CN114395108B - 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 a 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: and (3) a component A: 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; and the component B comprises the following components: 100-400 parts of isocyanate; the weight ratio of the component A to the component B is 1:1-1.5. The invention has excellent flame retardance, oil absorption and mechanical property 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 the main component in the cashew nut shell liquid, and has rich sources and low price. The cardanol is light yellow oily liquid at normal temperature, and has the characteristics of aromatic compounds, high temperature resistance and meta-unsaturated long linear hydrocarbon group structure, so that the cardanol has the characteristics of aliphatic compounds, good flexibility, self-drying property and the like. The cardanol derivative cardanol glycidyl ether is a reaction product of cardanol and epichlorohydrin, is easy to modify in chemical industry, has good hydrophobicity and chemical resistance, and plays an important role in replacing petroleum-based products.
Polyurethane (PU) materials are one of the most widely used polymer materials due to their good dimensional stability, heat and sound insulation, low temperature resistance, oil stain resistance and the like. Among the wide variety of polyurethane materials, polyurethane foam (PUF) has been widely used in real life due to its good heat insulating properties, 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 isocyanate and polyol and other additives used to adjust the properties of the final foam product. However, most of these agents come from petrochemicals and increase the dependence on petroleum. Accordingly, environmental concerns and the need for sustainable technology have prompted the use of renewable raw materials to produce polyurethane foams.
In recent years, the occurrence of serious marine environmental pollution caused by petroleum entering the marine environment is frequent, and leaked petroleum has become one of the main types of marine pollution. The polyurethane foam treatment for absorbing the greasy dirt has the advantages of large oil absorption, high oil absorption rate, easy recovery and the like, and is a relatively promising method.
Pure polyurethane foams have serious fire hazards, their limiting oxygen index is usually only 17-18%, which are flammable products, and their large surface area and good gas permeability accelerate the spread of fire upon combustion. Therefore, modification of polyurethane foam materials to improve their fire resistance has become a hot spot of research in recent years. The conventional flame retardant is generally difficult to achieve high flame retardant performance, but in recent years, inorganic flame retardant additives such as aluminum hydroxide and the like have the effect of inhibiting smoke, are non-volatile, non-toxic and low in price, are not influenced by water because the inorganic flame retardant additives do not generate toxic gas in the combustion process, and the importance of the inorganic flame retardant additives in the industrial field is gradually increasing.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a flame-retardant bio-based polyurethane foam and a preparation method thereof. The invention uses biological base material as raw material, introduces CO 2 And propylene carbonate diol prepared by epoxypropane combustion to develop 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:
and (3) a component A:
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 polypropylene carbonate glycol is one or more of Xingning chemical PPC-2A-1 (with a hydroxyl value of 56+/-2 mg KOH/g, a viscosity of 4000-6000 mPa.s/40 ℃ C., a molecular weight of 2000) and PPC-2B-1 (with a hydroxyl value of 56+/-2 mg KOH/g, a viscosity of 1000-2000 mPa.s/40 ℃ C., and a molecular weight of 2000).
The polyether polyol is one or more of Donol R4110 (with a hydroxyl value of 420-460mg KOH/g), donol R4040 (380-420 mg KOH/g) and Donol R8238 (385-405 mg KOH/g) manufactured by Shanghai Dongda chemical Co., ltd.
The preparation method of the cardanol-based polyol comprises the following steps: mixing cardanol glycidyl ether and diethanolamine, stirring at 40-80 ℃ for reaction for 8-48h, and cooling to room temperature after the reaction is finished to obtain cardanol-based 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-dimethyl cyclohexylamine, bis (2-dimethylaminoethyl) ether, N-ethylmorpholine, N '-diethyl piperazine, triethanolamine, pyridine, N' -dimethylpyridine and triethylenediamine;
the reaction catalyst is one or more of dibutyl tin dilaurate, 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, CGY-1.
The flame retardant is a mixture of trichloroethyl phosphate (TCCP), aluminum hydroxide and phytate aqueous solution; wherein, the mass ratio of trichloroethyl phosphate (TCCP), aluminum hydroxide and phytate aqueous solution is 1:1:1-2.
The preparation method of the phytate aqueous solution comprises the following steps:
uniformly mixing 70wt% of phytic acid aqueous solution with a neutralizer, stirring at room temperature for reaction for 1h, heating to 30-60 ℃ and continuing to react for 2-4h; after the reaction, cooling to room temperature to obtain an aqueous solution of phytate.
Preferably, the neutralizing agent is one or more of triethylamine, diethylamine, diethanolamine and urea; the mole 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 polyarylisocyanate.
A method for preparing the flame retardant bio-based polyurethane foam, the method comprising the steps of: the raw materials are calculated according to parts 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, and stirring at a high speed to uniformly disperse 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 800-1500rpm, mixing the component A and the component B according to the weight ratio of 1:1-1.5, stirring for 0.5-2h at the rotating speed of 1000-1800rpm, and stopping stirring; standing at room temperature for foaming for 2-5h, and curing at 50-80deg.C for 24-48h.
The beneficial technical effects of the invention are as follows:
the adopted polypropylene carbonate glycol is non-crystalline polyol, contains a large amount of ether bonds and carbonate bonds, has high molecular cohesion energy, and the prepared polyurethane material has high strength, good water resistance and good wear resistance, has secondary hydroxyl in a molecular structure, has weaker reaction activity than primary hydroxyl, and can regulate and control the reaction activity of the whole formula and regulate and control the mechanical property of polyurethane foam by being mixed with other alcohols with stronger activity.
The cardanol-based polyol is prepared by taking the biological-based material as the main raw material, so that the raw material source of the polyol is widened, and the problem of excessive use of petrochemical resources is solved to a certain extent. In addition, the reaction condition is mild, the one-step reaction is complete, no post-treatment and waste water and waste residue are generated, and the method is simple and easy to realize.
The flame retardant compounded with the phytate solution is good in compatibility in a system, and the bio-based content and the flame retardance of the polyurethane foam can be further improved.
The invention has excellent flame retardance, oil absorption and mechanical property through molecular design and formula adjustment, and has important application value.
Drawings
FIG. 1 is a schematic diagram of the mechanism of the synthesis reaction of cardanol-based polyols of the present invention;
FIG. 2 is an infrared spectrum of the cardanol-based polyol prepared in example 1;
FIG. 3 is a nuclear magnetic resonance spectrum of the cardanol-based polyol prepared in example 1.
Detailed Description
The present invention will be described in detail below with reference to the drawings and examples.
Example 1
Referring to fig. 1, a method for preparing cardanol-based polyol includes the steps of:
cardanol-based glycidyl ether (PLR-601) (35.7 g,0.1 mol) and Diethanolamine (DEA) (10.5 g,0.1 mol) were added to a flask equipped with a stirrer, a condensation reflux and a thermometer, and the reaction mass was stirred at 70℃for 8 hours, and after completion of the reaction, cooled to room temperature to give cardanol-based polyol (PLR-DEA).
The infrared and nuclear magnetic patterns of the obtained cardanol-based polyol (PLR-DEA) are shown in FIGS. 2 and 3, respectively, and it is clear from FIG. 2 that the infrared spectrum of PLR-DEA is 3330cm -1 The characteristic peak of stretching vibration of the hydroxyl appears at the position, and PLR-601 is originally positioned at 908cm -1 The 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 assigned to the proton absorption peak on the aromatic ring, and PLR-DEA is at the proton absorption peak where hydroxyl groups appear at δ=4.8 and 4.3, and the area ratio to the proton absorption peak 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 method for preparing cardanol-based polyol includes the steps of:
cardanol-based glycidyl ether (PLR-601) (35.7 g,0.1 mol) and Diethanolamine (DEA) (21.0 g,0.2 mol) were added to a flask equipped with a stirrer, a condensation reflux and a thermometer, and the reaction mass was stirred at 80℃for 8 hours, and after completion of the reaction, cooled to room temperature to give cardanol-based polyol (PLR-DEA).
Example 3
Referring to fig. 1, a method for preparing cardanol-based polyol includes the steps of:
cardanol-based glycidyl ether (PLR-601) (35.7 g,0.1 mol) and Diethanolamine (DEA) (5.25 g,0.05 mol) were added to a flask equipped with a stirrer, a condensate reflux and a thermometer, and the reaction mass was stirred at 80℃for 8 hours, and after completion of the reaction, cooled to room temperature to give 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 calculated according to parts by weight;
(1) 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) are mixed, stirred and dispersed for 0.5 hour at 1000rpm, and after uniform dispersion, the component A is obtained;
the preparation method of the phytate aqueous solution comprises the following steps: uniformly mixing 10g of 70wt% phytic acid aqueous solution with 7.07g of triethylamine, stirring at room temperature for reaction for 1h, and heating to 50 ℃ for continuous reaction for 2h; after the reaction, cooling to room temperature to obtain an aqueous solution of phytate.
(2) 200 parts of toluene isocyanate TDI is accurately weighed as a component B;
(3) Adding the component B into the component A at 1000rpm, and stopping stirring after stirring for 0.5h at 1000 rpm; the mixture was allowed to stand still at room temperature for foaming for 2 hours, and then cured at 80℃for 24 hours.
Example 5
A method of preparing a flame retardant bio-based polyurethane foam, the method comprising the steps of: the raw materials are calculated according to parts by weight;
(1) 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) are mixed, stirred and dispersed for 0.5 hour at 1000rpm, and after uniform dispersion, the component A is obtained;
the preparation method of the phytate aqueous solution comprises the following steps: uniformly mixing 10g of 70wt% phytic acid aqueous solution with 7.07g of triethylamine, stirring at room temperature for reaction for 1h, and heating to 50 ℃ for continuous reaction for 2h; after the reaction, cooling to room temperature to obtain an aqueous solution of phytate.
(2) 200 parts of toluene isocyanate TDI is accurately weighed as a component B;
(3) Adding the component B into the component A at 1000rpm, and stopping stirring after stirring for 0.5h at 1000 rpm; the mixture was allowed to stand still at room temperature for foaming for 2 hours, and then cured at 80℃for 24 hours.
Example 6
A method of preparing a flame retardant bio-based polyurethane foam, the method comprising the steps of: the raw materials are calculated according to parts by weight;
(1) 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) are mixed, stirred and dispersed for 0.5 hour at 1000rpm, and after uniform dispersion, the component A is obtained;
the preparation method of the phytate aqueous solution comprises the following steps: uniformly mixing 10g of 70wt% phytic acid aqueous solution with 7.07g of triethylamine, stirring at room temperature for reaction for 1h, and heating to 50 ℃ for continuous reaction for 2h; after the reaction, cooling to room temperature to obtain an aqueous solution of phytate.
(2) 200 parts of toluene isocyanate TDI is accurately weighed as a component B;
(3) Adding the component B into the component A at 1000rpm, and stopping stirring after stirring for 0.5h at 1000 rpm; the mixture was allowed to stand still at room temperature for foaming for 2 hours, and then cured at 80℃for 24 hours.
Example 7
A method of preparing a flame retardant bio-based polyurethane foam, the method comprising the steps of: the raw materials are calculated according to parts by weight;
(1) 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 foaming catalyst triethanolamine, 0.5 part of reaction catalyst dibutyl tin dilaurate, 5 parts of foaming agent water, 5 parts 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) are mixed, stirred and dispersed for 0.5h at 1000rpm, and after uniform dispersion, the component A is obtained;
the preparation method of the phytate aqueous solution comprises the following steps: uniformly mixing 10g of 70wt% phytic acid aqueous solution with 7.07g of triethylamine, stirring at room temperature for reaction for 1h, and heating to 50 ℃ for continuous reaction for 2h; after the reaction, cooling to room temperature to obtain an aqueous solution of phytate.
(2) 200 parts of toluene isocyanate TDI is accurately weighed as a component B;
(3) Adding the component B into the component A at 800rpm, and stopping stirring after stirring for 1h at 1200 rpm; the mixture was left to stand at room temperature for foaming for 4 hours, and then cured at 60℃for 48 hours.
Example 8
A method of preparing a flame retardant bio-based polyurethane foam, the method comprising the steps of: the raw materials are calculated according to parts by weight;
(1) 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 foaming catalyst triethanolamine, 0.5 part of reaction catalyst dibutyl tin dilaurate, 5 parts of foaming agent water, 5 parts of foam stabilizer PU-1254 and 40 parts of flame retardant (10 parts of TCCP,10 parts of aluminum hydroxide and 20 parts of phytate aqueous solution) are mixed, stirred and dispersed for 0.5h at 1000rpm, and after uniform dispersion, the component A is obtained;
the preparation method of the phytate aqueous solution comprises the following steps: uniformly mixing 10g of 70wt% phytic acid aqueous solution with 7.07g of triethylamine, stirring at room temperature for reaction for 1h, and heating to 50 ℃ for continuous reaction for 2h; after the reaction, cooling to room temperature to obtain an aqueous solution of phytate.
(2) 200 parts of toluene isocyanate TDI is accurately weighed as a component B;
(3) Adding the component B into the component A at 800rpm, and stopping stirring after stirring for 1h at 1200 rpm; the mixture was left to stand at room temperature for foaming for 4 hours, and then cured at 60℃for 48 hours.
Comparative example 1
A method of preparing a flame retardant bio-based polyurethane foam, the method comprising the steps of: the raw materials are calculated according to parts by weight;
(1) 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 foaming catalyst triethanolamine, 0.5 part of reaction catalyst dibutyl tin dilaurate, 5 parts of foaming agent water, 5 parts of foam stabilizer PU-1254 and 40 parts of flame retardant (20 parts of TCCP,20 parts of aluminum hydroxide) are mixed, stirred and dispersed for 0.5h at 1000rpm, and after uniform dispersion, the component A is obtained;
(2) 200 parts of toluene isocyanate TDI is accurately weighed as a component B;
(3) Adding the component B into the component A at 800rpm, and stopping stirring after stirring for 1h at 1200 rpm; the mixture was left to stand at room temperature for foaming for 4 hours, and then cured at 60℃for 48 hours.
Example 9
A method of preparing a flame retardant bio-based polyurethane foam, the method comprising the steps of: the raw materials are calculated according to parts by weight;
(1) 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 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) are mixed, stirred and dispersed for 0.5h at 1000rpm, and after uniform dispersion, the component A is obtained;
the preparation method of the phytate aqueous solution comprises the following steps: uniformly mixing 10g of 70wt% phytic acid aqueous solution with 7.07g of triethylamine, stirring at room temperature for reaction for 1h, and heating to 50 ℃ for continuous reaction for 2h; after the reaction, cooling to room temperature to obtain an aqueous solution of phytate.
(2) 200 parts of toluene isocyanate TDI is accurately weighed as a component B;
(3) Adding the component B into the component A at 1000rpm, and stopping stirring after stirring for 0.5h at 1800 rpm; the mixture was left to stand at room temperature for foaming for 4 hours, and then cured at 60℃for 48 hours.
Example 10
A method of preparing a flame retardant bio-based polyurethane foam, the method comprising the steps of: the raw materials are calculated according to parts by weight;
(1) 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' -diethyl piperazine, 1.5 parts of reaction catalyst dimethyl cyclohexylamine, 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) are mixed, stirred and dispersed for 0.5h at 1500rpm, and the component A is obtained after the mixture is uniformly dispersed;
the preparation method of the phytate aqueous solution comprises the following steps: uniformly mixing 10g of 70wt% phytic acid aqueous solution with 7.07g of triethylamine, stirring at room temperature for reaction for 1h, and heating to 50 ℃ for continuous reaction for 2h; after the reaction, cooling to room temperature to obtain an aqueous solution of phytate.
(2) 200 parts of toluene isocyanate TDI is accurately weighed as a component B;
(3) Adding the component B into the component A at 1500rpm, and stopping stirring after stirring for 2 hours at 1000 rpm; the mixture was left to stand at room temperature for foaming for 4 hours, and then cured at 50℃for 48 hours.
Test example:
the foams obtained in examples 4 to 8 and comparative examples 1 to 2 were tested for flame retardancy, oil absorption and the like, and the test results are shown in Table 1.
TABLE 1
Note that: oil absorption (in g/g) was measured by a weighing method. The oil selected in this experiment was simethicone, and the polyurethane foam obtained was cut into cubes of a regular size of 5cm 1cm, and the mass was designated M 0 Immersing the sample in a container containing oil for 24h, taking out the sample, dripping for 1h, weighing the sample, and marking the sample as M 1 . The oil absorption rate is as follows: w= (M 1 -Mo)/M 0
Tensile strength was measured by an Instron model 5967 universal mechanical tester manufactured by Instron, inc. of America.
As can be seen from table 1, as the content of cardanol polyol increases, the oil absorption and tensile strength of the prepared foam increases. As the phytate aqueous solution increases, the limiting oxygen index of the foam increases.
Claims (5)
1. The flame-retardant bio-based polyurethane foam is characterized by being prepared by mixing a component A and a component B, wherein the component A comprises the following raw materials in parts by weight:
and (3) a component A:
and the component B comprises the following components:
100-400 parts of isocyanate
The weight ratio of the component A to the component B is 1:1-1.5;
the polyether polyol is one or more of Donol R4110, donol R4040 and Donol R8238 manufactured by Shanghai Dong chemical Co., ltd;
the preparation method of the cardanol-based polyol comprises the following steps: mixing cardanol glycidyl ether and diethanolamine, stirring at 40-80 ℃ for reaction for 8-48 hours, and cooling to room temperature after the reaction is finished to obtain cardanol-based polyol;
the flame retardant is a mixture of trichloroethyl phosphate, aluminum hydroxide and phytate aqueous solution;
the preparation method of the phytate aqueous solution comprises the following steps: uniformly mixing 70wt% of phytic acid aqueous solution with a neutralizer, stirring at room temperature for reaction for 1h, heating to 30-60 ℃ and continuing to react for 2-4h; after the reaction is finished, cooling to room temperature to obtain an aqueous solution of phytate;
the neutralizer 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 and hexamethylene diisocyanate.
2. The flame retardant biobased polyurethane foam of claim 1, wherein said polypropylene carbonate diol has a hydroxyl number of 56±2mg KOH/g and a molecular weight of 2000.
3. The flame retardant biobased polyurethane foam of claim 1, wherein the molar ratio of cardanol glycidyl ether to diethanolamine is 1:0.5-3.
4. The flame retardant biobased polyurethane foam of 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, 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.
5. A method of preparing the flame retardant bio-based polyurethane foam of claim 1, comprising the steps of: the raw materials are calculated according to parts 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, and stirring at a high speed to uniformly disperse 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 800-1500rpm, mixing the component A and the component B according to the weight ratio of 1:1-1.5, stirring for 0.5-2h at the rotating speed of 1000-1800rpm, and stopping stirring; standing at room temperature for foaming for 2-5h, and curing at 50-80deg.C for 24-48h.
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| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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