Carbon dioxide-based refractory alloy and method for producing the same

Abstract

Carbon dioxide base high temperature alloy and preparation method belong to the technical field of degradable materials. The alloy is blended by PPCHC and PBAT according to the mass ratio of 10-60:40-90; the raw material weight composition of the foaming material is: 100 parts of the high temperature resistant carbon dioxide base alloy, 1-15 parts of functional additives, the functional additives are one or more of compatibilizers, chain extenders and fillers. The application adopts PPCHC and PBAT as the main body material of the alloy, the glass transition temperature and tensile strength of PPCHC are relatively high, but the elongation at break is low, the addition of PBAT with high elongation at break can effectively improve the toughness of PPCHC, and can maintain high temperature resistance, and can meet the use requirements of plastic products with high toughness requirements such as film bags.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of degradable materials, and particularly relates to a carbon dioxide-based high-temperature-resistant alloy and a preparation method thereof. BACKGROUND

[0002] The carbon dioxide-based degradable resin refers to a biodegradable binary or multi-copolymer generated by copolymerization of carbon dioxide and other monomers. The carbon dioxide-based degradable resin generally has high barrier property and transparency, but poor temperature resistance.

[0003] The binary copolymer generated by copolymerization of carbon dioxide and propylene oxide, i.e., polypropylene carbonate (PPC), is the earliest copolymer of this type. The glass transition temperature of PPC is 30-40 DEG C, which is relatively low, thereby limiting the application of PPC.

[0004] The glass transition temperature can be increased to 80-100 DEG C by introducing a rigid monomer, i.e., epoxy cyclohexane, but the elongation at break is less than 10%. Polybutylene adipate terephthalate (PBAT) is a plastic with excellent biodegradability, high toughness and high temperature resistance. However, the tensile strength of PBAT is not high due to the molecular structure of PBAT, thereby limiting the application of PBAT in the field of high-strength films. The blending of cyclohexene carbonate-propylene carbonate copolymer (PPCHC) and PBAT can compensate for the respective defects, thereby widening the application range. SUMMARY

[0005] The application aims to overcome the shortcomings of the prior art and provide a carbon dioxide-based high-temperature-resistant alloy with high toughness and a preparation method thereof.

[0006] The application adopts the technical scheme that the carbon dioxide-based high-temperature-resistant alloy is blended by PPCHC and PBAT at a mass ratio of 1-99:1-99.

[0007] The PPCHC and PBAT are mixed to obtain a high-temperature-resistant alloy with high tensile strength and good toughness.

[0008] Preferably, the mass ratio of the PPCHC to the PBAT is 10-60:40-90. The alloy with the preferred ratio can better combine the advantages of the two materials, better retain the glass transition temperature and tensile strength of the PPCHC, and increase the elongation at break and toughness.

[0009] More preferably, the mass ratio of the PPCHC to the PBAT is 20-50:50-80. The more preferred material ratio can achieve the best performance range of the application.

[0010] The tensile strength of the PBAT is 12-25 MPa; preferably, the tensile strength of the PBAT is 20-25 MPa.

[0011] The alloy can be used as an auxiliary material for other materials, blended with other materials to improve the strength and toughness of the materials; or can be used as a main material, directly adding a functional additive as a high-temperature-resistant composition. A carbon dioxide-based high-temperature-resistant composition has a raw material weight composition of 100 parts of a high-temperature-resistant carbon dioxide-based alloy and 0.1-20 parts of a functional additive. After adding the functional additive for performance adjustment, it can be applied to high-strength film bag products, bottle-shaped hollow containers, sheets, foamed products, etc.

[0012] Preferably, the raw material weight composition is: 100 parts of a high-temperature-resistant carbon dioxide-based alloy and 1-15 parts of a functional additive.

[0013] Specifically, the functional additive is one or more of a compatibilizer, a chain extender, and a filler.

[0014] Specifically, the compatibilizer is one or more of succinic anhydride, ethylene-methyl acrylate-glycidyl methacrylate, gamma-aminopropyl triethoxysilane, gamma-glycidyl ether oxygen propyl trimethoxysilane, gamma-(methacryloyloxy) propyl trimethoxysilane, titanate coupling agent, hexamethylene diisocyanate, polycaprolactone, epoxy compound chain extender, and oxazoline type chain extender. Adding a compatibilizer can ensure uniform distribution of the chain extender and the filler in the alloy.

[0015] Specifically, the mass ratio of the compatibilizer to the high-temperature-resistant carbon dioxide-based alloy is 1-5:100. Different compatibilizers have different compatibilization effects in the alloy, and the above amount can meet the compatibilization requirements of the compatibilizer.

[0016] Preferably, the compatibilizer is a composite compatibilizer of ethylene-methyl acrylate-glycidyl methacrylate and an epoxy compound chain extender, and the mass ratio is preferably 3-8:10; preferably, the mass ratio of the composite compatibilizer to the high-temperature-resistant carbon dioxide-based alloy is 1-1.5:100. The compatibilization effect of the compatibilizer in the alloy is more obvious, and the amount is less, which significantly reduces the precipitation of the compatibilizer and other additives, so the overall strength of the material is also improved.

[0017] Specifically, the chain extender is one or more of Joncryl ADR 4468, 4,4'-methylene-bis(3-chloro-2,6-diethyl aniline), 4,4'-bis-sec-butylaminodiphenylmethane, diethyltoluene diamine, dimethylthiuram toluene diamine, methylcyclohexane diamine, 2,2-dimethylol butyric acid, 2,2-dimethylol propionic acid, hydroquinone dihydroxyethyl ether, resorcinol di(2-hydroxyethyl) ether, 4-hydroxyethyl oxyethyl-1-hydroxyethyl benzene diether, polytetramethylene ether glycol bis-p-aminobenzoic acid ester, 4,4'-methylene bis(2-ethyl) aniline, 4,4'-methylene bis(2,6-diethyl aniline), 4,4'-methylene bis(6-methyl-2-ethyl aniline), 4,4'-diamino dicyclohexyl methane, 3,3'-dimethyl-4,4-diamino dicyclohexyl methane, 3-chloro-3'-ethyl-4,4'-diamino diphenyl methane, triallyl isocyanurate, 1,4-butanediol, 1,6-hexanediol, glycerol, trimethylolpropane, diethylene glycol, triethylene glycol, neopentyl glycol, sorbitol, diethylamino ethanol, dicumyl peroxide, toluene diisocyanate, and diphenyl methane diisocyanate. The addition of the chain extender to the alloy can combine the molecular chains of the two components in the alloy, thereby better improving the tensile strength and elongation at break of the material.

[0018] Specifically, the mass ratio of the chain extender to the high-temperature-resistant carbon dioxide-based alloy is 0.01-1:100. Depending on the performance of the chain extender, different amounts are added, and the above amount can better improve the tensile strength and elongation at break of the material without excessively affecting the processing performance of the material.

[0019] Preferably, the chain extender is a compounded chain extender of 2,2-dimethylol butyric acid or 2,2-dimethylol propionic acid and neopentyl glycol. Preferably, the compounded chain extender is better combined with the two components after being used, and can improve the tensile strength and elongation at break of the material to the best state of the present application at a lower amount without excessively affecting the processing performance of the material. Preferably, the amount added is that the mass ratio of the compounded chain extender to the high-temperature-resistant carbon dioxide-based alloy is 0.01-0.2:100. The lower amount can also reduce precipitation and is easier to distribute uniformly.

[0020] A preparation method of a carbon dioxide-based high-temperature-resistant composition, characterized in that:

[0021] 1) PPCHC and PBAT are added to a twin-screw extruder, extruded and granulated at 150-160°C to obtain a high-temperature-resistant alloy;

[0022] 2) The high-temperature-resistant alloy, the compatibilizer, the chain extender, and the filler are mixed uniformly and added to a twin-screw extruder, extruded and granulated again at 165-175°C to obtain a carbon dioxide-based high-temperature-resistant composition.

[0023] In the preparation process of the composition, the two components of PPCHC and PBAT are first mixed into an alloy to make them uniformly mixed before adding the additives, so as to prevent the mixing of the two from being affected after the addition of the additives; the additives are added after adjusting the temperature, so as to ensure that the materials are uniformly mixed, thereby fully exerting the effects of the components and producing a degradable material with high strength and good toughness.

[0024] The preparation method of the cyclohexene carbonate-propylene carbonate copolymer (PPCHC) comprises the following steps: in an environment where water and oxygen are removed, propylene oxide, cyclohexene oxide and a catalyst are put into a reactor, carbon dioxide is filled to make the reaction pressure reach 0.1 MPa-4.0 MPa, heating is performed to keep the reaction temperature at 40-100 ℃, ring-opening polymerization is generated, and the generated glue liquid is washed, devolatilized and dried to obtain a finished product.

[0025] PPCHC can well adjust the strength of PBAT, and the PPCHC with different molecular weights prepared by the above preparation process can all achieve the effect of improving the material strength.

[0026] Preferably, the molar ratio of propylene oxide and cyclohexene oxide is 2-10:1. Preferably, the reaction temperature is 60-80 ℃, and the reaction pressure is 1.0-2.0 MPa. The PPCHC prepared by the preferred preparation process can be quickly and uniformly mixed with PBAT, and can better improve the overall strength of the material.

[0027] Preferably, the catalyst is a combination of tetra-n-butyl ammonium halide and triethyl boron. The molar feeding ratio of tetra-n-butyl ammonium halide and triethyl boron is 1:2-3. Preferably, the molar feeding ratio of the catalyst to the total amount of epoxide is 1:100-3000.

[0028] The filler includes (but is not limited to) one or more of silica, heavy calcium carbonate, titanium dioxide and zinc oxide.

[0029] Compared with the prior art, the carbon dioxide-based high-temperature-resistant alloy and the preparation method thereof have the following beneficial effects: the cyclohexene carbonate-propylene carbonate copolymer (PPCHC) used in the application has high glass transition temperature and tensile strength, PBAT with high elongation at break is added to adjust the performance, which can effectively improve the toughness of PPCHC while maintaining high temperature resistance, and can meet the use requirements of plastic products such as film bags which have high toughness requirements. The composition of the application can be applied to high-strength film bag products, bottle-shaped hollow containers, sheets, foamed products and the like. DETAILED DESCRIPTION

[0030] The application will be described in detail below by examples. It is necessary to point out here that the following examples are only used to further illustrate the application and cannot be understood as limiting the protection scope of the application, and some non-essential improvements and adjustments made by the skilled in the art according to the content of the application still belong to the protection scope of the application.

[0031] In addition, if not otherwise specified, the raw materials used are commercially available.

[0032] PPCHC is produced in the laboratory of Shandong Lianxin Environmental Protection Technology Co., Ltd.

[0033] PBAT is purchased from Xinjiang Lanshan Tunhe Polyester Co., Ltd., model TH801T.

[0034] Preparation of PPCHC:

[0035] A material: In an environment where water and oxygen are removed by displacement, propylene oxide, epoxy cyclohexane, and catalyst are put into a 50L reactor, the molar ratio of propylene oxide to epoxy cyclohexane is 6:1, the molar feeding ratio of catalyst to total epoxide is 1:1000, the molar feeding ratio of catalyst to triethyl boron is 1:2.5, and triethyl boron is added in the form of triethyl boron solution (1 mol / L); carbon dioxide is filled to make the reaction pressure reach 1.5 MPa, and heating is used to keep the reaction temperature at 70℃; heating reaction for 6h to generate ring-opening polymerization. Cooling, pressure relief, dissolving the glue liquid in chloroform, precipitating with methanol, devolatilization, granulation, and drying to obtain A material, the number average molecular weight is 1.09×10 5 g / mol, and the glass transition temperature (Tg) is 82.6℃.

[0036] B material: In an environment where water and oxygen are removed by displacement, propylene oxide, epoxy cyclohexane, and catalyst are put into a 50L reactor, the molar ratio of propylene oxide to epoxy cyclohexane is 6:1, the molar feeding ratio of catalyst to total epoxide is 1:1000, the molar feeding ratio of catalyst to triethyl boron is 1:2, and triethyl boron is added in the form of triethyl boron solution (1 mol / L); carbon dioxide is filled to make the reaction pressure reach 2.0 MPa, and heating is used to keep the reaction temperature at 60℃; heating reaction for 6h to generate ring-opening polymerization. Cooling, pressure relief, dissolving the glue liquid in chloroform, precipitating with methanol, devolatilization, granulation, and drying to obtain B material, the number average molecular weight is 1.13×10 5 g / mol, and the glass transition temperature (Tg) is 82.7℃.

[0037] C material: In the environment of removing water and oxygen by displacement, propylene oxide, cyclohexene oxide and catalyst were put into a 50L reactor, the molar ratio of propylene oxide and cyclohexene oxide was 6:1, the molar feeding ratio of catalyst to total epoxide was 1:1000, the molar feeding ratio of catalyst tetra-n-butyl ammonium fluoride to triethyl boron was 1:3, triethyl boron was added in the form of triethyl boron solution (1 mol / L); carbon dioxide was filled to make the reaction pressure reach 1.0 MPa, heating was used to keep the reaction temperature at 80℃; ring-opening polymerization was generated by heating for 6h. After cooling, pressure relief, the glue solution was dissolved in chloroform, the precipitate was precipitated with methanol, and the C material was obtained by devolatilization, granulation and drying. The number average molecular weight was 1.01x10 5 g / mol, and the glass transition temperature (Tg) was 82.3℃.

[0038] D material: In the environment of removing water and oxygen by displacement, propylene oxide, cyclohexene oxide and catalyst were put into a 50L reactor, the molar ratio of propylene oxide and cyclohexene oxide was 8:1, the molar feeding ratio of catalyst to total epoxide was 1:1500, the molar feeding ratio of catalyst tetra-n-butyl ammonium chloride to triethyl boron was 1:2.5, triethyl boron was added in the form of triethyl boron solution (1 mol / L); carbon dioxide was filled to make the reaction pressure reach 0.1 MPa, heating was used to keep the reaction temperature at 40℃; ring-opening polymerization was generated by heating for 6h. After cooling, pressure relief, the glue solution was dissolved in chloroform, the precipitate was precipitated with methanol, and the D material was obtained by devolatilization, granulation and drying. The number average molecular weight was 1.23x10 5 g / mol, and the glass transition temperature (Tg) was 83.5℃.

[0039] Example 1

[0040] 1) A material PPCHC and PBAT were dehydrated and dried at 60℃, and were added into a twin-screw extruder at a mass ratio of 35:65, the tensile strength of PBAT was 22 MPa; extrusion granulation was carried out at 155℃ to obtain a high-temperature-resistant alloy;

[0041] 2) 100 parts of high-temperature-resistant carbon dioxide-based alloy, 1.2 parts of compatibilizer, 0.1 parts of chain extender, and 1.7 parts of silicon dioxide were uniformly mixed, wherein the compatibilizer was a compatibilizer compounded by ethylene-methyl acrylate-methyl methacrylate and an epoxy compound chain extender at a mass ratio of 6:10; the chain extender was a chain extender compounded by 2,2-dimethylol butyric acid and neopentyl glycol at a mass ratio of 1:1; the carbon dioxide-based high-temperature-resistant composition was obtained by adding a twin-screw extruder and extruding and granulating again at 170℃.

[0042] Example 2

[0043] B material was used to replace A material PPCHC in example 1, and other ingredients and process conditions were the same as in example 1.

[0044] Example 3

[0045] Replace material A (PPCHC) in Example 1 with material C, and keep the other ingredients and process conditions the same as in Example 1.

[0046] Example 4

[0047] Replace material A (PPCHC) in Example 1 with material D, while keeping other ingredients and process conditions the same as in Example 1.

[0048] Example 5

[0049] 1) Dehydrate and dry PPCHC and PBAT in material A at 60°C, and add them to a twin-screw extruder at a mass ratio of 20:80. The tensile strength of PBAT is 25MPa. Extrusion granulation is carried out at 155°C to obtain a high-temperature resistant alloy.

[0050] 2) Mix 100 parts of high-temperature resistant carbon dioxide-based alloy, 1 part of compatibilizer, 0.2 parts of chain extender, and 3 parts of silica evenly. The compatibilizer is a compound of ethylene-methyl acrylate-glycidyl methacrylate and epoxy compound chain extender in a mass ratio of 3:10; the chain extender is a compound of 2,2-dimethylolbutyric acid and neopentyl glycol in a mass ratio of 3:10. Add the mixture to a twin-screw extruder and extrude and granulate it again at 170°C to obtain the carbon dioxide-based high-temperature resistant composition.

[0051] Example 6

[0052] 1) Dehydrate and dry PPCHC and PBAT in material A at 60°C, and add them to a twin-screw extruder at a mass ratio of 50:50. The tensile strength of PBAT is 20MPa. Extrusion granulation is carried out at 155°C to obtain a high-temperature resistant alloy.

[0053] 2) Mix 100 parts of high-temperature resistant carbon dioxide-based alloy, 1.5 parts of compatibilizer, 0.01 parts of chain extender, and 8 parts of heavy calcium carbonate evenly. The compatibilizer is a compound of ethylene-methyl acrylate-glycidyl methacrylate and epoxy compound chain extender in a mass ratio of 8:10. The chain extender is a compound of 2,2-dimethylolpropionic acid and neopentyl glycol in a mass ratio of 3:10. Add the mixture to a twin-screw extruder and extrude and granulate again at 170°C to obtain a carbon dioxide-based high-temperature resistant composition.

[0054] Example 7

[0055] 1) Dehydrate and dry PPCHC and PBAT in material A at 60°C, and add them to a twin-screw extruder at a mass ratio of 35:65. The tensile strength of PBAT is 22MPa. Extrusion granulation is carried out at 155°C to obtain a high-temperature resistant alloy.

[0056] 2) Mix 100 parts of high-temperature resistant carbon dioxide-based alloy, 1.2 parts of ethylene-methyl acrylate-glycidyl methacrylate, 0.1 parts of 2,2-dimethylolbutyric acid, and 1.7 parts of silica evenly; add to a twin-screw extruder and extrude and granulate again at 170°C to obtain a carbon dioxide-based high-temperature resistant composition.

[0057] Example 8

[0058] 1) Dehydrate and dry PPCHC and PBAT in material A at 60°C, and add them to a twin-screw extruder at a mass ratio of 60:40. The tensile strength of PBAT is 12MPa. Extrusion granulation is carried out at 150°C to obtain a high-temperature resistant alloy.

[0059] 2) Mix 100 parts of high-temperature resistant carbon dioxide-based alloy, 1 part of γ-aminopropyltriethoxysilane, 1 part of Joncryl ADR4468, and 13 parts of zinc oxide evenly; add to a twin-screw extruder and extrude and granulate again at 165°C to obtain a carbon dioxide-based high-temperature resistant composition.

[0060] Example 9

[0061] 1) Dehydrate and dry PPCHC and PBAT in material A at 60°C, and add them to a twin-screw extruder at a mass ratio of 10:90. The tensile strength of PBAT is 25MPa. Extrusion granulation is carried out at 160°C to obtain a high-temperature resistant alloy.

[0062] 2) Mix 100 parts of high-temperature resistant carbon dioxide-based alloy, 5 parts of succinic anhydride, 0.8 parts of 4,4'-methylenebis(2,6-diethylaniline), and 9 parts of titanium dioxide evenly; add to a twin-screw extruder and extrude and granulate again at 175°C to obtain a carbon dioxide-based high-temperature resistant composition.

[0063] Performance testing:

[0064] The tensile strength and elongation at break of the composition samples of each embodiment were tested according to the national standards GB / T 1040.1 and GB / T 1040.2, and the data are recorded in Table 1.

[0065] Table 1. Partial Performance of Samples

[0066] Tensile strength / MPa Elongation at break / % Example 1 40 411 Example 2 42 407 Example 3 39 402 Example 4 37 365 Example 5 35 532 Example 6 44 278 Example 7 39 317 Example 8 45 232 Example 9 34 554

[0067] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention in any other way. Any person skilled in the art may make changes or modifications to the above-disclosed technical content to create equivalent embodiments. However, any simple modifications, equivalent changes, and modifications made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the protection scope of the present invention.

Claims

1. A carbon dioxide-based high temperature resistant composition, characterized in that, The raw material weight percentage composition is: 100 parts of high-temperature-resistant carbon dioxide-based alloy, 1-15 parts of functional additives; the high-temperature-resistant carbon dioxide-based alloy is blended by PPCHC and PBAT at a mass ratio of 20-50:50-80; the functional additives are one or more of a compatibilizer, a chain extender and a filler; The compatibilizer is a composite compatibilizer of ethylene-methyl acrylate-glycidyl methacrylate and an epoxidized compound at a mass ratio of 3-8:10, and the mass ratio of the composite compatibilizer to the high-temperature-resistant carbon dioxide-based alloy is 1-1.5:100; The chain extender is a compounded chain extender of 2,2-dimethylol butyric acid or 2,2-dimethylol propionic acid and neopentyl glycol, and the mass ratio of the compounded chain extender to the high-temperature-resistant carbon dioxide-based alloy is 0.01-0.2:

100.

2. A preparation method of the carbon dioxide-based high-temperature-resistant composition of claim 1, characterized in that: 1) PPCHC and PBAT are added to a double-screw extruder, extruded and granulated at an extrusion temperature of 150-160 DEG C to obtain a high-temperature-resistant alloy; 2) the high-temperature-resistant alloy, the compatibilizer, the chain extender and the filler are mixed uniformly and added to a double-screw extruder, extruded and granulated again at an extrusion temperature of 165-175 DEG C to obtain the carbon dioxide-based high-temperature-resistant composition.