CN104877102A - Flame-retardant rigid polyurethane foam heat insulation plate - Google Patents
Flame-retardant rigid polyurethane foam heat insulation plate Download PDFInfo
- Publication number
- CN104877102A CN104877102A CN201510300204.1A CN201510300204A CN104877102A CN 104877102 A CN104877102 A CN 104877102A CN 201510300204 A CN201510300204 A CN 201510300204A CN 104877102 A CN104877102 A CN 104877102A
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- flame
- retardant
- component
- foam heat
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
- C08G18/4684—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing phosphorus
-
- 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
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5003—Polyethers having heteroatoms other than oxygen having halogens
- C08G18/5006—Polyethers having heteroatoms other than oxygen having halogens having chlorine and/or bromine atoms
- C08G18/5012—Polyethers having heteroatoms other than oxygen having halogens having chlorine and/or bromine atoms having bromine atoms
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0066—Flame-proofing or flame-retarding additives
-
- 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
- C08K9/00—Use of pretreated ingredients
-
- 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
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/10—Rigid foams
Abstract
The invention relates to a flame-retardant rigid polyurethane foam heat insulation plate. The flame-retardant rigid polyurethane foam heat insulation plate comprises a component A and a component B, wherein the component A is formed by mixing flame-retardant polyether or flame-retardant polyether polyol, amidogen ether polyol, common polyether polyol, a foam stabilizer, a catalyst, a reactive flame retardant, modified expandable graphite and a foaming agent according to a certain proportion. The component B is isocyanate. The component A and the component B are mixed, and then are subjected to compression molding to obtain the flame-retardant heat insulation plate. According to the prepared flame-retardant rapid polyurethane foam heat insulation plate, flame-retardant testing data exceed a GB8624-2012B1-grade flame-retardant standard, the oxygen index is up to 48.9, and the heat conduction coefficient is about 0.02W/m.k. The flame-retardant rigid polyurethane foam heat insulation plate has excellent compressive strength and bending resistance strength. The flame-retardant rigid polyurethane foam heat insulation plate is suitable for being applied to the fields of flame retardance and heat insulation of building walls, refrigeration houses, refrigerators, solar water heaters and the like.
Description
Technical field
The present invention relates to construction wall, freezer, refrigerator, solar water heater fire-retardant heat insulation field, specifically a kind of not containing the flame retardant polyurethane rigid foam heat preservation plate material of additive flame retardant.
Background technology
Country pays much attention to building energy conservation, and heat preserving and insulating material is the key of building energy conservation.The current three large heat preservation plate materials occupying building heat preservation market maximum ratio are benzene plates, extruded sheet and hard polyurethane foam sheet material.Hard polyurethane foam sheet material compares benzene plate and extruded sheet has very large advantage in fire-retardant and heat-insulating property.Along with NFA department is to fire-retardant attention, the flame retardant properties of lagging material requires also to improve thereupon.In order to reach the fire-retardant B1 grade standard of GB 8624-2012, current heat preservation plate material all needs to adopt flame-retardant additive.No matter be organic fire-resisting additive or inorganic fire-retarded additive, excessive interpolation all can damage the physicochemical property of lagging material.Such as hard polyurethane foam lagging material, in order to reach fire-retardant B1 grade standard, adding the chloride phosphorous organic fire-retardant such as a large amount of TCPP, DMMP, causing liquid combination polyether glycol that side reaction storage period easily occurs short in combined polyether glycol.Such as publication number is the Chinese patent of CN104592481A, is namely to use DMMP and TCPP to do fire retardant to improve the flame retardant properties of hard polyurethane foam.This type of organic fire-retardant does not participate in the shaping reaction of hard polyurethane foam, and only as additive exist hard foamed poly urethane mutually in, As time goes on, fire retardant small molecules is free out, causes the reduction of fire-retardant index.In addition, in lagging material production, construction process, the existence of a large amount of organic fire-resisting additive can make construction environment severe, causes environmental pollution.Inorganic combustion inhibitor is also often used in the production of heat preservation plate material, such as magnesium hydroxide, aluminium hydroxide etc., and the excessive interpolation of this type of flame-retardant additive also can make lagging material mechanical property and heat-insulating property decline.
Whether fire retardant participates in forming materials reaction can be divided into additive flame retardant and reactive flame retardant.Reactive flame retardant is a kind of fire retardant that can participate in forming materials reaction.In macromolecular polymerization reaction process, join reaction system, become a part for polymkeric substance by chemical bonding, ignition-proof element can not move or volatilize in using and depositing in process of goods.Therefore on the impact of the over-all properties of foam article is little and flame retardant properties is lasting.The ignition-proof element often contained in reactive flame retardant molecular structure has P, N, Br, Cl etc.Expansible black lead, as a kind of environment friendly flame retardant, has boundless application prospect.The functional groups such as hydroxycarboxyl group are contained on expansible black lead surface in preparation process, with hard polyurethane foam recombination process, hydroxycarboxyl group functional group can participate in isocyanate reaction, by chemical bonds make expansible black lead be uniformly distributed in hard foamed poly urethane mutually in.The fire retardants such as expansible black lead can with phosphorous, bromine, chlorine form synergistic effect, and flame retardant properties is improved further.
Summary of the invention
Technical problem to be solved by this invention overcomes above-mentioned the deficiencies in the prior art, there is provided a kind of composition rationally, work in coordination with composite by adopting reactive flame retardant and expansible black lead, replace additive flame retardant completely, flame retardant properties is stablized, the flame retardant polyurethane rigid foam heat preservation plate material of good flame retardation effect.
The technical scheme that the present invention solves the problems of the technologies described above employing is: a kind of flame retardant polyurethane rigid foam heat preservation plate material, and comprise A, B two component, described B component is isocyanic ester, it is characterized in that: described component A is made up of the raw material of following weight part:
Flame retarding polyether or flame retardant polyester polyvalent alcohol 5 ~ 25%
Amidogen ether polyvalent alcohol 5 ~ 12%
Common polyether or polyester polyol 12 ~ 35%
Foam stabilizer 1.5 ~ 2%
TEDA liquid catalyst 0.5%
Catalyst for trimerization 2.5 ~ 3 %
Reactive flame retardant 5 ~ 25%
Whipping agent 20 ~ 25%
Modification expansible black lead 5 ~ 15%
Described component A mixes by 1:1.1 equivalence ratio with described B component, obtains flame retardant polyurethane rigid foam heat preservation plate material through compression molding.
Further, described modification expansible black lead surface is containing hydroxyl and carboxyl reaction functional group, and modification expansible black lead order number is 35-150 order, and expansion multiplying power is 200-450 times.
Further, described flame retardant polyether polyol take bromo-derivative as the polyether glycol of initiator, and its functionality is 2, and hydroxyl value is 190mgKOH/g.Flame retardant polyester polyvalent alcohol is formed by polycondensation by Halogen polyvalent alcohol and phosphoryl chloride, and the hydroxyl value of flame retardant polyester polyvalent alcohol is 240 mgKOH/g.
Further, described foam stabilizer is silicone oil.
Further, described catalyst for trimerization PT301 purchased from American gas companies.
Further, described reactive flame retardant is phosphorous, chlorine, bromo element mainly, viscosity 900-1100 (ps.25 DEG C), hydroxyl value 46 mgKOH/g, acid number < 0.2 mgKOH/g.
Further, described whipping agent is a fluorine ethylene dichloride HCFC-141b.
The present invention is above-mentioned not containing the flame retardant polyurethane rigid foam heat preservation plate material of additive flame retardant, and its preparation process comprises the steps:
(1) prepare that component A gets 5 ~ 25 parts of flame retarding polyethers or flame retardant polyester polyvalent alcohol, 5 ~ 12 parts of amidogen ether polyvalent alcohols, 12 ~ 35 parts of common polyether or polyester polyols load in reactors, start stirring; Get 1.5 ~ 2 parts of foam stabilizers, 0.5 part of TEDA liquid catalyst, 2.5 ~ 3 parts of catalyst for trimerization, the expansible black lead of 5 ~ 15 parts, 5 ~ 25 parts of reactive flame retardants, 20 ~ 25 parts of whipping agents join in reactor, stir 10 ~ 20 minutes at normal temperatures, obtain combined polyether glycol component A (amounting to 100 parts);
(2) convert according to reaction equivalent, the above component A and B component press 1:1.1 equivalence ratio mix and blend, treat that liquid foam injects mould rapidly after milky white, by the time hard polyurethane foam is swollen determine after die sinking, namely obtain hard polyurethane foam heat preservation plate material.
The present invention adopts technique scheme, adopts reactive flame retardant composite with the modification expansible black lead that can participate in the shaping reaction of hard polyurethane foam, has banned the use of additive flame retardant completely.P, Cl, Br ignition-proof element in expansible black lead and reactive flame retardant produces and acts synergistically, and flame retardant effect improves obviously.
Advantage of the present invention is: (1) has banned the use of additive flame retardant completely, and ignition-proof element is linked on hard polyurethane foam molecular skeleton, can not reduce flame retardant properties along with time lapse; (2) avoid the side reaction that addition type organic fire-retardant causes combined polyether glycol, thus make the combined polyether glycol shelf lives elongated; (3) not containing additive flame retardant, avoid migration and volatilization in lagging material construction and use and cause environmental pollution; (4) adopt modification expansible black lead with phosphorous, bromine, chlorine element reaction type fire retardant are composite, produce synergistic effect, reduce the consumption of general flame-retardant agent, oxygen index promotes obviously, simultaneously aflame smoke density and smoke toxicity reduction.Prepared fire-resistance thermal insulation board Fire retardant test data is more than GB8624-2012B1 level flame-retardant standard, and oxygen index is up to 48.9, and thermal conductivity is about 0.02W/m.k, has splendid ultimate compression strength and bend resistance intensity.Be suitable for being applied to the fire-retardant heat insulation fields such as construction wall, freezer, refrigerator, solar water heater.
Embodiment
Below in conjunction with embodiment, the present invention is further described.
Embodiment 1: a kind of not containing the flame retardant polyurethane rigid foam heat preservation plate material of additive flame retardant, comprise A, B two component, described B component is isocyanic ester.Described component A is made up of the raw material of following weight part:
Flame retardant polyether polyol 15%
Amidogen ether polyvalent alcohol 5%
Common polyether polyvalent alcohol 20%
Silicone oil 2%
TEDA liquid catalyst 0.5%
Catalyst for trimerization PT301 2.5 %
Reactive flame retardant 15%
Blowing agent H CFC-141b 25%
Modification expansible black lead 15%
In described component A, modification expansible black lead surface is containing hydroxyl and carboxyl reaction functional group.As preferred technical scheme, modification expansible black lead order number is 35-150 order, and expansion multiplying power is 200-450 times.
Described flame retardant polyether polyol take bromo-derivative as the polyether glycol of initiator, and its functionality is 2, and hydroxyl value is 190mgKOH/g.
Described reactive flame retardant is phosphorous, chlorine, bromo element mainly, viscosity 900-1100 (ps.25 DEG C), hydroxyl value 46 mgKOH/g, acid number < 0.2 mgKOH/g.
The present invention is above-mentioned not containing the fire-resistance thermal insulation board of additive flame retardant, and its preparation process comprises the steps:
(1) prepare component A to get in 15 parts of flame retardant polyether polyols, 5 parts of amidogen ether polyvalent alcohols, 20 parts of common polyether polyvalent alcohols loading reactors, start stirring; Get 2 parts of silicone oil, 0.5 part of TEDA liquid catalyst, 2.5 parts of catalyst for trimerization PT301, the modification expansible black lead of 15 parts, 15 parts of reactive flame retardants, 25 parts of blowing agent H CFC-141b join in reactor, stir 10 ~ 20 minutes at normal temperatures, obtain combined polyether glycol component A (amounting to 100 parts);
(2) convert according to reaction equivalent, the above component A and B component press 1:1.1 equivalence ratio mix and blend, treat that liquid foam injects mould rapidly after milky white, by the time hard polyurethane foam is swollen determine after die sinking, namely obtain hard polyurethane foam heat preservation plate material.
The present invention adopts technique scheme, adopts reactive flame retardant composite with the modification expansible black lead that can participate in the shaping reaction of hard polyurethane foam, has banned the use of additive flame retardant completely.P, Cl, Br ignition-proof element in expansible black lead and reactive flame retardant produces and acts synergistically, and flame retardant effect improves obviously.Prepared fire-resistance thermal insulation board Fire retardant test data is more than GB8624-2012B1 level flame-retardant standard, and oxygen index is up to 48.9, and thermal conductivity is about 0.02W/m.k, has splendid ultimate compression strength and bend resistance intensity.Be suitable for being applied to the fire-retardant heat insulation fields such as construction wall, freezer, refrigerator, solar water heater.
Embodiment 2: a kind of not containing the flame retardant polyurethane rigid foam heat preservation plate material of additive flame retardant, comprise A, B two component, described B component is isocyanic ester, and described component A is made up of the raw material of following weight part:
Flame retardant polyester polyvalent alcohol 10%
Amidogen ether polyvalent alcohol 10%
Conventional polyester polyvalent alcohol 35%
Silicone oil 2%
TEDA liquid catalyst 0.5%
Catalyst for trimerization PT301 2.5 %
Reactive flame retardant 10%
Blowing agent H CFC-141b 20%
Modification expansible black lead 10%
Described modification expansible black lead surface is containing hydroxyl and carboxyl reaction functional group.As preferred technical scheme, modification expansible black lead order number is 35-150 order, and expansion multiplying power is 200-450 times.
Described flame retardant polyester polyvalent alcohol is formed by polycondensation by Halogen polyvalent alcohol and phosphoryl chloride, and the hydroxyl value of flame retardant polyester polyvalent alcohol is 240 mgKOH/g.
Described reactive flame retardant is phosphorous, chlorine, bromo element mainly, viscosity 900-1100 (ps.25 DEG C), hydroxyl value 46 mgKOH/g, acid number < 0.2 mgKOH/g.
The present invention is above-mentioned not containing the fire-resistance thermal insulation board of additive flame retardant, and its preparation process comprises the steps:
(1) prepare component A to get in 10 parts of flame retardant polyester polyvalent alcohols, 10 parts of amidogen ether polyvalent alcohols, 35 parts of conventional polyester polyvalent alcohols loading reactors, start stirring; Get 2 parts of silicone oil, 0.5 part of TEDA liquid catalyst, 2.5 parts of catalyst for trimerization PT301, the modification expansible black lead of 10 parts, 10 parts of reactive flame retardants, 20 parts of blowing agent H CFC-141b join in reactor, stir 10 ~ 20 minutes at normal temperatures, obtain combined polyether glycol component A (amounting to 100 parts);
(2) convert according to reaction equivalent, the above component A and B component press 1:1.1 equivalence ratio mix and blend, treat that liquid foam injects mould rapidly after milky white, by the time hard polyurethane foam is swollen determine after die sinking, namely obtain hard polyurethane foam heat preservation plate material.
Embodiment 3: a kind of not containing the flame retardant polyurethane rigid foam heat preservation plate material of additive flame retardant, comprise A, B two component, described B component is isocyanic ester, and described component A is made up of the raw material of following weight part:
Flame retardant polyether polyol 18%
Amidogen ether polyvalent alcohol 12%
Conventional polyester polyvalent alcohol 30%
Silicone oil 2%
TEDA liquid catalyst 0.5%
Catalyst for trimerization PT301 2.5 %
Reactive flame retardant 5%
Blowing agent H CFC-141b 25%
Modification expansible black lead 5%
Described modification expansible black lead surface is containing hydroxyl and carboxyl reaction functional group.As preferred technical scheme, modification expansible black lead order number is 35-150 order, and expansion multiplying power is 200-450 times.
Described flame retardant polyether polyol take bromo-derivative as the polyether glycol of initiator, and its functionality is 2, and hydroxyl value is 190mgKOH/g.
Described reactive flame retardant is phosphorous, chlorine, bromo element mainly, viscosity 900-1100 (ps.25 DEG C), hydroxyl value 46 mgKOH/g, acid number < 0.2 mgKOH/g.
The present invention is above-mentioned not containing the fire-resistance thermal insulation board of additive flame retardant, and its preparation process comprises the steps:
(1) prepare component A to get in 18 parts of flame retardant polyether polyols, 12 parts of amidogen ether polyvalent alcohols, 30 parts of conventional polyester polyvalent alcohols loading reactors, start stirring; Get 2 parts of silicone oil, 0.5 part of TEDA liquid catalyst, 2.5 parts of catalyst for trimerization PT301, the modification expansible black lead of 5 parts, 5 parts of reactive flame retardants, 25 parts of blowing agent H CFC-141b join in reactor, stir 10 ~ 20 minutes at normal temperatures, obtain combined polyether glycol component A (amounting to 100 parts);
(2) convert according to reaction equivalent, the above component A and B component press 1:1.1 equivalence ratio mix and blend, treat that liquid foam injects mould rapidly after milky white, by the time hard polyurethane foam is swollen determine after die sinking, namely obtain hard polyurethane foam heat preservation plate material.
Embodiment 4: a kind of not containing the flame retardant polyurethane rigid foam heat preservation plate material of additive flame retardant, comprise A, B two component, described B component is isocyanic ester, and described component A is made up of the raw material of following weight part:
Flame retardant polyester polyvalent alcohol 5%
Amidogen ether polyvalent alcohol 10%
Common polyether polyvalent alcohol 25%
Silicone oil 2%
TEDA liquid catalyst 0.5%
Catalyst for trimerization PT301 2.5 %
Reactive flame retardant 25%
Blowing agent H CFC-141b 20%
Modification expansible black lead 10%
Described modification expansible black lead surface is containing hydroxyl and carboxyl reaction functional group.As preferred technical scheme, modification expansible black lead order number is 35-150 order, and expansion multiplying power is 200-450 times.
Described flame retardant polyester polyvalent alcohol is formed by polycondensation by Halogen polyvalent alcohol and phosphoryl chloride, and the hydroxyl value of flame retardant polyester polyvalent alcohol is 240 mgKOH/g.
Described reactive flame retardant is phosphorous, chlorine, bromo element mainly, viscosity 900-1100 (ps.25 DEG C), hydroxyl value 46 mgKOH/g, acid number < 0.2 mgKOH/g.
The present invention is above-mentioned not containing the fire-resistance thermal insulation board of additive flame retardant, and its preparation process comprises the steps:
(1) prepare component A to get in 5 parts of flame retardant polyester polyvalent alcohols, 10 parts of amidogen ether polyvalent alcohols, 25 parts of common polyether polyvalent alcohols loading reactors, start stirring; Get 2 parts of silicone oil, 0.5 part of TEDA liquid catalyst, 2.5 parts of catalyst for trimerization PT301, the modification expansible black lead of 10 parts, 25 parts of reactive flame retardants, 20 parts of blowing agent H CFC-141b join in reactor, stir 10 ~ 20 minutes at normal temperatures, obtain combined polyether glycol component A (amounting to 100 parts);
(2) convert according to reaction equivalent, the above component A and B component press 1:1.1 equivalence ratio mix and blend, treat that liquid foam injects mould rapidly after milky white, by the time hard polyurethane foam is swollen determine after die sinking, namely obtain hard polyurethane foam heat preservation plate material.
Embodiment 5: a kind of not containing the fire-resistance thermal insulation board of additive flame retardant, comprise A, B two component, described B component is isocyanic ester, and described component A is made up of the raw material of following weight part:
Flame retardant polyether polyol 25%
Amidogen ether polyvalent alcohol 5%
Common polyether polyvalent alcohol 12%
Silicone oil 2%
TEDA liquid catalyst 0.5%
Catalyst for trimerization PT301 2.5 %
Reactive flame retardant 18%
Blowing agent H CFC-141b 25%
Modification expansible black lead 10%
Described modification expansible black lead surface is containing hydroxyl and carboxyl reaction functional group.As preferred technical scheme, modification expansible black lead order number is 35-150 order, and expansion multiplying power is 200-450 times.
Described flame retardant polyether polyol take bromo-derivative as the polyether glycol of initiator, and its functionality is 2, and hydroxyl value is 190mgKOH/g.
Described reactive flame retardant is phosphorous, chlorine, bromo element mainly, viscosity 900-1100 (ps.25 DEG C), hydroxyl value 46 mgKOH/g, acid number < 0.2 mgKOH/g.
The present invention is above-mentioned not containing the fire-resistance thermal insulation board of additive flame retardant, and its preparation process comprises the steps:
(1) prepare component A to get in 25 parts of flame retardant polyether polyols, 5 parts of amidogen ether polyvalent alcohols, 12 parts of common polyether polyvalent alcohols loading reactors, start stirring; Get 2 parts of silicone oil, 0.5 part of TEDA liquid catalyst, 2.5 parts of catalyst for trimerization PT301, the modification expansible black lead of 10 parts, 18 parts of reactive flame retardants, 25 parts of blowing agent H CFC-141b join in reactor, stir 10 ~ 20 minutes at normal temperatures, obtain combined polyether glycol component A (amounting to 100 parts);
(2) convert according to reaction equivalent, the above component A and B component press 1:1.1 equivalence ratio mix and blend, treat that liquid foam injects mould rapidly after milky white, by the time hard polyurethane foam is swollen determine after die sinking, namely obtain hard polyurethane foam heat preservation plate material.
Hard polyurethane foam heat preservation plate material detection perform prepared by the various embodiments described above of the present invention the results are shown in Table 1.
Table 1
As can be seen from Table 1:
While this fire-resistance thermal insulation board not containing additive flame retardant maintains good mechanical property and lower thermal conductivity, flame retardant properties is very outstanding, and oxygen index exceedes hard polyurethane foam limiting oxygen index(LOI) more than one times.This hard polyurethane foam heat preservation plate material performance reaches the standard-required of GB JC/T998-2006.
The flame retardant test of hard polyurethane foam heat preservation plate material prepared by the various embodiments described above of the present invention the results are shown in Table 2.
Table 2
As can be seen from Table 2:
This does not have very high oxygen index containing the fire-resistance thermal insulation board of additive flame retardant, plays the preventive effect avoiding flame formation.And once flame formation, in combustion processes, fire growth rate and total heat release are all very low, prove that the rate of fire travel is slow, be convenient to control fire and avoid loss of life and personal injury.Above Fire retardant test data is all more than GB8624-2012 standard B1 level index.
Claims (8)
1. a flame retardant polyurethane rigid foam heat preservation plate material, comprise A, B two component, described B component is isocyanic ester, it is characterized in that: described component A is made up of the raw material of following weight part:
Flame retarding polyether or flame retardant polyester polyvalent alcohol 5 ~ 25%
Amidogen ether polyvalent alcohol 5 ~ 12%
Common polyether or polyester polyol 12 ~ 35%
Foam stabilizer 1.5 ~ 2%
TEDA liquid catalyst 0.5%
Catalyst for trimerization 2.5 ~ 3 %
Reactive flame retardant 5 ~ 25%
Whipping agent 20 ~ 25%
Modification expansible black lead 5 ~ 15%
Described component A mixes by 1:1.1 equivalence ratio with described B component, obtains flame retardant polyurethane rigid foam heat preservation plate material through compression molding.
2. flame retardant polyurethane rigid foam heat preservation plate material according to claim 1, is characterized in that: described modification expansible black lead surface is containing hydroxyl and carboxyl reaction functional group, and modification expansible black lead order number is 35-150 order, expansion multiplying power be 200-450 doubly.
3. flame retardant polyurethane rigid foam heat preservation plate material according to claim 1, is characterized in that: described flame retardant polyether polyol take bromo-derivative as the polyether glycol of initiator, and its functionality is 2, and hydroxyl value is 190mgKOH/g.
4. flame retardant polyurethane rigid foam heat preservation plate material according to claim 1, it is characterized in that: described flame retardant polyester polyvalent alcohol is formed by polycondensation by Halogen polyvalent alcohol and phosphoryl chloride, the hydroxyl value of flame retardant polyester polyvalent alcohol is 240 mgKOH/g.
5. flame retardant polyurethane rigid foam heat preservation plate material according to claim 1, is characterized in that: described foam stabilizer is silicone oil.
6. flame retardant polyurethane rigid foam heat preservation plate material according to claim 1, is characterized in that: described catalyst for trimerization PT301 purchased from American gas companies.
7. flame retardant polyurethane rigid foam heat preservation plate material according to claim 1, it is characterized in that: described reactive flame retardant is phosphorous, chlorine, bromo element, viscosity 900-1100 (ps.25 DEG C), hydroxyl value 46 mgKOH/g, acid number < 0.2 mgKOH/g.
8. flame retardant polyurethane rigid foam heat preservation plate material according to claim 1, is characterized in that: described whipping agent is a fluorine ethylene dichloride HCFC-141b.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510300204.1A CN104877102A (en) | 2015-06-03 | 2015-06-03 | Flame-retardant rigid polyurethane foam heat insulation plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510300204.1A CN104877102A (en) | 2015-06-03 | 2015-06-03 | Flame-retardant rigid polyurethane foam heat insulation plate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104877102A true CN104877102A (en) | 2015-09-02 |
Family
ID=53944800
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510300204.1A Pending CN104877102A (en) | 2015-06-03 | 2015-06-03 | Flame-retardant rigid polyurethane foam heat insulation plate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104877102A (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105218782A (en) * | 2015-09-22 | 2016-01-06 | 江苏中圣管道工程技术有限公司 | The preparation method that a kind of Modified by Expandable Graphite high flame-retardant polyurethane hard bubbles |
| CN105348470A (en) * | 2015-11-25 | 2016-02-24 | 山东一诺威新材料有限公司 | Foamed plastic for low-density and high-flame-retardant continuous slab and preparation method for foamed plastic |
| CN105566596A (en) * | 2015-12-30 | 2016-05-11 | 安徽安大华泰新材料有限公司 | Flame-retardant and water-resistant polyurethane elastomer and preparation method thereof |
| CN105601863A (en) * | 2015-12-30 | 2016-05-25 | 安徽安大华泰新材料有限公司 | Preparing method for heat-resistant and flame-retardant polyurethane elastomer |
| CN105820518A (en) * | 2015-11-30 | 2016-08-03 | 单成敏 | Preparation method for modified polyol with ultrahigh temperature resistance and high flame resistance |
| CN105924942A (en) * | 2016-04-27 | 2016-09-07 | 安徽广燕新材料科技有限责任公司 | High-strength and high-flame retardation polyurethane composite heat insulation plate |
| CN105924943A (en) * | 2016-04-27 | 2016-09-07 | 安徽广燕新材料科技有限责任公司 | High-flame retardation polyurethane composite heat insulation plate |
| CN105936664A (en) * | 2016-06-03 | 2016-09-14 | 日照易立保温材料科技有限公司 | GPIR high-performance heat insulation board and production technology thereof |
| CN107236445A (en) * | 2017-07-10 | 2017-10-10 | 江苏美鑫源绿色房屋有限公司 | A kind of fireproof coating and its application method for integrated house profile material |
| CN108264624A (en) * | 2018-01-18 | 2018-07-10 | 成都利亨聚氨酯新材料有限公司 | Polyurethane composition polyethers, hard polyurethane foam and preparation method thereof |
| CN109796750A (en) * | 2018-12-29 | 2019-05-24 | 广州市聚科聚氨酯有限公司 | A kind of polyurethane rigid foam combined polyether |
| CN110698714A (en) * | 2019-10-08 | 2020-01-17 | 长虹美菱股份有限公司 | Heat preservation foaming system based on heat preservation refrigerator |
| CN110819102A (en) * | 2019-11-07 | 2020-02-21 | 徐州飞云泡沫制品有限责任公司 | Antibacterial polyurethane foam board gives sound insulation |
| CN112979914A (en) * | 2021-03-11 | 2021-06-18 | 吉林省金越交通装备股份有限公司 | Graphite-filled high-efficiency flame-retardant high-resilience polyurethane sponge and preparation method thereof |
| CN117327251A (en) * | 2023-12-01 | 2024-01-02 | 山东一诺威聚氨酯股份有限公司 | High-strength flame-retardant polyurethane rigid foam and preparation method thereof |
| CN117467104A (en) * | 2023-12-08 | 2024-01-30 | 威海云山科技有限公司 | Homogeneous A-level hard polyurethane insulation board and preparation process thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1618834A (en) * | 2004-09-30 | 2005-05-25 | 青岛科技大学 | Preparation method of fire retardant high activity polymer polyether polyol and method for preparing high elastic resilience fire retardant golyurethane soft foam material therefrom |
| CN1626560A (en) * | 2003-12-12 | 2005-06-15 | 上海昊海化工有限公司 | Method for preparing isocyanurate foam in high flame retardant |
| WO2012163279A1 (en) * | 2011-05-31 | 2012-12-06 | Basf Se | Polyurethane rigid foams |
| CN103804621A (en) * | 2014-02-19 | 2014-05-21 | 哈尔滨工业大学 | Method for preparing intercalated graphite containing flame-retardant polyurethane foam |
| CN104558483A (en) * | 2015-02-04 | 2015-04-29 | 哈尔滨工业大学（威海） | Spraying polyurethane rigid foam and preparation method thereof |
-
2015
- 2015-06-03 CN CN201510300204.1A patent/CN104877102A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1626560A (en) * | 2003-12-12 | 2005-06-15 | 上海昊海化工有限公司 | Method for preparing isocyanurate foam in high flame retardant |
| CN1618834A (en) * | 2004-09-30 | 2005-05-25 | 青岛科技大学 | Preparation method of fire retardant high activity polymer polyether polyol and method for preparing high elastic resilience fire retardant golyurethane soft foam material therefrom |
| WO2012163279A1 (en) * | 2011-05-31 | 2012-12-06 | Basf Se | Polyurethane rigid foams |
| CN103804621A (en) * | 2014-02-19 | 2014-05-21 | 哈尔滨工业大学 | Method for preparing intercalated graphite containing flame-retardant polyurethane foam |
| CN104558483A (en) * | 2015-02-04 | 2015-04-29 | 哈尔滨工业大学（威海） | Spraying polyurethane rigid foam and preparation method thereof |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105218782A (en) * | 2015-09-22 | 2016-01-06 | 江苏中圣管道工程技术有限公司 | The preparation method that a kind of Modified by Expandable Graphite high flame-retardant polyurethane hard bubbles |
| CN105348470B (en) * | 2015-11-25 | 2018-05-01 | 山东一诺威新材料有限公司 | Low-density high fire-retardance continuous slab foamed plastics and preparation method thereof |
| CN105348470A (en) * | 2015-11-25 | 2016-02-24 | 山东一诺威新材料有限公司 | Foamed plastic for low-density and high-flame-retardant continuous slab and preparation method for foamed plastic |
| CN105820518A (en) * | 2015-11-30 | 2016-08-03 | 单成敏 | Preparation method for modified polyol with ultrahigh temperature resistance and high flame resistance |
| CN105566596A (en) * | 2015-12-30 | 2016-05-11 | 安徽安大华泰新材料有限公司 | Flame-retardant and water-resistant polyurethane elastomer and preparation method thereof |
| CN105601863A (en) * | 2015-12-30 | 2016-05-25 | 安徽安大华泰新材料有限公司 | Preparing method for heat-resistant and flame-retardant polyurethane elastomer |
| CN105924942A (en) * | 2016-04-27 | 2016-09-07 | 安徽广燕新材料科技有限责任公司 | High-strength and high-flame retardation polyurethane composite heat insulation plate |
| CN105924943A (en) * | 2016-04-27 | 2016-09-07 | 安徽广燕新材料科技有限责任公司 | High-flame retardation polyurethane composite heat insulation plate |
| CN105936664A (en) * | 2016-06-03 | 2016-09-14 | 日照易立保温材料科技有限公司 | GPIR high-performance heat insulation board and production technology thereof |
| CN107236445A (en) * | 2017-07-10 | 2017-10-10 | 江苏美鑫源绿色房屋有限公司 | A kind of fireproof coating and its application method for integrated house profile material |
| CN108264624A (en) * | 2018-01-18 | 2018-07-10 | 成都利亨聚氨酯新材料有限公司 | Polyurethane composition polyethers, hard polyurethane foam and preparation method thereof |
| CN109796750A (en) * | 2018-12-29 | 2019-05-24 | 广州市聚科聚氨酯有限公司 | A kind of polyurethane rigid foam combined polyether |
| CN110698714A (en) * | 2019-10-08 | 2020-01-17 | 长虹美菱股份有限公司 | Heat preservation foaming system based on heat preservation refrigerator |
| CN110819102A (en) * | 2019-11-07 | 2020-02-21 | 徐州飞云泡沫制品有限责任公司 | Antibacterial polyurethane foam board gives sound insulation |
| CN112979914A (en) * | 2021-03-11 | 2021-06-18 | 吉林省金越交通装备股份有限公司 | Graphite-filled high-efficiency flame-retardant high-resilience polyurethane sponge and preparation method thereof |
| CN117327251A (en) * | 2023-12-01 | 2024-01-02 | 山东一诺威聚氨酯股份有限公司 | High-strength flame-retardant polyurethane rigid foam and preparation method thereof |
| CN117327251B (en) * | 2023-12-01 | 2024-04-12 | 山东一诺威聚氨酯股份有限公司 | High-strength flame-retardant polyurethane rigid foam and preparation method thereof |
| CN117467104A (en) * | 2023-12-08 | 2024-01-30 | 威海云山科技有限公司 | Homogeneous A-level hard polyurethane insulation board and preparation process thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104877102A (en) | Flame-retardant rigid polyurethane foam heat insulation plate | |
| US6579911B1 (en) | Fire resistant styrene polymer foams with reduced brominated fire retardant | |
| CN104017154B (en) | Electric water heater combined polyether, urethane and feedstock composition and preparation method thereof | |
| CN102585148A (en) | Composition for preparing highly fire-resistant polyisocyanurate foam | |
| CN104847026B (en) | Basalt fiber cloth enhanced polyurethane hard foam composite heat-insulating board and manufacturing method thereof | |
| CN104628979A (en) | B1-grade flame-retardant polyurethane rigid foam used for continuous line production as well as preparation method and usage thereof | |
| CN102304237B (en) | Halogen-free smoke inhibition fire retardant | |
| CN102010587A (en) | Method for preparing novel flame-retardant flexible polyurethane foam and product thereof | |
| CN101508763B (en) | Spray finishing polyurethane rigid foam raw material and foam produced thereof | |
| CN101487299A (en) | Production method for multifunctional rigid foam polyurethane composite heat-conservation board | |
| Vitkauskienė et al. | Thermal properties of polyurethane-polyisocyanurate foams based on poly (ethylene terephthalate) waste | |
| CN101550241B (en) | Environment protection type high-efficiency multiple mixing aerating powder for PU rigid foam | |
| CN103739824A (en) | Polyurethane flame-retardant thermal-insulation material and preparation method thereof | |
| CN104130368A (en) | Flame-retardant polyurethane cast rigid foamed plastic sheet | |
| CN104558483A (en) | Spraying polyurethane rigid foam and preparation method thereof | |
| CN104829812A (en) | Flame-retardant hard polyurethane thermal-insulation foam material and preparation method thereof | |
| CN105859999A (en) | High-flame-retardation PIR-system polyurethane thermal-insulation material and preparation method thereof | |
| CN106750489A (en) | Foaming agent and hard polyurethane foam | |
| CN104774316A (en) | Polyurethane all-water foaming material for coal mine filling and preparation method thereof | |
| CN107312149A (en) | Polyurethane adiabatic heat-insulation foam material and preparation method thereof | |
| CN106700119A (en) | Foaming agent composition and polyurethane hard foam | |
| CN106167541B (en) | Continous way produces PIR bulk bubble combined polyether and its preparation method and application | |
| KR20130068781A (en) | Flame-retardant and eco-friendly expanded polyurethane composition | |
| CN105061715A (en) | HFC-245eb type combined polyether for polyurethane plastics for boards and preparation method of HFC-245eb type combined polyether | |
| WO2024011735A1 (en) | Spray-type environment-friendly polyurethane foam for heat preservation of modular container building |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150902 |
|
| WD01 | Invention patent application deemed withdrawn after publication |