CN116426056B - Anti-aging umbrella seat and preparation method thereof - Google Patents
Anti-aging umbrella seat and preparation method thereof Download PDFInfo
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- CN116426056B CN116426056B CN202310436956.5A CN202310436956A CN116426056B CN 116426056 B CN116426056 B CN 116426056B CN 202310436956 A CN202310436956 A CN 202310436956A CN 116426056 B CN116426056 B CN 116426056B
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- 230000003712 anti-aging effect Effects 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title abstract description 23
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000004698 Polyethylene Substances 0.000 claims abstract description 45
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 39
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 37
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- -1 polyethylene Polymers 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 25
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims abstract description 24
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical compound CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000012745 toughening agent Substances 0.000 claims abstract description 22
- 229920001684 low density polyethylene Polymers 0.000 claims abstract description 19
- 239000004702 low-density polyethylene Substances 0.000 claims abstract description 19
- 238000001179 sorption measurement Methods 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 18
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 17
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 15
- 229920000573 polyethylene Polymers 0.000 claims abstract description 14
- 239000006229 carbon black Substances 0.000 claims abstract description 13
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 13
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 13
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims abstract description 12
- 229940116335 lauramide Drugs 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000000600 sorbitol Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 238000002791 soaking Methods 0.000 claims abstract description 9
- 238000011282 treatment Methods 0.000 claims abstract description 9
- 239000001993 wax Substances 0.000 claims abstract description 7
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 22
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 19
- 235000012239 silicon dioxide Nutrition 0.000 claims description 15
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 12
- 229910002113 barium titanate Inorganic materials 0.000 claims description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 11
- 239000000395 magnesium oxide Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 229930185605 Bisphenol Natural products 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000001746 injection moulding Methods 0.000 claims description 2
- 229910021426 porous silicon Inorganic materials 0.000 claims description 2
- 238000004898 kneading Methods 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 31
- 230000000052 comparative effect Effects 0.000 description 27
- 150000001875 compounds Chemical class 0.000 description 13
- 230000000694 effects Effects 0.000 description 10
- 239000003112 inhibitor Substances 0.000 description 10
- 239000011148 porous material Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000004579 marble Substances 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical group O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 3
- 230000003044 adaptive effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- QCDFBFJGMNKBDO-UHFFFAOYSA-N Clioquinol Chemical compound C1=CN=C2C(O)=C(I)C=C(Cl)C2=C1 QCDFBFJGMNKBDO-UHFFFAOYSA-N 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 2
- 150000008442 polyphenolic compounds Chemical class 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical group C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- USHGAJAQQOPCNH-UHFFFAOYSA-N C[Sn]C.C(C)(=S)SCCCCCC(C)C Chemical compound C[Sn]C.C(C)(=S)SCCCCCC(C)C USHGAJAQQOPCNH-UHFFFAOYSA-N 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 206010051246 Photodermatosis Diseases 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000008845 photoaging Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application relates to the technical field of sun umbrellas, and particularly discloses an anti-aging umbrella base and a preparation method thereof. The utility model provides an ageing resistance umbrella stand, includes PE casing and sets up the balancing weight in the PE casing, the PE casing mainly is made by following raw materials: high density polyethylene, low density polyethylene, carbon black, polyethylene wax, silica, polytetrafluoroethylene, toughening agent, compatilizer, anti-aging agent, ethylene glycol lauramide and sorbitol; the anti-aging agent is prepared by a method comprising the following steps: 1) Dissolving maleimide in ethanol to prepare a precursor solution, then soaking a porous adsorption material into the precursor solution for treatment, filtering and drying to obtain an intermediate material; 2) Adding hindered phenol and intermediate into acetone, stirring uniformly, standing, and removing acetone. The anti-aging umbrella seat has the advantage of good anti-aging effect in a high-temperature environment.
Description
Technical Field
The application relates to the technical field of sun umbrellas, in particular to an anti-aging umbrella base and a preparation method thereof.
Background
When people perform outdoor activities, in order to shade sunlight, large-sized outdoor sunshades such as sunshades, roman umbrellas and the like are generally used, most ultraviolet rays can be blocked, and a shady and cool activity space is provided. Large outdoor sunshades are usually composed of canopy, support bars and umbrella holders. The umbrella seat is made of various materials and is roughly divided into a marble umbrella seat, a PE cement umbrella seat, a metal umbrella seat and the like, and the PE umbrella seat has the advantages of attractive appearance and low cost at present and is popular with public consumers.
The outdoor sunshade umbrella has wide umbrella surface, and can be folded when not in use, so that the umbrella surface is prevented from being scratched due to the influence of strong wind. After the outdoor sunshade is folded, the umbrella seat is directly exposed to strong sunlight, especially in summer, the air temperature is higher, when the umbrella seat is in a high-temperature and strong-illumination environment for a long time, PE materials can be caused to produce thermooxidative aging and photoaging, and the umbrella seat body can be embrittled, cracked and pulverized to lose mechanical properties.
In order to solve the above problems, some anti-aging agents are added to improve the anti-aging performance of PE plastic, for example, chinese patent application publication No. CN106589520a discloses an anti-aging weather-resistant PE plastic pipe, which is made from the following raw materials in parts by weight: 70-75 parts of high-density polyethylene, 18-24 parts of ethylene-octene block copolymer, 6-9 parts of polyethylene wax, 6-9 parts of silicon dioxide, 3-7 parts of dibutyl phthalate, 2-4 parts of dimethyl methylphosphonate, 5-9 parts of antioxidant 1076, 3-5 parts of isooctyl dithioacetate dimethyl tin, 10-15 parts of corn starch and 5-14 parts of bentonite, and ageing of PE materials is inhibited by adding a hindered phenol anti-ageing agent.
With respect to hindered phenol type anti-aging agents, the ability to donate protons when exposed to a high temperature environment becomes weak, and the thermal oxygen stability also decreases greatly, resulting in a decrease in anti-aging performance.
Disclosure of Invention
In order to improve the ageing resistance of the umbrella base in a high-temperature environment, the application provides an anti-ageing umbrella base and a preparation method thereof.
In a first aspect, the present application provides an anti-aging umbrella base, which adopts the following technical scheme:
the utility model provides an ageing resistance umbrella stand, includes PE casing and sets up the balancing weight in the PE casing, the PE casing mainly is made by the raw materials of following parts by weight: 30-50 parts of high-density polyethylene, 100-120 parts of low-density polyethylene, 15-20 parts of carbon black, 5-10 parts of polyethylene wax, 1-3 parts of silicon dioxide, 1.5-3 parts of polytetrafluoroethylene, 5-10 parts of toughening agent, 2-3.5 parts of compatilizer, 6.5-9 parts of anti-aging agent, 1-1.5 parts of ethylene glycol lauramide and 0.5-1 part of sorbitol; the anti-aging agent is prepared by a method comprising the following steps:
1) Dissolving maleimide in ethanol to prepare a precursor solution, then soaking a porous adsorption material into the precursor solution for treatment, filtering and drying to obtain an intermediate material;
2) Adding hindered phenol and intermediate into acetone, stirring uniformly, standing, and removing acetone.
By adopting the technical scheme, the high-density polyethylene and the low-density polyethylene are compounded and used, the long branched chain on the low-density polyethylene macromolecular chain and the high-density polyethylene molecular chain are entangled under the assistance of the compatilizer and the toughening agent, and the obtained compound has more reasonable network structure, uniform network density and better thermal stability. In addition, after active substances such as carbon black, polyethylene wax, silicon dioxide, polytetrafluoroethylene and the like are added, the microscopic state of the network structure is improved, and better crystallization characteristics are obtained.
After the anti-aging agent is introduced into the compound system, wherein maleimide is grafted and attached on the surfaces of the inner pore canal and the outer pore canal of the porous adsorption material to form an interface layer, then hindered phenol migrates and is permeated and adsorbed in the pore canal of the porous adsorption material, van der Waals force and intermolecular hydrogen bonds are formed between hindered phenol molecules and maleimide forming the interface layer, and the hindered phenol molecules migrate into the compound system at a certain release speed by utilizing the slow release effect of the interface layer and the porous adsorption material, so that the anti-aging effect is better.
In addition, due to the effect of concentration polarization, the release amount of the hindered phenol is relatively more in the early use stage of the umbrella base, and along with the rising of temperature, the interface layer has a higher energy level trap in a high-temperature and high-ultraviolet environment, so that the influence of high temperature on the release of protons by the hindered phenol can be reduced, the hindered phenol can continuously capture free radicals in the high-temperature environment, and the hindered phenol still has a better anti-aging effect and higher thermal oxygen stability.
Preferably, the hindered phenol is one or more of monophenol hindered phenol, bisphenol hindered phenol and polyphenol hindered phenol.
Through adopting above-mentioned technical scheme, the relative molecular mass of monophenol class hindered phenol is less, and volatility and mobility are great, consequently can fully combine with interface layer and porous adsorption material, can permeate the inside depths of pore structure, can play better ageing resistance under low temperature environment, simultaneously under the protection of pore structure and interface layer, can maintain good ageing resistance under high temperature environment. The bisphenol hindered phenol and the polyphenol hindered phenol have larger relative molecular mass and good thermal stability, can be slowly released and migrated under the high-temperature environment under the action of larger steric hindrance and the detention action of the pore canal structure, and play a better high-temperature anti-aging role, so that the variety composition of the hindered phenol is optimized and adjusted, and the performance of the anti-aging agent is further improved.
Preferably, the hindered phenol consists of monophenol hindered phenol and bisphenol hindered phenol in a mass ratio of (3.5-5): 1.
By adopting the technical scheme, the composition ratio of the hindered phenol is tested and screened, the release amount of the anti-aging agent in a low-temperature and high-temperature environment is balanced, and a more durable and stable anti-aging effect is obtained.
Preferably, the porous adsorption material is at least one of porous silica, porous graphite, porous alumina, porous calcium carbonate and porous magnesia.
By adopting the technical scheme, the variety composition of the porous adsorption material is optimized and regulated, and the porous silica, the porous graphite, the porous alumina, the porous calcium carbonate and the porous magnesium oxide can fully adsorb and protect the hindered phenol on the one hand, so that a stable and durable release effect is obtained. On the other hand, after the porous adsorption material is introduced into the compound system, a plurality of micro-nano holes can be formed, the network structure of the cross-linked matter is improved, and meanwhile, the migration and diffusion of hindered phenol molecules are facilitated.
Preferably, the mass ratio of the anti-aging agent to the low density polyethylene is (0.065-0.072): 1.
By adopting the technical scheme, when the addition amount of the anti-aging agent is too large, the defect of poor network structure in a compound system is easily caused, and the mechanical property of the umbrella base is reduced. When the adding amount of the anti-aging agent is small, free radicals cannot be comprehensively captured, so that the aging speeds of different parts of the umbrella seat are inconsistent, and the situation of stress unbalance cracking is easy to cause, so that the mass ratio of the anti-aging agent to the low-density polyethylene is optimized and adjusted, and the mechanical property and the aging resistance of the umbrella seat are further balanced.
Preferably, the mass fraction of maleimide in the precursor liquid is 10-15%.
By adopting the technical scheme, the thickness of the interface layer is adjusted, the penetration and migration of hindered phenol molecules into the porous adsorption material pore canal are easy to inhibit when the interface layer is too thick, the release speed of the hindered phenol can not be controlled well under the high temperature condition when the interface layer is too thin, the mass fraction concentration of maleimide in the precursor liquid is tested and screened, the interface layer with proper and uniform thickness is obtained, and the ageing resistance under the high temperature environment is further improved.
Preferably, in the step 1), nano barium titanate is also added into the precursor solution, and the mass ratio of the nano barium titanate to the maleimide is (0.15-0.22): 1.
By adopting the technical scheme, the nano barium titanate can be uniformly dispersed in the interface layer, so that on one hand, the high-temperature stability of the interface layer can be improved, and on the other hand, space charge polarization can be generated between the nano barium titanate and maleimide in a high-temperature environment, the electron delocalization of hindered phenol is enhanced, the stability of protected aryl free radicals is facilitated, and better ageing resistance is obtained.
In a second aspect, the present application provides a method for manufacturing an anti-aging umbrella base, which adopts the following technical scheme:
a preparation method of an anti-aging umbrella seat comprises the following steps:
s1: uniformly mixing high-density polyethylene, low-density polyethylene, carbon black, polyethylene wax, silicon dioxide, polytetrafluoroethylene, a toughening agent, a compatilizer, an anti-aging agent, ethylene glycol lauramide and sorbitol according to the formula amount, and mixing and granulating to obtain master batch;
s2: and drying, melting and injection molding the master batch to obtain a shell, and then assembling and combining the shell and the balancing weight.
By adopting the technical scheme, the raw materials with the formula amount are mixed and smelted, so that the components are fully compatible, and a compound system with a stable network structure is formed. Meanwhile, the anti-aging agent can be uniformly dispersed in the compound network system, so that the anti-aging performance of each part of the umbrella seat can be kept to be better consistent.
Preferably, the mixing temperature is 170-185 ℃.
By adopting the technical scheme, the mixing temperature is optimized and adjusted, the dispersion uniformity among the components is improved, the thermal decomposition effect of the components at high temperature is reduced as much as possible, and the performance stability of the product is improved.
In summary, the present application has the following beneficial effects:
1. because the application adopts the low-density polyethylene and the high-density polyethylene to compound, a plurality of active components are added, a stable compound system is formed under the assistance of the compatilizer and the toughening agent, and after the anti-aging agent is introduced into the compound network structure, the slow release effect of the porous adsorption material and the interface layer is utilized, the anti-aging performance of the anti-aging agent under the low-temperature and high-temperature environments is greatly improved, and the working time of the umbrella base under the high-temperature and high-ultraviolet environments is prolonged.
2. The composition of the hindered phenol and the type of the porous adsorption material is optimized and regulated, nano barium titanate is introduced into the interface layer, and the release and migration speed of hindered phenol molecules are further regulated, so that better ageing resistance is obtained.
3. The anti-aging umbrella seat prepared by the preparation method has higher anti-aging performance in a high-temperature environment.
Drawings
Fig. 1: results of thermal oxygen testing of the anti-aging umbrella base in examples 1-9 and comparative examples 1-6.
Detailed Description
The present application is described in further detail below with reference to examples.
The raw materials of the examples and comparative examples herein are commercially available in general unless otherwise specified.
Examples
Example 1
The ageing resistance umbrella stand of this embodiment includes PE casing and fixes the balancing weight in the PE casing, and the PE casing is the dome form, and the balancing weight is the cement balancing weight.
The PE shell of the embodiment is prepared from the following raw materials in weight: 30kg of high-density polyethylene, 120kg of low-density polyethylene, 15kg of carbon black, 10kg of polyethylene wax, 3kg of silicon dioxide, 1.5kg of polytetrafluoroethylene, 5kg of toughening agent, 2kg of compatilizer, 9kg of anti-aging agent, 1.5kg of ethylene glycol lauramide and 0.5kg of sorbitol.
Wherein the toughening agent is POE toughening agent. The compatilizer is triallyl isocyanurate.
The aging inhibitor of this example was prepared by a method comprising the steps of:
1) Dissolving maleimide into ethanol to prepare a precursor solution, wherein the mass fraction of the maleimide is 20%, then soaking the polysilica into the precursor solution for treatment, filtering and drying to obtain an intermediate material;
2) Pouring an acetone solution into a beaker, adding hindered phenol 1076 and an intermediate material into the beaker according to a mass ratio of 2:1, uniformly mixing at a stirring speed of 500rpm, standing for 15min, and removing acetone to obtain the modified phenol.
The preparation method of the anti-aging umbrella seat comprises the following steps:
s1: uniformly mixing high-density polyethylene, low-density polyethylene, carbon black, polyethylene wax, silicon dioxide, polytetrafluoroethylene, a toughening agent, a compatilizer, an anti-aging agent, ethylene glycol lauramide and sorbitol in a formula amount in a stirrer, and then putting the mixture into a mixer for mixing and granulating to obtain master batch, wherein the mixing temperature is 190 ℃;
s2: drying the master batch in a baking oven, adding the master batch into a double-screw extruder for melting, injecting the master batch into a mold through a nozzle, cooling and molding to obtain a shell, wherein the injection temperature is 180 ℃, the injection pressure is 70MPa, the nozzle temperature is 200 ℃, and finally assembling and combining the shell and a balancing weight with an adaptive size.
Example 2
The ageing resistance umbrella stand of this embodiment includes PE casing and fixes the balancing weight in the PE casing, and the PE casing is square lid form, and the balancing weight is marble balancing weight.
The PE shell of the embodiment is prepared from the following raw materials in weight: 50kg of high-density polyethylene, 100kg of low-density polyethylene, 20kg of carbon black, 5kg of polyethylene wax, 1kg of silicon dioxide, 3kg of polytetrafluoroethylene, 10kg of toughening agent, 3.5kg of compatilizer, 6.5kg of anti-aging agent, 1kg of ethylene glycol lauramide and 1kg of sorbitol.
Wherein the toughening agent is POE toughening agent. The compatilizer is styrene-maleic anhydride copolymer.
The aging inhibitor of this example was prepared by a method comprising the steps of:
1) Dissolving maleimide into ethanol to prepare a precursor solution, wherein the mass fraction of the maleimide is 10%, then soaking porous alumina into the precursor solution for treatment, filtering and drying to obtain an intermediate material;
2) Pouring an acetone solution into a beaker, adding hindered phenol 1010 and an intermediate material into the beaker according to a mass ratio of 7:15, uniformly mixing at a stirring speed of 500rpm, standing for 15min, and removing acetone to obtain the polyurethane foam.
The preparation method of the anti-aging umbrella seat comprises the following steps:
s1: uniformly mixing high-density polyethylene, low-density polyethylene, carbon black, polyethylene wax, silicon dioxide, polytetrafluoroethylene, a toughening agent, a compatilizer, an anti-aging agent, ethylene glycol lauramide and sorbitol in a formula amount in a stirrer, and then putting the mixture into a mixer for mixing and granulating to obtain master batch, wherein the mixing temperature is 170 ℃;
s2: drying the master batch in a drying oven, adding the master batch into a double-screw extruder for melting, injecting the master batch into a die through a nozzle, cooling and forming to obtain a shell, wherein the injection temperature is 185 ℃, the injection pressure is 75MPa, the nozzle temperature is 210 ℃, and finally assembling and combining the shell and a balancing weight with an adaptive size.
Example 3
The ageing resistance umbrella stand of this embodiment includes PE casing and fixes the balancing weight in the PE casing, and the PE casing is the dome form, and the balancing weight is marble balancing weight.
The PE shell of the embodiment is prepared from the following raw materials in weight: 35kg of high-density polyethylene, 110kg of low-density polyethylene, 18kg of carbon black, 7.5kg of polyethylene wax, 2kg of silicon dioxide, 2.2kg of polytetrafluoroethylene, 8kg of a toughening agent, 3kg of a compatilizer, 8kg of an anti-aging agent, 1.2kg of ethylene glycol lauramide and 0.85kg of sorbitol.
Wherein the toughening agent is POE toughening agent. The compatilizer is styrene-maleic anhydride copolymer.
The aging inhibitor of this example was prepared by a method comprising the steps of:
1) Dissolving maleimide into ethanol to prepare a precursor solution, wherein the mass fraction of the maleimide is 15%, then soaking porous magnesium oxide into the precursor solution for treatment, filtering and drying to obtain an intermediate material;
2) Pouring an acetone solution into a beaker, adding hindered phenol AO-80 and an intermediate material into the beaker according to the mass ratio of 9.5:12, uniformly mixing at the stirring speed of 500rpm, standing for 15min, and removing acetone to obtain the composite material.
The preparation method of the anti-aging umbrella seat comprises the following steps:
s1: uniformly mixing high-density polyethylene, low-density polyethylene, carbon black, polyethylene wax, silicon dioxide, polytetrafluoroethylene, a toughening agent, a compatilizer, an anti-aging agent, ethylene glycol lauramide and sorbitol in a formula amount in a stirrer, and then putting the mixture into a mixer for mixing and granulating to obtain master batch, wherein the mixing temperature is 185 ℃;
s2: drying the master batch in a baking oven, adding the master batch into a double-screw extruder for melting, injecting the master batch into a mold through a nozzle, cooling and molding to obtain a shell, injecting the master batch at 180 ℃, injecting the master batch at 75MPa, injecting the master batch at 195 ℃, and finally assembling and combining the shell and a balancing weight with an adaptive size.
Example 4
The anti-aging umbrella stand of this embodiment is different from embodiment 3 in that: in the preparation method of the anti-aging agent, hindered phenol consists of hindered phenol AO-80 and hindered phenol 1135 according to the mass ratio of 2:1, and the rest is the same as in the example 3.
The preparation method of the anti-aging umbrella base of the embodiment is the same as that of the embodiment 3.
Example 5
The anti-aging umbrella stand of this embodiment is different from embodiment 3 in that: in the preparation method of the anti-aging agent, hindered phenol consists of hindered phenol 1135 and hindered phenol AO-80 according to the mass ratio of 3.5:1, and the rest is the same as that in the example 3.
The preparation method of the anti-aging umbrella base of the embodiment is the same as that of the embodiment 3.
Example 6
The anti-aging umbrella stand of this embodiment is different from embodiment 3 in that: in the preparation method of the anti-aging agent, hindered phenol consists of hindered phenol 1135 and hindered phenol AO-80 according to the mass ratio of 5:1, and the rest is the same as in the example 3.
The preparation method of the anti-aging umbrella base of the embodiment is the same as that of the embodiment 3.
Example 7
The aging inhibitor of this example differs from that of example 5 in that: in the preparation method of the anti-aging agent, the porous adsorption material consists of porous silicon dioxide and porous graphite according to the mass ratio of 3:1, and the rest is the same as that of the example 5.
The preparation method of the anti-aging umbrella base of the embodiment is the same as that of the embodiment 5.
Example 8
The aging inhibitor of this example is different from that of example 7 in that: in the preparation method of the anti-aging agent, in the step 1), nano barium titanate is also added into the precursor liquid, the mass ratio of the nano barium titanate to the maleimide is 0.22:1, and the rest is the same as in the example 7.
The preparation method of the anti-aging umbrella base of the embodiment is the same as that of the embodiment 7.
Example 9
The aging inhibitor of this example is different from that of example 7 in that: in the preparation method of the anti-aging agent, in the step 1), nano barium titanate is also added into the precursor liquid, the mass ratio of the nano barium titanate to the maleimide is 0.15:1, and the rest is the same as in the example 7.
The preparation method of the anti-aging umbrella base of the embodiment is the same as that of the embodiment 7.
Comparative example
Comparative example 1
The anti-aging umbrella seat of the comparative example comprises a PE shell and a balancing weight fixed in the PE shell, wherein the PE shell is in a round cover shape, and the balancing weight is a marble balancing weight.
The PE shell of the comparative example is prepared from the following raw materials in weight: 35kg of high-density polyethylene, 110kg of low-density polyethylene, 18kg of carbon black, 7.5kg of polyethylene wax, 2kg of silicon dioxide, 2.2kg of polytetrafluoroethylene, 8kg of a toughening agent, 3kg of a compatilizer, 8kg of an anti-aging agent, 1.2kg of ethylene glycol lauramide and 0.85kg of sorbitol.
Wherein the toughening agent is POE toughening agent. The compatilizer is styrene-maleic anhydride copolymer. The anti-aging agent is hindered phenol AO-80.
The preparation method of the anti-aging umbrella base of the comparative example is the same as that of the example 3.
Comparative example 2
The anti-aging umbrella base of this comparative example is different from that of example 3 in that:
the aging inhibitor of this comparative example was prepared by a method comprising the steps of: pouring an acetone solution into a beaker, adding hindered phenol AO-80 and porous magnesium oxide into the beaker according to the mass ratio of 9.5:12, uniformly mixing at the stirring speed of 500rpm, standing for 15min, and removing acetone to obtain the composite material.
Comparative example 3
The anti-aging umbrella base of this comparative example is different from that of example 3 in that:
the aging inhibitor of this comparative example was prepared by a method comprising the steps of:
1) Dissolving maleimide into ethanol to prepare a precursor solution, wherein the mass fraction of the maleimide is 15%, then soaking nano magnesium oxide into the precursor solution for treatment, filtering and drying to obtain an intermediate material;
2) Pouring an acetone solution into a beaker, adding hindered phenol AO-80 and an intermediate material into the beaker according to the mass ratio of 9.5:12, uniformly mixing at the stirring speed of 500rpm, standing for 15min, and removing acetone to obtain the composite material.
Comparative example 4
The anti-aging umbrella base of this comparative example is different from that of example 3 in that:
the aging inhibitor of this comparative example was prepared by a method comprising the steps of:
1) Dissolving polyethylene glycol 400 in ethanol to prepare a precursor solution, wherein the mass fraction of the polyethylene glycol 400 is 15%, then soaking porous magnesium oxide into the precursor solution for treatment, filtering and drying to obtain an intermediate material;
2) Pouring an acetone solution into a beaker, adding hindered phenol AO-80 and an intermediate material into the beaker according to the mass ratio of 9.5:12, uniformly mixing at the stirring speed of 500rpm, standing for 15min, and removing acetone to obtain the composite material.
Comparative example 5
The anti-aging umbrella base of this comparative example is different from that of example 3 in that:
the aging inhibitor of this comparative example was prepared by a method comprising the steps of:
1) Dissolving ethyl acetate into ethanol to prepare a precursor solution, wherein the mass fraction of acetic acid is 15%, then soaking porous magnesium oxide into the precursor solution for treatment, filtering and drying to obtain an intermediate material;
2) Pouring an acetone solution into a beaker, adding hindered phenol AO-80 and an intermediate material into the beaker according to the mass ratio of 9.5:12, uniformly mixing at the stirring speed of 500rpm, standing for 15min, and removing acetone to obtain the composite material.
Performance test
Detection method
The anti-aging umbrella holders of examples 1-9 and comparative examples 1-5 were placed in a sealed test box, and the simulation test conditions in the test box were: the test temperature is 65 ℃, oxygen is filled into the test box until the pressure is 2MPa, the aging time is 0h, 48h, 96h and 144h respectively, the differential scanning calorimeter is used for carrying out thermo-oxidative aging resistance analysis on oxidation induction time after different aging time, and the test result is shown in figure 1.
Analysis of results
As can be seen from analysis of examples 1-3 and comparative examples 1-3 in combination with fig. 1, the low density polyethylene and the high density polyethylene are adopted to compound a compound system with a stable network structure, and the compound system has better thermal stability. Meanwhile, after the anti-aging agent is introduced, the hindered phenol molecules can fully play the roles of the porous adsorption material and the maleimide interface layer under the high-temperature environment by utilizing the dual slow-release and stabilization effects of the porous adsorption material and the maleimide interface layer, free radicals generated under the hot oxygen environment are eliminated, a durable and stable anti-aging effect is obtained, and the anti-aging umbrella base of the embodiment 3 still has the oxidation induction time of about 40 minutes after 144 hours. In comparative example 1, hindered phenol AO-80 was directly added to the composite system, and the short-term aging resistance was good, but the aging resistance was drastically reduced with the lapse of time. In comparative example 2, maleimide was not introduced, and the heat transfer loss of hindered phenol molecules could not be well suppressed, and the aging resistance in the middle and late stages was poor. In comparative example 3, the nano magnesium oxide is used for replacing porous magnesium oxide, so that the hindered phenol molecules cannot be protected, and the anti-aging effect is greatly reduced in a shorter time.
Further analysis of example 3 and comparative examples 4-5, in combination with fig. 1, it can be seen that when polyethylene glycol and ethyl acetate are used in comparative example 4 and comparative example 5, respectively, although some adsorption is possible on the surface of the porous adsorption material and in the pores, an interface layer having a stabilizing effect cannot be formed, and the corresponding slow-release and stabilizing adjustment effects cannot be achieved.
As can be seen from analysis of examples 4 to 6, example 7, and examples 8 to 9 in combination with fig. 1, optimizing and adjusting the type composition of hindered phenol and the composition ratio of porous adsorbent material further improves the anti-aging effect. And after the nano barium titanate is added, the nano barium carbonate can generate a certain synergistic effect with the interface layer, so that the regulation and control effect on the migration and release of hindered phenol is improved, and the long-term high-temperature service life of the anti-aging umbrella base is prolonged.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (4)
1. The anti-aging umbrella seat is characterized by comprising a PE shell and a balancing weight arranged in the PE shell, wherein the PE shell is mainly prepared from the following raw materials in parts by weight: 30-50 parts of high-density polyethylene, 100-120 parts of low-density polyethylene, 15-20 parts of carbon black, 5-10 parts of polyethylene wax, 1-3 parts of silicon dioxide, 1.5-3 parts of polytetrafluoroethylene, 5-10 parts of toughening agent, 2-3.5 parts of compatilizer, 6.5-9 parts of anti-aging agent, 1-1.5 parts of ethylene glycol lauramide and 0.5-1 part of sorbitol; the anti-aging agent is prepared by a method comprising the following steps:
1) Dissolving maleimide into ethanol to prepare a precursor solution, then soaking a porous adsorption material into the precursor solution for treatment, filtering and drying to obtain an intermediate material, wherein the mass fraction of maleimide in the precursor solution is 10-15%, nano barium titanate is also added into the precursor solution, and the mass ratio of the nano barium titanate to the maleimide is (0.15-0.22): 1;
2) Adding hindered phenol and intermediate materials into acetone, uniformly stirring, standing and removing the acetone to obtain the composition, wherein the mass ratio of the hindered phenol to the intermediate materials is (7-9.5) (12-15), and the hindered phenol consists of monophenol hindered phenol and bisphenol hindered phenol according to the mass ratio of (3.5-5) (1);
the porous adsorption material is at least one of porous silicon dioxide, porous graphite, porous alumina, porous calcium carbonate and porous magnesium oxide.
2. An anti-aging umbrella base according to claim 1, wherein the mass ratio of the anti-aging agent to the low density polyethylene is (0.065-0.072): 1.
3. A method for manufacturing an anti-aging umbrella base according to any one of claims 1-2, comprising the steps of:
s1: uniformly mixing high-density polyethylene, low-density polyethylene, carbon black, polyethylene wax, silicon dioxide, polytetrafluoroethylene, a toughening agent, a compatilizer, an anti-aging agent, ethylene glycol lauramide and sorbitol according to the formula amount, and mixing and granulating to obtain master batch;
s2: and drying, melting and injection molding the master batch to obtain a shell, and then assembling and combining the shell and the balancing weight.
4. A method for producing an anti-aging umbrella base according to claim 3, wherein the kneading temperature is 170-185 ℃.
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