CN116948231B - Heat-insulating polyurethane protective film and preparation method thereof - Google Patents
Heat-insulating polyurethane protective film and preparation method thereof Download PDFInfo
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- 230000001681 protective effect Effects 0.000 title claims abstract description 40
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 30
- 239000004814 polyurethane Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 76
- 239000002699 waste material Substances 0.000 claims abstract description 75
- 238000001035 drying Methods 0.000 claims abstract description 50
- 239000000463 material Substances 0.000 claims abstract description 44
- 229920005669 high impact polystyrene Polymers 0.000 claims abstract description 40
- 239000004797 high-impact polystyrene Substances 0.000 claims abstract description 40
- 239000000843 powder Substances 0.000 claims abstract description 33
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 25
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 239000012745 toughening agent Substances 0.000 claims abstract description 21
- 238000001816 cooling Methods 0.000 claims abstract description 19
- 239000007822 coupling agent Substances 0.000 claims abstract description 19
- 238000002844 melting Methods 0.000 claims abstract description 18
- 230000008018 melting Effects 0.000 claims abstract description 18
- 238000004140 cleaning Methods 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 239000011812 mixed powder Substances 0.000 claims description 21
- 238000012545 processing Methods 0.000 claims description 16
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 14
- XXLJGBGJDROPKW-UHFFFAOYSA-N antimony;oxotin Chemical compound [Sb].[Sn]=O XXLJGBGJDROPKW-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000004115 Sodium Silicate Substances 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 150000004645 aluminates Chemical class 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 11
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 8
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 8
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 238000005266 casting Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims 8
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000001125 extrusion Methods 0.000 abstract description 4
- 239000012943 hotmelt Substances 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 238000010345 tape casting Methods 0.000 abstract description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 44
- 230000000052 comparative effect Effects 0.000 description 17
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 16
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 16
- VHKFLUVQGQCGNO-UHFFFAOYSA-N buta-1,3-diene oxiran-2-ylmethyl 2-methylprop-2-enoate styrene Chemical group C(C(=C)C)(=O)OCC1CO1.C=CC=C.C=CC1=CC=CC=C1 VHKFLUVQGQCGNO-UHFFFAOYSA-N 0.000 description 7
- 229920001897 terpolymer Polymers 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- PIMBTRGLTHJJRV-UHFFFAOYSA-L zinc;2-methylprop-2-enoate Chemical compound [Zn+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O PIMBTRGLTHJJRV-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/04—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to rubbers
-
- 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
- C08J2455/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2423/00 - C08J2453/00
- C08J2455/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
- C08K2003/2213—Oxides; Hydroxides of metals of rare earth metal of cerium
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
Abstract
The invention relates to a heat-insulating polyurethane protective film and a preparation method thereof, and belongs to the technical field of heat-insulating films. The preparation method of the heat-insulating polyurethane protective film comprises the following steps: 1) Cleaning the ABS waste, and then heating and drying to obtain pretreated ABS waste; 2) Stirring and mixing TPU, pretreated ABS waste, modified powder, a coupling agent and an antioxidant to obtain a mixture; 3) Melting and blending the mixture and the toughening agent, cooling, granulating and drying to obtain a material A; 4) Melting and blending clean HIPS waste and ZDMA, cooling, granulating and drying to obtain material B; 5) And (3) carrying out melt blending, cooling, granulating and tape casting on the material A and the material B to obtain the heat-insulating polyurethane protective film. According to the invention, recycling is realized on the ABS waste and HIPS waste, and the performance of the protective film is obviously improved by introducing ZDMA and SBG-001 and combining a two-step hot melt blending extrusion mode.
Description
Technical Field
The invention belongs to the technical field of heat insulation films, and relates to a heat insulation polyurethane protective film and a preparation method thereof.
Background
High molecular flexible films, such as TPU (thermoplastic polyurethane) films, have excellent deformability while having high optical permeability, and thus are widely used in the field of protective films. However, the surface of the polymer film is easy to be stained and has limited heat insulation performance, and still has a large performance improvement space.
ABS plastic has the common properties of three components, and has the advantages of chemical corrosion resistance, heat resistance, high elasticity and toughness, and certain surface hardness. Therefore, the ABS plastic is a tough, hard and rigid material with easily obtained raw materials, good comprehensive performance, low price and wide application range.
In the modern society, the main consumption field of polystyrene PS is electronic and electric products, which account for about 60% of the total consumption of polystyrene; in the electronic and electric products, however, the plastic component is mainly High Impact Polystyrene (HIPS) and ABS resin. Therefore, when the electronic and electric products are scrapped, a huge amount of HIPS and ABS waste plastics are brought. If the environment-friendly recycling channel can be developed for the HIPS and ABS waste plastics, not only is the pollution of the waste to the environment relieved, but also the waste can be turned into wealth and the resource can be saved.
However, the ABS has poor compatibility with HIPS due to the existence of a cyano group which is a polar group, so that serious phase separation phenomenon occurs when the ABS and HIPS are melt blended, the morphology becomes more complex, and the mechanical properties are often reduced.
Disclosure of Invention
The invention aims to provide a heat-insulating polyurethane protective film and a preparation method thereof, and the heat-insulating polyurethane protective film realizes recycling of ABS waste and HIPS waste, and obviously improves the performance of the protective film by introducing ZDMA and SBG-001 and combining a two-step hot melt blending extrusion mode.
The aim of the invention can be achieved by the following technical scheme:
the preparation method of the heat-insulating polyurethane protective film comprises the following steps:
1) Cleaning the ABS waste, and then heating and drying to obtain pretreated ABS waste;
2) Stirring and mixing TPU, pretreated ABS waste, modified powder, a coupling agent and an antioxidant to obtain a mixture;
3) Melting and blending the mixture and the toughening agent, cooling, granulating and drying to obtain a material A;
4) Melting and blending clean HIPS waste and ZDMA, cooling, granulating and drying to obtain material B;
5) And (3) carrying out melt blending, cooling, granulating and tape casting on the material A and the material B to obtain the heat-insulating polyurethane protective film.
As a preferable technical scheme of the invention, in the step 1), the condition of heating and drying is that heating is carried out for 72-80 hours at 120-130 ℃; by heating the ABS waste for a long time, a large number of carbon-carbon double bonds in the polybutadiene phase of the ABS waste are broken, and an oxidation group such as carbonyl, hydroxyl and the like is generated.
As a preferable technical scheme of the invention, in the step 2), the mass ratio of the TPU, the pretreated ABS waste, the modified powder, the coupling agent and the antioxidant is 20-30:8-10:0.08-0.12:0.5-0.8:0.1-0.2, wherein the coupling agent is silane coupling agent KH-570; the antioxidant is hindered phenol antioxidant 1010.
As a preferred technical scheme of the invention, in the step 3), the mass ratio of the mixture to the toughening agent is 12-15:1, a step of; the condition of melt blending is that the melt blending is carried out in an extruder with the processing temperature of 210-220 ℃; the drying time is 8-10h.
As a preferable technical scheme of the invention, in the step 4), the clean HIPS waste is obtained by cleaning and drying the HIPS waste; the mass ratio of the clean HIPS waste to the ZDMA is 8-10:1, a step of; the condition of melt blending is that the melt blending is carried out in an extruder with the processing temperature of 230-235 ℃; wherein ZDMA is zinc dimethacrylate, the invention obtains material B by combining ZDMA and HIPS waste material by hot melting, generates free radical by ZDMA and generates grafting reaction with polybutadiene phase in ABS in material A, and uses Zn 2+ Ionic interactions with unsaturated carboxylates to improve compatibility between ABS and HIPS.
Further, according to the scheme, the SBG-001 and the mixture are firstly prepared into the material A, then the material A and the material B containing HIPS are subjected to hot melting blending extrusion, and the compatibility between the SBG-001 and the HIPS is better than that between the material A and the material B and ABS, so that the interaction force between the material A and the material B in the hot melting process is obviously improved, and the overall compatibility is obviously improved.
As a preferable technical scheme of the invention, in the step 5), the mass ratio of the material a to the material B is 3-4:1, a step of; the condition of melt blending is that the melt blending is carried out in an extruder with the processing temperature of 230-240 ℃ and the injection pressure of 25-28 MPa.
As a preferable technical scheme of the invention, the preparation method of the modified powder comprises the following steps: and (3) uniformly mixing the mixed powder with deionized water, adding sodium silicate, uniformly stirring, adjusting the pH value, aging, adding an aluminate coupling agent and an ethanol water solution, performing ultrasonic dispersion, filtering and drying to obtain the modified powder.
As a preferable technical scheme of the invention, the mixed powder is prepared from nano tin antimony oxide and cerium oxide according to a mass ratio of 2.5-3.0:1, mixing; the mass ratio of the mixed powder to deionized water to sodium silicate to the mass ratio of the aluminate coupling agent to the ethanol aqueous solution is 2-4:8-12:12-14:0.2-0.4:13-15; the pH value is adjusted to 9 by adopting dilute sulfuric acid with the mass concentration of 2%; the aging time is 3.0-3.5h; the mass concentration of the ethanol water solution is 70%; in the scheme of the invention, the 4f electronic structure of the nano cerium dioxide has strong ultraviolet absorption capability, no characteristic absorption to visible light, and the nano cerium dioxide has smaller size than light waves, can transmit visible light and has strong reflection or scattering effect on ultraviolet light, so that the nano cerium dioxide has the dual functions of absorbing and shielding ultraviolet light and reduces the damage of ultraviolet light to human skin and eyes; the nano tin antimony oxide has extremely weak absorptivity to visible light (380 nm-780 nm) and is composed of particles which are difficult to scatter to the visible light, so the nano tin antimony oxide has high transparency; according to the scheme, the mixed powder consisting of the nano tin antimony oxide and the nano cerium oxide is modified, so that the modified powder can be uniformly dispersed in the protective film, and the effects of reducing light transmission and heat transfer can be achieved through the mutual synergistic effect of the nano tin antimony oxide and the nano cerium oxide, so that the heat insulation performance of the protective film is remarkably improved.
The invention discloses a heat-insulating polyurethane protective film, which is prepared by adopting the preparation method.
In the step 3), the toughening agent is styrene-butadiene-glycidyl methacrylate terpolymer, SBG-001 is purchased from Shanghai, and the mass average molecular weight of the styrene-butadiene-glycidyl methacrylate terpolymer is 18000-25000; according to the scheme, the toughening agent is added, so that an elastomer is added to the system, the toughness of the protective film is improved, and meanwhile, the SBG-001 can be used as a chain extender to link broken molecular chains so as to improve the mechanical property of the protective film; further, SBG-001 can also be used as a compatibilizer to improve the compatibility of ABS and HIPS; the invention obviously protects the performance of the film through three functions of SBG-001 in a system.
As a preferred embodiment of the present invention, ABS waste and HIPS waste are available from Yangzhou Ningda noble metal Co.
The invention has the beneficial effects that:
1. according to the invention, the mixed powder consisting of nano tin antimony oxide and cerium dioxide is used for modifying the mixed powder, so that the modified powder can be uniformly dispersed in the protective film, and the effects of reducing light transmission and heat transfer can be achieved through the mutual synergistic effect of the nano tin antimony oxide and cerium dioxide, so that the heat insulation of the protective film is remarkably improved;
2. the ABS waste and HIPS waste are recycled, and the performance of the protective film is obviously improved by introducing ZDMA and SBG-001 and combining a two-step hot melt blending extrusion mode.
Detailed Description
In order to further describe the technical means and effects adopted by the present invention for achieving the intended purpose, the following detailed description is given below with reference to the embodiments, structures, features and effects according to the present invention.
Example 1
The preparation method of the modified powder comprises the following steps: uniformly mixing the mixed powder with deionized water, adding sodium silicate, uniformly stirring, adopting dilute sulfuric acid with the mass concentration of 2% to adjust the pH value to 9, aging for 3.0h, adding an aluminate coupling agent and an ethanol water solution with the mass concentration of 70%, performing ultrasonic dispersion, filtering and drying to obtain modified powder; wherein, the mixed powder is prepared from nano tin antimony oxide and cerium dioxide according to the mass ratio of 2.5:1, mixing; the mass ratio of the mixed powder to deionized water to sodium silicate to the mass ratio of the aluminate coupling agent to the ethanol aqueous solution is 2:8:12:0.2:13.
the preparation method of the heat-insulating polyurethane protective film comprises the following steps:
1) Cleaning the ABS waste, and then heating and drying to obtain pretreated ABS waste; wherein the condition of heating and drying is that heating is carried out for 72 hours at 120 ℃;
2) Stirring and mixing TPU, pretreated ABS waste, modified powder, silane coupling agent KH-570 and antioxidant to obtain a mixture; wherein, the mass ratio of TPU, pretreated ABS waste, modified powder, silane coupling agent KH-570 and antioxidant is 20:8:0.08:0.5:0.1; the antioxidant is hindered phenol antioxidant 1010;
3) Melting and blending the mixture and the toughening agent, cooling, granulating and drying to obtain a material A; wherein, the mass ratio of the mixture to the toughening agent is 12:1, a step of; the condition of melt blending is melt blending in an extruder with a processing temperature of 210 ℃; the drying time is 8 hours; the toughening agent is a styrene-butadiene-glycidyl methacrylate terpolymer;
4) Melting and blending clean HIPS waste and ZDMA, cooling, granulating and drying to obtain material B; wherein the clean HIPS waste is obtained by cleaning and drying HIPS waste; the mass ratio of the clean HIPS waste to the ZDMA is 8:1, a step of; the condition of melt blending is melt blending in an extruder with a processing temperature of 230 ℃;
5) Melting and blending the material A and the material B, cooling, granulating and casting to form a heat-insulating polyurethane protective film; wherein the mass ratio of the material A to the material B is 3:1, a step of; the melt blending condition is that the melt blending is carried out in an extruder with the processing temperature of 230 ℃ and the injection pressure of 25-28 MPa.
Example 2
The preparation method of the modified powder comprises the following steps: uniformly mixing the mixed powder with deionized water, adding sodium silicate, uniformly stirring, adopting dilute sulfuric acid with the mass concentration of 2% to adjust the pH value to 9, aging for 3.2 hours, adding an aluminate coupling agent and an ethanol water solution with the mass concentration of 70%, performing ultrasonic dispersion, filtering and drying to obtain modified powder; wherein, the mixed powder is prepared from nano tin antimony oxide and cerium dioxide according to the mass ratio of 2.8:1, mixing; the mass ratio of the mixed powder to deionized water to sodium silicate to the mass ratio of the aluminate coupling agent to the ethanol aqueous solution is 3:10:13:0.3:14.
the preparation method of the heat-insulating polyurethane protective film comprises the following steps:
1) Cleaning the ABS waste, and then heating and drying to obtain pretreated ABS waste; wherein the condition of heating and drying is that heating is carried out for 76 hours at 125 ℃;
2) Stirring and mixing TPU, pretreated ABS waste, modified powder, silane coupling agent KH-570 and antioxidant to obtain a mixture; wherein, the mass ratio of TPU, pretreated ABS waste, modified powder, silane coupling agent KH-570 and antioxidant is 25:9:0.1:0.65:0.15; the antioxidant is hindered phenol antioxidant 1010;
3) Melting and blending the mixture and the toughening agent, cooling, granulating and drying to obtain a material A; wherein, the mass ratio of the mixture to the toughening agent is 13:1, a step of; the condition of melt blending is melt blending in an extruder with a processing temperature of 215 ℃; the drying time is 9h; the toughening agent is a styrene-butadiene-glycidyl methacrylate terpolymer;
4) Melting and blending clean HIPS waste and ZDMA, cooling, granulating and drying to obtain material B; wherein the clean HIPS waste is obtained by cleaning and drying HIPS waste; the mass ratio of the clean HIPS waste to the ZDMA is 9:1, a step of; the condition of melt blending is melt blending in an extruder with a processing temperature of 232 ℃;
5) Melting and blending the material A and the material B, cooling, granulating and casting to form a heat-insulating polyurethane protective film; wherein the mass ratio of the material A to the material B is 3.5:1, a step of; the condition of melt blending is melt blending in an extruder with a processing temperature of 235 ℃ and an injection pressure of 27 MPa.
Example 3
The preparation method of the modified powder comprises the following steps: uniformly mixing the mixed powder with deionized water, adding sodium silicate, uniformly stirring, adopting dilute sulfuric acid with the mass concentration of 2% to adjust the pH value to 9, aging for 3.5 hours, adding an aluminate coupling agent and an ethanol water solution with the mass concentration of 70%, performing ultrasonic dispersion, filtering and drying to obtain modified powder; wherein, the mixed powder is prepared from nano tin antimony oxide and cerium dioxide according to the mass ratio of 3.0:1, mixing; the mass ratio of the mixed powder to deionized water to sodium silicate to the mass ratio of the aluminate coupling agent to the ethanol aqueous solution is 4:12:14:0.4:15.
the preparation method of the heat-insulating polyurethane protective film comprises the following steps:
1) Cleaning the ABS waste, and then heating and drying to obtain pretreated ABS waste; wherein the condition of heating and drying is that heating is carried out for 80 hours at 130 ℃;
2) Stirring and mixing TPU, pretreated ABS waste, modified powder, silane coupling agent KH-570 and antioxidant to obtain a mixture; wherein, the mass ratio of TPU, pretreated ABS waste, modified powder, silane coupling agent KH-570 and antioxidant is 30:10:0.12:0.8:0.2; the antioxidant is hindered phenol antioxidant 1010;
3) Melting and blending the mixture and the toughening agent, cooling, granulating and drying to obtain a material A; wherein, the mass ratio of the mixture to the toughening agent is 15:1, a step of; the condition of melt blending is melt blending in an extruder with a processing temperature of 220 ℃; the drying time is 10 hours; the toughening agent is a styrene-butadiene-glycidyl methacrylate terpolymer;
4) Melting and blending clean HIPS waste and ZDMA, cooling, granulating and drying to obtain material B; wherein the clean HIPS waste is obtained by cleaning and drying HIPS waste; the mass ratio of the clean HIPS waste to the ZDMA is 10:1, a step of; the condition of melt blending is melt blending in an extruder with a processing temperature of 235 ℃;
5) Melting and blending the material A and the material B, cooling, granulating and casting to form a heat-insulating polyurethane protective film; wherein the mass ratio of the material A to the material B is 4:1, a step of; the condition of melt blending is melt blending in an extruder with a processing temperature of 240 ℃ and an injection pressure of 28 MPa.
Example 4
Step 2) stirring and mixing TPU, pretreated ABS waste, modified powder, silane coupling agent KH-570 and antioxidant to obtain a mixture; wherein, the mass ratio of TPU, pretreated ABS waste, modified powder, silane coupling agent KH-570 and antioxidant is 25:9:0.12:0.65:0.15; the antioxidant is hindered phenol antioxidant 1010;
the difference compared with example 2 is that the amount of modified powder used, the remaining components, the preparation steps and the parameters are identical.
Comparative example 1
Step 2) stirring and mixing TPU, pretreated ABS waste, modified powder, silane coupling agent KH-570 and antioxidant to obtain a mixture; wherein, the mass ratio of TPU, pretreated ABS waste, modified powder, silane coupling agent KH-570 and antioxidant is 25:9:0.04:0.65:0.15; the antioxidant is hindered phenol antioxidant 1010;
the difference compared with example 2 is that the amount of modified powder used, the remaining components, the preparation steps and the parameters are identical.
Comparative example 2
In comparison with example 2, the difference is that comparative example 2 does not use nano tin antimony oxide, and the rest of components, preparation steps and parameters are identical.
Comparative example 3
In comparison with example 2, comparative example 3 does not use ceria, and the remaining components, preparation steps and parameters are identical.
Comparative example 4
Step 1), cleaning ABS waste, and then heating and drying to obtain pretreated ABS waste; wherein the condition of heating and drying is that heating is carried out for 48 hours at 125 ℃;
the difference compared to example 2 is the heat drying time of step 1), the remaining components, preparation steps and parameters are identical.
Comparative example 5
Step 1), cleaning ABS waste, and then heating and drying to obtain pretreated ABS waste; wherein the condition of heating and drying is that heating is carried out for 24 hours at 125 ℃;
the difference compared to example 2 is the heat drying time of step 1), the remaining components, preparation steps and parameters are identical.
Comparative example 6
In comparison with example 2, comparative example 6 was not prepared using a styrene-butadiene-glycidyl methacrylate terpolymer, and the remaining components, preparation steps and parameters were identical.
Comparative example 7
In comparison with example 2, the difference is that comparative example 7 does not use ZDMA, and the remaining components, preparation steps and parameters are identical.
Comparative example 8
The preparation method of the modified powder comprises the following steps: uniformly mixing the mixed powder with deionized water, adding sodium silicate, uniformly stirring, adopting dilute sulfuric acid with the mass concentration of 2% to adjust the pH value to 9, aging for 3.2 hours, adding an aluminate coupling agent and an ethanol water solution with the mass concentration of 70%, performing ultrasonic dispersion, filtering and drying to obtain modified powder; wherein, the mixed powder is prepared from nano tin antimony oxide and cerium dioxide according to the mass ratio of 2.8:1, mixing; the mass ratio of the mixed powder to deionized water to sodium silicate to the mass ratio of the aluminate coupling agent to the ethanol aqueous solution is 3:10:13:0.3:14.
the preparation method of the heat-insulating polyurethane protective film comprises the following steps:
1) Cleaning the ABS waste, and then heating and drying to obtain pretreated ABS waste; wherein the condition of heating and drying is that heating is carried out for 76 hours at 125 ℃;
2) Stirring and mixing TPU, pretreated ABS waste, modified powder, silane coupling agent KH-570 and antioxidant to obtain a mixture; wherein, the mass ratio of TPU, pretreated ABS waste, modified powder, silane coupling agent KH-570 and antioxidant is 25:9:1.2:0.65:0.15; the antioxidant is hindered phenol antioxidant 1010;
3) The mixture, the toughening agent, the clean HIPS waste and the ZDMA are subjected to melt blending, cooling, granulating and drying to obtain the heat-insulating polyurethane protective film; wherein, the mass ratio of the mixture to the toughening agent to HIPS waste to the ZDMA is 45.5:3.5:9:1, a step of; the drying time is 9h; the toughening agent is a styrene-butadiene-glycidyl methacrylate terpolymer; the clean HIPS waste is obtained by cleaning and drying HIPS waste; the condition of melt blending is melt blending in an extruder with a processing temperature of 235 ℃ and an injection pressure of 27 MPa.
1. According to GB/T13022-1991, the heat-insulating polyurethane protective films prepared in examples 1-4 and comparative examples 1-8 were cut into dumbbell-shaped strips respectively by a cutter, the width and thickness of the films were measured by a vernier caliper, the films were stretched at a speed of 300mm/min by a tensile tester, the tensile strength and elongation at break of the films were recorded, and the test results are shown in Table 1;
2. the heat-insulating polyurethane protective films prepared in examples 1 to 4 and comparative examples 1 to 3 were tested for UV blocking rate according to GB/T2680-2021, and the test results are shown in Table 1.
TABLE 1
From the test results of Table 1, it is understood that the tensile strength and elongation at break properties of the heat-insulating polyurethane protective films prepared in examples 1 to 4 of the present invention are significantly better than those of comparative examples 1 to 8, and the UV blocking rate of the heat-insulating polyurethane protective films prepared in examples 1 to 4 is significantly better than those of comparative examples 1 to 5, as compared with comparative examples 1 to 8.
The present invention is not limited to the above embodiments, but is capable of modification and variation in detail, and other modifications and variations can be made by those skilled in the art without departing from the scope of the present invention.
Claims (6)
1. The preparation method of the heat-insulating polyurethane protective film is characterized by comprising the following steps of:
1) Cleaning the ABS waste, and then heating and drying to obtain pretreated ABS waste; the heating and drying conditions are that heating is carried out for 72-80 hours at 120-130 ℃;
2) Stirring and mixing TPU, pretreated ABS waste, modified powder, a coupling agent and an antioxidant to obtain a mixture; the mass ratio of the TPU to the pretreated ABS waste to the modified powder to the coupling agent to the antioxidant is 20-30:8-10:0.08-0.12:0.5-0.8:0.1-0.2;
3) Melting and blending the mixture and the toughening agent, cooling, granulating and drying to obtain a material A; the toughening agent is a toughening agent SBG-001;
4) Melting and blending clean HIPS waste and ZDMA, cooling, granulating and drying to obtain material B;
5) Melting and blending the material A and the material B, cooling, granulating and casting to form a heat-insulating polyurethane protective film;
the preparation method of the modified powder comprises the following steps: uniformly mixing the mixed powder with deionized water, adding sodium silicate, uniformly stirring, adjusting the pH value, aging, adding an aluminate coupling agent and an ethanol water solution, performing ultrasonic dispersion, filtering and drying to obtain modified powder; the mixed powder is prepared from nano tin antimony oxide and cerium dioxide according to the mass ratio of 2.5-3.0:1, mixing; the mass ratio of the mixed powder to deionized water to sodium silicate to the mass ratio of the aluminate coupling agent to the ethanol aqueous solution is 2-4:8-12:12-14:0.2-0.4:13-15; the pH value is adjusted to 9 by adopting dilute sulfuric acid with the mass concentration of 2%; the aging time is 3.0-3.5h.
2. The method for preparing the heat-insulating polyurethane protective film according to claim 1, wherein the method comprises the following steps: in the step 2), the coupling agent is a silane coupling agent KH-570; the antioxidant is hindered phenol antioxidant 1010.
3. The method for preparing the heat-insulating polyurethane protective film according to claim 1, wherein the method comprises the following steps: in the step 3), the mass ratio of the mixture to the toughening agent is 12-15:1, a step of; the condition of melt blending is that the melt blending is carried out in an extruder with the processing temperature of 210-220 ℃; the drying time is 8-10h.
4. The method for preparing the heat-insulating polyurethane protective film according to claim 1, wherein the method comprises the following steps: in the step 4), the clean HIPS waste is obtained by cleaning and drying the HIPS waste; the mass ratio of the clean HIPS waste to the ZDMA is 8-10:1, a step of; the condition of melt blending is melt blending in an extruder with a processing temperature of 230-235 ℃.
5. The method for preparing the heat-insulating polyurethane protective film according to claim 1, wherein the method comprises the following steps: in the step 5), the mass ratio of the material A to the material B is 3-4:1, a step of; the condition of melt blending is that the melt blending is carried out in an extruder with the processing temperature of 230-240 ℃ and the injection pressure of 25-28 MPa.
6. A heat-insulating polyurethane protective film produced by the production method according to any one of claims 1 to 5.
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