CN106008890A - Preparation method of flame-retardant hard polyurethane foam - Google Patents

Preparation method of flame-retardant hard polyurethane foam Download PDF

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CN106008890A
CN106008890A CN201610469300.3A CN201610469300A CN106008890A CN 106008890 A CN106008890 A CN 106008890A CN 201610469300 A CN201610469300 A CN 201610469300A CN 106008890 A CN106008890 A CN 106008890A
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flame
gained
polyurethane foam
preparation
stirring
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仇颖超
薛培龙
许博伟
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
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    • 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
    • C08G18/4833—Polyethers containing oxyethylene units
    • 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
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6492—Lignin containing materials; Wood resins; Wood tars; Derivatives thereof
    • 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
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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    • 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
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
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    • C08K5/34922—Melamine; Derivatives thereof
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    • 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
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    • 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
    • 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
    • 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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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/322—Ammonium phosphate
    • C08K2003/323—Ammonium polyphosphate

Abstract

The invention relates to a preparation method of flame-retardant hard polyurethane foam and belongs to the technical field of material preparation. The preparation method comprises steps as follows: firstly, lignin in bamboo pulp is decomposed with xylanase contained in a yeast hypha suspension cultivated autonomously, and dry bleached bamboo chip powder is formed; then bamboo chips are liquefied under the condition of heating with the adoption of polyethylene glycol and glycerin as liquefiers and concentrated sulfuric acid as a catalyst, and an oily concentrated liquid is obtained; finally, N,N-dimethylformamide as a catalyst, silicone oil as a surfactant, dichlorofluoroethane as a foaming agent as well as melamine and ammonium polyphosphate as flame retardants are used for being matched with a benzene ring structure in the oily concentrated liquid, and the flame-retardant hard polyurethane foam can be prepared. The flame-retardant hard polyurethane foam prepared with the method has good flame retardance, and the oxygen index is 45-49; the flame retardance is stable instead of being reduced with time.

Description

A kind of preparation method of flame retarded rigid polyurethane foams
Technical field
The present invention relates to the preparation method of a kind of flame retarded rigid polyurethane foams, belong to technical field of material.
Background technology
Polyurethane is the abbreviation of polyurethanes, and foam plastics is one of principal item of polyurethane synthetic material.Polyurethane foam heat conductivity is low, only 0.022W/ (m K)～0.024W/ (m K), is that in current all insulation materials, heat conductivity is minimum.Due to the excellent properties of polyurethane foam, its range of application is quite varied, almost penetrates into each department of national economy, uses the most universal in departments such as building heat preservation, transport, cold preservation, thermal insulation especially, it has also become one of indispensable material.Polyurethane foam is combustible, and meeting fire can burn and decompose and be difficult to self-extinguishment, produces a large amount of toxic smog, brings difficulty to fire extinguishing.Many applications such as construction material, the insulation material etc. of polyurethane foam have flame-retardancy requirements, and therefore exploitation flame retardant grade polyurethane foam gets more and more people's extensive concerning.
The external polyol starting material for the hard polyurethane foams of building field mainly uses polyester polyol, simultaneously because the foam of the PEPA synthesis containing aromatic ring structure, its temperature tolerance and fire resistance are substantially better than polyether polyol, and the PEPA that therefore hard polyurethane foams used by building field uses is based on benzoic anhydride polyester polyol.The PEPA of domestic production at present is all two degree of functionality products, but for meeting the flame-retardancy requirements improved constantly, need to add substantial amounts of fire retardant with in its polyurethane foamed material prepared, the physical and mechanical properties the most often making material significantly declines, and prolongation over time, the fire retardant in material can occur to migrate so that the fire resistance of material declines.
Summary of the invention
nullThe technical problem to be solved: for adding substantial amounts of fire retardant to improve the fire resistance of hard polyurethane foams，And the physical and mechanical properties of material is significantly declined，And prolongation over time，Fire retardant in material can occur migrate so that material fire resistance decline problem，Provide a kind of first with xylanase contained in the yeast hyphal suspension cultivated voluntarily，Decompose and utilize the lignin in bamboo pulp，Formed and be dried bleaching bamboo powder，Recycling Polyethylene Glycol and glycerol are liquefier，Concentrated sulphuric acid is catalyst，In a heated condition，Make bamboo bits liquefaction，Obtain oily concentrated solution，Last with N,Dinethylformamide is catalyst，Silicone oil is surfactant，One fluorine dichloroethanes is foaming agent，Tripolycyanamide and APP are fire retardant，Coordinate the benzene ring structure in oily concentrated solution，The method that can be prepared into flame retarded rigid polyurethane foams，Flame retarded rigid polyurethane foams good flame retardation effect prepared by the present invention，And fire resistance will not prolongation over time and decline.
For solving above-mentioned technical problem, the present invention uses the technical scheme as described below to be:
(1) 2～4g glucoses are weighed successively, 1～3g peptone, 0.6～0.8g yeast extract, 15～20g agar are dissolved in 1.0～1.5L deionized waters, proceeded to again in pressure steam sterilizer, sterilizing 20～30min under the conditions of 0.09～0.11MPa, obtain culture medium, by 3～6% inoculation yeast bacterium of inoculum concentration, more postvaccinal culture medium is moved in constant-temperature table, 100～150r/min, after cultivating 2～4 days under the conditions of 30～35 DEG C, by 100～200mL deionized water drip washing media surface, collect leacheate, obtain hyphal suspension；
(2) 300～500g QINGZHU are taken, after manual cleaning remove impurity, it is placed in tissue pulverizer, grinding and sieving, collect 60～80 mesh bamboo powders, proceeding to gained bamboo powder to fill in the fermentation tank of 300～500mL deionized waters again, start agitator, setting speed is 300～500r/min, under stirring, add 60～80mL above-mentioned gained hyphal suspension, after reaction 6～8h, discharging, it is filtered to remove filtrate, gained filter cake is proceeded in 95～105 DEG C of baking ovens, dried 40～60min, bleaching bamboo powder must be dried；
(3) 400～600mL Polyethylene Glycol it are sequentially added in a kettle., 100～150mL glycerol and 15～20mL mass concentrations are 90～95% sulphuric acid, it is heated to 120～150 DEG C, set speed of agitator as 600～800r/min, under stirring, add 120～180g above-mentioned gained and be dried bleaching bamboo powder, after continuing constant temperature stirring reaction 1～3h, ON cycle cooling water, until material in reactor is cooled to room temperature, discharging, it is filtered to remove filtering residue, obtain filtrate, proceed to gained filtrate again fill in the rotary evaporator of dioxane aqueous solution that 200～300mL volumetric concentrations are 80%, with 70～80 DEG C of condition concentrated by rotary evaporations 3～5h, obtain oily concentrated solution；
(4) 150～180g above-mentioned gained oily concentrated solution and 2～5g diisocyanate are weighed successively, add in the batch mixer filling 10～20mL deionized waters, set speed of agitator as 600～800r/min, under stirring, it is sequentially added into 2～3gN, dinethylformamide, 2～5g silicone oil, 10～15g mono-fluorine dichloroethanes, 10～15g tripolycyanamide and 15～20g APPs, with 1600～2000r/min rotating speeds, stirring reaction is until there is milky white phenomenon, stop stirring, discharging, gained material is proceeded in mould, at room temperature natural foaming, curing and demolding i.e. obtains flame retarded rigid polyurethane foams.
Flame retarded rigid polyurethane foams prepared by the present invention is white, and heat conductivity is 0.023～0.029W/(m k), compressive strength 278～289kPa, hot strength is 250～265kPa, oxygen index (OI) is 45～49, and smoke density is 96～98Dm, and dimensional stability is 1.78～1.85%.
The present invention is compared with additive method, and Advantageous Effects is:
(1) the flame retarded rigid polyurethane foams good flame retardation effect that prepared by the present invention, oxygen index (OI) is 45～49；
(2) the flame retarded rigid polyurethane foams fire resistance that prepared by the present invention will not prolongation over time and decline, fire resistance is stable；
(3) preparation process of the present invention is simple, required low cost.
Detailed description of the invention
Weigh 2～4g glucoses the most successively, 1～3g peptone, 0.6～0.8g yeast extract, 15～20g agar are dissolved in 1.0～1.5L deionized waters, proceeded to again in pressure steam sterilizer, sterilizing 20～30min under the conditions of 0.09～0.11MPa, obtain culture medium, by 3～6% inoculation yeast bacterium of inoculum concentration, more postvaccinal culture medium is moved in constant-temperature table, 100～150r/min, after cultivating 2～4 days under the conditions of 30～35 DEG C, by 100～200mL deionized water drip washing media surface, collect leacheate, obtain hyphal suspension；Take 300～500g QINGZHU again, after manual cleaning remove impurity, it is placed in tissue pulverizer, grinding and sieving, collect 60～80 mesh bamboo powders, proceeding to gained bamboo powder to fill in the fermentation tank of 300～500mL deionized waters again, start agitator, setting speed is 300～500r/min, under stirring, add 60～80mL above-mentioned gained hyphal suspension, after reaction 6～8h, discharging, it is filtered to remove filtrate, gained filter cake is proceeded in 95～105 DEG C of baking ovens, dried 40～60min, bleaching bamboo powder must be dried；It is sequentially added into 400～600mL Polyethylene Glycol the most in a kettle., 100～150mL glycerol and 15～20mL mass concentrations are 90～95% sulphuric acid, it is heated to 120～150 DEG C, set speed of agitator as 600～800r/min, under stirring, add 120～180g above-mentioned gained and be dried bleaching bamboo powder, after continuing constant temperature stirring reaction 1～3h, ON cycle cooling water, until material in reactor is cooled to room temperature, discharging, it is filtered to remove filtering residue, obtain filtrate, proceed to gained filtrate again fill in the rotary evaporator of dioxane aqueous solution that 200～300mL volumetric concentrations are 80%, with 70～80 DEG C of condition concentrated by rotary evaporations 3～5h, obtain oily concentrated solution；Weigh 150～180g above-mentioned gained oily concentrated solution and 2～5g diisocyanate the most successively, add in the batch mixer filling 10～20mL deionized waters, set speed of agitator as 600～800r/min, under stirring, it is sequentially added into 2～3gN, dinethylformamide, 2～5g silicone oil, 10～15g mono-fluorine dichloroethanes, 10～15g tripolycyanamide and 15～20g APPs, with 1600～2000r/min rotating speeds, stirring reaction is until there is milky white phenomenon, stop stirring, discharging, gained material is proceeded in mould, at room temperature natural foaming, curing and demolding i.e. obtains flame retarded rigid polyurethane foams.
Example 1
Weigh 4g glucose, 3g peptone, 0.8g yeast extract the most successively, 20g agar is dissolved in 1.5L deionized water, then is proceeded in pressure steam sterilizer, sterilizing 30min under the conditions of 0.11MPa, obtain culture medium, by 6% inoculation yeast bacterium of inoculum concentration, more postvaccinal culture medium is moved in constant-temperature table, at 150r/min, after cultivating 4 days under the conditions of 35 DEG C, by 200mL deionized water drip washing media surface, collect leacheate, obtain hyphal suspension；Take 500g QINGZHU again, after manual cleaning remove impurity, be placed in tissue pulverizer, grinding and sieving, collects 80 mesh bamboo powders, then proceeds to fill in the fermentation tank of 500mL deionized water by gained bamboo powder, starting agitator, setting speed is 500r/min, under stirring, add 80mL above-mentioned gained hyphal suspension, after reaction 8h, discharging, it is filtered to remove filtrate, gained filter cake is proceeded in 105 DEG C of baking ovens, dried 60min, bleaching bamboo powder must be dried；It is sequentially added into 600mL Polyethylene Glycol the most in a kettle., 150mL glycerol and 20mL mass concentration are 95% sulphuric acid, it is heated to 150 DEG C, set speed of agitator as 800r/min, under stirring, add the above-mentioned gained of 180g and be dried bleaching bamboo powder, after continuing constant temperature stirring reaction 3h, ON cycle cooling water, until material in reactor is cooled to room temperature, discharging, it is filtered to remove filtering residue, obtain filtrate, proceed to fill in the rotary evaporator of the dioxane aqueous solution that 300mL volumetric concentration is 80% again by gained filtrate, with 80 DEG C of condition concentrated by rotary evaporations 5h, obtain oily concentrated solution；Weigh 180g above-mentioned gained oily concentrated solution and 5g diisocyanate the most successively, add in the batch mixer filling 20mL deionized water, set speed of agitator as 800r/min, under stirring, it is sequentially added into 3gN, dinethylformamide, 5g silicone oil, 15g mono-fluorine dichloroethanes, 15g tripolycyanamide and 20g APP, with 2000r/min rotating speed, stirring reaction, until there is milky white phenomenon, stops stirring, discharging, proceeding in mould by gained material, at room temperature natural foaming, curing and demolding i.e. obtains flame retarded rigid polyurethane foams.
After testing, flame retarded rigid polyurethane foams prepared by the present invention is white, and heat conductivity is 0.029W/(m k), compressive strength 289kPa, hot strength is 265kPa, and oxygen index (OI) is 49, and smoke density is 96Dm, and dimensional stability is 1.85%.
Example 2
Weigh 2g glucose, 1g peptone, 0.6g yeast extract the most successively, 15g agar is dissolved in 1.0L deionized water, then is proceeded in pressure steam sterilizer, sterilizing 20min under the conditions of 0.09MPa, obtain culture medium, by 3% inoculation yeast bacterium of inoculum concentration, more postvaccinal culture medium is moved in constant-temperature table, at 100r/min, after cultivating 2 days under the conditions of 30 DEG C, by 100mL deionized water drip washing media surface, collect leacheate, obtain hyphal suspension；Take 300g QINGZHU again, after manual cleaning remove impurity, be placed in tissue pulverizer, grinding and sieving, collects 60 mesh bamboo powders, then proceeds to fill in the fermentation tank of 300mL deionized water by gained bamboo powder, starting agitator, setting speed is 300r/min, under stirring, add 60mL above-mentioned gained hyphal suspension, after reaction 6h, discharging, it is filtered to remove filtrate, gained filter cake is proceeded in 95 DEG C of baking ovens, dried 40min, bleaching bamboo powder must be dried；It is sequentially added into 400mL Polyethylene Glycol the most in a kettle., 100mL glycerol and 15mL mass concentration are 90% sulphuric acid, it is heated to 120 DEG C, set speed of agitator as 600r/min, under stirring, add the above-mentioned gained of 120g and be dried bleaching bamboo powder, after continuing constant temperature stirring reaction 1h, ON cycle cooling water, until material in reactor is cooled to room temperature, discharging, it is filtered to remove filtering residue, obtain filtrate, proceed to fill in the rotary evaporator of the dioxane aqueous solution that 200mL volumetric concentration is 80% again by gained filtrate, with 70 DEG C of condition concentrated by rotary evaporations 3h, obtain oily concentrated solution；Weigh 150g above-mentioned gained oily concentrated solution and 2g diisocyanate the most successively, add in the batch mixer filling 10mL deionized water, set speed of agitator as 600r/min, under stirring, it is sequentially added into 2gN, dinethylformamide, 2g silicone oil, 10g mono-fluorine dichloroethanes, 10g tripolycyanamide and 15g APP, with 1600r/min rotating speed, stirring reaction, until there is milky white phenomenon, stops stirring, discharging, proceeding in mould by gained material, at room temperature natural foaming, curing and demolding i.e. obtains flame retarded rigid polyurethane foams.
After testing, flame retarded rigid polyurethane foams prepared by the present invention is white, and heat conductivity is 0.023W/(m k), compressive strength 278kPa, hot strength is 250kPa, and oxygen index (OI) is 45, and smoke density is 98Dm, and dimensional stability is 1.78%.
Example 3
Weigh 3g glucose, 2g peptone, 0.7g yeast extract the most successively, 17g agar is dissolved in 1.2L deionized water, then is proceeded in pressure steam sterilizer, sterilizing 25min under the conditions of 0.10MPa, obtain culture medium, by 5% inoculation yeast bacterium of inoculum concentration, more postvaccinal culture medium is moved in constant-temperature table, at 120r/min, after cultivating 3 days under the conditions of 32 DEG C, by 170mL deionized water drip washing media surface, collect leacheate, obtain hyphal suspension；Take 400g QINGZHU again, after manual cleaning remove impurity, be placed in tissue pulverizer, grinding and sieving, collects 70 mesh bamboo powders, then proceeds to fill in the fermentation tank of 400mL deionized water by gained bamboo powder, starting agitator, setting speed is 400r/min, under stirring, add 70mL above-mentioned gained hyphal suspension, after reaction 7h, discharging, it is filtered to remove filtrate, gained filter cake is proceeded in 100 DEG C of baking ovens, dried 50min, bleaching bamboo powder must be dried；It is sequentially added into 500mL Polyethylene Glycol the most in a kettle., 120mL glycerol and 17mL mass concentration are 92% sulphuric acid, it is heated to 130 DEG C, set speed of agitator as 700r/min, under stirring, add the above-mentioned gained of 150g and be dried bleaching bamboo powder, after continuing constant temperature stirring reaction 2h, ON cycle cooling water, until material in reactor is cooled to room temperature, discharging, it is filtered to remove filtering residue, obtain filtrate, proceed to fill in the rotary evaporator of the dioxane aqueous solution that 250mL volumetric concentration is 80% again by gained filtrate, with 75 DEG C of condition concentrated by rotary evaporations 4h, obtain oily concentrated solution；Weigh 150 ~ 180g above-mentioned gained oily concentrated solution and 3g diisocyanate the most successively, add in the batch mixer filling 15mL deionized water, set speed of agitator as 700r/min, under stirring, it is sequentially added into 2gN, dinethylformamide, 3g silicone oil, 12g mono-fluorine dichloroethanes, 12g tripolycyanamide and 17g APP, with 1700r/min rotating speed, stirring reaction, until there is milky white phenomenon, stops stirring, discharging, proceeding in mould by gained material, at room temperature natural foaming, curing and demolding i.e. obtains flame retarded rigid polyurethane foams.
Flame retarded rigid polyurethane foams prepared by the present invention is white, and heat conductivity is 0.026W/(m k), compressive strength 280kPa, hot strength is 260kPa, and oxygen index (OI) is 46, and smoke density is 97Dm, and dimensional stability is 1.82%.

Claims (1)

1. the preparation method of a flame retarded rigid polyurethane foams, it is characterised in that concrete preparation process is:
(1) 2～4g glucoses are weighed successively, 1～3g peptone, 0.6～0.8g yeast extract, 15～20g agar are dissolved in 1.0～1.5L deionized waters, proceeded to again in pressure steam sterilizer, sterilizing 20～30min under the conditions of 0.09～0.11MPa, obtain culture medium, by 3～6% inoculation yeast bacterium of inoculum concentration, more postvaccinal culture medium is moved in constant-temperature table, 100～150r/min, after cultivating 2～4 days under the conditions of 30～35 DEG C, by 100～200mL deionized water drip washing media surface, collect leacheate, obtain hyphal suspension；
(2) 300～500g QINGZHU are taken, after manual cleaning remove impurity, it is placed in tissue pulverizer, grinding and sieving, collect 60～80 mesh bamboo powders, proceeding to gained bamboo powder to fill in the fermentation tank of 300～500mL deionized waters again, start agitator, setting speed is 300～500r/min, under stirring, add 60～80mL above-mentioned gained hyphal suspension, after reaction 6～8h, discharging, it is filtered to remove filtrate, gained filter cake is proceeded in 95～105 DEG C of baking ovens, dried 40～60min, bleaching bamboo powder must be dried；
(3) 400～600mL Polyethylene Glycol it are sequentially added in a kettle., 100～150mL glycerol and 15～20mL mass concentrations are 90～95% sulphuric acid, it is heated to 120～150 DEG C, set speed of agitator as 600～800r/min, under stirring, add 120～180g above-mentioned gained and be dried bleaching bamboo powder, after continuing constant temperature stirring reaction 1～3h, ON cycle cooling water, until material in reactor is cooled to room temperature, discharging, it is filtered to remove filtering residue, obtain filtrate, proceed to gained filtrate again fill in the rotary evaporator of dioxane aqueous solution that 200～300mL volumetric concentrations are 80%, with 70～80 DEG C of condition concentrated by rotary evaporations 3～5h, obtain oily concentrated solution；
(4) 150～180g above-mentioned gained oily concentrated solution and 2～5g diisocyanate are weighed successively, add in the batch mixer filling 10～20mL deionized waters, set speed of agitator as 600～800r/min, under stirring, it is sequentially added into 2～3gN, dinethylformamide, 2～5g silicone oil, 10～15g mono-fluorine dichloroethanes, 10～15g tripolycyanamide and 15～20g APPs, with 1600～2000r/min rotating speeds, stirring reaction is until there is milky white phenomenon, stop stirring, discharging, gained material is proceeded in mould, at room temperature natural foaming, curing and demolding i.e. obtains flame retarded rigid polyurethane foams.
CN201610469300.3A 2016-06-25 2016-06-25 Preparation method of flame-retardant hard polyurethane foam Pending CN106008890A (en)

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