CN116694064A - Preparation method of flame-retardant rigid polyurethane foam - Google Patents

Preparation method of flame-retardant rigid polyurethane foam Download PDF

Info

Publication number
CN116694064A
CN116694064A CN202310819047.XA CN202310819047A CN116694064A CN 116694064 A CN116694064 A CN 116694064A CN 202310819047 A CN202310819047 A CN 202310819047A CN 116694064 A CN116694064 A CN 116694064A
Authority
CN
China
Prior art keywords
parts
flame retardant
component
modified lignin
polyurethane foam
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202310819047.XA
Other languages
Chinese (zh)
Inventor
朱晓君
江平
张大华
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.)
XUCHUAN CHEMICAL (SUZHOU) CO Ltd
Original Assignee
XUCHUAN CHEMICAL (SUZHOU) CO Ltd
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 XUCHUAN CHEMICAL (SUZHOU) CO Ltd filed Critical XUCHUAN CHEMICAL (SUZHOU) CO Ltd
Priority to CN202310819047.XA priority Critical patent/CN116694064A/en
Publication of CN116694064A publication Critical patent/CN116694064A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C08J9/141—Hydrocarbons
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/10—Rigid foams
    • 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
    • C08J2375/06—Polyurethanes from polyesters
    • 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
    • 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
    • C08J2487/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • C08J2497/00—Characterised by the use of lignin-containing materials
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The application discloses a flame-retardant rigid polyurethane foam and a preparation method thereof, wherein the mass ratio of the flame-retardant rigid polyurethane foam to the preparation method is 100: the component A and the component B of (100-150) are prepared, wherein the component A comprises the following raw materials in parts by mass: 100 parts of polyol, 4-10 parts of modified lignin, 1-5 parts of metal organic framework material, 10-30 parts of flame retardant, 0.1-1.5 parts of water, 0.5-3 parts of polyurethane hard foam additive, 0.5-4 parts of catalyst and 10-25 parts of foaming agent; the component B is polymethylene polyphenyl isocyanate PM-400; the modified lignin is at least one of DOPO modified lignin, phosphorus oxychloride modified lignin and dichlorobenzyl phosphate modified lignin. According to the application, the modified lignin is compounded with the metal organic framework material and the phosphorus flame retardant, so that the flame retardance of the rigid foam material is improved through the synergistic effect of the modified lignin, the metal organic framework material and the phosphorus flame retardant, and the addition amount of the flame retardant is greatly reduced.

Description

Preparation method of flame-retardant rigid polyurethane foam
Technical Field
The application belongs to the technical field of polyurethane foam, and particularly relates to a preparation method of flame-retardant rigid polyurethane foam.
Background
Polyurethane is known as the fifth largest plastic, polyurethane foam being a common form of application. The polyurethane foam can be classified into soft foam, hard foam and semi-hard foam according to the raw materials selected in the preparation of the polyurethane foam. The hard polyurethane foam is prepared by reacting hard foam polyether polyol with polymeric MDI and is classified into hard foam polyether polyol, wood-like polyether, cyclopentane system hard foam polyether polyol, all-water polyether, flame-retardant polyether and the like; has the characteristics of water resistance, heat preservation, corrosion resistance, convenient construction, reliable quality and the like, the coating is widely applied to the fields of refrigerators, cold storages, spraying, solar energy, heating pipelines, buildings and the like.
The flame-retardant polyurethane hard foam is prepared by adding a certain amount of flame retardant into raw materials, so that the flame retardant property of the foam is effectively improved. Traditional halogen-containing flame retardants are now severely limited by their environmental hazards. While inorganic additive flame retardants can have a certain flame retardant effect in foams, excessive amounts can lead to attenuation of the mechanical properties of the foams. Therefore, the halogen-free flame retardant has wide application prospect in the future.
Lignin is one of the renewable resources and the paper industry can produce about 5000 ten thousand tons of industrial lignin per year. The molecular structure of lignin contains a large number of active groups such as phenolic hydroxyl groups, alcoholic hydroxyl groups and the like, and flame-retardant elements are introduced into the lignin structure by modifying the lignin, so that the lignin can be prepared into an environment-friendly halogen-free flame retardant, and the added value of the environment-friendly halogen-free flame retardant is improved. In addition, a certain amount of transition metal such as Co, fe, cr and the like is introduced into the flame-retardant system, so that the formation of catalytic carbon in the flame-retardant system can be realized, and a small amount of transition metal and a halogen-free flame retardant are compounded and added into foam, so that a synergistic effect can be realized, and the flame-retardant effect is further improved.
For example: patent document CN113621124a discloses a bio-based green environment-friendly flame-retardant memory cotton and a preparation method thereof, wherein propylene carbonate is utilized to modify liquefied lignin, and then lignin-based polyol is prepared for preparing the environment-friendly flame-retardant memory cotton. However, since lignin has a complicated molecular structure and a low yield when liquefied with an alcohol solution, a large amount of bio-based raw materials are consumed in the process of preparing modified lignin.
Patent document CN111454465a discloses a modified lignin and its application in flame-retardant flexible polyurethane foam composition, which is prepared by uniformly mixing oligomer glycol and dipropylene glycol, adding neopentyl glycol to dissolve completely, adding lignin, castor oil polyoxyethylene ether, a composite dispersant under stirring, and preparing modified lignin in a microwave reactor at 200-250W and 150+ -5 ℃ for 5 min. However, the improvement of the flame retardance by the modified lignin is still not ideal, and if the flame retardance of the flexible polyurethane foam is further improved, more flame retardant needs to be added, and the performance of the foam is affected by excessive flame retardant.
Patent document CN112266463a discloses a flame retardant lignin-based polyurethane rigid foam for automotive interiors and a preparation method thereof, the raw materials comprise: polyether polyol, polymeric MDI and flame retardant; wherein the flame retardant is a mixture of nano titanium dioxide and tri (2-hydroxypropyl) phosphate; the mass ratio of the polyether polyol to the mixture of lignin-based polyether polyol, polyether polyol 4110 and polyether polyol 403 is (5-7): (2-4): 1. however, the lignin used in this document does not introduce certain flame retardant elements, so lignin provides a carbon source in the flame retardant system, while the acid source needs tris (2-hydroxypropyl) phosphate to provide.
Disclosure of Invention
The application aims to provide a preparation method of flame-retardant rigid polyurethane foam, which aims to solve the problems that biomass lignin resources are rich, the utilization rate is low, a large amount of flame retardants are required to be added to the flame-retardant rigid polyurethane foam if the flame retardance of the foam is required to be improved in the prior art.
In order to achieve the above object, the technical scheme of the present application is as follows:
the application discloses a flame-retardant rigid polyurethane foam which is characterized by comprising the following components in percentage by mass: the component A and the component B of (100-150) are prepared, wherein the component A comprises the following raw materials in parts by mass: 100 parts of polyol, 4-10 parts of modified lignin, 1-5 parts of metal organic framework material, 10-30 parts of flame retardant, 0.1-1.5 parts of water, 0.5-3 parts of polyurethane hard foam additive, 0.5-4 parts of catalyst and 10-25 parts of foaming agent; the component B is polymethylene polyphenyl isocyanate PM-400;
preferably, the flame-retardant rigid polyurethane foam comprises the following components in percentage by mass: 145 and a component B, wherein the component A comprises the following raw materials in parts by mass: 100 parts of polyol, 8 parts of modified lignin, 2 parts of metal organic framework material, 23 parts of flame retardant, 0.7 part of water, 2.5 parts of polyurethane hard foam additive, 1.3 parts of catalyst and 16 parts of foaming agent; the component B is polymethylene polyphenyl isocyanate PM-400;
at least one of an aromatic polyester polyol and a polyether polyol having a number average molecular weight of 200 to 700, for example, a polymer of phthalic anhydride and diethylene glycol, a polymer of phthalic anhydride and terephthalic acid and diethylene glycol, and a polyether polyol 4110; preferably aromatic polyester polyols, the structure of which contains a large number of aromatic rings, have relatively high flame retardant properties;
the modified lignin is at least one of DOPO modified lignin, phosphorus oxychloride modified lignin and dichlorobenzyl phosphate modified lignin; preferably DOPO modified lignin, wherein DOPO (9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) is introduced into the structure, so that the flame retardant property is more excellent;
the metal organic framework Material (MOF) comprises at least one of zeolite imidazole framework-8 (ZIF-8, CAS number 59061-53-9), zeolite imidazole framework-67 (ZIF-67, CAS number 46201-07-4), UIO-66 (CAS number 1072413-89-8), preferably ZIF-8 and/or ZIF-67;
the flame retardant is tri (2-chloropropyl) phosphate (TCPP) and/or triethyl phosphate (TEP);
the polyurethane hard foam additive is an organosilicon copolymer (for example, michaelcone L-6900); the catalyst is one or more of amine catalysts and metal salt catalysts, such as PC8 (N, N-dimethylcyclohexylamine), K-15 (2-ethyl potassium caproate solution) and polyurethane catalyst A33 (solution prepared by 33% of triethylene diamine and 67% of dipropylene glycol); the foaming agent is one or more of alkane foaming agents n-pentane and isopentane.
The application relates to a preparation method of flame-retardant rigid polyurethane foam, which is characterized by comprising the following steps: s1, uniformly mixing the polyol, the modified lignin, the metal organic framework material, the flame retardant, the water, the polyurethane hard foam additive, the catalyst and the foaming agent to obtain a component A;
s2, pouring 100-150 parts of the component B into 100 parts of the component A, stirring at a high speed for 2-15S, pouring into a constant temperature container at 25-70 ℃, curing for 12-30 h after foam molding, and obtaining the rigid polyurethane foam.
Compared with the prior art, the application has the following beneficial effects:
according to the application, the halogen-free flame retardant modified lignin is compounded with the metal organic framework material and the phosphorus flame retardant, so that the flame retardance of the rigid foam material is improved through the synergistic effect of the halogen-free flame retardant modified lignin, the metal organic framework material and the phosphorus flame retardant, and the addition amount of the flame retardant is greatly reduced on the premise of achieving the same flame retardance effect; in addition, the utilization rate of lignin is improved, and the influence of the compressive strength of the rigid foam material is extremely small.
Detailed Description
The application will be further illustrated with reference to specific examples. It is understood that these examples are for the purpose of illustrating the present application only and are not to be construed as limiting the scope of the present application, and that various changes and modifications can be made therein by one skilled in the art after reading the disclosure of the present application, and that such equivalents are intended to fall within the scope of the present application as defined by the appended claims.
Example 1
And (3) a component A: 100 parts of phthalic anhydride polyester polyol (polymerized by phthalic anhydride with Mn=450, terephthalic acid and diethylene glycol), 6 parts of DOPO modified lignin, 1 part of metal organic framework material ZIF-8 and 1 part of ZIF-67, 15 parts of flame retardant TCPP and 8 parts of TEP, 0.7 part of water, 2.5 parts of polyurethane hard foam additive (L-6900), 0.5 part of tertiary amine catalyst (PC-8), 0.8 part of organic metal catalyst (K-15) and 16 parts of foaming agent (n-pentane), and uniformly dispersing by a high-speed dispersing machine after mixing;
145 parts of the B-component isocyanate PM400 is poured into 100 parts of the A-component, stirred at a high speed for 8 seconds, poured into a constant temperature container at 60 ℃, and cured for 24 hours after foam molding, so that the rigid polyurethane foam is obtained.
Example 2
And (3) a component A: 100 parts of phthalic anhydride polyester polyol (formed by polymerizing phthalic anhydride with diethylene glycol with Mn=600), 8 parts of DOPO modified lignin, 1.4 parts of metal organic framework material ZIF-8 and 1 part of ZIF-67, 8 parts of flame retardant TCPP and 13 parts of TEP, 0.7 part of water, 2.5 parts of polyurethane hard foam additive (L-6900), 0.5 part of tertiary amine catalyst (PC-8), 0.8 part of organic metal catalyst (K-15) and 16 parts of foaming agent (n-pentane), and uniformly dispersing by a high-speed dispersing machine after mixing;
145 parts of the B-component isocyanate PM400 is poured into 100 parts of the A-component, stirred at a high speed for 8 seconds, poured into a constant temperature container at 60 ℃, and cured for 24 hours after foam molding, so that the rigid polyurethane foam is obtained.
Example 3
And (3) a component A: 100 parts of phthalic anhydride polyester polyol (polymerized by phthalic anhydride with Mn=680, terephthalic acid and diethylene glycol), 8 parts of DOPO modified lignin, 1.4 parts of metal organic framework material ZIF-8, 10 parts of flame retardant TCPP, 10 parts of TEP, 0.7 part of water, 2.5 parts of polyurethane hard foam additive (L-6900), 0.7 part of tertiary amine catalyst (PC-8), 0.7 part of organic metal catalyst (K-15) and 16 parts of foaming agent (n-pentane), and uniformly dispersing by a high-speed dispersing machine after mixing;
145 parts of the B-component isocyanate PM400 is poured into 100 parts of the A-component, stirred at a high speed for 8 seconds, poured into a constant temperature container at 70 ℃, and cured for 18 hours after foam molding, thus obtaining the rigid polyurethane foam.
Example 4
And (3) a component A: 100 parts of polyether polyol 4110, 5 parts of DOPO modified lignin, 3 parts of metal organic framework material UIO-66, 10 parts of flame retardant TCPP, 17 parts of TEP, 0.7 part of water, 2.5 parts of polyurethane hard foam additive (L-6900), 0.5 part of tertiary amine catalyst (PC-8), 1 part of organic metal catalyst (K-15) and 13 parts of foaming agent (n-pentane), and uniformly dispersing by a high-speed dispersing machine after mixing;
135 parts of the B-component isocyanate PM400 is poured into 100 parts of the A-component, stirred at a high speed for 5 seconds, poured into a constant temperature container at 70 ℃, and cured for 20 hours after foam molding, thus obtaining the rigid polyurethane foam.
Example 5
And (3) a component A: 100 parts of phthalic anhydride polyester polyol (formed by polymerizing phthalic anhydride with diethylene glycol with Mn=300), 8 parts of DOPO modified lignin, 1.8 parts of metal organic framework material ZIF-8, 8 parts of flame retardant TCPP, 15 parts of TEP, 0.5 part of water, 2.5 parts of polyurethane hard foam additive (L-6900), 0.5 part of tertiary amine catalyst (PC-8), 0.7 part of organic metal catalyst (K-15) and 14 parts of foaming agent (n-pentane), and uniformly dispersing by a high-speed dispersing machine after mixing;
150 parts of the B-component isocyanate PM400 is poured into 100 parts of the A-component, stirred at a high speed for 8 seconds, poured into a constant temperature container at 60 ℃, and cured for 24 hours after foam molding, so that the rigid polyurethane foam is obtained.
Example 6
And (3) a component A: 100 parts of phthalic anhydride polyester polyol (polymerized by phthalic anhydride with Mn=350 and diethylene glycol), 5 parts of phosphorus oxychloride modified lignin, 2 parts of metal organic framework material ZIF-8, 15 parts of flame retardant TCPP, 9 parts of TEP, 0.7 part of water, 2.5 parts of polyurethane hard foam additive (L-6900), 0.5 part of tertiary amine catalyst (PC-8), 1 part of polyurethane catalyst A33 and 16 parts of foaming agent (isopentane) are mixed and then uniformly dispersed by a high-speed dispersing machine;
150 parts of the B-component isocyanate PM400 is poured into 100 parts of the A-component, stirred at a high speed for 10s, poured into a constant temperature container at 50 ℃, and subjected to foam molding after-ripening for 18 hours to obtain the rigid polyurethane foam.
Comparative example 1
Comparative example 1 is a comparative example of example 1, except that no modified lignin and metal framework material were added.
And (3) a component A: 100 parts of phthalic anhydride polyester polyol (polymerized by phthalic anhydride with Mn=450, terephthalic acid and diethylene glycol), 15 parts of flame retardant TCPP, 8 parts of TEP, 0.7 part of water, 2.5 parts of polyurethane hard foam additive (L-6900), 0.5 part of tertiary amine catalyst (PC-8), 0.8 part of organic metal catalyst (K-15) and 16 parts of foaming agent (n-pentane), and uniformly dispersing by a high-speed dispersing machine after mixing;
145 parts of the B-component isocyanate PM400 is poured into 100 parts of the A-component, stirred at a high speed for 8 seconds, poured into a constant temperature container at 60 ℃, and cured for 24 hours after foam molding, so that the rigid polyurethane foam is obtained.
Comparative example 2
Comparative example 2 is a comparative example of example 1, except that no metal matrix material was added.
And (3) a component A: 100 parts of phthalic anhydride polyester polyol (polymerized by phthalic anhydride with Mn=450, terephthalic acid and diethylene glycol), 6 parts of DOPO modified lignin, 15 parts of flame retardant TCPP, 8 parts of TEP, 0.7 part of water, 2.5 parts of polyurethane hard foam additive (L-6900), 0.5 part of tertiary amine catalyst (PC-8), 0.8 part of organic metal catalyst (K-15) and 16 parts of foaming agent (n-pentane), and uniformly dispersing by a high-speed dispersing machine after mixing;
145 parts of the B-component isocyanate PM400 is poured into 100 parts of the A-component, stirred at a high speed for 8 seconds, poured into a constant temperature container at 60 ℃, and cured for 24 hours after foam molding, so that the rigid polyurethane foam is obtained.
Comparative example 3
Comparative example 3 is the comparative example of example 1, except that no modified lignin was added.
And (3) a component A: 100 parts of phthalic anhydride polyester polyol (polymerized by phthalic anhydride with Mn=450, terephthalic acid and diethylene glycol), 1 part of metal organic framework material ZIF-8 and 1 part of ZIF-67, 15 parts of flame retardant TCPP and 8 parts of TEP, 0.7 part of water, 2.5 parts of polyurethane hard foam additive (L-6900), 0.5 part of tertiary amine catalyst (PC-8), 0.8 part of organic metal catalyst (K-15) and 16 parts of foaming agent (n-pentane), and uniformly dispersing by a high-speed dispersing machine after mixing;
100 parts of the B-component isocyanate PM400 is poured into 100 parts of the A-component, stirred at a high speed for 5 seconds, poured into a constant temperature container at 55 ℃, and cured for 18 hours after foam molding, so as to obtain the rigid polyurethane foam.
Comparative example 4
Comparative example 4 is the comparative example of example 1, except that a different modified lignin was added.
And (3) a component A: 100 parts of phthalic anhydride polyester polyol (polymerized by phthalic anhydride with Mn=450, terephthalic acid and diethylene glycol), 6 parts of aminated lignin, 1 part of metal organic framework material ZIF-8 and 1 part of ZIF-67, 15 parts of flame retardant TCPP and 8 parts of TEP, 0.7 part of water, 2.5 parts of polyurethane hard foam additive (L-6900), 0.5 part of tertiary amine catalyst (PC-8), 0.8 part of organic metal catalyst (K-15) and 16 parts of foaming agent (n-pentane), and uniformly dispersing by a high-speed dispersing machine after mixing;
150 parts of the B-component isocyanate PM400 is poured into 100 parts of the A-component, stirred at a high speed for 5 seconds, poured into a constant temperature container at 70 ℃, and cured for 20 hours after foam molding, thus obtaining the rigid polyurethane foam.
Comparative example 5
Comparative example 1 is a comparative example of example 1, except that no modified lignin and metal framework material were added.
And (3) a component A: 100 parts of phthalic anhydride with Mn=450, polyester polyol formed by polymerizing terephthalic acid and diethylene glycol, 33 parts of TCPP, 15 parts of TEP, 0.6 part of water, 2.5 parts of L-6900, 0.5 part of PC-8, 1.2 parts of K15 and 16 parts of foaming agent n-pentane, and uniformly dispersing by a high-speed dispersing machine after mixing;
125 parts of B-component isocyanate PM400 is poured into 100 parts of the A-component, stirred at high speed for 9s, poured into a constant temperature container at 70 ℃, and cured for 24 hours after foam molding, thus obtaining the rigid polyurethane foam.
The rigid polyurethane foams of examples 1 to 6 and comparative examples 1 to 5 were tested, the limiting oxygen index LOI of the foam was measured in accordance with the specification of GB/T2406.2 standard, and the compressive strength was measured in accordance with the specification of ASTM D1621 standard, and the results are shown in Table 1.
Table 1 results of performance tests of examples 1 to 6 and comparative examples 1 to 5
As can be seen from table 1, by compounding the transition metal-containing MOF material with the phosphorus flame retardant, which was modified with the halogen-free flame retardant, excellent flame retardant performance was achieved in the polyurethane rigid foam, and the impact on the compression strength performance of the foam was low. The lignin itself contains a large amount of aromatic rings, and after acid source phosphorus is introduced through modification, the modified lignin serves as a carbon source and an acid source during combustion, transition metal contained in the MOF material can promote the formation of a carbon layer, and in the flame-retardant process, the high-quality carbon layer can play a role in isolating a heat source and isolating combustible gas from entering the system, so that better flame retardance is achieved.
Compared with example 1, comparative example 1 has no modified lignin and metal skeleton material added, and the limiting oxygen index is drastically reduced when the same amount of flame retardant is added; comparative example 2 without addition of metal framework material and comparative example 3 without addition of modified lignin, no synergistic effect was formed, resulting in a decrease in limiting oxygen index; in comparative example 4, although aminated lignin was added, since the aminated lignin did not contain phosphorus, a synergistic effect could not be formed with the metal skeleton material and the phosphorus flame retardant, resulting in a decrease in limiting oxygen index; in comparative example 5, modified lignin and a metal skeleton material were not added, and in order to achieve a limiting oxygen index equivalent to that of example 1, the amount of the phosphorus flame retardant added was drastically increased, and the compressive strength of the polyurethane rigid foam was greatly lowered due to the excessive amount of the flame retardant.

Claims (8)

1. A flame retardant rigid polyurethane foam characterized by comprising the following components in mass ratio of 100: the component A and the component B of (100-150) are prepared, wherein the component A comprises the following raw materials in parts by mass: 100 parts of polyol, 4-10 parts of modified lignin, 1-5 parts of metal organic framework material, 10-30 parts of flame retardant, 0.1-1.5 parts of water, 0.5-3 parts of polyurethane hard foam additive, 0.5-4 parts of catalyst and 10-25 parts of foaming agent; the component B is polymethylene polyphenyl isocyanate PM-400; the modified lignin is at least one of DOPO modified lignin, phosphorus oxychloride modified lignin and dichlorobenzyl phosphate modified lignin.
2. The flame retardant rigid polyurethane foam according to claim 1, characterized by consisting of a mass ratio of 100:145 and a component B, wherein the component A comprises the following raw materials in parts by mass: 100 parts of polyol, 8 parts of modified lignin, 2 parts of metal organic framework material, 23 parts of flame retardant, 0.7 part of water, 2.5 parts of polyurethane hard foam additive, 1.3 parts of catalyst and 16 parts of foaming agent; the component B is polymethylphenyl isocyanate PM-400.
3. The flame retardant rigid polyurethane foam according to claim 1, wherein the polyol is at least one of an aromatic polyester polyol and a polyether polyol having a number average molecular weight of 200 to 700.
4. The flame retardant rigid polyurethane foam according to claim 3, wherein the polyol is at least one of a polymer of phthalic anhydride and diethylene glycol, a polymer of phthalic anhydride and terephthalic acid and diethylene glycol, and a polyether polyol 4110.
5. The flame retardant rigid polyurethane foam according to claim 1, wherein the metal organic framework material is at least one of zeolite imidazole framework-8, zeolite imidazole framework-67, UIO-66.
6. The flame retardant rigid polyurethane foam according to claim 1, wherein the flame retardant is tris (2-chloropropyl) phosphate and/or triethyl phosphate.
7. The flame retardant rigid polyurethane foam according to claim 1, wherein the polyurethane rigid foam additive is a silicone-based copolymer; the catalyst is one or more of amine catalysts and metal salt catalysts; the foaming agent is one or more of alkane foaming agents n-pentane and isopentane.
8. The method for preparing a flame retardant rigid polyurethane foam according to claim 1, comprising the steps of: s1, uniformly mixing the polyol, the modified lignin, the metal organic framework material, the flame retardant, the water, the polyurethane hard foam additive, the catalyst and the foaming agent to obtain a component A;
s2, pouring 100-150 parts of the component B into 100 parts of the component A, stirring at a high speed for 2-15S, pouring into a constant temperature container at 25-70 ℃, curing for 12-30 h after foam molding, and obtaining the rigid polyurethane foam.
CN202310819047.XA 2023-07-05 2023-07-05 Preparation method of flame-retardant rigid polyurethane foam Pending CN116694064A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310819047.XA CN116694064A (en) 2023-07-05 2023-07-05 Preparation method of flame-retardant rigid polyurethane foam

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310819047.XA CN116694064A (en) 2023-07-05 2023-07-05 Preparation method of flame-retardant rigid polyurethane foam

Publications (1)

Publication Number Publication Date
CN116694064A true CN116694064A (en) 2023-09-05

Family

ID=87843302

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310819047.XA Pending CN116694064A (en) 2023-07-05 2023-07-05 Preparation method of flame-retardant rigid polyurethane foam

Country Status (1)

Country Link
CN (1) CN116694064A (en)

Similar Documents

Publication Publication Date Title
CN103910850B (en) A kind of fire-retardant enhancing hard polyurethane foam of phosphatization lignin-base and preparation method thereof
CA2725334C (en) Process for preparing rigid polyisocyanurate foams using natural-oil polyols
CN101519485A (en) Wide temperature domain damping polyurethane micropore elastomer material and preparation method thereof
CN102030977A (en) Conjugate polyether, polyurethane raw material composition, polyurethane foams and applications thereof
CN101062997A (en) Vegetable oil polyether polyatomic alcohol duromer polyurethane foam plastic pouring material
KR20040082548A (en) Hard polyurethane foam composition and insulation for keeping coolness using it
EP3519492A1 (en) Composite flame retardant and polyurethane materials comprising the same
CN112552474B (en) Composite material for preparing low-density heat distribution pipeline by spray coating method
EP3710506A1 (en) Polyurethane foam composite panel
CN107298748B (en) Environment-friendly degradable flame-retardant polyurethane rapid packaging material and preparation method thereof
CN103817841B (en) Method for producing anti-static floor and anti-static wallboard using macromolecule chemical material
CN109942774B (en) Flame-retardant polyurethane foam with molecular chain hard segment
CN116694064A (en) Preparation method of flame-retardant rigid polyurethane foam
CN110951022A (en) Conjugate polyether for manufacturing glass fiber composite material and preparation method and application thereof
CN114316187B (en) Low-density low-smoke-toxicity high-flame-retardance polyurethane rigid foam and preparation method thereof
CN107474209B (en) Foam composition, polyurethane plastic, and preparation method and application of polyurethane plastic
CN112266463B (en) Flame-retardant lignin-based rigid polyurethane foam for automotive interior and preparation method thereof
CN110003420B (en) Polyisocyanurate foaming material and preparation method thereof
CN111454417A (en) Full-water flame-retardant modified spraying polyurethane foam and preparation method thereof
CN109593176B (en) Polyurethane foam prepared by using acid-terminated oligomer as foaming agent and preparation method thereof
CN113121775B (en) High-temperature-resistant light high-strength heat-insulating material and preparation method thereof
CN111116893B (en) Method for synthesizing flame-retardant melamine phenolic hard foam polyether polyol
CN115490915B (en) Flame retardant, preparation method thereof and rigid polyurethane foam
CN115093553B (en) Tetrabromobisphenol A polyether ester polyol, preparation method thereof, polyurethane rigid foam and preparation method thereof
CN114381111A (en) Pentane type multicomponent high-flame-retardant polyurethane composite phenolic aldehyde continuous plate composite material and preparation method thereof

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