CN108102348A - 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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- CN108102348A CN108102348A CN201711443995.9A CN201711443995A CN108102348A CN 108102348 A CN108102348 A CN 108102348A CN 201711443995 A CN201711443995 A CN 201711443995A CN 108102348 A CN108102348 A CN 108102348A
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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
- C08G18/65—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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- 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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- 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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- 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 rigid polyurethane foam, 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 there is no the transport phenomenas 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 with excellent compressive strength, thermal stability and thermal insulation.Preparation method of the present invention is simple for process, and process conditions and equipment requirement are low, are conducive 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 materials 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 thermal insulation materials, rigid polyurethane foam is with it
The features such as excellent thermal insulation performance, the wide temperature range that can be on active service, waterproof anti humility performance is excellent and Comprehensive service life is long, is 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, generates substantial amounts of toxic gas, by the serious life security for endangering the people.The pole of untreated 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 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 rigid polyurethane foam,
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 there is no the transport phenomenas 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, includes the following steps：
(1) polyether polyol, foaming agent, stabilizer, catalyst and isocyanates are placed in container, use high-speed stirred
Machine is uniformly mixed, and obtains mixed material A；
(2) rigid polyurethane foam (RPUF), expansible graphite (EG) and fire retardant DOPO-HQ are placed in container
In, it is uniformly mixed with homogenizer, obtains mixed material B；
(3) mixed material B is added in mixed material A, high-speed stirred is uniformly mixed, and pours into foaming in mold
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 polyether polyol, foaming agent, stabilizer, catalyst and isocyanates
Mass ratio is 100:145.509:2:2:2.
Further, in step (2), by weight percentage, the rigid polyurethane foam, expansible graphite with
And the weight percent of fire retardant DOPO-HQ is respectively 85%, 15% and 0%.
Further, in step (2), by weight percentage, the rigid polyurethane foam, expansible graphite with
And the weight percent of fire retardant DOPO-HQ is respectively 85%, 14% and 1%.
Further, in step (2), by weight percentage, the rigid polyurethane foam, expansible graphite with
And the weight percent of fire retardant DOPO-HQ is respectively 85%, 12% and 3%.
Further, in step (2), by weight percentage, the rigid polyurethane foam, expansible graphite with
And the weight percent of fire retardant DOPO-HQ is respectively 85%, 10% and 5%.
Further, in step (3), the mixing quality ratio of mixed material A and mixed material B are 1:1~5.
Further, in step (3), the rotating speed of high-speed stirred mixing is 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 both gas phase and two kinds of fire retardant mechanisms of condensed phase.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 greatly increases, and superficial attractive forces enhance so that being increased by the gas of adsorption and fluid molecule concentration.It is 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 the role of anti-flaming thermal-insulation；The opposing party
Face, the substance that the absorption characteristic of graphite is effectively hindered in burning between gas phase and solid phase after EG expansions transfer, that is, prevent material
The imflammable gas that material thermal degradation generates is diffused into gas phase, while oxygen is also made to hardly diffuse to material matrix surface, hinders
The further oxidative degradation of material.Therefore, EG had not only followed condensed phase fire retardant mechanism, but also followed gas phase fire retardant mechanism.And DOPO-HQ
Decomposing to give off PO and PO2Free radical can play fire retardation in the gas phase, so as to fulfill condensed phase and gas phase collaboration resistance
Combustion；And DOPO-HQ can be on the premise of flame retardant property be ensured, existing transport phenomena and " puffed rice when mitigation EG is individually fire-retardant
Effect ".
DOPO-HQ is incorporated in a manner of polymerisation on the backbone structure of polyurethane, 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 enhance the cohesive force of DOPO-HQ and RPUF, subtract while containing a small amount of EG
Gently " popcorn effect ", and improve the fire-retardant continuation of RPUF.
A kind of phosphor-containing flame-proof hard polyurethane based on expansible graphite as made from preparation method described in any one of the above embodiments
Ester foam.
Compared with prior art, the invention has the advantages that and advantageous 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, thermal stability and thermal insulation, the especially weight percent of RPUF, EG and DOPO-HQ point
Not Wei 85%, 14% and 1% when comprehensive performance it is most notable；
(2) preparation method of the present invention is simple for process, and process conditions and equipment requirement are low, are conducive to industrialized production.
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 Examples 1 to 4
Figure；
Fig. 2 is the compressive strength of the phosphor-containing flame-proof hard polyurethane foams based on expansible graphite prepared by Examples 1 to 4
Graph；
The phosphor-containing flame-proof hard polyurethane foams based on expansible graphite that Fig. 3 is pure RPUF and prepared by Examples 1 to 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 Examples 1 to 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 Examples 1 to 4
Thermal conductivity factor graph.
Specific embodiment
Technical solution of the present invention is described in further detail below in conjunction with specific embodiment and attached drawing, but the present invention is unlimited
In this.
The structural formula of the response type halogen-free flame retardants DOPO-HQ used in the specific embodiment of the invention 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 polyether polyol, foaming agent, stabilizer, catalyst and isocyanates:
145.509:2:2:2 recipe ratio accurately weighs polyether polyol, blowing agent H2O, stabilizer silicone oil, catalyst A33 and isocyanide
Acid esters is placed in 500ml plastic beakers, is uniformly mixed with homogenizer, obtains mixed material A；
(2) by rigid polyurethane foam (RPUF), expansible graphite (EG) and response type halogen-free flame retardants DOPO-HQ
It is uniformly mixed with homogenizer in another beaker, obtains mixed material B；
By mass percentage, the weight percent of RPUF, EG and DOPO-HQ are respectively 85%, 15%, 0%；
(3) mixed material B is added to fill mixed material A (mass ratio of mixed material A and mixed material B be 1:1)
Plastic beaker in, 900r/min high-speed stirreds 10s is uniformly mixed, and obtained mixture is quickly poured into mold, freely
Foam after 20min shapings, then be placed in 70 DEG C of constant temperature ovens stand carry out polymerisation 24 it is small when, take out, obtain described be based on
The flame retarded rigid polyurethane foams RPUF/15EG of expansible graphite.
Embodiment 2
Based on the preparation of expansible graphite flame retarded rigid polyurethane foams RPUF/14EG/1HQ, specifically comprise the following steps：
(1) according to mass ratio=100 of polyether polyol, foaming agent, stabilizer, catalyst and isocyanates:
145.509:2:2:2 recipe ratio accurately weighs polyether polyol, blowing agent H2O, stabilizer silicone oil, catalyst A33 and isocyanide
Acid esters is placed in 500ml plastic beakers, is uniformly mixed with homogenizer, obtains mixed material A；
(2) by rigid polyurethane foam (RPUF), expansible graphite (EG) and response type halogen-free flame retardants DOPO-HQ
It is uniformly mixed with homogenizer in another beaker, obtains mixed material B；
By mass percentage, the weight percent of RPUF, EG and DOPO-HQ are respectively 85%, 14%, 1%；
(3) mixed material B is added to fill mixed material A (mass ratio of mixed material A and mixed material B be 1:2)
Plastic beaker in, 1500r/min high-speed stirreds 30s is uniformly mixed, and obtained mixture is quickly poured into mold, freely
Foam after 50min shapings, then be placed in 70 DEG C of constant temperature ovens stand carry out polymerisation 35 it is small when, take out, obtain 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 polyether polyol, foaming agent, stabilizer, catalyst and isocyanates:
145.509:2:2:2 recipe ratio accurately weighs polyether polyol, blowing agent H2O, stabilizer silicone oil, catalyst A33 and isocyanide
Acid esters is placed in 500ml plastic beakers, is uniformly mixed with homogenizer, obtains mixed material A；
(2) by rigid polyurethane foam (RPUF), expansible graphite (EG) and response type halogen-free flame retardants DOPO-HQ
It is uniformly mixed with homogenizer in another beaker, obtains mixed material B；
By mass percentage, the weight percent of RPUF, EG and DOPO-HQ are respectively 85%, 12%, 3%；
(3) mixed material B is added to fill mixed material A (mass ratio of mixed material A and mixed material B be 1:5)
Plastic beaker in, 2000r/min high-speed stirreds 60s is uniformly mixed, and obtained mixture is quickly poured into mold, freely
Foam after 70min shapings, then be placed in 70 DEG C of constant temperature ovens stand carry out polymerisation 40 it is small when, take out, obtain 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 polyether polyol, foaming agent, stabilizer, catalyst and isocyanates:
145.509:2:2:2 recipe ratio accurately weighs polyether polyol, blowing agent H2O, stabilizer silicone oil, catalyst A33 and isocyanide
Acid esters is placed in 500ml plastic beakers, is uniformly mixed with homogenizer, obtains mixed material A；
(2) by rigid polyurethane foam (RPUF), expansible graphite (EG) and response type halogen-free flame retardants DOPO-HQ
It is uniformly mixed with homogenizer in another beaker, obtains mixed material B；
By mass percentage, the weight percent of RPUF, EG and DOPO-HQ are respectively 85%, 10%, 5%；
(3) mixed material B is added to fill mixed material A (mass ratio of mixed material A and mixed material B be 1:5)
Plastic beaker in, 2500r/min high-speed stirreds 90s is uniformly mixed, and obtained mixture is quickly poured into mold, freely
Foam after 100min shapings, then be placed in 70 DEG C of constant temperature ovens stand carry out polymerisation 48 it is small when, take out, obtain 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 Examples 1 to 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 the weight fraction of DOPO-HQ is 1%, the density value for preparing RPUF/14EG/1HQ is in close proximity to the density of pure RPUF, is
0.074g/cm3；When the weight fraction of EG is 12%, the weight fraction of DOPO-HQ is 3%, prepare RPUF/12EG/3HQ's
Density 0.073g/cm of the density already below pure RPUF3, it is 0.072g/cm3；And the density of RPUF/10EG/5HQ is minimum, is
0.070g/cm3, still reach the standard required by national standard (according to flame-retardant polyurethane thermal insulation board performance indicator, GB 50404-
2007 national standard：The density of flame-retardant polyurethane rigid foam at least answers >=35kg/m3)；The reduction of density is conducive 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 Examples 1 to 4
Figure is as shown in Fig. 2, as shown in Figure 2, the addition of DOPO-HQ can make the compressive strength of hard RPUF foams reduce the (pressure of pure RPUF
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 more than 0.18MPa, be met national standard and (hard for being used for building field is gathered
The compressive strength of urethane foamed plastics, GB/T-21558-2008《Building insulation rigid polyurethane foam》In have three classes
Standard requirement, to being used for highest three classes (be suitable for having higher bearing requirements, and have resistance to compression, the occasion of creep resistant requirement)
The compressive strength of RPUF require its >=0.18MPa)；And the phosphor-containing flame-proof hard based on expansible graphite prepared by Examples 1 to 4
In polyurethane foam, after adding in DOPO-HQ, the compressive strength of RPUF/14EG/1HQ declines at least, and mechanical property is best.
Phosphor-containing flame-proof hard polyurethane foams (RPUF/EG/HQ) based on expansible graphite prepared by Examples 1 to 4
Limit oxygen index (LOI) data are as shown in table 1.
The limit oxygen index data of RPUF/EG/HQ prepared by 1 Examples 1 to 4 of table
Analytical table 1 is understood, when adding DOPO-HQ, sample RPUF/14EG/1HQ, RPUF/12EG/3HQ and RPUF/
The limit oxygen index of 10EG/5HQ is respectively 28.5%, 28.8% and 28.7%, belongs to nonflammable material, and three kinds of samples
Limit 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 (limit oxygen index of pure RPUF is 19.2%) illustrates flame retardant property of the addition to RPUF/EG/HQ of DOPO-HQ
Influence that less but still there is excellent flame retardant property.
Phosphor-containing flame-proof hard polyurethane foams (RPUF/EG/HQ) based on expansible graphite prepared by Examples 1 to 4
Horizontal firing test result is as shown in table 2.
The horizontal firing test result of RPUF/EG/HQ prepared by 2 Examples 1 to 4 of table
As shown in Table 2, in three samples for adding in 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
Grade, it is consistent with the test result of limit oxygen index；Compared with the sample RPUF/15EG for being not added with DOPO-HQ, DOPO-HQ's
Adding in the flame retardant property of RPUF fire-retardant on EG/DOPO-HQ influences less, but still have excellent flame retardant property.
Phosphor-containing flame-proof hard polyurethane foams (RPUF/EG/HQ) based on expansible graphite prepared by Examples 1 to 4 and
The heat analysis related data of pure RPUF is as shown in table 3；Wherein, T5%Temperature corresponding during sample thermal weight loss 5% is represented, for heat
Decompose initial temperature；TmaxIt represents the temperature corresponding to test sample maximum heat weight loss rate, 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 Examples 1 to 4
Thermogravimetric curve figure；The phosphor-containing flame-proof hard polyaminoester based on expansible graphite that Fig. 4 is pure RPUF and prepared by Examples 1 to 4
The differential thermogravimetric curve figure of foam.
RPUF/EG/HQ and the heat analysis related data of pure RPUF prepared by 3 Examples 1 to 4 of table
As shown in Table 3, the initial decomposition temperature (T of pure RPUF5%) for 263 DEG C, and RPUF/15EG, RPUF/14EG/1HQ,
The initial decomposition temperature of RPUF/12EG/3HQ and RPUF/10EG/5HQ is respectively 254 DEG C, 247 DEG C, 251 DEG C and 265 DEG C, can
See with the increase of HQ contents, the initial decomposition temperature of RPUF rises after falling before；The weight loss of pure RPUF is 82.7%, and
The weight loss of RPUF/15EG, RPUF/14EG/1HQ, RPUF/12EG/3HQ and RPUF/10EG/5HQ 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
It is decomposed between 250~590 DEG C, and temperature range corresponds to the degradation of isocyanates and polyether polyol；
In summary the analysis of Fig. 3, Fig. 4 and table 3, between 250~590 DEG C, the heat of pure RPUF and RPUF/EG/HQ
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 in DOPO-HQ, with the increase of the amount of DOPO-HQ so that RPUF heat
Decomposition rate and weight loss rise, and reduce carbon yield so that its thermal stability has decline by a small margin；Adding DOPO-
In three samples of HQ, although RPUF/14EG/1HQ and two sample initial decomposition temperatures of RPUF/12EG/3HQ are slightly relatively low,
Rhermal decomposition rate and weight loss are relatively low, and carbon yield is higher, and thermal stability 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 Examples 1 to 4
For graph as shown in figure 5, as shown in Figure 5, the thermal conductivity factor of pure RPUF is 0.02958W/mK, and sample RPUF/15EG,
The thermal conductivity factor of RPUF/14EG/1HQ, RPUF/12EG/3HQ and RPUF/10EG/5HQ be respectively 0.03302W/mK,
0.03195W/mK, 0.04043W/mK and 0.03735W/mK；By comparison as can be seen that RPUF/14EG/1HQ's leads
The hot pure RPUF of coefficient ratio is slightly larger, and less than other three samples, illustrates that RPUF/14EG/1HQ has good heat-insulation and heat-preservation
Can, thermal insulation material can be functioned well as.
In summary analysis understands that, with the increase of DOPO-HQ contents, the density of RPUF/EG/HQ is gradually reduced, RPUF/
The density of 14EG/1HQ and the density of pure RPUF approach；The compression performance of RPUF/EG/HQ is also with the increase of DOPO-HQ contents
And it is gradually small, the sample of wherein than other two addition fire retardant DOPO-HQ of the compressive strength of RPUF/14EG/1HQ is high, meets
National standard.
In the RPUF/EG/HQ samples for adding in fire retardant DOPO-HQ, limit oxygen index is both greater than 28%, is incombustibe material
Material, and horizontal burn rate all reaches FH-1 grades, illustrates the flame retardant property for adding in the RPUF/EG/HQ samples of fire retardant DOPO-HQ
It is very good；
The compounding of DOPO-HQ and EG 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 three samples for adding DOPO-HQ, 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 thermal stability is excellent
In RPUF/10EG/5HQ；The compounding of DOPO-HQ and EG causes the thermal conductivity factor of RPUF to have certain fluctuation simultaneously, wherein, RPUF/
The pure RPUF of thermal conductivity ratio of 14EG/1HQ is slightly larger, and the sample of less than other three addition EG, has good heat-insulated guarantor
Warm nature energy；This is because DOPO-HQ and EG have both gas phase and two kinds of fire retardant mechanisms of condensed phase, 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 from analyzing above, in the sample prepared in Examples 1 to 4, sample RPUF/14EG/1HQ is in density, pressure
The performance of contracting intensity, thermal stability and heat-proof quality etc. is most excellent.
Above is only the preferred embodiment of the present invention, it is noted that for those of ordinary skill in 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, which is characterized in that including such as
Lower step：
（1）Polyether polyol, foaming agent, stabilizer, catalyst and isocyanates are placed in container, mixed with homogenizer
It closes uniformly, obtains mixed material A；
（2）Rigid polyurethane foam, expansible graphite and fire retardant DOPO-HQ are placed in container, use high-speed stirred
Machine is uniformly mixed, and obtains mixed material B；
（3）Mixed material B is added in mixed material A, high-speed stirred is uniformly mixed, and is poured into mold after foaming, then
It is placed in stand in constant temperature oven and carries out polymerisation, take out, obtain the phosphor-containing flame-proof hard polyurethane based on expansible graphite
Ester foam.
2. a kind of preparation side of phosphor-containing flame-proof hard polyurethane foams based on expansible graphite according to claim 1
Method, which is characterized in that step（1）In, the foaming agent includes water；The stabilizer includes silicone oil；The catalyst includes urging
Agent A33.
3. a kind of preparation side of phosphor-containing flame-proof hard polyurethane foams based on expansible graphite according to claim 1
Method, which is characterized in that step（1）In, the polyether polyol, foaming agent, stabilizer, the quality of catalyst and isocyanates
Than for 100:145.509:2:2:2.
4. a kind of preparation side of phosphor-containing flame-proof hard polyurethane foams based on expansible graphite according to claim 1
Method, which is characterized in that step（2）In, by weight percentage, the rigid polyurethane foam, expansible graphite and
The weight percent of fire retardant DOPO-HQ is respectively 85%, 15% and 0%.
5. a kind of preparation side of phosphor-containing flame-proof hard polyurethane foams based on expansible graphite according to claim 1
Method, which is characterized in that step（2）In, by weight percentage, the rigid polyurethane foam, expansible graphite and
The weight percent of fire retardant DOPO-HQ is respectively 85%, 14% and 1%.
6. a kind of preparation side of phosphor-containing flame-proof hard polyurethane foams based on expansible graphite according to claim 1
Method, which is characterized in that step（2）In, by weight percentage, the rigid polyurethane foam, expansible graphite and
The weight percent of fire retardant DOPO-HQ is respectively 85%, 12% and 3%.
7. a kind of preparation side of phosphor-containing flame-proof hard polyurethane foams based on expansible graphite according to claim 1
Method, which is characterized in that step（2）In, by weight percentage, the rigid polyurethane foam, expansible graphite and
The weight percent of fire retardant DOPO-HQ is respectively 85%, 10% and 5%.
8. a kind of preparation side of phosphor-containing flame-proof hard polyurethane foams based on expansible graphite according to claim 1
Method, which is characterized in that step（3）In, the mixing quality ratio of mixed material A and mixed material B are 1:1~5.
9. a kind of preparation side of phosphor-containing flame-proof hard polyurethane foams based on expansible graphite according to claim 1
Method, which is characterized 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, when the time of polymerisation is 24 ~ 48 small.
10. a kind of phosphor-containing flame-proof based on expansible graphite is hard as made from claim 1 ~ 9 any one of them preparation method
Matter polyurethane foam.
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| CN116284649A (en) * | 2023-04-10 | 2023-06-23 | 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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| 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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| 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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