CN107353391A - Halogen-free flameproof rigid polyurethane foam and preparation method thereof - Google Patents

Halogen-free flameproof rigid polyurethane foam and preparation method thereof Download PDF

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Publication number
CN107353391A
CN107353391A CN201710586698.3A CN201710586698A CN107353391A CN 107353391 A CN107353391 A CN 107353391A CN 201710586698 A CN201710586698 A CN 201710586698A CN 107353391 A CN107353391 A CN 107353391A
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component
parts
halogen
polyurethane foam
rigid polyurethane
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刘涛
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Hefei Guangneng New Material Technology Co Ltd
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Hefei Guangneng New Material Technology Co Ltd
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Priority to CN201710586698.3A priority Critical patent/CN107353391A/en
Publication of CN107353391A publication Critical patent/CN107353391A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/54—Polycondensates of aldehydes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/487—Polyethers containing cyclic groups
    • C08G18/4883—Polyethers containing cyclic groups containing cyclic groups having at least one oxygen atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/61—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224—Magnesium hydroxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams

Abstract

The present invention proposes a kind of halogen-free flameproof rigid polyurethane foam and preparation method thereof, it is made up of component A and B component, the weight of component A and B component ratio is 1: 1~1.5, according to the number of parts by weight, component A is by 6~20 parts of phenolic resin, 60~80 parts of PPG, 5~10 parts of expansile graphite, 1~4 part of catalyst, 16~30 parts of composite flame-retardant agent, 15~30 parts of compositions of 1~3 part of polysiloxane-based foam stabiliser and foaming agent, B component is isocyanates, wherein, the composite flame-retardant agent is by magnesium hydroxide, waterglass, silane coupler is prepared with nano imvite.The foamed material improves fire resistance, reduces fire retardant to foamed material Effect on Mechanical Properties, also improves its foam performance.

Description

Halogen-free flameproof rigid polyurethane foam and preparation method thereof
Technical field
The invention belongs to insulation material technical field, and in particular to a kind of halogen-free flameproof rigid polyurethane foam and its Preparation method.
Background technology
In recent years, because fire of high-rise building frequently occurs, serious loss is brought to the country and people.It is former to study carefully it Cause, mainly inflammable external-wall heat-insulation material cause, so the anti-flammability for improving external-wall heat-insulation material becomes people's research Focus.Present organic insulation material most important on the market has two kinds, and one kind is polystyrene foam, and another kind is polyurethane foam Foam.Wherein polystyrene foam is thermoplastic macromolecule material, and in heated combustion, polystyrene foam will melt trickling, It is difficult to it is carried out fire-retardant.Contraction can be only decomposed and polyurethane foam belongs to thermoset macromolecule material, during heated combustion, will not Trickling is melted as polystyrene foam, so causing the attention of people.
But these blown polyurethane materials face the major test in terms of fire prevention fire-fighting when acting on art work, by In itself and do not have fire performance in polyurethane material, the normal quick ignition melting when touching burning things which may cause a fire disaster, and expand the condition of a disaster, because This improves blown polyurethane materials and makes it have fire performance as the key subjects in this field.
The fire performance for improving blown polyurethane materials now is that enough fire prevention powders, example are added in polyurethane material Such as aluminium hydroxide, nitrogen system fire prevention composition such as melamine, its heat discharges nitrogen and ammonia reduction combustable gas concentration, phosphorus system prevent Fiery composition such as APP, it produces metaphosphoric acid after heated makes organics dehydration, carbon system fire prevention composition such as pentaerythrite.But this Though the addition Deng composition can obviously improve the fire performance of blown polyurethane materials, the foaminess of polyurethane material is simultaneously big Width reduces, all corners that can not be completely filled with the die cavity of foaming mould, therefore exquisite surface details can not be made.This Outside, blown polyurethane materials also make the overall weight of material increase, while be unfavorable for indoor dress because of the addition of foregoing flameproof composition The utilization of pool.
Therefore, the foaminess for proposing that blown polyurethane materials can be taken into account simultaneously and the fire prevention for improving weight are needed in this area badly Polyurethane material and fire proof construction, in favor of the demand for development of each application field.
The content of the invention
The present invention proposes a kind of halogen-free flameproof rigid polyurethane foam, and the foamed material improves fire resistance, drops Low fire retardant also improves its foam performance to foamed material Effect on Mechanical Properties.
The technical proposal of the invention is realized in this way：
A kind of halogen-free flameproof rigid polyurethane foam, is made up of component A and B component, the weight of component A and B component Than for 1: 1~1.5, according to the number of parts by weight, component A is by 6~20 parts of phenolic resin, 60~80 parts of PPG, expansion 5~10 parts of graphite of property, 1~4 part of catalyst, 16~30 parts of composite flame-retardant agent, 1~3 part of polysiloxane-based foam stabiliser and 15~30 parts of compositions of foaming agent, B component is isocyanates, wherein, the composite flame-retardant agent is by magnesium hydroxide, waterglass, silane Coupling agent is prepared with nano imvite.
Preferably, the preparation method of the composite flame-retardant agent：
After first magnesium hydroxide is mixed with waterglass, silane coupler is added after being again heated to 100~120 DEG C, side is stirred, Reaction time is 20~25min, is subsequently cooled to 50~60 DEG C, adds nano imvite and stirs, is cooled to room temperature i.e. Can.
Preferably, the silane coupler is KH570, KH792 or DL602.
Preferably, the PPG is 350~500mgKOH/g PPG, and including but not limited to sucrose gathers Ethoxylated polyhydric alcohol 4110 (hydroxyl value 430-470mgKOH/g) and/or Sucrose polyethers polyalcohol 835 (hydroxyl value 420-480mgKOH/g).
Preferably, the catalyst is N, the mixing of N- dimethyl cyclohexyl amines, dibutyl tin laurate and stannous octoate Thing.
Preferably, the polysiloxane-based foam stabiliser is polyether modified silicon oil, and the foaming agent is ether, such Foaming agent is free of halogen, environmentally friendly.
Preferably, the polyisocyanates is the more benzene of polymethylene that the mass percent of NCO group is 30~32wt% Quito isocyanates.
It is a further object to provide a kind of preparation method of halogen-free flameproof rigid polyurethane foam, including Following steps：
By phenolic resin, PPG, foaming agent premixing, while add expansile graphite, polysiloxanes class A foam A Stabilizer, catalyst and composite flame-retardant agent obtain component A, and using isocyanates as B component, component A is mixed into hair with B component Bubble, obtains polyurethane adiabatic heat-insulation foam material.
Beneficial effects of the present invention：
Composite flame-retardant agent in the halogen-free flameproof rigid polyurethane foam of the present invention is by magnesium hydroxide, waterglass, silicon Alkane coupling agent is prepared with nano imvite, its not only increase dispersiveness of the magnesium hydroxide in polyurethane and its with it is poly- Compatibility between urethane macromolecular chain, plays synergistic effect to the flame retardant effect of magnesium hydroxide, and wherein waterglass not only acts as pair Magnesium hydroxide modified effect, additionally it is possible to promote polyurethane foam to foam.
The good basic reason of phenolic resin fire resistance is the free radical capture effect of its high fixing carbon and phenolic hydroxyl group, at this Phenolic resin and polyurethane are combined in invention, had complementary advantages, the fire resistance of hard polyurethane foam can be significantly improved.The present invention Halogen-free flameproof rigid polyurethane foam simultaneously there is higher fire resistance and excellent mechanical property.
Embodiment
Embodiment 1
A kind of halogen-free flameproof rigid polyurethane foam, is made up of component A and B component, the weight of component A and B component Than for 1: 1.3, according to the number of parts by weight, component A is by 13 parts of phenolic resin, 411070 parts of Sucrose polyethers polyalcohol, dilatancy 22 parts of 7 parts of graphite, 2 parts of catalyst, 24 parts of composite flame-retardant agent, 2 parts of polyether modified silicon oil and ether compositions, B component is quality Percentage is 30wt% poly methylene poly phenyl poly isocyanate.Catalyst is N, N- dimethyl cyclohexyl amines, tin dilaurate two The mixture of butyl tin and stannous octoate.
The preparation method of composite flame-retardant agent：
After first magnesium hydroxide is mixed with waterglass, KH570 is added after being again heated to 100 DEG C, side stirring, the reaction time is 25min, 50 DEG C are subsequently cooled to, add nano imvite and stir, be cooled to room temperature.
The preparation method of halogen-free flameproof rigid polyurethane foam：
By phenolic resin, Sucrose polyethers polyalcohol 4110, ether premixing, while add expansile graphite, polyether-modified Silicone oil, catalyst and composite flame-retardant agent obtain component A, by the polymethylene polyphenyl polyisocyanic acid that mass percent is 30wt% Ester, by component A and B component mixed foaming, obtains polyurethane adiabatic heat-insulation foam material as B component.
Embodiment 2
A kind of halogen-free flameproof rigid polyurethane foam, is made up of component A and B component, the weight of component A and B component Than for 1: 1, according to the number of parts by weight, component A is by 6 parts of phenolic resin, 83560 parts of Sucrose polyethers polyalcohol, expansile graphite 15 parts of 10 parts, 1 part of catalyst, 16 parts of composite flame-retardant agent, 1 part of polyether modified silicon oil and ether form, and B component is quality percentage Number is 32wt% poly methylene poly phenyl poly isocyanate, wherein, the composite flame-retardant agent is by magnesium hydroxide, waterglass, silicon Alkane coupling agent is prepared with nano imvite.Catalyst is N, N- dimethyl cyclohexyl amines, dibutyl tin laurate and octanoic acid The mixture of stannous.
The preparation method of composite flame-retardant agent：
After first magnesium hydroxide is mixed with waterglass, KH792 is added after being again heated to 120 DEG C, side stirring, the reaction time is 20min, 60 DEG C are subsequently cooled to, add nano imvite and stir, be cooled to room temperature.
The preparation method of halogen-free flameproof rigid polyurethane foam：
By phenolic resin, Sucrose polyethers polyalcohol 835, ether premixing, while add expansile graphite, polyether-modified silicon Oil, catalyst and composite flame-retardant agent obtain component A, by the poly methylene poly phenyl poly isocyanate that mass percent is 32wt% As B component, by component A and B component mixed foaming, polyurethane adiabatic heat-insulation foam material is obtained.
Embodiment 3
A kind of halogen-free flameproof rigid polyurethane foam, is made up of component A and B component, the weight of component A and B component Than for 1: 1.5, according to the number of parts by weight, component A is by 20 parts of phenolic resin, 83580 parts of Sucrose polyethers polyalcohol, dilatancy stone 30 parts of 5 parts of ink, 4 parts of catalyst, 30 parts of composite flame-retardant agent, 3 parts of polyether modified silicon oil and ether compositions, B component is quality hundred Fraction be 32wt% poly methylene poly phenyl poly isocyanate, wherein, the composite flame-retardant agent by magnesium hydroxide, waterglass, Silane coupler is prepared with nano imvite.Catalyst is N, N- dimethyl cyclohexyl amines, dibutyl tin laurate with it is pungent The mixture of sour stannous.
The preparation method of composite flame-retardant agent：
After first magnesium hydroxide is mixed with waterglass, DL602 is added after being again heated to 110 DEG C, side stirring, the reaction time is 20min, 50 DEG C are subsequently cooled to, add nano imvite and stir, be cooled to room temperature.
The preparation method of halogen-free flameproof rigid polyurethane foam：
By phenolic resin, Sucrose polyethers polyalcohol 835, ether premixing, while add expansile graphite, polyether-modified silicon Oil, catalyst and composite flame-retardant agent obtain component A, by the poly methylene poly phenyl poly isocyanate that mass percent is 32wt% As B component, by component A and B component mixed foaming, polyurethane adiabatic heat-insulation foam material is obtained.
Test example
The halogen-free flameproof rigid polyurethane foam that embodiment 1-3 is prepared is subjected to compression strength and oxidation refers to The performance measurements such as number, the results are shown in Table 1.
The embodiment 1-3 halogen-free flameproof rigid polyurethane foam performance parameters of table 1
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention God any modification, equivalent substitution and improvements made etc., should be included in the scope of the protection with principle.

Claims (8)

1. a kind of halogen-free flameproof rigid polyurethane foam, it is characterised in that be made up of component A and B component, component A and B groups The weight ratio divided is 1: 1~1.5, and according to the number of parts by weight, component A is by 6~20 parts of phenolic resin, PPG 60~80 Part, 5~10 parts of expansile graphite, 1~4 part of catalyst, 16~30 parts of composite flame-retardant agent, polysiloxane-based foam stabiliser 1~3 15~30 parts of compositions of part and foaming agent, B component is isocyanates, wherein, the composite flame-retardant agent is by magnesium hydroxide, water glass Glass, silane coupler and nano imvite are prepared.
2. halogen-free flameproof rigid polyurethane foam according to claim 1, it is characterised in that the composite flame-retardant agent Preparation method：
After first magnesium hydroxide is mixed with waterglass, silane coupler, side stirring, reaction are added after being again heated to 100~120 DEG C Time is 20~25min, is subsequently cooled to 50~60 DEG C, adds nano imvite and stirs, is cooled to room temperature.
3. halogen-free flameproof rigid polyurethane foam according to claim 2, it is characterised in that the silane coupler For KH570, KH792 or DL602.
4. halogen-free flameproof rigid polyurethane foam according to claim 1, it is characterised in that the PPG For 350~500mgKOH/g PPG.
5. halogen-free flameproof rigid polyurethane foam according to claim 1, it is characterised in that the catalyst is N, The mixture of N- dimethyl cyclohexyl amines, dibutyl tin laurate and stannous octoate.
6. halogen-free flameproof rigid polyurethane foam according to claim 1, it is characterised in that described polysiloxane-based Foam stabiliser is polyether modified silicon oil, and the foaming agent is ether.
7. halogen-free flameproof rigid polyurethane foam according to claim 1, it is characterised in that the polyisocyanates The poly methylene poly phenyl poly isocyanate that mass percent for NCO group is 30~32wt%.
8. the preparation method of halogen-free flameproof rigid polyurethane foam as claimed in claim 1, it is characterised in that including with Lower step：
By phenolic resin, PPG, foaming agent premixing, while add expansile graphite, polysiloxane-based foam stabilization Agent, catalyst and composite flame-retardant agent obtain component A, and using isocyanates as B component, component A and B component mixed foaming obtain To polyurethane adiabatic heat-insulation foam material.
CN201710586698.3A 2017-07-18 2017-07-18 Halogen-free flameproof rigid polyurethane foam and preparation method thereof Pending CN107353391A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111961249A (en) * 2020-08-30 2020-11-20 宁波耀众模塑科技有限公司 Production and manufacturing formula of surface flame-retardant layer of polyurethane foaming product
CN112226070A (en) * 2020-10-19 2021-01-15 山东博顺新材料有限责任公司 High-flame-retardant polyurethane material added with expanded graphite and preparation method thereof

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CN102276778A (en) * 2011-06-15 2011-12-14 上海大唐盛隆制冷科技有限公司 Fire-retardant polyurethane hard foam material and preparation method thereof
CN102675582A (en) * 2012-05-17 2012-09-19 西南科技大学 Preparation method of polyurethane foam materials based on liquefied lignin calcium sulfonate polyalcohol
CN102911334A (en) * 2012-11-14 2013-02-06 滕州市华海新型保温材料有限公司 B1-grade high-fire-retardant low-smoke-generation rigid polyurethane foam
CN105199069A (en) * 2015-10-09 2015-12-30 上海应用技术学院 Preparation method of structural flame-retardant polyurethane soft foam
CN105670039A (en) * 2014-11-21 2016-06-15 合肥杰事杰新材料股份有限公司 High-char-forming expandable graphite and application thereof in rigid polyurethane foam
CN105924757A (en) * 2016-05-31 2016-09-07 李小涛 Halogen-free and high-flame-retardancy cable material and preparation method thereof
CN106478915A (en) * 2016-10-09 2017-03-08 合肥广能新材料科技有限公司 Polyurethane rigid foam exterior wall thermal insulation material and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102276778A (en) * 2011-06-15 2011-12-14 上海大唐盛隆制冷科技有限公司 Fire-retardant polyurethane hard foam material and preparation method thereof
CN102675582A (en) * 2012-05-17 2012-09-19 西南科技大学 Preparation method of polyurethane foam materials based on liquefied lignin calcium sulfonate polyalcohol
CN102911334A (en) * 2012-11-14 2013-02-06 滕州市华海新型保温材料有限公司 B1-grade high-fire-retardant low-smoke-generation rigid polyurethane foam
CN105670039A (en) * 2014-11-21 2016-06-15 合肥杰事杰新材料股份有限公司 High-char-forming expandable graphite and application thereof in rigid polyurethane foam
CN105199069A (en) * 2015-10-09 2015-12-30 上海应用技术学院 Preparation method of structural flame-retardant polyurethane soft foam
CN105924757A (en) * 2016-05-31 2016-09-07 李小涛 Halogen-free and high-flame-retardancy cable material and preparation method thereof
CN106478915A (en) * 2016-10-09 2017-03-08 合肥广能新材料科技有限公司 Polyurethane rigid foam exterior wall thermal insulation material and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111961249A (en) * 2020-08-30 2020-11-20 宁波耀众模塑科技有限公司 Production and manufacturing formula of surface flame-retardant layer of polyurethane foaming product
CN112226070A (en) * 2020-10-19 2021-01-15 山东博顺新材料有限责任公司 High-flame-retardant polyurethane material added with expanded graphite and preparation method thereof

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