Foamed compositions and their use, foamed materials and methods of making and using same

Abstract

This invention relates to the field of polymer materials, and discloses a foaming composition and its application, a foaming material and its preparation method and application. The composition comprises 5-50 parts by weight of POE, 50-95 parts by weight of EVA, and 0.1-1 parts by weight of a composite weathering agent; wherein the composite weathering agent comprises maleic anhydride copolymer microspheres, an antioxidant, a UV absorber, a UV shielding agent, a light stabilizer, and an N-vinylamide polymer. The specific composite weathering agent in this composition can simultaneously act as an interface compatibilizer and a cell nucleating agent, significantly reducing the volatilization of VOCs and other gases while ensuring uniform cell structure in the foamed material, and significantly improving the mechanical properties and weather resistance of the foamed material.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of high molecular materials, in particular, to a foaming composition and its application, a foaming material and its preparation method and application. BACKGROUND

[0002] Thermoplastic elastomer foaming material has good cell structure, by controlling the content of polyolefin elastomer component in it, the product resilience can be effectively improved, and it is widely used in shoe materials, battery pack cushioning materials and other fields. The surface of polyolefin elastomer foaming material is discolored, the mechanical properties are decreased and cracking occurs under long-term sunlight, research shows that this is because the ultraviolet rays with high energy in sunlight can destroy the molecular chain. The energy of ultraviolet rays with a wavelength range of 290-350 nm is higher than the bond energy of C-H bond (380-420 kJ / mol), that is, the ultraviolet rays can break the molecular chain on the side chain of polyolefin elastomer, thereby causing photodegradation.

[0003] CN112004870A discloses a granular foam of thermoplastic polyurethane and polypropylene, a molded part prepared therefrom, a method for preparing the granular foam and the molded part, and the molded part for use in shoe midsoles, insole, combined sole, cushioning element for shoes, bicycle saddle, bicycle tire, damping element, indoor decoration, mattress, support, handle, protective film, parts for use in the interior and exterior of a car, ball and sports equipment, or as a floor covering, but does not involve improvement measures for weather resistance.

[0004] CN112961488A discloses a method for foaming thermoplastic elastomer by incorporating gaseous or supercritical blowing agent into a molten thermoplastic elastomer containing polymer crystalline domains under pressure, and then releasing the pressure, but does not involve a modification method for the weather resistance of the elastomer foaming material. SUMMARY

[0005] In order to solve the above-mentioned problems existing in the prior art, the present application provides a foaming composition and its application, a foaming material and its preparation method and application, the foaming composition takes thermoplastic elastomer as the base resin, and contains a maleic anhydride copolymer microsphere loaded with an antioxidant, an ultraviolet absorber, an ultraviolet screen, a light stabilizer and an N-vinyl amide compound as a composite weathering aid. The composite weathering aid can simultaneously play the roles of an interfacial compatibilizer and a cell nucleating agent, can significantly reduce the volatilization of VOC gas, at the same time, make the cell of the foaming material prepared from the composition uniform, and significantly improve the mechanical properties and excellent weather resistance of the foaming material.

[0006] In order to achieve the above-mentioned purpose, the first aspect of the present application provides a foaming composition, wherein the composition comprises POE, EVA and a composite weathering aid.

[0007] The composite weather-resistant additive comprises maleic anhydride copolymer microspheres, antioxidants, ultraviolet absorbers, ultraviolet shielding agents, light stabilizers, and N-vinylamide polymers.

[0008] The content of POE is 5-50 parts by weight, the content of EVA is 50-95 parts by weight, and the content of composite weather-resistant additive is 0.1-1 parts by weight.

[0009] A second aspect of the present invention provides a foaming material, wherein the foaming material is obtained by foaming the above-mentioned foaming composition.

[0010] A third aspect of the present invention provides a method for preparing the above-mentioned foamed material, wherein the method includes: mixing the components in the above-mentioned foamed composition, extruding and granulating them, and then foaming them.

[0011] A fourth aspect of the present invention provides the use of the above-described foaming composition or foaming material in at least one of footwear, sports equipment, and seating.

[0012] Through the above technical solutions, the foaming composition and its application, the foaming material and its preparation method and application provided by the present invention achieve the following beneficial effects:

[0013] The foaming composition provided by this invention uses thermoplastic elastomer as the base resin and contains maleic anhydride copolymer microspheres loaded with antioxidants, ultraviolet absorbers, ultraviolet shielding agents, light stabilizers, and N-vinylamide compounds as a composite weather-resistant additive. This composite weather-resistant additive can simultaneously act as an interface compatibilizer and a cell nucleating agent, significantly reducing the volatilization of gases such as VOCs while ensuring uniform cell structure in the foamed material made from this composition, and significantly improving the mechanical properties and weather resistance of the foamed material.

[0014] The method for preparing foamed materials provided by this invention is simple, effective, and easy to operate. Attached Figure Description

[0015] Figure 1 This is a SEM image of the foamed material prepared in Example 1 of the present invention.

[0016] Figure 2 This is a SEM image of the foamed material prepared in Example 1 of the present invention.

[0017] Figure 3 This is a SEM image of the foamed material prepared in Example 1 of the present invention.

[0018] Figure 4 This is a SEM image of the foamed material prepared in Example 1 of the present invention.

[0019] Figure 5The image shows the SEM image of the foamed material prepared in Comparative Example 6. Detailed Implementation

[0020] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0021] A first aspect of the present invention provides a foaming composition, wherein the composition comprises POE, EVA and a composite weather-resistant additive;

[0022] The composite weather-resistant additive comprises maleic anhydride copolymer microspheres, antioxidants, ultraviolet absorbers, ultraviolet shielding agents, light stabilizers, and N-vinylamide compounds.

[0023] The content of POE is 5-50 parts by weight, the content of EVA is 50-95 parts by weight, and the content of composite weather-resistant additive is 0.1-1 parts by weight.

[0024] In this invention, the foaming composition uses a thermoplastic elastomer as the base resin and contains maleic anhydride copolymer microspheres loaded with antioxidants, ultraviolet absorbers, ultraviolet shielding agents, light stabilizers, and N-vinylamide compounds as a composite weather-resistant additive. This composite weather-resistant additive can simultaneously act as an interface compatibilizer and a cell nucleating agent, significantly reducing the volatilization of gases such as VOCs while ensuring uniform cell structure in the foamed material made from the composition, and significantly improving the mechanical properties and weather resistance of the foamed material.

[0025] In this invention, when the amount of each component in the foaming composition is controlled to meet the above-mentioned range, the weather resistance (e.g., aging resistance and yellowing resistance) of the foaming material is further improved, and the service life of the foaming material can be extended while maintaining the mechanical properties and weather resistance of the foaming material to meet actual needs.

[0026] In this invention, the total content of POE and EVA is 100 parts by weight.

[0027] Further, in the composition, the content of POE is 10-45 parts by weight, the content of EVA is 55-90 parts by weight, and the composite weather-resistant agent is 0.2-0.8 parts by weight.

[0028] In this invention, the POE is a copolymer of ethylene and a comonomer, wherein the content of structural units derived from the comonomer in the POE is 10-20 mol%.

[0029] In this invention, the comonomer is selected from at least one of 1-butene, 1-hexene, 1-octene, 1-nonene, or 4-methyl-pentene, 5-vinyl-2-norbornene, 1,9-decadiene, 5-ethylidene-2-norbornene, 1,3-cyclopentadiene, 1,3-cycloheptadiene, 1,5-cyclooctadiene, 1,6-octadiene, 1,7-octadiene, and 1,2-cyclononadiene.

[0030] In one specific embodiment of the present invention, the comonomer is selected from at least one of 1-butene, 1-hexene, 1-octene, 1-nonene and 4-methyl-pentene, preferably selected from 1-hexene and / or 1-octene.

[0031] In this invention, the inventors discovered that when POE containing the aforementioned specific comonomer is used in combination with the composite weather-resistant additive of this invention, the uniformity of the foamed material's cell structure can be significantly improved. Furthermore, when the effective content of each component in the composite weather-resistant additive meets the requirements of this invention, it ensures the uniformity of the foamed material's cell structure while simultaneously giving the foamed material excellent mechanical properties and weather resistance.

[0032] In this invention, the POE can be selected from conventional POEs in the art.

[0033] According to the present invention, the weight-average molecular weight of the POE is 100,000-200,000 g / mol, preferably 120,000-170,000 g / mol, and the molecular weight distribution of the POE is 1-3, preferably 1.5-2.5.

[0034] According to the present invention, at 190°C and a load of 2.16 kg, the mass melt flow rate of the POE is 0.1-2 g / 10 min, preferably 0.4-1.5 g / 10 min.

[0035] In this invention, the EVA is an ethylene-vinyl acetate copolymer, wherein the content of structural units derived from vinyl acetate in the EVA is 5-35 mol%.

[0036] In this invention, the content of structural units derived from vinyl acetate in the EVA is determined by NMR, specifically on an Agilent 400-MR DD2 nuclear magnetic resonance spectrometer, using CDCl3 as the solvent and at a test temperature of 40°C.

[0037] According to the present invention, at 190°C and a load of 2.16 kg, the mass melt flow rate of the EVA is 1-10 g / 10 min, preferably 2-7 g / 10 min.

[0038] Composite weather-resistant additives

[0039] In this invention, the composite weather-resistant additive comprises maleic anhydride copolymer microspheres, antioxidants, ultraviolet absorbers, ultraviolet shielding agents, light stabilizers, and N-vinylamide polymers. The antioxidants, ultraviolet absorbers, ultraviolet shielding agents, light stabilizers, and N-vinylamide compounds are loaded onto the maleic anhydride copolymer microspheres. The antioxidants, ultraviolet absorbers, ultraviolet shielding agents, and light stabilizers in the composite weather-resistant additive significantly improve the weather resistance of the foamed material prepared from this foaming composition under heat and light conditions. The N-vinylamide polymer inhibits the precipitation of anti-aging additives, ensuring that the aging resistance of shoe materials and shock-absorbing materials does not significantly decrease after encountering water or other media during use. Furthermore, when used in the foaming composition, this composite weather-resistant additive not only significantly improves the weather resistance of the foamed material but also simultaneously acts as an interface compatibilizer and cell nucleating agent, resulting in uniform cell structure and excellent mechanical properties in the prepared foamed material.

[0040] According to the present invention, based on the total weight of the composite weather-resistant additives, the effective content of the maleic anhydride copolymer microspheres is 5-60 wt%, the effective content of the antioxidant is 3-35 wt%, the effective content of the ultraviolet absorber is 8-20 wt%, the effective content of the ultraviolet shielding agent is 15-30 wt%, the effective content of the light stabilizer is 6-35 wt%, and the effective content of the N-vinylamide polymer is 3-20 wt%.

[0041] In this invention, when the effective content of each component in the composite weather-resistant additive meets the above-mentioned range, the antioxidant and other components can be uniformly dispersed, and the maleic anhydride copolymer microspheres can have excellent interfacial bonding force with the POE elastomer. This results in the foamed materials such as shoe materials prepared after foaming of the composition having excellent weather resistance and not yellowing after long-term use. At the same time, it can significantly improve the abrasion resistance of foamed materials such as shoe soles.

[0042] In this invention, the effective content of each component in the composite weather-resistant additive is calculated based on the amount of raw materials fed during the preparation process. Testing revealed that, except for some solid additives, such as ultraviolet shielding agents, which were not fully loaded onto the maleic anhydride copolymer microspheres during the preparation of the composite weather-resistant additive and thus had some residue, no residue was detected in the remaining components, indicating that they were all loaded onto the maleic anhydride copolymer microspheres. Therefore, the effective content of each component in the composite weather-resistant additive can be determined by the amount of raw materials fed.

[0043] Furthermore, based on the total weight of the composite weather-resistant additives, the effective content of the maleic anhydride copolymer microspheres is 10-50 wt%, the effective content of the antioxidant is 10-30 wt%, the effective content of the ultraviolet absorber is 10-16 wt%, the effective content of the ultraviolet shielding agent is 16-28 wt%, the effective content of the light stabilizer is 10-30 wt%, and the effective content of the N-vinylamide polymer is 6-18 wt%.

[0044] In this invention, the antioxidant can be any antioxidant conventionally used in the art. Preferably, the antioxidant is a hindered phenolic antioxidant and a phosphite antioxidant mixed in a mass ratio of 1:3 to 3:1; wherein the hindered phenolic antioxidant can be selected from antioxidant 1010 (pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; CAS No.: 6683-19-8), 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanuric acid; CAS No.: 27676-62-6), or 330 (1,3,5-trimethyl-2,4,6-tris(β-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanuric acid). At least one of (3,5-tert-butyl-4-hydroxybenzyl)benzene; CAS: 1709-70-2); the phosphite antioxidant may be selected from at least one of antioxidant 168 (tris[2,4-di-tert-butylphenyl]phosphite; CAS: 31570-04-4), antioxidant 618 (pentaerythritol distearate diphosphite; CAS: 3806-34-6) or antioxidant 2,2'-ethylenedi(4,6-di-tert-butylphenyl)fluorophosphite; CAS: 118337-09-0).

[0045] In this invention, the ultraviolet absorber is preferably an organic ultraviolet absorber, which refers to a compound whose molecule contains -C=N-, -N=N-, -C=O, -N=O, -NH2, -OH, -SO3H, or -COO, has hydrogen bonds and conjugated structure, and can form tautomers by oxygen bonds. When irradiated by ultraviolet light, the molecule changes from one structure to another, and then releases energy in the form of light and heat to restore the original molecular structure. For example, the ultraviolet absorber may be selected from 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-dipentylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-pentylphenyl)benzotriazole, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, phenyl benzoate, resorcinol monobenzoate, o-nitroaniline, p-cresol, 2,4,6-tris(2- Hydroxy-4-n-butoxyphenyl)-1,3,5-triazine, 2-cyano-3,3-diphenylacrylate 2-ethylhexyl ester, p-tert-butylphenyl salicylate, bisphenol A ester of bissalicylate, bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester), 2,2'-thiobis(4-tert-octylphenoloxy)nickel, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxy-phenol, 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-octyloxyphenol, N,N'-diphenyloxamide, etc. The ultraviolet absorber is preferably at least one of 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-hydroxy-4-n-octyloxybenzophenone, and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol.

[0046] In this invention, the light stabilizer may be selected from poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol) ester, bis(1-octoxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, a polymer of succinic acid and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol, bis(1,2,2,6,6-pentamethylpiperidinol) sebacate, 1-(methyl)-8-(1,2,2,6,6-pentamethyl-4-piperidinol) sebacate, bis(2,2,6,6-tetramethyl... -4-piperidinyl) sebacate, poly{[6-[(1,1,3,3-tetramethylbutyl)amino]]-1,3,5-triazine-2,4-[(2,2,6,6,-tetramethyl-piperidinyl)imino]-1,6-hexamethylene[(2,2,6,6-tetramethyl-4-piperidinyl)imino]}(944), preferably poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol) ester, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, N, N”'-1,2-Ethylenedi[N-[3-[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazin-2-yl]amino]propyl]-N,N”-dibutyl-N,N”-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-1,3,5-triazin-2,4,6-triamine. Preferably selected from poly{[6-[(1,1,3,3-tetramethylbutyl)amino]]-1,3,5-triazin-2,4-[(2,2,6,6]... [(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexamethylene[(2,2,6,6-tetramethyl-4-piperidinyl)imino]} and / or N,N”'-1,2-ethylenedimethyldi[N-[3-[[4,6-di[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazin-2-yl]amino]propyl]-N,N”-dibutyl-N,N”-di(1,2,2,6,6-pentamethyl-4-piperidinyl)-1,3,5-triazin-2,4,6-triamine].

[0047] In this invention, preferably, the ultraviolet shielding agent is an inorganic ultraviolet shielding agent; specifically, the inorganic ultraviolet shielding agent may be selected from KAl2(AlSi3O) 10 The components include (OH)₂, silicon dioxide, calcium carbonate, carbon black, cerium dioxide, titanium dioxide (rutile and anatase), zinc oxide, and hydrotalcite. The basic structural composition of hydrotalcite has the general formula: Where M 2+ and M 3+ These represent divalent and trivalent metal cations, respectively. M 2+ It can be Mg 2+ Ca 2+ Ba 2+Fe 2+ or Zn 2+ M 3+ It can be Al 3+ Fe 3+ Ni 3+ or Cr 3+ .

[0048] In this invention, the N-vinylamide polymer is selected from N-vinylamide homopolymers and / or N-vinylamide copolymers.

[0049] In this invention, the N-vinylamide polymer is selected from N-vinylamide homopolymers or copolymers; the N-vinylamide homopolymer is a homopolymer selected from the following N-vinylamide monomers, and the N-vinylamide copolymer is a copolymer selected from any two or three of the following N-vinylamide monomers. Specifically, the N-vinylamide monomer is selected from N-vinylheptamide, N-vinyloctamide, N-vinylnonamide, N-vinyldecamide, N-methyl-N-vinylformamide, N-methyl-N-vinylacetamide, N-methyl-N-vinylpropamide, N-methyl-N-vinylbutamide, N-methyl-N-vinylpentamide, N-methyl-N-vinylhexamide, N-methyl-N-vinylheptamide, N-methyl-N-vinyloctamide, N-methyl-N-vinylnonamide, N-methyl-N-vinyldecamide, N-ethyl-N-vinylformamide, N-ethyl-N-vinylacetamide, N-ethyl-N-vinylpropamide, N-ethyl-N-vinylbutamide, N-ethyl-N-vinylpentamide, N-ethyl-N-vinylhexamide, N-ethyl-N-vinylheptamide, N-ethyl-N-vinyloctamide, N-ethyl-N-vinyldecamide, N-ethyl-N-vinylformamide, N-ethyl-N-vinylacetamide, N-ethyl-N-vinylpropamide, N-ethyl-N-vinylbutamide, N-ethyl-N-vinylpentamide, N-ethyl-N-vinylhexamide, N-ethyl-N-vinylheptamide, N-ethyl-N-vinyloctamide, and N-ethyl-N-vinylnonamide. N-Ethyl-N-vinyldecanoamide, N-n-propyl-N-vinylformamide, N-n-propyl-N-vinylacetamide, N-n-propyl-N-vinylpropanoamide, N-n-propyl-N-vinylbutanoamide, N-n-propyl-N-vinylpentanoamide, N-n-propyl-N-vinylhexanoamide, N-n-propyl-N-vinylheptanoamide, N-n-propyl-N-vinyloctanoamide, N-n-propyl-N-vinylnonanoamide, N-n-propyl-N-vinyl At least one of the following: decanoamide, N-isopropyl-N-vinylformamide, N-isopropyl-N-vinylacetamide, N-isopropyl-N-vinylpropionamide, N-isopropyl-N-vinylbutyramide, N-isopropyl-N-vinylpentanamide, N-isopropyl-N-vinylhexamide, N-isopropyl-N-vinylheptamide, N-isopropyl-N-vinyloctamide, N-isopropyl-N-vinylnonamide, and N-isopropyl-N-vinyldecanoamide.

[0050] In this invention, preferably, the N-vinylamide polymer is selected from at least one of N-vinyloctamide, N-isopropyl-N-vinylnonamide, and N-methyl-N-vinyldecamide.

[0051] In this invention, preferably, the relative molecular mass of the N-vinylamide polymer is less than or equal to 1000.

[0052] Maleic anhydride copolymer microspheres

[0053] In this invention, the surface of the maleic anhydride copolymer microspheres is clean and free of pollution, and the polymer is in the form of microspheres with uniform particle size. No polluting additives such as emulsifiers are used in the preparation process, which significantly reduces the environmental pollution caused by the preparation process. The polymer material obtained is spherical and has no special odor of ester solvents such as isoamyl acetate.

[0054] According to the present invention, the particle size of the maleic anhydride copolymer microspheres is 500-920 nm.

[0055] In this invention, controlling the particle size of the maleic anhydride copolymer microspheres to meet the aforementioned range significantly improves the dispersibility of the composite weather-resistant additive, including the copolymer microspheres, in the POE and EVA matrices. This effectively enhances the abrasion resistance of foamed materials such as shoe materials in contact with the ground while simultaneously increasing the addition efficiency of the composite weather-resistant additive. Furthermore, using maleic anhydride copolymer microspheres with the aforementioned specific particle size allows for further control of the cell size in the foamed material, increasing the cell density and improving the mechanical properties of the foamed material.

[0056] Furthermore, the particle size of the maleic anhydride copolymer microspheres is 530-800 nm.

[0057] According to the present invention, the copolymer in the maleic anhydride copolymer microspheres comprises structural unit A provided by maleic anhydride, structural unit B provided by isobutylene, and structural unit C provided by styrene. Based on the total molar amount of each structural unit in the copolymer, the content of structural unit A is 47-52 mol%, and the molar ratio of structural unit B to structural unit C is 1:0.2-7.5.

[0058] In this invention, when the content of each structural unit in the maleic anhydride copolymer microspheres meets the above-mentioned range, the interfacial bonding force between the microspheres and the polar component EVA and the optional modifier thermoplastic polyamide elastomer in the composition can be improved, thereby significantly improving the tear resistance of foamed materials such as shoe materials made from the composition.

[0059] Furthermore, based on the total molar amount of each structural unit in the copolymer, the content of structural unit A is 48-51 mol%, and the molar ratio of structural unit B to structural unit C is 1:1-5.

[0060] In this invention, the molar content of each structural unit in the copolymer is determined by... 1 The test was performed using H NMR, and the test method was as follows: 1 The ratio of the peak area corresponding to the characteristic hydrogen in the corresponding structural unit in H NMR is calculated.

[0061] In this invention, the maleic anhydride copolymer microspheres are prepared according to the following steps:

[0062] S1. In an inert atmosphere, the monomers and initiators are dissolved in the reaction medium to form a homogeneous solution;

[0063] S2. After the homogeneous solution undergoes a polymerization reaction to obtain a copolymer emulsion suspension, the maleic anhydride copolymer microspheres are separated.

[0064] The polymer monomers are maleic anhydride, styrene and isobutylene;

[0065] Based on the total mass of the polymerized monomers, the molar content of the maleic anhydride is 47-52 mol%.

[0066] The molar ratio of isobutylene to styrene is 1:0.2-7.5.

[0067] In this invention, maleic anhydride monomer, isobutylene monomer, and styrene monomer are polymerized in a specific ratio using a copolymerization method, resulting in a maleic anhydride-isobutylene-styrene copolymer that exhibits excellent uniformity in the form of microspheres. Furthermore, the maleic anhydride copolymer has the characteristics of clean surface and uniform particle size. The resulting maleic anhydride copolymer microspheres are polar, which can improve the interfacial bonding force between them and EVA in the composition.

[0068] According to the present invention, based on the total mass of the polymeric monomers, the molar content of the maleic anhydride is 48-51 mol%; the molar ratio of the isobutylene to the styrene is 1:1-5.

[0069] According to the present invention, the mass concentration of the polymeric monomer is 4-23 wt%, preferably 6-21 wt%, based on the total weight of the homogeneous solution.

[0070] According to the present invention, the initiator is an organic peroxide and / or an azo compound.

[0071] According to the present invention, the organic peroxide is selected from at least one of benzoyl peroxide, dicumyl peroxide, ditert-butyl peroxide, dodecyl peroxide, tert-butyl peroxide, diisopropyl peroxide, and dicyclohexyl peroxide.

[0072] According to the present invention, the azo compound is selected from azobisisobutyronitrile and / or azobisisoheptanenitrile.

[0073] According to one embodiment of the present invention, the reaction medium is an organic acid alkyl ester.

[0074] According to one embodiment of the present invention, the reaction medium is a mixed solvent of ketone compounds and alkane compounds.

[0075] According to one embodiment of the present invention, the reaction medium is a mixed solvent of organic acid alkyl esters, ketone compounds and alkane compounds.

[0076] In this invention, compounds selected from the above-mentioned types are used as reaction media, which can cooperate with the polymeric monomers in specific amounts as described in this invention. Without the need for additional stabilizers or precipitants, they can achieve self-stabilizing precipitation polymerization of maleic anhydride, isobutylene, and styrene. No stabilizers or co-stabilizers are added to the polymerization reaction system, which has a self-stabilizing dispersion effect. The obtained copolymer microspheres have clean surfaces and uniform particle sizes. The obtained copolymer microspheres are polar and can improve the interfacial bonding force between them and EVA in the composition.

[0077] Furthermore, when using a mixed solvent of ketone compounds and alkane compounds, or a mixed solvent of organic acid alkyl esters, ketone compounds and alkane compounds, the problem of the material having a special odor caused by using ester solvents alone can be improved.

[0078] According to the present invention, the general formula of the organic acid alkyl ester is R1COOR2, wherein R1 is selected from H and C. 1-5 alkyl or C 6-10 Aryl group, R2 is C 1-10 Alkyl groups.

[0079] In this invention, C 1-5 The alkyl groups include straight-chain alkyl groups of C1-C5 and branched alkyl groups of C3-C5, and specific examples may include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl and isopentyl, etc.

[0080] In this invention, the term "aryl group" can be represented as Ar. x -N-, where x Ar atoms are the same or different, each independently being an aryl group, N is an alkyl group, and x is an integer from 1 to 3. In this invention, C6-C 10 Specific examples of aralkyl groups may include, but are not limited to: phenylmethyl, phenylethyl, phenyl-n-propyl, phenyl-n-butyl, phenyl-tert-butyl, phenylisopropyl, and phenyl-n-butyl.

[0081] Furthermore, R1 is C 1-5alkyl or C 6-9 Aryl group, R2 is C 1-7 Alkyl groups.

[0082] According to a particularly preferred embodiment of the present invention, the organic acid alkyl ester is selected from at least one of ethyl formate, propyl formate, isobutyl formate, amyl formate, ethyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, amyl acetate, isoamyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, isoamyl butyrate, ethyl isovalerate, isoamyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate, and ethyl phenylacetate.

[0083] According to the present invention, the ketone compound has the structure shown in Formula I:

[0084]

[0085] Among them, R3 and R4 are alkyl groups with 1-6 carbon atoms.

[0086] Furthermore, R3 and R4 are alkyl groups with 1-3 carbon atoms.

[0087] According to the present invention, the alkane compound is an alkane with 6-12 carbon atoms, preferably an alkane with 6-10 carbon atoms.

[0088] According to one embodiment of the present invention, the reaction medium is a mixed solvent of a ketone compound and an alkane compound, wherein the amount of the alkane compound is 50-90 vol% of the mixed solvent of the ketone compound and the alkane compound.

[0089] In this invention, the amount of the alkane compound used meets the above-mentioned range, which enables the prepared copolymer microspheres to be polar and improves the interfacial bonding force between them and EVA in the composition.

[0090] Furthermore, the amount of the alkane compound used is 50-80 vol% of the mixed solvent of the ketone compound and the alkane compound.

[0091] According to one embodiment of the present invention, the reaction medium is a mixed solvent of organic acid alkyl ester, ketone compound and alkane compound, wherein the amount of alkane compound is 0-50 vol%, preferably 1-30 vol%, of the mixed solvent; and the amount of ketone compound is 1-10 vol%, preferably 1-5 vol%, of the mixed solvent of organic acid alkyl ester, ketone compound and alkane compound.

[0092] In this embodiment of the invention, it should be noted that when the reaction medium is a mixed solvent of organic acid alkyl esters, ketone compounds and alkane compounds, the amounts of ketone compounds and alkane compounds are not both 0.

[0093] In this invention, the polymerization reaction is carried out in a protective atmosphere, which can be provided by conventional inert gases or nitrogen.

[0094] According to the present invention, the conditions for the polymerization reaction include: a polymerization temperature of 40-95°C, preferably 50-80°C; and a polymerization time of 1-24 h, preferably 3-10 h.

[0095] In this invention, to achieve self-stabilization of the polymerization system and thus obtain copolymer microspheres with uniform particle size and clean, uncontaminated surfaces, the inventors studied the conditions of the polymerization reaction. The study showed that when the polymerization temperature is 40-95℃ and the polymerization time is 1-24h, a stable, self-stabilized system is formed. In this system, maleic anhydride, isobutylene, and styrene polymerize to form microspheres, which do not aggregate and exhibit good dispersibility.

[0096] In this invention, the separation can be a conventional solid-liquid separation method in the art, such as centrifugal separation.

[0097] In this invention, when centrifugation is used, the centrifugation speed is 1500-5000 rad / min and the centrifugation time is 5-60 min.

[0098] According to the present invention, the composite weather-resistant additive is prepared according to the following method:

[0099] In the presence of a solvent, maleic anhydride copolymer microspheres, antioxidants, ultraviolet absorbers, ultraviolet shielding agents, light stabilizers, and N-vinylamide compounds are mixed and reacted, followed by solid-liquid separation to obtain the composite weather-resistant additive.

[0100] In this invention, the types of raw materials used in the preparation method are exactly the same as those used in the aforementioned composite weather-resistant additives. To avoid repetition, this invention will not repeat them here, and those skilled in the art should not understand this as a limitation of the invention.

[0101] In this invention, the solvent can be a conventional solvent in the art, such as ethanol.

[0102] In this invention, according to the above preparation method, in the presence of a solvent and an N-vinylamide polymer, antioxidants, ultraviolet absorbers, ultraviolet shielding agents, and light stabilizers are mixed and reacted with maleic anhydride copolymer microspheres. The antioxidants, ultraviolet absorbers, ultraviolet shielding agents, and light stabilizers are then loaded onto the maleic anhydride copolymer microspheres to obtain the composite weather-resistant agent described in this invention. This composite weather-resistant agent exhibits good compatibility with polyolefin elastomers, such as POE and EVA. It significantly improves the anti-aging efficiency of the composite weather-resistant agent while ensuring that foamed materials such as shoe materials made from this composition are less prone to aging and yellowing during long-term use, and that the parts in contact with the ground have improved abrasion resistance.

[0103] According to the present invention, the amount of the maleic anhydride copolymer microspheres is 0.1-5 parts by weight, the amount of the antioxidant is 0.1-10 parts by weight, the amount of the ultraviolet absorber is 0.5-6 parts by weight, the amount of the ultraviolet shielding agent is 1-10 parts by weight, the amount of the light stabilizer is 0.1-10 parts by weight, and the amount of the N-vinylamide polymer is 0.1-7 parts by weight.

[0104] Further, the amount of the maleic anhydride copolymer microspheres is 1-6 parts by weight, the amount of the antioxidant is 1.5-8 parts by weight, the amount of the ultraviolet absorber is 1.5-5 parts by weight, the amount of the ultraviolet shielding agent is 2-8 parts by weight, the amount of the light stabilizer is 1.5-7 parts by weight, and the amount of the N-vinylamide polymer is 0.5-6 parts by weight.

[0105] According to the present invention, the conditions for the mixed reaction include: a reaction temperature of 70-80°C and a reaction time of 15-90 min.

[0106] In one specific embodiment of the present invention, the preparation method of the composite antibacterial agent includes:

[0107] At 70-80℃, the solvent and N-vinylamide polymer are mixed evenly, and then antioxidants, ultraviolet absorbers, ultraviolet shielding agents and light stabilizers are added and reacted for 10-60 min. Then maleic anhydride copolymer microspheres are added and the reaction is continued for 5-30 min. After separation and drying, the composite antibacterial agent is obtained.

[0108] In this invention, there are no particular limitations on the separation and drying methods and drying conditions; conventional separation and drying methods and drying conditions in the art can be used.

[0109] According to the present invention, the composition further comprises 0.1-10 parts by weight of a foaming agent.

[0110] Furthermore, the composition also includes 2-7 parts by weight of a foaming agent.

[0111] In this invention, the foaming agent may be selected from physical foaming agents and / or chemical foaming agents.

[0112] In this invention, the physical foaming agent is selected from carbon dioxide, nitrogen, or organic compounds such as aliphatic hydrocarbons, chlorinated hydrocarbons, and chlorofluorocarbons.

[0113] In this invention, the chemical foaming agent is selected from at least one of azodicarbonamide (AC), azobisisobutyronitrile (AIBN), barium azodicarbonate (BaAC), azodicarbonate ester, dinitrospentamethylenetetramine (DPT), N,N'-dinitrospentamethylenetetramine, N,N'-dimethyl-N,N-dinitrosterephthalamide (NTA), trinitrostrimethylenetriamine, 4,4'-oxobis(benzenesulfonylhydrazine) (OBSH), toluenesulfonamide (TSSC), triphosphatidyltriazine (CTHT), 5-phenyltetrazole, 2,4-toluenedisulfonylhydrazine, and p-toluenesulfonylhydrazine.

[0114] According to the present invention, the composition further comprises 0.1-1 parts by weight of a crosslinking agent.

[0115] Furthermore, the composition also includes 0.3-0.9 parts by weight of a crosslinking agent.

[0116] In this invention, the crosslinking agent is an organic peroxide. Specifically, the crosslinking agent is selected from at least one of dicumyl peroxide, peroxyneoheptanoic acid, 1-dimethyl-3-hydroxybutyl ester, peroxyneodecanic acid, tert-amyl perbenzoate, tert-butyl perbenzoate, tert-amyl peroctanoate, tert-butyl peroctanoate, di-tert-butyl peroxide, and triallyl isocyanurate.

[0117] According to the present invention, the composition further comprises 0.3-12 parts by weight of a foaming agent.

[0118] Furthermore, the composition also includes 0.9-3 parts by weight of a foaming agent.

[0119] According to the present invention, the foaming agent is selected from at least one of stearic acid, zinc stearate and zinc oxide.

[0120] In one specific embodiment of the present invention, the composition comprises 0.1-1 parts by weight of stearic acid, 0.1-1 parts by weight of zinc stearate and 0.1-10 parts by weight of zinc oxide.

[0121] In a preferred embodiment of the present invention, the composition comprises 0.2-0.5 parts by weight of stearic acid, 0.2-0.5 parts by weight of zinc stearate and 0.5-0.2 parts by weight of zinc oxide.

[0122] According to the present invention, the composition further comprises 1-10 parts by weight, preferably 2-5 parts by weight, of a thermoplastic polyamide elastomer.

[0123] In this invention, the thermoplastic polyamide elastomer (TPAE) is a block copolymer composed of hard segments and soft segments. The hard segments of the polyamide are one or more of PA612, PA11, PA12, PA1012, and PA1212; the soft segments of the polyamide elastomer are one or more of polyethylene glycol, polypropylene glycol, polybutane glycol, polytetrahydrofuran, polytetramethylene ether, polyethylene oxide, polyethylene oxide ether, polypropylene oxide ether, polytetramethylene oxide ether, and polysiloxane polyolefin.

[0124] A second aspect of the present invention provides a foaming material, wherein the foaming material is obtained by foaming the above-mentioned foaming composition.

[0125] In this invention, the foaming composition described in the first aspect of the invention is foamed to obtain a foamed material with uniform pores, and the foamed material has excellent weather resistance and mechanical properties.

[0126] According to the present invention, the density of the foamed material is 0.01-0.5 g / cm³. 3 Preferably, it is 0.1-0.4 g / cm³. 3 .

[0127] According to the present invention, the cell density of the foamed material is 1×10⁻⁶. 7 -9×10 7 / cm 3 The preferred value is 1.2 × 10⁻⁶. 7 -7.5×10 7 / cm 3 .

[0128] According to the present invention, the tensile strength of the foamed material is greater than or equal to 2 MPa, preferably greater than or equal to 2.2 MPa, for example, the tensile strength of the foamed material is 2-4 MPa.

[0129] According to the present invention, the elongation at break of the foamed material should be greater than or equal to 250%, preferably greater than or equal to 300%, for example, the elongation at break of the foamed material is 250-400%.

[0130] According to the present invention, the resilience of the foamed material is greater than or equal to 50%, preferably greater than or equal to 60%, for example, the resilience of the foamed material is 50-80%.

[0131] According to the present invention, the compression set of the foamed material is less than or equal to 33%, preferably less than or equal to 25%.

[0132] According to the present invention, the edge length of the abrasion mark of the foamed material is less than or equal to 6.3 mm, preferably less than or equal to 5.8 mm.

[0133] A third aspect of the present invention provides a method for preparing the above-mentioned foamed material, wherein the method includes:

[0134] The components in the foaming composition are mixed, extruded, granulated, and then foamed.

[0135] According to the present invention, preferably, the foaming is compression molding foaming.

[0136] In one specific embodiment of the present invention, the foaming material can be prepared according to the following steps:

[0137] POE, EVA, composite weather-resistant additives, optional foaming agents, optional crosslinking agents, and optional thermoplastic polyamide elastomers are mixed and then granulated; the granulated particles are then foamed to obtain the foamed material.

[0138] In this invention, there are no particular limitations on the equipment used for mixing; for example, it can be a Banbury mixer.

[0139] In this invention, the mixing conditions include: mixing time of 5-20 min, mixing speed of 20-70 rpm, and mixing temperature of 80-120℃.

[0140] In this invention, there is no particular limitation on the granulation method. Conventional granulation methods in the art can be used, such as crushing and granulating after tableting on a two-roll mill or extruding and granulating on a screw extruder. The granulation temperature is preferably 140-180℃.

[0141] According to the present invention, the conditions for molding foaming include: foaming temperature of 100-150℃; foaming pressure of 4-16MPa; and saturated impregnation time of 0.1-3 hours.

[0142] Furthermore, the conditions for the molding foaming include: a foaming temperature of 108-140℃; a foaming pressure of 8-12MPa; and a saturated impregnation time of 0.35-1.6 hours.

[0143] In one specific embodiment of the present invention, the physical molding foaming includes the following steps:

[0144] The mold installed between the molding presses is heated to the foaming temperature. Granulated particles of the above-mentioned composition are placed into the mold, the presses are closed, and the mold is sealed. Supercritical carbon dioxide is diffused into the POE / EVA composition granules as a foaming agent. After heating to the process temperature, the amount of supercritical carbon dioxide injected is adjusted to reach the process pressure. After maintaining constant temperature and pressure for a certain period to achieve diffusion equilibrium, the pressure is released once through the pressure relief valve to open the mold and foam. The foamed material is then cooled and solidified.

[0145] A fourth aspect of the present invention provides the use of the above-described foaming composition or foaming material in at least one of footwear, sports equipment, and seating.

[0146] In this invention, the shoe materials include, but are not limited to, athletic shoe materials and specialized shoe materials for individuals such as chefs or nurses. Shoe materials include, but are not limited to, the midsole and the outsole.

[0147] In this invention, the sports equipment includes, but is not limited to, cushioning mats and yoga mats.

[0148] In this invention, the seats include, but are not limited to, seats in transportation vehicles such as high-speed trains and airplanes.

[0149] The present invention will be described in detail below through embodiments. In the following embodiments,

[0150] The content of each structural unit in the copolymer of maleic anhydride copolymer microspheres is adopted as follows: 1 The test was performed using H NMR, and the test method was as follows: 1 The content of each structural unit is calculated by measuring the proportion of the peak area corresponding to the characteristic hydrogen in the corresponding structural unit in H NMR.

[0151] The effective content of each component in the composite weather-resistant additive is calculated by the amount of material fed.

[0152] Density of foamed materials: GB / T 533 Determination of density of vulcanized rubber or thermoplastic rubber.

[0153] Tensile strength and elongation at break: GB / T 6344 Determination of tensile strength and elongation at break of flexible foam polymer materials.

[0154] Resilience: GB / T 1681 Determination of resilience of vulcanized rubber.

[0155] Compression set: GB / T 6669 Determination of compression set of flexible foam polymer materials.

[0156] Abrasion resistance: GB / T3903.2017 Test method for abrasion resistance of whole footwear.

[0157] Aging performance test: GB / T 16422.1 Laboratory light source exposure.

[0158] Cell uniformity of foamed materials: Observation using scanning electron microscopy (SEM) shows that the presence of multiple cells that are significantly larger or smaller than the average pore size indicates poor cell uniformity, while a small number of cells that are larger or smaller than the average pore size indicates good cell uniformity.

[0159] Polyolefin thermoplastic elastomers (POE):

[0160] 1-Butene is the comonomer, POE101, with a comonomer content of 13.6 mol% and a density of 0.868 g / cm³. 3 At 190℃ and a load of 2.16 kg, the mass melt flow rate was 0.5 g / 10 min, the weight-average molecular weight was 149,000 g / mol, and the molecular weight distribution was 1.89.

[0161] 1-Hexene is the comonomer, POE102, with a comonomer content of 13.1 mol% and a density of 0.866 g / cm³. 3 At 190℃ and a load of 2.16 kg, the mass melt flow rate was 1.1 g / 10 min, the weight-average molecular weight was 162,000 g / mol, and the molecular weight distribution was 2.14.

[0162] 1-Octenene is a comonomer, POE103, with a comonomer content of 13.8 mol% and a density of 0.870 g / cm³. 3 At 190℃ and a load of 2.16 kg, the mass melt flow rate was 0.9 g / 10 min, the weight-average molecular weight was 157,000 g / mol, and the molecular weight distribution was 2.31.

[0163] 1-Nonene is a comonomer, POE104, with a comonomer content of 13.5 mol% and a density of 0.869 g / cm³. 3 At 190℃ and a load of 2.16 kg, the mass melt flow rate was 0.7 g / 10 min, the weight-average molecular weight was 159,000 g / mol, and the molecular weight distribution was 2.26.

[0164] 4-Methylpentene is the comonomer, POE105, with a comonomer content of 13.2 mol% and a density of 0.867 g / cm³. 3 At 190℃ and a load of 2.16 kg, the melt flow rate was 1.2 g / 10 min, the weight-average molecular weight was 161,000 g / mol, and the molecular weight distribution was 2.23.

[0165] EVA101 has a VA content of 7.6 mol%, and a mass melt flow rate of 2.7 g / 10 min at 190 °C and a load of 2.16 kg.

[0166] EVA102 has a VA content of 10.2 mol% and a melt flow rate of 5.9 g / 10 min at 190 °C and a load of 2.16 kg.

[0167] Foaming agent OBSH: 4,4'-oxobisbenzenesulfonylhydrazine.

[0168] Crosslinking agent BIPB: Di-tert-butyl peroxide dicumylbenzene.

[0169] Crosslinking agent TAIC: triallyl isocyanurate;

[0170] Thermoplastic polyamide elastomer: PEBAX4033, purchased from Arkema;

[0171] Thermoplastic polyamide elastomer: 1012, purchased from Boxing Risheng Plastics Co., Ltd.;

[0172] All other raw materials used in the examples and comparative examples are commercially available products.

[0173] Preparation Example

[0174] This preparation example illustrates the preparation of composite weather-resistant additives.

[0175] NHWQ101

[0176] 49g of maleic anhydride, 1g of azobisisobutyronitrile (AIBN), 8.4g of isobutylene, 36.4g of styrene, and 500mL of isoamyl acetate (R1 is a C1 alkyl group, R2 is a C5 alkyl group) were added to a 2L reactor. After the materials were mixed evenly, the temperature was raised to 70℃ and the reaction was carried out for 4 hours. After the reaction was completed, the resulting polymer emulsion suspension was centrifuged at 2000 rad / min for 20 minutes to obtain 85.43g of maleic anhydride-isobutylene-styrene terpolymer microspheres, corresponding to a copolymer yield of 90.12%. The particle size of the maleic anhydride-isobutylene-styrene terpolymer microspheres A1 was 650nm. The molar content of maleic anhydride was 50%, and the molar ratio of isobutylene to styrene was 1:2.3.

[0177] Add 85 mL of anhydrous ethanol to a 250 mL round-bottom flask and heat in an oil bath to 75 °C. Then, add 2 g of N-vinyloctamide to the reaction vessel and dissolve it completely. Next, add 1 g of antioxidant 1010 (pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1 g of antioxidant 618 (distearate diphosphite), 2 g of UV absorber 2-(2-hydroxy-5-methylphenyl)benzotriazole, and the light stabilizer poly-{[6-[(1,1,3,3,-tetramethylbutyl)-amino]-1,3, 5g of 5,-triazine-2,4-[(2,2,6,6-tetramethyl-piperidinyl)-imino]-1,6-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidinyl)imino]} and 5g of rutile titanium dioxide (UV shielding agent) were reacted with mechanical stirring for 40 min. Then, 2.5g of the above polymer microspheres were added and stirring continued for 15 min. After centrifugation and spray drying, the composite weathering agent NHWQ101 was obtained. 1.3g of the UV shielding agent remained in anhydrous ethanol. Based on the total weight of the composite weathering agent, the effective content of maleic anhydride copolymer microspheres was 14.5wt%, the total effective content of antioxidants was 11.6wt%, the effective content of light stabilizers was 29.1wt%, the effective content of UV absorbers was 11.6wt%, the effective content of UV shielding agents was 21.5wt%, and the content of N-vinylamide polymers was 11.6wt%.

[0178] NHWQ 102

[0179] 49g of maleic anhydride, 1g of azobisisobutyronitrile (AIBN), 4.66g of isobutylene, 43.43g of styrene, and 500mL of isoamyl acetate (R1 is a C1 alkyl group, R2 is a C5 alkyl group) were added to a 2L reactor. After the materials were mixed evenly, the temperature was raised to 70℃ and the reaction was carried out for 6 hours. After the reaction was completed, the resulting polymer emulsion suspension was centrifuged at 2000 rad / min for 20 minutes to obtain 88.08g of maleic anhydride-isobutylene-styrene terpolymer microspheres, corresponding to a copolymer yield of 89.79%. The particle size of the maleic anhydride-isobutylene-styrene terpolymer microspheres A2 was 750nm. The molar content of maleic anhydride was 50%, and the molar ratio of isobutylene to styrene was 1:5.

[0180] Add 90 mL of anhydrous ethanol to a 250 mL round-bottom flask and heat in an oil bath to 80 °C. Then, add 1.5 g of N-isopropyl-N-vinylnonamide to the reaction vessel and dissolve it completely. Next, add 2 g of antioxidant 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanuric acid), 1.5 g of antioxidant 168 (tris[2,4-di-tert-butylphenyl]phosphite), and 3 g of UV absorber 2-hydroxy-4-n-octyloxybenzophenone. Light stabilizer N,N”'-1,2-ethylenedimethyldi[N-[3-[[4,6-di[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazin-2-yl]amino]propyl]-N,N”-dibutyl-N,N”-di(1,2,2,6,6-pentamethyl-4-piperidinyl)-1,3,5-triazin-2,4,6-triamine 6g, UV shielding agent zinc magnesium-based hydrotalcite Mg3ZnAl2-CO3-LDHs 5g of the above polymer microspheres were added after mechanical stirring for 60 min, and stirring was continued for 20 min. The mixture was then centrifuged and spray-dried to obtain the composite weathering agent NHWQ 102. 0.8g of UV shielding agent remained in anhydrous ethanol. Based on the total weight of the composite weathering agent, the effective content of maleic anhydride copolymer microspheres was 14.2 wt%, the effective content of antioxidant was 16.5 wt%, the effective content of light stabilizer was 28.3 wt%, the effective content of UV absorber was 14.2 wt%, the effective content of UV shielding agent was 19.8 wt%, and the content of N-vinylamide polymer was 7.1 wt%.

[0181] NHWQ103

[0182] 51g maleic anhydride, 1g azobisisobutyronitrile, 14g isobutylene, 26g styrene, and 500mL butyl acetate (R1 is a C1 alkyl group, R2 is a C4 alkyl group) were added to a 2L reactor. After the materials were mixed evenly, the temperature was raised to 65℃ and the reaction was carried out for 6 hours. After the reaction was completed, the resulting polymer emulsion suspension was centrifuged at 2000 rad / min for 20 minutes to obtain 78.38g of maleic anhydride-isobutylene-styrene terpolymer microspheres, corresponding to a copolymer yield of 85.2%. The particle size of the maleic anhydride-isobutylene-styrene terpolymer microspheres A3 was 590nm. The molar content of maleic anhydride was 51%, and the molar ratio of isobutylene to styrene was 1:1.

[0183] Add 90 mL of anhydrous ethanol to a 250 mL round-bottom flask and heat in an oil bath to 80 °C. Then, add 5 g of N-methyl-N-vinyldecylamide to the reaction vessel and dissolve it completely. Add 3 g of antioxidant 330 (1,3,5-trimethyl-2,4,6-tris(3,5-tert-butyl-4-hydroxybenzyl)benzene), 5 g of antioxidant 618 (pentaerythritol distearate diphosphite), 4 g of UV absorber 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol, 3 g of light stabilizer succinic acid and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol polymer, and 7 g of UV shielding agent NiMgFe-LDHs hydrotalcite. After mechanically stirring for 55 min, add 3.5 g of the above polymer microspheres and continue stirring for 30 min. After centrifugation, spray dry to obtain the composite weathering agent NHWQ103. 2.1 g of UV shielding agent remained in anhydrous ethanol. Based on the total weight of the composite weathering agent, the effective content of maleic anhydride copolymer microspheres was 12.3 wt%, the effective content of antioxidant was 28.2 wt%, the effective content of light stabilizer was 10.6 wt%, the effective content of UV absorber was 14.1 wt%, the effective content of UV shielding agent was 17.3 wt%, and the content of N-vinylamide polymer was 17.6 wt%.

[0184] NHWQ104

[0185] The preparation method is the same as that for the maleic anhydride-isobutylene-styrene terpolymer microspheres in NHWO101.

[0186] Add 85 mL of anhydrous ethanol to a 250 mL round-bottom flask and heat in an oil bath to a constant temperature of 75 °C. Then, add 2 g of N-vinyloctamide to the reaction vessel and dissolve it completely. Add 1 g of antioxidant 1010 (pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]), 1 g of antioxidant 618 (distearate pentaerythritol diphosphite), 2 g of UV absorber 2-(2-hydroxy-5-methylphenyl)benzotriazole, and 5 g of UV shielding agent rutile titanium dioxide. After stirring the mixture mechanically for 40 min, add the polymer microspheres A1. After stirring for 15 minutes, 2.5g of the mixture was centrifuged and spray-dried to obtain the composite weathering agent NHWQ104. 0.9g of the UV shielding agent remained in anhydrous ethanol. Based on the total weight of the composite weathering agent, the effective content of maleic anhydride copolymer microspheres was 19.8wt%, the effective content of antioxidant was 15.9wt%, the effective content of UV absorber was 15.9wt%, the UV shielding agent was 32.5wt%, and the content of N-vinylamide polymer was 15.9wt%.

[0187] NHWQ105

[0188] The preparation method is the same as that for the maleic anhydride-isobutylene-styrene terpolymer microspheres in NHWO101.

[0189] Add 85 mL of anhydrous ethanol to a 250 mL round-bottom flask and heat in an oil bath to a constant temperature of 75 °C. Then, add 2 g of N-vinyloctamide to the reaction vessel and dissolve it completely. Add 1 g of antioxidant 1010 (pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1 g of antioxidant 618 (distearate diphosphite), 5 g of light stabilizer poly-{[6-[(1,1,3,3,-tetramethylbutyl)-amino]-1,3,5,-triazine-2,4-[(2,2,6,6-tetramethyl-piperidinyl)-imino]-1,6-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidinyl)imino]}, and 5 g of UV shielding agent rutile titanium dioxide. After mechanically stirring for 40 min, add the above polymer microspheres A1. After stirring for 15 minutes, 2.5g of the mixture was centrifuged and spray-dried to obtain the composite weathering agent NHWQ105. 0.7g of the UV shielding agent remained in anhydrous ethanol. Based on the total weight of the composite weathering agent, the effective content of maleic anhydride copolymer microspheres was 15.8wt%, the effective content of antioxidant was 12.7wt%, the effective content of light stabilizer was 31.6wt%, the effective content of UV shielding agent was 27.2wt%, and the content of N-vinylamide polymer was 12.7wt%.

[0190] NHWQ106

[0191] The preparation method is the same as that for the maleic anhydride-isobutylene-styrene terpolymer microspheres in NHWO101.

[0192] Add 85 mL of anhydrous ethanol to a 250 mL round-bottom flask and heat in an oil bath to a constant temperature of 75 °C. Then, add 2 g of N-vinyloctamide to the reaction vessel and dissolve it completely. Add 1 g of antioxidant 1010 (pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1 g of antioxidant 618 (distearate diphosphite), 2 g of UV absorber 2-(2-hydroxy-5-methylphenyl)benzotriazole, and 5 g of light stabilizer poly-{[6-[(1,1,3,3,-tetramethylbutyl)-amino]-1,3,5,-triazine-2,4-[(2,2,6,6-tetramethyl-piperidinyl)-imino]-1,6-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidinyl)imino]}. After mechanically stirring for 40 min, add the above polymer microspheres A1. After stirring for 15 minutes, 2.5g of the mixture was centrifuged and spray-dried to obtain the composite weathering agent NHWQ106. Based on the total weight of the composite weathering agent, the effective content of maleic anhydride copolymer microspheres was 18.5wt%, the effective content of antioxidant was 14.8wt%, the effective content of light stabilizer was 37wt%, the effective content of ultraviolet absorber was 14.8wt%, and the content of N-vinylamide polymer was 14.8wt%.

[0193] NHWQ107

[0194] The preparation method is the same as that for the maleic anhydride-isobutylene-styrene terpolymer microspheres in NHWO101.

[0195] Add 85 mL of anhydrous ethanol to a 250 mL round-bottom flask, heat in an oil bath to 75 °C and maintain the temperature. Then add 0.4 g of [unspecified ingredient] to the reaction vessel. After fully dissolving N-vinyloctamide, add antioxidant 1010 (pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] 0.5g, antioxidant 618 (distearate pentaerythritol diphosphite) 0.6g, light stabilizer poly-{[6-[(1,1,3,3,-tetramethylbutyl)-amino]-1,3,5,-triazine-2,4-[(2,2,6,6-tetramethyl-piperidinyl)-imino]-1,6-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidinyl)imino]} 1.5g, UV absorber 2-hydroxy-4-n-octyloxybenzophenone 1.8g, and UV shielding agent rutile titanium dioxide 3g. After mechanically stirring for 40 min, add the above polymer microspheres A1. After stirring for 15 minutes, 5g of the mixture was centrifuged and spray-dried to obtain the composite weathering agent NHWQ105. 0.3g of the UV shielding agent remained in anhydrous ethanol. Based on the total weight of the composite weathering agent, the effective content of maleic anhydride copolymer microspheres was 40wt%, the effective content of antioxidant was 8.8wt%, the effective content of light stabilizer was 12wt%, the effective content of UV absorber was 14.4%, the effective content of UV shielding agent was 21.6wt%, and the content of N-vinylamide polymer was 3.2wt%.

[0196] Examples 1-9

[0197] Examples are provided to illustrate the preparation method of foamed materials:

[0198] A certain amount of POE, EVA, foaming agent, foaming aids (zinc oxide 0.8g, stearic acid 0.18g and zinc stearate 0.18g), crosslinking agent, thermoplastic polyamide elastomer (TPAE) and the weather-resistant composite aids in the preparation example were mixed in an internal mixer, granulated in a screw extruder, and then molded and foamed to obtain a foamed material. The mixing temperature was 100℃, the mixing time was 10min, and the internal mixer speed was 50rpm. The granulation temperature was 160℃, the molding and foaming temperature was 140℃, the pressure was 8.5MPa, and the saturated impregnation time was 0.5h. The specific formulation is shown in Table 1.

[0199] Example 10

[0200] Same as Example 1, except that NHWQ107 was used as the composite weather-resistant additive.

[0201] Comparative Example 1

[0202] Similar to Example 1, except that 1g of antioxidant 1010, 1g of antioxidant 618, 2g of ultraviolet absorber, 5g of light stabilizer and 5g of ultraviolet shielding agent from the preparation of composite weather-resistant agent NHWQ101 were directly added to the composition.

[0203] Comparative Example 2

[0204] Similar to Example 1, except that maleic anhydride copolymer microspheres A1 were used instead of the composite weather-resistant agent NHWQ101.

[0205] Comparative Example 3

[0206] Same as Example 1, except that NHWQ104 is used instead of NHWQ101.

[0207] Comparative Example 4

[0208] Same as Example 1, except that NHWQ105 is used instead of NHWQ101.

[0209] Comparative Example 5

[0210] Same as Example 1, except that NHWQ106 replaces NHWQ101.

[0211] Comparative Example 6

[0212] Same as in Example 1, except that the amount of composite weather-resistant agent NHWQ101 used is 0.01 parts.

[0213] Table 1

[0214]

[0215]

[0216] Examples 11-13

[0217] A certain amount of POE, EVA, foaming aids (0.8 parts zinc oxide, 0.18 parts stearic acid, and 0.18 parts zinc stearate), crosslinking agent, thermoplastic polyamide elastomer, and weather-resistant composite aids from the preparation example were mixed in an internal mixer, granulated in a screw extruder, and then supercritical carbon dioxide was introduced for compression molding to obtain a foamed material. The mixing temperature was 100℃, the mixing time was 10 min, and the internal mixer speed was 50 rpm. The granulation temperature was 160℃. The specific formulation is shown in Table 2, and the foaming process is shown in Table 2 (continued).

[0218] Table 2

[0219]

[0220] Table 2 (continued)

[0221]

[0222] Test Example 1

[0223] The density, cell density, tensile strength, elongation at break, resilience, compression set, and abrasion resistance of the foamed materials prepared in the examples and comparative examples were tested, and the test results are shown in Table 3.

[0224] Table 3

[0225]

[0226] ○ Dense and uniform cell structure; × Sparse and uneven cell structure.

[0227] Test Example 2

[0228] According to GB16422.1, the foamed materials prepared in the examples and comparative examples were aged under the following conditions: aging at 65°C for 100 hours. The tensile strength, breaking productivity, resilience, compression set and abrasion resistance of the aged samples were tested, and the results are shown in Table 4.

[0229] Table 4

[0230]

[0231]

[0232] As shown in Tables 3 and 4, the maleic anhydride ternary microspheres provided by this invention, loaded with ultraviolet absorbers, ultraviolet shielders, and light stabilizers, exhibit good weather resistance. Furthermore, the foamed material has lower density (lighter shoe material), higher tensile strength and elongation at break (less prone to sole breakage), better resilience, and better abrasion resistance. Comparative Example 1 shows that the ultraviolet absorbers, ultraviolet shielders, and light stabilizers not loaded on the ternary microspheres are less efficient, and their aging resistance is inferior to Examples 1-12. Comparative Examples 3-5 show that the ultraviolet absorbers, ultraviolet shielders, and light stabilizers are all indispensable; otherwise, the aging resistance will decrease. Comparative Example 6 shows that when the amount of composite weather-resistant additives is low, it cannot effectively improve the mechanical properties and weather resistance of the foamed material.

[0233] Figure 1 This is a SEM image of the foamed material prepared in Example 1. Figure 1 It can be seen that the bubbles are relatively dense and uniform, with a few large pores.

[0234] Figure 2 The SEM image of the foamed material obtained in Example 6 of this invention is shown in the figure. Figure 2It can be seen that the cell density and uniformity are better than those in Example 1, indicating that the POE with 1-octene as a comonomer and the composite weather-resistant additive can further promote the improvement of cell uniformity.

[0235] Figure 3 This is a SEM image of the foamed material prepared in Comparative Example 1. Figure 3 It can be seen that instead of using the composite weather-resistant additive of the present invention, which loads antioxidants and other additives onto maleic anhydride copolymer microspheres, antioxidants and other additives are directly added to the foaming composition, resulting in large cell size and decreased cell uniformity.

[0236] Figure 4 The image shows the SEM image of the foamed material prepared in Comparative Example 3. Figure 4 It can be seen that the high content of ultraviolet shielding agent (inorganic substance) in the added composite anti-aging additive system affected the growth and development of the cells, resulting in low cell uniformity.

[0237] Figure 5 The image shows the SEM image of the foamed material prepared in Comparative Example 6. Figure 5 It can be seen that due to the very low amount of composite additives, the effective content of maleic anhydride copolymer microspheres in the composition is also low, which cannot play a role in cell nucleation and results in low cell uniformity.

[0238] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A foaming composition, characterized in that, The composition includes POE, EVA, and composite weather-resistant additives; The composite weather-resistant additive comprises maleic anhydride copolymer microspheres, antioxidants, ultraviolet absorbers, ultraviolet shielding agents, light stabilizers, and N-vinylamide polymers. The content of POE is 5-50 parts by weight, the content of EVA is 50-95 parts by weight, and the content of composite weather-resistant additive is 0.1-1 parts by weight. The ultraviolet absorber is selected from 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-dipentylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-pentylphenyl)benzotriazole, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, phenyl benzoate, resorcinol monobenzoate, o-nitroaniline, p-cresol, 2,4,6-tris(2-hydroxy-4- At least one of the following: (n-butoxyphenyl)-1,3,5-triazine, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, p-tert-butylphenyl salicylate, bisphenol A bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester), 2,2'-thiobis(4-tert-octylphenoloxy)nickel, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxy-phenol, 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-octyloxyphenol, and N,N'-diphenyloxamide; The light stabilizer is selected from poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol) ester, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, polymers of succinic acid and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol, bis(1,2,2,6,6-pentamethylpiperidinol) sebacate, and 1-(methyl)-8-(1,2,2,6,6, At least one of 6-pentamethyl-4-piperidinyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, and poly{[6-[(1,1,3,3-tetramethylbutyl)amino]]-1,3,5-triazine-2,4-[(2,2,6,6,-tetramethyl-piperidinyl)imino]-1,6-hexamethylene[(2,2,6,6-tetramethyl-4-piperidinyl)imino]}; The ultraviolet shielding agent is an inorganic ultraviolet shielding agent.

2. The foaming composition according to claim 1, wherein, The content of POE is 10-45 parts by weight, the content of EVA is 55-90 parts by weight, and the content of composite weather-resistant additive is 0.2-0.8 parts by weight. And / or, based on the total weight of the composite weather-resistant additives, the effective content of the maleic anhydride copolymer microspheres is 5-60 wt%, the effective content of the antioxidant is 3-35 wt%, the effective content of the ultraviolet absorber is 8-20 wt%, the effective content of the ultraviolet shielding agent is 15-30 wt%, the effective content of the light stabilizer is 6-35 wt%, and the effective content of the N-vinylamide polymer is 3-20 wt%; And / or, the particle size of the maleic anhydride copolymer microspheres is 500-920 nm.

3. The foaming composition according to claim 2, wherein, The particle size of the maleic anhydride copolymer microspheres is 530-800 nm.

4. The foaming composition according to claim 1 or 2, wherein, The content of structural units derived from comonomers in the POE is 10-20 mol%; And / or, the weight-average molecular weight of the POE is 100,000-200,000 g / mol, and the molecular weight distribution is 1-3; And / or, at 190°C and a load of 2.16 kg, the mass melt flow rate of the POE is 0.1-2 g / 10 min; And / or, the content of structural units derived from vinyl acetate in the EVA is 5-35 mol%; And / or, at 190°C and a load of 2.16 kg, the mass melt flow rate of the EVA is 1-10 g / 10 min.

5. The foaming composition according to claim 1 or 2, wherein, The copolymer in the maleic anhydride copolymer microspheres comprises structural unit A provided by maleic anhydride, structural unit B provided by isobutylene, and structural unit C provided by styrene. Based on the total molar amount of each structural unit in the copolymer, the content of structural unit A is 47-52 mol%, and the molar ratio of structural unit B to structural unit C is 1:0.2-7.

5.

6. The foaming composition according to claim 1 or 2, wherein, The composite weather-resistant additive is prepared according to the following method: In the presence of a solvent, maleic anhydride copolymer microspheres, antioxidants, ultraviolet absorbers, ultraviolet shielding agents, light stabilizers, and N-vinylamide polymers are mixed and reacted, followed by solid-liquid separation to obtain the composite weather-resistant additive.

7. The foaming composition according to claim 6, wherein, The amount of the maleic anhydride copolymer microspheres is 0.1-10 parts by weight, the amount of the antioxidant is 0.5-6 parts by weight, the amount of the ultraviolet absorber is 1-10 parts by weight, the amount of the ultraviolet shielding agent is 0.1-10 parts by weight, the amount of the light stabilizer is 0.1-10 parts by weight, and the amount of the N-vinylamide polymer is 0.1-7 parts by weight. And / or, the conditions for the mixed reaction include: a reaction temperature of 70-80°C and a reaction time of 15-90 min.

8. The foaming composition according to claim 1 or 2, wherein, The composition further includes 0.1-10 parts by weight of a foaming agent; And / or, the composition further comprises 0.1-1 parts by weight of a crosslinking agent; And / or, the composition further comprises 0.3-12 parts by weight of a foaming agent; And / or, the foaming agent is selected from at least one of stearic acid, zinc stearate and zinc oxide; And / or, the composition further comprises 1-10 parts by weight of thermoplastic polyamide elastomer.

9. The foaming composition according to claim 8, wherein, The composition further includes 2-7 parts by weight of a foaming agent; And / or, the composition further comprises 0.3-0.9 parts by weight of a crosslinking agent; And / or, the composition further comprises 0.9-3 parts by weight of a foaming agent; And / or, the composition further comprises 2-5 parts by weight of thermoplastic polyamide elastomer.

10. A foamed material, characterized in that, The foaming material is obtained by foaming a foaming composition; Wherein, the foaming composition is the foaming composition according to any one of claims 1-9.

11. The foamed material according to claim 10, wherein, The density of the foamed material is 0.01-0.5 g / cm³. 3 ; And / or, the cell density of the foamed material is 1×10⁻⁶. 7 -9×10 7 / cm 3 ; And / or, the tensile strength of the foamed material is greater than or equal to 2 MPa; And / or, the elongation at break of the foamed material should be greater than or equal to 250%; And / or, the resilience of the foamed material is greater than or equal to 50%; And / or, the compression set of the foamed material is less than or equal to 33%; And / or, the edge length of the abrasion mark of the foamed material is less than or equal to 6.3 mm.

12. The foamed material according to claim 11, wherein, The density of the foamed material is 0.1-0.4 g / cm³. 3 ; And / or, the cell density of the foamed material is 1.2 × 10⁻⁶. 7 -7.5×10 7 / cm 3 ; And / or, the tensile strength of the foamed material is greater than or equal to 2.2 MPa; And / or, the elongation at break of the foamed material should be greater than or equal to 300%; And / or, the resilience of the foamed material is greater than or equal to 60%; And / or, the compression set of the foamed material is less than or equal to 25%; And / or, the edge length of the abrasion mark of the foamed material is less than or equal to 5.8 mm.

13. A method for preparing the foamed material according to any one of claims 10-12, characterized in that, The method includes: The components in the foaming composition are mixed, extruded, granulated, and then foamed.

14. The preparation method according to claim 13, wherein, The foaming process is compression molding foaming.

15. The preparation method according to claim 14, wherein, The conditions for molding and foaming include: foaming temperature of 100-150℃; foaming pressure of 4-16MPa; and saturated impregnation time of 0.1-3 hours.

16. The preparation method according to claim 15, wherein, The conditions for compression molding foaming include: foaming temperature of 108-140℃; foaming pressure of 8-12MPa; and saturated impregnation time of 0.35-1.6 hours.

17. The use of the foaming composition according to any one of claims 1-9 or the foaming material according to any one of claims 10-12 in at least one of footwear materials, sports equipment and seating.

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