CN114395108A - Flame-retardant bio-based polyurethane foam and preparation method thereof - Google Patents
Flame-retardant bio-based polyurethane foam and preparation method thereof Download PDFInfo
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Abstract
The invention discloses flame-retardant bio-based polyurethane foam which is prepared by mixing a component A and a component B, wherein the component A comprises the following raw materials in parts by weight: the component A comprises: 10-30 parts of poly (propylene carbonate) glycol, 50-90 parts of polyether polyol, 10-90 parts of cardanol-based polyol, 0.1-2 parts of a foaming catalyst, 0.1-1.5 parts of a reaction catalyst, 1-15 parts of a foaming agent, 0.5-5 parts of a foam stabilizer and 30-45 parts of a flame retardant; and B component: 100 portions and 400 portions of isocyanate; the weight ratio of the component A to the component B is 1: 1-1.5. The flame-retardant oil-absorbing material has excellent flame retardance, oil absorption and mechanical properties through molecular design and formula adjustment, and has important application value.
Description
Technical Field
The invention relates to the technical field of polyurethane foam, in particular to flame-retardant bio-based polyurethane foam and a preparation method thereof.
Background
The cardanol is used as a main component in the cashew nut shell liquid, and has rich sources and low price. The cardanol is a light yellow oily liquid at normal temperature, the benzene ring structure of the cardanol enables the cardanol to have the characteristics of aromatic compounds and high temperature resistance, and the meta-unsaturated long linear chain alkyl structure enables the cardanol to have the characteristics of aliphatic compounds, good flexibility, self-drying performance and the like. The cardanol derivative cardanol glycidyl ether is a reaction product of cardanol and epoxy chloropropane, is easy for chemical industrial modification, has good hydrophobicity and chemical resistance, and plays an important role in replacing petroleum-based products.
Polyurethane (PU) materials are becoming one of the most widely used polymer materials due to their good dimensional stability, thermal and acoustic insulation, low temperature resistance, oil stain resistance, and the like. Among a wide variety of polyurethane materials, polyurethane foam (PUF) has been widely used in real life due to its excellent heat insulation performance, water resistance, and high chemical stability. In the furniture industry, including upholstery, insulation and packaging, and automotive applications, including seating, bumpers and sound insulation. Such polymers are produced by the reaction of isocyanates and polyols, as well as other additives used to adjust the properties of the final foam product. However, most of these agents are petrochemical in origin, increasing the dependence on petroleum. Thus, environmental concerns and the need for sustainable technology have driven the production of polyurethane foams using renewable feedstocks.
In recent years, the event that oil enters the marine environment to cause serious marine environmental pollution frequently occurs, and leaked oil becomes one of the main types of marine pollution. The polyurethane foam has the advantages of large oil absorption, high oil absorption rate, easy recovery and the like, and is a method with development prospect.
Pure polyurethane foams present a serious fire hazard, their limiting oxygen index is usually only 17-18%, they are flammable products, and their large surface area and good breathability accelerate the spread of the fire on burning. Therefore, modifying polyurethane foams to improve their fire resistance has been a focus of recent research. While high flame retardant performance is generally difficult to achieve by using conventional flame retardants, in recent years, inorganic flame retardant additives such as aluminum hydroxide and the like have smoke suppression effect, are nonvolatile, nontoxic, low in price and free from the influence of water because they do not generate toxic gas in the combustion process, and have increasing importance in the industrial field.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides flame-retardant bio-based polyurethane foam and a preparation method thereof. The invention uses bio-based material as raw material, and introduces CO2And the polypropylene carbonate glycol prepared by burning propylene oxide develops the flame-retardant bio-based polyurethane foam with excellent performance.
The technical scheme of the invention is as follows:
the flame-retardant bio-based polyurethane foam is prepared by mixing a component A and a component B, and comprises the following raw materials in parts by weight:
the component A comprises:
the weight ratio of the component A to the component B is 1: 1-1.5.
The hydroxyl value of the polypropylene carbonate glycol is 56 +/-2 mg KOH/g, and the molecular weight is 2000.
Preferably, the poly (propylene carbonate) diol is one or more of PPC-2A-1 (hydroxyl value is 56 +/-2 mg KOH/g, viscosity is 4000-6000 mPa.s/40 ℃, molecular weight is 2000) and PPC-2B-1 (hydroxyl value is 56 +/-2 mg KOH/g, viscosity is 1000-2000 mPa.s/40 ℃, molecular weight is 2000) in the Xinning chemical industry.
The polyether polyol is one or more of Donald R4110 (hydroxyl value of 420-460mg KOH/g), Donald R4040(380-420mg KOH/g) and Donol R8238(385-405 mg KOH/g) produced by Shanghai Dongdong chemical Co., Ltd.
The preparation method of the cardanol-based polyol comprises the following steps: mixing cardanol glycidyl ether with diethanol amine, stirring and reacting for 8-48h at 40-80 ℃, and cooling to room temperature after the reaction is finished to obtain cardanol polyol. The molar ratio of the cardanol glycidyl ether to the diethanolamine is 1: 0.5-3.
The foaming catalyst is one or more of N, N-dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, N-ethylmorpholine, N '-diethylpiperazine, triethanolamine, pyridine, N' -dimethylpyridine and triethylene diamine;
the reaction catalyst is one or more of dibutyl tin dilaurate, bis-dimethylaminoethyl ether, pentamethyl diethylenetriamine and dimethyl cyclohexylamine;
the foaming agent is one of n-pentane, water and 141 b;
the foam stabilizer is one or more of BD-3086, PU-1254, PU-1257, DC-193, DC-200 and CGY-1.
The flame retardant is a mixture of trichloroethyl phosphate (TCCP), aluminum hydroxide and phytate aqueous solution; wherein the mass ratio of the trichloroethyl phosphate (TCCP), the aluminum hydroxide and the phytate aqueous solution is 1:1: 1-2.
The preparation method of the phytate aqueous solution comprises the following steps:
uniformly mixing 70 wt% of phytic acid aqueous solution with a neutralizer, stirring and reacting for 1h at room temperature, heating to 30-60 ℃, and continuing to react for 2-4 h; after the reaction is finished, cooling to room temperature to obtain the aqueous solution of the phytate.
Preferably, the neutralizing agent is one or more of triethylamine, diethylamine, diethanolamine and urea; the mol ratio of the phytic acid to the neutralizer is 1: 1-12.
The isocyanate is one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and polymethylene polyaryl isocyanate.
A method for preparing the flame retardant bio-based polyurethane foam, the method comprising the steps of: the raw materials are counted by weight;
(1) mixing 10-30 parts of polypropylene carbonate glycol, 50-90 parts of polyether polyol, 10-90 parts of cardanol-based polyol, 0.1-2 parts of foaming catalyst, 0.1-1.5 parts of reaction catalyst, 1-15 parts of foaming agent, 0.5-5 parts of foam stabilizer and 30-45 parts of flame retardant, stirring at a high speed and dispersing uniformly to obtain a component A;
(2) accurately weighing 100-400 parts of isocyanate as a component B;
(3) adding the component B into the component A at 1500 rpm-; standing at room temperature for foaming for 2-5h, and aging at 50-80 deg.C for 24-48 h.
The beneficial technical effects of the invention are as follows:
the poly (propylene carbonate) diol adopted by the invention is non-crystalline polyol, contains a large amount of ether bonds and carbonate bonds, has high molecular cohesive energy, and the prepared polyurethane material has high strength, good water resistance and good wear resistance, and the hydroxyl in the molecular structure is secondary hydroxyl, has weaker reaction activity than primary hydroxyl, is mixed with other alcohols with stronger activity, can regulate and control the reaction activity of the whole formula, and regulates and controls the mechanical property of polyurethane foam.
The cardanol-based polyol is prepared by taking a bio-based material as a main raw material, so that the raw material source of the polyol is widened, and the problem of overuse of petrochemical resources is solved to a certain extent. In addition, the reaction condition is mild, one-step reaction is complete, post-treatment and waste water and waste residues are avoided, and the method is simple and easy to implement.
The flame retardant compounded with the phytate solution has good compatibility in a system, and can further improve the content of the bio-based and the flame retardance of polyurethane foam.
The flame-retardant oil-absorbing material has excellent flame retardance, oil absorption and mechanical properties through molecular design and formula adjustment, and has important application value.
Drawings
FIG. 1 is a schematic diagram of a synthetic reaction mechanism of cardanol-based polyol according to the present invention;
FIG. 2 is an infrared spectrum of cardanol-based polyol obtained in example 1;
fig. 3 is a nuclear magnetic spectrum of cardanol-based polyol obtained in example 1.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples.
Example 1
Referring to fig. 1, a preparation method of cardanol-based polyol includes the following steps:
cardanol-based glycidyl ether (PLR-601) (35.7g, 0.1mol) and Diethanolamine (DEA) (10.5g, 0.1mol) were added to a flask equipped with a stirrer, a reflux condenser and a thermometer, the reaction mass was stirred at 70 ℃ for 8h, and after the reaction was completed, it was cooled to room temperature to obtain cardanol-based polyol (PLR-DEA).
The obtained cardanol-based polyol (PLR-DEA) has infrared and nuclear magnetic spectra shown in FIGS. 2 and 3, respectively, and it can be seen from FIG. 2 that the infrared spectrum of PLR-DEA is 3330cm-1The characteristic peak of the stretching vibration of the hydroxyl appears, and the PLR-601 is originally positioned at 908cm-1The disappearance of the stretching vibration peak of the epoxy group confirms the successful progress of the reaction. As can be seen from fig. 3, in the nuclear magnetic hydrogen spectra of PLR-601 and PLR-DEA, δ 6.6 to 7.2 is attributed to the proton absorption peak on the aromatic ring, PLR-DEA is at the proton absorption peak where a hydroxyl group appears at δ 4.8 and 4.3, and the ratio to the proton absorption peak area on the aromatic ring is 4: 1 and 2: 1, successful progress of the reaction, successful preparation of PLR-DEA.
Example 2
Referring to fig. 1, a preparation method of cardanol-based polyol includes the following steps:
cardanol-based glycidyl ether (PLR-601) (35.7g, 0.1mol) and Diethanolamine (DEA) (21.0g, 0.2mol) were added to a flask equipped with a stirrer, a reflux condenser and a thermometer, the reaction mass was stirred at 80 ℃ for 8h, and after the reaction was completed, it was cooled to room temperature to obtain cardanol-based polyol (PLR-DEA).
Example 3
Referring to fig. 1, a preparation method of cardanol-based polyol includes the following steps:
cardanol-based glycidyl ether (PLR-601) (35.7g, 0.1mol) and Diethanolamine (DEA) (5.25g, 0.05mol) were added to a flask equipped with a stirrer, a reflux condenser and a thermometer, the reaction mass was stirred at 80 ℃ for 8h, and after the reaction was completed, it was cooled to room temperature to obtain cardanol-based polyol (PLR-DEA).
Example 4
A method of preparing a flame retardant bio-based polyurethane foam, the method comprising the steps of: the raw materials are counted by weight;
(1) mixing 10 parts of polypropylene carbonate glycol PPC-2A-1, 50 parts of polyether polyol Donol R4110, 30 parts of cardanol-based polyol prepared in example 1, 2 parts of foaming catalyst triethylene diamine, 0.5 part of reaction catalyst dibutyl tin dilaurate, 10 parts of foaming agent n-pentane, 1 part of foam stabilizer DC-193 and 30 parts of flame retardant (10 parts of TCCP, 10 parts of aluminum hydroxide and 10 parts of phytate aqueous solution), stirring and dispersing at 1000rpm for 0.5h, and uniformly dispersing to obtain a component A;
the preparation method of the phytate aqueous solution comprises the following steps: uniformly mixing 10g of 70 wt% phytic acid aqueous solution and 7.07g of triethylamine, stirring at room temperature for reaction for 1 hour, heating to 50 ℃, and continuing to react for 2 hours; after the reaction is finished, cooling to room temperature to obtain the aqueous solution of the phytate.
(2) Accurately weighing 200 parts of toluene isocyanate TDI as a component B;
(3) adding the component B into the component A at 1000rpm, and stopping stirring after continuously stirring for 0.5h at the rotating speed of 1000 rpm; standing at room temperature for foaming for 2h, and aging at 80 deg.C for 24 h.
Example 5
A method of preparing a flame retardant bio-based polyurethane foam, the method comprising the steps of: the raw materials are counted by weight;
(1) mixing 10 parts of polypropylene carbonate glycol PPC-2A-1, 50 parts of polyether polyol Donol R4110, 60 parts of cardanol-based polyol prepared in example 1, 2 parts of foaming catalyst triethylene diamine, 0.5 part of reaction catalyst dibutyl tin dilaurate, 10 parts of foaming agent n-pentane, 1 part of foam stabilizer DC-193 and 30 parts of flame retardant (10 parts of TCCP, 10 parts of aluminum hydroxide and 10 parts of phytate aqueous solution), stirring and dispersing at 1000rpm for 0.5h, and uniformly dispersing to obtain a component A;
the preparation method of the phytate aqueous solution comprises the following steps: uniformly mixing 10g of 70 wt% phytic acid aqueous solution and 7.07g of triethylamine, stirring at room temperature for reaction for 1 hour, heating to 50 ℃, and continuing to react for 2 hours; after the reaction is finished, cooling to room temperature to obtain the aqueous solution of the phytate.
(2) Accurately weighing 200 parts of toluene isocyanate TDI as a component B;
(3) adding the component B into the component A at 1000rpm, and stopping stirring after continuously stirring for 0.5h at the rotating speed of 1000 rpm; standing at room temperature for foaming for 2h, and aging at 80 deg.C for 24 h.
Example 6
A method of preparing a flame retardant bio-based polyurethane foam, the method comprising the steps of: the raw materials are counted by weight;
(1) mixing 10 parts of polypropylene carbonate glycol PPC-2A-1, 50 parts of polyether polyol Donol R4110, 90 parts of cardanol-based polyol prepared in example 1, 2 parts of foaming catalyst triethylene diamine, 0.5 part of reaction catalyst dibutyl tin dilaurate, 10 parts of foaming agent n-pentane, 1 part of foam stabilizer DC-193 and 30 parts of flame retardant (10 parts of TCCP, 10 parts of aluminum hydroxide and 10 parts of phytate aqueous solution), stirring and dispersing at 1000rpm for 0.5h, and uniformly dispersing to obtain a component A;
the preparation method of the phytate aqueous solution comprises the following steps: uniformly mixing 10g of 70 wt% phytic acid aqueous solution and 7.07g of triethylamine, stirring at room temperature for reaction for 1 hour, heating to 50 ℃, and continuing to react for 2 hours; after the reaction is finished, cooling to room temperature to obtain the aqueous solution of the phytate.
(2) Accurately weighing 200 parts of toluene isocyanate TDI as a component B;
(3) adding the component B into the component A at 1000rpm, and stopping stirring after continuously stirring for 0.5h at the rotating speed of 1000 rpm; standing at room temperature for foaming for 2h, and aging at 80 deg.C for 24 h.
Example 7
A method of preparing a flame retardant bio-based polyurethane foam, the method comprising the steps of: the raw materials are counted by weight;
(1) mixing 30 parts of polypropylene carbonate glycol PPC-2B-1, 80 parts of polyether polyol Donol R4040, 30 parts of cardanol-based polyol prepared in example 2, 1 part of triethanolamine serving as a foaming catalyst, 0.5 part of dibutyltin dilaurate serving as a reaction catalyst, 5 parts of foaming agent water, 5 parts of PU-1254 serving as a foam stabilizer and 30 parts of flame retardant (10 parts of TCCP, 10 parts of aluminum hydroxide and 10 parts of phytate aqueous solution), stirring and dispersing at 1000rpm for 0.5h, and uniformly dispersing to obtain a component A;
the preparation method of the phytate aqueous solution comprises the following steps: uniformly mixing 10g of 70 wt% phytic acid aqueous solution and 7.07g of triethylamine, stirring at room temperature for reaction for 1 hour, heating to 50 ℃, and continuing to react for 2 hours; after the reaction is finished, cooling to room temperature to obtain the aqueous solution of the phytate.
(2) Accurately weighing 200 parts of toluene isocyanate TDI as a component B;
(3) adding the component B into the component A at 800rpm, and stopping stirring after continuing stirring for 1h at 1200 rpm; standing at room temperature for foaming for 4h, and aging at 60 deg.C for 48 h.
Example 8
A method of preparing a flame retardant bio-based polyurethane foam, the method comprising the steps of: the raw materials are counted by weight;
(1) mixing 30 parts of polypropylene carbonate glycol PPC-2B-1, 80 parts of polyether polyol Donol R4040, 30 parts of cardanol-based polyol prepared in example 2, 1 part of triethanolamine serving as a foaming catalyst, 0.5 part of dibutyltin dilaurate serving as a reaction catalyst, 5 parts of foaming agent water, 5 parts of PU-1254 serving as a foam stabilizer and 40 parts of flame retardant (10 parts of TCCP, 10 parts of aluminum hydroxide and 20 parts of phytate aqueous solution), stirring and dispersing at 1000rpm for 0.5h, and uniformly dispersing to obtain a component A;
the preparation method of the phytate aqueous solution comprises the following steps: uniformly mixing 10g of 70 wt% phytic acid aqueous solution and 7.07g of triethylamine, stirring at room temperature for reaction for 1 hour, heating to 50 ℃, and continuing to react for 2 hours; after the reaction is finished, cooling to room temperature to obtain the aqueous solution of the phytate.
(2) Accurately weighing 200 parts of toluene isocyanate TDI as a component B;
(3) adding the component B into the component A at 800rpm, and stopping stirring after continuing stirring for 1h at 1200 rpm; standing at room temperature for foaming for 4h, and aging at 60 deg.C for 48 h.
Comparative example 1
A method of preparing a flame retardant bio-based polyurethane foam, the method comprising the steps of: the raw materials are counted by weight;
(1) mixing 30 parts of polypropylene carbonate glycol PPC-2B-1, 80 parts of polyether polyol Donol R4040, 30 parts of cardanol-based polyol prepared in example 2, 1 part of triethanolamine serving as a foaming catalyst, 0.5 part of dibutyltin dilaurate serving as a reaction catalyst, 5 parts of foaming agent water, 5 parts of PU-1254 serving as a foam stabilizer and 40 parts of flame retardant (20 parts of TCCP and 20 parts of aluminum hydroxide), stirring and dispersing at 1000rpm for 0.5h, and uniformly dispersing to obtain a component A;
(2) accurately weighing 200 parts of toluene isocyanate TDI as a component B;
(3) adding the component B into the component A at 800rpm, and stopping stirring after continuing stirring for 1h at 1200 rpm; standing at room temperature for foaming for 4h, and aging at 60 deg.C for 48 h.
Example 9
A method of preparing a flame retardant bio-based polyurethane foam, the method comprising the steps of: the raw materials are counted by weight;
(1) mixing 20 parts of polypropylene carbonate glycol PPC-2A-1, 60 parts of polyether polyol Donol R4040, 30 parts of cardanol-based polyol prepared in example 3, 0.1 part of foaming catalyst N-ethylmorpholine, 1 part of reaction catalyst bis-dimethylaminoethyl ether, 15 parts of foaming agent 141b, 3 parts of foam stabilizer DC-200 and 30 parts of flame retardant (10 parts of TCCP, 10 parts of aluminum hydroxide and 10 parts of phytate aqueous solution), stirring and dispersing at 1000rpm for 0.5h, and uniformly dispersing to obtain a component A;
the preparation method of the phytate aqueous solution comprises the following steps: uniformly mixing 10g of 70 wt% phytic acid aqueous solution and 7.07g of triethylamine, stirring at room temperature for reaction for 1 hour, heating to 50 ℃, and continuing to react for 2 hours; after the reaction is finished, cooling to room temperature to obtain the aqueous solution of the phytate.
(2) Accurately weighing 200 parts of toluene isocyanate TDI as a component B;
(3) adding the component B into the component A at 1000rpm, and stopping stirring after continuously stirring for 0.5h at the rotation speed of 1800 rpm; standing at room temperature for foaming for 4h, and aging at 60 deg.C for 48 h.
Example 10
A method of preparing a flame retardant bio-based polyurethane foam, the method comprising the steps of: the raw materials are counted by weight;
(1) mixing 15 parts of polypropylene carbonate glycol PPC-2A-1, 90 parts of polyether polyol Donol R4040, 50 parts of cardanol-based polyol prepared in example 3, 2 parts of foaming catalyst N, N' -diethylpiperazine, 1.5 parts of reaction catalyst dimethylcyclohexylamine, 5 parts of foaming agent water, 0.5 part of foam stabilizer PU-1254 and 30 parts of flame retardant (10 parts of TCCP, 10 parts of aluminum hydroxide and 10 parts of phytate aqueous solution), stirring and dispersing at 1500rpm for 0.5h, and dispersing uniformly to obtain a component A;
the preparation method of the phytate aqueous solution comprises the following steps: uniformly mixing 10g of 70 wt% phytic acid aqueous solution and 7.07g of triethylamine, stirring at room temperature for reaction for 1 hour, heating to 50 ℃, and continuing to react for 2 hours; after the reaction is finished, cooling to room temperature to obtain the aqueous solution of the phytate.
(2) Accurately weighing 200 parts of toluene isocyanate TDI as a component B;
(3) adding the component B into the component A at 1500rpm, and stopping stirring after continuously stirring for 2 hours at the rotating speed of 1000 rpm; standing at room temperature for foaming for 4h, and aging at 50 deg.C for 48 h.
Test example:
the foams obtained in examples 4 to 8 and comparative examples 1 to 2 were subjected to tests for flame retardancy, oil absorption, etc., and the test results are shown in Table 1.
TABLE 1
Note: the oil absorption (in g/g) is determined by weighing. The oil selected in the experiment was dimethicone, and the polyurethane foam produced was cut into cubes of 5cm x1cm regular size, the mass obtained being reported as M0Immersing the sample in a container containing oil for 24h, taking out the sample, dripping for 1h, weighing the mass, and recording as M1. The oil absorption rate is as follows: w ═ M1-Mo)/M0
Tensile strength was measured by an Instron model 5967 universal mechanical tester, manufactured by Instron corporation, USA.
As can be seen from table 1, as the cardanol polyol content increases, the oil absorption and tensile strength of the prepared foam increases. The limiting oxygen index of the foam increases with increasing phytate aqueous solution.
Claims (10)
1. The flame-retardant bio-based polyurethane foam is characterized by being prepared by mixing a component A and a component B, wherein the components comprise the following raw materials in parts by weight:
the component A comprises:
and B component:
100 portions of isocyanate
The weight ratio of the component A to the component B is 1: 1-1.5.
2. The flame retardant bio-based polyurethane foam according to claim 1, wherein said polypropylene carbonate glycol has a hydroxyl value of 56 ± 2mg KOH/g and a molecular weight of 2000.
3. The flame retardant biobased polyurethane foam of claim 1, wherein the polyether polyol is one or more of Donol R4110, Donol R4040 and Donol R8238 manufactured by shanghai great chemicals limited.
4. The flame retardant bio-based polyurethane foam according to claim 1, wherein the cardanol-based polyol is prepared by:
mixing cardanol glycidyl ether with diethanol amine, stirring and reacting for 8-48h at 40-80 ℃, and cooling to room temperature after the reaction is finished to obtain cardanol polyol.
5. The flame retardant bio-based polyurethane foam according to claim 4, wherein the molar ratio of cardanol based glycidyl ether to diethanolamine is 1: 0.5-3.
6. The flame retarded biobased polyurethane foam according to claim 1, wherein said blowing catalyst is one or more of N, N-dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, N-ethylmorpholine, N '-diethylpiperazine, triethanolamine, pyridine, N' -dimethylpyridine, triethylenediamine; the reaction catalyst is one or more of dibutyl tin dilaurate, bis-dimethylaminoethyl ether, pentamethyl diethylenetriamine and dimethyl cyclohexylamine;
the foaming agent is one of n-pentane, water and 141 b;
the foam stabilizer is one or more of BD-3086, PU-1254, PU-1257, DC-193, DC-200 and CGY-1.
7. The flame retardant biobased polyurethane foam of claim 1, wherein the flame retardant is a mixture of trichloroethyl phosphate, aluminum hydroxide and an aqueous phytate solution;
the preparation method of the phytate aqueous solution comprises the following steps:
uniformly mixing 70 wt% of phytic acid aqueous solution with a neutralizer, stirring and reacting for 1h at room temperature, heating to 30-60 ℃, and continuing to react for 2-4 h; after the reaction is finished, cooling to room temperature to obtain the aqueous solution of the phytate.
8. The flame retardant biobased polyurethane foam of claim 7, wherein the neutralizing agent is one or more of triethylamine, diethylamine, diethanolamine, urea; the mol ratio of the phytic acid to the neutralizer is 1: 1-12.
9. The flame retardant biobased polyurethane foam according to claim 1, wherein the isocyanate is one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, polymethylene polyaryl isocyanate.
10. A method of preparing the flame retardant bio-based polyurethane foam of claim 1, comprising the steps of: the raw materials are counted by weight;
(1) mixing 10-30 parts of polypropylene carbonate glycol, 50-90 parts of polyether polyol, 10-90 parts of cardanol-based polyol, 0.1-2 parts of foaming catalyst, 0.1-1.5 parts of reaction catalyst, 1-15 parts of foaming agent, 0.5-5 parts of foam stabilizer and 30-45 parts of flame retardant, stirring at a high speed and dispersing uniformly to obtain a component A;
(2) accurately weighing 100-400 parts of isocyanate as a component B;
(3) adding the component B into the component A at 1500 rpm-; standing and foaming for 2-5h at room temperature, and aging at 50-80 deg.C for 24-48 h.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080139685A1 (en) * | 2006-12-08 | 2008-06-12 | Bayer Materialscience Llc | Novel polyether polyols based on cashew nutshell liquid, a process for the production of these polyether polyols, flexible foams produced from these polyether polyols, and a process for the production of these foams |
| EP2677030A1 (en) * | 2012-06-21 | 2013-12-25 | Latvijas Valsts Koksnes kimijas instituts | Polyurethane rigid and flexible foams as composite obtained from wood origin raw materials and used as support for immobilization of microorganisms that produce ligninolytic enzymes |
| CN103709395A (en) * | 2013-12-16 | 2014-04-09 | 中国林业科学研究院林产化学工业研究所 | Biomass base structure flame retardant polyol and preparation method and application thereof |
| CN105085983A (en) * | 2015-09-22 | 2015-11-25 | 清华大学深圳研究生院 | Halogen-free synergistic flame retardant, preparation method and composite flame retardant |
| CN105295018A (en) * | 2015-11-19 | 2016-02-03 | 滕州市科米特新材料有限责任公司 | Modified cardanol-based polyether polyol and high-fire-resistant hard polyurethane foam prepared by modified cardanol-based polyether polyol and preparation method thereof |
-
2022
- 2022-02-18 CN CN202210151915.7A patent/CN114395108B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080139685A1 (en) * | 2006-12-08 | 2008-06-12 | Bayer Materialscience Llc | Novel polyether polyols based on cashew nutshell liquid, a process for the production of these polyether polyols, flexible foams produced from these polyether polyols, and a process for the production of these foams |
| EP2677030A1 (en) * | 2012-06-21 | 2013-12-25 | Latvijas Valsts Koksnes kimijas instituts | Polyurethane rigid and flexible foams as composite obtained from wood origin raw materials and used as support for immobilization of microorganisms that produce ligninolytic enzymes |
| CN103709395A (en) * | 2013-12-16 | 2014-04-09 | 中国林业科学研究院林产化学工业研究所 | Biomass base structure flame retardant polyol and preparation method and application thereof |
| CN105085983A (en) * | 2015-09-22 | 2015-11-25 | 清华大学深圳研究生院 | Halogen-free synergistic flame retardant, preparation method and composite flame retardant |
| CN105295018A (en) * | 2015-11-19 | 2016-02-03 | 滕州市科米特新材料有限责任公司 | Modified cardanol-based polyether polyol and high-fire-resistant hard polyurethane foam prepared by modified cardanol-based polyether polyol and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115232280A (en) * | 2022-07-26 | 2022-10-25 | 山东蓝天新材料科技有限公司 | Polyurethane foam for water treatment and preparation method thereof |
| CN115232280B (en) * | 2022-07-26 | 2024-02-23 | 山东蓝天新材料科技有限公司 | Polyurethane foam for water treatment and preparation method thereof |
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