CN111171270A - Flame-retardant polyurethane thermal insulation material prepared from crude glycerol bio-based polyol and preparation method thereof - Google Patents

Flame-retardant polyurethane thermal insulation material prepared from crude glycerol bio-based polyol and preparation method thereof Download PDF

Info

Publication number
CN111171270A
CN111171270A CN202010110160.7A CN202010110160A CN111171270A CN 111171270 A CN111171270 A CN 111171270A CN 202010110160 A CN202010110160 A CN 202010110160A CN 111171270 A CN111171270 A CN 111171270A
Authority
CN
China
Prior art keywords
bio
based polyol
flame retardant
flame
retardant polyurethane
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.)
Granted
Application number
CN202010110160.7A
Other languages
Chinese (zh)
Other versions
CN111171270B (en
Inventor
常春
刘利威
李攀
方书起
陈俊英
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhengzhou University
Original Assignee
Zhengzhou University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Zhengzhou University filed Critical Zhengzhou University
Priority to CN202010110160.7A priority Critical patent/CN111171270B/en
Publication of CN111171270A publication Critical patent/CN111171270A/en
Application granted granted Critical
Publication of CN111171270B publication Critical patent/CN111171270B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • C08G18/65—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
    • 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
    • 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
    • C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular 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
    • C08G18/48—Polyethers
    • C08G18/4829—Polyethers containing at least three hydroxy groups
    • 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
    • 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
    • C08J9/0014—Use of organic additives
    • C08J9/0038—Use of organic additives containing phosphorus
    • 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
    • C08J9/0066—Use of inorganic compounding ingredients
    • 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
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00—Manufacture of cellular products
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/08—Polyurethanes from polyethers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention belongs to the field of industrial and agricultural waste recycling, and particularly relates to a flame-retardant polyurethane thermal insulation material prepared from crude glycerol bio-based polyol, which is prepared by mixing bio-based polyol and polyether polyol in a mass ratio of 1: 2-5, and adding a flame retardant, a foaming agent, a catalyst mixture, silicone oil and PMDI; the bio-based polyol comprises the following components in percentage by mass, wherein the straw, the crude glycerol, the alkali catalyst and the fatty acid are = 1: 5-20: 0.05-2: 0.5-8. The invention takes crude glycerine and straw with wide sources as main raw materials, and adopts a simple and convenient process to synthesize low-cost bio-based polyol, thereby further preparing the polyurethane material with good flame-retardant and heat-insulating properties.

Description

Flame-retardant polyurethane thermal insulation material prepared from crude glycerol bio-based polyol and preparation method thereof
Technical Field
The invention belongs to the field of industrial and agricultural waste recycling, and particularly relates to a flame-retardant polyurethane thermal insulation material prepared from crude glycerol bio-based polyol and a preparation method thereof.
Background
Polyurethane is a high molecular material formed by polycondensation of polyol (polyether or polyester) and isocyanate. With the increasing emphasis on resources and environmental issues, in order to reduce the excessive use of fossil resources, the development of bio-based polyols that can replace petroleum-based polyols is receiving attention. The crude glycerol is used as a byproduct generated by processing the biomass energy, namely the biodiesel, and is a novel biomass resource with wide application potential. In addition, the straws are a kind of agricultural biomass resource with huge amount in China. The biomass resources are used for preparing the bio-based polyol, and have very important significance for the development and application of bio-based polyurethane materials.
Crude glycerol usually needs to be refined to be used as a raw material for polyol synthesis. Patent 10139205A discloses a method for preparing polyether polyol by reacting crude glycerin, a by-product of biodiesel, with an alkylene oxide, wherein the crude glycerin is refined and then synthesized with petroleum-based raw materials to obtain polyol. Patents CN101186559A and CN101186560A disclose methods for preparing polyols from straw, which use organic solvent (such as glycerol/ethylene glycol) and sulfuric acid as catalyst to liquefy straw to obtain polyols. The solvent used in the method has high price, and the used glycerin can be applied only after being refined. The invention provides a method for liquefying straws by directly using crude glycerol without refining as a solvent, and the liquefied product is further synthesized into bio-based polyol with industrial fatty acid and is applied to the preparation of flame-retardant polyurethane thermal insulation materials. The biomass raw materials required by the invention have wide sources, purification and refining are not required, the synthesis process is simple, the preparation cost of the bio-based polyol is effectively reduced, and the prepared flame-retardant polyurethane thermal insulation material has good performance.
Disclosure of Invention
The invention aims to provide a flame-retardant polyurethane thermal insulation material prepared from crude glycerol bio-based polyol, and a preparation method thereof. The method takes crude glycerol and straws with wide sources as main raw materials, synthesizes low-cost bio-based polyol by adopting a simple and convenient process, and further prepares the polyurethane material with good flame-retardant and heat-preservation properties, and for realizing the purpose, the invention adopts the following technical scheme:
a flame-retardant polyurethane thermal insulation material prepared from crude glycerol bio-based polyol is prepared by mixing bio-based polyol and polyether polyol in a mass ratio of 1: 2-5, and adding a flame retardant, a foaming agent, a catalyst mixture, silicone oil and PMDI; the bio-based polyol comprises the following components in percentage by mass, wherein the straw, the crude glycerol, the alkali catalyst and the fatty acid are = 1: 5-20: 0.05-2: 0.5-8.
The straw is wheat straw or corn straw.
The crude glycerol is unrefined crude glycerol generated in the production process of the biodiesel.
The alkali catalyst is sodium hydroxide or potassium hydroxide.
The fatty acid is an industrial-grade fatty acid.
The polyether polyol is polyether 4110.
The addition amounts of the flame retardant, the foaming agent, the catalyst mixture and the silicone oil are respectively 20-30%, 20-40%, 1-4% and 1-4% of the total mass of the polyol, and the addition amount of the PMDI is calculated according to an isocyanate index of 1.2.
The flame retardant is a mixture of dimethyl methyl phosphate and expanded graphite, and the mass ratio of the dimethyl methyl phosphate to the expanded graphite is 1: 0.5-2.
The foaming agent is HCFC-141b, the catalyst is composed of triethylene diamine and dibutyltin dilaurate in a mass ratio of 1: 1-3, the silicone oil is AK8805, and the PMDI is crude diphenylmethane-4, 4 diisocyanate.
A preparation method of a flame-retardant polyurethane thermal insulation material prepared from crude glycerol bio-based polyol comprises the following steps:
s1, uniformly mixing the crude glycerol and the straws according to the proportion, adding an alkali catalyst, heating and stirring at 180-240 ℃ for 1-5 hours, adding fatty acid, continuously reacting for 2-10 hours, and carrying out reduced pressure distillation to remove by-product water to obtain liquefied bio-based polyol;
s2, mixing the prepared bio-based polyol and polyether polyol in proportion, sequentially adding a flame retardant, a foaming agent, a catalyst mixture and silicone oil in proportion, uniformly mixing, adding PMDI, mixing and stirring, and then feeding into a mold for foaming to obtain the flame-retardant polyurethane heat-preservation foam.
The term "isocyanate index" in the present invention means: the ratio of the number of isocyanate equivalents to the number of polyol equivalents. The isocyanate equivalent number refers to the mole number of isocyanate groups in isocyanate, and the polyol equivalent number refers to the mole number of alcoholic hydroxyl groups of polyol.
Advantageous effects
(1) The invention uses crude glycerine, straw and industrial fatty acid as raw materials, has low price, can realize the complete substitution of petroleum-based raw materials, and prepares the all-bio-based polyol with flexibly adjustable hydroxyl value. (2) The crude glycerol of the invention does not need to be refined, can be used as a liquefier to be directly used for straw liquefaction, and does not need to be compounded with a petroleum-based solvent. (3) The preparation process of the bio-based polyol is simple, the reaction condition is mild, the reaction can be carried out under normal pressure, and the production cost is low. (4) The obtained bio-based flame-retardant polyurethane thermal insulation material has good performance and industrial application prospect.
Detailed Description
The present invention will be further described with reference to the following examples. The following examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.
Example 1:
mixing the crude glycerol and the wheat straw according to the mass ratio of 5: 1 proportion, then adding NaOH accounting for 10 percent of the mass of the crude glycerol, heating and stirring for 3 hours at 200 ℃, then adding fatty acid accounting for 10 percent of the mass of the crude glycerol for reaction for 3 hours, and distilling under reduced pressure to removeAfter removing the by-product water, the bio-based polyol with a hydroxyl value of 650 mgKOH/g and an acid value of 1.5% is prepared. Mixing bio-based polyol and polyether polyol according to a mass ratio of 1: 2, adding methyl dimethyl phosphate 6.7 percent of the mass of the polyhydric alcohol and expanded graphite 13.3 percent of the mass of the polyhydric alcohol, stirring uniformly, sequentially adding HCFC-141b 20 percent of the mass of the polyhydric alcohol, triethylene diamine 1 percent, dibutyltin dilaurate 1 percent and silicone oil AK8805, mixing uniformly, adding PMDI (isocyanate index of 1.2), mixing and stirring, and then placing into a mold for foaming to obtain the flame retardant polyurethane thermal insulation foam. The polyurethane has the compression strength of 182 kpa and the density of 42.3 kg/m when the polyurethane is placed for 24 hours3The thermal conductivity coefficient is 28.5 mW/(m ∙ K), the oxygen index is 26.0 percent, and the UL94 vertical burning grade is V-0 grade.
Example 2:
mixing the crude glycerol and the corn straws according to the mass ratio of 10: 1, adding KOH accounting for 7 percent of the mass of the crude glycerol, heating and stirring for 4 hours at 220 ℃, adding fatty acid accounting for 20 percent of the mass of the crude glycerol, reacting for 5 hours, and removing by-product water by reduced pressure distillation to obtain the bio-based polyol with the hydroxyl value of 580 mgKOH/g and the acid value of 1.8 percent. Mixing bio-based polyol and polyether polyol according to a mass ratio of 1: 3, adding methyl dimethyl phosphate 15 percent of the mass of the polyhydric alcohol and expanded graphite 15 percent of the mass of the polyhydric alcohol, stirring uniformly, sequentially adding HCFC-141b 20 percent of the mass of the polyhydric alcohol, triethylene diamine 1 percent, dibutyltin dilaurate 3 percent and silicone oil AK8805, mixing uniformly, adding PMDI (isocyanate index of 1.2), mixing and stirring, and then placing into a mold for foaming to obtain the flame retardant polyurethane thermal insulation foam. The polyurethane has a compressive strength of 160 kpa and a density of 41.1 kg/m when the polyurethane is placed for 24 hours3The thermal conductivity coefficient is 25.5 mW/(m ∙ K), the oxygen index is 26.2 percent, and the UL94 vertical burning grade is V-0 grade.
Example 3:
mixing the crude glycerol and the wheat straw according to a mass ratio of 15: 1, then adding NaOH accounting for 5 percent of the mass of the crude glycerol, heating and stirring for 5 hours at 190 ℃, then adding fatty acid accounting for 30 percent of the mass of the crude glycerol to react for 7 hours, and obtaining the bio-based polyol with the hydroxyl value of 524 mgKOH/g and the acid value of 1.6 percent after removing byproduct water through reduced pressure distillation. Mixing bio-based polyol and polyether polyol according to massThe ratio of 1: 4, adding 13.5 percent of methyl dimethyl phosphate and 6.5 percent of expanded graphite by mass of polyol, stirring uniformly, sequentially adding 30 percent of HCFC-141b, 1.5 percent of triethylene diamine, 2 percent of dibutyltin dilaurate and 4 percent of silicone oil AK8805 by mass of polyol, mixing uniformly, adding PMDI (isocyanate index of 1.2), mixing and stirring, and then placing into a mold for foaming to obtain the flame-retardant polyurethane thermal insulation foam. The polyurethane has a compressive strength of 158 kpa and a density of 38.6kg/m when the polyurethane is placed for 24 hours3The thermal conductivity coefficient is 24.9 mW/(m ∙ K), the oxygen index is 26.0 percent, and the UL94 vertical burning grade is V-0 grade.
Example 4:
mixing the crude glycerol and the wheat straw according to a mass ratio of 20: 1, adding KOH accounting for 3 percent of the mass of the crude glycerol, heating and stirring for 3 hours at 240 ℃, adding fatty acid accounting for 40 percent of the mass of the crude glycerol, reacting for 10 hours, and removing by-product water by reduced pressure distillation to obtain the bio-based polyol with the hydroxyl value of 453 mgKOH/g and the acid value of 1.8 percent. Mixing bio-based polyol and polyether polyol according to a mass ratio of 1: 5, adding 10% of methyl dimethyl phosphate and 10% of expanded graphite by mass of polyol, stirring uniformly, sequentially adding 40% of HCFC-141b, 1% of triethylene diamine, 1.5% of dibutyltin dilaurate and 2.5% of silicone oil AK8805 by mass of polyol, mixing uniformly, adding PMDI (isocyanate index of 1.2), mixing and stirring, and then placing into a mold for foaming to obtain the flame-retardant polyurethane thermal insulation foam. The polyurethane has the compression strength of 156 kpa and the density of 37.5 kg/m when the polyurethane is placed for 24 hours3The thermal conductivity coefficient is 27.4 mW/(m ∙ K), the oxygen index is 25.7 percent, and the UL94 vertical burning grade is V-0 grade.
Example 5:
mixing the crude glycerol and the wheat straw according to the mass ratio of 7.5: 1, then adding NaOH accounting for 5 percent of the mass of the crude glycerol, heating and stirring for 2 hours at 180 ℃, then adding fatty acid accounting for 15 percent of the mass of the crude glycerol to react for 4 hours, and obtaining the bio-based polyol with the hydroxyl value of 624 mgKOH/g and the acid value of 1.3 percent after removing byproduct water through reduced pressure distillation. Mixing bio-based polyol and polyether polyol according to a mass ratio of 1: 2.5 mixing, adding dimethyl methyl phosphate accounting for 8 percent of the mass of the polyhydric alcohol and expanded graphite accounting for 12 percent of the mass of the polyhydric alcohol, stirring uniformly, and then sequentially adding the polyhydric alcoholHCFC-141b accounting for 25% of the mass, triethylene diamine accounting for 2% of the mass, dibutyltin dilaurate accounting for 2% of the mass and silicone oil AK8805 accounting for 1.5% of the mass are uniformly mixed, PMDI (isocyanate index of 1.2) is added, and the mixture is mixed, stirred and injected into a mold for foaming to obtain the flame-retardant polyurethane heat-preservation foam. The polyurethane has a compressive strength of 192 kpa and a density of 40.3 kg/m when the polyurethane is placed for 24 hours3The thermal conductivity coefficient is 26.8 mW/(m ∙ K), the oxygen index is 25.9 percent, and the UL94 vertical burning grade is V-0 grade.
Example 6:
mixing the crude glycerol and the wheat straw according to the mass ratio of 12: 1, adding KOH accounting for 3.5 percent of the mass of the crude glycerol, heating and stirring for 4 hours at 200 ℃, adding fatty acid accounting for 35 percent of the mass of the crude glycerol, reacting for 6 hours, and removing by-product water by reduced pressure distillation to obtain the bio-based polyol with the hydroxyl value of 518 mgKOH/g and the acid value of 1.5 percent. Mixing bio-based polyol and polyether polyol according to a mass ratio of 1: 3.5, adding 10 percent by mass of methyl dimethyl phosphate and 20 percent by mass of expanded graphite into the mixture, stirring the mixture evenly, then sequentially adding 35 percent by mass of HCFC-141b, 1.5 percent by mass of triethylene diamine, 1.5 percent by mass of dibutyltin dilaurate and 3.5 percent by mass of silicone oil AK8805 into the mixture, mixing the mixture evenly, adding PMDI (isocyanate index of 1.2), mixing and stirring the mixture, and then feeding the mixture into a mold for foaming to obtain the flame retardant polyurethane thermal insulation foam. The polyurethane has the compression strength of 174 kpa and the density of 38.9kg/m when the polyurethane is placed for 24 hours3The thermal conductivity coefficient is 25.8 mW/(m ∙ K), the oxygen index is 26.0 percent, and the UL94 vertical burning grade is V-0 grade.

Claims (10)

1. A flame-retardant polyurethane thermal insulation material prepared from crude glycerol bio-based polyol is characterized in that the flame-retardant polyurethane thermal insulation material is prepared by mixing bio-based polyol and polyether polyol in a mass ratio of 1: 2-5, and adding a flame retardant, a foaming agent, a catalyst mixture, silicone oil and PMDI; the bio-based polyol comprises the following components in percentage by mass, wherein the straw, the crude glycerol, the alkali catalyst and the fatty acid are = 1: 5-20: 0.05-2: 0.5-8.
2. The flame retardant polyurethane insulation material prepared from crude glycerol bio-based polyol according to claim 1, wherein said straw is wheat straw or corn straw.
3. The flame retardant polyurethane insulation of claim 1, wherein the crude glycerin is unrefined crude glycerin produced in a biodiesel production process.
4. The flame retardant polyurethane insulation of claim 1, wherein the base catalyst is sodium hydroxide or potassium hydroxide.
5. The flame retardant polyurethane insulation of claim 1, wherein the fatty acid is a technical grade fatty acid.
6. The flame retardant polyurethane insulation of claim 1, wherein the polyether polyol is polyether 4110.
7. The flame retardant polyurethane insulation material prepared from crude glycerin bio-based polyol according to claim 1, wherein the flame retardant, the foaming agent, the catalyst mixture and the silicone oil are added in amounts of 20-30%, 20-40%, 1-4% and 1-4% of the total mass of the polyol, respectively, and the amount of the PMDI is calculated according to the isocyanate index of 1.2.
8. The flame retardant polyurethane thermal insulation material prepared from crude glycerol bio-based polyol according to claim 1, wherein the flame retardant is a mixture of dimethyl methyl phosphate and expanded graphite, and the mass ratio of the dimethyl methyl phosphate to the expanded graphite is 1: 0.5-2.
9. The flame retardant polyurethane insulation material prepared from crude glycerol bio-based polyol according to claim 1, wherein the foaming agent is HCFC-141b, the catalyst is composed of triethylene diamine and dibutyl tin dilaurate in a mass ratio of 1: 1-3, the silicone oil is AK8805, and the PMDI is crude diphenylmethane-4, 4 diisocyanate.
10. The method of claim 1, wherein the method comprises the steps of:
s1, uniformly mixing the crude glycerol and the straws according to the proportion, adding an alkali catalyst, heating and stirring at 180-240 ℃ for 1-5 hours, adding fatty acid, continuously reacting for 2-10 hours, and carrying out reduced pressure distillation to remove by-product water to obtain liquefied bio-based polyol;
s2, mixing the prepared bio-based polyol and polyether polyol in proportion, sequentially adding a flame retardant, a foaming agent, a catalyst mixture and silicone oil in proportion, uniformly mixing, adding PMDI, mixing and stirring, and then feeding into a mold for foaming to obtain the flame-retardant polyurethane heat-preservation foam.
CN202010110160.7A 2020-02-23 2020-02-23 Flame-retardant polyurethane thermal insulation material prepared from crude glycerol bio-based polyol and preparation method thereof Active CN111171270B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010110160.7A CN111171270B (en) 2020-02-23 2020-02-23 Flame-retardant polyurethane thermal insulation material prepared from crude glycerol bio-based polyol and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010110160.7A CN111171270B (en) 2020-02-23 2020-02-23 Flame-retardant polyurethane thermal insulation material prepared from crude glycerol bio-based polyol and preparation method thereof

Publications (2)

Publication Number Publication Date
CN111171270A true CN111171270A (en) 2020-05-19
CN111171270B CN111171270B (en) 2022-01-07

Family

ID=70619744

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010110160.7A Active CN111171270B (en) 2020-02-23 2020-02-23 Flame-retardant polyurethane thermal insulation material prepared from crude glycerol bio-based polyol and preparation method thereof

Country Status (1)

Country Link
CN (1) CN111171270B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111471153A (en) * 2020-05-13 2020-07-31 齐鲁工业大学 Method for preparing polyol and polyurethane damping foam thereof based on crude glycerol
CN112920377A (en) * 2021-01-29 2021-06-08 青岛海力威新材料科技股份有限公司 Polyurethane soft foam material for railway solidified track bed and preparation method thereof
CN113817124A (en) * 2021-10-08 2021-12-21 宏业生物科技股份有限公司 High-solid-content fly ash foam material and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102675851A (en) * 2012-05-28 2012-09-19 华峰集团有限公司 Liquid expanded graphite flame retardant and preparation method for flame-retardant polyurethane foam material

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102675851A (en) * 2012-05-28 2012-09-19 华峰集团有限公司 Liquid expanded graphite flame retardant and preparation method for flame-retardant polyurethane foam material

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HU S ETAL: "Polyols and polyurethane foams from base-catalyzed liquefaction of lignocellulosic biomass by crude glycerol: effects of crude glycerol impurities", 《INDUSTRIAL CROPS AND PRODUCTS》 *
HU S ETAL: "Production and characterization of biopolyols and polyurethane foams from crude glycerol based liquefaction of soybean straw", 《BIORESOURCE TECHNOLOGY》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111471153A (en) * 2020-05-13 2020-07-31 齐鲁工业大学 Method for preparing polyol and polyurethane damping foam thereof based on crude glycerol
CN111471153B (en) * 2020-05-13 2023-04-18 齐鲁工业大学 Method for preparing polyol and polyurethane damping foam thereof based on crude glycerol
CN112920377A (en) * 2021-01-29 2021-06-08 青岛海力威新材料科技股份有限公司 Polyurethane soft foam material for railway solidified track bed and preparation method thereof
CN113817124A (en) * 2021-10-08 2021-12-21 宏业生物科技股份有限公司 High-solid-content fly ash foam material and preparation method thereof

Also Published As

Publication number Publication date
CN111171270B (en) 2022-01-07

Similar Documents

Publication Publication Date Title
CN111171270B (en) Flame-retardant polyurethane thermal insulation material prepared from crude glycerol bio-based polyol and preparation method thereof
CN101362818B (en) Method for preparing biodegradable polyurethane rigid foam from bamboo waste liquefaction products
CN105175681A (en) Preparation method of starch-base rigid polyurethane foam thermal insulation material
CN111499861A (en) Method for preparing polyether polyol by liquefying agricultural wastes
CN102002157B (en) Aromatic polyester modified polyether polyol and preparation method thereof
CN109232847B (en) Flame-retardant polyurethane foam plastic and preparation method thereof
CN101704938A (en) Preparation method of bean pulp polyurethane foam plastics
CN110527136A (en) The method of waste and old hard polyurethane material hydro-thermal catalytic degradation preparation polyether polyol
CN103030965A (en) Method for preparing castor-oil-based flame-retardant polyurethane elastomer
CN104004175B (en) Flame retardant polyether polyol, combined polyether, polyurethane foam and preparation method thereof
CN112194784A (en) Preparation method of starch-based flame-retardant polyether polyol
CN108948067B (en) Silicon-containing flame-retardant tung oil-based polyol and preparation method and application thereof
KR20100081133A (en) Manufacturing method thereof of recycled polyol increased functionality and polyurethane using the same
CN112194785A (en) Method for preparing flame-retardant polyether polyol by liquefying bagasse
Li et al. Preparation of polyurethane foams based on liquefied corn stalk enzymatic hydrolysis lignin
CN102304223B (en) Plant oil polyether glycol and preparation method thereof
CN106380887A (en) Preparation method of lignin-base phenolic aldehyde molding compound
CN111171264A (en) Preparation method of lignin polyurethane
CN116396458A (en) High-strength, fireproof and anti-dripping lignin-based polyurethane foam and preparation method thereof
CN115785370A (en) Bio-based flame-retardant polyurethane and preparation method thereof
CN112679719B (en) Preparation method and application of hydroxymethyl melamine-ethylene oxide/propylene oxide polyether polyol
CN102093698B (en) Polyurethane foam plastic composition, polyurethane foam and reutilization method of lignin-containing material
CN112225866A (en) Bio-based polyurethane hard foam material and preparation method thereof
CN113929858A (en) Preparation method of bio-based polyurethane material
CN102993409B (en) Method for synthesizing heat-resistant polyurethane based on soybean oil

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant