CN107459619A - A kind of phosphor-containing flame-proof hard polyurethane foams based on expansible graphite and preparation method thereof - Google Patents
A kind of phosphor-containing flame-proof hard polyurethane foams based on expansible graphite and preparation method thereof Download PDFInfo
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- 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
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- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
- C08G18/388—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having phosphorus bound to carbon and/or to hydrogen
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/125—Water, e.g. hydrated salts
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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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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- 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
- C08G2110/0025—Foam properties rigid
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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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/10—Water or water-releasing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention discloses a kind of phosphor-containing flame-proof hard polyurethane foams based on expansible graphite and preparation method thereof.Preparation method uses the flame-retardant modified raw material of expansible graphite and response type halogen-free flame retardants DOPO HQ as RPUF, by carrying out polymerisation after mixing, foaming, response type halogen-free flame retardants DOPO HQ are incorporated on the backbone structure of polyurethane, phosphor-containing flame-proof hard polyurethane foams are prepared, the anti-flammability of hard polyurethane foams is put forward on the premise of polyurethane structural is not changed, and in the absence of the transport phenomena of long service.The phosphor-containing flame-proof hard polyurethane foams density based on expansible graphite of the present invention is low, has good anti-flammability, and have excellent compressive strength, heat endurance and thermal insulation.Preparation method technique of the present invention is simple, and process conditions and equipment requirement are low, are advantageous to industrialized production.
Description
Technical field
The present invention relates to building thermal insulation material field, more particularly to a kind of phosphor-containing flame-proof hard based on expansible graphite gathers
Urethane foam and preparation method thereof.
Background technology
Wall thermal insulation technology concept is to be proposed by European countries the forties in last century, and wall heat insulation material used is main
Including the heat preserving and insulating material such as styrofoam and rock cotton board.With the continuous development of polyurethane industrial, hard polyurethane foams modeling
Expect that the dosage as wall heat insulation material is also increasing.Compared to other insulation materials, RPUF is with it
Excellent thermal insulation performance, the wide temperature range that can be on active service, the features such as waterproof anti humility performance is excellent and Comprehensive service life is long, are building
Walling body field of thermal insulation is rapidly developed.
However, " this bell of Ah noise made in coughing or vomiting's coloured glaze " of the polyurethane foam of existing process manufacture is easily to burn, and burned
Cheng Zhonghui, which is decomposed, produces substantial amounts of toxic gas, by the serious life security for endangering the people.The pole of undressed polyurethane
Limited oxygen index is only 16~18%.It is limited in the single fire retardant effect of polyurethane addition, and anti-flammability is being provided
The other performance of polyurethane foam matrix can be damaged simultaneously.
The content of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of phosphor-containing flame-proof based on expansible graphite
Hard polyurethane foams.
The present invention also aims to provide a kind of described phosphor-containing flame-proof rigid polyurethane foam based on expansible graphite
The preparation method of foam.The preparation method uses expansible graphite and response type halogen-free flame retardants DOPO-HQ (10- (2,5- dihydroxy
Phenyl) -10- hydrogen -9- oxa- -10- phospho hetero phenanthrene -10- oxides) flame-retardant modified raw material as RPUF,
By carrying out polymerisation after mixing, foaming, response type halogen-free flame retardants DOPO-HQ is incorporated in the backbone structure of polyurethane
On, phosphor-containing flame-proof hard polyurethane foams are prepared, rigid polyurethane foam is improved on the premise of polyurethane structural is not changed
The anti-flammability of foam, and in the absence of the transport phenomena of long service.
The purpose of the present invention is achieved through the following technical solutions.
A kind of preparation method of the phosphor-containing flame-proof hard polyurethane foams based on expansible graphite, comprises the following steps：
(1) PPG, foaming agent, stabilizer, catalyst and isocyanates are placed in container, use high-speed stirred
Machine is well mixed, and obtains mixed material A；
(2) RPUF (RPUF), expansible graphite (EG) and fire retardant DOPO-HQ are placed in container
In, it is well mixed with homogenizer, obtains mixed material B；
(3) mixed material B is added in mixed material A, high-speed stirred is well mixed, and pours into foaming in mould
Afterwards, then standing progress polymerisation in constant temperature oven is placed in, takes out, obtain the phosphor-containing flame-proof hard based on expansible graphite
Polyurethane foam (RPUF/EG/HQ).
Further, in step (1), the foaming agent includes water.
Further, in step (1), the stabilizer includes silicone oil.
Further, in step (1), the catalyst includes catalyst A33.
Further, in step (1), the PPG, foaming agent, stabilizer, catalyst and isocyanates
Mass ratio is 100:145.509:2:2:2.
Further, in step (2), by weight percentage, the RPUF, expansible graphite with
And fire retardant DOPO-HQ percetage by weight is respectively 85%, 15% and 0%.
Further, in step (2), by weight percentage, the RPUF, expansible graphite with
And fire retardant DOPO-HQ percetage by weight is respectively 85%, 14% and 1%.
Further, in step (2), by weight percentage, the RPUF, expansible graphite with
And fire retardant DOPO-HQ percetage by weight is respectively 85%, 12% and 3%.
Further, in step (2), by weight percentage, the RPUF, expansible graphite with
And fire retardant DOPO-HQ percetage by weight is respectively 85%, 10% and 5%.
Further, in step (3), mixed material A and mixed material B mixing quality ratio are 1:1~5.
Further, in step (3), the rotating speed of high-speed stirred mixing be 600~3000r/min, the time for 10s~
90s。
Further, in step (3), the time of the foaming is 10~120min.
Further, in step (3), the temperature of the polymerisation is 70 DEG C, and the time of polymerisation is small for 24~48
When.
Preparation method of the present invention is used as hard polyurethane using response type halogen-free flame retardants DOPO-HQ and expansible graphite (EG)
The flame-retardant modified raw material of ester foam (RPUF)；DOPO-HQ and EG has gas phase and two kinds of fire retardant mechanisms of condensed phase concurrently.Fire-retardant process
In, EG is in material surface meeting expanded by heating, the foamed char of appearance " vermiform "；And EG is after expanded by heating, volume and surface
Product is greatly increased, and superficial attractive forces, which strengthen, to be increased by the gas of adsorption and fluid molecule concentration.Examined from fire-retardant angle
Consider, on the one hand, EG absorbs substantial amounts of heat in expansion process, while the layer of charcoal expanded plays anti-flaming thermal-insulation effect；The opposing party
Face, the absorption characteristic of graphite effectively hinders the material transmission in burning between gas phase and solid phase after EG expansions, that is, prevents material
Imflammable gas caused by material thermal degradation is diffused into gas phase, while oxygen is hardly diffused to material matrix surface, hinders
The further oxidative degradation of material.Therefore, EG had both followed condensed phase fire retardant mechanism, followed gas phase fire retardant mechanism again.And DOPO-HQ
Decomposing to give off PO and PO2Free radical, fire retardation can be played in the gas phase, so as to realize condensed phase and gas phase collaboration resistance
Combustion；And DOPO-HQ can be on the premise of fire resistance be ensured, existing transport phenomena and " puffed rice when mitigation EG is individually fire-retardant
Effect ".
DOPO-HQ is incorporated on the backbone structure of polyurethane in a manner of polymerisation, make it is flame-retardant modified after hard
The transport phenomena of long service is not present in polyurethane foam；DOPO-HQ generates thick liquid film at high temperature simultaneously, increases EG's
The compactness and intensity of " vermiform " foamed char, DOPO-HQ and RPUF cohesive force are enhanced, subtracted while containing a small amount of EG
Gently " popcorn effect ", and improve RPUF fire-retardant continuation.
A kind of phosphor-containing flame-proof hard polyurethane based on expansible graphite as made from the preparation method described in any of the above-described
Ester foam.
Compared with prior art, the invention has the advantages that and beneficial effect：
(1) the phosphor-containing flame-proof hard polyurethane foams based on expansible graphite of the invention have good anti-flammability, and
With excellent density, compressive strength, heat endurance and thermal insulation, especially RPUF, EG and DOPO-HQ percetage by weight point
Not Wei 85%, 14% and 1% when combination property it is most notable；
(2) preparation method technique of the present invention is simple, and process conditions and equipment requirement are low, are advantageous to industrialized production.
Brief description of the drawings
Fig. 1 is the density curve of the phosphor-containing flame-proof hard polyurethane foams based on expansible graphite prepared by embodiment 1~4
Figure；
Fig. 2 is the compressive strength of the phosphor-containing flame-proof hard polyurethane foams based on expansible graphite prepared by embodiment 1~4
Curve map；
The phosphor-containing flame-proof hard polyurethane foams based on expansible graphite that Fig. 3 is pure RPUF and prepared by embodiment 1~4
Thermogravimetric curve figure；
The phosphor-containing flame-proof hard polyurethane foams based on expansible graphite that Fig. 4 is pure RPUF and prepared by embodiment 1~4
Differential thermogravimetric curve figure；
The phosphor-containing flame-proof hard polyurethane foams based on expansible graphite that Fig. 5 is pure RPUF and prepared by embodiment 1~4
Thermal conductivity factor curve map.
Embodiment
Technical solution of the present invention is described in further detail below in conjunction with specific embodiment and accompanying drawing, but the present invention is unlimited
In this.
The response type halogen-free flame retardants DOPO-HQ used in the specific embodiment of the invention structural formula is as follows：
Embodiment 1
The preparation of phosphor-containing flame-proof hard polyurethane foams RPUF/15EG based on expansible graphite, specifically includes following step
Suddenly：
(1) according to mass ratio=100 of PPG, foaming agent, stabilizer, catalyst and isocyanates:
145.509:2:2:2 recipe ratio, accurately weigh PPG, blowing agent H2O, stabilizer silicone oil, catalyst A33 and isocyanide
Acid esters is placed in 500ml plastic beakers, is well mixed with homogenizer, obtains mixed material A；
(2) by RPUF (RPUF), expansible graphite (EG) and response type halogen-free flame retardants DOPO-HQ
It is well mixed with homogenizer in another beaker, obtains mixed material B；
By mass percentage, RPUF, EG and DOPO-HQ percetage by weight are respectively 85%, 15%, 0%；
(3) mixed material B is added to fill mixed material A (mixed material A and mixed material B mass ratio be 1:1)
Plastic beaker in, 900r/min high-speed stirreds 10s is well mixed, and resulting mixture is quickly poured into mould, freely
After the 20min that foams is molded, then it is placed in 70 DEG C of constant temperature ovens to stand and carries out polymerisation 24 hours, take out, obtains described be based on
The flame retarded rigid polyurethane foams RPUF/15EG of expansible graphite.
Embodiment 2
Based on expansible graphite flame retarded rigid polyurethane foams RPUF/14EG/1HQ preparation, specifically comprise the following steps：
(1) according to mass ratio=100 of PPG, foaming agent, stabilizer, catalyst and isocyanates:
145.509:2:2:2 recipe ratio, accurately weigh PPG, blowing agent H2O, stabilizer silicone oil, catalyst A33 and isocyanide
Acid esters is placed in 500ml plastic beakers, is well mixed with homogenizer, obtains mixed material A；
(2) by RPUF (RPUF), expansible graphite (EG) and response type halogen-free flame retardants DOPO-HQ
It is well mixed with homogenizer in another beaker, obtains mixed material B；
By mass percentage, RPUF, EG and DOPO-HQ percetage by weight are respectively 85%, 14%, 1%；
(3) mixed material B is added to fill mixed material A (mixed material A and mixed material B mass ratio be 1:2)
Plastic beaker in, 1500r/min high-speed stirreds 30s is well mixed, and resulting mixture is quickly poured into mould, freely
After the 50min that foams is molded, then it is placed in 70 DEG C of constant temperature ovens to stand and carries out polymerisation 35 hours, take out, obtains described be based on
The phosphor-containing flame-proof hard polyurethane foams RPUF/14EG/1HQ of expansible graphite.
Embodiment 3
The preparation of phosphor-containing flame-proof hard polyurethane foams RPUF/12EG/3HQ based on expansible graphite, specifically include as
Lower step：
(1) according to mass ratio=100 of PPG, foaming agent, stabilizer, catalyst and isocyanates:
145.509:2:2:2 recipe ratio, accurately weigh PPG, blowing agent H2O, stabilizer silicone oil, catalyst A33 and isocyanide
Acid esters is placed in 500ml plastic beakers, is well mixed with homogenizer, obtains mixed material A；
(2) by RPUF (RPUF), expansible graphite (EG) and response type halogen-free flame retardants DOPO-HQ
It is well mixed with homogenizer in another beaker, obtains mixed material B；
By mass percentage, RPUF, EG and DOPO-HQ percetage by weight are respectively 85%, 12%, 3%；
(3) mixed material B is added to fill mixed material A (mixed material A and mixed material B mass ratio be 1:5)
Plastic beaker in, 2000r/min high-speed stirreds 60s is well mixed, and resulting mixture is quickly poured into mould, freely
After the 70min that foams is molded, then it is placed in 70 DEG C of constant temperature ovens to stand and carries out polymerisation 40 hours, take out, obtains described be based on
The phosphor-containing flame-proof hard polyurethane foams RPUF/12EG/3HQ of expansible graphite.
Embodiment 4
The preparation of phosphor-containing flame-proof hard polyurethane foams RPUF/10EG/5HQ based on expansible graphite, specifically include as
Lower step：
(1) according to mass ratio=100 of PPG, foaming agent, stabilizer, catalyst and isocyanates:
145.509:2:2:2 recipe ratio, accurately weigh PPG, blowing agent H2O, stabilizer silicone oil, catalyst A33 and isocyanide
Acid esters is placed in 500ml plastic beakers, is well mixed with homogenizer, obtains mixed material A；
(2) by RPUF (RPUF), expansible graphite (EG) and response type halogen-free flame retardants DOPO-HQ
It is well mixed with homogenizer in another beaker, obtains mixed material B；
By mass percentage, RPUF, EG and DOPO-HQ percetage by weight are respectively 85%, 10%, 5%；
(3) mixed material B is added to fill mixed material A (mixed material A and mixed material B mass ratio be 1:5)
Plastic beaker in, 2500r/min high-speed stirreds 90s is well mixed, and resulting mixture is quickly poured into mould, freely
After the 100min that foams is molded, then it is placed in 70 DEG C of constant temperature ovens to stand and carries out polymerisation 48 hours, take out, obtains described be based on
The phosphor-containing flame-proof hard polyurethane foams RPUF/10EG/5HQ of expansible graphite.
Performance evaluation
The densogram of phosphor-containing flame-proof hard polyurethane foams based on expansible graphite prepared by embodiment 1~4 is such as
Shown in Fig. 1, as shown in Figure 1, with the increase of DOPO-HQ contents, the phosphor-containing flame-proof hard based on expansible graphite of preparation gathers
The density of urethane foam is gradually reduced, up to RPUF/15EG, is 0.077g/cm3；When EG weight fraction for 14%,
When DOPO-HQ weight fraction is 1%, the density value for preparing RPUF/14EG/1HQ is in close proximity to pure RPUF density, is
0.074g/cm3；When EG weight fraction is 12%, DOPO-HQ weight fraction is 3%, prepare RPUF/12EG/3HQ's
Density 0.073g/cm of the density already below pure RPUF3, it is 0.072g/cm3；And RPUF/10EG/5HQ density is minimum, it is
0.070g/cm3, still reach the standard required by national standard (according to flame-retardant polyurethane warming plate performance indications, GB 50404-
2007 Standard：The density of flame-retardant polyurethane rigid foam at least answers >=35kg/m3)；The reduction of density is advantageous to subtract
Cost during few production and transport, it is significant in production practices.
The compressive strength curve of phosphor-containing flame-proof hard polyurethane foams based on expansible graphite prepared by embodiment 1~4
Figure is as shown in Fig. 2 as shown in Figure 2, DOPO-HQ addition can make the compressive strength of hard RPUF foams reduce (pure RPUF pressure
Contracting intensity is 0.43MPa), and with the increase of DOPO-HQ contents, the phosphor-containing flame-proof rigid polyurethane foam based on expansible graphite
The compressive strength of foam will be gradually reduced, but still be more than 0.18MPa, be met Standard and (hard for building field be gathered
The compressive strength of urethane foamed plastics, GB/T-21558-2008《Building insulation RPUF》In have three classes
Standard requirement, to for the class of highest the 3rd (be applied to have the requirement of more high-mechanic, and have resistance to compression, the occasion of creep resistant requirement)
RPUF compressive strength require its >=0.18MPa)；And the phosphor-containing flame-proof hard based on expansible graphite prepared by embodiment 1~4
In polyurethane foam, after adding DOPO-HQ, RPUF/14EG/1HQ compressive strength declines at least, and mechanical property is best.
Phosphor-containing flame-proof hard polyurethane foams (RPUF/EG/HQ) based on expansible graphite prepared by embodiment 1~4
Limited oxygen index (LOI) data are as shown in table 1.
RPUF/EG/HQ prepared by the embodiment 1~4 of table 1 limited oxygen index data
Analytical table 1 is understood, when adding DOPO-HQ, sample RPUF/14EG/1HQ, RPUF/12EG/3HQ and RPUF/
10EG/5HQ limited oxygen index is respectively 28.5%, 28.8% and 28.7%, belongs to nonflammable material, and three kinds of samples
Limited oxygen index gap is little, more only add EG when sample RPUF/15EG slightly decrease, but for pure RPUF still have compared with
Big raising (pure RPUF limited oxygen index is 19.2%), illustrate DOPO-HQ fire resistance of the addition to RPUF/EG/HQ
Influence less but still has excellent fire resistance.
Phosphor-containing flame-proof hard polyurethane foams (RPUF/EG/HQ) based on expansible graphite prepared by embodiment 1~4
Horizontal firing test result is as shown in table 2.
RPUF/EG/HQ prepared by the embodiment 1~4 of table 2 horizontal firing test result
As shown in Table 2, in three samples for adding fire retardant DOPO-HQ, RPUF/14EG/1HQ, RPUF/12EG/3HQ
It can extinguish after annealing with RPUF/10EG/5HQ, and without residual flame, reach the FH-1 in GB/T 2408-1996 standards
Level, it is consistent with the test result of limited oxygen index；Relative to the sample RPUF/15EG for being not added with DOPO-HQ, DOPO-HQ's
Adding RPUF fire-retardant on EG/DOPO-HQ fire resistance influences less, but still have excellent fire resistance.
Phosphor-containing flame-proof hard polyurethane foams (RPUF/EG/HQ) based on expansible graphite prepared by embodiment 1~4 and
Pure RPUF heat analysis related data is as shown in table 3；Wherein, T5%Temperature corresponding during sample thermal weight loss 5% is represented, for heat
Decompose initial temperature；TmaxThe temperature corresponding to test sample maximum heat weight loss rate is represented, is maximum heat weight loss rate temperature；
RmaxRepresent maximum heat weight loss rate；CR represents carbon yield.
The phosphor-containing flame-proof hard polyurethane foams based on expansible graphite that Fig. 3 is pure RPUF and prepared by embodiment 1~4
Thermogravimetric curve figure；The phosphor-containing flame-proof hard polyaminoester based on expansible graphite that Fig. 4 is pure RPUF and prepared by embodiment 1~4
The differential thermogravimetric curve figure of foam.
RPUF/EG/HQ and pure RPUF heat analysis related data prepared by the embodiment 1~4 of table 3
As shown in Table 3, pure RPUF initial decomposition temperature (T5%) it is 263 DEG C, and RPUF/15EG, RPUF/14EG/1HQ,
RPUF/12EG/3HQ and RPUF/10EG/5HQ initial decomposition temperature is respectively 254 DEG C, 247 DEG C, 251 DEG C and 265 DEG C, can
See with the increase of HQ contents, RPUF initial decomposition temperature rises after falling before；Pure RPUF weight loss is 82.7%, and
RPUF/15EG, RPUF/14EG/1HQ, RPUF/12EG/3HQ and RPUF/10EG/5HQ weight loss is respectively 70.2%,
73.2%th, 73.1%, 76.9%, downward trend is presented compared to pure RPUF, and with the increase of DOPO-HQ contents, weight loss base
This gradually increases；
Analysis chart 3, it can be found that the heat decomposition curve of all samples is similar, has similar thermal decomposition course, all with Fig. 4
Decomposed between 250~590 DEG C, and temperature range corresponds to the degraded of isocyanates and PPG；
In summary the analysis of Fig. 3, Fig. 4 and table 3, between 250~590 DEG C, pure RPUF and RPUF/EG/HQ heat
Decomposition course is closely similar, and maximum rhermal decomposition rate rises with the increase of DOPO-HQ contents, and carbon yield is with DOPO-HQ
The increase of content and fluctuated；And in the sample for adding DOPO-HQ, with the increase of DOPO-HQ amount so that RPUF heat
Decomposition rate and weight loss rise, and reduce carbon yield so that its heat endurance has decline by a small margin；Adding DOPO-
In HQ three samples, although RPUF/14EG/1HQ and the sample initial decomposition temperatures of RPUF/12EG/3HQ two are slightly relatively low,
Rhermal decomposition rate and weight loss are relatively low, and carbon yield is higher, and heat endurance is better than RPUF/10EG/5HQ.
The thermal conductivity factor of flame retarded rigid polyurethane foams based on expansible graphite prepared by pure RPUF and embodiment 1~4
Curve map as shown in figure 5, as shown in Figure 5, pure RPUF thermal conductivity factor is 0.02958W/mK, and sample RPUF/15EG,
RPUF/14EG/1HQ, RPUF/12EG/3HQ and RPUF/10EG/5HQ thermal conductivity factor be respectively 0.03302W/mK,
0.03195W/mK, 0.04043W/mK and 0.03735W/mK；By contrast as can be seen that RPUF/14EG/1HQ's leads
The hot pure RPUF of coefficient ratio is slightly larger, and is less than other three samples, illustrates that RPUF/14EG/1HQ has good heat-insulation and heat-preservation
Can, insulation material can be functioned well as.
In summary analysis understands that, with the increase of DOPO-HQ contents, RPUF/EG/HQ density is gradually reduced, RPUF/
14EG/1HQ density and pure RPUF density approach；Increase of the RPUF/EG/HQ compression performance also with DOPO-HQ contents
And it is gradually small, wherein than other two addition fire retardant DOPO-HQ of RPUF/14EG/1HQ compressive strength sample is high, meets
Standard.
In the RPUF/EG/HQ samples for adding fire retardant DOPO-HQ, limited oxygen index is both greater than 28%, is incombustibe material
Material, and horizontal burn rate all reaches FH-1 levels, illustrates the fire resistance for adding fire retardant DOPO-HQ RPUF/EG/HQ samples
It is very good；
DOPO-HQ and EG compounding causes RPUF rhermal decomposition rates and weight loss to rise, and reduces carbon yield so that its heat
Stability has decline by a small margin；In DOPO-HQ three samples are added, RPUF/14EG/1HQ and RPUF/12EG/3HQ
Although two sample initial decomposition temperatures are slightly relatively low, rhermal decomposition rate and weight loss are relatively low, and carbon yield is higher, and heat endurance is excellent
In RPUF/10EG/5HQ；DOPO-HQ and EG compounding causes RPUF thermal conductivity factor to have certain fluctuation simultaneously, wherein, RPUF/
The 14EG/1HQ pure RPUF of thermal conductivity ratio is slightly larger, and less than other three addition EG sample, has good heat-insulated guarantor
Warm nature energy；This is due to that DOPO-HQ and EG have gas phase and two kinds of fire retardant mechanisms of condensed phase concurrently, and DOPO-HQ can ensure to hinder
On the premise of firing performance, existing transport phenomena and " popcorn effect " when mitigation EG is individually fire-retardant.
And analyzed more than, in sample prepared by embodiment 1~4, sample RPUF/14EG/1HQ is in density, pressure
The performance of contracting intensity, heat endurance and heat-proof quality etc. is most excellent.
The above is only the preferred embodiment of the present invention, it is noted that for the person of ordinary skill of the art,
Without departing from the concept of the premise of the invention, various modifications and improvements can be made, these belong to the guarantor of the present invention
Protect scope.
Claims (10)
1. a kind of preparation method of the phosphor-containing flame-proof hard polyurethane foams based on expansible graphite, it is characterised in that including such as
Lower step：
（1）PPG, foaming agent, stabilizer, catalyst and isocyanates are placed in container, mixed with homogenizer
Close uniformly, obtain mixed material A；
（2）RPUF, expansible graphite and fire retardant DOPO-HQ are placed in container, use high-speed stirred
Machine is well mixed, and obtains mixed material B；
（3）Mixed material B is added in mixed material A, high-speed stirred is well mixed, and is poured into mould after foaming, then
It is placed in stand in constant temperature oven and carries out polymerisation, take out, obtains the phosphor-containing flame-proof hard polyurethane based on expansible graphite
Ester foam.
A kind of 2. preparation side of phosphor-containing flame-proof hard polyurethane foams based on expansible graphite according to claim 1
Method, it is characterised in that step（1）In, the foaming agent includes water；The stabilizer includes silicone oil；The catalyst includes urging
Agent A33.
A kind of 3. preparation side of phosphor-containing flame-proof hard polyurethane foams based on expansible graphite according to claim 1
Method, it is characterised in that step（1）In, the PPG, foaming agent, stabilizer, the quality of catalyst and isocyanates
Than for 100:145.509:2:2:2.
A kind of 4. preparation side of phosphor-containing flame-proof hard polyurethane foams based on expansible graphite according to claim 1
Method, it is characterised in that step（2）In, by weight percentage, the RPUF, expansible graphite and
Fire retardant DOPO-HQ percetage by weight is respectively 85%, 15% and 0%.
A kind of 5. preparation side of phosphor-containing flame-proof hard polyurethane foams based on expansible graphite according to claim 1
Method, it is characterised in that step（2）In, by weight percentage, the RPUF, expansible graphite and
Fire retardant DOPO-HQ percetage by weight is respectively 85%, 14% and 1%.
A kind of 6. preparation side of phosphor-containing flame-proof hard polyurethane foams based on expansible graphite according to claim 1
Method, it is characterised in that step（2）In, by weight percentage, the RPUF, expansible graphite and
Fire retardant DOPO-HQ percetage by weight is respectively 85%, 12% and 3%.
A kind of 7. preparation side of phosphor-containing flame-proof hard polyurethane foams based on expansible graphite according to claim 1
Method, it is characterised in that step（2）In, by weight percentage, the RPUF, expansible graphite and
Fire retardant DOPO-HQ percetage by weight is respectively 85%, 10% and 5%.
A kind of 8. preparation side of phosphor-containing flame-proof hard polyurethane foams based on expansible graphite according to claim 1
Method, it is characterised in that step（3）In, mixed material A and mixed material B mixing quality ratio are 1:1~5.
A kind of 9. preparation side of phosphor-containing flame-proof hard polyurethane foams based on expansible graphite according to claim 1
Method, it is characterised in that step（3）In, the rotating speed of the high-speed stirred mixing is 600 ~ 3000r/min, and the time is 10s ~ 90s；
The time of the foaming is 10 ~ 120min；The temperature of the polymerisation is 70 DEG C, and the time of polymerisation is 24 ~ 48 hours.
10. a kind of phosphor-containing flame-proof based on expansible graphite is hard as made from the preparation method described in any one of claim 1 ~ 9
Matter polyurethane foam.
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| CN201711443995.9A CN108102348A (en) | 2017-08-30 | 2017-12-27 | A kind of phosphor-containing flame-proof hard polyurethane foams based on expansible graphite and preparation method thereof |
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| CN112358804A (en) * | 2020-11-20 | 2021-02-12 | 兰州理工大学白银新材料研究院 | Preparation method of efficient flame-retardant polyurethane material |
| CN112585185A (en) * | 2018-08-23 | 2021-03-30 | 美国圣戈班性能塑料公司 | Polyurethane foam and method of forming same |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109354669A (en) * | 2018-09-12 | 2019-02-19 | 北京工商大学 | A kind of highly effective flame-retardant rigid polyurethane foam accessing phospho hetero phenanthrene group |
| CN109593173B (en) * | 2018-11-20 | 2022-03-18 | 高鼎精细化工(昆山)有限公司 | Silicon-based thermoplastic vulcanized rubber with flame retardance and synthetic method thereof |
| CN116284649B (en) * | 2023-04-10 | 2024-04-05 | 上海玓墨节能科技有限公司 | Fireproof blocking polyurethane foam and preparation method and application thereof |
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| US9234137B2 (en) * | 2009-12-16 | 2016-01-12 | Basf Se | Flame retardant |
| EP2687534A1 (en) * | 2012-07-20 | 2014-01-22 | LANXESS Deutschland GmbH | Halogen-free poly(alkylene phosphate) |
| DE102014211276A1 (en) * | 2014-06-12 | 2015-12-17 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Use of hydroxybenzotriazole derivatives and / or hydroxyindazole derivatives as flame retardants for plastics and flame-retardant plastic molding compound |
| CN106279606A (en) * | 2016-08-08 | 2017-01-04 | 常州大学 | A kind of expanded graphite flame retarded rigid polyurethane foams material working in coordination with phosphonium flame retardant and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112585185A (en) * | 2018-08-23 | 2021-03-30 | 美国圣戈班性能塑料公司 | Polyurethane foam and method of forming same |
| US11851521B2 (en) | 2018-08-23 | 2023-12-26 | Saint-Gobain Performance Plastics Corporation | Polyurethane foam and methods of forming the same |
| CN112358804A (en) * | 2020-11-20 | 2021-02-12 | 兰州理工大学白银新材料研究院 | Preparation method of efficient flame-retardant polyurethane material |
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