CN115093530A - Bio-based flame-retardant thermoplastic polyurethane elastomer and preparation method thereof - Google Patents
Bio-based flame-retardant thermoplastic polyurethane elastomer and preparation method thereof Download PDFInfo
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- CN115093530A CN115093530A CN202210889262.2A CN202210889262A CN115093530A CN 115093530 A CN115093530 A CN 115093530A CN 202210889262 A CN202210889262 A CN 202210889262A CN 115093530 A CN115093530 A CN 115093530A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
- C08G18/4684—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6926—Dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2230/00—Compositions for preparing biodegradable polymers
Abstract
The invention relates to a bio-based flame-retardant thermoplastic polyurethane elastomer and a preparation method thereof, wherein the raw materials of the bio-based flame-retardant thermoplastic polyurethane elastomer comprise polyester polyol and diisocyanate, and the polyester polyol is prepared by reacting bio-based micromolecular dihydric alcohol, bio-based micromolecular saturated dibasic acid, bio-based micromolecular unsaturated dibasic acid, DOPO and/or DOPO derivatives. Compared with the conventional petroleum-based flame-retardant polyurethane elastomer, the thermoplastic polyurethane elastomer has high content of bio-based raw materials, does not need to add inorganic or organic flame-retardant additives with high proportion, maintains the biodegradability and has higher physical and mechanical properties.
Description
Technical Field
The invention belongs to the technical field of thermoplastic polyurethane elastomers, and particularly relates to a bio-based flame-retardant thermoplastic polyurethane elastomer and a preparation method thereof.
Background
Compared with the traditional material, the biological base material effectively reduces carbon emission in the production process, and meanwhile, when the biological material is discarded, the biological material can be converted into non-toxic small molecules such as water and carbon dioxide through biological degradation methods such as combustion or composting, and then enters the natural circulation again to maintain the whole ecological balance without worrying about environmental pollution. For a long time, the conversion of new and old kinetic energy between the bio-based industry and the traditional petrochemical industry with high energy consumption and high emission is a great trend.
There are reports in patents relating to biobased thermoplastic polyurethane elastomers, such as:
chinese patent CN114044875A discloses a thermoplastic polyurethane elastomer, a preparation method and application thereof, and discloses that 2, 5-furandicarboxylic acid, bio-based 1, 2-ethylene glycol, 1, 3-propylene glycol and 1, 4-butanediol are used for preparing bio-based polyol, bio-based polylactic acid glycol and the like as raw materials, and a proper amount of curcumin is added to prepare the photodegradable thermoplastic polyurethane elastomer. However, the material has excessive rigid structure, so that the processing operability of the material is deviated, and the thermoplastic polyurethane elastomer has no flame retardance and is limited in application.
Chinese patent CN113121786B discloses a polyurethane elastomer with bio-based amorphous multi-polyester as a soft segment and a preparation method thereof, wherein the soft segment is a hydroxyl-terminated amorphous polyester obtained by the reaction of at least four bio-based diols and diacids, and the soft segment comprises isocyanate and a micromolecular polyol chain extender which are combined to prepare the thermoplastic polyurethane elastomer with good mechanical property, oil resistance and excellent wear resistance. Such products exhibit good general performance but lack flame retardancy.
There are also some patents dealing with bio-based thermoplastic polyurethane resins having flame retardant properties, but the bio-based thermoplastic polyurethane resins are generally made flame retardant by adding a higher proportion of flame retardant, which however damages other properties of the polyurethane elastomer, such as mechanical properties.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a bio-based flame-retardant thermoplastic polyurethane elastomer with flame retardance and higher physical and mechanical properties while maintaining biodegradability and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
the bio-based flame-retardant thermoplastic polyurethane elastomer comprises polyester polyol and diisocyanate, wherein the polyester polyol is prepared by reacting bio-based micromolecular dihydric alcohol, bio-based micromolecular saturated dibasic acid, bio-based micromolecular unsaturated dibasic acid, DOPO and/or DOPO derivatives.
In the present invention, the DOPO means 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and the derivative of DOPO means a derivative of DOPO having a P-H bond.
According to the invention, a hyperconjugation system is formed by the carbon-carbon double bond in the bio-based small molecular unsaturated dibasic acid and two carboxylate radicals, the density of pi electron cloud on the alkene carbon is reduced, and a nucleophile is facilitated to approach to the alkene carbon atom, while the DOPO or the DOPO derivative has a phosphorus heterocyclic structure, and a P atom has a lone pair electron and is easy to perform a nucleophilic addition reaction with the carbon-carbon double bond on the unsaturated dibasic acid, so that the DOPO group is grafted to the main chain of the bio-based polyester polyol.
According to some embodiments of the invention, the mass of the bio-based small-molecule unsaturated dibasic acid accounts for 1-20 wt% of the total mass of the polyester polyol. Preferably, the mass of the bio-based small molecular unsaturated dibasic acid accounts for 2-20 wt% of the total mass of the polyester polyol.
According to some embodiments of the invention, the mass of DOPO and/or a derivative of DOPO is 2 to 30 wt% of the total mass of the polyester polyol. Preferably, the mass of the DOPO and/or the DOPO derivative accounts for 3-15 wt% of the total mass of the polyester polyol.
Further, the bio-based small molecule unsaturated dibasic acid is one or more of fumaric acid, itaconic acid and maleic acid.
Further, the bio-based small molecule diol is one or a combination of more of bio-based 1, 2-ethylene glycol, bio-based 1, 3-propylene glycol, bio-based 1, 4-butanediol, bio-based 1, 5-pentanediol, bio-based 1, 6-hexanediol, bio-based 1, 10-decanediol, bio-based diethylene glycol, bio-based dipropylene glycol and bio-based isosorbide.
Further, the bio-based small molecule saturated dibasic acid is one or more of bio-based succinic acid, bio-based adipic acid, bio-based glutaric acid, bio-based 1, 9-nonane dicarboxylic acid, bio-based sebacic acid, 2, 5-furandicarboxylic acid and bio-based dodecyl dibasic acid.
The polyester polyol is prepared by adopting a polyester polyol synthesis process known in the industry, and the number average molecular weight of the polyester polyol is required to be 500-6000 g/mol, preferably 800-4500 g/mol; the polyester polyol has a hydroxyl number of 18 to 140mg KOH/g, preferably 28 to 115mg KOH/g; the acid value of the polyester polyol is 1mg KOH/g or less, preferably 0.5mg KOH/g or less. The polyester polyol has a moisture content of 300ppm or less, preferably 200ppm or less. The amount of the catalyst to be added in the preparation of the polyester polyol is 300ppm or less, preferably 200ppm or less.
The polyester polyol has a biobased content of 50 wt% or more, and preferably, the biobased content is 60 wt% or more. The biobased content here refers to the percentage of components of biological origin in the total mass of the polyester polyol.
According to some embodiments of the invention, the raw material of the bio-based flame retardant thermoplastic polyurethane elastomer further comprises a chain extender.
Further, the raw materials of the bio-based flame-retardant thermoplastic polyurethane elastomer comprise, by mass, 40-90 wt% of the polyester polyol, 5-45 wt% of the diisocyanate, and 0-20 wt% of the chain extender.
Preferably, the raw materials of the bio-based flame-retardant thermoplastic polyurethane elastomer comprise, by mass, 45-80 wt% of the polyester polyol, 7-40 wt% of the diisocyanate, and 2-15% of the chain extender.
Further, the chain extender is a bio-based chain extender. In some embodiments, the chain extender is a combination of one or more of bio-based 1, 2-ethanediol, bio-based 1, 3-propanediol, bio-based 1, 4-butanediol, bio-based 1, 5-pentanediol.
In some embodiments, the raw material of the bio-based flame-retardant thermoplastic polyurethane elastomer further comprises a catalyst with an addition amount of 0-0.1 wt% of the total mass of the raw material of the bio-based flame-retardant thermoplastic polyurethane elastomer. Preferably, the catalyst is used in an amount of 0.001 to 0.1 wt%. More preferably, the amount of the catalyst added is 0.005-0.05%.
Further, the catalyst is preferably a tin environment-friendly catalyst.
In some embodiments, the raw material of the bio-based flame-retardant thermoplastic polyurethane elastomer further comprises an auxiliary flame retardant in an amount of 0 to 15 wt% of the total mass of the raw material of the bio-based flame-retardant thermoplastic polyurethane elastomer. Preferably, the addition amount of the auxiliary flame retardant is 1.5-10 wt%. More preferably, the addition amount of the auxiliary flame retardant is 1.5 to 7 wt%.
Further, the auxiliary flame retardant includes, but is not limited to, one or more of melamine cyanurate, tris (2-ethylhexyl) phosphate, aluminum diethylphosphinate, and polyphosphazene in combination.
In some embodiments, the raw material of the bio-based flame-retardant thermoplastic polyurethane elastomer further comprises an auxiliary agent which is added in an amount of 0.05-5 wt% of the total mass of the raw material of the bio-based flame-retardant thermoplastic polyurethane elastomer. Preferably, the addition amount of the auxiliary agent is 0.05-2 wt%. Further preferably, the addition amount of the auxiliary agent is 0.1-2 wt%.
Further, the auxiliary agents include, but are not limited to, one or more of antioxidants, ultraviolet absorbers and lubricants, and the specific dosage and details of each auxiliary agent can be referred to the handbook of polyurethane raw materials and auxiliary agents (second edition).
In some preferred and specific embodiments, the raw materials of the bio-based flame-retardant thermoplastic polyurethane elastomer comprise, by mass percentage, 45 to 80 wt% of the polyester polyol, 15 to 40 wt% of the diisocyanate, 2 to 10 wt% of the chain extender, 0 to 2 wt% of the auxiliary flame retardant, and 0 to 10 wt% of the auxiliary flame retardant.
According to some embodiments of the invention, the diisocyanates are all petroleum-based diisocyanates or contain 0 to 20 wt% of bio-based diisocyanates based on the total weight of the diisocyanates.
Further, the diisocyanate is one or more of 4, 4-diphenylmethane diisocyanate (MDI), 1, 5-naphthalene diisocyanate, toluene diisocyanate, p-phenylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate (H12MDI), hexamethylene diisocyanate and lysine diisocyanate.
According to some embodiments of the invention, the bio-based flame retardant thermoplastic polyurethane elastomer has a bio-based content of 40 wt% or more. Preferably, the biobased content is 45 wt% or more. More preferably, the bio-based content is 45 to 80 wt%. The bio-based content referred to herein means the percentage of the bio-derived component to the total mass of the bio-based flame retardant thermoplastic polyurethane elastomer.
The bio-based in the invention is of biological origin, and the petroleum-based is of petroleum origin.
The second technical scheme adopted by the invention is as follows: the preparation method of the bio-based flame-retardant thermoplastic polyurethane elastomer adopts a one-step method, a batch method or a prepolymerization method.
The one-step method or the indirect method comprises the steps of mixing polyester polyol and diisocyanate, and then extruding the mixture through a double-screw extruder to prepare the bio-based flame-retardant thermoplastic polyurethane elastomer. When the raw materials of the bio-based flame-retardant thermoplastic polyurethane elastomer also comprise a chain extender and/or other components, the chain extender and/or other components are mixed with polyester polyol and diisocyanate and then are extruded by the twin-screw extruder to prepare the bio-based flame-retardant thermoplastic polyurethane elastomer.
The prepolymerization method comprises the steps of prepolymerizing polyester polyol and diisocyanate, and then adding a chain extender to react to prepare the bio-based flame-retardant thermoplastic polyurethane elastomer.
In the prepolymerization method, the molar ratio of the polyester polyol to the diisocyanate is 1: 1.5-3, wherein the molar ratio of the chain extender to the polyester polyol is 1: 0.8 to 1.2.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
according to the invention, the bio-based unsaturated dibasic acid is introduced into the main chain of the bio-based polyester polyol, and the unsaturated double bond of the bio-based unsaturated dibasic acid and the P-H in the free DOPO phosphorous heterocyclic structure are utilized to carry out nucleophilic addition reaction, so that the high-efficiency flame retardant group is introduced into the side chain of the bio-based polyester polyol, the structural physical property of a molecular chain is not damaged, and the flame retardant property of the main chain is improved. In addition, except for a branched flame-retardant functional group DOPO, the soft segment of the thermoplastic polyurethane elastomer is all bio-based polyester polyol obtained by condensation polymerization of bio-based monomers, so that partial renewability of polyurethane is ensured, and compared with the conventional petroleum-based thermoplastic polyurethane elastomer, the thermoplastic polyurethane elastomer disclosed by the invention has high content of bio-based raw materials, and meanwhile, inorganic or organic flame-retardant additives with high proportion are not required to be added, so that the thermoplastic polyurethane elastomer not only maintains the biodegradability, but also has higher physical and mechanical properties.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications may be made by those skilled in the art after reading the disclosure of the present invention, and such equivalents may fall within the scope of the invention as defined by the appended claims.
Examples 1a to 6a and comparative example 1a below were used to prepare bio-based polyester polyols under the same temperature program and vacuum condition, specifically, the temperature program was: esterification and dehydration are carried out for 2-5h at 140-200 ℃, then the temperature is raised to 250 ℃ for ester exchange reaction for 2-4h, the acid value is continuously tested in the constant temperature process, when the acid value is qualified, the hydroxyl value is tested until the hydroxyl value is qualified, and the reaction is stopped after the temperature is reduced.
Example 1a
This example provides a bio-based flame retardant polyester polyol P1, prepared by the following method:
bio-based 1, 4-succinic acid, itaconic acid, DOPO and bio-based 1, 2-glycol are mixed according to a molar ratio of 38: 1: 1.02: 40, adding the mixture into a reaction kettle with a fractionating tower and a distillation receiver, carrying out programmed heating and vacuumizing, and preparing the bio-based flame-retardant polyester polyol P1 with the hydroxyl value of 112.2mg KOH/g, the corresponding number average molecular weight of 1000g/mol, the acid value of 0.3mg KOH/g and the moisture content of 300ppm, wherein the mass content of DOPO accounts for 3 percent of the total mass of the bio-based flame-retardant polyester polyol P1.
Example 2a
This example provides a bio-based flame retardant polyester polyol P2 prepared by the following method:
bio-based sebacic acid, fumaric acid, DOPO and bio-based 1, 3-propylene glycol are mixed according to the molar ratio of 6: 1: 1.05: 8, adding the mixture into a reaction kettle with a fractionating tower and a distillation receiver, carrying out programmed heating and vacuumizing, and preparing the bio-based flame-retardant polyester polyol P2 with the hydroxyl value of 56.1mg KOH/g, the corresponding number average molecular weight of 2000g/mol, the acid value of 0.5mg KOH/g and the moisture content of 200ppm, wherein the mass content of DOPO accounts for 10% of the total mass of the bio-based flame-retardant polyester polyol P2.
Example 3a
This example provides a bio-based flame retardant polyester polyol P3, prepared by the following method:
bio-based 1, 4-succinic acid, maleic acid, DOPO and bio-based diethylene glycol are mixed according to a molar ratio of 4.5: 1: 1: 6, adding the mixture into a reaction kettle with a fractionating tower and a distillation receiver, carrying out programmed heating and vacuumizing to prepare the bio-based flame-retardant polyester polyol P3 with the hydroxyl value of 56.1mg KOH/g, the corresponding number average molecular weight of 2000, the acid value of 0.4mg KOH/g and the moisture content of 100ppm, wherein the mass content of DOPO accounts for 15 percent of the total mass of the bio-based flame-retardant polyester polyol P3.
Example 4a
This example provides a bio-based flame retardant polyester polyol P4, prepared by the following method:
bio-based 1, 4-succinic acid, itaconic acid, DOPO and bio-based 1, 6-hexanediol are mixed according to a molar ratio of 7.3: 1: 1.01: 8.5 adding the mixture into a reaction kettle with a fractionating tower and a distillation receiver, carrying out programmed heating and vacuumizing to prepare the bio-based flame-retardant polyester polyol P4 with the hydroxyl value of 112.2mg KOH/g, the corresponding number average molecular weight of 1000g/mol, the acid value of 0.1mg KOH/g and the moisture content of 400ppm, wherein the mass content of DOPO accounts for 10 percent of the total mass of the bio-based flame-retardant polyester polyol P4.
Example 5a
This example provides a bio-based flame retardant polyester polyol P5, prepared by the following method:
bio-based 1, 4-succinic acid, fumaric acid, DOPO and bio-based 1, 3-propylene glycol are mixed according to the mol ratio of 11.8: 1: 1: 13, adding the mixture into a reaction kettle with a fractionating tower and a distillation receiver, carrying out programmed heating and vacuum pumping, and preparing the bio-based flame-retardant polyester polyol P5 with the hydroxyl value of 37.4mg KOH/g, the corresponding number average molecular weight of 3000g/mol, the acid value of 0.2mg KOH/g and the moisture content of 100ppm, wherein the mass content of DOPO accounts for 8 percent of the total mass of the bio-based flame-retardant polyester polyol P5.
Example 6a
This example provides a bio-based flame retardant polyester polyol P6, prepared by the following method:
bio-based sebacic acid, itaconic acid, DOPO and bio-based diethylene glycol are mixed according to a molar ratio of 12.8: 1: 1: 14.3 into a reaction kettle with a fractionating tower and a distillation receiver, carrying out programmed heating and vacuum pumping to prepare the bio-based flame-retardant polyester polyol P6 with the hydroxyl value of 24.93mg KOH/g, the corresponding number average molecular weight of 4500g/mol, the acid value of 0.1mg KOH/g and the moisture content of 100ppm, wherein the mass content of DOPO accounts for 6 percent of the total mass of the bio-based flame-retardant polyester polyol P6.
Comparative example 1a
This comparative example provides a bio-based polyester polyol P7, prepared by the following method:
bio-based 1, 4-succinic acid and bio-based 1, 3-propylene glycol are mixed according to a molar ratio of 1: 1.2 into a reaction vessel equipped with a fractionating column and a distillation receiver, and was subjected to temperature programming and vacuum pumping to prepare a biobased polyester polyol P7 having a hydroxyl value of 112.2mg KOH/g, a number average molecular weight of 1000g/mol, an acid value of 0.1mg KOH/g, and a moisture content of 100 ppm.
The following examples 1 to 6 and comparative examples 1 to 2 respectively adopt a twin-screw extruder to prepare the thermoplastic polyurethane elastomer by extrusion, specifically, the twin-screw extruder has 14 heating zones, a first pouring port (for liquid feeding) is located in the first heating zone, a second pouring port (for powder feeding) is located in the ninth heating zone, the temperature from the first pouring port to the second pouring port is 160-160 ℃, the temperature from the second pouring port to a die head is 200-160 ℃, the length-diameter ratio of the twin-screw is 70:1, and the screw rotation speed is 200 r/min. Here, the liquid means polyester polyol, diisocyanate, chain extender and auxiliary agent.
Example 1
This example provides a bio-based flame retardant thermoplastic polyurethane elastomer prepared by the following method:
uniformly mixing 62.3 wt% of polyester polyol P1 with the molecular weight of 1000g/mol, 31.6 wt% of 4, 4-diphenylmethane diisocyanate, 6.0 wt% of bio-based 1, 4-butanediol and 0.1 wt% of antioxidant, and performing reaction and extrusion by using a double-screw extruder to obtain the bio-based flame-retardant thermoplastic polyurethane elastomer.
Example 2
This example provides a bio-based flame retardant thermoplastic polyurethane elastomer prepared by the following method:
63.7 weight percent of polyester polyol P2 with molecular weight of 2000g/mol, 29.5 weight percent of 4, 4-diphenylmethane diisocyanate, 6.6 weight percent of bio-based 1, 3-propylene glycol and 0.2 weight percent of antioxidant are mixed uniformly, and then the mixture is reacted and extruded by a double screw extruder to prepare the bio-based flame-retardant thermoplastic polyurethane elastomer.
Example 3
This example provides a bio-based flame retardant thermoplastic polyurethane elastomer prepared by the following method:
57.2 wt% of polyester polyol P3 with molecular weight of 2000g/mol, 33.3 wt% of 4, 4-diphenylmethane diisocyanate, 9.2 wt% of bio-based 1, 3-propylene glycol and 0.3 wt% of antioxidant are uniformly mixed, 5% of tris (2-ethylhexyl) phosphate is added at a powder feeding port of a double-screw extruder relative to the total amount of liquid (the total amount of the liquid refers to the total amount of the polyester polyol, the 4, 4-diphenylmethane diisocyanate, the bio-based 1, 3-propylene glycol and the antioxidant), and the mixture is reacted and extruded by the double-screw extruder to prepare the bio-based flame-retardant thermoplastic polyurethane elastomer.
Example 4
This example provides a bio-based flame retardant thermoplastic polyurethane elastomer prepared by the following method:
50.7 wt% of polyester polyol P4 with molecular weight of 1000g/mol, 39.8 wt% of dicyclohexylmethane diisocyanate, 9.1 wt% of bio-based 1, 4-butanediol and 0.4 wt% of antioxidant are uniformly mixed, tri (2-ethylhexyl) phosphate which is 10% of the total amount of liquid is added at a powder feeding port of a double-screw extruder, and then the bio-based flame-retardant thermoplastic polyurethane elastomer is prepared by reaction and extrusion of the double-screw extruder.
Example 5
This example provides a bio-based flame retardant thermoplastic polyurethane elastomer, prepared by the following method:
73.0 wt% of polyester polyol P5 with molecular weight of 3000g/mol, 21.0 wt% of 4, 4-diphenylmethane diisocyanate, 5.0 wt% of bio-based 1, 4-butanediol and 1.0 wt% of antioxidant are uniformly mixed, tris (2-ethylhexyl) phosphate accounting for 2% of the total amount of liquid is added at a powder feeding port of a double-screw extruder, and the mixture is reacted and extruded by the double-screw extruder to prepare the bio-based flame-retardant thermoplastic polyurethane elastomer.
Example 6
This example provides a bio-based flame retardant thermoplastic polyurethane elastomer prepared by the following method:
72.8 wt% of polyester polyol P6 with the molecular weight of 4500g/mol, 21.5 wt% of 4, 4-diphenylmethane diisocyanate, 5.6 wt% of bio-based 1, 4-butanediol and 0.1 wt% of antioxidant are uniformly mixed, tri (2-ethylhexyl) phosphate which is 7% of the total amount of liquid is added at a powder feeding port of a double-screw extruder, and the mixture is reacted and extruded by the double-screw extruder to prepare the bio-based flame-retardant thermoplastic polyurethane elastomer.
Comparative example 1
The bio-based flame-retardant thermoplastic polyurethane elastomer provided by the comparative example is prepared by the following method:
63.2 wt% of polyester polyol P7 with molecular weight of 1000g/mol, 31.6 wt% of 4, 4-diphenylmethane diisocyanate, 5.1 wt% of bio-based 1, 3-propylene glycol and 0.1 wt% of antioxidant are uniformly mixed, tri (2-ethylhexyl) phosphate accounting for 10% of the total amount of liquid is added at a powder feed port of a double-screw extruder, and the mixture is reacted and extruded by the double-screw extruder to prepare the bio-based thermoplastic polyurethane elastomer.
Comparative example 2
The thermoplastic polyurethane elastomer provided by the comparative example is prepared by the following method:
61.7 weight percent of petroleum-based adipic acid butanediol polyol P8 with the molecular weight of 1000g/mol, 31.9 weight percent of 4, 4-diphenylmethane diisocyanate, 6.1 weight percent of petroleum-based 1, 4-butanediol and 0.3 weight percent of antioxidant are mixed uniformly, and then the mixture is reacted and extruded by a double-screw extruder to prepare the thermoplastic polyurethane elastomer.
Table 1 below is a summary of the use of the raw materials of the thermoplastic polyurethane elastomers of examples 1 to 6 and comparative examples 1 to 2
TABLE 1
Note: in table 1, the polyol ratio refers to the percentage of the polyester polyol used in the total amount of the liquid; the content of the biological micromolecule chain extender is the percentage of the biological chain extender in the total amount of the liquid; biobased content refers to the percentage of biobased material in the total liquid. The total amount of liquid here refers to the total mass of polyester polyol, diisocyanate, bio-based chain extender and antioxidant.
The thermoplastic polyurethane elastomers of examples 1 to 6 and comparative examples 1 to 2 were dried, and then introduced into an injection molding machine, and injection-molded into test pieces, which were cut into standard sample strips, and the test pieces were subjected to a performance test, the results of which are shown in table 2.
Table 2 shows the results of the performance tests of the thermoplastic polyurethane elastomers of examples 1 to 6 and comparative examples 1 to 2
In table 2, the flame retardant rating was measured using a vertical burn test method, specifically: the test was performed according to the vertical method of GB/T2408-1996, with at least 5 splines per group. The flame retardant rating test is that the flame spread delaying performance of the material or the treated material is marked, and the flame retardant rating is gradually increased from V2, V1 to V0 according to the rating system divided by the flame retardant rating: v0 shows that after the sample is subjected to two 10-second combustion tests, the flame is extinguished within 30 seconds, and no combustible can fall off; v1 shows that after the sample is subjected to two 10-second combustion tests, the flame is extinguished within 60 seconds, and no combustible can fall off, and V2 shows that after the sample is subjected to two 10-second combustion tests, the flame is extinguished within 60 seconds, and the combustible can fall off.
The test standards for tensile strength, elongation at break, and tear strength are ASTM D412, respectively.
As shown in Table 2, the bio-based thermoplastic polyurethane elastomers of examples 1 to 6 have high bio-based content and excellent flame retardancy and mechanical properties.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Claims (10)
1. A bio-based flame-retardant thermoplastic polyurethane elastomer comprises polyester polyol and diisocyanate as raw materials, and is characterized in that: the polyester polyol is prepared by reacting bio-based micromolecular dihydric alcohol, bio-based micromolecular saturated dibasic acid, bio-based micromolecular unsaturated dibasic acid, DOPO and/or DOPO derivatives.
2. The bio-based flame retardant thermoplastic polyurethane elastomer according to claim 1, wherein: the mass of the bio-based small molecular unsaturated dibasic acid accounts for 1-20 wt% of the total mass of the polyester polyol; and/or the mass of the DOPO and/or the DOPO derivative accounts for 2-30 wt% of the total mass of the polyester polyol.
3. The bio-based flame retardant thermoplastic polyurethane elastomer according to claim 1 or 2, characterized in that: the bio-based small molecule unsaturated dibasic acid is one or more of fumaric acid, itaconic acid and maleic acid; and/or the bio-based small molecule diol is one or more of bio-based 1, 2-ethanediol, bio-based 1, 3-propanediol, bio-based 1, 4-butanediol, bio-based 1, 5-pentanediol, bio-based 1, 6-hexanediol, bio-based 1, 10-decanediol, bio-based diethylene glycol, bio-based dipropylene glycol and bio-based isosorbide; and/or the bio-based small molecule saturated dibasic acid is one or more of bio-based succinic acid, bio-based adipic acid, bio-based glutaric acid, bio-based 1, 9-nonane dicarboxylic acid, bio-based sebacic acid, 2, 5-furandicarboxylic acid and bio-based dodecyl dibasic acid.
4. The bio-based flame retardant thermoplastic polyurethane elastomer according to claim 1, wherein: the number average molecular weight of the polyester polyol is 500-6000 g/mol.
5. The bio-based flame retardant thermoplastic polyurethane elastomer according to claim 1, wherein: the raw materials of the bio-based flame-retardant thermoplastic polyurethane elastomer comprise, by mass, 40-90 wt% of the polyester polyol, 5-45 wt% of the diisocyanate and 0-20 wt% of the chain extender.
6. The bio-based flame retardant thermoplastic polyurethane elastomer according to claim 5, wherein: the chain extender is one or a combination of more of bio-based 1, 2-ethylene glycol, bio-based 1, 3-propylene glycol, bio-based 1, 4-butanediol and bio-based 1, 5-pentanediol.
7. The bio-based flame retardant thermoplastic polyurethane elastomer according to claim 5, wherein: the raw materials of the bio-based flame-retardant thermoplastic polyurethane elastomer also comprise a catalyst with the addition amount of 0-0.1 wt% of the total mass of the raw materials of the bio-based flame-retardant thermoplastic polyurethane elastomer; and/or the raw materials of the bio-based flame-retardant thermoplastic polyurethane elastomer also comprise an auxiliary flame retardant with the addition amount of 0-15 wt% of the total mass of the raw materials of the bio-based flame-retardant thermoplastic polyurethane elastomer; and/or the raw materials of the bio-based flame-retardant thermoplastic polyurethane elastomer also comprise an additive with the addition amount of 0.05-5 wt% of the total mass of the raw materials of the bio-based flame-retardant thermoplastic polyurethane elastomer.
8. The bio-based flame retardant thermoplastic polyurethane elastomer according to claim 1, wherein: the diisocyanates are either all petroleum-based diisocyanates or contain 0-20 wt% of bio-based diisocyanates based on the total weight of the diisocyanates.
9. The bio-based flame retardant thermoplastic polyurethane elastomer according to claim 8, wherein: the diisocyanate is one or a combination of more of 4, 4-diphenylmethane diisocyanate, 1, 5-naphthalene diisocyanate, toluene diisocyanate, p-phenylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate.
10. A method for preparing the bio-based flame retardant thermoplastic polyurethane elastomer according to any one of claims 1 to 9, wherein: the preparation method comprises the step of extruding the polyester polyol and the diisocyanate by a double-screw extruder.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114031742A (en) * | 2021-12-15 | 2022-02-11 | 河北邦泰氨纶科技有限公司 | Biodegradable melt-spun spandex slice and preparation method and application thereof |
| CN115521434A (en) * | 2022-09-20 | 2022-12-27 | 中国科学院宁波材料技术与工程研究所 | Birch alcohol-based thermoplastic polyurethane elastomer and preparation method thereof |
| CN117467105A (en) * | 2023-12-28 | 2024-01-30 | 山东一诺威聚氨酯股份有限公司 | Bio-based solvent-resistant polyurethane prepolymer and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104004171A (en) * | 2014-06-16 | 2014-08-27 | 旭川化学（苏州）有限公司 | Preparation method of phosphorus-containing halogen-free environmentally-friendly flame-retardant polyester polyol |
| CN104558570A (en) * | 2015-01-22 | 2015-04-29 | 泉州市德诚高新树脂有限公司 | Synthesis of phosphorus containing polyester polyol and application of phosphorus containing polyester polyol in polyurethane |
| CN104927038A (en) * | 2015-06-18 | 2015-09-23 | 福建师范大学泉港石化研究院 | Method for preparing DOPO-base flame-retarding polyester polyol in solvent-free mode |
| CN109354668A (en) * | 2018-09-11 | 2019-02-19 | 东莞市吉鑫高分子科技有限公司 | A kind of high fire-retardance thermoplastic polyurethane elastomer and preparation method thereof |
| CN110408015A (en) * | 2019-08-07 | 2019-11-05 | 美瑞新材料股份有限公司 | A kind of flame retardant polyester polyalcohol and preparation method thereof |
| CN112079987A (en) * | 2020-09-29 | 2020-12-15 | 江苏登科聚氨酯材料有限公司 | Body flame-retardant thermoplastic polyurethane elastomer and preparation method thereof |
| US20210087326A1 (en) * | 2019-09-19 | 2021-03-25 | Sunko Ink Co., Ltd. | Polyester polyol, thermoplastic polyurethane and article thereof |
| CN113512170A (en) * | 2021-08-06 | 2021-10-19 | 宁波长阳科技股份有限公司 | Flame-retardant thermoplastic polyurethane elastomer film and preparation method thereof |
-
2022
- 2022-07-27 CN CN202210889262.2A patent/CN115093530A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104004171A (en) * | 2014-06-16 | 2014-08-27 | 旭川化学（苏州）有限公司 | Preparation method of phosphorus-containing halogen-free environmentally-friendly flame-retardant polyester polyol |
| CN104558570A (en) * | 2015-01-22 | 2015-04-29 | 泉州市德诚高新树脂有限公司 | Synthesis of phosphorus containing polyester polyol and application of phosphorus containing polyester polyol in polyurethane |
| CN104927038A (en) * | 2015-06-18 | 2015-09-23 | 福建师范大学泉港石化研究院 | Method for preparing DOPO-base flame-retarding polyester polyol in solvent-free mode |
| CN109354668A (en) * | 2018-09-11 | 2019-02-19 | 东莞市吉鑫高分子科技有限公司 | A kind of high fire-retardance thermoplastic polyurethane elastomer and preparation method thereof |
| CN110408015A (en) * | 2019-08-07 | 2019-11-05 | 美瑞新材料股份有限公司 | A kind of flame retardant polyester polyalcohol and preparation method thereof |
| US20210087326A1 (en) * | 2019-09-19 | 2021-03-25 | Sunko Ink Co., Ltd. | Polyester polyol, thermoplastic polyurethane and article thereof |
| CN112079987A (en) * | 2020-09-29 | 2020-12-15 | 江苏登科聚氨酯材料有限公司 | Body flame-retardant thermoplastic polyurethane elastomer and preparation method thereof |
| CN113512170A (en) * | 2021-08-06 | 2021-10-19 | 宁波长阳科技股份有限公司 | Flame-retardant thermoplastic polyurethane elastomer film and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 林飞: ""DOPO基聚酯多元醇和含P/N扩链剂的合成及其在聚氨酯弹性体中的应用"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114031742A (en) * | 2021-12-15 | 2022-02-11 | 河北邦泰氨纶科技有限公司 | Biodegradable melt-spun spandex slice and preparation method and application thereof |
| CN115521434A (en) * | 2022-09-20 | 2022-12-27 | 中国科学院宁波材料技术与工程研究所 | Birch alcohol-based thermoplastic polyurethane elastomer and preparation method thereof |
| CN115521434B (en) * | 2022-09-20 | 2023-11-03 | 中国科学院宁波材料技术与工程研究所 | Birch alcohol-based thermoplastic polyurethane elastomer and preparation method thereof |
| CN117467105A (en) * | 2023-12-28 | 2024-01-30 | 山东一诺威聚氨酯股份有限公司 | Bio-based solvent-resistant polyurethane prepolymer and preparation method and application thereof |
| CN117467105B (en) * | 2023-12-28 | 2024-04-23 | 山东一诺威聚氨酯股份有限公司 | Bio-based solvent-resistant polyurethane prepolymer and preparation method and application thereof |
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