CN115746541B - Polyurethane composite material special for inner tube of bicycle - Google Patents
Polyurethane composite material special for inner tube of bicycle Download PDFInfo
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- CN115746541B CN115746541B CN202211318511.9A CN202211318511A CN115746541B CN 115746541 B CN115746541 B CN 115746541B CN 202211318511 A CN202211318511 A CN 202211318511A CN 115746541 B CN115746541 B CN 115746541B
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 80
- 239000004814 polyurethane Substances 0.000 title claims abstract description 80
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims abstract description 80
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 79
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 73
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims abstract description 30
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 26
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 24
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 230000004048 modification Effects 0.000 claims abstract description 6
- 238000012986 modification Methods 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 238000000975 co-precipitation Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 41
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 239000000155 melt Substances 0.000 claims description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 11
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 8
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 8
- 229920000570 polyether Polymers 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 230000018044 dehydration Effects 0.000 claims description 7
- 238000006297 dehydration reaction Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 239000004970 Chain extender Substances 0.000 claims description 6
- KEQFTVQCIQJIQW-UHFFFAOYSA-N N-Phenyl-2-naphthylamine Chemical compound C=1C=C2C=CC=CC2=CC=1NC1=CC=CC=C1 KEQFTVQCIQJIQW-UHFFFAOYSA-N 0.000 claims description 6
- 125000005442 diisocyanate group Chemical group 0.000 claims description 6
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 claims description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 5
- 229920005862 polyol Polymers 0.000 claims description 5
- 150000003077 polyols Chemical class 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 150000002009 diols Chemical class 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- AOFIWCXMXPVSAZ-UHFFFAOYSA-N 4-methyl-2,6-bis(methylsulfanyl)benzene-1,3-diamine Chemical compound CSC1=CC(C)=C(N)C(SC)=C1N AOFIWCXMXPVSAZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000006084 composite stabilizer Substances 0.000 claims description 2
- 239000002905 metal composite material Substances 0.000 claims 1
- -1 then Chemical class 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 13
- 230000004888 barrier function Effects 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 238000001125 extrusion Methods 0.000 abstract description 2
- 238000005469 granulation Methods 0.000 abstract description 2
- 230000003179 granulation Effects 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 229920005549 butyl rubber Polymers 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- ZRMMVODKVLXCBB-UHFFFAOYSA-N 1-n-cyclohexyl-4-n-phenylbenzene-1,4-diamine Chemical compound C1CCCCC1NC(C=C1)=CC=C1NC1=CC=CC=C1 ZRMMVODKVLXCBB-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 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
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a special polyurethane composite material for a bicycle inner tube, belonging to the technical field of preparation of high-performance polymer materials; the polyurethane composite material is prepared by preparing dodecyl sodium sulfate doped magnesium aluminum double metal hydroxide through coprecipitation reaction, carrying out surface modification on the magnesium aluminum double metal hydroxide through gamma-aminopropyl triethoxysilane to prepare amino grafted magnesium aluminum double metal hydroxide, adding the amino grafted magnesium aluminum double metal hydroxide into a polymerization reaction system of polyurethane to prepare magnesium aluminum double metal hydroxide/polyurethane composite master batch, and finally carrying out melt blending on the composite master batch, polyurethane and an anti-aging agent, and carrying out extrusion and granulation. The polyurethane composite material prepared by the invention has excellent barrier property and thermal oxidative aging resistance, is mainly used for manufacturing inner tubes of bicycles, and has higher economic value and social benefit.
Description
Technical Field
The invention belongs to the technical field of preparation of high-performance polymer materials, and particularly relates to a special polyurethane composite material for a bicycle inner tube.
Background
In modern society of energy shortage and traffic jam, bicycles are an important tool for short distance travel. At present, the inner tube of a bicycle is mainly made of butyl rubber. Because the butyl rubber has more side methyl groups and a small number of double bonds on the molecular main chain, the butyl rubber has the characteristics of good air tightness, low air permeability, good heat resistance, ageing resistance, acid and alkali resistance and the like. However, the butyl rubber inner tube has the defects of low vulcanization rate, poor self-adhesiveness of rubber materials and the like during production, and further wide application of the butyl rubber inner tube in the bicycle inner tube is limited. Polyurethane is a polymer synthetic material with more carbamate groups on the main chain, has high elasticity of rubber materials, has easy processability and high strength of plastics, and has more excellent puncture resistance compared with butyl rubber, so that the polyurethane is the first choice material for manufacturing inner tubes of bicycles by replacing the butyl rubber. However, polyurethane has poor barrier properties and poor resistance to thermal oxidative aging, which limit the application of polyurethane in bicycle inner tubes.
Disclosure of Invention
Aiming at the problems of poor barrier property and weak thermo-oxidative aging resistance of the existing polyurethane when the polyurethane is applied to manufacturing the inner tube of the bicycle, the invention provides a special polyurethane composite material for the inner tube of the bicycle and a preparation method thereof. The polyurethane composite material prepared by the invention has excellent barrier property and thermal oxidative aging resistance, is mainly used for manufacturing inner tubes of bicycles, and has higher economic value and social benefit. In order to achieve the above purpose, the invention adopts the following technical scheme:
the special polyurethane composite material for the inner tube of the bicycle is prepared by taking magnesium nitrate, aluminum nitrate, sodium dodecyl sulfate and sodium hydroxide as raw materials, preparing sodium dodecyl sulfate doped magnesium aluminum double metal hydroxide through coprecipitation reaction, carrying out surface modification on the prepared magnesium aluminum double metal hydroxide by using gamma-aminopropyl triethoxysilane to prepare amino grafted magnesium aluminum double metal hydroxide, then taking polyalcohol, amino grafted magnesium aluminum double metal hydroxide, diisocyanate and chain extender as raw materials, carrying out prepolymerization and chain extension to prepare magnesium aluminum double metal hydroxide/polyurethane composite master batch, finally carrying out melt blending on the composite master batch, polyurethane and anti-aging agent, and carrying out extrusion and granulation; the preparation method of the polyurethane composite material comprises the following steps:
(1) Sequentially adding 3-12 g of magnesium nitrate and 2-4 g of aluminum nitrate into 100-200 mL of deionized water, and magnetically stirring for 10-20 min at room temperature to prepare a mixed solution of magnesium nitrate and aluminum nitrate; firstly, adding 10-15 g of sodium dodecyl sulfate into the mixed solution, magnetically stirring for 2-4 hours at 60-80 ℃, then adding 10-30 mL of deionized water solution of sodium hydroxide with the concentration of 1 mol/L into the mixed solution, magnetically stirring for 20-60 minutes, cooling, standing, filtering, washing and drying to obtain sodium dodecyl sulfate doped magnesium aluminum double metal hydroxide; adding the prepared sodium dodecyl sulfate doped magnesium aluminum double metal hydroxide into 200-400 mL of toluene, carrying out ultrasonic treatment at room temperature for 4-8 hours, adding 20-40 g of gamma-aminopropyl triethoxysilane, carrying out magnetic stirring at room temperature for 24-48 hours, and carrying out filtration, washing and drying to obtain the amino grafted magnesium aluminum double metal hydroxide.
(2) Adding 6-10 g of amino grafted magnesium-aluminum double metal hydroxide into 15-40 g of poly polyol, mechanically stirring for 30-60 min at room temperature, performing ultrasonic treatment for 2-4 h, and performing vacuum dehydration at 105-120 ℃ for 1-2 h to obtain a mixture of the amino grafted magnesium-aluminum double metal hydroxide and the poly polyol; under the protection of nitrogen, adding 20-40 g of diisocyanate into the mixture, magnetically stirring for 1-2 hours at room temperature, adding 2-4 g of chain extender, magnetically stirring for 1-2 hours, and carrying out vacuum defoaming and crushing to obtain a magnesium-aluminum double-metal hydroxide/polyurethane composite master batch; mixing 10-20 g of magnesium aluminum double metal hydroxide/polyurethane composite master batch, 10-40 g of polyurethane and 1-5 g of anti-aging agent for 5-10 min by using a high-speed mixer, carrying out melt blending on the primary mixing material by using a double-screw extruder, wherein the melt temperature is 160-200 ℃, the screw rotating speed is 40-80 rpm, and extruding, granulating and drying the melt blending material to obtain the special polyurethane composite material for the bicycle inner tube.
The polyalcohol is any one of polyoxypropylene glycol, polyether triol and polyester diol.
The diisocyanate is any one of diphenylmethane diisocyanate and toluene diisocyanate.
The chain extender is any one of diethanolamine, triethanolamine, diethyl toluene diamine and dimethyl thio toluene diamine.
The anti-aging agent is any one of N-phenyl-2-naphthylamine, N-phenyl-N' -cyclohexyl p-phenylenediamine and a calcium zinc compound stabilizer.
The invention has the remarkable advantages that:
(1) Compared with bentonite, the layered double hydroxide has the advantages of high purity and easy stripping, and compared with graphene, the layered double hydroxide has the advantages of simple preparation process and low cost. According to the invention, the gamma-aminopropyl triethoxysilane is used for modifying the sodium dodecyl sulfate doped magnesium aluminum double metal hydroxide, so that not only can a magnesium aluminum double metal hydroxide sheet be peeled off, but also amino groups can be grafted on the surface of the magnesium aluminum double metal hydroxide, and then the amino groups grafted magnesium aluminum double metal hydroxide is added into a polymerization reaction system of polyurethane, so that the magnesium aluminum double metal hydroxide/polyurethane composite master batch with high magnesium aluminum double metal hydroxide content can be prepared. In the magnesium-aluminum double metal hydroxide/polyurethane composite master batch, because of the action of amino groups on the surface of the magnesium-aluminum double metal hydroxide, the magnesium-aluminum double metal hydroxide is compounded with polyurethane molecular chains in a covalent bond mode, so that on one hand, the compatibility of the magnesium-aluminum double metal hydroxide and polyurethane can be effectively improved, and on the other hand, the magnesium-aluminum double metal hydroxide can be effectively prevented from agglomerating.
(2) Because the lamellar magnesium aluminum double metal hydroxide can endow polyurethane with excellent gas barrier property and the anti-aging agent can endow polyurethane with excellent thermo-oxidative aging resistance, the polyurethane composite material prepared by the invention has excellent gas barrier property and thermo-oxidative aging resistance, and the oxygen permeability coefficient is 58.4-86.7 cm 3 /cm 2 The tensile strength of the polyurethane composite material is 39.7-44.6 MPa before a thermal oxidation aging test, the elongation at break is 373-411%, the tensile strength of the polyurethane composite material is 37.9-40.5 MPa after the thermal oxidation aging test, and the elongation at break is 340-395%, and the polyurethane composite material is mainly used for manufacturing inner tubes of bicycles and has higher economic value and social benefit.
Detailed Description
The advantages of the method for producing the polyurethane composite material of the present embodiment and the effects thereof are further described below by way of three sets of examples and three sets of comparative examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
(1) Sequentially adding 7 g magnesium nitrate and 3 g aluminum nitrate into 150 mL deionized water, and magnetically stirring for 15 min at room temperature to prepare a mixed solution of magnesium nitrate and aluminum nitrate; firstly adding 12 g sodium dodecyl sulfate into the mixed solution, magnetically stirring for 3 h at 70 ℃, then adding 20 mL sodium hydroxide deionized water solution with the concentration of 1 mol/L into the mixed solution, magnetically stirring for 40 min, cooling, standing, filtering, washing and drying to obtain sodium dodecyl sulfate doped magnesium aluminum double metal hydroxide; adding the prepared sodium dodecyl sulfate doped magnesium aluminum double metal hydroxide into 300 mL toluene, carrying out ultrasonic treatment on the mixture at room temperature for 6 h, adding 30 g gamma-aminopropyl triethoxysilane, magnetically stirring the mixture at room temperature for 36 h, and carrying out filtration, washing and drying to obtain the amino grafted magnesium aluminum double metal hydroxide.
(2) Adding 8 g amino grafted magnesium aluminum double metal hydroxide into 25 g polyether triol, mechanically stirring for 45 min at room temperature, then carrying out ultrasonic treatment for 3 h, and then carrying out vacuum dehydration for 1.5 h at 115 ℃ to prepare a mixture of amino grafted magnesium aluminum double metal hydroxide and polyether triol; under the protection of nitrogen, 30 g diphenylmethane diisocyanate is added into the mixture, at room temperature, the mixture is magnetically stirred for 1.5 h, 3 g diethyl toluenediamine is added, the magnetic stirring is continued for 1.5 h, and the magnesium-aluminum double-metal hydroxide/polyurethane composite master batch is prepared through vacuum defoaming and crushing; mixing 15 g magnesium aluminum double metal hydroxide/polyurethane composite master batch, 25 g polyurethane and 3 g N-phenyl-N ʹ -cyclohexyl p-phenylenediamine for 8 min by using a high-speed mixer, carrying out melt blending on the primary mixed material by using a double-screw extruder, wherein the melt temperature is 180 ℃, the screw rotating speed is 60 rpm, and extruding, granulating and drying the melt blended material to obtain the special polyurethane composite material for the bicycle inner tube.
Example 2
(1) Sequentially adding 3 g magnesium nitrate and 2 g aluminum nitrate into 100 mL deionized water, and magnetically stirring for 10 min at room temperature to prepare a mixed solution of magnesium nitrate and aluminum nitrate; firstly adding 10 g sodium dodecyl sulfate into the mixed solution, magnetically stirring for 4h at 60 ℃, then adding 10 mL sodium hydroxide deionized water solution with the concentration of 1 mol/L into the mixed solution, magnetically stirring for 20 min, cooling, standing, filtering, washing and drying to obtain sodium dodecyl sulfate doped magnesium aluminum double metal hydroxide; adding the prepared sodium dodecyl sulfate doped magnesium aluminum double metal hydroxide into 200 mL toluene, ultrasonically treating at room temperature for 4h, adding 20 g gamma-aminopropyl triethoxysilane, magnetically stirring at room temperature for 24h, filtering, washing and drying to obtain amino grafted magnesium aluminum double metal hydroxide.
(2) Adding 6 g amino grafted magnesium aluminum double metal hydroxide into 15 g polyoxypropylene glycol, mechanically stirring for 30 min at room temperature, then performing ultrasonic treatment for 2 h, and then performing vacuum dehydration for 2 h at 105 ℃ to prepare a mixture of amino grafted magnesium aluminum double metal hydroxide and polyoxypropylene glycol; under the protection of nitrogen, adding 20 g toluene diisocyanate into the mixture, magnetically stirring at room temperature for 1 h, adding 2 g diethanolamine, magnetically stirring for 1 h, and carrying out vacuum defoaming and crushing to obtain the magnesium-aluminum double-metal hydroxide/polyurethane composite master batch; mixing 10 g magnesium aluminum double metal hydroxide/polyurethane composite master batch, 10 g polyurethane and 1 g N-phenyl-2-naphthylamine for 5 min by a high-speed mixer, carrying out melt blending on the primary mixture by a double screw extruder, extruding, granulating and drying the melt blend at a melting temperature of 160 ℃ and a screw rotating speed of 40 rpm to obtain the special polyurethane composite material for the inner tube of the bicycle.
Example 3
(1) Sequentially adding 12 g magnesium nitrate and 4 g aluminum nitrate into 200 mL deionized water, and magnetically stirring for 20 min at room temperature to prepare a mixed solution of magnesium nitrate and aluminum nitrate; firstly adding 15 g sodium dodecyl sulfate into the mixed solution, magnetically stirring for 2 h at 80 ℃, then adding 30 mL sodium hydroxide deionized water solution with the concentration of 1 mol/L into the mixed solution, magnetically stirring for 60 min, cooling, standing, filtering, washing and drying to obtain sodium dodecyl sulfate doped magnesium aluminum double metal hydroxide; adding the prepared sodium dodecyl sulfate doped magnesium aluminum double metal hydroxide into 400 mL toluene, ultrasonically treating at room temperature for 8 h, adding 40 g gamma-aminopropyl triethoxysilane, magnetically stirring at room temperature for 48 h, filtering, washing and drying to obtain amino grafted magnesium aluminum double metal hydroxide.
(2) Adding 10 g amino grafted magnesium aluminum double metal hydroxide into 40 g polyester diol, mechanically stirring for 60 min at room temperature, then performing ultrasonic treatment for 4h, and then performing vacuum dehydration for 1 h at 120 ℃ to prepare a mixture of amino grafted magnesium aluminum double metal hydroxide and polyester diol; under the protection of nitrogen, adding 40 g toluene diisocyanate into the mixture, magnetically stirring at room temperature for 2 h, adding 4 g triethanolamine, magnetically stirring for 2 h, and vacuum defoaming and crushing to obtain magnesium-aluminum double metal hydroxide/polyurethane composite master batch; mixing 20 g magnesium aluminum double metal hydroxide/polyurethane composite master batch, 40 g polyurethane and 5 g calcium zinc composite stabilizer for 10 min by using a high-speed mixer, carrying out melt blending on the primary mixture by using a double-screw extruder, extruding, granulating and drying the melt blend at the melting temperature of 200 ℃ and the screw rotating speed of 80 rpm to obtain the special polyurethane composite material for the inner tube of the bicycle.
Comparative example 1
(1) Sequentially adding 7 g magnesium nitrate and 3 g aluminum nitrate into 150 mL deionized water, and magnetically stirring for 15 min at room temperature to prepare a mixed solution of magnesium nitrate and aluminum nitrate; adding 12 g sodium dodecyl sulfate into the mixed solution, magnetically stirring at 70 ℃ for 3 h, adding 20 mL sodium hydroxide deionized water solution with the concentration of 1 mol/L into the mixed solution, magnetically stirring for 40 min, cooling, standing, filtering, washing and drying to obtain the sodium dodecyl sulfate doped magnesium aluminum double metal hydroxide.
(2) Adding 8 g sodium dodecyl sulfate doped magnesium aluminum double metal hydroxide into 25 g polyether triol, mechanically stirring for 45 min at room temperature, then carrying out ultrasonic treatment for 3 h, and then carrying out vacuum dehydration for 1.5 h at 115 ℃ to prepare a mixture of sodium dodecyl sulfate doped magnesium aluminum double metal hydroxide and polyether triol; under the protection of nitrogen, 30 g diphenylmethane diisocyanate is added into the mixture, at room temperature, the mixture is magnetically stirred for 1.5 h, 3 g diethyl toluenediamine is added, the magnetic stirring is continued for 1.5 h, and the magnesium-aluminum double-metal hydroxide/polyurethane composite master batch is prepared through vacuum defoaming and crushing; mixing 15 g magnesium aluminum double metal hydroxide/polyurethane composite master batch, 25 g polyurethane and 3 g N-phenyl-N ʹ -cyclohexyl p-phenylenediamine for 8 min by using a high-speed mixer, carrying out melt blending on the primary mixed material by using a double-screw extruder, wherein the melt temperature is 180 ℃, the screw rotating speed is 60 rpm, and extruding, granulating and drying the melt blended material to obtain the polyurethane composite material.
Comparative example 2
(1) Sequentially adding 7 g magnesium nitrate and 3 g aluminum nitrate into 150 mL deionized water, and magnetically stirring for 15 min at room temperature to prepare a mixed solution of magnesium nitrate and aluminum nitrate; firstly adding 12 g sodium dodecyl sulfate into the mixed solution, magnetically stirring for 3 h at 70 ℃, then adding 20 mL sodium hydroxide deionized water solution with the concentration of 1 mol/L into the mixed solution, magnetically stirring for 40 min, cooling, standing, filtering, washing and drying to obtain sodium dodecyl sulfate doped magnesium aluminum double metal hydroxide; adding the prepared sodium dodecyl sulfate doped magnesium aluminum double metal hydroxide into 300 mL toluene, carrying out ultrasonic treatment on the mixture at room temperature for 6 h, adding 30 g gamma-aminopropyl triethoxysilane, magnetically stirring the mixture at room temperature for 36 h, and carrying out filtration, washing and drying to obtain the amino grafted magnesium aluminum double metal hydroxide.
(2) Adding 8 g amino grafted magnesium aluminum double metal hydroxide into 25 g polyether triol, mechanically stirring for 45 min at room temperature, then carrying out ultrasonic treatment for 3 h, and then carrying out vacuum dehydration for 1.5 h at 115 ℃ to prepare a mixture of amino grafted magnesium aluminum double metal hydroxide and polyether triol; under the protection of nitrogen, 30 g diphenylmethane diisocyanate is added into the mixture, at room temperature, the mixture is magnetically stirred for 1.5 h, 3 g diethyl toluenediamine is added, the magnetic stirring is continued for 1.5 h, and the magnesium-aluminum double-metal hydroxide/polyurethane composite master batch is prepared through vacuum defoaming and crushing; mixing 15 g magnesium aluminum double metal hydroxide/polyurethane composite master batch and 25 g polyurethane for 8 min by a high-speed mixer, carrying out melt blending on the primary mixed material by a double-screw extruder, extruding, granulating and drying the melt blend at the melting temperature of 180 ℃ and the screw rotating speed of 60 rpm to obtain the polyurethane composite material.
Comparative example 3
Mixing 25 g polyurethane and 3 g N-phenyl-N ʹ -cyclohexyl p-phenylenediamine for 8 min by a high-speed mixer, carrying out melt blending on the primary mixed material by a double-screw extruder, extruding, granulating and drying the melt blend at the melting temperature of 180 ℃ and the screw rotating speed of 60 rpm to obtain the polyurethane composite material.
The polyurethane composite materials prepared by the three groups of examples and the three groups of comparative examples are subjected to air permeability test according to GB/T1038-2000, the test gas is oxygen, and the heat-resistant and oxygen aging performance of the polyurethane composite material is represented by testing the change of mechanical properties of the polyurethane composite material before and after heat treatment in a hot air aging tester, and the heat treatment conditions are as follows: the tensile strength and elongation at break were measured at 120℃for 7 d in accordance with GB/T1040-2018, and the results are shown in the following table.
TABLE 1 Performance test results
From the test results of the three groups of examples and the three groups of comparative examples, the oxygen permeability coefficient and the thermal-oxidative aging resistance of the polyurethane composite material prepared in the three groups of examples are superior to those of the polyurethane composite material prepared in the three groups of comparative examples, and are far superior to those of polyurethane, which means that sodium dodecyl sulfate doped with magnesium aluminum double metal hydroxide prepared by coprecipitation reaction is firstly subjected to surface modification by gamma-aminopropyl triethoxysilane so as to enable the surface of the sodium dodecyl sulfate doped with magnesium aluminum double metal hydroxide to be grafted with amino, then the amino grafted magnesium aluminum double metal hydroxide is added into a polymerization reaction system of polyurethane, so that a magnesium aluminum double metal hydroxide/polyurethane composite master batch with high magnesium aluminum double metal hydroxide content can be prepared, and finally the composite master batch, polyurethane and an anti-aging agent are subjected to melt blending, and are extruded and granulated, so that the polyurethane composite material with excellent gas barrier property and thermal-oxidative aging resistance can be prepared.
While the foregoing description illustrates and describes the preferred embodiments of the present invention, as noted above, it is to be understood that the invention is not limited to the forms disclosed herein but is not to be construed as excluding other embodiments, and that various other combinations, modifications and environments are possible and may be made within the scope of the inventive concepts described herein, either by way of the foregoing teachings or by those of skill or knowledge of the relevant art. And that modifications and variations which do not depart from the spirit and scope of the invention are intended to be within the scope of the appended claims.
Claims (5)
1. The special polyurethane composite material for the bicycle inner tube is characterized in that: firstly, magnesium nitrate, aluminum nitrate, sodium dodecyl sulfate and sodium hydroxide are used as raw materials, sodium dodecyl sulfate doped magnesium aluminum double metal hydroxide is prepared through coprecipitation reaction, then gamma-aminopropyl triethoxysilane is used for carrying out surface modification on the prepared magnesium aluminum double metal hydroxide to prepare amino grafted magnesium aluminum double metal hydroxide, then, polyol, amino grafted magnesium aluminum double metal hydroxide, diisocyanate and chain extender are used as raw materials, and the raw materials are subjected to prepolymerization and chain extension to prepare magnesium aluminum double metal hydroxide/polyurethane composite master batch, and finally, the composite master batch, polyurethane and an anti-aging agent are subjected to melt blending, and are extruded and granulated to prepare the magnesium aluminum double metal composite master batch;
the preparation method comprises the following steps:
(1) Sequentially adding 3-12 g of magnesium nitrate and 2-4 g of aluminum nitrate into 100-200 mL of deionized water, and magnetically stirring for 10-20 min at room temperature to prepare a mixed solution of magnesium nitrate and aluminum nitrate; firstly, adding 10-15 g of sodium dodecyl sulfate into the mixed solution, magnetically stirring for 2-4 hours at 60-80 ℃, then adding 10-30 mL of deionized water solution of sodium hydroxide with the concentration of 1 mol/L into the mixed solution, magnetically stirring for 20-60 minutes, cooling, standing, filtering, washing and drying to obtain sodium dodecyl sulfate doped magnesium aluminum double metal hydroxide; adding the prepared sodium dodecyl sulfate doped magnesium aluminum double metal hydroxide into 200-400 mL of toluene, carrying out ultrasonic treatment at room temperature for 4-8 hours, adding 20-40 g of gamma-aminopropyl triethoxysilane, magnetically stirring at room temperature for 24-48 hours, and carrying out filtration, washing and drying to obtain amino grafted magnesium aluminum double metal hydroxide;
(2) Adding 6-10 g of amino grafted magnesium-aluminum double metal hydroxide into 15-40 g of poly polyol, mechanically stirring for 30-60 min at room temperature, performing ultrasonic treatment for 2-4 h, and performing vacuum dehydration at 105-120 ℃ for 1-2 h to obtain a mixture of the amino grafted magnesium-aluminum double metal hydroxide and the poly polyol; under the protection of nitrogen, adding 20-40 g of diisocyanate into the mixture, magnetically stirring for 1-2 hours at room temperature, adding 2-4 g of chain extender, magnetically stirring for 1-2 hours, and carrying out vacuum defoaming and crushing to obtain a magnesium-aluminum double-metal hydroxide/polyurethane composite master batch; mixing 10-20 g of magnesium aluminum double metal hydroxide/polyurethane composite master batch, 10-40 g of polyurethane and 1-5 g of anti-aging agent for 5-10 min by using a high-speed mixer, carrying out melt blending on the primary mixing material by using a double-screw extruder, wherein the melt temperature is 160-200 ℃, the screw rotating speed is 40-80 rpm, and extruding, granulating and drying the melt blending material to obtain the special polyurethane composite material for the bicycle inner tube.
2. The special polyurethane composite material for the inner tube of the bicycle according to claim 1, wherein the polyalcohol is any one of polyoxypropylene glycol, polyether triol and polyester diol.
3. The polyurethane composite material special for the inner tube of the bicycle according to claim 1, wherein the diisocyanate is any one of diphenylmethane diisocyanate and toluene diisocyanate.
4. The special polyurethane composite material for the inner tube of the bicycle according to claim 1, wherein the chain extender is any one of diethanolamine, triethanolamine, diethyltoluenediamine and dimethylthiotoluenediamine.
5. The polyurethane composite material special for the inner tube of the bicycle according to claim 1, wherein the anti-aging agent is any one of N-phenyl-2-naphthylamine, N-phenyl-N ʹ -cyclohexyl p-phenylenediamine and a calcium zinc composite stabilizer.
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