CN108102070A - The method of plant fiber production nonflammable rigid polyurethane foam combination material - Google Patents
The method of plant fiber production nonflammable rigid polyurethane foam combination material Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/346—Clay
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34922—Melamine; Derivatives thereof
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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Abstract
A kind of method that nonflammable rigid polyurethane foam combination material is produced using wood fibre as raw material, is carried out by following five steps:When the selection of plant fiber material, second is that the pretreatment of raw material, three be the preparation of plant fiber polyalcohols, four be the preparation of composite flame-retardant agent, five be combination material preparation.The fire retardant rigid polyurethane foam made from this combination material, oxygen index (OI) are more than 34, reach the A grade incombustible materials of defined in GB8624 2012 " construction material and product burns grading performance ".Part polyalcohol is substituted with plant fiber powder, and it is structurally-modified to the progress of polyhydric alcohol conjugate material, and production cost is low, environmentally friendly, and flame retardant effect is more preferable, is the innovative approach of a plant fiber raw material higher value application.
Description
Technical field
The invention belongs to hard polyurethane foams to combine material technology of preparing, and in particular to and it is a kind of using wood fibre as raw material,
Produce full water foamed, Halogen, the method for fire retardant rigid polyurethane foam combination material.
Background technology
Rigid polyurethane foam is because of the excellent properties such as its thermal insulation, sound insulation, heat-insulated, corrosion-resistant, and product lightweight, Yi Cheng
The characteristics such as type are widely used in the fields such as building, communications and transportation, freezer, refrigerator, refrigerator-freezer, petrochemical pipe, aviation.In recent years
Come, with deep development of the construction industry energy-saving material in China, the various excellent performances of hard polyurethane foams are by building trade
Personage have an optimistic view of, gradually the positions such as building roof, wall use rigid polyurethane foam.But the defects of polyurethane is maximum
It is inflammability, and generates substantial amounts of flue gas in burning and even release toxic gas, becomes fatal harm.Thus fire-retardant spy
It is not that Non-halogen Flame Retardant Technology gets more and more people's extensive concerning.
Polyurethane foamed material be polyalcohol mixed with a variety of auxiliary agents such as foaming agent, catalyst, fire retardant, inorganic filler and
Into combination material and isocyanates the high molecular polymer that forms of foaming is uniformly mixed by special equipment.In urethane foamed material
Containing a large amount of phenyl ring, heat resistance, the anti-flammability of material had both been improved, has also had many advantages, such as that good toughness, intensity are high, at low cost.Therefore,
Rigid polyurethane foam uses the poly methylene poly phenyl poly isocyanate (polymeric MDI) with phenyl ring.Combination material is by more
First alcohol, catalyst, foaming agent, fire retardant etc. are uniformly mixed in the ratio of optimization.Combining the composition expected, proportioning, structure is
Determine the principal element of rigid polyurethane foam performance, thus in the process of research and development New Rigid polyurethane foamed material
In, the optimization for combining material is the focus of research.CN103965432A discloses a kind of halogen-free phosphorus-containing fire retardant hard polyurethane foams
Plastics and preparation method thereof add the miscellaneous -10- phosphas -10- oxidations phenanthryl terephthalyl alcohol of 9,10- dihydro-9-oxies in combination is expected
Reactive flame retardant, fire retardant are halogen-free, and rigid polyurethane foam oxygen index (OI) is up to more than 33%.But this method hinders
It is complicated to fire agent preparation process, and fire retardant additive amount is more, oxygen index (OI) is just reachable when dosage is 4 times or more of polyether polyol
More than 33%.CN106008890A discloses the side that flame retarded rigid polyurethane foams are prepared using the liquefied concentrate of bamboo scraps as raw material
Method, oxygen index (OI) is up to 45%.But this method uses the concentrated sulfuric acid of the mass concentration for 90-95% in bamboo scraps liquefaction process, dense
Sulfuric acid is strong to the corrosivity of equipment, recycling is difficult, tedious process, and foaming agent is fluorine-containing, chlorine compound, has destruction to ozone layer
Effect.Japan Patent JP2005-350637A discloses flame retardancy polyurethane and its manufacturing method, and lignin/or molasses are dissolved
In polyalcohol, add in the inorganic fillers such as barium sulfate, calcium carbonate, magnesium hydroxide, aluminium hydroxide and improve anti-flammability.But this method is only
Heat decomposition temperature is determined, does not survey flame retardant property according to Japanese Industrial Specifications (JIS) or ISO standards.It is prepared by this method
Polyurethane foamed material thermal stability increase, but since the dosage of inorganic filler is high, the density of polyurethane foamed material
Up to 0.8g/cm3。
The content of the invention
For the above-mentioned deficiency of the prior art, the technical problem to be solved by the present invention is to design it is a kind of using plant fiber as
Raw material, it is structurally-modified to combination material progress, using water as foaming agent, production Halogen, environment-friendly type, fire retardant rigid polyurethane foam
The method for combining material.
Technical solution is used by solving above-mentioned technical problem:
This produces the method for nonflammable rigid polyurethane foam combination material using plant fiber as raw material, as follows
It carries out:
(1) selection of plant fiber material:Mildew and rot softwood, broadleaf, bamboo wood, wooden bamboo processing do not occur and remains for selection
Excess, straw, wheat straw, maize straw, bagasse, axis, branch, root, leaf, shell are appointed in reed, awns stalk these plant fibers
It is one or more.
(2) pretreatment of raw material:Impurity elimination is dried to natural moisture content 8%-12%, -600 mesh of 100 mesh of mechanical crushing, then
It is dried under the conditions of 80-110 DEG C to over dry;
(3) preparation of plant fiber polyalcohols:The wood fibre 1-10 parts by weight of over dry are added in a kettle, are added more
First alcohol 30-39 parts by weight stir in normal pressure and under room temperature 0.5-2h, and rotating speed 1000-2000r/min makes wood fibre
Uniformly, it is well dispersed in polyalcohol, that is, plant fiber polyalcohols is made;
(4) preparation of composite flame-retardant agent:By ammonium polyphosphate:Melamine:Methyl-phosphoric acid dimethyl ester=(20-40):(5-
10):The weight distribution ratio value of (10-20) is mixed to prepare compound sex flame retardant;
(5) preparation of combination material:The tin dilaurate as catalyst is added in plant fiber polyalcohols made from step (3)
Dibutyl tin 0.02-0.06 parts by weight, the water 0.1-0.4 parts by weight as foaming agent, the series of the DOW CORNING OFX as foam stabilizer
Silicone oil 3-6 parts by weight add in composite flame-retardant agent 35-70 parts by weight, the montmorillonite 1-3 as inorganic filler made from step (4)
0.5h is stirred at room temperature in parts by weight and magnesia 4-6 parts by weight, rotating speed 2000r/min, makes uniformly, combination material to be made;
It is finally being made and applying for this nonflammable rigid polyurethane foam it is still necessary to what is made a presentation:In step (5)
100 parts by weight isocyanates are added in the combination material of acquisition, wait to start to generate heat, injecting immediately in designed mold on request makes
Shaping, aging 1-2 days under field conditions (factors) are made and apply this and gather by raw material production nonflammable hard of plant fiber
The combination material of urethane foamed material.
Described polyalcohol is the glycerine of liquid, ethylene glycol, diethylene glycol, polyethylene glycol 200, polyethylene glycol under room temperature
300th, in polyethylene glycol 400, Macrogol 600, benzoic anhydride polyester polyol PS-400, flame retardant type benzoic anhydride polyester polyol PS-400
One or more, preferred polyethylene glycol 400.
Described inorganic filler is that particle mean size is de- for 30-500 μm of powdered alumina, magnesia, calcium oxide, illiteracy
Soil, calcium carbonate, magnesium carbonate, calcium sulfate, magnesium sulfate, barium sulfate, calcium sulfite are one or two kinds of, preferably montmorillonite and/or oxidation
Magnesium.
Described isocyanates is polymethylene multi-phenenyl isocyanate MDI-200, polymethylene multi-phenenyl isocyanate
Any one of MDI-400, preferably polymethylene multi-phenenyl isocyanate MDI-400.
The beneficial effects of the invention are as follows:
1st, the rigid polyurethane foam flame retardant property that this combination material is configured to is good, and oxygen index (OI) >=30, reaches
GB8624-2012《Construction material and product burns grading performance》Defined B1 grades of nonflammable rigid polyurethane foam will
It asks, No. 1 of contrast test table 3 and No. 2 oxygen index (OI)s more than 34%, the total thermal discharge (THR of 600s600)<The total flue gas generation of 3MJ, 600s
Measure (TSP600) < 4M2, reach GB8624-2012《Construction material and product burns grading performance》Defined A grades of fire-retardant type hard
Polyurethane foamed material requirement.
2nd, composite flame-retardant agent is halogen-free, does not cause greenhouse effects, will not destroy ozone layer, is environment friendly flame retardant.It is multiple
Closing fire retardant and the montmorillonite as inorganic filler and magnesia has synergistic effect, further improves anti-flammability.
3rd, the lignin in wood fibre contains a large amount of benzene ring structures, and the benzene ring structure of these naturally occurring is exactly pair
The structure of polyurethane foamed material is modified required, it is not necessary to separately add the industrial chemicals containing phenyl ring, improve foamed material
Heat resistance, flame resistance and free from environmental pollution.
4th, the cellulose of plant material, hemicellulose and three big key component of lignin are without separation, all of production
In the process without pollutants such as strong acid, black liquor, Halogen in foaming agent does not cause the harm to environment.
5th, this method is energy saving, easy to operate, process is few, the pollution during eliminating separating lignin, cellulose from source.
Scene can also be collected in plant fiber material to crush raw material, solve plant fiber material collection, transportation cost height, it is high-valued
Using it is hindered the problem of.
Specific embodiment
The present invention is described in further detail in conjunction with the embodiments:
Cellulose and hemicellulose are the natural polymers of the polysaccharide rich in hydroxyl, and lignin is that phosphorus content is high and rich
The aromatic series natural polymer of the hydroxyls such as phenolic hydroxy group, alcoholic extract hydroxyl group.Part is substituted using the plant fiber for crushing -600 mesh of 100 mesh
Polyalcohol, while structurally-modified, raising flame retardant property is carried out to combination material.The applicant is fully able to through series of contrast
The nonflammable hard polyurethane foam material of oxygen index (OI) more than 34% is made using wood fibre as raw material.
In five steps of this method, in addition to step (5), remaining step (1), (2), (4) belong to it is very clear can
Implement, repeat no more.Only step (3) and (5) are illustrated with list mode by eight embodiments below:
Each raw material and its weight value are listed in table 1 by the present invention by 8 embodiments below:
Note:APP in table 1 is ammonium polyphosphate, and DMMP is methyl-phosphoric acid dimethyl ester, and DBTDL is dibutyl tin laurate.
Embodiment 1 (accordingly implements 1 raw material and its with ratio) in the table of comparisons 1:
1 parts by weight of willow wood powder of 400 mesh will be ground into, 39 parts by weight of polyalcohol stir 4h in normal pressure and room temperature, turn
Speed for 2000r/min, make wood fibre uniformly, be well dispersed in polyalcohol, add in catalyst dibutyltin dilaurylate
0.02 parts by weight, 0.1 parts by weight of foaming agent, that is, water, DOW CORNING silicone oil OFX-093 is as 3 parts by weight of foam stabilizer, by ammonium polyphosphate:
Melamine:Methyl-phosphoric acid dimethyl ester=20:20:45 parts by weight of composite flame-retardant agent of 5 weights, 1 parts by weight of montmorillonite
With 6 parts by weight of magnesia, 0.5h, rotating speed 2000r/min is stirred at room temperature, is stirring evenly and then adding into the more methylenes of 100 parts by weight
Quito phenyl isocyanate MDI-200 waits to start to generate heat, and injects immediately in designed mold on request and is allowed to be molded, certainly
Aging 1-2 days, that is, be made nonflammable rigid polyurethane foam under the conditions of so.
Embodiment 2 (accordingly implements 2 raw material and its with ratio) in the table of comparisons 1:
6 parts by weight of bamboo wood powder of 400 mesh will be ground into, 34 parts by weight of polyalcohol stir 4h in normal pressure and room temperature, turn
Speed for 2000r/min, make wood fibre uniformly, be well dispersed in the polyethylene glycol of molecular weight 400, add in catalyst dibutyltin osmanthus
Sour 0.04 parts by weight of dibutyl tin, 0.2 parts by weight of foaming agent, that is, water, foam stabilizer DOW CORNING silicone oil OFX-093 add in 4 parts by weight,
By ammonium polyphosphate:Melamine:Methyl-phosphoric acid dimethyl ester=30:15:52 parts of the composite flame-retardant agent of 7 weights, montmorillonite 2
5 parts by weight of parts by weight and magnesia, are stirred at room temperature 0.5h, and rotating speed 2000r/min is stirring evenly and then adding into 100 parts by weight
Polymethylene multi-phenenyl isocyanate MDI-400 waits to start to generate heat, and injects in designed mold on request and is allowed into immediately
Type, aging 1-2 days, that is, be made fire retardant rigid polyurethane foam under field conditions (factors).
Embodiment 3 (accordingly implements 8 raw material and its with ratio) in the table of comparisons 1:
10 parts by weight of maize straw powder of 400 mesh, 30 parts by weight of polyalcohol, in normal pressure with being stirred in room temperature will be ground into
4h, rotating speed 2000r/min, make wood fibre uniformly, be well dispersed in the polyethylene glycol of molecular weight 400, add in catalyst
0.06 parts by weight of dibutyl tin laurate, 0.4 parts by weight of foaming agent, that is, water, foam stabilizer DOW CORNING silicone oil OFX-093 add in 6 weights
Part is measured, by ammonium polyphosphate:Melamine:Methyl-phosphoric acid dimethyl ester=40:10:70 weight of composite flame-retardant agent of 20 weights
Part, 0.5h is stirred at room temperature in 9 parts by weight of inorganic filler, and how sub- rotating speed 2000r/min be stirring evenly and then adding into 100 parts by weight
The more phenyl isocyanate MDI-400 of methyl, wait to start to generate heat, and inject immediately in designed mold on request and are allowed to be molded,
Fire retardant rigid polyurethane foam is made in aging 1-2 days under natural conditions.
The applicant has done series of contrast, is confirmed and confirmed the feasibility of this method with specific practice and selected
Preferred embodiment, it is now that intermediate portions brief is as follows:
1st, test material
Plant fiber material:The plant fiber materials such as bamboo surplus material of processing, stalk, poplar wood rotary-cut piece, it is naturally dry
It is dry, it crushes, 200 mesh, 300 mesh, 400 mesh powders, is dried respectively at 105 DEG C of drying box to over dry.
Polyalcohol:Glycerine, ethylene glycol, diethylene glycol (DEG), polyethylene glycol 200 (PEG200), Liquid Macrogol
(PEG300), polyethylene glycol 400 (PEG400), Macrogol 600 (PEG600), (PS-400, Qingdao are auspicious for benzoic anhydride polyester polyol
Promise Chemical Co., Ltd.), flame retardant type benzoic anhydride polyester polyol (flame retardant type PS-400, Qingdao Rui Nuo Chemical Co., Ltd.s);
Fire retardant:Ammonium polyphosphate (APP232 types, Shandong Chang Sheng flame-retarding new materials Co., Ltd), methyl-phosphoric acid dimethyl ester
(DMMP, Hebei Xin Hang Chemical Co., Ltd.s), melamine;
Inorganic filler:Particle mean size is 30-500 μm of powdered alumina, magnesia, calcium oxide, montmorillonite, carbonic acid
Calcium, magnesium carbonate, calcium sulfate, magnesium sulfate, barium sulfate, calcium sulfite;
Two dilaurylates (DBTDL, Shanghai Ling Feng chemical reagent Co., Ltd) are catalyst;(DOW CORNING has silicone oil
Limit company OFX-093) it is foam stabilizer;Distilled water (laboratory self-control) is foaming agent;
material raw material:MDI-200:Polymethylene multi-phenenyl isocyanate WANNATE PM-200, MDI-400:More methylenes
Quito phenyl isocyanate WANNATE PM-400.
2nd, test method
By bamboo powder, willow wood powder, Wheat Straw crush 200 mesh, 300 mesh, 400 mesh be raw material, instead of part polyalcohol with it is different
Cyanate (MDI) synthesizes rigid polyurethane foam.Empirically designing scheme weigh a certain amount of over dry plant fiber powder and
Polyalcohol, using water as foaming agent, dibutyl tin laurate (DBTDL) is used as catalyst, and silicone oil is as foam stabilizer, polyphosphoric acid
Ammonium (APP), methyl-phosphoric acid dimethyl ester (DMMP), melamine are fire retardant, add inorganic filler, 0.5h is stirred at room temperature,
Rotating speed is 2000r/min, after mixing, adds in 100 parts of MDI200 or MDI400, waits to start to generate heat, inject immediately on request
It is allowed to be molded in designed mold, under field conditions (factors) aging 1-2 days.
Table 2:The bamboo powder 100g for being ground into 300 mesh is dispersed in 400g diethylene glycols (DEG), in normal pressure with being stirred in room temperature
0.5h is mixed to uniformly dispersing, is denoted as bamboo powder/DEG in the following table.
Note:DEG in table 2 is diethylene glycol, and PEG400 is polyethylene glycol 400, and flame retardant type PS-400 is flame retardant type phthalic anhydride
Polyester polyol (Qingdao Rui Nuo Chemical Co., Ltd.s), for 232 type of ammonium polyphosphate, (Shandong long day contains the limited public affairs of flame-retarding new material to APP
Department), DMMP is methyl-phosphoric acid dimethyl ester (Hebei Xin Hang Chemical Co., Ltd.s), and DBTDL is two dilaurylates (Shanghai Ling Feng
Chemical reagent Co., Ltd), MDI-200 is polymethylene multi-phenenyl isocyanate WANNATE PM-200, and MDI-400 is mostly sub-
The more phenyl isocyanate WANNATE PM-400 of methyl.
Table 3:The bamboo powder 75g for being ground into 300 mesh is dispersed in 325g polyethylene glycol 400s (PEG400), in normal pressure and room
Middle benefit gas stirs 0.5h to uniformly dispersing, and is denoted as bamboo powder/PEG400 in the following table.
Table 4:The willow wood powder 100g for being ground into 200 mesh is dispersed in 100g diethylene glycols (DEG), in normal pressure and room temperature
Middle stirring 1h is denoted as willow wood powder/DEG in the following table to uniformly dispersing.
Table 5:The straw powder 20g for being ground into 200 mesh is dispersed in 80g diethylene glycols (DEG), in normal pressure with being stirred in room temperature
1h is mixed to uniformly dispersing, is denoted as straw powder/DEG in the following table.
3rd, rigid polyurethane foam anti-flammability measures
Construction material and product burns grading performance GB8624-2012, B grade nonflammable material:Oxygen index (OI) >=30, B1 grade;A
Grade:Incombustible material, total thermal discharge THR of 600s600Total smoke growing amount TSP of≤4.0MJ, 600s600≤50M2。
Oxygen index (OI) (LOI) presses GB/T 2406.2-2009 national standards, and in Jiangning county, analytical instrument factory produces
It is carried out on JF-3 oxygen index instruments, sample size 100x10x10mm.Each equal oxygen determination index of sample is listed in last column of table, oxygen
Index >=30, reaches nonflammable rigid polyurethane foam requirement.
Total calorific value (the THR of 600s600), the total smoke growing amount (TSP of 600s600) be measured using cone calorimetry,
The FTT UK types that cone calorimetry test is produced by ISO 5660&ASTME1354-94 in Stanton Redcroft companies of Britain
Cone calorimetry carries out, thermal radiation flux 35kW/m2, sample size 100x100x30mm.
Table 6:Cone calorimetry tests the total calorific value (THR of 600s600), the total smoke growing amount (TSP of 600s600) result
Note:1 in table 6 is No. 1 material of table 3, and 2 be No. 2 materials of table 3, and 3 be No. 2 materials of table 2, and 4 be No. 2 of table 4
Material, 5 be No. 3 materials of table 5.
Cone calorimetry analysis result shows the total smoke growing amount (TSP of 600s600) it is below GB/T 2406.2-2009
Total smoke growing amount TSP of the 600s of A grades of the incombustible material of national Specification600≤50M2, No. 1 and No. 2 material 600s's is total
Caloric value (THR600) less than GB/T 2406.2-2009 national Specifications A grades of incombustible material 600s total thermal discharge
THR600≤ 4.0MJ, illustrates No. 1 and No. 2 materials have reached A grades.
Claims (7)
1. a kind of method that nonflammable rigid polyurethane foam combination material is produced using plant fiber as raw material, it is characterized in that pressing
Following steps carry out:
(1)The selection of plant fiber material:It is remaining that mildew and rot softwood, broadleaf, bamboo wood, wooden bamboo processing do not occur for selection
Object, straw, wheat straw, maize straw, bagasse, axis, branch, root, leaf, shell are any in reed, awns stalk these plant fibers
Kind is a variety of;
(2)The pretreatment of raw material:Impurity elimination is dried to natural moisture content 8%-12%, -600 mesh of 100 mesh of mechanical crushing, then in 80-
It is dried under the conditions of 110 DEG C to over dry;
(3)The preparation of plant fiber polyalcohols:The wood fibre 1-10 parts by weight of over dry are added in a kettle, add polyalcohol
30-39 parts by weight and are stirring 0.5-2h, rotating speed 1000-2000r/min at normal pressure under room temperature, make wood fibre uniformly,
It is well dispersed in polyalcohol, that is, plant fiber polyalcohols is made;
(4)The preparation of composite flame-retardant agent:By ammonium polyphosphate:Melamine:Methyl-phosphoric acid dimethyl ester=(20-40):(5-10):
(10-20)Weight distribution ratio value be mixed to prepare compound sex flame retardant;
(5)Combine the preparation of material:In step(3)Two fourth of tin dilaurate as catalyst is added in plant fiber polyalcohols obtained
Base tin 0.02-0.06 parts by weight, the water 0.1-0.4 parts by weight as foaming agent, the DOW CORNING OFX series silicone oil as foam stabilizer
3-6 parts by weight, composite flame-retardant agent 35-70 parts by weight, the montmorillonite 1-3 parts by weight as inorganic filler and magnesia 4-6 weight
Part, 0.5h is stirred at room temperature in rotating speed 2000r/min, makes uniformly, combination material to be made.
2. the side of nonflammable rigid polyurethane foam combination material is produced using wood fibre as raw material as described in claim 1
Method, it is characterized in that the polyalcohol is the glycerine of liquid under room temperature, ethylene glycol, diethylene glycol, polyethylene glycol 200, poly- second
In glycol 300, polyethylene glycol 400, Macrogol 600, benzoic anhydride polyester polyol 400, flame retardant type benzoic anhydride polyester polyol 400
It is one or more.
3. the side of nonflammable rigid polyurethane foam combination material is produced using wood fibre as raw material as claimed in claim 2
Method, it is characterized in that the polyalcohol is the polyethylene glycol 400 of liquid.
4. the side of nonflammable rigid polyurethane foam combination material is produced using wood fibre as raw material as described in claim 1
Method, it is characterized in that the inorganic filler is the powdered alumina that particle mean size is 30-500 μm, magnesia, calcium oxide, illiteracy
De- soil, calcium carbonate, magnesium carbonate, calcium sulfate, magnesium sulfate, barium sulfate, calcium sulfite are one or two kinds of.
5. the side of nonflammable rigid polyurethane foam combination material is produced using wood fibre as raw material as claimed in claim 4
Method, it is characterized in that the inorganic filler is montmorillonite and/or magnesia.
6. the side of nonflammable rigid polyurethane foam combination material is produced using wood fibre as raw material as described in claim 1
Method, it is characterized in that the isocyanates is polymethylene multi-phenenyl isocyanate MDI-200, polymethylene polyphenyl isocyanic acid
Any one of ester MDI-400.
7. the side of nonflammable rigid polyurethane foam combination material is produced using wood fibre as raw material as claimed in claim 6
Method, it is characterized in that the isocyanates is polymethylene multi-phenenyl isocyanate MDI-400.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110478981A (en) * | 2019-08-28 | 2019-11-22 | 安徽伟创聚合材料科技有限公司 | A kind of novel biomass foamed material and preparation method thereof for sewage treatment |
CN111073325A (en) * | 2019-12-31 | 2020-04-28 | 华南理工大学 | Lignin/fiber thermoplastic composite material and preparation method thereof |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4521544A (en) * | 1983-02-24 | 1985-06-04 | Patrick J. Crehan | Polyurethane foam from cellulosic products |
US4882112A (en) * | 1985-07-08 | 1989-11-21 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Process for producing shaped articles from vegetable particulate materials |
JPH06248042A (en) * | 1993-02-23 | 1994-09-06 | Agency Of Ind Science & Technol | New polyurethane, its production and container for cultivation |
DE19817541C2 (en) * | 1998-04-16 | 2002-08-01 | Gerhard Behrendt | Composite material and process for its manufacture |
CN101704938A (en) * | 2009-11-27 | 2010-05-12 | 青岛生物能源与过程研究所 | Preparation method of bean pulp polyurethane foam plastics |
CN101724255A (en) * | 2009-12-09 | 2010-06-09 | 南京林业大学 | Wood powder reinforced polyurethane wood-imitation material for furniture and production method thereof |
CN102167897A (en) * | 2010-11-29 | 2011-08-31 | 山东东大聚合物股份有限公司 | Rigid polyurethane foam special for laminboard |
CN102408535A (en) * | 2011-11-23 | 2012-04-11 | 吴江明峰聚氨酯制品有限公司 | Plant fiber-enhanced rigid polyurethane foam plastic |
CN103483531A (en) * | 2013-09-23 | 2014-01-01 | 安徽济峰节能材料有限公司 | Polyurethane foam material prepared from bean pulp |
CN103483806A (en) * | 2013-09-23 | 2014-01-01 | 安徽济峰节能材料有限公司 | Grape vine-polyurethane composite foam materiel |
CN105348838A (en) * | 2015-11-24 | 2016-02-24 | 安徽继宏环保科技有限公司 | Straw foamed antibacterial material and preparation method therefor |
CN107118542A (en) * | 2017-05-18 | 2017-09-01 | 宿州市逢源生物科技有限公司 | A kind of biomass-based fire-retardant hard polyurethane foam insulation material and preparation method thereof |
-
2017
- 2017-12-01 CN CN201711249099.9A patent/CN108102070A/en active Pending
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4521544A (en) * | 1983-02-24 | 1985-06-04 | Patrick J. Crehan | Polyurethane foam from cellulosic products |
US4882112A (en) * | 1985-07-08 | 1989-11-21 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Process for producing shaped articles from vegetable particulate materials |
JPH06248042A (en) * | 1993-02-23 | 1994-09-06 | Agency Of Ind Science & Technol | New polyurethane, its production and container for cultivation |
DE19817541C2 (en) * | 1998-04-16 | 2002-08-01 | Gerhard Behrendt | Composite material and process for its manufacture |
CN101704938A (en) * | 2009-11-27 | 2010-05-12 | 青岛生物能源与过程研究所 | Preparation method of bean pulp polyurethane foam plastics |
CN101724255A (en) * | 2009-12-09 | 2010-06-09 | 南京林业大学 | Wood powder reinforced polyurethane wood-imitation material for furniture and production method thereof |
CN102167897A (en) * | 2010-11-29 | 2011-08-31 | 山东东大聚合物股份有限公司 | Rigid polyurethane foam special for laminboard |
CN102408535A (en) * | 2011-11-23 | 2012-04-11 | 吴江明峰聚氨酯制品有限公司 | Plant fiber-enhanced rigid polyurethane foam plastic |
CN103483531A (en) * | 2013-09-23 | 2014-01-01 | 安徽济峰节能材料有限公司 | Polyurethane foam material prepared from bean pulp |
CN103483806A (en) * | 2013-09-23 | 2014-01-01 | 安徽济峰节能材料有限公司 | Grape vine-polyurethane composite foam materiel |
CN105348838A (en) * | 2015-11-24 | 2016-02-24 | 安徽继宏环保科技有限公司 | Straw foamed antibacterial material and preparation method therefor |
CN107118542A (en) * | 2017-05-18 | 2017-09-01 | 宿州市逢源生物科技有限公司 | A kind of biomass-based fire-retardant hard polyurethane foam insulation material and preparation method thereof |
Non-Patent Citations (2)
Title |
---|
戈进杰,姜良斌: "天然植物原料改性聚氨酯及其应用", 《聚氨酯工业》 * |
盖广清 等: "秸秆纤维对硬泡聚氨酯性能影响的研究", 《吉林建筑工程学院学报》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110478981A (en) * | 2019-08-28 | 2019-11-22 | 安徽伟创聚合材料科技有限公司 | A kind of novel biomass foamed material and preparation method thereof for sewage treatment |
CN111073325A (en) * | 2019-12-31 | 2020-04-28 | 华南理工大学 | Lignin/fiber thermoplastic composite material and preparation method thereof |
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