CN111440434A - Flame-retardant composite material of polyurethane-polylactic acid block copolymer and preparation method thereof - Google Patents
Flame-retardant composite material of polyurethane-polylactic acid block copolymer and preparation method thereof Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/40—High-molecular-weight compounds
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- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
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- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The invention relates to the technical field of polylactic acid composite materials, and discloses a polyurethane-polylactic acid block copolymer flame-retardant composite material, which comprises the following formula raw materials: cyclotriphosphazene derivative, polypropylene carbonate polyol, 1,5-Naphthalene diisocyanate, D L-lactide, poly-caprolactone diol, SnCl2. According to the flame-retardant polyurethane-polylactic acid block copolymer composite material, the flexible chain segment poly-caprolactone diol and the polylactic acid form a stereocrystalline linear stereocomplex, the toughness and the melt thermal stability of a polylactic acid material are enhanced, the polyurethane modified polylactic acid is synthesized by an in-situ polymerization method, the tensile strength and the breaking strength of the composite material are enhanced, and the phosphate-cyclotriphosphazene derivative is decomposed by heating to generate non-combustible NH (NH)3、N2And the polylactic acid material is dehydrated to form a compact carbonized layer, so that the further combustion of the material is hindered.
Description
Technical Field
The invention relates to the technical field of polylactic acid composite materials, in particular to a polyurethane-polylactic acid block copolymer flame-retardant composite material and a preparation method thereof.
Background
The polylactic acid is mainly formed into a polymer through dehydration condensation of hydroxyl and carboxyl among lactic acid molecules, the raw material source for preparing the polylactic acid is sufficient and can be regenerated, the production process of the polylactic acid is pollution-free, and the product has biodegradability and realizes circulation in nature, so that the polylactic acid material is an ideal green high polymer material.
The polylactic acid material can be processed by various melting methods, such as extrusion, biaxial stretching, injection blow molding and the like, has the advantages of excellent biocompatibility, high glossiness, strong transparency and the like, and is widely applied to the fields of packaging materials, fibers, non-woven fabrics, agriculture and forestry industries, medical treatment and health care and the like.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a polyurethane-polylactic acid segmented copolymer flame-retardant composite material and a preparation method thereof, which solve the problems of low high temperature resistance and flame retardance of polylactic acid and solve the problems of high brittleness, poor mechanical properties such as tensile strength and breaking strength and the like of polylactic acid materials.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme that the flame-retardant polyurethane-polylactic acid block copolymer composite material comprises the following formula raw materials, by weight, 7-26 parts of cyclotriphosphazene derivative, 20-23 parts of polypropylene carbonate polyol, 5-9 parts of 1, 5-diisocyanato naphthalene, 40-47 parts of D L-lactide, 6-9 parts of poly-caprolactone diol and 3-5 parts of poly-lactic acid block copolymerPart SnCl2。
Preferably, the molecular weight of the polycondensation propylene carbonate polyol is 3300-3700, and the hydroxyl content is 25-35%.
Preferably, the preparation method of the phosphate-cyclotriphosphazene derivative comprises the following steps:
(1) introducing N into the reaction bottle2Discharging air, adding a toluene solvent, diphenyl phosphate and 1, 4-benzenedimethanol, adding concentrated hydrochloric acid to regulate the reaction temperature to 3-4, adding catalysts of methylbenzenesulfonic acid (TsOH) and a condensing agent of Dicyclohexylcarbodiimide (DCC), placing a reaction bottle in an oil bath pot, heating to 110 ℃ and 120 ℃, uniformly stirring to react for 20-25h, observing the reaction process through T L C thin-layer chromatography, concentrating the solution under reduced pressure to remove the solvent after the diphenyl phosphate completely reacts, separating the concentrated mixture through a silica gel chromatographic column by using petroleum ether and ethyl acetate as eluent, wherein the ethyl acetate is 1:1-2, enriching the eluent containing the product, and removing the eluent through reduced pressure concentration and vacuum suction filtration distillation to prepare the diphenyl phosphate benzyl alcohol compound, wherein the reaction equation is as follows:
(2) introducing N into the reaction flask2Discharging air, adding a mixed solvent of anhydrous acetonitrile and anhydrous toluene, wherein the volume ratio of the anhydrous acetonitrile to the anhydrous toluene is 1.5-2:1, sequentially adding a diphenyl phosphate benzyl alcohol compound, hexachlorocyclotriphosphazene and 4-Dimethylaminopyridine (DMAP), placing a reaction bottle in an oil bath pot, heating to 85-95 ℃, uniformly stirring for reaction for 15-20h, observing the reaction process through a T L C thin-layer chromatography, concentrating the solution under reduced pressure to remove the solvent after the diphenyl phosphate benzyl alcohol compound completely reacts, washing a solid product by using a proper amount of anhydrous ethanol, and fully drying to prepare the phosphate-cyclotriphosphazene derivative, wherein the reaction equation is as follows:
preferably, the molar ratio of the diphenyl phosphate to the 1, 4-benzenedimethanol to the methylbenzene sulfonic acid to the dicyclohexylcarbodiimide is 1:3-3.8:0.15-0.25: 2-2.5.
Preferably, the diphenyl phosphate benzyl alcohol compound, the hexachlorocyclotriphosphazene and the 4-dimethylaminopyridine are mixed according to the molar ratio of 6-8:1: 15-20.
Preferably, the oil bath pot comprises a box body, the right side of the box body is fixedly connected with a controller, a groove is formed in the front face of the box body, a screw rod is movably connected inside the groove, a bath pot is movably connected to the top of the box body, and a mounting frame is fixedly connected to the top of the box body and located on the left side of the bath pot.
Preferably, the preparation method of the polyurethane-polylactic acid block copolymer flame-retardant composite material comprises the following steps:
(1) adding a proper amount of N, N-dimethylformamide solvent, 40-47 parts of D L-lactide and 3-5 parts of initiator SnCl into a reaction bottle2Placing the reaction bottle in an oil bath pot, heating to 150-.
(2) Adding a proper amount of N, N-dimethylformamide solvent, 20-23 parts of polypropylene carbonate polyol and the polycaprolactone diol-polylactic acid block copolymer prepared in the step (1) into a reaction bottle, placing the reaction bottle in an oil bath pot, heating to 170 ℃ and 180 ℃, uniformly stirring for reaction for 2-3h, adding 5-9 parts of 1, 5-naphthalene diisocyanate, uniformly stirring for reaction for 12-18h, cooling the solution to room temperature, decompressing and concentrating to remove the solvent, washing the solid product by using a proper amount of ether solvent, and fully drying to prepare the polyurethane modified polylactic acid block copolymer.
(3) And (3) placing 7-26 parts of cyclotriphosphazene derivative and the polyurethane modified polylactic acid block copolymer prepared in the step (2) into a double-screw extruder, blending for 1-2h at 180-190 ℃, and extruding master batches to prepare the polyurethane-polylactic acid block copolymer flame-retardant composite material.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
according to the flame-retardant polyurethane-polylactic acid block copolymer composite material, poly-caprolactone diol of a flexible chain segment is crosslinked with polylactic acid to form a block copolymer serving as a matrix component of a polylactic acid material, the block copolymer is a linear polymer stereo composite of stereo crystals, the melt stability is good, the crystallinity of the crystals is good, a fully stereo composite can be quickly formed, the thermal stability of the polylactic acid material is enhanced, the melt processing and forming are easy, the brittleness and the toughness of the polylactic acid are reduced due to the structure of the flexible chain segment, and processes such as film blowing and foaming are easier to perform in the preparation of the polylactic acid material.
The flame-retardant composite material of the polyurethane-polylactic acid block copolymer uses polypropylene carbonate polyol and 1, 5-diisocyanato naphthalene as grafting monomers, polyurethane modified polylactic acid is synthesized through an in-situ polymerization method, one isocyanate group of the 1, 5-diisocyanato naphthalene and hydroxyl on poly-caprolactone diol in the polylactic acid block copolymer form polyurethane with a carbamate group, and the other isocyanate group and the hydroxyl group of the polypropylene carbonate polyol form the carbamate group, so that the polyurethane graft chain extension polylactic acid block copolymer is realized, the compatibility of the two is enhanced through the connection of chemical bonds, the polyurethane and the polylactic acid are organically combined to form the composite material, the crystallization speed of the polylactic acid is increased through the elastomer structure of the polyurethane, the crystallinity of the polylactic acid is reduced, and the tensile strength and the breaking strength of the composite material are enhanced, meanwhile, the rigidity structure of the naphthyl of the 1, 5-diisocyanato naphthalene enhances the toughness of the composite material.
The flame-retardant polyurethane-polylactic acid block copolymer composite material is prepared by reacting diphenyl phosphate benzyl alcohol compound with hexachlorocyclotriphosphazene, so as to obtain the phosphate-cyclotriphosphazene derivative which contains abundant N, P elements and can be heated and decomposed at high temperature to generate non-combustible NH3、N2Substantially diluting O around the material2Content of, at the same time, phosphate-cyclotriphosphazeneWhen the derivative is heated and decomposed, a large amount of heat is absorbed to reduce the surface temperature of the polylactic acid material, the combustion process of the material is inhibited, and the phosphate-cyclotriphosphazene derivative is decomposed at high temperature to form a phosphoric acid and phosphorous acid structure, so that the phosphate-cyclotriphosphazene derivative has good dehydration performance, can dehydrate the polylactic acid material to form a compact carbonization layer, and inhibits high-temperature conduction and O2The contact of the components further hinders the combustion of the material, so that the polylactic acid composite material has excellent flame retardant performance, and the research in the polyurethane carbamate group and ether bonds and tertiary amine in the phosphate-cyclotriphosphazene derivative form hydrogen bonds, so that the compatibility of the phosphate-cyclotriphosphazene derivative and the polylactic acid material is enhanced.
Drawings
FIG. 1 is a front view of the connection structure of the present invention;
fig. 2 is a top view of the connection structure of the present invention.
In the figure: 1-box, 2-controller, 3-groove, 4-screw, 5-bath and 6-mounting rack.
Detailed Description
In order to realize the purpose, the invention provides the following specific embodiment and example, the polyurethane-polylactic acid block copolymer flame-retardant composite material comprises the following formula raw materials, by weight, 7-26 parts of cyclotriphosphazene derivative, 20-23 parts of polypropylene carbonate polyol, 5-9 parts of 1, 5-naphthalene diisocyanate, 40-47 parts of D L-lactide, 6-9 parts of poly-caprolactone diol and 3-5 parts of SnCl2The molecular weight of the polycondensation propylene carbonate polyol is 3300-3700, and the hydroxyl content is 25-35%.
The preparation method of the phosphate-cyclotriphosphazene derivative comprises the following steps:
(1) introducing N into the reaction bottle2Discharging air, adding a toluene solvent, diphenyl phosphate and 1, 4-benzenedimethanol, adding concentrated hydrochloric acid to regulate the temperature to 3-4 ℃, adding catalysts of methylbenzenesulfonic acid (TsOH) and a condensing agent of Dicyclohexylcarbodiimide (DCC), diphenyl phosphate, 1, 4-benzenedimethanol, methylbenzenesulfonic acid and dicyclohexylcarbodiimide in a molar ratio of 1:3-3.8:0.15-0.25:2-2.5, placing a reaction bottle in an oil bath, heating to the temperature of 110-The method comprises a box body, wherein a controller is fixedly connected to the right side of the box body, a groove is formed in the front side of the box body, a screw rod is movably connected inside the groove, a bath kettle is movably connected to the top of the box body, a mounting frame is fixedly connected to the top of the box body and positioned on the left side of the bath kettle, the stirring is carried out at a constant speed for 20-25 hours, the reaction process is observed through a T L C thin-layer chromatography method, after diphenyl phosphate completely reacts, a solution is subjected to reduced pressure concentration to remove a solvent, a concentrated mixture is subjected to thin-layer chromatography separation through a silica gel chromatographic column, an eluant is petroleum ether, ethyl acetate is 1:1-2, the eluant containing a product is enriched, the eluant is removed through reduced pressure concentration and vacuum filtration distillation, and the diphenyl phosphate:
(2) introducing N into the reaction flask2Discharging air, adding a mixed solvent of anhydrous acetonitrile and anhydrous toluene, wherein the volume ratio of the two is 1.5-2:1, sequentially adding diphenyl phosphate benzyl alcohol compound, hexachlorocyclotriphosphazene and 4-Dimethylaminopyridine (DMAP), wherein the molar ratio of the substances is 6-8:1:15-20, placing a reaction bottle in an oil bath pot, heating to 85-95 ℃, uniformly stirring for reaction for 15-20h, observing the reaction process through T L C thin-layer chromatography, after the diphenyl phosphate benzyl alcohol compound completely reacts, decompressing and concentrating the solution to remove the solvent, washing a solid product by using a proper amount of anhydrous ethanol, and fully drying to prepare the phosphate ester-cyclotriphosphazene derivative, wherein the reaction equation is as follows:
the preparation method of the polyurethane-polylactic acid block copolymer flame-retardant composite material comprises the following steps:
(1) adding a proper amount of N, N-dimethylformamide solvent, 40-47 parts of D L-lactide and 3-5 parts of initiator SnCl into a reaction bottle2Placing the reaction bottle in an oil bath pot, heating to 160 ℃, stirring at constant speed for reaction for 25-30h, and then addingAdding 6-9 parts of poly-caprolactone diol, stirring at a constant speed for reaction for 10-15h, cooling the solution to room temperature, carrying out reduced pressure concentration to remove the solvent, washing the solid product with a proper amount of absolute ethyl alcohol, and fully drying to prepare the polycaprolactone diol-polylactic acid block copolymer.
(2) Adding a proper amount of N, N-dimethylformamide solvent, 20-23 parts of polypropylene carbonate polyol and the polycaprolactone diol-polylactic acid block copolymer prepared in the step (1) into a reaction bottle, placing the reaction bottle in an oil bath pot, heating to 170 ℃ and 180 ℃, uniformly stirring for reaction for 2-3h, adding 5-9 parts of 1, 5-naphthalene diisocyanate, uniformly stirring for reaction for 12-18h, cooling the solution to room temperature, decompressing and concentrating to remove the solvent, washing the solid product by using a proper amount of ether solvent, and fully drying to prepare the polyurethane modified polylactic acid block copolymer.
(3) And (3) placing 7-26 parts of cyclotriphosphazene derivative and the polyurethane modified polylactic acid block copolymer prepared in the step (2) into a double-screw extruder, blending for 1-2h at 180-190 ℃, and extruding master batches to prepare the polyurethane-polylactic acid block copolymer flame-retardant composite material.
Example 1
(1) Preparation of diphenyl phosphate benzyl alcohol compound 1: introducing N into the reaction bottle2Discharging air, adding a toluene solvent, diphenyl phosphate and 1, 4-benzenedimethanol, adding concentrated hydrochloric acid to regulate 4, adding catalysts of methylbenzenesulfonic acid (TsOH) and a condensing agent of Dicyclohexylcarbodiimide (DCC), diphenyl phosphate, 1, 4-benzenedimethanol, methylbenzenesulfonic acid and dicyclohexylcarbodiimide in a molar ratio of 1:3:0.15:2, placing a reaction bottle in an oil bath pot, heating to 110 ℃, wherein the oil bath pot comprises a box body, the right side of the box body is fixedly connected with a controller, the front side of the box body is provided with a groove, a screw rod is movably connected inside the groove, the top of the box body is movably connected with the bath pot, an eluent is fixedly connected to the top of the box body and the left side of the bath pot, uniformly stirring and reacting for 20 hours, observing the reaction process through a T L C thin-layer chromatography method, after diphenyl phosphate completely reacts, concentrating the solution under reduced pressure to remove the solvent, and performing thin-layer chromatography separation on the concentrated mixture through a silica gel chromatography column to obtain the eluentAnd (3) concentrating the eluent containing the product, and removing the eluent by vacuum concentration and vacuum suction filtration distillation to prepare the diphenyl phosphate benzyl alcohol compound 1.
(2) Preparation of phosphate-cyclotriphosphazene derivative 1: introducing N into the reaction flask2Discharging air, adding a mixed solvent of anhydrous acetonitrile and anhydrous toluene, wherein the volume ratio of the anhydrous acetonitrile to the anhydrous toluene is 1.5:1, sequentially adding diphenyl phosphate benzyl alcohol compound 1, hexachlorocyclotriphosphazene and 4-Dimethylaminopyridine (DMAP), wherein the molar ratio of the substances is 6:1:15, placing a reaction bottle in an oil bath pot, heating to 85 ℃, uniformly stirring for reaction for 15 hours, observing the reaction process through a T L C thin-layer chromatography, when the diphenyl phosphate benzyl alcohol compound completely reacts, decompressing and concentrating the solution to remove the solvent, washing the solid product with a proper amount of anhydrous ethanol, and fully drying to prepare the phosphate-cyclotriphosphazene derivative 1.
(3) Preparing polycaprolactone diol-polylactic acid block copolymer component 1, adding a proper amount of N, N-dimethylformamide solvent, 40 parts of D L-lactide and 3 parts of initiator SnCl into a reaction bottle2Placing the reaction bottle in an oil bath pot, heating to 150 ℃, stirring at a constant speed for reaction for 25h, adding 6 parts of poly-caprolactone diol, stirring at a constant speed for reaction for 10h, cooling the solution to room temperature, concentrating under reduced pressure to remove the solvent, washing the solid product with a proper amount of absolute ethyl alcohol, and fully drying to prepare the polycaprolactone diol-polylactic acid block copolymer component 1.
(4) Preparation of polyurethane modified polylactic acid block copolymer component 1: adding a proper amount of N, N-dimethylformamide solvent, 20 parts of polypropylene carbonate polyol and the polycaprolactone diol-polylactic acid block copolymer component 1 prepared in the step (3) into a reaction bottle, placing the reaction bottle in an oil bath pot, heating to 170 ℃, stirring at a constant speed for reaction for 2 hours, adding 5 parts of 1, 5-naphthalene diisocyanate, stirring at a constant speed for reaction for 12 hours, cooling the solution to room temperature, decompressing and concentrating to remove the solvent, washing the solid product with a proper amount of ether solvent, and fully drying to prepare the polyurethane modified polylactic acid block copolymer component 1.
(5) Preparing a polyurethane-polylactic acid block copolymer flame-retardant composite material 1: and (3) placing 26 parts of cyclotriphosphazene derivative 1 and the polyurethane modified polylactic acid block copolymer component 1 prepared in the step (4) in a double-screw extruder, blending for 1 hour at 180 ℃, and extruding master batches to prepare the polyurethane-polylactic acid block copolymer flame-retardant composite material 1.
Example 2
(1) Preparation of diphenyl phosphate benzyl alcohol compound 2: introducing N into the reaction bottle2Discharging air, adding a toluene solvent, diphenyl phosphate and 1, 4-benzenedimethanol, adding concentrated hydrochloric acid to regulate 4, adding catalysts of methylbenzenesulfonic acid (TsOH) and a condensing agent of Dicyclohexylcarbodiimide (DCC), diphenyl phosphate, 1, 4-benzenedimethanol, methylbenzenesulfonic acid and dicyclohexylcarbodiimide in a molar ratio of 1:3.8:0.15:2.5, placing a reaction bottle in an oil bath kettle to be heated to 120 ℃, wherein the oil bath kettle comprises a box body, the right side of the box body is fixedly connected with a controller, the front side of the box body is provided with a groove, a screw is movably connected inside the groove, the top of the box body is movably connected with the bath kettle, the top of the box body and the left side of the bath kettle are fixedly connected with a mounting frame, stirring at a constant speed for reaction for 20 hours, observing the reaction process through a T L C thin-layer chromatography, when the diphenyl phosphate completely reacts, concentrating the solution under reduced pressure to remove the solvent, carrying out thin-layer separation on the concentrated mixture through a silica gel chromatography column, and obtaining the eluant of petroleum ether ethyl acetate 1:2, wherein the eluant is ethyl acetate.
(2) Preparation of phosphate-cyclotriphosphazene derivative 2: introducing N into the reaction flask2Discharging air, adding a mixed solvent of anhydrous acetonitrile and anhydrous toluene, wherein the volume ratio of the anhydrous acetonitrile to the anhydrous toluene is 2:1, sequentially adding diphenyl phosphate benzyl alcohol compound 2, hexachlorocyclotriphosphazene and 4-Dimethylaminopyridine (DMAP), the molar ratio of the substances in the three is 8:1:15, placing a reaction bottle in an oil bath pot, heating to 95 ℃, uniformly stirring for reaction for 15 hours, observing the reaction process through a T L C thin-layer chromatography, when the diphenyl phosphate benzyl alcohol compound completely reacts, decompressing and concentrating the solution to remove the solvent, washing the solid product with a proper amount of anhydrous ethanol, and fully dryingAnd drying to obtain the phosphate-cyclotriphosphazene derivative 2.
(3) Preparing polycaprolactone diol-polylactic acid block copolymer component 2, adding a proper amount of N, N-dimethylformamide solvent, 42 parts of D L-lactide and 3.5 parts of initiator SnCl into a reaction bottle2Placing the reaction bottle in an oil bath pot, heating to 160 ℃, stirring at a constant speed for reaction for 30h, adding 7 parts of poly-caprolactone diol, stirring at a constant speed for reaction for 10h, cooling the solution to room temperature, concentrating under reduced pressure to remove the solvent, washing the solid product with a proper amount of absolute ethyl alcohol, and fully drying to prepare the polycaprolactone diol-polylactic acid block copolymer component 2.
(4) Preparing a polyurethane modified polylactic acid block copolymer component 2: adding a proper amount of N, N-dimethylformamide solvent, 21 parts of polypropylene carbonate polyol and the polycaprolactone diol-polylactic acid block copolymer component 2 prepared in the step (3) into a reaction bottle, placing the reaction bottle in an oil bath pot, heating to 170 ℃, stirring at a constant speed for reaction for 3 hours, adding 6.5 parts of 1, 5-naphthalene diisocyanate, stirring at a constant speed for reaction for 18 hours, cooling the solution to room temperature, concentrating under reduced pressure to remove the solvent, washing the solid product with a proper amount of ether solvent, and fully drying to prepare the polyurethane modified polylactic acid block copolymer component 2.
(5) Preparing a polyurethane-polylactic acid block copolymer flame-retardant composite material 2: and (3) placing 20 parts of cyclotriphosphazene derivative 2 and the polyurethane modified polylactic acid block copolymer component 2 prepared in the step (4) into a double-screw extruder, blending for 2 hours at 180 ℃, and extruding master batches to prepare the polyurethane-polylactic acid block copolymer flame-retardant composite material 2.
Example 3
(1) Preparation of diphenyl phosphate benzyl alcohol compound 3: introducing N into the reaction bottle2Discharging air, adding a toluene solvent, diphenyl phosphate and 1, 4-benzenedimethanol, adding concentrated hydrochloric acid to regulate the concentration to 3, adding catalysts of methylbenzenesulfonic acid (TsOH) and a condensing agent of Dicyclohexylcarbodiimide (DCC), diphenyl phosphate, 1, 4-benzenedimethanol, methylbenzenesulfonic acid and dicyclohexylcarbodiimide in a molar ratio of 1:3.4:0.2:2.3, placing a reaction bottle in an oil bath pan, heating to 115 ℃, and packaging the oil bath panThe method comprises the steps of drawing a box body, fixedly connecting a controller to the right side of the box body, forming a groove in the front of the box body, movably connecting a screw rod in the groove, movably connecting a bath pot to the top of the box body, fixedly connecting a mounting frame to the top of the box body and the left side of the bath pot, stirring at a constant speed for reaction for 22 hours, observing the reaction process through a T L C thin-layer chromatography, concentrating a solution under reduced pressure to remove a solvent after diphenyl phosphate completely reacts, separating the concentrated mixture through a silica gel chromatographic column by using thin-layer chromatography, wherein an eluant is petroleum ether and ethyl acetate is 1:1, enriching the product, and removing the eluant through concentration under reduced pressure and vacuum filtration distillation to prepare the diphenyl phosphate benzyl alcohol compound 3.
(2) Preparation of phosphate-cyclotriphosphazene derivative 3: introducing N into the reaction flask2Discharging air, adding a mixed solvent of anhydrous acetonitrile and anhydrous toluene, wherein the volume ratio of the anhydrous acetonitrile to the anhydrous toluene is 1.8:1, sequentially adding diphenyl phosphate benzyl alcohol compound 3, hexachlorocyclotriphosphazene and 4-Dimethylaminopyridine (DMAP), wherein the molar ratio of the substances is 7:1:18, placing a reaction bottle in an oil bath pot, heating to 90 ℃, uniformly stirring for reacting for 18 hours, observing the reaction process through a T L C thin-layer chromatography, when the diphenyl phosphate benzyl alcohol compound completely reacts, decompressing and concentrating the solution to remove the solvent, washing the solid product with a proper amount of anhydrous ethanol, and fully drying to prepare the phosphate-cyclotriphosphazene derivative 3.
(3) Preparing polycaprolactone diol-polylactic acid block copolymer component 3, adding a proper amount of N, N-dimethylformamide solvent, 44 parts of D L-lactide and 4 parts of initiator SnCl into a reaction bottle2Placing the reaction bottle in an oil bath pot, heating to 155 ℃, stirring at a constant speed for reaction for 28h, adding 7.5 parts of poly-caprolactone diol, stirring at a constant speed for reaction for 12h, cooling the solution to room temperature, concentrating under reduced pressure to remove the solvent, washing the solid product with a proper amount of absolute ethyl alcohol, and fully drying to prepare the polycaprolactone diol-polylactic acid block copolymer component 3.
(4) Preparing a polyurethane modified polylactic acid block copolymer component 3: adding a proper amount of N, N-dimethylformamide solvent, 21.5 parts of polypropylene carbonate polyol and the polycaprolactone diol-polylactic acid block copolymer component 3 prepared in the step (3) into a reaction bottle, placing the reaction bottle in an oil bath pot, heating to 175 ℃, uniformly stirring for reaction for 2.5 hours, adding 7 parts of 1, 5-naphthalene diisocyanate, uniformly stirring for reaction for 15 hours, cooling the solution to room temperature, decompressing and concentrating to remove the solvent, washing the solid product with a proper amount of ether solvent, and fully drying to prepare the polyurethane modified polylactic acid block copolymer component 3.
(5) Preparing a polyurethane-polylactic acid block copolymer flame-retardant composite material 3: and (3) placing 16 parts of cyclotriphosphazene derivative 3 and the polyurethane modified polylactic acid block copolymer component 3 prepared in the step (4) in a double-screw extruder, blending for 1.2 hours at 185 ℃, and extruding master batches to prepare the polyurethane-polylactic acid block copolymer flame-retardant composite material 3.
Example 4
(1) Preparation of diphenyl phosphate benzyl alcohol compound 4: introducing N into the reaction bottle2Discharging air, adding a toluene solvent, diphenyl phosphate and 1, 4-benzenedimethanol, adding concentrated hydrochloric acid to regulate 4, adding catalysts of methylbenzenesulfonic acid (TsOH) and a condensing agent of Dicyclohexylcarbodiimide (DCC), diphenyl phosphate, 1, 4-benzenedimethanol, methylbenzenesulfonic acid and dicyclohexylcarbodiimide in a molar ratio of 1:3.8:0.25:2.5, placing a reaction bottle in an oil bath kettle to be heated to 120 ℃, wherein the oil bath kettle comprises a box body, the right side of the box body is fixedly connected with a controller, the front side of the box body is provided with a groove, a screw is movably connected inside the groove, the top of the box body is movably connected with the bath kettle, the top of the box body and the left side of the bath kettle are fixedly connected with a mounting frame, stirring at a constant speed for reaction for 25 hours, observing the reaction process through a T L C thin-layer chromatography, when the diphenyl phosphate completely reacts, concentrating the solution under reduced pressure to remove the solvent, carrying out thin-layer separation on a silica gel chromatography column, and obtaining the diphenyl phosphate eluent of ethyl acetate 1:2, and concentrating the eluent under reduced pressure and distilling the eluent to prepare the diphenyl phosphate compound through vacuum concentration and vacuum filtration.
(2) Preparation of phosphate-cyclotriphosphazene derivative 4: introducing N into the reaction flask2The air is discharged and thenAdding a mixed solvent of anhydrous acetonitrile and anhydrous toluene, wherein the volume ratio of the anhydrous acetonitrile to the anhydrous toluene is 2:1, sequentially adding a diphenyl phosphate benzyl alcohol compound, hexachlorocyclotriphosphazene and 4-Dimethylaminopyridine (DMAP), wherein the molar ratio of the substances is 8:1:15, placing a reaction bottle in an oil bath pot, heating to 95 ℃, uniformly stirring for reaction for 20 hours, observing the reaction process through a T L C thin-layer chromatography, concentrating the solution under reduced pressure to remove the solvent after the diphenyl phosphate benzyl alcohol compound completely reacts, washing the solid product with a proper amount of anhydrous ethanol, and fully drying to prepare the phosphate-cyclotriphosphazene derivative 4.
(3) Preparing polycaprolactone diol-polylactic acid block copolymer component 4 adding proper amount of N, N-dimethylformamide solvent, 45.5 portions of D L-lactide and 4.5 portions of initiator SnCl into a reaction bottle2Placing the reaction bottle in an oil bath pot, heating to 160 ℃, stirring at a constant speed for reaction for 30h, adding 8 parts of poly-caprolactone diol, stirring at a constant speed for reaction for 10h, cooling the solution to room temperature, concentrating under reduced pressure to remove the solvent, washing the solid product with a proper amount of absolute ethyl alcohol, and fully drying to prepare the polycaprolactone diol-polylactic acid block copolymer component 4.
(4) Preparing a polyurethane modified polylactic acid block copolymer component 4: adding a proper amount of N, N-dimethylformamide solvent, 22-polypropylene carbonate polyol and the polycaprolactone diol-polylactic acid block copolymer component 4 prepared in the step (3) into a reaction bottle, placing the reaction bottle in an oil bath pot, heating to 170 ℃, stirring at a constant speed for reaction for 3 hours, adding 8 parts of 1, 5-naphthalene diisocyanate, stirring at a constant speed for reaction for 12 hours, cooling the solution to room temperature, concentrating under reduced pressure to remove the solvent, washing the solid product with a proper amount of ether solvent, and fully drying to prepare the polyurethane modified polylactic acid block copolymer component 4.
(5) Preparing a polyurethane-polylactic acid block copolymer flame-retardant composite material 4: and (3) placing 12 parts of cyclotriphosphazene derivative 4 and the polyurethane modified polylactic acid block copolymer component 4 prepared in the step (4) in a double-screw extruder, blending for 1h at 190 ℃, and extruding master batches to prepare the polyurethane-polylactic acid block copolymer flame-retardant composite material 4.
Example 5
(1) Preparation of diphenyl phosphate benzyl alcohol compound 5: introducing N into the reaction bottle2Discharging air, adding a toluene solvent, diphenyl phosphate and 1, 4-benzenedimethanol, adding concentrated hydrochloric acid to regulate the concentration by 3, adding catalysts of methylbenzenesulfonic acid (TsOH) and a condensation agent of Dicyclohexylcarbodiimide (DCC), diphenyl phosphate, 1, 4-benzenedimethanol, methylbenzenesulfonic acid and dicyclohexylcarbodiimide in a molar ratio of 1:3.8:0.25:2.5, placing a reaction bottle in an oil bath kettle to be heated to 120 ℃, wherein the oil bath kettle comprises a box body, the right side of the box body is fixedly connected with a controller, the front side of the box body is provided with a groove, a screw is movably connected inside the groove, the top of the box body is movably connected with the bath kettle, the top of the box body and the left side of the bath kettle are fixedly connected with a mounting frame, stirring at a constant speed for reaction for 25 hours, observing the reaction process through a T L C thin-layer chromatography, concentrating the solution under reduced pressure to remove the solvent after the diphenyl phosphate reaction is completely reacted, carrying out thin-layer separation on a silica gel chromatography column, and obtaining the eluent of ethyl acetate 1:2, and concentrating the diphenyl phosphate by vacuum distillation and vacuum distillation to obtain the diphenyl phosphate compound.
(2) Preparation of phosphate-cyclotriphosphazene derivative 5: introducing N into the reaction flask2Discharging air, adding a mixed solvent of anhydrous acetonitrile and anhydrous toluene, wherein the volume ratio of the anhydrous acetonitrile to the anhydrous toluene is 2:1, sequentially adding a diphenyl phosphate benzyl alcohol compound, hexachlorocyclotriphosphazene and 4-Dimethylaminopyridine (DMAP), wherein the molar ratio of the substances is 8:1:20, placing a reaction bottle in an oil bath pot, heating to 95 ℃, uniformly stirring for reaction for 20 hours, observing the reaction process through T L C thin-layer chromatography, when the diphenyl phosphate benzyl alcohol compound completely reacts, decompressing and concentrating the solution to remove the solvent, washing the solid product with a proper amount of anhydrous ethanol, and fully drying to prepare the phosphate-cyclotriphosphazene derivative 5.
(3) Preparing polycaprolactone diol-polylactic acid block copolymer component 5, adding a proper amount of N, N-dimethylformamide solvent, 47 parts of D L-lactide and 5 parts of initiator SnCl into a reaction bottle2Heating the reaction bottle in an oil bathAnd (2) reacting at 160 ℃ under uniform stirring for 30h, adding 9 parts of poly-caprolactone diol, reacting for 15h under uniform stirring, cooling the solution to room temperature, concentrating under reduced pressure to remove the solvent, washing the solid product with a proper amount of absolute ethyl alcohol, and fully drying to obtain the polycaprolactone diol-polylactic acid block copolymer component 5.
(4) Preparing a polyurethane modified polylactic acid block copolymer component 5: adding a proper amount of N, N-dimethylformamide solvent, 23 parts of polypropylene carbonate polyol and the polycaprolactone diol-polylactic acid block copolymer component 5 prepared in the step (3) into a reaction bottle, placing the reaction bottle in an oil bath pot, heating to 180 ℃, stirring at a constant speed for reaction for 3 hours, adding 9 parts of 1, 5-naphthalene diisocyanate, stirring at a constant speed for reaction for 18 hours, cooling the solution to room temperature, decompressing and concentrating to remove the solvent, washing the solid product with a proper amount of ether solvent, and fully drying to prepare the polyurethane modified polylactic acid block copolymer component 5.
(5) Preparing a polyurethane-polylactic acid block copolymer flame-retardant composite material 5: and (3) placing 7 parts of cyclotriphosphazene derivative 5 and the polyurethane modified polylactic acid block copolymer component 5 prepared in the step (4) in a double-screw extruder, blending for 2 hours at 190 ℃, and extruding master batches to prepare the polyurethane-polylactic acid block copolymer flame-retardant composite material 5.
The flame retardant performance of the polyurethane-polylactic acid block copolymer flame retardant composite materials 1-5 is respectively tested by using a YW-1101 horizontal vertical combustion tester, and the test standard is a U L-94 vertical combustion method.
In summary, the polyurethane-polylactic acid block copolymer flame-retardant composite material uses the poly-caprolactone diol of the flexible chain segment to crosslink with the polylactic acid, the formed block copolymer is used as the matrix component of the polylactic acid material, the block copolymer is a linear polymer stereo composite of stereo crystals, the melt stability is good, the crystallinity of the crystals is good, the full stereo composite can be quickly formed, the thermal stability of the polylactic acid material is enhanced, the melt processing and forming are easy, the brittleness of the polylactic acid is reduced by the structure of the flexible chain segment, the toughness is enhanced, and the processes of film blowing, foaming and the like are easier to perform in the preparation of the polylactic acid material.
The preparation method comprises the steps of using polypropylene carbonate polyol and 1, 5-diisocyanatonaphthalene as grafting monomers, synthesizing polyurethane modified polylactic acid through an in-situ polymerization method, wherein one isocyanate group of the 1, 5-diisocyanatonaphthalene forms polyurethane with a hydroxyl group on poly-caprolactone diol in a polylactic acid block copolymer to form a carbamate group, and the other isocyanate group forms a carbamate group with a hydroxyl group of polypropylene carbonate polyol, so that polyurethane graft chain extension of the polylactic acid block copolymer is realized, the compatibility of the two is enhanced through the connection of chemical bonds, the polyurethane and the polylactic acid are organically combined to form a composite material, the elastomer structure of the polyurethane increases the crystallization speed of the polylactic acid, the crystallinity of the polylactic acid is reduced, the tensile strength and the breaking strength of the composite material are enhanced, and meanwhile, the naphthyl rigid structure of the 1, 5-diisocyanatonaphthalene is adopted, the toughness of the composite material is enhanced.
Reacting diphenyl phosphate benzyl alcohol compound with hexachlorocyclotriphosphazene to prepare the phosphate-cyclotriphosphazene derivative which contains rich N, P elements and is heated and decomposed at high temperature to generate non-combustible NH3、N2Substantially diluting O around the material2The phosphate-cyclotriphosphazene derivative absorbs a large amount of heat to reduce the surface temperature of the polylactic acid material and inhibit the combustion process of the material when being heated and decomposed, and the phosphate-cyclotriphosphazene derivative is decomposed at high temperature to form a phosphoric acid and phosphorous acid structure, has good dehydration performance, can dehydrate the polylactic acid material to form a compact carbonized layer, and inhibits high-temperature conduction and O2The combustion of the material is further hindered, the U L-94 grades are all high grades of V-0, so that the polylactic acid composite material has excellent flame retardant performance, and the research in the polyurethane carbamate group and ether bonds and tertiary amine in the phosphate-cyclotriphosphazene derivative form hydrogen bonds, so that the compatibility of the phosphate-cyclotriphosphazene derivative and the polylactic acid material is enhanced.
Claims (7)
1. The flame-retardant polyurethane-polylactic acid block copolymer composite material comprises the following raw materials in parts by weight, and is characterized in that 7-26 parts of cyclotriphosphazene derivative, 20-23 parts of polypropylene carbonate polyol, 5-9 parts of 1, 5-diisocyanatonaphthalene, 40-47 parts of D L-lactide, 6-9 parts of poly-caprolactone diol and 3-5 parts of SnCl2。
2. The flame-retardant polyurethane-polylactic acid block copolymer composite material according to claim 1, wherein: the molecular weight of the polycondensation propylene carbonate polyol is 3300-3700, and the hydroxyl content is 25-35%.
3. The flame-retardant polyurethane-polylactic acid block copolymer composite material according to claim 1, wherein: the preparation method of the phosphate-cyclotriphosphazene derivative comprises the following steps:
(1) adding diphenyl phosphate and 1, 4-benzenedimethanol into toluene solvent, adding concentrated hydrochloric acid to adjust 3-4, adding p-catalyst methyl benzene sulfonic acid (TsOH) and condensing agent Dicyclohexylcarbodiimide (DCC), and dissolving the solution in N2Heating the mixture in an oil bath kettle to 110-120 ℃ in the atmosphere, reacting for 20-25h, concentrating the solution under reduced pressure to remove the solvent, and separating the concentrated mixture by a silica gel chromatographic column, wherein the eluent is petroleum ether and ethyl acetate is 1:1-2 to prepare the diphenyl phosphate benzyl alcohol compound, and the reaction equation is as follows:
(2) adding diphenyl phosphate benzyl alcohol compound, hexachlorocyclotriphosphazene and 4-dimethylamino pyridine into a mixed solvent of anhydrous acetonitrile and anhydrous toluene at a volume ratio of 1.5-2:1, and dissolving the solution in N2Heating to 85-95 ℃ in the atmosphere, reacting for 15-20h, concentrating the solution under reduced pressure to remove the solvent, washing the solid product, and drying to prepare the phosphate-cyclotriphosphazene derivative, wherein the reaction equation is as follows:
4. the phosphate-cyclotriphosphazene derivative of claim 3, wherein: the molar ratio of the diphenyl phosphate to the 1, 4-benzenedimethanol to the methylbenzene sulfonic acid to the dicyclohexylcarbodiimide is 1:3-3.8:0.15-0.25: 2-2.5.
5. The flame-retardant polyurethane-polylactic acid block copolymer composite material according to claim 3, wherein: the diphenyl phosphate benzyl alcohol compound, the hexachlorocyclotriphosphazene and the 4-Dimethylaminopyridine (DMAP) are mixed according to the molar ratio of 6-8:1: 15-20.
6. The flame-retardant polyurethane-polylactic acid block copolymer composite material according to claim 3, wherein: the oil bath pot comprises a box body (1), a controller (2) is fixedly connected to the right side of the box body (1), a groove (3) is formed in the front face of the box body (1), a screw rod (4) is movably connected to the inside of the groove (3), a bath pot (5) is movably connected to the top of the box body (1), and a mounting frame (6) is fixedly connected to the left side of the bath pot (5) and located at the top of the box body (1).
7. The flame-retardant polyurethane-polylactic acid block copolymer composite material according to claim 1, wherein: the preparation method of the polyurethane-polylactic acid block copolymer flame-retardant composite material comprises the following steps:
(1) adding 40-47 parts of D L-lactide and 3-5 parts of initiator SnCl into N, N-dimethylformamide solvent2Heating the solution to 150 ℃ and 160 ℃, reacting for 25-30h, adding 6-9 parts of poly-caprolactone diol, stirring at constant speed and reacting for 10-15h, removing the solvent from the solution, washing the solid product, and drying to prepare the polycaprolactone diol-polylactic acid segmented copolymer.
(2) Adding 20-23 parts of polypropylene carbonate polyol and the polycaprolactone diol-polylactic acid block copolymer prepared in the step (1) into an N, N-dimethylformamide solvent, heating the solution to 170-180 ℃, reacting for 2-3h, adding 5-9 parts of 1, 5-naphthalene diisocyanate, reacting for 12-18h, removing the solvent from the solution, washing a solid product, and drying to prepare the polyurethane modified polylactic acid block copolymer.
(3) And (3) placing 7-26 parts of cyclotriphosphazene derivative and the polyurethane modified polylactic acid block copolymer prepared in the step (2) into a double-screw extruder, blending for 1-2h at 180-190 ℃, and extruding master batches to prepare the polyurethane-polylactic acid block copolymer flame-retardant composite material.
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