CN103739824A - Polyurethane flame-retardant thermal-insulation material and preparation method thereof - Google Patents

Polyurethane flame-retardant thermal-insulation material and preparation method thereof Download PDF

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Publication number
CN103739824A
CN103739824A CN201310725014.5A CN201310725014A CN103739824A CN 103739824 A CN103739824 A CN 103739824A CN 201310725014 A CN201310725014 A CN 201310725014A CN 103739824 A CN103739824 A CN 103739824A
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component
flame
retardant
polyurethane
insulation material
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李益忠
梁志坚
吴定超
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Binyang County Guangxi Rong Liang Novel Material Science And Technology Ltd
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Binyang County Guangxi Rong Liang Novel Material Science And Technology Ltd
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/77Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/773Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur halogens
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    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/16Catalysts
    • C08G18/161Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
    • C08G18/163Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
    • C08G18/165Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22 covered by C08G18/18 and C08G18/24
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    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/4009Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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    • C08G18/40High-molecular-weight compounds
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    • C08G18/00Polymeric products of isocyanates or isothiocyanates
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    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
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    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12Working-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
    • C08J9/14Working-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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    • C08J2203/00Foams characterized by the expanding agent
    • C08J2203/14Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142Halogenated saturated hydrocarbons, e.g. H3C-CF3
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    • C08J2375/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04Polyurethanes
    • C08J2375/08Polyurethanes from polyethers

Abstract

The invention provides a polyurethane flame-retardant thermal-insulation material and a preparation method thereof. The polyurethane flame-retardant thermal-insulation material is composed of a component A and a component B, wherein the component A is composed of phenol formaldehyde resin, a brominated epoxy resin, phosphorous flame-retardant polyether glycol, an organosilicon foam stabilizer, a catalyst dimethylethanolamine, a catalyst dibutyltin dilaurate, a flame retardant and a foaming agent monofluorodichloroethane; and the component B is a flame-retardant polyisocyanate curing agent. The invention also provides a preparation method of the outer wall thermal-insulation material. The thermal-insulation material has excellent mechanical properties and high flame retardancy, solves the problem of contradiction between the flame retardancy and mechanical properties of the original polyurethane hard foam thermal-insulation material, and is suitable for outer wall thermal-insulation construction with higher requirements for fire-protection rating.

Description

A kind of polyurethane flame-proof lagging material and preparation method thereof
Technical field
The present invention relates to a kind of polyurethane flame-proof lagging material and preparation method thereof.
Background technology
In recent years, along with deepening continuously of China's dwelling construction energy conservation, and the improving constantly of energy conservation standard, introduce and developed many novel power-saving technologies and material, in residential housing, vigorously promote the use.Wherein be applied to the various porous plastics lagging materials of exterior-wall heat insulation, as its excellent combination properties of factor such as EPS plate, XPS plate material and polyurathamc sheet materials, attract people's attention.
At present, the extensive organic insulation material using of China mainly contains EPS (polystyrene foam), PS (extruded polystyrene foam) and PU (polyurethane foam), all belong to inflammable organic insulation material, maximum advantage is that light weight, insulation, thermal insulation are good; Shortcoming is that fire savety is poor, inflammable easily aging.In burning, time discharge a large amount of toxic smogs, can make people poisoning and suffocate at short notice.In the actual use of China PU porous plastics, fire failure constantly occurs.If therefore can not solve effectively, effectively the problem of its fire savety, can not find an approach with abundant scientific evidence and solve the fire savety problem in its use procedure, PU porous plastics just cannot obtain large-scale promotion application in China's building energy conservation so.So the problems such as the resistance to combustion of urethane foam, fire prevention become important topic in the urgent need to address.
Summary of the invention
For the subject matter of the current domestic and international existence in conjunction with hard polyurethane foam heat-insulation system, in conjunction with the progress of current hard polyurethane foam fire protection flame retarding technology, polyurethane heat insulation material reaches GB B1 level or higher fire-protection rating, single interpolation fire retardant technology can not be dealt with problems, and there is the conflicting problem of Polyurethane Thermal Insulation Building Materials fire retardant performance and mechanical property, the present invention adopts high flame retardant resin to carry out modification to combined polyether, improve flame retardant resistance and keep its excellent mechanical property simultaneously, simultaneously in conjunction with adding fire retardant, flame retardant type solidifying agent has proposed a systematized solution.
The present invention is achieved through the following technical solutions:
A kind of polyurethane flame-proof lagging material, by A component and B component, formed, it is characterized in that, A component is comprised of resol 10-18 weight part, brominated epoxy resin 10-15 weight part, phosphorous flame retardant polyether polyol 65-85 weight part, silicon foams stablizer 4 weight parts, catalyzer dimethylethanolamine 3 weight parts, catalyzer dibutyl tin laurate 1 weight part, fire retardant 20-40 weight part and whipping agent one fluorine ethylene dichloride 25-35 weight part, and B component is many phenyl of bromination polymethine isocyanic ester.
Described brominated epoxy resin is that raw material prepares by tetrabromobisphenol and epoxy chloropropane, and its epoxy equivalent (weight) is 440-470g/eq, and bromine content is 47-51wt%, and viscosity is 140-215cSt.
Concrete method for making is:
By resol, brominated epoxy resin and phosphorous flame retardant polyether polyol pre-mixing, add silicon foams stablizer, catalyzer dimethylethanolamine, catalyzer dibutyl tin laurate, fire retardant and whipping agent one fluorine ethylene dichloride to obtain A component simultaneously, using many phenyl of bromination polymethine isocyanic ester as B component, by A component and B component mixed foaming, isocyanate index is 1.2, obtains the polyurethane rigid foam exterior wall thermal insulation material of high flame retardant.
In the present invention, resol used is heat-reactive phenolic resin, requires moisture to be less than 3%, and solid content is greater than 80%, and viscosity 9000-11000cps is commercially available prod.The most outstanding feature of resol is fire-retardant, low cigarette, high temperature resistance distortion, has the features such as quality is light, heat insulating ability good, resistance toheat is good, good stability of the dimension.The basic reason that resol flame retardant properties is good is the free radical capture effect of its high carbon yield and phenolic hydroxyl group, in the present invention by resol and urethane combination, has complementary advantages, and can obviously improve the flame retardant properties of hard polyurethane foam.
Adopt the main purpose of epoxy resin modification hard polyurethane foam to have 2 points: epoxide group and isocyanate reaction generate high heat-resisting Ju azolactone compound, therefore introduce different epoxy resin and can obtain different stable on heating urethane foams; Second point epoxy resin and polyethers consistency are better, add epoxy resin can improve the mechanical strength of hard polyurethane foam, if but adopt common epoxy resin can reduce the flame retardant properties of hard polyurethane foam, therefore the present invention adopts the fire-retarded epoxy resin brominated epoxy resin of the marketization, and the thermotolerance that improves hard polyurethane foam improves again its flame retardant resistance.
Along with people are more and more higher to the requirement of Polyurethane Rigid Foam Flame Retardance performance, because additive flame retardant exists easily migration, can not keep lastingly flame retardant effect and destroys the shortcomings such as foam physics performance, additive flame retardant is difficult to reach and meet current service requirements, therefore promoted the appearance of flame-proof polyol, solved preferably the problems referred to above, the application that high flame-retardant polyurethane hard bubbles is guaranteed.Flame-proof polyol refers to the polyvalent alcohol that contains ignition-proof element in molecule, with the difference of its contained ignition-proof element, roughly can be divided into phosphorous flame-retardant polyvalent alcohol, halogen is flame-proof polyol, compound flame-proof polyol and fragrant heterocyclic flame-proof polyol etc.The polyvalent alcohol with fragrant heterocycle structure not only has fire-retardant, firing resistance preferably, and the heterocycle structures such as phenyl ring, isocyanurate ring due to it, in molecular structure, have been introduced, make polyurethane product possess higher thermotolerance, dimensional stability and mechanical property, thereby can be applied to and prepare hard polyurethane foams goods.The invention has the beneficial effects as follows that product has higher flame retardant properties and excellent mechanical property simultaneously.
Embodiment
Embodiment 1
A kind of polyurethane flame-proof lagging material, by A component and B component, formed, it is characterized in that, A component is comprised of resol 10 weight parts, brominated epoxy resin 10 weight parts, phosphorous flame retardant polyether polyol 65 weight parts, silicon foams stablizer 4 weight parts, catalyzer dimethylethanolamine 3 weight parts, catalyzer dibutyl tin laurate 1 weight part, fire retardant 20 weight parts and whipping agent one fluorine ethylene dichloride 25 weight parts, and B component is many phenyl of bromination polymethine isocyanic ester.
Described brominated epoxy resin is that raw material prepares by tetrabromobisphenol and epoxy chloropropane, and its epoxy equivalent (weight) is 440-470g/eq, and bromine content is 47-51wt%, and viscosity is 140-215cSt.
Embodiment 2
A kind of polyurethane flame-proof lagging material, by A component and B component, formed, it is characterized in that, A component is comprised of resol 15 weight parts, brominated epoxy resin 13 weight parts, phosphorous flame retardant polyether polyol 75 weight parts, silicon foams stablizer 4 weight parts, catalyzer dimethylethanolamine 3 weight parts, catalyzer dibutyl tin laurate 1 weight part, fire retardant 30 weight parts and whipping agent one fluorine ethylene dichloride 30 weight parts, and B component is many phenyl of bromination polymethine isocyanic ester.
Described brominated epoxy resin is that raw material prepares by tetrabromobisphenol and epoxy chloropropane, and its epoxy equivalent (weight) is 440-470g/eq, and bromine content is 47-51wt%, and viscosity is 140-215cSt.
Embodiment 3
A kind of polyurethane flame-proof lagging material, by A component and B component, formed, it is characterized in that, A component is comprised of resol 18 weight parts, brominated epoxy resin 15 weight parts, phosphorous flame retardant polyether polyol 85 weight parts, silicon foams stablizer 4 weight parts, catalyzer dimethylethanolamine 3 weight parts, catalyzer dibutyl tin laurate 1 weight part, fire retardant 40 weight parts and whipping agent one fluorine ethylene dichloride 35 weight parts, and B component is many phenyl of bromination polymethine isocyanic ester.
Described brominated epoxy resin is that raw material prepares by tetrabromobisphenol and epoxy chloropropane, and its epoxy equivalent (weight) is 440-470g/eq, and bromine content is 47-51wt%, and viscosity is 140-215cSt.
Preparation method is:
By resol, brominated epoxy resin and phosphorous flame retardant polyether polyol pre-mixing, add silicon foams stablizer, catalyzer dimethylethanolamine, catalyzer dibutyl tin laurate, fire retardant and whipping agent one fluorine ethylene dichloride to obtain A component simultaneously, using many phenyl of bromination polymethine isocyanic ester as B component, by A component and B component mixed foaming, isocyanate index is 1.2, obtains the polyurethane rigid foam exterior wall thermal insulation material of high flame retardant.

Claims (3)

1. a polyurethane flame-proof lagging material, by A component and B component, formed, it is characterized in that, A component is comprised of resol 10-18 weight part, brominated epoxy resin 10-15 weight part, phosphorous flame retardant polyether polyol 65-85 weight part, silicon foams stablizer 4 weight parts, catalyzer dimethylethanolamine 3 weight parts, catalyzer dibutyl tin laurate 1 weight part, fire retardant 20-40 weight part and whipping agent one fluorine ethylene dichloride 25-35 weight part, and B component is many phenyl of bromination polymethine isocyanic ester.
2. a kind of polyurethane flame-proof lagging material according to claim 1, it is characterized in that, described brominated epoxy resin is that raw material prepares by tetrabromobisphenol and epoxy chloropropane, and its epoxy equivalent (weight) is 440-470g/eq, bromine content is 47-51wt%, and viscosity is 140-215cSt.
3. a kind of polyurethane flame-proof lagging material according to claim 1, is characterized in that making by the following method:
By resol, brominated epoxy resin and phosphorous flame retardant polyether polyol pre-mixing, add silicon foams stablizer, catalyzer dimethylethanolamine, catalyzer dibutyl tin laurate, fire retardant and whipping agent one fluorine ethylene dichloride to obtain A component simultaneously, using many phenyl of bromination polymethine isocyanic ester as B component, by A component and B component mixed foaming, isocyanate index is 1.2, obtains the polyurethane rigid foam exterior wall thermal insulation material of high flame retardant.
CN201310725014.5A 2013-12-25 2013-12-25 Polyurethane flame-retardant thermal-insulation material and preparation method thereof Pending CN103739824A (en)

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Cited By (11)

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Publication number Priority date Publication date Assignee Title
CN104788643A (en) * 2015-04-02 2015-07-22 上海应用技术学院 Rigid polyurethane foam plastic and preparation method thereof
CN105176066A (en) * 2015-09-30 2015-12-23 安徽省思维新型建材有限公司 Heat-resistant and flame-retardant polyurethane foam
CN105294977A (en) * 2015-11-10 2016-02-03 中科院广州化灌工程有限公司 High-strength high-fire-retardant low-heat-release mining polyurethane grouting reinforcement material and preparation method and application thereof
CN105646821A (en) * 2016-01-29 2016-06-08 吴婷婷 Molecular structure modified rigid polyurethane foam thermal insulation material
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
CN106496497A (en) * 2016-10-09 2017-03-15 合肥广能新材料科技有限公司 Glass bead polyurethane foam composite and preparation method thereof
CN106497020A (en) * 2016-10-09 2017-03-15 合肥广能新材料科技有限公司 Polyurethane rigid foam exterior wall thermal insulation material of high fire-retardance and preparation method thereof
CN106497021A (en) * 2016-10-09 2017-03-15 合肥广能新材料科技有限公司 Polyurethane rigid foam exterior wall flame-retardant thermal insulation material and preparation method thereof
CN106543399A (en) * 2015-09-18 2017-03-29 天津奇才科技发展有限公司 A kind of phenolic resin modified poly-isocyanurate warming plate
CN107619461A (en) * 2017-09-06 2018-01-23 绵阳旺通科技有限公司 A kind of high-strength polyurethane flame-retardant thermal insulation material and preparation method thereof
CN109608604A (en) * 2018-11-14 2019-04-12 安徽明光中兴阳光新能源科技有限公司 A kind of polyurethane heat-insulating heat-preserving material and preparation method thereof

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CN101148515A (en) * 2007-09-12 2008-03-26 北京莱恩斯涂料有限公司 Composite pnenolic aldehyde foam heat-insulating board for building and forming method thereof
CN101565541A (en) * 2008-04-25 2009-10-28 北京化工大学 Method for preparing polyurethane/phenolic aldehyde foam thermal insulation material
CN101831168A (en) * 2010-05-14 2010-09-15 上海克络蒂材料科技发展有限公司 Polyurethane rigid foam exterior wall thermal insulation material with high flame retardancy and preparation method thereof

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CN101148515A (en) * 2007-09-12 2008-03-26 北京莱恩斯涂料有限公司 Composite pnenolic aldehyde foam heat-insulating board for building and forming method thereof
CN101565541A (en) * 2008-04-25 2009-10-28 北京化工大学 Method for preparing polyurethane/phenolic aldehyde foam thermal insulation material
CN101831168A (en) * 2010-05-14 2010-09-15 上海克络蒂材料科技发展有限公司 Polyurethane rigid foam exterior wall thermal insulation material with high flame retardancy and preparation method thereof

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104788643A (en) * 2015-04-02 2015-07-22 上海应用技术学院 Rigid polyurethane foam plastic and preparation method thereof
CN104788643B (en) * 2015-04-02 2017-06-23 上海应用技术学院 A kind of RPUF and preparation method thereof
CN106543399A (en) * 2015-09-18 2017-03-29 天津奇才科技发展有限公司 A kind of phenolic resin modified poly-isocyanurate warming plate
CN105176066A (en) * 2015-09-30 2015-12-23 安徽省思维新型建材有限公司 Heat-resistant and flame-retardant polyurethane foam
CN105176066B (en) * 2015-09-30 2018-11-23 安徽省思维新型建材有限公司 A kind of heat-proof combustion-resistant polyurethane foam
CN105294977A (en) * 2015-11-10 2016-02-03 中科院广州化灌工程有限公司 High-strength high-fire-retardant low-heat-release mining polyurethane grouting reinforcement material and preparation method and application thereof
CN105294977B (en) * 2015-11-10 2018-05-01 中科院广州化灌工程有限公司 Low heat release mine polyurethane slip casting strengthening material of high strength and high flame retardant and preparation method and application
CN105646821A (en) * 2016-01-29 2016-06-08 吴婷婷 Molecular structure modified rigid polyurethane foam thermal insulation material
CN106497021A (en) * 2016-10-09 2017-03-15 合肥广能新材料科技有限公司 Polyurethane rigid foam exterior wall flame-retardant thermal insulation material and preparation method thereof
CN106497020A (en) * 2016-10-09 2017-03-15 合肥广能新材料科技有限公司 Polyurethane rigid foam exterior wall thermal insulation material of high fire-retardance and preparation method thereof
CN106496497A (en) * 2016-10-09 2017-03-15 合肥广能新材料科技有限公司 Glass bead polyurethane foam composite 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
CN107619461A (en) * 2017-09-06 2018-01-23 绵阳旺通科技有限公司 A kind of high-strength polyurethane flame-retardant thermal insulation material and preparation method thereof
CN109608604A (en) * 2018-11-14 2019-04-12 安徽明光中兴阳光新能源科技有限公司 A kind of polyurethane heat-insulating heat-preserving material and preparation method thereof

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Application publication date: 20140423