| CN108358589A (en) * | 2018-02-27 | 2018-08-03 | 合肥雅克丽新型建材有限公司 | A kind of water-proof high-intensity weather-resistance flame-retardant environmental protection heat-insulating board and preparation method thereof |
| CN108947574A (en) * | 2018-06-22 | 2018-12-07 | 佛山陵朝新材料有限公司 | A kind of preparation method of wheat straw fiber composite material |
-
2019
- 2019-01-04 CN CN201910007105.2A patent/CN109777138B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1386122A (en) * | 2000-07-28 | 2002-12-18 | 大日本油墨化学工业株式会社 | Water-absorbing material and absorbent article employing the same |
| CN103131035A (en) * | 2011-12-05 | 2013-06-05 | 江南大学 | Environment-friendly paper fiber foaming material and preparation method thereof |
| WO2015066806A1 (en) * | 2013-11-05 | 2015-05-14 | Fpinnovations | Method of producing ultra-low density fiber composite materials |
| CN107057391A (en) * | 2017-04-19 | 2017-08-18 | 广西大学 | A kind of non-migratory antibacterial cellulose base foam and preparation method thereof |
| CN108358589A (en) * | 2018-02-27 | 2018-08-03 | 合肥雅克丽新型建材有限公司 | A kind of water-proof high-intensity weather-resistance flame-retardant environmental protection heat-insulating board and preparation method thereof |
| CN108947574A (en) * | 2018-06-22 | 2018-12-07 | 佛山陵朝新材料有限公司 | A kind of preparation method of wheat straw fiber composite material |
Non-Patent Citations (8)
| Title |
|---|
| KHAN M.A. UDDIN等: "Hybrid films of chitosan, cellulose nanofibrils and boric acid: Flame", 《CARBOHYDRATE POLYMERS》 * |
| 何天白等: "《功能高分子与新技术》", 31 January 2001, 化学工业出版社 * |
| 何小维等: "《碳水化合物功能材料》", 31 January 2007, 中国轻工业出版社 * |
| 姚守信: "《无机精细化工》", 31 March 1994, 四川大学出版社 * |
| 张道真: "《建筑防水》", 30 June 2014, 中国城市出版社 * |
| 王彤等: "缓蚀型玉米秸秆纤维发泡包装材料的研究", 《包装工程》 * |
| 祝志峰: "《纺织工程化学》", 30 June 2010, 东华大学出版社 * |
| 马保国等: "《建筑功能材料》", 31 July 2004, 武汉理工大学出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114012858A (en) * | 2021-11-08 | 2022-02-08 | 河南佳诺威木业有限公司 | Production process of light high-strength PB plate |
| CN114230868A (en) * | 2022-01-14 | 2022-03-25 | 宋金华 | Light heat-insulating flame-retardant composite natural polymer foam material and preparation method and application thereof |
| CN116063730A (en) * | 2023-02-22 | 2023-05-05 | 国际竹藤中心 | Natural flame-retardant bamboo pulp foam material and preparation method and application thereof |
| CN116063730B (en) * | 2023-02-22 | 2023-08-11 | 国际竹藤中心 | Natural flame-retardant bamboo pulp foam material and preparation method and application thereof |
| CN116903921A (en) * | 2023-09-13 | 2023-10-20 | 山东科迈生物制浆有限公司 | Pulp foam material and preparation method thereof |
| CN116903921B (en) * | 2023-09-13 | 2023-12-26 | 山东科迈生物制浆有限公司 | Pulp foam material and preparation method thereof |
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