CN106893074A - A kind of preparation method of high fire-retardance smoke-inhibiting type RPUF - Google Patents
A kind of preparation method of high fire-retardance smoke-inhibiting type RPUF Download PDFInfo
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
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- 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
- C08J9/14—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 organic
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- C08K5/00—Use of organic ingredients
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- 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
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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Abstract
The invention discloses a kind of preparation method of high fire-retardance smoke-inhibiting type RPUF, its step is：PPG, APP, pentaerythrite, expanded graphite, smoke suppressant, Halogen liquid flame retardant, foaming agent, organic amine catalyst, foam stabiliser are mixed and made into urethane composition A；Isocyanates, catalyst are mixed and made into urethane composition B；Quickly stirred during urethane composition B is added into urethane composition A；It is subsequently poured into mould, is foamed under normal temperature, high fire-retardance smoke-inhibiting type RPUF is obtained after foam curing.The present invention is using halogen-free environment-friendly type solid flame retardant APP, pentaerythrite, expanded graphite, smoke suppressant and Halogen liquid flame retardant, substitute conventional halogen containing flame-retardant, reach the fire-retardant effect of synergistic, the problems such as smoke delivery is big when efficiently solving ordinary rigid polyurethane foam plastics poor flame retardant properties, burning, while also maintaining the physicochemical property of RPUF.
Description
Technical field
The present invention relates to polyurethane material and preparation method thereof, more particularly to a kind of high fire-retardance smoke-inhibiting type hard polyaminoester
The preparation method of foamed plastics.
Background technology
RPUF（Abbreviation RPU）It is one of most important kind in polyurethane material system, with excellent
Good physical and mechanical properties, acoustical behavior, electric property and acid-fast alkali-proof performance.The rate of closed hole of the material belongs to more than 90%
Hydrophobic material, with preferable moistureproof and waterproof performance and good thermal insulation, sound insulation, shockproof properties, with very strong cohesive force,
It is widely used as the heat-insulation material of petrochemical pipe, refrigerating equipment, transporting equipment and building etc..However, without resistance
The RPU for the treatment of is fired because its density is small, specific surface area big, and anti-flammability is poor, and oxygen index (OI) is only 17% or so, belongs to combustible material,
After fire, propagation of flame is rapid, and discharges substantial amounts of poison gas（Such as CO, CO2, HCN etc.）, brought very to fire extinguishing and escape from fire
Big difficulty.Because RPU causes fire and causes the case of huge economic losses and casualties existing many at home and abroad.Cause
This, the fire safety evaluating hidden danger existing for RPU materials causes great attention both domestic and external.Over nearly twenties years, Duo Jia sections of China
Grind unit and have developed various new fire retardant, such as dimethyl methyl phosphonate (DMMP), trichloroethyl phosphate (TCEP), three (2,
3- dibromopropyls) phosphorous, halogen the organic liquid fire retardant such as melamine ester (TBC), although RPU material oxygen index (OI)s can be carried
Height is to 26% or so, but disaster hidden-trouble of the material in use occasion is larger.The halogen containing flame-retardant added in RPU is in burning
Time can discharge substantial amounts of corrosivity, the hydrogen halide of severe toxicity, be unfavorable for fire rescue.
Continuous improvement with country to environmental requirement, the fire retardant applied in RPU materials there has also been certain environmental protection
Limitation.Therefore high fire-retardance, smoke-inhibiting type RPU materials are the trend of the Materials.
The content of the invention
It is an object of the invention to provide a kind of preparation method of high fire-retardance smoke-inhibiting type RPUF.Using this
High fire-retardance RPUF obtained in method uses polyhydroxy based high-polymer, isocyanates, APP, Ji Wusi
The processing of the Material claddings such as alcohol, expanded graphite, smoke suppressant, Halogen liquid flame retardant, foaming agent, catalyst, foam stabiliser is obtained
Target product, the various mechanical performances and physicochemical property of product are not reduced on the premise of RPU fire resistances are improved（Such as：Impact
Intensity, water absorption rate, tensile strength etc.）, while have the APP of fire retardation, pentaerythrite, expanded graphite, smoke suppressant,
The equal Halogen of Halogen liquid flame retardant, environmental protection.
The present invention is adopted the technical scheme that：A kind of preparation method of high fire-retardance smoke-inhibiting type RPUF,
Characterized in that, described preparation method has following steps：
A) PPG, APP, pentaerythrite, expanded graphite, smoke suppressant, Halogen liquid are hindered according to parts by weight,
Combustion agent, foaming agent, organic amine catalyst, foam stabiliser are well mixed, and are made urethane composition A, urethane composition A
Stirring incorporation time≤2 minute, after stirring evenly, encrypt capping, room temperature standing time≤5 minute on blending tank.
B) isocyanates, organic tin catalyst are well mixed according to parts by weight, urethane composition B is made, are gathered
Urethane composition B stirs incorporation time≤5 minute, after stirring evenly, capping, room temperature standing time≤10 minute is encrypted on blending tank.
C), by urethane composition B addition urethane compositions A, quickly stir, incorporation time≤1 minute.
d）, by step c）In be well mixed material pour into mould, under normal temperature foam, curing, foam cure 24 hours
Described high fire-retardance smoke-inhibiting type RPUF is obtained afterwards.
In step a) of the present invention, PPG is amine PPG and Sucrose polyethers polyalcohol, polyethers
Parts by weight shared by polyalcohol are the 20~30 of urethane composition A and urethane composition B weight summations.
In step a) of the present invention, APP selected from the industrial products that the degree of polymerization is 500, shared by APP
Parts by weight are the 3~5 of urethane composition A and urethane composition B weight summations.
In step a) of the present invention, it is 95% that pentaerythrite is selected from content, and fineness is the industrial products of 200 mesh, season penta
Parts by weight shared by tetrol are the 3~5 of urethane composition A and urethane composition B weight summations.
In step a) of the present invention, it is 32 mesh that expanded graphite is selected from granularity, and moisture content is 1%, initial bubble temperature
200 DEG C, expansion multiplying power is the industrial products of 200ml/g, and the parts by weight shared by expanded graphite are urethane composition A and poly- ammonia
The 9~13 of ester composition B weight summations.
In step a) of the present invention, smoke suppressant be selected from Firebrake ZB, aluminium hydroxide, magnesium hydroxide in any one,
Parts by weight shared by smoke suppressant are the 8~12 of urethane composition A and urethane composition B weight summations.
In step a) of the present invention, Halogen liquid flame retardant be selected from dimethyl methyl phosphonate, ethyl phosphonic acid diethylester,
Any one in trimethyl phosphate, triphenyl phosphate, the parts by weight shared by Halogen liquid flame retardant are urethane composition A
With the 5~7 of urethane composition B weight summations.
In step a) of the present invention, foaming agent is HCFC-141 foaming agents, HCFC-141b foaming agents, CFC-11 hairs
Any one in infusion or water, the parts by weight shared by foaming agent are that urethane composition A and urethane composition B weight are total
The 6~10 of sum.
In step a) of the present invention, foam stabiliser is organosilicon foam stabilizer, selected from polysiloxane-polyether copolymerization
Any one in thing, H3605 or H3603 polysiloxane surfactants, the parts by weight shared by foam stabiliser are poly- ammonia
The 0.6~0.8 of ester composition A and urethane composition B weight summations.
In step a) of the present invention, organic amine catalyst is selected from triethylene diamine, N, N, N, N, N- pentamethyl two
Any one in ethene triamine, the parts by weight shared by organic amine catalyst are urethane composition A and polyurethane composition
The 0.4~0.6 of thing B weight summations.
In step b) of the present invention, it is many that isocyanates is selected from '-diphenylmethane diisocyanate, polyphenyl polymethylene
Any one in isocyanates, the parts by weight shared by isocyanates are urethane composition A and urethane composition B weight
The 30~45 of summation.
In step b) of the present invention, organic tin catalyst is selected from dibutyltin dilaurate and two (dodecanes
Base sulphur) any one in dibutyl tin, the parts by weight shared by organic tin catalyst are urethane composition A and polyurethane
The 0.4~0.6 of composition B weight summations.
The RPUF that prior art is prepared, it is generally halogen containing flame-retardant to be chosen due to fire retardant, because
It receives the problems such as thermal decomposition poisonous hydrogen halide of release causes personnel escape, rescue is difficult, so being subject in actual applications
Very big limitation.The present invention is specially using Halogen, phosphorous environmentally friendly solid-liquid composite fire retardant, the fire retardant of recommendation：It is poly-
Ammonium phosphate, pentaerythrite, expanded graphite, smoke suppressant and liquid phosphonium flame retardant.Wherein APP is a kind of inorganic polymer
Fire retardant, phosphorus content is high（31%）, degree of polymerization ＞ 50, the strong dehydrating agent such as formation polyphosphoric acid, poly-metaphosphoric acid under high temperature, and play solid
Phase fire retardation, uses in various plastics as flame-retardant additive；Pentaerythrite is polyhydroxy solid powder, strong under high temperature
Acid（Polyphosphoric acid, poly-metaphosphoric acid）Charcoal is dehydrated under effect, solid phase fire retardation is played.The expanded graphite of selection is more than 200 DEG C
Be expanded into charcoal, with APP, pentaerythrite synergistic formed with some strength foamed char, play solid phase it is fire-retardant, fire prevention
Heat-insulated effect.Smoke suppressant is selected from Firebrake ZB, aluminium hydroxide and magnesium hydroxide, and substantial amounts of knot is contained in three kinds of products molecule structures
Brilliant water, the crystallization water that Disassembling Products go out under high temperature not only absorbs heat, and has watered down toxic gas, reaches the work of flame-retardant smoke inhibition
With.Liquid phosphonium flame retardant is selected from dimethyl methyl phosphonate（DMMP）, ethyl phosphonic acid diethylester (DEEP), trimethyl phosphate, phosphorus
Triphenyl phosphate ester, liquid phosphonium flame retardant has obvious due to good dispersiveness and molecular structure to polyurethane foam plastics
Flame retardant effect.
According to the preparation technology of RPUF, it is divided into two kinds of components of PPG and isocyanates, two
5 to 10 minutes generating polyurethane foamed plastics of immediate response after component mixing.By APP, pentaerythrite, expanded graphite, suppression cigarette
Agent and liquid phosphonium flame retardant are uniformly dispersed in polyhydroxylated polymer, are then well mixed with isocyanate component, room temperature hair
Bubble, curing, are obtained high fire-retardance smoke-inhibiting type RPUF.
Beneficial effects of the present invention are：The present invention is using APP, pentaerythrite, expanded graphite, smoke suppressant and contains
Phosphorus liquid flame retardant substitutes conventional halogen containing flame-retardant as synergistic flame retardant, has reached the fire-retardant effect of synergistic, effective to solve
The problems such as smoke delivery is big when ordinary rigid polyurethane foam plastics poor flame retardant properties, burning, while also maintaining hard
The physicochemical property of polyurethane foam plastics.The material is environment-friendly type not halogen-containing flame retardant product, may be uniformly dispersed in polyhydroxy
In based polyalcohol, its synergistic flame retardant effect not only substantially increases the oxygen index (OI) of RPU（Oxygen index (OI) is up to 42）, while the material
Material is expanded into charcoal at high temperature, with certain refractory heat-insulating performance.RPU obtained by the present invention, it is former RPU materials are maintained
On the premise of rationalization performance, its anti-flammability is greatly improved, meets country for RPU materials in the side such as insulation, thermal insulation
The flame-retardancy requirements in face, material has certain fire insulation, and preparation process is simple, and process conditions are easily controllable, are suitable to work
Industry metaplasia is produced and popularization and application.
Specific embodiment
The invention will be further described with reference to embodiments：
Embodiment one
1. urethane composition A is prepared
Weigh 23gWANOL R8245 Sucrose polyethers polyalcohols, APP 3g, pentaerythrite 4g, expanded graphite 10g, boric acid
Zinc 10g and dimethyl methyl phosphonate 5g, organic amine catalyst（Triethylene diamine）0.5g, foam stabiliser（H3605）
0.7g, foaming agent（HCFC-141b）9.3g, quickly stirs, and is made urethane composition A.Urethane composition A stirrings are mixed
Close 1 minute, after stirring evenly, capping is encrypted on blending tank, room temperature is placed 3 minutes.
2. urethane composition B is prepared
Weigh 34g isocyanates (PAPI), organic tin catalyst（Dibutyltin dilaurate）0.5g, 3 points of stirring mixing
Clock, is made urethane composition B.After stirring evenly, capping is encrypted on blending tank, room temperature is placed 3 minutes.
The foaming that 3.PU hard bubbles
Urethane composition B is poured into urethane composition A, quick stirring 1 minute is poured into mould, it is room temperature foaming, ripe
Change, after curing 24h, you can obtain a kind of high fire-retardance smoke-inhibiting type RPUF.
Properties of product test result：Density 40.0kg/cm3, oxygen index (OI) 36.0, thermal conductivity factor 0.024W/ (m2·K)。
Embodiment two
1. urethane composition A is prepared
Weigh 23gWANOL R8245 Sucrose polyethers polyalcohols, APP 3g, pentaerythrite 4g, expanded graphite 10g, hydrogen-oxygen
Change aluminium 10g and dimethyl methyl phosphonate 5g, organic amine catalyst（Triethylene diamine）0.5g, foam stabiliser（H3605）
0.7g, foaming agent（HCFC-141b）9.3g, quickly stirs, and is made urethane composition A.Urethane composition A stirrings are mixed
Close 1 minute, after stirring evenly, capping is encrypted on blending tank, room temperature is placed 3 minutes.
2. urethane composition B is prepared
Weigh 34g isocyanates (PAPI), organic tin catalyst（Dibutyltin dilaurate）0.5g, 3 points of stirring mixing
Clock, is made urethane composition B.After stirring evenly, capping is encrypted on blending tank, room temperature is placed 3 minutes.
The foaming that 3.PU hard bubbles
Urethane composition B is poured into urethane composition A, quick stirring 1 minute is poured into mould, it is room temperature foaming, ripe
Change, after curing 24h, you can obtain a kind of high fire-retardance smoke-inhibiting type RPUF.
Properties of product test result：Density 44.0kg/cm3, oxygen index (OI) 35.5, thermal conductivity factor 0.024W/ (m2·K)。
Embodiment three
1. urethane composition A is prepared
Weigh 23gWANOL R8245 Sucrose polyethers polyalcohols, APP 3g, pentaerythrite 4g, expanded graphite 10g, hydrogen-oxygen
Change magnesium 10g and dimethyl methyl phosphonate 5g, organic amine catalyst（Triethylene diamine）0.5g, foam stabiliser（H3605）
0.7g, foaming agent（HCFC-141b）9.3g, quickly stirs, and is made urethane composition A.Urethane composition A stirrings are mixed
Close 1 minute, after stirring evenly, capping is encrypted on blending tank, room temperature is placed 3 minutes.
2. urethane composition B is prepared
Weigh 34g isocyanates (PAPI), organic tin catalyst（Dibutyltin dilaurate）0.5g, 3 points of stirring mixing
Clock, is made urethane composition B.After stirring evenly, capping is encrypted on blending tank, room temperature is placed 3 minutes.
The foaming that 3.PU hard bubbles
Urethane composition B is poured into urethane composition A, quick stirring 1 minute is poured into mould, it is room temperature foaming, ripe
Change, after curing 24h, you can obtain a kind of high fire-retardance smoke-inhibiting type RPUF.
Properties of product test result：Density 42.5kg/cm3, oxygen index (OI) 33.0, thermal conductivity factor 0.024W/ (m2·K)。
Example IV
1. urethane composition A is prepared
Weigh 20gWANOL R8245 Sucrose polyethers polyalcohols, APP 3g, pentaerythrite 5g, expanded graphite 13g, hydrogen-oxygen
Change aluminium 12g and dimethyl methyl phosphonate 7g, organic amine catalyst（Triethylene diamine）0.5g, foam stabiliser（H3605）
0.7g, foaming agent（HCFC-141b）8.3g, stirring mixing 1 minute after stirring evenly, encrypts capping on blending tank, be made polyurethane group
Compound A, room temperature is placed 3 minutes.
2. urethane composition B is prepared
Weigh isocyanates (PAPI) 30g, organic tin catalyst（Dibutyltin dilaurate）0.5g, 3 points of stirring mixing
Clock, is made urethane composition B.After stirring evenly, capping is encrypted on blending tank, room temperature is placed 3 minutes.
The foaming that 3.PU hard bubbles
Urethane composition B is poured into urethane composition A, quick stirring 1 minute is poured into mould, it is room temperature foaming, ripe
Change, after curing 24h, you can obtain a kind of high fire-retardance smoke-inhibiting type RPUF.
Properties of product test result：The kg/cm of density 51.83；Oxygen index (OI) 42.0（GB2406）；Thermal conductivity factor 0.029W/
(mK), water absorption rate 0.2kg/m2, dimensional stability 1.67%.
Embodiment five
1. urethane composition A is prepared
Weigh 20gWANOL R2438A amine PPGs, APP 3g, pentaerythrite 5g, expanded graphite 13g, hydrogen-oxygen
Change aluminium 12g and dimethyl methyl phosphonate 7g, organic amine catalyst（Triethylene diamine）0.5g, foam stabiliser（H3605）
0.7g, foaming agent（HCFC-141b）8.3g, stirring mixing 1 minute after stirring evenly, encrypts capping on blending tank, be made polyurethane group
Compound A, room temperature is placed 3 minutes.
2. urethane composition B is prepared
Weigh isocyanates (PAPI) 30g, organic tin catalyst（Dibutyltin dilaurate）0.5g, 3 points of stirring mixing
Clock, is made urethane composition B.After stirring evenly, capping is encrypted on blending tank, room temperature is placed 3 minutes.
The foaming that 3.PU hard bubbles
Urethane composition B is poured into urethane composition A, quick stirring 1 minute is poured into mould, it is room temperature foaming, ripe
Change, after curing 24h, you can obtain a kind of high fire-retardance smoke-inhibiting type RPUF.
Properties of product test result：The kg/cm of density 42.53；Oxygen index (OI) 37.0（GB2406）.
Embodiment six
1. urethane composition A is prepared
Weigh 20gWANOL R8245 Sucrose polyethers polyalcohols, APP 3g, pentaerythrite 5g, expanded graphite 13g, hydrogen-oxygen
Change aluminium 12g and ethyl phosphonic acid diethylester 7g, organic amine catalyst（Triethylene diamine）0.5g, foam stabiliser（H3605）
0.7g, foaming agent（HCFC-141b）8.3g, stirring mixing 1 minute after stirring evenly, encrypts capping on blending tank, be made polyurethane group
Compound A, room temperature is placed 3 minutes.
2. urethane composition B is prepared
Weigh isocyanates (PAPI) 30g, organic tin catalyst（Dibutyltin dilaurate）0.5g, 3 points of stirring mixing
Clock, is made urethane composition B.After stirring evenly, capping is encrypted on blending tank, room temperature is placed 3 minutes.
The foaming that 3.PU hard bubbles
Urethane composition B is poured into urethane composition A, quick stirring 1 minute is poured into mould, it is room temperature foaming, ripe
Change, after curing 24h, you can obtain a kind of high fire-retardance smoke-inhibiting type RPUF.
Properties of product test result：Density 60kg/cm3；Oxygen index (OI) 38.0（GB2406）；
Middle different smoke suppressants according to embodiment one, embodiment two and embodiment three influence on the anti-flammability of product, Firebrake ZB effect
Preferably, aluminium hydroxide slightly takes second place fruit, and magnesium hydroxide is worst.According to considering for performance and cost, it is proposed that selection hydrogen-oxygen
Change aluminium as smoke suppressant.
According to example IV and the result of the test of embodiment six, the dispersiveness of liquid phosphonium flame retardant dimethyl methyl phosphonate and
The fire resistance of RPUF product is substantially better than ethyl phosphonic acid diethylester, it is proposed that selection dimethyl methyl phosphonate
As liquid phosphonium flame retardant.
Example IV and embodiment five have mainly carried out contrast test to amine polyethers and Sucrose polyethers, by Sucrose polyethers system
Standby RPUF fire resistance is more excellent, it is therefore proposed that selection Sucrose polyethers are used as PPG.
By the comparison of test results to one~embodiment of embodiment six, the anti-flammability of example IV, physicochemical property and
Cost of raw material combination property is the most excellent, therefore selection example IV carries out high fire-retardance, the modeling of smoke-inhibiting type hard polyurethane foams
Expect the fire resistance test of composite plate：
According to the formula of example IV, using the technique for pouring, plywood material is made（Steel plate thickness 1.0mm, RPU thickness degree 50mm）
120mm × 120mm × 50mm, is placed on muffle furnace mouthful, and iron sheet aligns with stove collar extension on the outside of plate, and surrounding gap is stifled tight laggard with rock wool
Row fire resistance test, and the temperature of composite board outer layer iron sheet is determined with thermocouple.Muffle furnace control is with reference to GB9978 " buildings
The heating curve of component fire resistance test method ", when experiment carries out 30 minutes, 930 DEG C of furnace temperature is combined 142 DEG C of backboard temperature.By implementing
The technique of example four and the high fire-retardance of formula preparation, smoke-inhibiting type RPUF composite board have good refractory heat-insulating
Performance.
Claims (12)
1. a kind of preparation method of high fire-retardance smoke-inhibiting type RPUF, it is characterised in that described preparation method
There are following steps：
A) PPG, APP, pentaerythrite, expanded graphite, smoke suppressant, Halogen liquid are hindered according to parts by weight,
Combustion agent, foaming agent, organic amine catalyst, foam stabiliser are well mixed, and are made urethane composition A, urethane composition A
Stirring incorporation time≤2 minute, after stirring evenly, encrypt capping, room temperature standing time≤5 minute on blending tank；
B) isocyanates, organic tin catalyst are well mixed according to parts by weight, urethane composition B, polyurethane is made
Composition B stirs incorporation time≤5 minute, after stirring evenly, capping, room temperature standing time≤10 minute is encrypted on blending tank；
C), by urethane composition B addition urethane compositions A, quickly stir, incorporation time≤1 minute；
d）, by step c）In be well mixed material pour into mould, under normal temperature foam, curing, foam cure 24 hours after i.e.
Described high fire-retardance smoke-inhibiting type RPUF is obtained.
2. a kind of preparation method of high fire-retardance smoke-inhibiting type RPUF according to claim 1, its feature
It is that in described step a), PPG is amine PPG and sucrose PPG, PPG institute
The parts by weight for accounting for are the 20~30 of urethane composition A and urethane composition B weight summations.
3. a kind of preparation method of high fire-retardance smoke-inhibiting type RPUF according to claim 1, its feature
It is that in described step a), APP is selected from the industrial products of the degree of polymerization 500, the parts by weight shared by APP are
The 3~5 of urethane composition A and urethane composition B weight summations.
4. a kind of preparation method of high fire-retardance smoke-inhibiting type RPUF according to claim 1, its feature
It is that in described step a), it is 95% that pentaerythrite is selected from content, and fineness is the industrial products of 200 mesh, shared by pentaerythrite
Parts by weight be the 3~5 of urethane composition A and urethane composition B weight summations.
5. a kind of preparation method of high fire-retardance smoke-inhibiting type RPUF according to claim 1, its feature
It is that in described step a), it is 32 mesh that expanded graphite is selected from granularity, and moisture content is 1%, initial bubble temperature is 200 DEG C, swollen
Swollen multiplying power is the industrial products of 200ml/g, and the parts by weight shared by expanded graphite are urethane composition A and urethane composition
The 9~13 of B weight summations.
6. a kind of preparation method of high fire-retardance smoke-inhibiting type RPUF according to claim 1, its feature
Be, in described step a), smoke suppressant be selected from Firebrake ZB, aluminium hydroxide, magnesium hydroxide in any one, shared by smoke suppressant
Parts by weight be the 8~12 of urethane composition A and urethane composition B weight summations.
7. a kind of preparation method of high fire-retardance smoke-inhibiting type RPUF according to claim 1, its feature
It is that in described step a), Halogen liquid flame retardant is selected from dimethyl methyl phosphonate, ethyl phosphonic acid diethylester, tripotassium phosphate
Any one in ester, triphenyl phosphate, the parts by weight shared by Halogen liquid flame retardant are urethane composition A and polyurethane
The 5~7 of composition B weight summations.
8. a kind of preparation method of high fire-retardance smoke-inhibiting type RPUF according to claim 1, its feature
It is that in described step a), foaming agent is in HCFC-141 foaming agents, HCFC-141b foaming agents, CFC-11 foaming agents or water
Any one, parts by weight shared by foaming agent are the 6~10 of urethane composition A and urethane composition B weight summations.
9. a kind of preparation method of high fire-retardance smoke-inhibiting type RPUF according to claim 1, its feature
Be, in described step a), foam stabiliser be organosilicon foam stabilizer, selected from polysiloxane-polyether copolymer, H3605 or
Any one in H3603 polysiloxane surfactants, parts by weight shared by foam stabiliser for urethane composition A and
The 0.6~0.8 of urethane composition B weight summations.
10. a kind of preparation method of high fire-retardance smoke-inhibiting type RPUF according to claim 1, its feature
It is that in described step a), organic amine catalyst is selected from triethylene diamine, N, N, N, N, N- pentamethyl-diethylenetriamine
In any one, parts by weight shared by organic amine catalyst are that urethane composition A and urethane composition B weight are total
The 0.4~0.6 of sum.
A kind of 11. preparation methods of high fire-retardance smoke-inhibiting type RPUF according to claim 1, its feature
It is that in described step b), isocyanates is selected from '-diphenylmethane diisocyanate, polyphenyl polymethylene polyisocyanates
Any one, parts by weight shared by isocyanates for urethane composition A and urethane composition B weight summations 30~
45。
A kind of 12. preparation methods of high fire-retardance smoke-inhibiting type RPUF according to claim 1, its feature
It is that in described step b), organic tin catalyst is selected from dibutyltin dilaurate and two (dodecyl sulphur) two fourths
Any one in base tin, the parts by weight shared by organic tin catalyst are urethane composition A and urethane composition B weights
The 0.4~0.6 of amount summation.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109205095A (en) * | 2018-08-08 | 2019-01-15 | 宿松县佳宜装饰有限公司 | One kind filling heating heat-insulating case |
| CN109593226A (en) * | 2018-11-16 | 2019-04-09 | 山东省海洋化工科学研究院 | A kind of method of low-shrinkage flame retardant polyurethane rigid foam material being formulated and its prepare foamed material |
| CN110272560A (en) * | 2019-05-06 | 2019-09-24 | 什邡市太丰新型阻燃剂有限责任公司 | A kind of novel halogen-free flame-retardant hard polyurethane foam and preparation method thereof |
| CN111961328A (en) * | 2020-08-30 | 2020-11-20 | 宁波耀众模塑科技有限公司 | Flame-retardant polyether reinforced polyurea mixture for polyurethane foaming product |
| CN112358647A (en) * | 2020-10-23 | 2021-02-12 | 舒伟伟 | High-strength polyurethane rigid foam plastic and preparation method thereof |
| WO2021044002A1 (en) * | 2019-09-05 | 2021-03-11 | Basf Se | A flexible polyurethane foam, process for preparing the same and use thereof |
| CN113372528A (en) * | 2021-01-11 | 2021-09-10 | 安徽科技学院 | High-strength flame-retardant polyurethane foam plastic and preparation method thereof |
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| CN116217861A (en) * | 2023-02-23 | 2023-06-06 | 山东奥卓新材料有限公司 | Polyurethane vibration damping and sound insulation pad with high flame retardance and no combustion droppings/particles and preparation method thereof |
| CN116814063A (en) * | 2023-06-29 | 2023-09-29 | 杭州康诚汽车附件有限公司 | Flame-retardant semi-rigid polyurethane foam and preparation method thereof |
| KR102649459B1 (en) * | 2023-07-14 | 2024-03-19 | 신장균 | Manufacturing method of flame-retardant urethane foam |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103709432A (en) * | 2013-12-18 | 2014-04-09 | 南京师范大学 | High-flame retardant rigid polyurethane foaming plastic and preparation method thereof |
| CN105601864A (en) * | 2014-11-21 | 2016-05-25 | 合肥杰事杰新材料股份有限公司 | Low-smoke low-toxicity flame-retardation hard polyurethane foam plastics and preparation method thereof |
| CN105884992A (en) * | 2015-01-26 | 2016-08-24 | 大连理工大学 | Flame-retardant polyurethane rigid foam plastic and preparation method and application thereof |
-
2017
- 2017-03-03 CN CN201710122742.5A patent/CN106893074A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103709432A (en) * | 2013-12-18 | 2014-04-09 | 南京师范大学 | High-flame retardant rigid polyurethane foaming plastic and preparation method thereof |
| CN105601864A (en) * | 2014-11-21 | 2016-05-25 | 合肥杰事杰新材料股份有限公司 | Low-smoke low-toxicity flame-retardation hard polyurethane foam plastics and preparation method thereof |
| CN105884992A (en) * | 2015-01-26 | 2016-08-24 | 大连理工大学 | Flame-retardant polyurethane rigid foam plastic and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 胡胜利: "高阻燃性硬质聚氨酯泡沫塑料", 《聚氨酯工业》 * |
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| CN109205095A (en) * | 2018-08-08 | 2019-01-15 | 宿松县佳宜装饰有限公司 | One kind filling heating heat-insulating case |
| CN109593226A (en) * | 2018-11-16 | 2019-04-09 | 山东省海洋化工科学研究院 | A kind of method of low-shrinkage flame retardant polyurethane rigid foam material being formulated and its prepare foamed material |
| CN110272560A (en) * | 2019-05-06 | 2019-09-24 | 什邡市太丰新型阻燃剂有限责任公司 | A kind of novel halogen-free flame-retardant hard polyurethane foam and preparation method thereof |
| CN114341223A (en) * | 2019-09-05 | 2022-04-12 | 巴斯夫欧洲公司 | Flexible polyurethane foam, preparation method and application thereof |
| WO2021044002A1 (en) * | 2019-09-05 | 2021-03-11 | Basf Se | A flexible polyurethane foam, process for preparing the same and use thereof |
| CN111961328A (en) * | 2020-08-30 | 2020-11-20 | 宁波耀众模塑科技有限公司 | Flame-retardant polyether reinforced polyurea mixture for polyurethane foaming product |
| CN112358647A (en) * | 2020-10-23 | 2021-02-12 | 舒伟伟 | High-strength polyurethane rigid foam plastic and preparation method thereof |
| CN113372528A (en) * | 2021-01-11 | 2021-09-10 | 安徽科技学院 | High-strength flame-retardant polyurethane foam plastic and preparation method thereof |
| CN113861664A (en) * | 2021-10-20 | 2021-12-31 | 荣威达光电(东莞)有限公司 | Wear-resistant flame-retardant TPU material and preparation method thereof |
| CN116217861A (en) * | 2023-02-23 | 2023-06-06 | 山东奥卓新材料有限公司 | Polyurethane vibration damping and sound insulation pad with high flame retardance and no combustion droppings/particles and preparation method thereof |
| CN116217861B (en) * | 2023-02-23 | 2024-03-12 | 山东奥卓新材料有限公司 | Polyurethane vibration damping and sound insulation pad with high flame retardance and no combustion droppings/particles and preparation method thereof |
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| KR102649459B1 (en) * | 2023-07-14 | 2024-03-19 | 신장균 | Manufacturing method of flame-retardant urethane foam |
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