CN116042044A - TPU (thermoplastic polyurethane) product post-treatment flame-retardant coating liquid and TPU product flame-retardant treatment method - Google Patents
TPU (thermoplastic polyurethane) product post-treatment flame-retardant coating liquid and TPU product flame-retardant treatment method Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 158
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- 238000006243 chemical reaction Methods 0.000 claims description 12
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- 238000004140 cleaning Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 8
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 7
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 4
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- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 2
- 229940044654 phenolsulfonic acid Drugs 0.000 claims description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 2
- 150000003017 phosphorus Chemical class 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
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- 239000000047 product Substances 0.000 abstract description 86
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 22
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/05—Forming flame retardant coatings or fire resistant coatings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2461/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
- C08J2483/06—Polysiloxanes containing silicon bound to oxygen-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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Abstract
The invention belongs to the technical field of functional modification of polymer materials, and particularly relates to a TPU (thermoplastic polyurethane) product post-treatment flame-retardant coating liquid and a TPU product flame-retardant treatment method. According to the invention, allyl glycidyl ether is reacted with organic silicon to synthesize an organic silicon solution containing epoxy groups, and then the organic silicon solution is blended with phenolic resin and a phosphorus-containing flame retardant to obtain the flame-retardant coating, and the flame-retardant coating liquid is regulated to a proper viscosity through an organic solvent. The flame retardant coating is used for carrying out surface coating modification on the TPU part, in the process, the epoxy modified organic silicon/phenolic resin can permeate into micro-voids of the surface layer of the TPU part and the physical network of the surface layer of the TPU part, after curing, the epoxy modified organic silicon/phenolic resin is crosslinked into a network structure, and a semi-interpenetrating polymer network with a bicontinuous phase is formed on the surface layer of the TPU part, so that the flame retardant coating and the TPU substrate can be prevented from being separated, and the flame retardant effect and the mechanical property of the TPU part can be improved. The invention has simple process, low cost and good flame retardant effect and can be produced in large scale.
Description
Technical Field
The invention belongs to the technical field of functional modification of polymer materials, and particularly relates to a TPU (thermoplastic polyurethane) product post-treatment flame-retardant coating liquid and a TPU product flame-retardant treatment method.
Background
Selective Laser Sintering (SLS) is a method of selectively fusing multiple layers of particulate material to produce three-dimensional objects using a laser as a heat source for fusion bonding of the particulate material, and is primarily capable of forming polymeric, metallic, and ceramic materials. The SLS forming method can theoretically manufacture any product with a complex structure, and for the processing and forming of complex components, the method can greatly reduce the cost, shorten the forming period and improve the utilization rate of materials.
Thermoplastic polyurethane elastomers (TPU) are one of the important materials for selective laser sintering. Because the TPU material has good flexibility, rebound performance, wear resistance and weather resistance, the TPU material can be suitable for manufacturing products with different hardness requirements, and can be widely applied to industries such as shoemaking, medical treatment, cables, automobiles and the like. In some application scenarios of TPU materials, for example, when the TPU materials are used as automotive interior parts, the TPU materials are required to have certain flame retardant properties. But TPU material is used as an organic high molecular compound, has very low limiting oxygen index (LOI is about 18%), is inflammable when meeting fire, and is easy to ignite other materials to cause large-area combustion along with molten drops. Moreover, when the TPU material burns, a great amount of heat and smoke are released, and the safety of life and property is greatly threatened. Therefore, flame retardant modification is required for TPU materials for such applications.
The flame-retardant property of the existing high polymer material is mainly obtained by adding a flame-retardant component into a polymer. However, the flame retardant is usually a phosphorus flame retardant or an inorganic carbon-forming material, and has larger particle size and poor compatibility with a high polymer material. If the traditional extrusion, injection and other melt-state molding processes are adopted, the flame retardant can be well dispersed and distributed in the polymer matrix due to the strong shearing action. However, if the SLS molding process is adopted, on the one hand, since the SLS molding principle is to build up a single horizontal layer with laser fusion material, then repeatedly stack through a fine height drop, and gradually complete the material molding by sintering the powder of the current flat surface and bonding with the part that has been molded below. In the whole forming process, no external stress is applied, and the single-layer microcells of the polymer flow, so that the flow shearing effect is very small, and the interface combination of the polymer matrix and the flame retardant in the material is weak, so that the mechanical property is poor. On the other hand, the addition amount of the flame-retardant filler is larger, the morphology structure is irregular, and the flame-retardant filler has great morphology mismatch with the spherical structure of the TPU powder special for SLS, so that the powder is spread unevenly and piled loosely in molding, the sintering process is seriously influenced, the density of the molded material is low, the surface is rough, the mechanical property is poor, and even the molded material cannot be molded normally when the morphology mismatch is serious.
Disclosure of Invention
Aiming at the problems that the material performance is difficult to be reduced to a certain extent or even the molding cannot be realized due to the influence of stress state change and powder spreading effect when the conventional flame retardant modification method suitable for the melt state molding processes such as extrusion, injection and the like is transferred to SLS molding, the invention provides a TPU (thermoplastic polyurethane) post-treatment flame retardant coating liquid and a TPU flame retardant treatment method, and aims to basically maintain and even improve the mechanical property of a TPU while endowing the TPU with the flame retardant property in an SLS molding system.
The invention achieves the above object by the following technical scheme.
The first aspect of the invention provides a TPU (thermoplastic polyurethane) product post-treatment flame-retardant coating liquid, which can be coated on the surface of the TPU product, and is solidified to be tightly meshed with the surface of the TPU product, so that the TPU product is endowed with excellent flame retardant property, the mechanical property is enhanced, and the surface of the TPU product is smoother and smoother.
The TPU product post-treatment flame-retardant coating liquid provided by the invention comprises the following raw components: 10-20 parts of allyl glycidyl ether, 20-30 parts of organosilicon polymer, 40-50 parts of phenolic resin, 20-10 parts of flame retardant, 10-30 parts of organic solvent, 1-2 parts of catalyst and 2-5 parts of curing agent.
In the post-treatment flame-retardant coating liquid for TPU parts, phenolic resin belongs to an intrinsic flame-retardant high polymer material, has the characteristics of fire prevention and low smoke and large residual carbon content, and can be used as a carbon source substance in flame retardants. In addition, the liquid phenolic resin has high adhesion performance and has the advantage of firmly combining the coating and the TPU. The organosilicon polymer can form a ceramic-like barrier when being burnt, improves the carbon forming quality, has good thermal resistance and has good synergistic flame retardant function in the flame retardant coating.
In the practice of the present invention, it has been found that a critical problem that must be further overcome is that the silicone polymer is not reactive with the phenolic resin, which can result in uncontrollable properties of the coating after curing. In order to overcome the problems, the invention modifies the organosilicon polymer, and grafts the epoxy groups on the organosilicon polymer by a chemical method, so that the epoxy groups on the organosilicon polymer have the capability of forming a copolymer by chemical reaction with phenolic resin. In the epoxy modified organosilicon/phenolic resin matrix, the flame retardant is uniformly dispersed, so that the flame retardant coating liquid is formed. The proper viscosity of the flame-retardant coating liquid is regulated by an organic solvent, the epoxy modified organic silicon/phenolic resin can permeate into the micro-gaps of the surface layer of the TPU part and the physical network of the surface layer of the TPU part in the process of coating the TPU part, after curing, the epoxy modified organic silicon/phenolic resin is crosslinked into a network structure, a semi-interpenetrating polymer network with a bicontinuous phase is formed on the surface layer of the TPU part, the functions are mutually cooperated, the separation of the coating and the matrix is prevented, and the mechanical strength of the matrix material is improved. Meanwhile, after the coating on the TPU product is cured, matrix resin which is uniformly dispersed with the flame retardant is formed and is tightly anchored on the surface of the TPU product, so that the flame retardant property of the TPU product is endowed, and the mechanical property of the TPU product is improved to a certain extent.
Furthermore, in the TPU product post-treatment flame-retardant coating liquid, the organosilicon polymer is in a liquid state at room temperatureThe structural formula of the long-chain polysiloxane is shown in figure 1. Wherein m is 1 Is 10 to 20 m 2 20-30, the organosilicon polymer is difficult to oxidize or decompose, and has high-temperature stability.
Further, in the post-treatment flame-retardant coating liquid for the TPU product, the phenolic resin is alcohol-soluble phenolic resin, and the molecular chain contains phenolic hydroxyl groups, and the structural formula of the phenolic resin is shown in figure 2.
Further, in the post-treatment flame-retardant coating liquid for the TPU parts, the flame retardant is one or more of phosphorus-containing flame retardants such as ammonium polyphosphate, phosphite, phosphonate, organic phosphorus salt and the like, and is preferably ammonium polyphosphate.
Further, in the post-treatment flame-retardant coating liquid for the TPU parts, the organic solvent takes organic matters as media, and comprises one or more of acetone, tetrahydrofuran, methanol and diethyl ether, and preferably acetone.
Further, in the post-treatment flame-retardant coating liquid for the TPU parts, the catalyst is one or more of dibutyl tin dilaurate, stannous octoate, diethylenetriamine and triethylenetetramine, and is preferably dibutyl tin dilaurate and stannous octoate.
Further, in the post-treatment flame-retardant coating liquid for the TPU parts, the curing agent is one or more of paraformaldehyde, hexamethylenetetramine, p-toluenesulfonic acid and phenolsulfonic acid, and is preferably paraformaldehyde.
Further, the TPU finished piece post-treatment flame-retardant coating liquid is prepared according to the following method and comprises the following steps:
step 1.1: heating 10-20 parts by mass of allyl glycidyl ether to 65 ℃ under stirring, slowly adding 20-30 parts by mass of organosilicon polymer, keeping stirring and preserving heat for 3.5 hours, and then heating to 85 ℃ for continuous reaction for 4 hours to obtain a solution of the epoxy group grafted modified organosilicon polymer, wherein the reaction chemical formula is shown in figure 3.
Step 1.2: slowly adding 40-50 parts by mass of phenolic resin into 10-30 parts by mass of organic solvent, mechanically stirring for 30-60 min at normal temperature, and obtaining solution with uniform color at the rotating speed of 100-300 r/min.
Step 1.3: slowly adding the modified organosilicon solution obtained in the step 1.1 and 10-20 parts by mass of flame retardant into the solution obtained in the step 1.2, mechanically stirring for 60-90 min at normal temperature, and obtaining a homogeneous suspension at the rotating speed of 100-300 r/min.
Step 1.4: and (3) adding 1-2 parts by mass of catalyst and 2-5 parts by mass of curing agent into the suspension obtained in the last step, mechanically stirring for 60-90 min at normal temperature, and obtaining the flame-retardant coating liquid at the rotating speed of 300-500 r/min.
The second aspect of the invention provides a flame-retardant treatment method for TPU (thermoplastic polyurethane) products, which comprises the following steps of:
step 2.1: cleaning the powder on the surface of the TPU product by using an ethanol solution with the concentration of 20% -30%, and then naturally drying for 1-3 hours in a clean environment;
step 2.2: immersing the TPU product obtained in the previous step and dried in the flame-retardant coating liquid for 1-5 min, then pulling out the flame-retardant coating liquid, and staying for 15-60 s, and repeating the immersing, pulling-staying for 3-8 times. After the TPU product is lifted out of the flame-retardant coating liquid for the last time, the TPU product stays for 1 to 5 minutes to naturally drip the surface coating liquid;
step 2.3: putting the TPU product with the surface immersed with the flame-retardant coating liquid into a vacuum oven, and drying for 24-72 h at 60-70 ℃ to obtain a coated TPU product;
step 2.4: and (3) placing the coated TPU product obtained in the step (2.3) in an oven, and curing according to the following curing mechanism: and (3) taking out from the oven after solidification is completed at 90-120 ℃/3-6h+130-135 ℃/6-12 h, and naturally cooling to room temperature to obtain the flame-retardant TPU product with the post-treatment coating.
Furthermore, in the flame retardant treatment method for the TPU product, the TPU product is preferably formed by an SLS technology, for example, the TPU product can be a hollowed-out structure containing cubic or octahedral lattices, and the TPU product with the structure has extremely high rebound performance.
Compared with the prior art, the invention has the following beneficial effects.
(1) The surface of the TPU part formed by SLS can be provided with micro-voids, the flame-retardant coating liquid is coated on the surface of the TPU part, resin in the coating liquid can permeate into the micro-voids on the surface of the TPU part, the coating can be tightly meshed with the TPU part after solidification, the durability of the coating is maintained, and the coating can not fall off even if larger elastic deformation occurs, so that the use requirement of the high-resilience TPU part is met.
(2) The flame-retardant coating can greatly reduce the original roughness of the surface of the TPU part, so that the surface of the part is smoother and smoother, and the appearance of the material is greatly improved.
(3) The flame-retardant coating liquid has good heat resistance and carbon forming performance by the synergistic flame-retardant function of the phenolic resin and the organic silicon, when a heat source appears outside, the base material can be well protected, the phenomenon of dripping does not appear after combustion, and further combustion is avoided.
(4) The TPU product is subjected to post-treatment by adopting the flame-retardant coating liquid, and a flame-retardant coating layer is formed on the surface of the formed material, so that the mode does not involve chemical reaction between the flame retardant and the inside of the matrix, and the physical properties of the base material are hardly reduced. In contrast, in the modification process of the surface coating, the epoxy modified organic silicon/phenolic resin can permeate into micro-gaps on the surface layer of the TPU part and the physical network of the surface layer of the TPU part, the cured epoxy modified organic silicon/phenolic resin is crosslinked into a network structure, and a semi-interpenetrating polymer network with a bicontinuous phase is formed on the surface layer of the TPU part, so that the separation of the flame retardant coating and the TPU substrate can be prevented, and the mechanical property of the material can be improved.
(5) The process of the scheme of the invention is simple and convenient to operate, and the raw material cost is low, but the excellent modification effect of improving the mechanical properties of the TPU parts while obviously improving the flame retardant properties of the TPU parts can be obtained, and the TPU parts can be produced in a large scale.
Drawings
FIG. 1 is a structural formula of a long chain polysiloxane.
FIG. 2 is a structural formula of a phenolic resin.
FIG. 3 is a modification reaction scheme for long chain polysiloxanes.
Detailed Description
The invention is further illustrated by the following specific examples, which are intended to illustrate the problem and to explain the invention, without limiting it.
The TPU product subjected to the flame-retardant post-treatment coating in each of the following examples is a standard sample obtained by adopting industrial-grade selective laser sintering equipment suitable for polymer materials and molding according to the following technological parameters: the laser power is 40-45W; the scanning speed is 5700-7000 mm/s; the scanning interval is 1mm; the powder spreading thickness is 0.1mm; the preheating temperature is 110 ℃.
Example 1
(1) 10g of allyl glycidyl ether is poured into a flask, the temperature is raised to 65 ℃ under stirring, 15g of organic silicon and 1g of Pt are slowly added, the temperature is kept for 3.5h, the temperature is raised to 85 ℃ again, and the reaction is continued for 4h, so as to obtain a modified organic silicon solution.
(2) 40g of phenolic resin is slowly added into 15g of acetone, and the mixture is mechanically stirred for 30min at normal temperature at the rotating speed of 200r/min until the color of the solution is uniform.
(3) To the solution obtained in the previous step, 17g of ammonium polyphosphate and the whole modified silicone solution were slowly added. Mechanically stirring for 60min at normal temperature at the rotating speed of 100r/min to obtain flame-retardant coating liquid with uniform texture;
(4) And (3) adding 2g of hexamethylenetetramine and 1g of dibutyltin dilaurate into the flame-retardant coating liquid obtained in the last step, and mechanically stirring at normal temperature for 60min at the rotating speed of 300r/min to obtain the curable flame-retardant coating liquid.
(5) And cleaning the surface powder of the TPU product by using an ethanol solution with the concentration of 30%, and then naturally drying the TPU product in a clean environment.
(6) Immersing the TPU product obtained in the previous step and dried in the flame-retardant coating liquid for 1min, then pulling out the flame-retardant coating liquid, and staying for 15s, and repeating the immersing, pulling and staying for 3 times. After the TPU product is lifted out of the flame-retardant coating liquid for the last time, the TPU product stays for 1min to naturally drip the surface coating liquid; and (3) putting the TPU product with the surface immersed with the flame-retardant coating liquid into a vacuum oven, and drying for 24 hours at 60 ℃.
(7) The product coated with the curable flame-retardant coating liquid is placed into an oven and cured according to the following curing mechanism: and (3) taking out the mixture from the oven after solidification at 120 ℃/3 hours and 135 ℃/12 hours, and naturally cooling the mixture to room temperature to obtain the flame-retardant TPU product with the post-treatment coating.
Example 2
(1) 10g of allyl glycidyl ether is poured into a flask, the temperature is raised to 65 ℃ under stirring, 15g of organic silicon is slowly added, the temperature is kept for 3.5h, the temperature is raised to 85 ℃ again, and the reaction is continued for 4h, so as to obtain a modified organic silicon solution.
(2) 40g of phenolic resin is slowly added into 15g of acetone, and the mixture is mechanically stirred for 30min at normal temperature at the rotating speed of 200r/min until the color of the solution is uniform.
(3) To the solution obtained in the previous step, 17g of ammonium polyphosphate and the whole modified silicone solution were slowly added. Mechanical stirring is used for 60min at normal temperature, and the rotating speed is 100r/min. Obtaining a flame-retardant coating liquid with uniform texture;
(4) And 2g of hexamethylenetetramine and 1g of stannous octoate are added into the flame-retardant coating liquid obtained in the last step, and the curable flame-retardant coating liquid is obtained by mechanical stirring for 60min at normal temperature at the rotating speed of 300 r/min.
(5) And cleaning the surface powder of the TPU product by using an ethanol solution with the concentration of 30%, and then naturally drying the TPU product in a clean environment.
(6) Immersing the TPU product obtained in the previous step and dried in the flame-retardant coating liquid for 5min, then pulling out the flame-retardant coating liquid, and staying for 60s, and repeating the immersing, pulling and staying for 8 times. After the TPU product is lifted out of the flame-retardant coating liquid for the last time, the TPU product stays for 5min to naturally drip the surface coating liquid; and (3) putting the TPU product with the surface immersed with the flame-retardant coating liquid into a vacuum oven, and drying for 72 hours at 70 ℃.
(7) The product coated with the curable flame-retardant coating liquid is placed into an oven and cured according to the following curing mechanism: and (3) taking out the mixture from the oven after solidification at 120 ℃/3 hours and 135 ℃/12 hours, and naturally cooling the mixture to room temperature to obtain the flame-retardant TPU product with the post-treatment coating.
Example 3
(1) 10g of allyl glycidyl ether is poured into a flask, the temperature is raised to 65 ℃ under stirring, 15g of organic silicon is slowly added, the temperature is kept for 3.5h, the temperature is raised to 85 ℃ again, and the reaction is continued for 4h, so as to obtain a modified organic silicon solution.
(2) 35g of phenolic resin is slowly added into 20g of acetone, and the mixture is mechanically stirred for 30min at normal temperature at the rotating speed of 200r/min until the color of the solution is uniform.
(3) To the solution obtained in the previous step, 17g of ammonium polyphosphate and the whole modified silicone solution were slowly added. Mechanical stirring is used for 60min at normal temperature, and the rotating speed is 100r/min. Obtaining a flame-retardant coating liquid with uniform texture;
(4) And 2g of hexamethylenetetramine and 1g of stannous octoate are added into the flame retardant coating obtained in the last step, and the flame retardant coating is mechanically stirred for 60min at normal temperature at the rotating speed of 300r/min to obtain the curable flame retardant coating liquid.
(5) And cleaning the surface powder of the TPU product by using an ethanol solution with the concentration of 30%, and then naturally drying the TPU product in a clean environment.
(6) Immersing the TPU product obtained in the previous step and dried in the flame-retardant coating liquid for 3min, then pulling out the flame-retardant coating liquid, and staying for 30s, and repeating the immersing, pulling and staying for 5 times. After the TPU product is lifted out of the flame-retardant coating liquid for the last time, the TPU product stays for 3min to naturally drip the surface coating liquid; and (3) putting the TPU product with the surface immersed with the flame-retardant coating liquid into a vacuum oven, and drying for 24 hours at 70 ℃.
(7) The product coated with the curable flame-retardant coating liquid is placed into an oven and cured according to the following curing mechanism: and (3) taking out the mixture from the oven after solidification at 120 ℃/3 hours and 135 ℃/12 hours, and naturally cooling the mixture to room temperature to obtain the flame-retardant TPU product with the post-treatment coating.
Example 4
(1) 10g of allyl glycidyl ether is poured into a flask, the temperature is raised to 65 ℃ under stirring, 15g of organic silicon is slowly added, the temperature is kept for 3.5h, the temperature is raised to 85 ℃ again, and the reaction is continued for 4h, so as to obtain a modified organic silicon solution.
(2) 35g of phenolic resin is slowly added into 20g of acetone, and the mixture is mechanically stirred for 30min at normal temperature at the rotating speed of 200r/min until the color of the solution is uniform.
(3) To the solution obtained in the previous step, 17g of ammonium polyphosphate and the whole modified silicone solution were slowly added. Mechanical stirring is used for 60min at normal temperature, and the rotating speed is 100r/min. Obtaining a flame-retardant coating liquid with uniform texture;
(4) And 2g of hexamethylenetetramine and 1g of stannous octoate are added into the flame retardant coating obtained in the last step, and the flame retardant coating is mechanically stirred for 60min at normal temperature at the rotating speed of 300r/min to obtain the curable flame retardant coating liquid.
(5) And cleaning the surface powder of the TPU product by using an ethanol solution with the concentration of 30%, and then naturally drying the TPU product in a clean environment.
(6) Immersing the TPU product obtained in the previous step and dried in the flame-retardant coating liquid for 3min, then pulling out the flame-retardant coating liquid, and staying for 30s, and repeating the immersing, pulling and staying for 5 times. After the TPU product is lifted out of the flame-retardant coating liquid for the last time, the TPU product stays for 3min to naturally drip the surface coating liquid; and (3) putting the TPU product with the surface immersed with the flame-retardant coating liquid into a vacuum oven, and drying for 24 hours at 70 ℃.
(7) The product coated with the curable flame-retardant coating liquid is placed into an oven and cured according to the following curing mechanism: and (3) taking out from the oven after solidification at 90 ℃/3h+130 ℃/12h, and naturally cooling to room temperature to obtain the flame-retardant TPU product with the post-treatment coating.
Example 5
(1) 10g of allyl glycidyl ether is poured into a flask, the temperature is raised to 65 ℃ under stirring, 15g of organic silicon is slowly added, the temperature is kept for 3.5h, the temperature is raised to 85 ℃ again, and the reaction is continued for 4h, so as to obtain a modified organic silicon solution.
(2) 35g of phenolic resin is slowly added into 20g of acetone, and the mixture is mechanically stirred for 30min at normal temperature at the rotating speed of 200r/min until the color of the solution is uniform.
(3) To the solution obtained in the previous step, 17g of ammonium polyphosphate and the whole modified silicone solution were slowly added. Mechanical stirring is used for 60min at normal temperature, and the rotating speed is 100r/min. Obtaining a flame-retardant coating liquid with uniform texture;
(4) And 2g of hexamethylenetetramine and 1g of stannous octoate are added into the flame retardant coating obtained in the last step, and the flame retardant coating is mechanically stirred for 60min at normal temperature at the rotating speed of 300r/min to obtain the curable flame retardant coating liquid.
(5) And cleaning the surface powder of the TPU product by using an ethanol solution with the concentration of 30%, and then naturally drying the TPU product in a clean environment.
(6) Immersing the TPU product obtained in the previous step and dried in the flame-retardant coating liquid for 3min, then pulling out the flame-retardant coating liquid, and staying for 30s, and repeating the immersing, pulling and staying for 5 times. After the TPU product is lifted out of the flame-retardant coating liquid for the last time, the TPU product stays for 3min to naturally drip the surface coating liquid; and (3) putting the TPU product with the surface immersed with the flame-retardant coating liquid into a vacuum oven, and drying for 24 hours at 70 ℃.
(7) The product coated with the curable flame-retardant coating liquid is placed into an oven and cured according to the following curing mechanism: and (3) taking out from the oven after solidification at 90 ℃/3h+130 ℃/12h, and naturally cooling to room temperature to obtain the flame-retardant TPU product with the post-treatment coating.
Example 6
(1) 10g of allyl glycidyl ether is poured into a flask, the temperature is raised to 65 ℃ under stirring, 15g of organic silicon is slowly added, the temperature is kept for 3.5h, the temperature is raised to 85 ℃ again, and the reaction is continued for 4h, so as to obtain a modified organic silicon solution.
(2) 35g of phenolic resin is slowly added into 20g of acetone, and mechanical stirring is performed for 30min at normal temperature, wherein the rotating speed is 200r/min until the color of the solution is uniform.
(3) To the solution obtained in the previous step, 17g of ammonium polyphosphate and the whole modified silicone solution were slowly added. Mechanical stirring is used for 60min at normal temperature, and the rotating speed is 100r/min. Obtaining a flame-retardant coating liquid with uniform texture;
(4) And adding 2g of p-toluenesulfonic acid and 1g of stannous octoate into the flame retardant coating obtained in the last step, and mechanically stirring at normal temperature for 60min at the rotating speed of 300r/min to obtain the curable flame retardant coating liquid.
(5) And cleaning the surface powder of the TPU product by using an ethanol solution with the concentration of 30%, and then naturally drying the TPU product in a clean environment.
(6) Immersing the TPU product obtained in the previous step and dried in the flame-retardant coating liquid for 3min, then pulling out the flame-retardant coating liquid, and staying for 30s, and repeating the immersing, pulling and staying for 5 times. After the TPU product is lifted out of the flame-retardant coating liquid for the last time, the TPU product stays for 3min to naturally drip the surface coating liquid; and (3) putting the TPU product with the surface immersed with the flame-retardant coating liquid into a vacuum oven, and drying for 24 hours at 70 ℃.
(7) The product coated with the curable flame-retardant coating liquid is placed into an oven and cured according to the following curing mechanism: and (3) taking out from the oven after solidification at 90 ℃/3h+130 ℃/12h, and naturally cooling to room temperature to obtain the flame-retardant TPU product with the post-treatment coating.
Comparative example 1
(1) And cleaning the surface powder of the TPU product by using an ethanol solution with the concentration of 30 percent, and then naturally drying the TPU product in a clean environment for 1 to 3 hours.
Comparative example 2
(1) The TPU and APP flame retardant are placed in an oven, heated to 80 ℃ and dried for 12 hours to remove the moisture.
(2) 100g of TPU and 12g of APP powder are weighed and put into a high-speed blender to be blended for 2 hours, so as to obtain dry composite powder.
(3) And (3) performing laser sintering molding on the flame-retardant TPU composite powder by using an SLS 3D printer. The SLS process parameters of the intumescent flame retardant TPU composite material are set as follows: the laser power is 40-45W; the scanning speed is 5700-7000 mm/s; the scanning interval is 1mm; powder spreading thickness; the powder spreading thickness is 0.1mm; preheating temperature; the preheating temperature is 112-114 ℃.
Effect verification
The performance test was performed on the standard samples obtained in the above examples 1, 2, 3, 4, 5, 6, comparative example 1 and 2 according to the following criteria, in which the test bars were subjected to a tensile test according to the GB/T1040-2006 standard, the test bars were dumbbell-shaped, the total length of the bars was 150mm, the distance between the jigs was 115mm, the gauge length was 50mm, and the tensile speed was 50mm/min; limiting Oxygen Index (LOI) test was performed according to ASTM D2863/77, with spline sizes of 130mm by 6mm by 3mm; vertical burn test (UL-94) was performed according to ASTM (D63-77), with spline sizes of 125X 13X 3mm 3 。
The results of the flame retardant post treatment material performance test of the TPU parts of each example 3D printed are shown in Table 1.
TABLE 1 Performance test results
The results in Table 1 show that comparative example 1 has the lowest oxygen index and is extremely flammable. Vertical combustion is not rated because the combustion process is dripping and does not self-extinguish. This is also why pure TPU is modified. Control 2 is a sample molded from SLS with the addition of a mass fraction flame retardant, and can be seen to have a reduced mechanical property and an improved flame retardant property, reaching a V-2 rating in the burn test. The addition of the flame retardant weakens the compactness in the printing process and thus reduces the mechanical properties. The mechanical properties of the samples after the coating, i.e.examples 1 to 6, were increased by up to 27.4. The improvement in mechanical properties is due to the thermosetting nature of the coating, which after curing on the TPU surface increases the tensile strength. The limiting oxygen index is relatively close because the amount of flame retardant added is the same and the effect on oxygen index is substantially comparable. But the addition of the flame retardant improves the limiting oxygen index, the increase range is about 51%, and the effect is remarkable. It can be seen from the vertical burning that the flame retardant properties of the coatings are improved, especially for examples 3 and 4, and a V-0 rating is achieved. This shows that the components, ratios and operating process parameters in the implementation of examples 3 and 4 form an optimal fit relationship, so that the product achieves an optimal char formation effect during combustion, and the vertical combustion rating is improved.
The above embodiments are illustrative for the purpose of illustrating the technical concept and features of the present invention so that those skilled in the art can understand the content of the present invention and implement it accordingly, and thus do not limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
Claims (10)
1. The TPU finished piece aftertreatment flame-retardant coating liquid is characterized in that: the composition comprises the following components:
30-50 parts by mass of epoxy group grafted and modified organosilicon polymer;
40-50 parts by mass of phenolic resin;
10-20 parts by mass of flame retardant;
10-30 parts by mass of an organic solvent;
1-2 parts by mass of a catalyst;
2-5 parts of curing agent.
2. The post-treatment flame retardant coating liquid for TPU parts according to claim 1, which is characterized in that: the epoxy group grafted and modified organosilicon polymer is prepared by double bond addition reaction of 10-20 parts by mass of allyl glycidyl ether and 20-30 parts by mass of organosilicon polymer.
3. The post-treatment flame retardant coating liquid for TPU parts according to claim 2, wherein: the reaction formula for preparing the epoxy group grafted and modified organosilicon polymer is as follows:
4. a TPU post treatment flame retardant coating according to any one of claims 1 to 3, characterized in that: the flame retardant is one or more of phosphorus-containing flame retardants such as ammonium polyphosphate, phosphite, phosphonate, organic phosphorus salt and the like.
5. A TPU post treatment flame retardant coating according to any one of claims 1 to 3, characterized in that: the organic solvent is one or more of acetone, tetrahydrofuran, methanol and diethyl ether.
6. A TPU post treatment flame retardant coating according to any one of claims 1 to 3, characterized in that: the catalyst is one or more of dibutyl tin dilaurate, stannous octoate, diethylenetriamine and triethylenetetramine.
7. A TPU post treatment flame retardant coating according to any one of claims 1 to 3, characterized in that: the curing agent is one or more of paraformaldehyde, hexamethylenetetramine, p-toluenesulfonic acid and phenolsulfonic acid.
8. The post-treatment flame retardant coating liquid for TPU parts according to claim 2, wherein: the TPU product post-treatment flame-retardant coating liquid is prepared by the following steps:
step 1.1: heating 10-20 parts by mass of allyl glycidyl ether to 65 ℃ in a stirring state, slowly adding 20-30 parts by mass of organosilicon polymer, keeping stirring and preserving heat for 3.5 hours, and heating to 85 ℃ for continuous reaction for 4 hours to obtain a solution of the epoxy group grafted modified organosilicon polymer;
step 1.2: slowly adding 40-50 parts by mass of phenolic resin into 10-30 parts by mass of organic solvent, mechanically stirring for 30-60 min at normal temperature, and obtaining a solution with uniform color at the rotating speed of 100-300 r/min;
step 1.3: slowly adding the modified organosilicon solution obtained in the step 1.1 and 10-20 parts by mass of flame retardant into the solution obtained in the step 1.2, mechanically stirring for 60-90 min at normal temperature at the rotating speed of 100-300 r/min to obtain a homogeneous suspension;
step 1.4: and (3) adding 1-2 parts by mass of catalyst and 2-5 parts by mass of curing agent into the suspension obtained in the last step, mechanically stirring for 60-90 min at normal temperature, and obtaining the flame-retardant coating liquid at the rotating speed of 300-500 r/min.
9. A flame-retardant treatment method for TPU (thermoplastic polyurethane) products is characterized by comprising the following steps of: immersing the dried and clean TPU product in the post-treatment flame-retardant coating liquid of the TPU product according to any one of claims 1 to 8, and heating to solidify the flame-retardant coating liquid on the surface of the TPU product so as to anchor the TPU product.
10. The flame retardant treatment method of a TPU article according to claim 9, wherein: the method comprises the following steps:
step 2.1: cleaning the surface of the TPU product by using an ethanol solution with the concentration of 20-30%, and naturally drying in a clean environment;
step 2.2: dipping the clean and dried TPU product into the flame-retardant coating liquid for 1-5 min, then lifting out the flame-retardant coating liquid, and staying for 15-60 s, wherein the dipping-lifting-staying is repeated for 3-8 times; the last time of stay for 1-5 min to allow the surface coating liquid to naturally drip;
step 2.3: vacuum drying the TPU product with the surface immersed with the flame-retardant coating liquid at 60-70 ℃ for 24-72 h to obtain a coated TPU product;
step 2.4: and (3) solidifying the coated TPU product obtained in the step (2.3) under a temperature control program of 90-120 ℃/3-6h+130-135 ℃/6-12 h, and cooling to obtain the flame-retardant TPU product.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1724591A (en) * | 2005-07-07 | 2006-01-25 | 中国科学院广州化学研究所 | Organic silicon fibre retardant of a kind of phosphorous and epoxy group(ing) and preparation method thereof |
| CN108795218A (en) * | 2018-06-13 | 2018-11-13 | 安庆越球建筑防水材料有限公司 | A kind of corrosion-resistant building water-proof material |
| CN112940656A (en) * | 2021-03-01 | 2021-06-11 | 华南理工大学 | Packaging adhesive for mini LED screen and preparation method thereof |
| CN113667265A (en) * | 2021-07-23 | 2021-11-19 | 华南理工大学 | High-flame-retardance water-based phenolic resin, preparation method thereof and method for applying high-flame-retardance water-based phenolic resin to laminated board |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1724591A (en) * | 2005-07-07 | 2006-01-25 | 中国科学院广州化学研究所 | Organic silicon fibre retardant of a kind of phosphorous and epoxy group(ing) and preparation method thereof |
| CN108795218A (en) * | 2018-06-13 | 2018-11-13 | 安庆越球建筑防水材料有限公司 | A kind of corrosion-resistant building water-proof material |
| CN112940656A (en) * | 2021-03-01 | 2021-06-11 | 华南理工大学 | Packaging adhesive for mini LED screen and preparation method thereof |
| CN113667265A (en) * | 2021-07-23 | 2021-11-19 | 华南理工大学 | High-flame-retardance water-based phenolic resin, preparation method thereof and method for applying high-flame-retardance water-based phenolic resin to laminated board |
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