CN116396458A - High-strength, fireproof and anti-dripping lignin-based polyurethane foam and preparation method thereof - Google Patents
High-strength, fireproof and anti-dripping lignin-based polyurethane foam and preparation method thereof Download PDFInfo
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- CN116396458A CN116396458A CN202310482268.2A CN202310482268A CN116396458A CN 116396458 A CN116396458 A CN 116396458A CN 202310482268 A CN202310482268 A CN 202310482268A CN 116396458 A CN116396458 A CN 116396458A
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- lignin
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- polyol
- foam
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- 229920005610 lignin Polymers 0.000 title claims abstract description 187
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000006260 foam Substances 0.000 claims abstract description 55
- -1 phosphonate polyol Chemical class 0.000 claims abstract description 55
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 46
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- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
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- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 3
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Abstract
The invention discloses a high-strength, fireproof and anti-dripping lignin-based polyurethane foam material and a preparation method thereof. The preparation method comprises the following steps: adding lignin into polyalcohol by adopting a one-pot method, mixing for liquefaction reaction, adding phosphorus pentoxide for dehydration condensation esterification reaction, finally adding melamine for salifying reaction to obtain lignin-based phosphonate polyalcohol, then carrying out nucleophilic addition reaction with isocyanate, molding, demolding and curing to obtain the lignin-based phosphonate polyalcohol. The lignin phosphonate polyol prepared by the invention contains a large amount of nitrogen/phosphorus flame retardant elements, no acid-base catalyst is introduced in the preparation process, and 100% substitution of the lignin-based phosphonate polyol for petroleum-based polyol is realized. The prepared lignin-based polyurethane foam has the characteristics of excellent flame retardant effect (V-0 grade), no molten drop phenomenon, high mechanical strength, uniform foam holes, small heat conductivity coefficient and the like, and meets the performance requirements of commercial halogen-free flame retardant polyurethane rigid foam.
Description
Technical Field
The invention belongs to the field of polyurethane foam material synthesis, and particularly relates to a high-strength, fireproof and anti-dripping lignin-based polyurethane foam material and a preparation method thereof.
Background
Polyurethanes (PU) are a class of high molecular polymers containing repeating urethane (-NH-COO-) features, typically obtained by stepwise nucleophilic addition polymerization of isocyanates and polyols (including polyether polyols and polyester polyols), and have rapidly evolved into a diverse, widely used and growing market share plastic industry (Kausar a, polymer Plastics Technologyand Engineering, 2018). Among them, polyurethane rigid foam (PURF) has low density, small heat conductivity, low moisture permeability, high strength-weight ratio and strong dimensional stability, and is widely applied to the fields of building energy conservation, solar water heater, wood-like furniture, pipeline heat preservation and the like (Chanlert P et al Journal of Physics: conference Series, 2021). However, since the PURF contains a rich hydrocarbon oxygen segment, it has a low carbon content and a high porosity, and thus has a very flammable characteristic. The Limiting Oxygen Index (LOI) of PURF is typically around 17%, and a large amount of toxic smoke is released during combustion, which poses a serious threat to the safety of human life and property (MODESTI M et al Polymer Degradation & Stability, 2001).
Lignin is the most abundant natural aromatic polymer in nature, has high carbon content (more than 65%) in molecular structure, abundant hydroxyl groups and low cost, and is an ideal raw material for preparing bio-based flame-retardant polyurethane foam by replacing petroleum-based polyol (Tan Z et al, renewable & Sustainable Energy Reviews, 2015). Direct addition and liquefaction modification are two typical methods for preparing polyurethane foam by lignin instead of petroleum-based polyols. Compared with the traditional polyurethane foam material, the lignin-based polyurethane foam has the characteristics of slow burning rate and obviously improved carbon residue, but still has difficulty in achieving the flame retardant grade of V1 or V0. For this reason, large amounts of flame retardant are often required to improve the flame retardant properties of lignin-based polyurethane foams (Agrawal a et al Integrated Ferroelectrics,2019; chang C et al Industrial Crops and Products, 2021) during the preparation thereof, however, the addition of large amounts of flame retardant tends to reduce the mechanical and thermal insulation properties thereof. In addition, lignin-based polyurethane foams also generally suffer from large brittleness, low mechanical strength, low lignin substitution rate, and the like. Therefore, there is a need to develop a lignin polyol which is simple in preparation process and environment-friendly, and can replace petroleum-based polyol by 100% for preparing lignin-based polyurethane foam with high flame retardance and high mechanical strength.
In the prior art, strong acid (such as concentrated sulfuric acid) is generally used as a dehydrating agent or a catalyst for preparing lignin polyol to promote the dehydration condensation reaction of lignin and polyol, and a large amount of phenolic hydroxyl groups in lignin are converted into alcoholic hydroxyl groups, so that lignin polyol with high reactivity with isocyanate is obtained, and the flame retardant effect of foam is enhanced by adding an inorganic or organic flame retardant. However, the substitution rate of lignin polyol is low, and the use of concentrated sulfuric acid can cause equipment corrosion and environmental pollution.
CN113929857A discloses a preparation method and application of lignin polyol suitable for flame-retardant polyurethane rigid foam, wherein lignin and melamine are dissolved in a solvent DMF, stirred and reacted for 3-9 hours at 60-100 ℃, water is added into a reaction solution, and the reaction solution is filtered and then washed to obtain a product A; mixing allyl polyether with cysteine or a cysteine derivative, adding a catalyst, and stirring for reacting for 2-4 hours to obtain a product B; and finally, mixing the product A and the product B, and stirring and reacting for 20-48 hours at 60-100 ℃ under the protection of protective gas to obtain lignin polyol. However, the preparation process of the method is complicated and is not a one-pot method, and a large amount of DMF organic solvent and water are used, so that the method does not meet the environment-friendly concept; in addition, the allyl polyether, the cysteine and the derivatives thereof used in the invention are all expensive reagents, and do not meet the economic benefit.
CN 112778540A discloses a lignin-based polyol for synthesizing polyurethane and a preparation method thereof, the method of the invention is that lignin acetate is subjected to hydrothermal degradation under the catalysis of metal oxide, and degradation products are precipitated by dilute acid; and carrying out hydroxylation modification on the degraded lignin to obtain polyhydroxy lignin polyol. However, the lignin polyol prepared is lengthy in process, the steps of separation and purification are numerous, and the lignin polyol obtained is solid, so that the replacement of petroleum-based polyol with the lignin polyol requires the compounding of a diluent or a commercial liquid polyol, resulting in a lower substitution rate.
CN102585141a discloses a flame-retardant polyurethane foam and a preparation method thereof, the invention contacts and reacts lignin and polyol in the presence of an acid catalyst to obtain a mixed liquid of the lignin and the polyol; polyether polyol, ammonium polyphosphate and melamine are added into reactants of phosphoric acid and pentaerythritol to prepare a flame retardant; and uniformly mixing the lignin and polyol mixed liquid, the flame retardant, polyether polyol and various assistants, and foaming with isocyanate to obtain the flame-retardant polyurethane foam. However, the invention needs to adopt sulfuric acid strong acid substances as catalysts to complete alcoholysis of lignin, which causes certain corrosion to production equipment and environment; the prepared lignin-based polyol has low activity, the foam material is prepared with the assistance of commercial polyether polyol, the prepared flame-retardant polyurethane foam has poor mechanical property, and the highest compressive strength is only 0.115KPa.
CN115417971a discloses a flame-retardant isocyanate composite material prepared by using TDI rectifying tower bottom liquid as raw material, active substances containing TDI, dichlorine, carbodiimide and uretonimine in the TDI rectifying tower bottom liquid generate high-ring rigid macromolecular structure which is favorable for char formation under the action of catalyst, and bromine and chlorine elements are introduced, so that the polyurethane foam prepared by using the isocyanate composite material has good flame-retardant property and high bidirectional compressive strength. However, the isocyanate prepared by the method is tedious and tedious in process, does not meet economic benefit, and the obtained polyurethane foam material contains halogen elements, so that combustion products can cause serious harm to human health and environmental protection.
In summary, the existing lignin-based polyol preparation method has the following technical shortcomings:
1. the limited reactivity of lignin-based polyols results in the inability to 100% replace petroleum-based polyols to prepare rigid polyurethane foams;
2. the use and removal of a large amount of solvents in the preparation process of lignin-based polyol cannot embody the concept of green chemistry;
3. the preparation of lignin-based polyol often adopts acid catalysts such as concentrated sulfuric acid and the like and dehydrating agents, so that the corrosion of production equipment and the environmental problem are easily caused;
4. polyurethane foam materials prepared from lignin-based polyols have poor flame retardant properties or contain halogen elements which have serious harm to human health and environment after combustion.
Disclosure of Invention
The invention aims to overcome at least one defect of the prior art and provides a high-strength, fireproof and anti-dripping lignin-based polyurethane foam material and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
in a first aspect of the invention, there is provided: a preparation method of high-strength, fireproof and anti-dripping lignin-based polyurethane foam comprises the following steps:
1) Adding lignin into polyalcohol, mixing for liquefaction reaction, adding phosphorus pentoxide for dehydration condensation esterification reaction, finally adding melamine for salifying reaction, stirring, cooling and discharging to obtain lignin-based phosphonate polyalcohol;
2) Uniformly mixing lignin-based phosphonate polyol with a catalyst, a chain extender, a foam stabilizer, a foaming agent and a flame retardant, adding isocyanate raw materials, mixing for nucleophilic addition reaction, pouring into a mold for foam molding, demolding and curing to obtain the lignin-based polyurethane rigid flame retardant foam.
In some examples, the esterification reaction temperature in step 1) is 90 to 220 ℃ and/or the reaction time is 1 to 5 hours.
In some examples, the phosphorus pentoxide is used in an amount of 1.5 to 10.5wt% of the lignin-based phosphonate polyol, the melamine is used in an amount of 1.5 to 7.5wt% of the lignin-based phosphonate polyol, the lignin is used in an amount of 0.5 to 60wt% of the total mass of the lignin-based phosphonate polyol, and the remainder is polyol.
In some examples, the salt forming reaction temperature in step 1) is 25 ℃ to 150 ℃ and/or the reaction time is 0.5 to 3 hours.
In some examples, the liquefaction reaction temperature in step 1) is 25 ℃ to 150 ℃ and/or the reaction time is 0.5 to 3 hours.
In some examples, the lignin is selected from any one of alkali lignin, kraft lignin, enzymatic lignin, organosolv lignin, or sulfonic lignin.
In some examples, the polyol is selected from any one of ethylene glycol, glycerol, and polyethylene glycol.
In some examples, each starting material for the nucleophilic addition reaction in step 2) is independently selected from:
the catalyst is at least one selected from triethylene diamine, triethanolamine, stannous octoate, dibutyl tin dilaurate, dibutyl tin (dodecyl sulfide) and monobutyl tin oxide;
the chain extender is at least one selected from 1, 4-butanediol, propylene glycol, glycerol, triethanolamine and diethylene glycol;
the foam homogenizing agent is at least one selected from simethicone, tween 40, tween 60 and Tween 80;
the foaming agent is at least one selected from the group consisting of monofluorodichloroethane, diethyl ether, deionized water, cyclopentane and n-pentane;
the flame retardant is any one of expanded graphite, ammonium polyphosphate, tri (2-chloroethyl) phosphate and methyl dimethyl phosphate;
the isocyanate is selected from any one of diphenylmethane diisocyanate, toluene diisocyanate and polymethylene polyphenyl polyisocyanate.
In some examples, the nucleophilic addition reaction comprises the following components in parts by mass: 100 parts of lignin-based phosphonate polyol, 1-5 parts of catalyst, 1-6 parts of chain extender, 1-5 parts of foam homogenizing agent, 1-7 parts of foaming agent, 4-16 parts of flame retardant and 105-125 parts of isocyanate.
In a second aspect of the invention, there is provided: the invention provides a heat insulation material, which comprises lignin-based polyurethane foam obtained by the preparation method according to the first aspect of the invention.
The beneficial effects of the invention are as follows:
1) The invention adopts a one-pot method to prepare lignin phosphonate polyol, and the preparation process is obviously different from the prior invention in which strong acid (such as concentrated sulfuric acid, phosphoric acid and the like) is used as a catalyst, and the phosphorus pentoxide is phosphoric acid anhydride, but the process system is free from the introduction of water, and the phosphoric acid anhydride is not hydrolyzed into phosphoric acid, so that the lignin phosphonate polyol has no corrosiveness to production equipment and is environment-friendly. In addition, phosphorus pentoxide is more susceptible to esterification than phosphoric acid, so that the efficiency of preparing lignin phosphonate polyol using phosphorus pentoxide is much higher than that of preparing lignin phosphonate polyol using phosphoric acid;
2) Based on the prepared lignin phosphonate polyol, the lignin-based polyurethane foam material can be directly prepared by reacting with isocyanate, and the process does not need to add commercial petroleum-based polyol, so that the lignin substitution rate is higher than that of most of the existing lignin-based polyurethane foam;
3) The lignin phosphonate polyol prepared by the invention can be used for preparing polyurethane foam materials with high mechanical strength, the highest compression strength and Young modulus of the foam respectively reach 394.5KPa and 11.82MPa (the mechanical property is far higher than that of similar products in the prior report), and compared with polyurethane foam prepared by lignin phosphonate polyol without melamine, the strength and modulus are respectively improved by 338.9 percent and 720.8 percent;
4) The lignin-based polyurethane foam has a complete closed cell structure, a low pore diameter and excellent hydrophobicity;
5) The lignin-based polyurethane foam provided by the invention has low heat conductivity coefficient (about 0.04W/m K) and excellent fireproof and anti-dripping performance as a heat insulation material, and the UL94 method tests that the flame retardant rating reaches V0 level and the limiting oxygen index is up to 33.4%.
Drawings
FIG. 1 is a photograph of high strength, fire resistant and anti-dripping lignin-based polyurethane foam prepared in examples 1-4.
FIG. 2 is a graph of the microscopic morphology and pore size distribution of lignin-based polyurethane foams prepared in examples 1-4.
FIG. 3 is a graph of compressive strength versus Young's modulus and a graph of compressive stress versus strain for lignin-based polyurethane foams prepared in examples 1-4 and comparative example 4.
FIG. 4 shows the thermal conductivity of lignin-based polyurethane foams prepared in examples 1-4 and comparative example 4.
Fig. 5 is a water contact angle of lignin-based polyurethane foams prepared in examples 1 to 4 and comparative example 4.
FIG. 6 is a comparison of the fire performance of lignin-based polyurethane foams prepared in examples 1-4 and comparative example 4.
Detailed Description
The following disclosure provides many different embodiments or examples for carrying out various aspects of the invention, and reagents used in the examples and comparative examples are commercially available as usual unless otherwise specified.
A preparation method of high-strength, fireproof and anti-dripping lignin-based polyurethane foam comprises the following steps:
1) Adding lignin into polyalcohol, mixing for liquefaction reaction, adding phosphorus pentoxide for dehydration condensation esterification reaction, finally adding melamine for salifying reaction, stirring, cooling and discharging to obtain lignin-based phosphonate polyalcohol;
2) Uniformly mixing lignin-based phosphonate polyol with a catalyst, a chain extender, a foam stabilizer, a foaming agent and a flame retardant, adding isocyanate raw materials, mixing for nucleophilic addition reaction, pouring into a mold for foam molding, demolding and curing to obtain the lignin-based polyurethane rigid flame retardant foam.
In some embodiments, the esterification reaction temperature in step 1) is 90 to 220 ℃.
In some embodiments, the esterification reaction time in step 1) is 1 to 5 hours.
The specific reaction temperature and time can be adjusted correspondingly according to the progress of the reaction.
In some embodiments, the esterification reaction temperature in step 1) is 150 ℃ and the reaction time is 3 hours. The data show that under this reaction condition, lignin-based polyurethane foams with more excellent properties are favored.
In some embodiments, the phosphorus pentoxide is used in an amount of 1.5 to 10.5wt% of the lignin-based phosphonate polyol, the melamine is used in an amount of 1.5 to 7.5wt% of the lignin-based phosphonate polyol, the lignin is used in an amount of 0.5 to 60wt% of the total mass of the lignin-based phosphonate polyol, and the remainder is polyol.
In some embodiments, the phosphorus pentoxide is present in an amount of 5.5wt% of the lignin-based phosphonate polyol, the melamine is present in an amount of 4.5wt% of the lignin-based phosphonate polyol, the lignin is present in an amount of 10 to 35wt% of the lignin-based phosphonate polyol, and the remainder is polyol.
In some embodiments, the phosphorus pentoxide is used in an amount of 4.5 to 6.5wt% of the lignin-based phosphonate polyol, the melamine is used in an amount of 3.5 to 5.5wt% of the lignin-based phosphonate polyol, the lignin is used in an amount of 10 to 35wt% of the total lignin-based phosphonate polyol, and the remainder is polyol.
In some embodiments, the salt forming reaction temperature in step 1) is 25 ℃ to 150 ℃, preferably 100 ℃ to 150 ℃.
In some embodiments, the salification reaction time in step 1) is from 0.5 to 3 hours.
The specific reaction temperature and time can be adjusted correspondingly according to the progress of the reaction.
In some embodiments, the salt forming reaction temperature in step 1) is 150 ℃ and the reaction time is 1h. The data show that under this reaction condition, lignin-based polyurethane foams with more excellent properties are favored.
In some embodiments, the liquefaction reaction temperature in step 1) is 25 ℃ to 150 ℃, preferably 60 ℃ to 130 ℃.
In some embodiments, the liquefaction reaction time in step 1) is between 0.5 and 3 hours.
The specific reaction temperature and time can be adjusted correspondingly according to the progress of the reaction.
In some embodiments, the liquefaction reaction temperature in step 1) is 110 ℃ and the reaction time is 1h. The data show that under this reaction condition, lignin-based polyurethane foams with more excellent properties are favored.
Lignin can be a variety of common lignin. In some embodiments, the lignin is selected from any one of alkali lignin, kraft lignin, enzymatic lignin, organosolv lignin, or sulfonic lignin.
In some embodiments, the polyol is selected from any one of ethylene glycol, glycerol, and polyethylene glycol. These polyols are widely available and less costly.
In some embodiments, each starting material for the nucleophilic addition reaction in step 2) is independently selected from:
the catalyst is at least one selected from triethylene diamine, triethanolamine, stannous octoate, dibutyl tin dilaurate, dibutyl tin (dodecyl sulfide) and monobutyl tin oxide;
the chain extender is at least one selected from 1, 4-butanediol, propylene glycol, glycerol, triethanolamine and diethylene glycol;
the foam homogenizing agent is at least one selected from simethicone, tween 40, tween 60 and Tween 80;
the foaming agent is at least one selected from the group consisting of monofluorodichloroethane, diethyl ether, deionized water, cyclopentane and n-pentane;
the flame retardant is any one of expanded graphite, ammonium polyphosphate, tri (2-chloroethyl) phosphate and methyl dimethyl phosphate;
the isocyanate is selected from any one of diphenylmethane diisocyanate, toluene diisocyanate and polymethylene polyphenyl polyisocyanate.
In some examples and comparative examples, kraft lignin was used as lignin, stannous octoate was used as catalyst, triethanolamine was used as chain extender, dimethicone was used as foam stabilizer, n-pentane was used as foaming agent, PMDI200 was used as isocyanate, and expanded graphite was used as flame retardant.
In some embodiments, 100 parts of lignin-based phosphonate polyol, 1-5 parts of catalyst, 1-6 parts of chain extender, 1-5 parts of foam stabilizer, 1-7 parts of foaming agent, 4-16 parts of flame retardant and 105-125 parts of isocyanate.
In some examples and comparative examples, 100 parts of lignin-based phosphonate polyol, 4 parts of catalyst, 5 parts of chain extender, 4 parts of foam stabilizer, 6 parts of foaming agent, 4 to 16 parts of flame retardant, and 115 parts of isocyanate.
Example 1
1) Preparation of lignin-based phosphonate polyol: weighing 150g of ethylene glycol and 75g of lignin, adding the mixture into a three-neck flask, stirring the mixture at a constant temperature for 1h under the reaction condition of 110 ℃ and 400r/min to carry out lignin liquefaction reaction, cooling the mixture to room temperature in an ice bath after the reaction is finished, slowly adding 13.75g of phosphorus pentoxide, heating the mixture to 150 ℃ in a programmed manner, stirring the mixture at a constant temperature for 3h to carry out esterification reaction, adding 11.25g of melamine, and continuing to carry out salification reaction for 1h to obtain lignin-based phosphonate Polyol (PMLOH);
2) Preparation of lignin-based polyurethane foam: 100 parts of PMLOH, 4 parts of catalyst, 5 parts of chain extender, 4 parts of foam stabilizer, 6 parts of foaming agent and 4 parts of flame retardant are mixed for 5min at a stirring rate of 1000r/min, then are rapidly stirred with 115 parts of isocyanate for 20s, are poured into a mold for foaming, and are demoulded and cured for 24 hours after the foam stops growing, so that the high-strength, fireproof and anti-dripping lignin-based polyurethane foam (EPLF 1) is obtained.
Example 2
1) Preparation of lignin-based phosphonate polyol: weighing 150g of ethylene glycol and 75g of lignin, adding the mixture into a three-neck flask, stirring the mixture at a constant temperature for 1h under the reaction condition of 110 ℃ and 400r/min to carry out lignin liquefaction reaction, cooling the mixture to room temperature in an ice bath after the reaction is finished, slowly adding 13.75g of phosphorus pentoxide, heating the mixture to 150 ℃ in a programmed manner, stirring the mixture at a constant temperature for 3h to carry out esterification reaction, adding 11.25g of melamine, and continuing to carry out salification reaction for 1h to obtain lignin-based phosphonate Polyol (PMLOH);
2) Preparation of lignin-based polyurethane foam: 100 parts of PMLOH, 4 parts of catalyst, 5 parts of chain extender, 4 parts of foam stabilizer, 6 parts of foaming agent and 8 parts of flame retardant are mixed for 5min at a stirring rate of 1000r/min, then the mixture is rapidly stirred with 115 parts of isocyanate for 20s, and the mixture is poured into a mold for foaming, and after the foam stops growing, the foam is demolded and cured for 24 hours, so that the high-strength, fireproof and anti-dripping lignin-based polyurethane foam (EPLF 2) is obtained.
Example 3
1) Preparation of lignin-based phosphonate polyol: weighing 150g of ethylene glycol and 75g of lignin, adding the mixture into a three-neck flask, stirring the mixture at a constant temperature for 1h under the reaction condition of 110 ℃ and 400r/min to carry out lignin liquefaction reaction, cooling the mixture to room temperature in an ice bath after the reaction is finished, slowly adding 13.75g of phosphorus pentoxide, heating the mixture to 150 ℃ in a programmed manner, stirring the mixture at a constant temperature for 3h to carry out esterification reaction, adding 11.25g of melamine, and continuing to carry out salification reaction for 1h to obtain lignin-based phosphonate Polyol (PMLOH);
2) Preparation of lignin-based polyurethane foam: 100 parts of PMLOH, 4 parts of catalyst, 5 parts of chain extender, 4 parts of foam stabilizer, 6 parts of foaming agent and 12 parts of flame retardant are mixed for 5min at a stirring rate of 1000r/min, then the mixture is rapidly stirred with 115 parts of isocyanate for 20s, and the mixture is poured into a mold for foaming, and after the foam stops growing, the foam is demolded and cured for 24 hours, so that the high-strength, fireproof and anti-dripping lignin-based polyurethane foam (EPLF 3) is obtained.
Example 4
1) Preparation of lignin-based phosphonate polyol: weighing 150g of ethylene glycol and 75g of lignin, adding the mixture into a three-neck flask, stirring the mixture at a constant temperature for 1h under the reaction condition of 110 ℃ and 400r/min to carry out lignin liquefaction reaction, cooling the mixture to room temperature in an ice bath after the reaction is finished, slowly adding 13.75g of phosphorus pentoxide, heating the mixture to 150 ℃ in a programmed manner, stirring the mixture at a constant temperature for 3h to carry out esterification reaction, adding 11.25g of melamine, and continuing to carry out salification reaction for 1h to obtain lignin-based phosphonate Polyol (PMLOH);
2) Preparation of lignin-based polyurethane foam: 100 parts of PMLOH, 4 parts of catalyst, 5 parts of chain extender, 4 parts of foam stabilizer, 6 parts of foaming agent and 16 parts of flame retardant are mixed for 5min at a stirring rate of 1000r/min, then the mixture is rapidly stirred with 115 parts of isocyanate for 20s, and the mixture is poured into a mold for foaming, and after the foam stops growing, the foam is demolded and cured for 24 hours, so that the high-strength, fireproof and anti-dripping lignin-based polyurethane foam (EPLF 4) is obtained.
Comparative example 1
This comparative example differs from examples 1 to 4 in that no flame retardant and lignin are added, and the preparation steps are as follows:
1) Preparation of lignin-based phosphonate polyol: weighing 225g of ethylene glycol, adding the ethylene glycol into a three-neck flask, slowly adding 13.75g of phosphorus pentoxide at a stirring rate of 400r/min, heating to 150 ℃ in a programmed manner, stirring for 3 hours at constant temperature, performing esterification reaction, adding 11.25g of melamine, and continuing to perform salification reaction for 1 hour to obtain lignin-based phosphonate polyol (PMLOH 0);
2) Preparation of lignin-based polyurethane foam: 100 parts of PMLOH0, 4 parts of catalyst, 5 parts of chain extender, 4 parts of foam stabilizer and 6 parts of foaming agent are mixed for 5min at a stirring rate of 1000r/min, then are rapidly stirred with 115 parts of isocyanate for 20s, are poured into a mold for foaming, and are demoulded and cured for 24h after the foam stops growing, so that lignin-based polyurethane foam (PMLF 0) is obtained.
Comparative example 2
This comparative example differs from examples 1 to 4 in that no flame retardant was added, and the preparation steps are as follows:
1) Preparation of lignin-based phosphonate polyol: 200g of ethylene glycol and 25g of lignin are weighed and added into a three-neck flask, stirring is carried out for 1h at a constant temperature under the reaction condition of 110 ℃ and 400r/min to carry out lignin liquefaction reaction, after the reaction is finished, ice bath cooling is carried out to room temperature, 13.75g of phosphorus pentoxide is slowly added, programming is carried out to raise the temperature to 150 ℃ and stirring is carried out for 3h at a constant temperature to carry out esterification reaction, then 11.25g of melamine is added, and salt formation reaction is carried out for 1h to obtain lignin-based phosphonate Polyol (PMLOH);
2) Preparation of lignin-based polyurethane foam: 100 parts of PMLOH, 4 parts of catalyst, 5 parts of chain extender, 4 parts of foam stabilizer and 6 parts of foaming agent are mixed for 5min at a stirring rate of 1000r/min, then are rapidly stirred with 115 parts of isocyanate for 20s, are poured into a mold for foaming, and are demoulded and cured for 24h after the foam stops growing, so that lignin-based polyurethane foam (PMLF 1) is obtained.
Comparative example 3
This comparative example differs from examples 1 to 4 in that no flame retardant was added, and the preparation steps are as follows:
1) Preparation of lignin-based phosphonate polyol: weighing 175g of ethylene glycol and 50g of lignin, adding into a three-neck flask, stirring at a constant temperature of 110 ℃ for 1h under the reaction condition of 400r/min to carry out lignin liquefaction reaction, cooling to room temperature in an ice bath after the reaction is finished, slowly adding 13.75g of phosphorus pentoxide, heating to 150 ℃ in a programmed manner, stirring at a constant temperature for 3h to carry out esterification reaction, adding 11.25g of melamine, and continuing to carry out salification reaction for 1h to obtain lignin-based phosphonate Polyol (PMLOH);
2) Preparation of lignin-based polyurethane foam: 100 parts of PMLOH, 4 parts of catalyst, 5 parts of chain extender, 4 parts of foam stabilizer and 6 parts of foaming agent are mixed for 5min at a stirring rate of 1000r/min, then are rapidly stirred with 115 parts of isocyanate for 20s, are poured into a mold for foaming, and are demoulded and cured for 24h after the foam stops growing, so that lignin-based polyurethane foam (PMLF 2) is obtained.
Comparative example 4
This comparative example differs from examples 1 to 4 in that no flame retardant was added, and the preparation steps are as follows:
1) Preparation of lignin-based phosphonate polyol: weighing 150g of ethylene glycol and 75g of lignin, adding the mixture into a three-neck flask, stirring the mixture at a constant temperature for 1h under the reaction condition of 110 ℃ and 400r/min to carry out lignin liquefaction reaction, cooling the mixture to room temperature in an ice bath after the reaction is finished, slowly adding 13.75g of phosphorus pentoxide, heating the mixture to 150 ℃ in a programmed manner, stirring the mixture at a constant temperature for 3h to carry out esterification reaction, adding 11.25g of melamine, and continuing to carry out salification reaction for 1h to obtain lignin-based phosphonate Polyol (PMLOH);
2) Preparation of lignin-based polyurethane foam: 100 parts of PMLOH, 4 parts of catalyst, 5 parts of chain extender, 4 parts of foam stabilizer and 6 parts of foaming agent are mixed for 5min at a stirring rate of 1000r/min, then are rapidly stirred with 115 parts of isocyanate for 20s, are poured into a mold for foaming, and are demoulded and cured for 24h after the foam stops growing, so that lignin-based polyurethane foam (PMLF 3) is obtained.
Comparative example 5
This comparative example differs from examples 1 to 4 in that no flame retardant and melamine are added, and the preparation steps are as follows:
1) Preparation of lignin-based phosphonate polyol: weighing 150g of ethylene glycol and 75g of lignin, adding the mixture into a three-neck flask, stirring the mixture at a constant temperature of 110 ℃ for 1h under a reaction condition of 400r/min to carry out lignin liquefaction reaction, cooling the mixture to room temperature in an ice bath after the reaction is finished, slowly adding 13.75g of phosphorus pentoxide, and heating the mixture to 150 ℃ in a programmed manner to carry out esterification reaction under a constant temperature of 3h to obtain lignin-based phosphonate Polyol (PLOH);
2) Preparation of lignin-based polyurethane foam: 100 parts of PMLOH, 4 parts of catalyst, 5 parts of chain extender, 4 parts of foam stabilizer and 6 parts of foaming agent are mixed for 5min at a stirring rate of 1000r/min, then are rapidly stirred with 115 parts of isocyanate for 20s, are poured into a mold for foaming, and are demoulded and cured for 24h after the foam stops growing, so that lignin-based polyurethane foam (PLF) is obtained.
Comparative example 6
This comparative example differs from examples 1 to 4 in that no flame retardant was added, and the preparation steps are as follows:
1) Preparation of lignin-based phosphonate polyol: weighing 137.5g of ethylene glycol and 87.5g of lignin, adding into a three-neck flask, stirring at a constant temperature of 110 ℃ and 400r/min for 1h to carry out lignin liquefaction reaction, cooling to room temperature in an ice bath after the reaction is finished, slowly adding 13.75g of phosphorus pentoxide, heating to 150 ℃ by programming, stirring at a constant temperature for 3h to carry out esterification reaction, adding 11.25g of melamine, and continuing to carry out salification reaction for 1h to obtain lignin-based phosphonate Polyol (PMLOH);
2) Preparation of lignin-based polyurethane foam: 100 parts of PMLOH, 4 parts of catalyst, 5 parts of chain extender, 4 parts of foam stabilizer and 6 parts of foaming agent are mixed for 5min at a stirring rate of 1000r/min, then are rapidly stirred with 115 parts of isocyanate for 20s, are poured into a mold for foaming, and are demoulded and cured for 24h after the foam stops growing, so that lignin-based polyurethane foam (PMLF 4) is obtained.
Performance testing
The polyurethane foams prepared in comparative examples 1 to 6 were subjected to performance test, and specific indexes are shown in the following table
Comparison of polyurethane foam pore size distribution
FIG. 1 is a photograph of high strength, fire resistant and anti-dripping lignin-based polyurethane foam prepared in examples 1-4. From the graph, lignin-based polyurethane foam with different addition amounts of flame retardants can be successfully prepared, and different samples have the characteristics of uniform foam holes, close color, uniform macroscopic morphology and the like.
The microscopic morphology of the cells was observed using an electron scanning microscope (SEM), the foam was cut into 5 x 2mm pieces, stuck to a stage with conductive glue and subjected to a metal spraying treatment, and the microscopic morphology of the cells was observed at an accelerating voltage of 10 kV. SEM images were processed using Image J and pore size was measured.
As can be seen from fig. 2, examples 1 to 4 and comparative example 4 show that the pore size of the cells becomes smaller and the pore size distribution becomes more concentrated as the content of the flame retardant in the polyurethane system increases, and the minimum average pore size and normal distribution trend are shown when the addition amount of the flame retardant reaches 12 parts, and the obvious cracking phenomenon of the cells starts to appear when the flame retardant is continuously added.
Compression mechanical property comparison of polyurethane foam
Compression mechanical properties of the composite aerogels prepared in examples 1 to 5 were tested on a UTM-16555 mechanical tester (Shenzhen solar technologies Co., ltd.) equipped with 100N and 1000N mechanical sensors. Regular cube samples were tested at a compression rate of 5 mm/min.
As can be seen from FIG. 3, the introduction of the additive flame retardant in examples 1 to 4 causes deterioration of mechanical properties of the material, which is reflected in both compressive strength and Young's modulus. With the increase of the addition amount of the flame retardant, the compressive strength and the Young modulus show the trend of increasing and then decreasing, which shows that within a certain range, EG can be used as filler to be compatible with polyurethane matrix. In the four groups of samples containing the flame retardant, the compressive strength and the Young modulus of EPLF3 reach the maximum value, the compressive strength is reduced by continuously adding the flame retardant, and a stress-strain curve shows a continuous sharp peak, so that the brittleness of the material is obviously increased.
Polyurethane foam thermal insulation performance comparison
The thermal insulation properties of the foam are characterized by thermal conductivity. The measurement of the heat conductivity coefficient adopts a transient flat plate heat source method and is characterized by adopting a heat conductivity coefficient meter manufactured by HOT DISK company.
As can be seen from FIG. 4, the introduction of the added flame retardants in examples 1 to 4 has a more or less negative effect on the heat-insulating properties of the rigid polyurethane foam. As the content of EG in the system increases, the thermal conductivity of the foam continues to increase, mainly because the carbon structure of EG is a good thermal conductor. When the EG addition amount is higher than 12 parts, the heat conductivity is from 50.7mW m -1 K -1 The rise to 53.5mW m -1 K -1 This is because the addition of high EG content results in a decrease in polyurethane crosslink density, which increases the apparent density of the hard bubbles and increases the thermal conductivity of the material. All foam samples prepared in examples 1-3 had thermal conductivity of less than 60mW m -1 K -1 Can be used as a good pipeline heat-insulating material.
Polyurethane foam hydrophobicity comparison
The hydrophilic-hydrophobic properties of the foam are characterized by contact angle testing. The contact angle test was performed by a droplet shape analyzer (DSA 100, KR Ü SS, germany) with 2 μl of water droplets for 300 s. Fig. 5 shows the surface water contact angles of 300s of the lignin polyurethane foams prepared in examples 1 to 4 and comparative example 4, and it is known from the graph that the lignin polyurethane foam has excellent hydrophobic properties, the average static Water Contact Angle (WCA) is 110 to 130 °, and the retention rate of WCA of the rest samples except for the sample PMLF3 within 300s is more than 97%.
Flame retardant Properties comparison of polyurethane foam
Foam flame retardant rating and burn behavior were evaluated jointly by Limiting Oxygen Index (LOI), vertical burn test (UL-94), CONE calorimeter test (CONE). Vertical burn tests were performed according to the method described in ASTM D3801-10: sample sizes were 130mm 13mm 10mm; the LOI value of the sample was determined using a limiting oxygen index instrument according to the method described in ASTM D2863-13, sample size 130mm 10mm 3mm; according to ISO 5660-1: the method described in 2015 was used for the test of combustion parameters of cone calorimeter with sample dimensions of 100mm x 10mm and heat flow radiation of 35kW/m 2 。
Fig. 6 (a) shows digital photographs of vertical burning of five groups of samples, all lignin-based polyurethane foams do not have a molten drop phenomenon in the burning process, and carbon residue can be kept intact after the burning is finished. The self-extinguishing phenomenon of the sample occurs after the flame retardant is added, and the self-extinguishing time is shortened along with the increase of the content of the flame retardant; when the flame retardant addition amount reaches more than 12 parts, the sample is not ignited after two 10s ignition, and UL94 reaches V-0.
FIGS. 6 (b) - (d) show the results of the cone calorimeter test on 5 sets of samples. The example foam sample has a significantly reduced peak heat release rate, compared to the comparative example, wherein the peak EPLF3 heat release rate is 181.3kW/m 2 Peak heat release rate (284.1 kW/m) compared to PMLF3 2 ) The reduction is 36.2 percent. When the amount of EG added is more than 12 parts, the smoke release rate of the foam sample is obviously reduced, and the smoke release rate of the EPLF3 and the EPLF4 in the whole combustion process is 0.1m 2 And the addition of EG has a good smoke suppression effect on the polyurethane hard foam, and the intensity in the smoke generation process is effectively reduced. And with the increase of EG addition, the mass of the sample after testThe addition of expanded graphite was shown to be effective in enhancing char formation.
Polyurethane rigid foams generally have limiting oxygen indices of less than 19% and are flammable materials. From fig. 6 (e), it can be seen that PLF oxygen index prepared from lignin-based phosphonate reaches 24.6%, increasing the combustion grade of combustible material to combustible material; the grade of flame-retardant materials (LOI > 27%) can be achieved by adding 4 parts of EG materials, the oxygen index of EPLF is gradually increased along with the increase of the content of the additives, when more than 12 parts of EG is added, the oxygen index of EPLFs can reach more than 30%, the flame-retardant grade is further improved, and the flame-retardant polyurethane rigid foam plastic has excellent flame-retardant performance.
The above description of the present invention is further illustrated in detail and should not be taken as limiting the practice of the present invention. It is within the scope of the present invention for those skilled in the art to make simple deductions or substitutions without departing from the concept of the present invention.
Claims (10)
1. The preparation method of the high-strength, fireproof and anti-dripping lignin-based polyurethane foam is characterized by comprising the following steps of:
adding lignin into polyalcohol, mixing for liquefaction reaction, adding phosphorus pentoxide for dehydration condensation esterification reaction, finally adding melamine for salifying reaction, stirring, cooling and discharging to obtain lignin-based phosphonate polyalcohol;
uniformly mixing lignin-based phosphonate polyol with a catalyst, a chain extender, a foam stabilizer, a foaming agent and a flame retardant, adding isocyanate raw materials, mixing for nucleophilic addition reaction, pouring into a mold for foam molding, demolding and curing to obtain the lignin-based polyurethane rigid flame retardant foam.
2. The process according to claim 1, wherein the esterification reaction temperature in step 1) is 90 to 220 ℃ and/or the reaction time is 1 to 5 hours.
3. The preparation method according to claim 1, wherein the phosphorus pentoxide is used in an amount of 1.5 to 10.5wt% of the lignin-based phosphonate polyol, the melamine is used in an amount of 1.5 to 7.5wt% of the lignin-based phosphonate polyol, the lignin is used in an amount of 0.5 to 60wt% of the total mass of the lignin-based phosphonate polyol, and the balance is the polyol.
4. The process according to claim 1, wherein the salt formation reaction temperature in step 1) is 25 to 150 ℃ and/or the reaction time is 0.5 to 3 hours.
5. The process according to claim 1, wherein the liquefaction reaction temperature in step 1) is 25 ℃ to 150 ℃ and/or the reaction time is 0.5 to 3 hours.
6. The method according to claim 1, wherein the lignin is any one selected from alkali lignin, kraft lignin, enzymatic lignin, organic solvent lignin and sulfonic acid lignin.
7. The method according to claim 1, wherein the polyhydric alcohol is selected from any one of ethylene glycol, glycerin, and polyethylene glycol.
8. The method according to claim 1, wherein each raw material for the nucleophilic addition reaction in step 2) is independently selected from:
the catalyst is at least one selected from triethylene diamine, triethanolamine, stannous octoate, dibutyl tin dilaurate, dibutyl tin (dodecyl sulfide) and monobutyl tin oxide;
the chain extender is at least one selected from 1, 4-butanediol, propylene glycol, glycerol, triethanolamine and diethylene glycol;
the foam homogenizing agent is at least one selected from simethicone, tween 40, tween 60 and Tween 80;
the foaming agent is at least one selected from the group consisting of monofluorodichloroethane, diethyl ether, deionized water, cyclopentane and n-pentane;
the flame retardant is any one of expanded graphite, ammonium polyphosphate, tri (2-chloroethyl) phosphate and methyl dimethyl phosphate;
the isocyanate is selected from any one of diphenylmethane diisocyanate, toluene diisocyanate and polymethylene polyphenyl polyisocyanate.
9. The preparation method according to claim 1 or 8, wherein the nucleophilic addition reaction in step 2) comprises the following components in parts by mass: 100 parts of lignin-based phosphonate polyol, 1-5 parts of catalyst, 1-6 parts of chain extender, 1-5 parts of foam homogenizing agent, 1-7 parts of foaming agent, 4-16 parts of flame retardant and 105-125 parts of isocyanate.
10. A thermal insulation material characterized by comprising the lignin-based polyurethane foam obtained by the preparation method of any one of claims 1 to 9.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101143876A (en) * | 2007-09-26 | 2008-03-19 | 公安部四川消防研究所 | Method for preparing melamine phosphate (borate) fire retardant |
| CN104371116A (en) * | 2014-11-04 | 2015-02-25 | 南京林业大学 | Preparation method and application of lignin-based intumescent flame retardant |
| CN108659228A (en) * | 2018-04-25 | 2018-10-16 | 中南林业科技大学 | A kind of modified lignin resin fire retardant and preparation method thereof |
| US20200199455A1 (en) * | 2017-09-13 | 2020-06-25 | Daren Laboratories & Scientific Consultants Ltd. | Lignin based flame retardant compositions and processes for the preparation thereof |
| CN112920377A (en) * | 2021-01-29 | 2021-06-08 | 青岛海力威新材料科技股份有限公司 | Polyurethane soft foam material for railway solidified track bed and preparation method thereof |
| CN114426678A (en) * | 2020-10-10 | 2022-05-03 | 中国石油化工股份有限公司 | Lignin-based flame-retardant char-forming agent and synthesis method and application thereof |
-
2023
- 2023-04-29 CN CN202310482268.2A patent/CN116396458A/en active Pending
-
2024
- 2024-04-27 CN CN202410516109.4A patent/CN118240166A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101143876A (en) * | 2007-09-26 | 2008-03-19 | 公安部四川消防研究所 | Method for preparing melamine phosphate (borate) fire retardant |
| CN104371116A (en) * | 2014-11-04 | 2015-02-25 | 南京林业大学 | Preparation method and application of lignin-based intumescent flame retardant |
| US20200199455A1 (en) * | 2017-09-13 | 2020-06-25 | Daren Laboratories & Scientific Consultants Ltd. | Lignin based flame retardant compositions and processes for the preparation thereof |
| CN108659228A (en) * | 2018-04-25 | 2018-10-16 | 中南林业科技大学 | A kind of modified lignin resin fire retardant and preparation method thereof |
| CN114426678A (en) * | 2020-10-10 | 2022-05-03 | 中国石油化工股份有限公司 | Lignin-based flame-retardant char-forming agent and synthesis method and application thereof |
| CN112920377A (en) * | 2021-01-29 | 2021-06-08 | 青岛海力威新材料科技股份有限公司 | Polyurethane soft foam material for railway solidified track bed and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| BIXIA ZHENG等: "Spider silk-inspired dynamic covalent polyurethane with fast repairing, shape memory, and strong dynamic adhesion via lignin enhanced microphase separation", COMPOSITES PART B-ENGINEERING, vol. 257, 27 March 2023 (2023-03-27), pages 110697 * |
| HAIBIN ZHU等: "Preparation and characterization of flame retardant polyurethane foams containing phosphorus-nitrogen-functionalized lignin", RSC ADVANCES, vol. 4, no. 98, 20 November 2014 (2014-11-20), pages 55271 - 55279 * |
| WU, JL等: "Superhydrophobic lignin-based multifunctional polyurethane foam with SiO2 nanoparticles for efficient oil adsorption and separation", SCIENCE OF THE TOTAL ENVIRONMENT, vol. 860, 17 November 2022 (2022-11-17), pages 160276, XP087245946, DOI: 10.1016/j.scitotenv.2022.160276 * |
| 马东;赵培华;李娟;: "生物基阻燃剂的设计、制备和应用研究进展", 工程塑料应用, no. 10, 10 October 2016 (2016-10-10), pages 137 - 140 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117103617A (en) * | 2023-10-23 | 2023-11-24 | 中投(天津)智能管道股份有限公司 | Manufacturing process of heat-preservation bent pipe based on seamless outer protection pipe and polyurethane for heat preservation |
| CN117103617B (en) * | 2023-10-23 | 2023-12-26 | 中投(天津)智能管道股份有限公司 | Manufacturing process of heat-preservation bent pipe based on seamless outer protection pipe and polyurethane for heat preservation |
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