CN106478920A - A kind of inorganic compounding flame retardant polyurethane rigid foam material and preparation method thereof - Google Patents
A kind of inorganic compounding flame retardant polyurethane rigid foam material and preparation method thereof 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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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
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
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- 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
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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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
- 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
- C08K2003/2224—Magnesium hydroxide
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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
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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Abstract
The invention discloses a kind of inorganic compounding flame retardant polyurethane rigid foam and preparation method thereof, the fire retardant be made up of using polyether polyol N220, polyether polyol N330, distilled water, organotin triethanolamine and magnesium hydroxide, aluminium hydroxide, ethylene glycol is as component A, using isocyanates as component B, both mix homogeneously free foamings simultaneously carry out ripening.The present invention is using water as CBA, and with the addition of compounding fire retardant, has a dimensional stability of more preferable resistance combustion polyurethane foam with respect to existing hard polyurethane foam, higher compressive strength, and better flame resistance.
Description
Technical field
The invention belongs to field of heat insulating materials, especially a kind of inorganic compounding flame retardant polyurethane rigid foam and its preparation side
Method.
Background technology
Polyurethane (PU) is that have carbamate with what polyether polyol and cyanate drew under certain conditions
The polymer of segment.The various material properties of polyurethane are more outstanding, and product is abundanter, and species also compares many, rigid polyurethane
Matter foam is exactly major product.Polyurethane foam has lightweight, intensity height, chemical stability, and electrical insulating property is good, heat conductivity
Low, the features such as vibration is little, in building materials, petrochemical industry, traffic, the field such as Aero-Space using extensively, yet with containing flammable
Molecular skeleton-hydrogen segment, leads to polyurethane foam to be easy to burn, and produces toxic smog and the corrosivity of substantial amounts of in the air
Gas, so that hard polyurethane foam has certain fire resistance, often adds inorganic combustion inhibitor in polyurethane foam.
Preparation inorganic compounding flame retardant polyurethane, the advantage of inorganic combustion inhibitor is：Low toxicity, non-volatility, heat stability is good, no separates out,
Price is low, and smog is few；Shortcoming is the impact of physical property due to fire proofing and processing characteristics, will lead to polymer physicss
The reduction of energy.
Content of the invention
Instant invention overcomes shortcoming of the prior art, there is provided a kind of system of inorganic compounding flame retardant polyurethane insulation material
Preparation Method.
In order to solve above-mentioned technical problem, the present invention is achieved by the following technical solutions：
A kind of inorganic compounding flame retardant polyurethane rigid foam material, density is 59-77kg m-3, the compression of horizontal direction is strong
Spend for 0.5-0.6MPa, the compressive strength of vertical direction is 0.4-0.5MPa, and its preparation method is to carry out according to the following step：
Step one：Weigh 150-170 mass parts polyether polyol N330 of polyether polyol N220,30-50 mass parts,
The distilled water of 1-5 mass parts, the triethanolamine of organotin T-20,2-4 mass parts of 1-3 mass parts and the resistance of 30-50 mass parts
Stirring in beaker is put in combustion agent, forms component A.
Step 2：Weigh the isocyanates of 230 mass fractions, as component B.
Step 3：The temperature adjusting mould, to 25-30 DEG C, component A and component B is poured in mould simultaneously, stirring mixing
It is allowed to free foaming 3-5 minute after the 10-30 second.
Step 4：Make hard foam ripening 24-48h under the conditions of 40-60 DEG C, ripening completes hard bubble after terminating
The preparation of foam material.
And, in step one, the mass fraction of described distilled water is preferably 2-4 part.
And, in step 2, described isocyanates are preferably MDI-50, and MDI-50 is that 2,4- diphenyl methane two is different
Cyanate and the mixture of 4,4'- methyl diphenylene diisocyanate.
And, in step 3, described mixing time is preferably the 18-20 second.
And, in step 4, the curing temperature of described foam is preferably 48-52 DEG C, and the curing time is preferably 35-
37h.
And, in step one, described fire retardant, it is prepared according to the following step：
Step 1：Weigh quality parts ratio 1:(1-3) Mg (OH)2And ethylene glycol, put into as component A in beaker, or claim
Take quality parts ratio 1:(1-3) Al (OH)3And ethylene glycol, put into as component A in beaker, or weigh quality parts ratio 1:1:
(1-3) Mg (OH)2、Al(OH)3And ethylene glycol, put in beaker as component A.
Step 2：In beaker, with water for solvent polyethylene dissolving alcohol, form poly-vinyl alcohol solution as component B.
Step 3：Component A and component B are mixed in beaker, and adds dodecylbenzene sodium sulfonate, constant temperature in beaker
Heating 2-3h.
Step 4：Sucking filtration is carried out to the reaction product in beaker, obtains solid residue.
Step 5：The solid residue obtaining in step 4 is put in electric heating forced air drying and is dried.
Step 6：Form solid flame retardant after the completion of drying, solid flame retardant is loaded standby in bag.
And, in step 1, described Mg (OH)2It is preferably 1 with the quality parts ratio of ethylene glycol:1, described Al (OH)3
It is preferably 1 with the quality parts ratio of ethylene glycol:1, described Mg (OH)2、Al(OH)3It is preferably with the quality parts ratio of ethylene glycol
1:1:1.
And, in step 2, the solution temperature of described polyvinyl alcohol is 95-100 DEG C.
And, in step 3, described mode of heating is heating in water bath.
And, in step 3, the time of described heated at constant temperature is preferably 2-2.5h.
Compared with prior art, the invention has the beneficial effects as follows：A kind of inorganic compounding flame retardant polyurethane rigid foam, with water
As CBA, and with the addition of compounding fire retardant, have with respect to existing hard polyurethane foam preferably fire-retardant poly-
The dimensional stability of urethane foam, higher compressive strength, and better flame resistance.
Brief description
Fig. 1 is the preparation technology flow chart of inorganic compounding flame retardant polyurethane rigid foam material.
Fig. 2 is FT-IR spectrogram under different flame retardant for the polyurethane, wherein a) pure PU；B) aluminium hydroxide；C) hydroxide
Magnesium；D) expanded graphite.
Fig. 3 is Mg (OH)2Press the modified flame-retardant effect FT-IR spectrogram of different proportion, wherein Mg (OH) with EG2/EG：a)0；
b)1：1；c)1/2；d)1/3
Fig. 4 is the broken line graph of the impact to density for the water foaming agent consumption.
Fig. 5 is the broken line graph of the impact to dimensional stability for the water foaming agent addition.
Fig. 6 is the broken line graph of the impact to polyurethane foam compressive strength for the addition of water foaming agent, wherein a) level side
To；B) vertical direction.
Fig. 7 is the broken line graph of the different impact to polyurethane density of R value.
Fig. 8 is the broken line graph of the different impact to dimensional stability of R value.
Fig. 9 is the broken line graph of the compressive strength of polyurethane foam that leads to of difference of R value, wherein a) horizontal direction；B) hang down
Nogata to.
Figure 10 is the impact schematic diagram to oxygen index (OI) for the different flame retardant.
Figure 11 is Mg (OH)2With the proportioning of the EG impact schematic diagram to oxygen index (OI).
Figure 12 is Al (OH)3With the proportioning of the EG impact schematic diagram to oxygen index (OI).
Figure 13 is to add fire retardant the TG-DTA of polyurethane foam is schemed, and wherein a) is not added with fire retardant；B) interpolation is fire-retardant
Agent.
Specific embodiment
With specific embodiment, the present invention is described in further detail below in conjunction with the accompanying drawings：
The model of the experimental apparatus of present invention use and medicine, purchase company are as follows：
Experimental apparatus：
Bottle,suction (GG-17, Shanghai Shen Xian thermostatic equipment factory)
Numerical control ultrasonic cleaner (KH2200DE, Kunshan He Chuan ultrasonic instrument company limited)
Vacuum drying oven (DZF-6090, Shu Niu glass apparatus factory)
Electronic balance (JE1001, Shanghai Pu Chun Metrologic Instr Inc.)
Multiplex vavuum pump of circulating water type (SHB-III, Zhengzhou Greatwall Scientific Industrial ＆ Trading Co., Ltd.)
Thermal-arrest constant-temperature heating magnetic stirring apparatus (DF-101D, Yu Hua Instrument Ltd. of Gongyi City)
Electric drying oven with forced convection (WGL-65B, Shu Niu glass apparatus factory)
Digital display oxygen index measurer (LDX-QS-M606B, Shandong Li Daxin instrumentation devices company limited)
Medicine：
Isocyanates (MDI-50, Jining Bai Chuan Chemical Co., Ltd.)
Polyether polyol (N330, Jining Bai Chuan Chemical Co., Ltd.)
Polyether polyol (N220, Jining Bai Chuan Chemical Co., Ltd.)
Triethanolamine (analysis is pure, and Fine Chemical Co., Ltd is recovered in Tianjin)
Organotin T-20 (analysis is pure, and Fine Chemical Co., Ltd is recovered in Tianjin)
Silicones polyethers emulsion (FM-550, Jining Bai Chuan Chemical Co., Ltd.)
Dodecylbenzene sodium sulfonate (analyzes pure, Ke Wei company of University Of Tianjin)
Embodiment 1：A kind of preparation method of inorganic compounding flame retardant polyurethane rigid foam material, enters according to the following step
OK：
Step one：Weigh the distilled water of polyether polyol N330,1g of polyether polyol N220,30g of 150g, the having of 1g
Stirring in beaker put into by the fire retardant of the triethanolamine of machine stannum T-20,2g and 30g, forms component A.
Step 2：Weigh the isocyanates of 230g, as component B.
Step 3：The temperature adjusting mould, to 25 DEG C, component A and component B is poured in mould simultaneously, stirring mixing 10 seconds
After be allowed to free foaming 3 minutes.
Step 4：Make hard foam ripening 24h under the conditions of 40 DEG C, ripening completes hard foam after terminating
Preparation.
In step one, described fire retardant, it is prepared according to the following step：
Step 1：Weigh the Mg (OH) of 10g2With the ethylene glycol of 10g, put in beaker as component A.
Step 2：In beaker, with water for solvent polyethylene dissolving alcohol, form poly-vinyl alcohol solution as component B.
Step 3：Component A and component B are mixed in beaker, and adds dodecylbenzene sodium sulfonate, constant temperature in beaker
Heating 2h.
Step 4：Sucking filtration is carried out to the reaction product in beaker, obtains solid residue.
Step 5：The solid residue obtaining in step 4 is put in electric heating forced air drying and is dried.
Step 6：Form solid flame retardant after the completion of drying, solid flame retardant is loaded standby in bag.
Embodiment 2：A kind of preparation method of inorganic compounding flame retardant polyurethane rigid foam material, enters according to the following step
OK：
Step one：Weigh the distilled water of polyether polyol N330,3g of polyether polyol N220,40g of 160g, the having of 2g
Stirring in beaker put into by the fire retardant of the triethanolamine of machine stannum T-20,3g and 40g, forms component A.
Step 2：Weigh the isocyanates of 230 mass fractions, as component B.
Step 3：The temperature adjusting mould, to 27 DEG C, component A and component B is poured in mould simultaneously, stirring mixing 20 seconds
After be allowed to free foaming 4 minutes.
Step 4：Make hard foam ripening 36h under the conditions of 50 DEG C, ripening completes hard foam after terminating
Preparation.
In step one, described fire retardant, it is prepared according to the following step：
Step 1：Weigh the Al (OH) of 10g3With the ethylene glycol of 10g, put in beaker as component A.
Step 2：In beaker, with water for solvent polyethylene dissolving alcohol, form poly-vinyl alcohol solution as component B.
Step 3：Component A and component B are mixed in beaker, and adds dodecylbenzene sodium sulfonate, constant temperature in beaker
Heating 2.5h.
Step 4：Sucking filtration is carried out to the reaction product in beaker, obtains solid residue.
Step 5：The solid residue obtaining in step 4 is put in electric heating forced air drying and is dried.
Step 6：Form solid flame retardant after the completion of drying, solid flame retardant is loaded standby in bag.
Embodiment 3：A kind of preparation method of inorganic compounding flame retardant polyurethane rigid foam material, enters according to the following step
OK：
Step one：Weigh the distilled water of polyether polyol N330,5g of polyether polyol N220,50g of 170g, the having of 3g
Stirring in beaker put into by the fire retardant of the triethanolamine of machine stannum T-20,4g and 50g, forms component A.
Step 2：Weigh the isocyanates of 230 mass fractions, as component B.
Step 3：The temperature adjusting mould, to 30 DEG C, component A and component B is poured in mould simultaneously, stirring mixing 30 seconds
After be allowed to free foaming 5 minutes.
Step 4：Make hard foam ripening 48h under the conditions of 60 DEG C, ripening completes hard foam after terminating
Preparation.
In step one, described fire retardant, it is prepared according to the following step：
Step 1：Weigh the Mg (OH) of 10g2, the Al (OH) of 10g3With the ethylene glycol of 30g, put in beaker as component A.
Step 2：In beaker, with water for solvent polyethylene dissolving alcohol, form poly-vinyl alcohol solution as component B.
Step 3：Component A and component B are mixed in beaker, and adds dodecylbenzene sodium sulfonate, constant temperature in beaker
Heating 3h.
Step 4：Sucking filtration is carried out to the reaction product in beaker, obtains solid residue.
Step 5：The solid residue obtaining in step 4 is put in electric heating forced air drying and is dried.
Step 6：Form solid flame retardant after the completion of drying, solid flame retardant is loaded standby in bag.
It is below the property representation method of polyurethane foam：
1. water foaming agent density analysis
Take the polyurethane foam of certain mass, put in the water of certain volume, water before polyurethane foam is put in first measurement
Volume, then measure the volume putting into water after polyurethane, take difference, be the volume of polyurethane.
According to density formula：
ρ=m/v
In formula, ρ is the density of polyurethane foam, and unit is kg m-3；M is the quality of polyurethane foam, and unit is kg；V is
The volume of polyurethane foam, unit is m3.
2. isocyanates R value analysis
Isocyanate index R value directly affects the density of foam, mechanical property, dimensional stability etc..
As R=NCO/OH=1.0, reactive group reacts completely, investigates the impact to foam density for the R value.The calculating of R value
Formula is：
R=NCO/OH
3. dimensional stability
Take a certain amount of polyurethane to cut sample by standard given size, keep flat after the graticule distance of regulation is marked on surface
In detection case；After depositing the regular hour in uniform temperature, in case, it is cooled to room temperature, detect graticule distance immediately.Then mould
The graticule size changing rate of material samples is：
S1=(L1-L0)/L0100%
S in formula1It is sample rate of change, unit is %；L0It is that sample graticule initial (before test) is long, unit is mm；L1It is examination
Long after the test of sample graticule, unit is mm.
4. oxygen index (OI) analysis
When there is biomass combustion, need to consume substantial amounts of oxygen, different combustible, the burning of varying number consumes
Oxygen, by determining the amount of oxygen minimum of material consumption in combustion process, calculates the material of oxygen index value.Polyurethane foam is pure
Oxygen index (OI) generally 17 to 18, this foamed materials is that anti-flammability reaches standard.Magnesium hydroxide, aluminium hydroxide and inorganic combustion inhibitor belong to
In expanded graphite, it is widely used in the preparation of flame-retardant foam.Adopt LDX-QS-M606B type numeral oxygen index (OI) analyser herein
Measurement.By the discussion of polyurethane foam combustion oxygen index (OI), to weigh their performance.
5. FTIR spectrum analysis
FTIR spectrum (FT-IR) be furnished with DTGS detector on complete.Used herein to be the U.S. heat
The Fourier infrared spectrograph of model TN-380 that electric company produces.The analysis of inorganic compounding flame retardant polyurethane is by unrestrained anti-
Penetrate FTIR spectrum equipment to complete.
Dried sample is taken out, take micro in mortar, add dry potassium bromide to grind to form superfine micronized
Granule.Put in Fourier infrared spectrograph with tablet machine extrusion sample strip and tested.
6.TG-DTA analyzes
Thermogravimetric analysiss (Thermogravimetric Analysis, TG or TGA) refer to temperature under program, to material
The method of the relation of quality and temperature.The thermal analyzer of this paper used DTU-2B model, adjust heating rate be 20 DEG C/
Min, temperature range controls nitrogen to be added before 50 DEG C -500 DEG C heat up, and sample mass is between 5-10mg.
It is below Property Verification and the analysis of polyurethane foam：
1. the impact of the fire resistance of interpolation hard polyurethane foam of fire retardant
It is taken at during preparing polyurethane and add different fire retardants, the examination of acquisition miscible with hard polyurethane foam
The infrared spectrum spectrogram of sample is as shown in Figure 2.In Fig. 2, wave number is in 3460cm-1Peak be O-H stretching vibration and N-H stretching vibration, be
, broad peak and is because that the intermolecular hydrogen bond that defines can not divide, affected by hydrogen bond in wide absworption peak；2920cm in a-1
Place absworption peak be synthesis of polyurethane raw material in unreacted completely ternary cyclic ethers；2373cm-1Place is the carbon dioxide of saturation
Stretching vibration peak；Wave number 1639cm-1Corresponding peak is the bending vibration of N-H；1520cm-1Place is the amide groups in polyurethane
Vibration absorption peak；672cm-1Left and right is the absworption peak occurring, and the peak value occurring herein is because the amido link of polyurethane
Modest absorbance peak.Even if as can be seen that changing fire retardant, the structure not too big change of polyurethane from curve Fig. 2
Change, because inorganic combustion inhibitor is through anion-modified, Surface coating lipophilic group, so fire retardant can be uniform with polyurethane
Miscible, do not change internal structure and the key property of polyurethane.It is taken at and add different proportion during preparing polyurethane
Mg (OH)2With EG, miscible with hard polyurethane foam, the infrared spectrum spectrogram of the sample of acquisition is as shown in Figure 3.Fig. 3 medium wave
Number is in 3454cm-1Peak be O-H stretching vibration and N-H stretching vibration, be wide absworption peak, broad peak occur and is because intermolecular shape
Become hydrogen bond can not divide, affected into money peak by hydrogen bond；2362cm-1Place is the stretching vibration peak of the carbon dioxide of saturation；
Wave number 1658cm-1Corresponding peak is the bending vibration of N-H；1547cm-1Place is the vibration absorption peak of the amide groups in polyurethane；
660cm-1Left and right is the absworption peak occurring, and is the modest absorbance peak of the amido link of polyurethane.
2. the impact to polyurethane foam density and dimensional stability for the water foaming agent consumption
The impact to polyurethane density and dimensional stability for the difference of water foaming agent consumption, respectively as shown in Figure 4 and Figure 5.
As shown in Figure 4, the increase of the consumption with foaming agent water for the density of polyurethane and decline, water foaming agent addition is from 1
When part becomes two parts, the degree of decline is big, and rate of descent has reached 23.8%.This is because, in water foaming agent addition certain
In the range of, water and isocyanates react the CO producing2Many, the bubble sent out is relatively more, so density reduces.
Contrast Fig. 4 and Fig. 5, when water foaming agent consumption is 3 parts, the density 48.3kg cm of hard polyurethane foam-3, gather
The dimensional stability highest of urethane, is 0.2%, so when the addition that water cooks foam stabilizer is 3 parts, the dimensional stability of polyurethane
Best.
Dimensional stability high energy makes polyurethane have more preferable processing characteristics, is easy to the machine-shaping of material.
3. the impact to compressive strength for the addition of water foaming agent
The impact of the compressive strength of the polyurethane foam being led to due to the difference of water foaming agent addition is as shown in Figure 6.
As shown in fig. 6, the consumption of water foaming agent increases, the compressive strength of polyurethane foam declines therewith.In vertical direction, press
Contracting intensity reaches maximum 0.51MPa, and water foaming agent consumption now is 1 part；When maximum slope is 3 parts of water consumption, rate of descent
Reach 60% when the addition of water foaming agent is at 5 parts, the compressive strength of polyurethane foam reduces to minimum.
4. isocyanate index R analysis
The impact analysis to density and dimensional stability for the 4.1 R values
Isocyanates R value affects the density of foam, mechanical property, dimensional stability etc..In synthesis, the ratio one of R
As be 0.9-1.4.As R=NCO/OH=1.0, polyether polyol and isocyanates can react completely, formed and have certain friendship
The network structure of connection density.Because the purity of MDI-50 is inadequate, in practical situations both, the amount of isocyanates is excessive slightly.Investigate R
The impact to foam density for the value.The impact to polyurethane density for the difference of R value, as shown in fig. 7, with this urethane rigid foam density
Also improve therewith, because R value is the ratio of NCO and two reactive groups of OH, in this method, foaming agent is done with water, in water and MDI
NCO reaction, generate CO2.R value increases, and represents MDI excessively, and the NCO group that can react with water becomes many, leads in certain model
The density enclosing interior hard polyurethane foam increases with the increase of R value.
As shown in figure 8, the dimensional stability of polyurethane improves with the increase of R value, when isocyanate index (R) is less than
When 1.1, the OH in the standby experiment of polyurethane does not react so that the crosslink density of polyurethane is inadequate completely, intermolecular force
Decline, the dimensional stability of polyurethane is relatively poor, and this is because, in whole system, deionized water makees CBA with MDI-
50 react and generate CO2, consume the MDI-50 of some；When R value is in 1.1-1.3, foam places 48h, chi at 90 DEG C
Very little be held essentially constant, in this molecule contain hard segment thus intensity higher.Hard segment includes carbamate, urea and biuret etc.
Group.
The compressive strength analysis of the polyurethane foam that the difference of 4.2 R values leads to
The impact of the compressive strength of the polyurethane foam being led to due to the difference of R value is as shown in Figure 9.
As shown in figure 9, the compressive strength of horizontal direction improves with the increase of R, the cohesiveness of polyurethane molecular with
The crosslink density of the hard chain forging of rigid structure increases and strengthens, and the hard polyurethane foam of gained has excellent compressive strength.
Contrast Fig. 7, Fig. 8 and Fig. 9, when R value controls between 1.1-1.4, the dimensional stability of polyurethane tends to be steady,
Affected to reduce by R value, so, for dimensional stability, R value should control between 1.1-1.4.When R value is in 1.4,
The dimensional stability of polyurethane foam and compressive strength are all relatively good, but the crosslink density of polyurethane foam is too big, its matter
Ground is very crisp, and adhesive property is poor, and the one-tenth that increased hard polyurethane foam produces cost.Seat R value should control in 1.1-1.2
Between.
The impact to oxygen index (OI) for 5 different flame retardant
Magnesium hydroxide, aluminium hydroxide and expanded graphite belong to inorganic combustion inhibitor, are widely used in the system of fire retardant foam
Standby.Mixed with polyurethane with different fire retardants, drawn different oxygen index (OI)s, as shown in Figure 10, be with the addition of fire retardant
The oxygen index (OI) of polyurethane improves.It may also be seen that the polyurethane that with the addition of aluminium hydroxide slightly higher than adds on oxygen index (OI)
Hydro-oxidation magnesium polyurethane, but two kinds of fire retardants are very nearly the same, obvious weak and other two fire retardants of expanded graphite,
So a kind of fire retardant of simple interpolation is concluded that：Aluminium hydroxide ＞ magnesium hydroxide ＞ expanded graphite.
Add different fire retardants to be compounded, verified further by different ratios.Draw different oxygen index (OI)s,
As shown in figure 11.Different compounding proportionings, has a certain impact to the oxygen index (OI) of polyurethane as shown in Figure 11, wherein without
Mg(OH)2Polyurethane in, its oxygen index (OI) be 24%, by 1：1、1：2 and 1：3 with the addition of EG, and flame retardant polyurethane hard steeps
The oxygen index (OI) of foam all has increase.But effect is most notably therein to press 1：It is the most obvious that 1 proportioning adds expanded graphite.Add
Plus different fire retardants is compounded, verified further by different ratios.Draw different oxygen index (OI)s, as Figure 12 institute
Show.As shown in Figure 12 at Al (OH)3The middle oxygen index (OI) adding expanded graphite can improve polyurethane, wherein Al (OH)3：EG=1：1
When, maximum to the active influence ability of the oxygen index (OI) of polyurethane.
Contrast Figure 11 and 12 understands, Mg (OH)2From 1：0 to 1：1 increases about 9.58%, Al (OH)3From 1：0 to 1：1 increasing
Grow about 9.88%.Al(OH)3Proportioning with EG is 1：Reaching maximum when 1 is 26.7%, Mg (OH)2With proportioning be 1：1
Reaching maximum is 26.3%, by contrast, Al (OH)3Fire resistance be better than Mg (OH)2Fire resistance with EG.
6 TG-DTA analyses
It is taken at during preparing polyurethane and adds different fire retardants, polyurethane is carried out with fire resistance modification, obtains
Sample TG-DTA spectrogram as shown in figure 13.
Thermogravimetric analysiss reflect the heat stability of material, can draw decomposition temperature T0 and weightless 50% temperature during analysis
This two values of T50 can be used as the quantitative parameter of material heat stability.Wherein the bigger material of the numerical value of T0 and T50 is thermally-stabilised
Performance is better.As shown in Figure 13 shown in T0 the and T50 data of polyurethane and its composite, make following table：
| Sample | T0/℃ | T50/℃ |
| No added polyurethane | 240 | 364 |
| Add magnesium hydroxide | 300.5 | 375 |
Add the impact to heat stability for the fire retardant
From Figure 13 and upper table, add fire retardant and the thermal stability of polyurethane is had a certain impact, with the addition of resistance
The polyurethane of combustion agent thermally-stabilised to being better than un-added heat stability.Decomposition temperature improves 60 DEG C about, because of polyurethane
Foam has loose structure, and fire retardant, through anion-modified, can be mixed with polyurethane, fire retardant is when being heated well
Decompose and absorb heat so that the heat stability of whole flame retardant polyurethane rigid foam improves.
Above the present invention has been described in detail, but described content be only the present invention the impartial change of preferable enforcement with
Improve etc., all should still belong within the patent covering scope of the present invention.
Claims (10)
1. a kind of inorganic compounding flame retardant polyurethane rigid foam material it is characterised in that：Density is 59-77kg m-3, level side
To compressive strength be 0.5-0.6MPa, the compressive strength of vertical direction is 0.4-0.5MPa, carries out according to the following step：
Step one：Weigh polyether polyol N330,1-5 of polyether polyol N220, the 30-50 mass parts of 150-170 mass parts
The distilled water of mass parts, the triethanolamine of organotin T-20,2-4 mass parts of 1-3 mass parts and the fire retardant of 30-50 mass parts
Put into stirring in beaker, form component A；
Step 2：Weigh the isocyanates of 230 mass fractions, as component B；
Step 3：The temperature adjusting mould, to 25-30 DEG C, component A and component B is poured in mould simultaneously, stirring mixing 10-30
It is allowed to free foaming 3-5 minute after second；
Step 4：Make hard foam ripening 24-48h under the conditions of 40-60 DEG C, ripening completes rigid foam material after terminating
The preparation of material；
Used in step one, fire retardant the following step is carried out：
Step 1：Weigh quality parts ratio 1:(1-3) Mg (OH)2And ethylene glycol, put into as component A in beaker, or weigh matter
Amount portion rate 1:(1-3) Al (OH)3And ethylene glycol, put into as component A in beaker, or weigh quality parts ratio 1:1:(1-
3) Mg (OH)2、Al(OH)3And ethylene glycol, put in beaker as component A；
Step 2：In beaker, with water for solvent polyethylene dissolving alcohol, form poly-vinyl alcohol solution as component B；
Step 3：Component A and component B are mixed in beaker, and adds dodecylbenzene sodium sulfonate, heated at constant temperature in beaker
2-3h；
Step 4：Sucking filtration is carried out to the reaction product in beaker, obtains solid residue；
Step 5：The solid residue obtaining in step 4 is put in electric heating forced air drying and is dried；
Step 6：Form solid flame retardant after the completion of drying, solid flame retardant is loaded standby in bag.
2. a kind of inorganic compounding flame retardant polyurethane rigid foam material according to claim 1 it is characterised in that：In step
In one, the mass fraction of described distilled water is preferably 2-4 part；In step 2, described isocyanates are preferably MDI-50.
3. a kind of inorganic compounding flame retardant polyurethane rigid foam material according to claim 1 it is characterised in that：In step
In three, described mixing time is preferably the 18-20 second.
4. a kind of inorganic compounding flame retardant polyurethane rigid foam material according to claim 1 it is characterised in that：In step
In four, the curing temperature of described foam is preferably 48-52 DEG C, and the curing time is preferably 35-37h.
5. a kind of inorganic compounding flame retardant polyurethane rigid foam material according to claim 1 it is characterised in that：Carry out
During fire retardant preparation, in step 1, described Mg (OH)2It is preferably 1 with the quality parts ratio of ethylene glycol:1, described Al (OH)3
It is preferably 1 with the quality parts ratio of ethylene glycol:1, described Mg (OH)2、Al(OH)3It is preferably with the quality parts ratio of ethylene glycol
1:1:1；In step 2, the solution temperature of described polyvinyl alcohol is 95-100 DEG C；In step 3, described mode of heating is water-bath
Heating, the time of heated at constant temperature is preferably 2-2.5h.
6. a kind of preparation method of inorganic compounding flame retardant polyurethane rigid foam material it is characterised in that：Enter according to the following step
OK：
Step one：Weigh polyether polyol N330,1-5 of polyether polyol N220, the 30-50 mass parts of 150-170 mass parts
The distilled water of mass parts, the triethanolamine of organotin T-20,2-4 mass parts of 1-3 mass parts and the fire retardant of 30-50 mass parts
Put into stirring in beaker, form component A；
Step 2：Weigh the isocyanates of 230 mass fractions, as component B；
Step 3：The temperature adjusting mould, to 25-30 DEG C, component A and component B is poured in mould simultaneously, stirring mixing 10-30
It is allowed to free foaming 3-5 minute after second；
Step 4：Make hard foam ripening 24-48h under the conditions of 40-60 DEG C, ripening completes rigid foam material after terminating
The preparation of material；
Used in step one, fire retardant the following step is carried out：
Step 1：Weigh quality parts ratio 1:(1-3) Mg (OH)2And ethylene glycol, put into as component A in beaker, or weigh matter
Amount portion rate 1:(1-3) Al (OH)3And ethylene glycol, put into as component A in beaker, or weigh quality parts ratio 1:1:(1-
3) Mg (OH)2、Al(OH)3And ethylene glycol, put in beaker as component A；
Step 2：In beaker, with water for solvent polyethylene dissolving alcohol, form poly-vinyl alcohol solution as component B；
Step 3：Component A and component B are mixed in beaker, and adds dodecylbenzene sodium sulfonate, heated at constant temperature in beaker
2-3h；
Step 4：Sucking filtration is carried out to the reaction product in beaker, obtains solid residue；
Step 5：The solid residue obtaining in step 4 is put in electric heating forced air drying and is dried；
Step 6：Form solid flame retardant after the completion of drying, solid flame retardant is loaded standby in bag.
7. the preparation method of a kind of inorganic compounding flame retardant polyurethane rigid foam material according to claim 6, its feature
It is, in step one, the mass fraction of described distilled water is preferably 2-4 part；In step 2, described isocyanates are excellent
Elect MDI-50 as.
8. the preparation method of a kind of inorganic compounding flame retardant polyurethane rigid foam material according to claim 6, its feature
It is, in step 3, described mixing time is preferably the 18-20 second.
9. the preparation method of a kind of inorganic compounding flame retardant polyurethane rigid foam material according to claim 6, its feature
It is, in step 4, the curing temperature of described foam is preferably 48-52 DEG C, and the curing time is preferably 35-37h.
10. the preparation method of a kind of inorganic compounding flame retardant polyurethane rigid foam material according to claim 6, its feature
It is, when carrying out fire retardant preparation, in step 1, described Mg (OH)2It is preferably 1 with the quality parts ratio of ethylene glycol:1, institute
The Al (OH) stating3It is preferably 1 with the quality parts ratio of ethylene glycol:1, described Mg (OH)2、Al(OH)3Mass parts with ethylene glycol
Number ratio preferably 1:1:1；In step 2, the solution temperature of described polyvinyl alcohol is 95-100 DEG C；In step 3, described heating
Mode is heating in water bath, and the time of heated at constant temperature is preferably 2-2.5h.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06271639A (en) * | 1993-03-19 | 1994-09-27 | Polyurethan Kasei Kk | Production of inorganic substance-packed flame-retardant rigid urethane foam |
| US20100151225A1 (en) * | 2007-12-28 | 2010-06-17 | Michael John Mabey | Thermal barrier mineral foam polyurethane and so forth |
| CN103497557A (en) * | 2013-09-24 | 2014-01-08 | 北京工商大学 | Flame-retardant hard polyurethane foam |
| CN105670039A (en) * | 2014-11-21 | 2016-06-15 | 合肥杰事杰新材料股份有限公司 | High-char-forming expandable graphite and application thereof in rigid polyurethane foam |
-
2016
- 2016-10-20 CN CN201610915835.9A patent/CN106478920A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06271639A (en) * | 1993-03-19 | 1994-09-27 | Polyurethan Kasei Kk | Production of inorganic substance-packed flame-retardant rigid urethane foam |
| US20100151225A1 (en) * | 2007-12-28 | 2010-06-17 | Michael John Mabey | Thermal barrier mineral foam polyurethane and so forth |
| CN103497557A (en) * | 2013-09-24 | 2014-01-08 | 北京工商大学 | Flame-retardant hard polyurethane foam |
| CN105670039A (en) * | 2014-11-21 | 2016-06-15 | 合肥杰事杰新材料股份有限公司 | High-char-forming expandable graphite and application thereof in rigid polyurethane foam |
Non-Patent Citations (5)
| Title |
|---|
| WANJIN WANG,等: ""Synergistic Effect of Aluminum Hydroxide and Expandable Graphite on the Flame Retardancy of Polyisocyanurate–Polyurethane Foams"", 《APPLIED POLYMER》 * |
| 刘源等，编著: ""全水发泡聚氨酯/Al(OH)3阻燃硬质泡沫的研究"", 《塑料工业》 * |
| 舒中俊，等: ""可膨胀石墨／氢氧化铝复配改性聚氨酯泡沫的阻燃性能"", 《机械工程材料》 * |
| 赵秀丽，等: ""无卤型阻燃聚氨酯泡沫塑料研究"", 《塑料工业》 * |
| 陶亚秋，等: ""无卤添加型阻燃剂对硬质聚氨酯泡沫阻燃性能研究"", 《化工新型材料》 * |
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