CN104262566A - Flame-retardant polyurethane hard foam containing nitrogen intrinsic structure and preparation method thereof - Google Patents
Flame-retardant polyurethane hard foam containing nitrogen intrinsic structure and preparation method thereof Download PDFInfo
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- CN104262566A CN104262566A CN201410454203.8A CN201410454203A CN104262566A CN 104262566 A CN104262566 A CN 104262566A CN 201410454203 A CN201410454203 A CN 201410454203A CN 104262566 A CN104262566 A CN 104262566A
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—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
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5054—Polyethers having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
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- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
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- C08G18/72—Polyisocyanates or polyisothiocyanates
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- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
- C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
- C08G65/263—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing heterocyclic amine groups
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- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—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 chemical blowing agent
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- 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
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- 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
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- C08J9/143—Halogen containing compounds
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- C08G2650/50—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing nitrogen, e.g. polyetheramines or Jeffamines(r)
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Abstract
The invention discloses a flame-retardant polyurethane hard foam containing nitrogen intrinsic structure and a preparation method thereof. The flame-retardant polyurethane hard foam containing nitrogen intrinsic structure is composed of a component A and a component B in a weight ratio of 1:(1-1.7). The component A is composed of the following components in parts by weight: 20-40 parts of flame-retardant polyether glycol containing nitrogen structure, 1-5 parts of foaming catalyst, 0.5-1.0 part of foam stabilizer, 1-3 parts of physical foaming agent and 1-3 parts of water. The component B is polyphenyl polymethylene polyisocyanate. The preparation method comprises the following steps: preparing flame-retardant polyether glycol containing nitrogen structure, preparing the component A, and finally, mixing and curing the component A and component B to obtain the flame-retardant polyurethane hard foam containing nitrogen intrinsic structure, which is in a uniform, compact and regular hexagonal foam structure. The density is 41.5-44.3 kg/m<3>, the compression strength is 0.18-0.22 MPa, and the limited oxygen index is 24.3-24.8%.
Description
Technical field
The present invention relates to anti-inflaming polyurethane hard foam of a kind of nitrogenous intrinsic structure and preparation method thereof, belong to flame-retardant high-molecular technical field.
Background technology
Hard polyurethane foam is called for short hard polyurethane foam, is by polyether glycol, polyester polyol or both composite uses, reacts prepare gained with polymeric MDI.Without the oxygen index of the hard polyurethane foam of fire-retardant finish about 18, belong to inflammable material.Carrying out fire-retardant finish to it mainly contains two kinds of methods at present: one is additional fire retardant method, as added the organic or inorganic compound containing the element such as phosphorus, chlorine, bromine, antimony, aluminium such as three (chloro isopropyl) phosphoric acid ester (TCPP), three (2-chloroethyl) phosphoric acid ester (TCEP), dimethyl methyl phosphonate (DMMP), trimeric cyanamide, ANTIMONY TRIOXIDE SB 203 99.8 PCT, aluminium hydroxide, but additional fire retardant method exists, and hard polyurethane foam life-time service easily moves, flame retardant effect declines and the shortcoming such as foam physics performance impairment; Another kind is structure flame-retarded technology, this method is incorporated on polyether segment or isocyanic ester by ignition-proof element (phosphorus, chlorine, bromine etc.) or fire-retardant group (phenyl ring, large heterocycle etc.) by chemical bond, its stability is better, not easily move, the structural flame retardant polyurethane lagging material mainly contained containing N, P and halogen (Cl and Br) supplied in the market, this kind of material has that price is high, combustion gases toxicity large more, the smog defect such as heavily, limits it to a great extent and applies.
Summary of the invention
The object of the invention is to cause fire-retardant not lasting, existing structure type polyurethane to hard bubble the more high deficiency of production cost to solve additive flame retardant hard polyurethane foam because fire retardant dialysis migration, thus provide a kind of low cost, the anti-inflaming polyurethane hard foam of the nitrogenous intrinsic structure of high flame retardant and preparation method thereof.
technical scheme of the present invention
An anti-inflaming polyurethane hard foam for nitrogenous intrinsic structure, is made up of component A and B component, by weight calculating, and component A: the weight ratio of B component is 1:1 ~ 1.7;
Wherein said component A, calculates by weight, its raw material composition and content as follows:
Containing the flame retardant polyether polyol 20 ~ 40 parts of N structure
Kicker 1 ~ 5 part
Suds-stabilizing agent 0.5 ~ 1.0 part
Pneumatogen 1 ~ 3 part
1 ~ 3 part, water
Described kicker is the mixture of one or more compositions in triethylene diamine, N, N-dimethyl cyclohexane, Tetramethyl Ethylene Diamine, dimethylethanolamine;
The mixture that described suds-stabilizing agent is silicone oil, silicon-carbon type stablizer or silicone oil and silicon-carbon type stablizer form;
Described pneumatogen is the one or two in HCFC-141b, pentamethylene, F-11, HFC-245fa
The mixture of composition more than kind;
The described flame retardant polyether polyol containing N structure, calculates by weight, its raw material composition and content as follows:
Phenol 5 ~ 20 parts
15 ~ 45 parts, formaldehyde
Basic catalyst 0.01 ~ 0.08 part
Trimeric cyanamide 5 ~ 15 parts
Initiator 2 ~ 5 parts altogether
Epoxy chloropropane 55 ~ 150 parts
Polymerizing catalyst 0.5 ~ 1.9 part;
Wherein said formaldehyde to be mass percent concentration be 35 ~ 40% formalin;
Described basic catalyst to be mass percent concentration be 20 ~ 40% baryta water,
The KOH aqueous solution that the NaOH aqueous solution that mass percent concentration is 10 ~ 50%, mass percent concentration are 10 ~ 50%, mass percent concentration be 5 ~ 25% ammoniacal liquor or mass percent concentration be 5 ~ 10% aqueous sodium carbonates;
Described common initiator is ethylene glycol, glycerol, BDO, trolamine, diethanolamine, sucrose or TriMethylolPropane(TMP);
Described polymerizing catalyst to be mass percent concentration be 10 ~ 50% the NaOH aqueous solution, mass percent concentration be 10 ~ 50% the KOH aqueous solution or boron trifluoride ethyl ether complex;
Described B component is polyphenyl polymethylene polyisocyanates (hereinafter referred to as PAPI).
The preparation method of the anti-inflaming polyurethane hard foam of above-mentioned a kind of nitrogenous intrinsic structure, specifically comprises following steps:
(1), containing the preparation of the flame retardant polyether polyol of N structure
By phenol heating and melting, then add basic catalyst wherein, after being warming up to 50 ~ 90 DEG C, add 50 ~ 90% of formaldehyde total weight parts, reaction 1 ~ 3 h, obtains the reaction solution containing resole;
Add the formaldehyde of trimeric cyanamide and surplus to gained containing in the reaction solution of resole, control temperature is 60 ~ 90 DEG C to carry out reacting to mixture clear, obtains the reaction solution containing methylolated melamine-resol;
Common initiator, polymerizing catalyst and epoxy chloropropane is added to containing in the reaction solution of methylolated melamine-resol of gained, stir and be heated to 70 ~ 100 DEG C, isothermal reaction 16 ~ 24 h, then be 100 ~ 130 DEG C by the reaction solution control temperature of gained, pressure carries out distillation 1 ~ 2 h with small molecules such as distilling off solvent for-0.1 MPa, the residue after distillation is the flame retardant polyether polyol containing N structure;
(2), the preparation of component A
In step (1) gained containing in N structure flame retardant polyether polyol, add kicker, suds-stabilizing agent, pneumatogen and water, after being uniformly mixed, obtain component A;
(3), by B component isocyanic ester join in the component A of step (2) gained, rapid stirring 5 ~ 20 s, pour in grinding tool and solidify 30 ~ 60 s, then continue solidification 48 h under room temperature, obtain the anti-inflaming polyurethane hard foam of nitrogenous intrinsic structure.
The anti-inflaming polyurethane hard foam of nitrogenous intrinsic structure prepared by aforesaid method, being 24.3 ~ 24.8% according to its limiting oxygen index(LOI) of GB/T 2406.2-2009 standard test, is 41.5 ~ 44.3 kg/m according to its density of GB/T6343-1995 standard test
3, be 0.18 ~ 0.22Mpa according to its compressive strength of GB/T 8813-2008 standard test, adopt Dutch FEI Co. Quanta200 FEG type sem observation, its have even compact, the foam structure of regular hexagonal.
Useful achievement of the present invention
In anti-inflaming polyurethane hard foam of nitrogenous intrinsic structure of the present invention and preparation method thereof, flame retardant polyether polyol containing N structure used, trimeric cyanamide structure containing rich nitrogen in its molecule segment, distil in thermal histories, volatilize, the thermo-negative reaction such as decomposition, discharge non-flammable gases, formed to expand at foam surface and intercept carbon-coating, and contain the resole structure of low incendivity and low smokiness, can give polyurethane rigid foam material better flame retardant properties thus, solve the problem of conventional urethane rigid foam material flame retardant properties difference.
Further, anti-inflaming polyurethane hard foam of nitrogenous intrinsic structure of the present invention and preparation method thereof, the anti-inflaming polyurethane hard foam of the nitrogenous intrinsic structure of gained have even compact, the foam structure of regular hexagonal, its oxygen index is 24.3 ~ 24.8%, and density is 41.5 ~ 44.3 kg/m
3, compressive strength is 0.18 ~ 0.22 Mpa.
Accompanying drawing explanation
The scanning electron microscope (SEM) photograph of the anti-inflaming polyurethane hard foam of the nitrogenous intrinsic structure of Fig. 1, embodiment 1 gained.
Embodiment
Also by reference to the accompanying drawings the present invention is described in further detail below by embodiment, but do not limit the present invention.
Various raw materials used in various embodiments of the present invention, are commercially available.
embodiment 1
An anti-inflaming polyurethane hard foam for nitrogenous intrinsic structure, is made up of component A and B component, by weight calculating, and component A: the weight ratio of B component is 1:1.5;
Wherein said component A, calculates by weight, its raw material composition and content as follows:
Containing the flame retardant polyether polyol 22.5 parts of N structure
Kicker 1.5 parts
Suds-stabilizing agent 0.8 part
Pneumatogen 2 parts
1.5 parts, water
Described kicker is triethylene diamine;
Described suds-stabilizing agent is silicone oil;
Described pneumatogen is HCFC-141b;
The described flame retardant polyether polyol containing N structure, calculates by weight, its raw material composition and content as follows:
Phenol 10.0 parts
18.0 parts, formaldehyde
Basic catalyst 0.01 part
Trimeric cyanamide 5.0 parts
Initiator 3.0 parts altogether
Epoxy chloropropane 100.0 parts
Polymerizing catalyst 1.0 parts;
Wherein said formaldehyde to be mass percent concentration be 37% formalin;
Described basic catalyst to be mass percent concentration be 15% the NaOH aqueous solution;
Described common initiator is glycerol;
Described polymerizing catalyst to be mass percent concentration be 30% the NaOH aqueous solution;
Described B component is polyphenyl polymethylene polyisocyanates.
The preparation method of the anti-inflaming polyurethane hard foam of above-mentioned a kind of nitrogenous intrinsic structure, specifically comprises following steps:
(1), containing the preparation of the flame retardant polyether polyol of N structure
By phenol heating and melting, then add basic catalyst wherein, after being warming up to 60 DEG C, add 90% of formaldehyde total weight parts, react 4 h, obtain the reaction solution containing resole;
Add the formaldehyde of trimeric cyanamide and surplus to gained containing in the reaction solution of resole, control temperature is 60 DEG C to carry out reacting to mixture clear, obtains the reaction solution containing methylolated melamine-resol;
Common initiator, polymerizing catalyst and epoxy chloropropane is added to containing in the reaction solution of methylolated melamine-resol of gained, stir and be heated to 80 DEG C, isothermal reaction 24 h, then be 120 DEG C by the reaction solution control temperature of gained, pressure carries out distillation 1.5 h with small molecules such as distilling off solvent for-0.1MPa, the residue after distillation is the flame retardant polyether polyol containing N structure;
Should containing the flame retardant polyether polyol of N structure after measured, its hydroxyl value is 138.3 mgKOH/g, and viscosity is 5866 mPa.s/25 DEG C;
(2), the preparation of component A
In step (1) gained containing in N structure flame retardant polyether polyol, add kicker, suds-stabilizing agent, pneumatogen and water, control rotating speed at 300 rmp, after stirring at room temperature 20 s mixes, obtain component A;
(3), by the B component of 1.5 parts join in the component A of step (2) gained of 1 part, rapid stirring 5 s, pours in grinding tool and solidifies 30 s, then continues solidification 48 h under room temperature, obtains the anti-inflaming polyurethane hard foam of nitrogenous intrinsic structure.
The anti-inflaming polyurethane hard foam of the nitrogenous intrinsic structure of above-mentioned gained, being 24.5% according to its limiting oxygen index(LOI) of GB/T 2406.2-2009 standard test, is 42.1 kg/m according to its density of GB/T6343-1995 standard test
3, be 0.20 Mpa according to its compressive strength of GB/T 8813-2008 standard test.
The anti-inflaming polyurethane hard foam of the nitrogenous intrinsic structure of above-mentioned gained adopts Dutch FEI Co. Quanta200 FEG type sem observation, and as shown in Figure 1, as can be seen from Figure 1, it has even compact, hexagonal foam structure to result.
embodiment 2
An anti-inflaming polyurethane hard foam for nitrogenous intrinsic structure, is made up of component A and B component, by weight calculating, and component A: the weight ratio of B component is 1:1.3;
Wherein said component A, calculates by weight, its raw material composition and content as follows:
Containing the flame retardant polyether polyol 22.5 parts of N structure
Kicker 1 part
Suds-stabilizing agent 0.9 part
Pneumatogen 2.5 parts
2.5 parts, water
Described kicker is N, N-dimethyl cyclohexane;
Described suds-stabilizing agent is silicon-carbon type stablizer;
Described pneumatogen is that HCFC-141b and pentamethylene calculate in mass ratio, i.e. HCFC-141b: pentamethylene is the mixture of 1:1.5 composition;
The described flame retardant polyether polyol containing N structure, calculates by weight, its raw material composition and content as follows:
Phenol 10.0 parts
18.0 parts, formaldehyde
Basic catalyst 0.01 part
Trimeric cyanamide 5.0 parts
Initiator 3.0 parts altogether
Epoxy chloropropane 100.0 parts
Polymerizing catalyst 1.0 parts;
Wherein said formaldehyde to be mass percent concentration be 37% formalin;
Described basic catalyst to be mass percent concentration be 15% the NaOH aqueous solution;
Described common initiator is glycerol;
Described polymerizing catalyst to be mass percent concentration be 30% NaOH;
Described B component is polyphenyl polymethylene polyisocyanates.
The preparation method of the anti-inflaming polyurethane hard foam of above-mentioned a kind of nitrogenous intrinsic structure, specifically comprises following steps:
(1), containing the preparation of the flame retardant polyether polyol of N structure
By phenol heating and melting, then add basic catalyst wherein, after being warming up to 60 DEG C, add 90% of formaldehyde total weight parts, react 4 h, obtain the reaction solution containing resole;
Add the formaldehyde of trimeric cyanamide and surplus to gained containing in the reaction solution of resole, control temperature is 60 DEG C to carry out reacting to mixture clear, obtains the reaction solution containing methylolated melamine-resol;
Common initiator, polymerizing catalyst and epoxy chloropropane is added to containing in the reaction solution of methylolated melamine-resol of gained, stir and be heated to 80 DEG C, isothermal reaction 24 h, then be 120 DEG C by the reaction solution control temperature of gained, pressure carries out distillation 1.5 h with small molecules such as distilling off solvent for-0.1MPa, the residue after distillation is the flame retardant polyether polyol containing N structure;
After measured, its hydroxyl value is 138.3 mgKOH/g to the flame retardant polyether polyol containing N structure of gained, and viscosity is 5866 mPa.s/25 DEG C.
(2), the preparation of component A
In step (1) gained containing in N structure flame retardant polyether polyol, add kicker, suds-stabilizing agent, pneumatogen and water, control rotating speed at 300 rmp, after stirring at room temperature 20 s mixes, obtain component A;
(3), by the B component of 1.3 parts join in the component A of step (2) gained of 1 part, rapid stirring 20 s, pours in grinding tool and solidifies 60 s, then continues solidification 48 h under room temperature, obtains the anti-inflaming polyurethane hard foam of nitrogenous intrinsic structure.
After measured, its limiting oxygen index(LOI) is 24.3% to the nitrogenous intrinsic structure anti-inflaming polyurethane hard foam of above-mentioned gained, density is 41.5 kg/m
3, compressive strength is 0.18 Mpa, has rule, fine and close hexagon foam structure.
embodiment 3
An anti-inflaming polyurethane hard foam for nitrogenous intrinsic structure, is made up of component A and B component, by weight calculating, and component A: the weight ratio of B component is 1:1.6;
Wherein said component A, calculates by weight, its raw material composition and content as follows:
Containing the flame retardant polyether polyol 22.5 parts of N structure
Kicker 1.2 parts
Suds-stabilizing agent 0.8 part
Pneumatogen 2 parts
1.5 parts, water
Described kicker is Tetramethyl Ethylene Diamine;
Described suds-stabilizing agent be silicone oil and silicon-carbon type stablizer in mass ratio, i.e. silicone oil: silicon-carbon type stablizer is the mixture of 1:1 composition;
Described pneumatogen is HFC-245fa;
The described flame retardant polyether polyol containing N structure, calculates by weight, its raw material composition and content as follows:
Phenol 10.0 parts
18.0 parts, formaldehyde
Basic catalyst 0.01 part
Trimeric cyanamide 5.0 parts
Initiator 3.0 parts altogether
Epoxy chloropropane 100.0 parts
Polymerizing catalyst 1.0 parts;
Wherein said formaldehyde to be mass percent concentration be 37% formalin;
Described basic catalyst to be mass percent concentration be 15% the NaOH aqueous solution;
Described common initiator is glycerol;
Described polymerizing catalyst to be mass percent concentration be 30% the NaOH aqueous solution;
Described B component is polyphenyl polymethylene polyisocyanates.
The preparation method of the anti-inflaming polyurethane hard foam of above-mentioned a kind of nitrogenous intrinsic structure, specifically comprises following steps:
(1), containing the preparation of the flame retardant polyether polyol of N structure
By phenol heating and melting, then add basic catalyst wherein, after being warming up to 60 DEG C, add 90% of formaldehyde total weight parts, react 4 h, obtain the reaction solution containing resole;
Add the formaldehyde of trimeric cyanamide and surplus to gained containing in the reaction solution of resole, control temperature is 60 DEG C to carry out reacting to mixture clear, obtains the reaction solution containing methylolated melamine-resol;
Common initiator, polymerizing catalyst and epoxy chloropropane is added to containing in the reaction solution of methylolated melamine-resol of gained, stir and be heated to 80 DEG C, isothermal reaction 24 h, then be 120 DEG C by the reaction solution control temperature of gained, pressure carries out distillation 1.5 h with small molecules such as distilling off solvent for-0.1MPa, the residue after distillation is the flame retardant polyether polyol containing N structure;
After measured, its hydroxyl value is 138.3 mgKOH/g to the flame retardant polyether polyol containing N structure of gained, and viscosity is 5866 mPa.s/25 DEG C;
(2), the preparation of component A
In step (1) gained containing in N structure flame retardant polyether polyol, add kicker, suds-stabilizing agent, pneumatogen and water, control rotating speed at 300 rmp, after stirring at room temperature 20 s mixes, obtain component A;
(3), the B component polyphenyl polymethylene polyisocyanates of 1.6 parts is joined in the component A of step (2) gained of 1 part, rapid stirring 10 s, pour in grinding tool and solidify 50 s, then under room temperature, continue solidification 48 h, obtain the anti-inflaming polyurethane hard foam of nitrogenous intrinsic structure.
After measured, its limiting oxygen index(LOI) is 24.5% to the anti-inflaming polyurethane hard foam of the nitrogenous intrinsic structure of above-mentioned gained, density is 42.7 kg/m
3, compressive strength is 0.21 Mpa, has even compact, polygonal foam structure.
embodiment 4
An anti-inflaming polyurethane hard foam for nitrogenous intrinsic structure, is made up of component A and B component, by weight calculating, and component A: the weight ratio of B component is 1:1.7;
Wherein said component A, calculates by weight, its raw material composition and content as follows:
Containing the flame retardant polyether polyol 22.5 parts of N structure
Kicker 2 parts
Suds-stabilizing agent 1.0 parts
Pneumatogen 2 parts
1 part, water
Described kicker is triethylene diamine and dimethylethanolamine is mixture that 1:1 forms in mass ratio;
Described suds-stabilizing agent is silicone oil;
Described pneumatogen is HCFC-141b and pentamethylene is mixture that 1:1 forms in mass ratio;
The described flame retardant polyether polyol containing N structure, calculates by weight, its raw material composition and content as follows:
Phenol 10.0 parts
18.0 parts, formaldehyde
Basic catalyst 0.01 part
Trimeric cyanamide 5.0 parts
Initiator 3.0 parts altogether
Epoxy chloropropane 100.0 parts
Polymerizing catalyst 1.0 parts;
Wherein said formaldehyde to be mass percent concentration be 37% formalin;
Described basic catalyst to be mass percent concentration be 15% the NaOH aqueous solution;
Described common initiator is glycerol;
Described polymerizing catalyst to be mass percent concentration be 30% the NaOH aqueous solution;
Described B component is polyphenyl polymethylene polyisocyanates.
The preparation method of the anti-inflaming polyurethane hard foam of above-mentioned a kind of nitrogenous intrinsic structure, specifically comprises following steps:
(1), containing the preparation of the flame retardant polyether polyol of N structure
By phenol heating and melting, then add basic catalyst wherein, after being warming up to 60 DEG C, add 90% of formaldehyde total weight parts, react 4 h, obtain the reaction solution containing resole;
Add the formaldehyde of trimeric cyanamide and surplus to gained containing in the reaction solution of resole, control temperature is 60 DEG C to carry out reacting to mixture clear, obtains the reaction solution containing methylolated melamine-resol;
Common initiator, polymerizing catalyst and epoxy chloropropane is added to containing in the reaction solution of methylolated melamine-resol of gained, stir and be heated to 80 DEG C, isothermal reaction 24 h, then be 120 DEG C by the reaction solution control temperature of gained, pressure carries out distillation 1.5h with small molecules such as distilling off solvent for-0.1MPa, the residue after distillation is the flame retardant polyether polyol containing N structure;
After measured, its hydroxyl value is 138.3 mgKOH/g to the flame retardant polyether polyol containing N structure of gained, and viscosity is 5866 mPa.s/25 DEG C;
(2), the preparation of component A
In step (1) gained containing in N structure flame retardant polyether polyol, add kicker, suds-stabilizing agent, pneumatogen and water, control rotating speed at 300 rmp, after stirring at room temperature 20 s mixes, obtain component A;
(3), by the B component of 1.7 parts join in the component A of step (2) gained of 1 part, rapid stirring 15 s, pours in grinding tool and solidifies 40 s, then continues solidification 48 h under room temperature, obtains the anti-inflaming polyurethane hard foam of nitrogenous intrinsic structure.
The anti-inflaming polyurethane hard foam of the nitrogenous intrinsic structure of above-mentioned gained, its limiting oxygen index(LOI) is 24.8%, density is 44.3 kg/m
3, compressive strength is 0.22 Mpa, abscess is fine and close, hexagonal structure.
In sum, the anti-inflaming polyurethane hard foam of nitrogenous intrinsic structure of the present invention, because the feature structure of trimeric cyanamide and phenolic aldehyde is introduced on pfpe molecule main chain by covalent linkage, so can be stable be present in hard bubble in do not move; Meanwhile, carbon, the nitrogen virtue heterocycle structure of trimeric cyanamide have good thermostability, and resol has low incendivity and high fixing carbon, and both actings in conjunction can give polyether glycol better flame retardant properties.Simple to operate and the low production cost of the method.The anti-inflaming polyurethane hard foam of the nitrogenous intrinsic structure of gained has even compact, polygonal foam structure, its limiting oxygen index(LOI) 24.3 ~ 24.8%, density 41.5 ~ 44.3kg/m
3, compressive strength 0.18 ~ 0.22Mpa.
Above said content be only the present invention conceive under basic explanation, and according to any equivalent transformation that technical scheme of the present invention is done, all should protection scope of the present invention be belonged to.
Claims (8)
1. an anti-inflaming polyurethane hard foam for nitrogenous intrinsic structure, it is characterized in that the anti-inflaming polyurethane hard foam of described nitrogenous intrinsic structure has even compact, regular hexagon foam structure, density is 41.5 ~ 44.3 kg/m
3, compressive strength is 0.18 ~ 0.22 Mpa, and limiting oxygen index(LOI) is 24.3 ~ 24.8%;
The anti-inflaming polyurethane hard foam of described nitrogenous intrinsic structure is made up of component A and B component, by weight calculating, and component A: the weight ratio of B component is 1:1 ~ 1.7;
Wherein said component A, calculates by weight, its raw material composition and content as follows:
Containing the flame retardant polyether polyol 20 ~ 40 parts of N structure
Kicker 1 ~ 5 part
Suds-stabilizing agent 0.5 ~ 1.0 part
Pneumatogen 1 ~ 3 part
1 ~ 3 part, water;
Wherein said kicker is the mixture of one or more compositions in triethylene diamine, N, N-dimethyl cyclohexane, Tetramethyl Ethylene Diamine, dimethylethanolamine;
The mixture that described suds-stabilizing agent is silicone oil, silicon-carbon type stablizer or silicone oil and silicon-carbon type stablizer form;
Described pneumatogen is the mixture of one or more compositions in HCFC-141b, pentamethylene, F-11, HFC-245fa;
The described flame retardant polyether polyol containing N structure, calculates by weight, its raw material composition and content as follows:
Phenol 5 ~ 20 parts
15 ~ 45 parts, formaldehyde
Basic catalyst 0.01 ~ 0.08 part
Trimeric cyanamide 5 ~ 15 parts
Initiator 2 ~ 5 parts altogether
Epoxy chloropropane 55 ~ 150 parts
Polymerizing catalyst 0.5 ~ 1.9 part;
Wherein said formaldehyde to be mass percent concentration be 35 ~ 40% formalin;
Described basic catalyst to be mass percent concentration be 20 ~ 40% baryta water, the mass percent concentration NaOH aqueous solution that is 10 ~ 50%, the mass percent concentration KOH aqueous solution that is 10 ~ 50%, mass percent concentration be 5 ~ 25% ammoniacal liquor or mass percent concentration be 5 ~ 10% aqueous sodium carbonates;
Described common initiator is ethylene glycol, glycerol, BDO, trolamine, diethanolamine, sucrose or TriMethylolPropane(TMP);
Described polymerizing catalyst to be mass percent concentration be 10 ~ 50% the NaOH aqueous solution, mass percent concentration be 10 ~ 50% the KOH aqueous solution or boron trifluoride ethyl ether complex;
Described B component is polyphenyl polymethylene polyisocyanates.
2. the anti-inflaming polyurethane hard foam of a kind of nitrogenous intrinsic structure as claimed in claim 1, is characterized in that:
Wherein said component A, calculates by weight, its raw material composition and content as follows:
Containing the flame retardant polyether polyol 22.5 parts of N structure
Kicker 1 ~ 2 part
Suds-stabilizing agent 0.8 ~ 1.0 part
Pneumatogen 2 ~ 2.5 parts
1 ~ 2.5 part, water.
3. the anti-inflaming polyurethane hard foam of a kind of nitrogenous intrinsic structure as claimed in claim 2, it is characterized in that in described component A containing the flame retardant polyether polyol of N structure, calculate by weight, its raw material composition and content as follows:
Phenol 10.0 parts
18.0 parts, formaldehyde
Basic catalyst 0.01 part
Trimeric cyanamide 5.0 parts
Initiator 3.0 parts altogether
Epoxy chloropropane 100.0 parts
Polymerizing catalyst 1.0 parts;
Wherein said formaldehyde to be mass percent concentration be 37% formalin;
Described basic catalyst to be mass percent concentration be 15% the NaOH aqueous solution;
Described common initiator is glycerol;
Described polymerizing catalyst to be mass percent concentration be 30% NaOH.
4. the anti-inflaming polyurethane hard foam of a kind of nitrogenous intrinsic structure as claimed in claim 3, is characterized in that the anti-inflaming polyurethane hard foam of described nitrogenous intrinsic structure, by weight calculating, and component A: the weight ratio of B component is 1:1.5;
Wherein said component A, calculates by weight, its raw material composition and content as follows:
Containing the flame retardant polyether polyol 22.5 parts of N structure
Kicker 1.5 parts
Suds-stabilizing agent 0.8 part
Pneumatogen 2 parts
1.5 parts, water
Described kicker is triethylene diamine;
Described suds-stabilizing agent is silicone oil;
Described pneumatogen is HCFC-141b.
5. the anti-inflaming polyurethane hard foam of a kind of nitrogenous intrinsic structure as claimed in claim 3, is characterized in that the anti-inflaming polyurethane hard foam of described nitrogenous intrinsic structure, by weight calculating, and component A: the weight ratio of B component is 1:1.3;
Wherein said component A, calculates by weight, its raw material composition and content as follows:
Containing the flame retardant polyether polyol 22.5 parts of N structure
Kicker 1 part
Suds-stabilizing agent 0.9 part
Pneumatogen 2.5 parts
2.5 parts, water
Described kicker is N, N-dimethyl cyclohexane;
Described suds-stabilizing agent is silicon-carbon type stablizer;
Described pneumatogen is that HCFC-141b and pentamethylene calculate in mass ratio, i.e. HCFC-141b: pentamethylene is the mixture of 1:1.5 composition.
6. the anti-inflaming polyurethane hard foam of a kind of nitrogenous intrinsic structure as claimed in claim 3, is characterized in that the anti-inflaming polyurethane hard foam of described nitrogenous intrinsic structure, by weight calculating, and component A: the weight ratio of B component is 1:1.6;
Wherein said component A, calculates by weight, its raw material composition and content as follows:
Containing the flame retardant polyether polyol 22.5 parts of N structure
Kicker 1.2 parts
Suds-stabilizing agent 0.8 part
Pneumatogen 2 parts
1.5 parts, water
Described kicker is Tetramethyl Ethylene Diamine;
Described suds-stabilizing agent be silicone oil and silicon-carbon type stablizer in mass ratio, i.e. silicone oil: silicon-carbon type stablizer is the mixture of 1:1 composition;
Described pneumatogen is HFC-245fa.
7. the anti-inflaming polyurethane hard foam of a kind of nitrogenous intrinsic structure as claimed in claim 3, is characterized in that the anti-inflaming polyurethane hard foam of described nitrogenous intrinsic structure, by weight calculating, and component A: the weight ratio of B component is 1:1.7;
Wherein said component A, calculates by weight, its raw material composition and content as follows:
Containing the flame retardant polyether polyol 22.5 parts of N structure
Kicker 2 parts
Suds-stabilizing agent 1.0 parts
Pneumatogen 2 parts
1 part, water
Described kicker is triethylene diamine and dimethylethanolamine is mixture that 1:1 forms in mass ratio;
Described suds-stabilizing agent is silicone oil;
Described pneumatogen is HCFC-141b and pentamethylene is mixture that 1:1 forms in mass ratio.
8. the preparation method of the anti-inflaming polyurethane hard foam of a kind of nitrogenous intrinsic structure as described in as arbitrary in claim 1-7, is characterized in that specifically comprising the steps:
(1), containing the preparation of the flame retardant polyether polyol of N structure
By phenol heating and melting, then add basic catalyst wherein, after being warming up to 50 ~ 90 DEG C, add 50 ~ 90% of formaldehyde total weight parts, reaction 1 ~ 4 h, obtains the reaction solution containing resole;
Add the formaldehyde of trimeric cyanamide and surplus to gained containing in the reaction solution of resole, control temperature is 60 ~ 90 DEG C to carry out reacting to mixture clear, obtains the reaction solution containing methylolated melamine-resol;
Common initiator, polymerizing catalyst and epoxy chloropropane is added to containing in the reaction solution of methylolated melamine-resol of gained, stir and be heated to 70 ~ 100 DEG C, isothermal reaction 16 ~ 24 h, then be 100 ~ 130 DEG C by the reaction solution control temperature of gained, pressure carries out distillation 1 ~ 2 h for-0.1MPa, the residue after distillation is the flame retardant polyether polyol containing N structure;
(2), the preparation of component A
In step (1) gained containing in N structure flame retardant polyether polyol, add kicker, suds-stabilizing agent, pneumatogen and water, after being uniformly mixed, obtain component A;
(3), by B component join in the component A of step (2) gained, rapid stirring 5 ~ 20 s, pour in grinding tool and solidify 30 ~ 60 s, then continue solidification 48 h under room temperature, obtain the anti-inflaming polyurethane hard foam of nitrogenous intrinsic structure.
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