CN104829812B - A kind of flame-retardant hard polyurethane heat-insulating foam and preparation method thereof - Google Patents

A kind of flame-retardant hard polyurethane heat-insulating foam and preparation method thereof Download PDF

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CN104829812B
CN104829812B CN201510228209.8A CN201510228209A CN104829812B CN 104829812 B CN104829812 B CN 104829812B CN 201510228209 A CN201510228209 A CN 201510228209A CN 104829812 B CN104829812 B CN 104829812B
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retardant
flame
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hard polyurethane
polyurethane heat
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CN104829812A (en
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孙军坤
蔡志祥
靳蔷薇
俞炜
张洪斌
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Shanghai Jiaotong University
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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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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    • C08G18/16—Catalysts
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    • 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
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    • 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
    • C08J9/14—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
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
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    • C08K5/00—Use of organic ingredients
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    • C08G2110/00—Foam properties
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    • C08G2110/00—Foam properties
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    • C08G2110/0058—≥50 and <150kg/m3
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    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
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    • 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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Abstract

The invention discloses a kind of hard polyurethane adiabatic heat-insulation foam material of technical field of polymer materials and preparation method thereof.Its component and content parts by weight are：PPG 100, poly methylene poly phenyl poly isocyanate 140~160, physical blowing agent HFC 365mfc30~50, foam stabiliser 1.5~5, catalyst 1~3, fire retardant：50~105.Preparation method is：Processing is dried in PPG, poly methylene poly phenyl poly isocyanate, fire-retardant powder, room temperature is placed stand-by；Poly methylene poly phenyl poly isocyanate is component A, is component B after other components mixed processing, then carries out polymerization foaming processing, obtains pouring mold base；Mold base will be poured after the demoulding and carries out maturation process, density is obtained between 60~80kg/m3Expanded material.Foamed material prepared by the present invention has high flame resistance concurrently and good heat-insulating property and mechanical property, and employs HFCs classes third generation zero odp green-blowing agent and environmentally friendly fire retardant.

Description

A kind of flame-retardant hard polyurethane heat-insulating foam and preparation method thereof
Technical field
The present invention relates to a kind of polyurethane foam material of technical field of polymer materials and preparation method thereof, particularly one Plant hard polyurethane adiabatic heat-insulation foam material of high fire-retardance low thermal conductivity and preparation method thereof.
Background technology
Rigid polyurethane foam is because of its excellent combination property, particularly with relatively low thermal conductivity factor, it has also become The heat-insulating material being widely used in numerous areas such as building, ship, chemical industry, communications and transportation.However, hard polyurethane foam sheet Body is inflammable, and limited oxygen index can produce a large amount of smog and pernicious gas after generally there was only 18 or so, and burning, so with merely Hard polyurethane foam make insulation material, using above there is very big potential safety hazard.Therefore, how to keep polyurethane rigid foam material good While good adiabatic heat-insulation property, its fire resistance is improved extremely important to safety applications.Improve Polyurethane Thermal Insulation Building Materials Fire resistance, realized typically by the means of addition fire retardant.Additive flame retardant is generally divided into metal oxide (hydrogen Oxide) class, halogen, organophosphorus compounds and expanding fire retardant class.Wherein although halogen based flame retardant flame retarding efficiency is high, Product self-extinguishment is good, but can produce toxic gas during due to burning, is not used in recent years by promotion.However, simultaneously not all contains Halogen fire retardant is all harmful to environment.For example, TDE is carry out Development and Production the nineties in last century a kind of new, wide Spectrum, efficient and environmentally friendly additive flame retardant, poisonous many bromo dibenzo dioxanes are not produced when its thermal cracking or burning (PBDO) and PBDF (PBDF), be entirely capable of meeting with its fire-retardant material Europe on dioxin regulations will Ask, environment is not caused harm.TDE is also non-toxic in itself, will not produce teratogenesis to biology, to aquatic organism such as Fish etc. has no side effect, and meets the requirement of environmental protection.
Polyurethane foam material mainly generates CO in preparing by using CBA and polyisocyanates reaction2To send out Bubble, and in order to reduce density or improve insulation effect, and use physical blowing agent.With fluorochlorohydrocarbon class (CFCs) foaming agent The limitation with hydrogen fluorochlorohydrocarbon class (HCFCs) foaming agent is prohibitted the use of to use, zero odp (Ozone Depression Potential, Ozone depletion potential) research of foaming agent turns into focus, such as using water, supercritical carbon dioxide, pentane class and HFC (such as HFC-245fa, HFC-365mfc) etc..Among these, at 10 DEG C, CO2The thermal conductivity factor of gas is 15.3mW/mK, pentamethylene The thermal conductivity factor of gas is that the thermal conductivity factor of 11.5mW/mK, HFC-245fa gas is 11.6mW/mK, and HFC-365mfc The thermal conductivity factor of gas is 9.6mW/mK.It can be seen that in the foaming agent of zero odp, HFC-365mfc thermal conductivity factor will be less than it His similar foaming agent.In addition, pentane class foaming agent is inflammable, it can be exploded under certain condition after being mixed with air, and in polyethers Middle poor solubility；Water and CO2The polyurethane foam of production, foam is more crisp during low-density, and thermal conductivity factor is higher, and CO2Gas point Son is small, is easily slowly escaped from abscess, causes heat-insulating property to decline.HFC-365mfc in HFCs class foaming agents has minimum Gas phase thermal conductivity factor, higher boiling point (40 DEG C) is at room temperature liquid, has preferable compatibility with PPG so that It had both facilitated storage and added, and gasification can be easy to again, the effect foamed rapidly is reached.HFC-365mfc also has higher Security, relatively low toxicity, and ODP values are zero.
In published patent and document, using the rigid polyurethane foam heat insulation material of HFCs class foaming agents, ensureing While having compared with low thermal conductivity, preferable fire resistance is not often reached；And excellent fireproof performance, the bubble of oxygen index (OI) energy >=30 Foam material, is difficult to ensure that it has low thermal conductivity factor again.For example authorize the A and CN of Publication No. CN 101781395 101781396 A Chinese patent, using HFC-365mfc as main foaming agent, a small amount of water is used as auxiliary blowing agent DEEP and DMMP, as hard polyurethane foams density made from fire retardant, is 60~80kg/m in density3When, 25 DEG C of heat conduction systems Number is 0.024~0.027W/mK, but its highest oxygen index (OI) all can only achieve 27.0.Patent application CN1724577A, Expanded graphite (EG) is with the addition of in CN2003611A, CN1495213A and CN101088435 as fire retardant, but all can be because of EG Addition so that product thermal conductivity factor increases.Application publication number is the A of CN 102875762 patent, has used brominated and chlorine Fire retardant, works as bromine:Chlorine is 5:1st, when bromine content is 33 parts, obtained rigid polyurethane foam oxygen index (OI) can reach 30, but Patent does not provide other performances of foamed material, such as thermal conductivity factor, compressive strength, rate of closed hole.
In terms of document：(Kim S.H., the H.Lim and B.K.Kim.Effects of such as Sung Hee Kim initiator type in rigid polyurethane foams.Polymer Engineering& Science.2008.48(8):1518-1523) using HFC-365mfc as foaming agent, obtained density is between 60~80kg/m3's Rigid polyurethane foam, thermal conductivity factor is 0.022~0.024W/mK, yet with system and being not added with fire retardant, because The limited oxygen index of this material is less than 20；(the Zhang A.et al.Synergistic effects of such as Anzhen Zhang hydroxides and dimethyl methylphosphonate on rigid halogen-free and flame- retarding polyurethane foams.Journal of Applied Polymer Science.2013.128(1): The compositional flame-retardant effect to rigid polyurethane foam that 347-353) have studied DMMP and aluminium hydroxide is found, when DMMP's Mass fraction is 10%, when the mass fraction of aluminium hydroxide is more than 45%, and obtained foamed material oxygen index (OI) is more than 30, and now Mechanical Properties of Materials have declined to a great extent, and greatest compressive strength only has 0.17Mpa, and document do not provide material thermal conductivity factor and Rate of closed hole etc.；(Modesti M, Lorenzetti A, Simioni F, the et al.Expandable graphite such as Modesti as an intumescent flame retardant in polyisocyanurate–polyurethane foams.Polymer Degradation and Stability.2002.77(2):EG filling hard 195-202) is have studied to gather The fire resistance of urethane foamed composite finds that EG addition can improve the fire resistance of foamed material, but with EG contents Increase, abscess-size increase, thermal conductivity factor improve；(Meng X., et al., the Effects of such as Xianyan Meng expandable graphite and ammonium polyphosphate on the flame-retardant and mechanical properties of rigid polyurethane foams.Journal of Applied Polymer Science.2009.114(2):EG 853-863) is have studied to hinder hard polyurethane foams with APP (APP) compound system The influence of performance is fired, EG is worked as in discovery:APP is 1:1, during filling quality fraction 15%, the limited oxygen index of system can reach 31, but Document does not provide the performance parameters such as heat conduction and the mechanics of material.
Therefore, those skilled in the art is directed to developing a kind of density between 60~80kg/m3, limited oxygen index >= 30, thermal conductivity factor<0.03W/mK, and the hard polyurethane foams heat-insulating material of good mechanical properties.
The content of the invention
In view of the drawbacks described above of prior art, the technical problems to be solved by the invention are to provide a kind of the hard of high fire-retardance Matter polyurethane adiabatic heat-insulation foam material and preparation method thereof, the foamed material has high rate of closed hole, has good thermal insulation concurrently Energy, mechanical property and high flame resistance, and the foaming agent used is environment-friendly type physical blowing agent, to ozone layer without destruction, Fire retardant used at the same time is environmentally friendly fire retardant.
The flame-retardant hard polyurethane heat-insulating foam that the present invention is provided, includes the component of following mass fraction：Polyethers 100 parts of polyalcohol, 140~160 parts of poly methylene poly phenyl poly isocyanate, 30~50 parts of physical blowing agent, foam stabilizer 1~4 Part, 1~3 part of catalyst, 50~105 parts of fire retardant.
Further, described PPG is using sucrose as initiator, and the sucrose hydroxyl value is 480~500mg KOH/ G, viscosity is 6000~9000Pas at 25 DEG C.
Further, 500~800mPas of viscosity during 25 DEG C of described poly methylene poly phenyl poly isocyanate, official Energy degree is 2.6~3.1, and wherein the content of isocyano is 30~32wt%.
Further, described physical blowing agent is 1,1,1,3,3- 3-pentafluorobutane HFC-365mfc.
Further, described foam stabilizer is a kind of silicon class surfactant of polyether-modified structure containing Si-C.
Further, described catalyst is 80%-100% dibutyl tin laurate and 0-20% triethanolamine The catalyst mixed.
Further, described fire retardant is the compound flame retardant containing two kinds of fire retardants, respectively environmentally friendly bromine Flame retardant TDE, and synergistic flame retardant antimony oxide, wherein TDE is in composite flame-retardant agent Mass fraction be 50~80%.
Further, the compound flame retardant is the TDE and the three of mass fraction 20% of mass fraction 80% Aoxidize the fire retardant of two antimony compounding.
The present invention also provides a kind of preparation method of flame-retardant hard polyurethane heat-insulating foam, it is characterised in that Comprise the following steps：
A) PPG, poly methylene poly phenyl poly isocyanate, fire-retardant powder are dried, place room temperature and treat With；
B) PPG, catalyst, foaming agent, fire retardant, foam stabiliser are mixed, mechanical agitation is obtained Component B；
C) it will be mixed as the poly methylene poly phenyl poly isocyanate of component A with B component, while being filled with mechanical agitator Divide stirring, be poured into progress polymerization foaming in mould, acquisition pours mould Bear-grudge, mold base will be poured and carry out maturation process, foamed Material.
Further, the drying process described in step (a) refers to：By PPG and polymethylene polyphenyl polyisocyanate Cyanate is dried in vacuo 8h at 40 DEG C, and fire-retardant powder is dried in vacuo 4h at 80 DEG C.
Further, the maturation process in the step (c) refers to：Mold base first reacts 20 points at room temperature together with mould Mold base, is then stripped by clock, is put into baking oven, and 12h or more than 12h is cured at 70 DEG C.
The present invention uses HFCs class third generation zero odp environment-friendly foaming agent, using environmentally friendly bromide fire retardant --- TDE, coordinates synergist antimony oxide as fire retardant, has prepared density between 60-80kg/m3Hard Polyurethane insulation foam.The Flame Retardancy can be excellent, and limited oxygen index is up to more than 30, thermal conductivity factor<0.03W/mK, Self-extinguishment is good, while possessing relatively low thermal conductivity factor and good compression performance, it is adaptable to as heat-insulating material.
Embodiment
The present invention is elaborated below with reference to specific embodiment.
Embodiment 1-5, comparative example 1-2 formula as shown in table 1, operating procedure is：By PPG and isocyanates 8h is dried in vacuo at 40 DEG C, TDE and antimony oxide composite flame-retardant agent are dried in vacuo 4h, room at 80 DEG C Temperature is placed stand-by.It is added to after dried composite flame-retardant agent is weighed by formula in PPG, catalysis is added by formula Agent, foam stabiliser and physical blowing agent, are sufficiently mixed uniformly with mechanical stirring device, then isocyanates is rapidly added to In blending ingredients, it is sufficiently stirred for simultaneously, free foaming in mould is poured into after 30~50 seconds, acquisition pours mold base.Together with mould React 20 minutes at room temperature, after mold base is stripped, is put into air dry oven and cures 24h at 70 DEG C, obtain product.
As shown in table 1, operating procedure is the formula of comparative example 3：By PPG and isocyanates at 40 DEG C vacuum 8h is dried, room temperature is placed stand-by.Catalyst, foam stabiliser, fire retardant DMMP and physical blowing agent are added by formula, with machinery Agitating device is sufficiently mixed uniformly, then isocyanates is rapidly added in blending ingredients, is sufficiently stirred for simultaneously, 30~50 seconds After be poured into free foaming in mould, acquisition pours mold base.React 20 minutes, after mold base is stripped, put at room temperature together with mould Enter in air dry oven and cure 24h at 70 DEG C, obtain product.
As shown in table 1, operating procedure is the formula of comparative example 4：By PPG and isocyanates at 40 DEG C vacuum 8h is dried, expanded graphite is dried in vacuo 4h at 80 DEG C, room temperature is placed stand-by.It is as shown in the table for the formula of embodiment, by drying Expanded graphite afterwards is added in PPG after being weighed by formula, and catalyst, foam stabiliser and physics are added by formula Foaming agent, is sufficiently mixed uniformly with mechanical stirring device, then isocyanates is rapidly added in blending ingredients, while fully Stirring, is poured into free foaming in mould after 30~50 seconds, acquisition pours mold base.Reacted at room temperature together with mould 20 minutes, will After the mold base demoulding, it is put into air dry oven and cures 24h at 70 DEG C, obtain product.
The material quality fraction proportioning of above example 1~5 and comparative example 1~4 is shown in such as table 1 below：
Table 1
It is as follows that foaming material performance obtained by above-described embodiment and comparative example preparation comments method to estimate：
Compression performance：By integral foam material cut growth 50mm, wide 50mm, high 50mm sample according to GB/T 8813- 2008 test its greatest compressive strength and modulus of compressibility, and compression speed is 5mm/min.
Combustibility：Integral foam material is cut into 130mm × 10mm × 10mm batten, according to GB/T 2406.2- 2009 determine its limited oxygen index；Integral foam material is cut into 150mm × 50mm × 13mm batten, according to GB/T 8332-2008 determines its horizontal firing distance and self-extinguishing time.
Heat-insulating property：By integral foam material cut growth 300mm, wide 300mm, high 50mm sample is resistance to using Germany Speed company hot-fluid conductometer HFM436 according to ASTM C518 or ISO 8301 test its thermal conductivity factor.
Apparent density：Integral foam material cut growth 50mm, wide 50mm, high 50mm sample are pressed into GB/T 6343- 2009 are tested.
Rate of closed hole：By integral foam material cut growth 30mm, wide 30mm, high 60mm sample is public using U.S.'s health tower The full-automatic real density analyzers of ULTRAPYC 1200e of department are tested by GB/T 10799-2008.
Example 1-5 and comparative example 1-4 Performance Evaluation are shown in Table 2：
Table 2
Preferred embodiment of the invention described in detail above.It should be appreciated that the ordinary skill of this area is without wound The property made work just can make many modifications and variations according to the design of the present invention.Therefore, all technical staff in the art Pass through the available technology of logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea Scheme, all should be in the protection domain being defined in the patent claims.

Claims (9)

1. a kind of flame-retardant hard polyurethane heat-insulating foam, it is characterised in that include the component of following mass fraction：Polyethers 100 parts of polyalcohol, 140~160 parts of poly methylene poly phenyl poly isocyanate, 30~50 parts of physical blowing agent, foam stabilizer 1~4 Part, 1~3 part of catalyst, 50~105 parts of fire retardant；The fire retardant is the compound flame retardant containing two kinds of fire retardants, the compounding Fire retardant is formed by the TDE of mass fraction 80% with the antimony oxide compounding of mass fraction 20%.
2. a kind of flame-retardant hard polyurethane heat-insulating foam as claimed in claim 1, it is characterised in that described polyethers Polyalcohol using sucrose as initiator, the sucrose hydroxyl value be 480~500mg KOH/g, at 25 DEG C viscosity be 6000~ 9000Pa·s。
3. a kind of flame-retardant hard polyurethane heat-insulating foam as claimed in claim 1, it is characterised in that described is more sub- 500~800mPas of viscosity during 25 DEG C of methyl polyphenyl polyisocyanate, degree of functionality is 2.6~3.1, wherein isocyano Content be 30~32wt%.
4. a kind of flame-retardant hard polyurethane heat-insulating foam as claimed in claim 1, it is characterised in that described physics Foaming agent is HFC-365.
5. a kind of flame-retardant hard polyurethane heat-insulating foam as claimed in claim 1, it is characterised in that described even bubble Agent is a kind of silicon class surfactant of polyether-modified structure containing Si-C.
6. a kind of flame-retardant hard polyurethane heat-insulating foam as claimed in claim 1, it is characterised in that described catalysis Dibutyl tin laurate and the catalyst mixed of 0-20% triethanolamine that agent is 80%-100%.
7. a kind of preparation method of flame-retardant hard polyurethane heat-insulating foam as claimed in claim 1, it is characterised in that Comprise the following steps：
A) PPG, poly methylene poly phenyl poly isocyanate, fire-retardant powder are dried, place room temperature stand-by；
B) PPG, catalyst, foaming agent, fire retardant, foam stabiliser are mixed, stirs, obtain component B；
C) it will be mixed as the poly methylene poly phenyl poly isocyanate of component A with B component, while fully being stirred with mechanical agitator Mix, be poured into progress polymerization foaming in mould, acquisition pours mold base, mold base will be poured and carry out maturation process, expanded material is obtained.
8. a kind of preparation method of flame-retardant hard polyurethane heat-insulating foam as claimed in claim 7, it is characterised in that Drying process described in step a) refers to：By PPG and poly methylene poly phenyl poly isocyanate at 40 DEG C vacuum 8h is dried, fire-retardant powder is dried in vacuo 4h at 80 DEG C.
9. a kind of preparation method of flame-retardant hard polyurethane heat-insulating foam as claimed in claim 7, it is characterised in that Maturation process in the step c) refers to：Mold base first reacts 20 minutes at room temperature together with mould, is then stripped mold base, puts Enter in baking oven, 12h is cured at 70 DEG C.
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