CN116355250A - Modified halloysite nanotube in-situ reinforced PVB material and preparation method and application thereof - Google Patents
Modified halloysite nanotube in-situ reinforced PVB material and preparation method and application thereof Download PDFInfo
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- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical class O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000002071 nanotube Substances 0.000 title claims abstract description 65
- 239000000463 material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000011065 in-situ storage Methods 0.000 title abstract description 10
- 239000005336 safety glass Substances 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 23
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 23
- 239000003995 emulsifying agent Substances 0.000 claims description 22
- 239000003963 antioxidant agent Substances 0.000 claims description 21
- 230000003078 antioxidant effect Effects 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 17
- 229910052621 halloysite Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- 230000001804 emulsifying effect Effects 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 229920001427 mPEG Polymers 0.000 claims description 6
- 229910000077 silane Inorganic materials 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- -1 silane modified halloysite Chemical class 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims 2
- JMGZBMRVDHKMKB-UHFFFAOYSA-L disodium;2-sulfobutanedioate Chemical compound [Na+].[Na+].OS(=O)(=O)C(C([O-])=O)CC([O-])=O JMGZBMRVDHKMKB-UHFFFAOYSA-L 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000002715 modification method Methods 0.000 claims 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 27
- 238000012545 processing Methods 0.000 abstract description 7
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 239000005357 flat glass Substances 0.000 abstract description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 53
- MQKXWEJVDDRQKK-UHFFFAOYSA-N bis(6-methylheptyl) butanedioate Chemical group CC(C)CCCCCOC(=O)CCC(=O)OCCCCCC(C)C MQKXWEJVDDRQKK-UHFFFAOYSA-N 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 239000000945 filler Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
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- 239000003054 catalyst Substances 0.000 description 2
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- 230000001965 increasing effect Effects 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
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- 229910003849 O-Si Inorganic materials 0.000 description 1
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- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
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- 239000010410 layer Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical group [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
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Abstract
The invention discloses a modified halloysite nanotube reinforced PVB material and a preparation method and application thereof. The PVB composite material is prepared by introducing m-HNTs into PVB material in an in-situ polymerization mode, and the obtained PVB composite material has good processing fluidity and mechanical properties. And has good application prospect in laminated safety glass including automobile front windshields and high-rise building door and window glass.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a modified halloysite nanotube in-situ reinforced PVB material, and a preparation method and application thereof.
Background
Polyvinyl butyral, PVB for short, is a thermoplastic resin having a six-membered cyclic acetal structure obtained from polyvinyl alcohol and n-butyraldehyde in the presence of an inorganic acid as a catalyst. Because of its unique molecular structure, it has better tensile strength, high viscosity and impact resistance than other polymers, and is widely used in laminated safety glass. When the collision event happens, PVB can play a role in bonding glass on two sides, so that not only can the splashing of fine glass fragments be reduced, but also the expansion of cracks can be prevented, and the secondary injury to a user is reduced to the greatest extent. With the increasing requirements of people on safety performance, the common PVB cannot better meet market demands, so that PVB composite materials with more excellent performance are obtained through modification, and the application of the PVB composite materials in the field of laminated safety glass is further widened.
The inorganic nano filler is widely applied to the preparation of composite materials, and the halloysite nano tube can effectively enhance the mechanical properties of the composite materials by virtue of the smaller size and the larger specific surface area. However, halloysite nanotubes have poor dispersibility in polymers and are easy to agglomerate, so that the processing fluidity of the composite material is affected, and the melt index of the composite material is reduced. The invention mainly aims to prepare a modified halloysite nanotube (m-HNTs) for improving the dispersibility of the halloysite nanotube in a PVB matrix and enhancing the mechanical property and processing fluidity of a PVB material so as to prepare a transparent PVB film with good ultraviolet shielding property.
Disclosure of Invention
The invention aims to provide a preparation method of a modified halloysite nanotube in-situ reinforced PVB material, and simultaneously provides the modified halloysite nanotube reinforced PVB material prepared by the method and application thereof, which are the second invention aims to provide the modified halloysite nanotube reinforced PVB material.
Based on the above purpose, the invention adopts the following technical scheme:
the preparation method of the modified halloysite nanotube reinforced PVB material comprises the following steps: 1) Stirring polyvinyl alcohol, water and an antioxidant at a high speed, heating to 90-95 ℃, and preserving heat for 1-2h to completely dissolve the polyvinyl alcohol; the weight ratio of the polyvinyl alcohol to the water to the antioxidant is 25 g: (180-220) g: (0.02-0.1) g; the stirring speed is 500rpm-800rpm;
2) Cooling the system to 22-26 ℃, adding an emulsifying agent and a modified halloysite nanotube for homogenizing and emulsifying for 1-1.5h, adding n-butyraldehyde, continuously cooling to 10-20 ℃, adding a proper amount of hydrochloric acid, and keeping the temperature unchanged for 1-1.5h; the dosage ratio of the emulsifier, the modified halloysite nanotube, the n-butyraldehyde, the hydrochloric acid and the polyvinyl alcohol is (0.02-0.1) g: (0.12-0.16) g: (12-16) ml: (18-22) ml:25g;
3) Heating the system to 70 ℃ at constant speed, preserving heat for 1.5-2h, adding sodium hydroxide to adjust pH=4, maintaining for 1-1.5h, washing, adding sodium hydroxide to adjust pH=13 into the washed sample, magnetically stirring for 1.5-2h, washing to neutrality, and centrifuging and drying to obtain the product. In the step 3), the heating rate is 0.5-2 ℃/min, the reaction rate is easy to be too high due to the fact that the heating rate is too high, the generated PVB product is easy to agglomerate, the reaction rate is easy to be too low due to the fact that the heating rate is too low, and the reaction time is too long.
The different dissolution sequences of the materials are due to the process flow of the synthesis of PVB. For the invention, firstly, the polyvinyl alcohol is dissolved to ensure complete dissolution, an antioxidant is added to prevent oxidation, then an emulsifier and a modified halloysite nanotube are added in a cooling way, and the modified halloysite nanotube is used for reinforcing PVB materials. N-butyraldehyde is used as a reactant, hydrochloric acid is used as a catalyst, and the effect of the emulsifier ensures that the reaction is more uniform.
The invention also includes the steps of forming the PVB material into a film material: and (3) redissolving the dried sample in the step (3) into an ethanol solvent, stirring for 2 hours, pouring into a self-made mold, and drying in a 50 ℃ oven for standby.
Preferably, the modified halloysite nanotubes are derived from methoxy PEG silane modified halloysite.
Further preferably, the method of modification is: after mixing 1g of halloysite with 0.3g-0.5g of methoxy PEG silane, 100mL of absolute ethyl alcohol is added, stirring is carried out at 80 ℃ for 12-14h, and centrifugal washing and drying are carried out, thus obtaining the product.
Preferably, in the step 1), the antioxidant is one or more than two of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, tri (2, 4-di-tert-butylphenyl) phosphite and tetra [ beta- (3, 5-di-tert-butyl, 4-hydroxyphenyl) propionate ] pentaerythritol;
further preferably, the antioxidant is stearyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
In the invention, the antioxidant has the main function of preventing the oxidation of the product, and for the invention, the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate is preferable, so that the PVB film of the final product is not easy to yellow.
Preferably, in step 2), the emulsifier is diisooctyl succinate sodium sulfonate. The emulsifier is used for making the reaction more uniform, and the quality of the products obtained by different emulsifiers is different.
Preferably, in step 2), the concentration of hydrochloric acid is 5-8wt%.
The invention further discloses the modified halloysite nanotube reinforced PVB material prepared by the method. The thickness of the prepared film is 0.15-0.25mm.
The invention further provides a modified halloysite nanotube reinforced PVB material prepared by the method. The application of the modified halloysite nanotube reinforced PVB material in the laminated safety glass comprises that the laminated safety glass comprises an automobile front windshield and high-rise building door and window glass, PVB is used as a safety glass interlayer, and the interlayer is clamped between two pieces of glass in a two-to-one mode.
The invention is prepared by introducing m-HNTs into PVB material in an in-situ polymerization mode, and the obtained PVB composite material has good processing fluidity and mechanical property, and particularly, compared with the prior art, the invention has the following technical effects:
1. the infrared characterization, TEM and other characterization show that the halloysite nanotube is successfully modified, and the modified halloysite has good dispersion degree and good interaction in the PVB matrix.
2. In-situ reinforced PVB experiment comparison of the modified halloysite nanotubes and the unmodified halloysite nanotubes, as can be seen from the mechanical property comparison of FIG. 3, the addition of the modified halloysite nanotubes enhances the tensile strength of PVB.
3. The modified halloysite nanotube improves the processing fluidity of the PVB composite material, and the melt index is increased.
4. The modified halloysite nanotube has low influence on the transmittance of the PVB composite film, and has good ultraviolet shielding effect while ensuring the transparency of the film.
Drawings
In order to more clearly illustrate the technical solutions of the present invention, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an infrared absorption spectrum of HNTs and m-HNTs;
FIG. 2 TEM images of HNTs and m-HNTs;
FIG. 3 shows a graph of mechanical properties of an m-HNTs-PVB composite;
FIG. 4 shows a plot of melt index change for m-HNTs-PVB composites;
FIG. 5 UV-Vis absorption spectra of m-HNTs-PVB composite;
FIG. 6 is a graph of the transparency effect of an m-HNTs-PVB composite.
Detailed Description
The invention will be further described with reference to the drawings and the specific examples. Detailed descriptionthe technical solutions of the present invention are exemplary and not to be construed as limiting the invention, and all other embodiments obtained by persons of ordinary skill in the art without making inventive efforts are intended to fall within the scope of protection of the present invention.
In the invention, the preparation method of the modified halloysite nanotube comprises the following steps: mixing 1g of halloysite with 0.3g-0.5g of methoxy PEG silane, adding 100-120mL of absolute ethyl alcohol, performing ultrasonic treatment for 30-35min for dispersion, stirring at 75-80 ℃ for 12-14h, and performing centrifugal washing and drying to obtain the product. Particularly preferred, in examples 1-6, the modified halloysite nanotubes are prepared by the steps of: 1g of halloysite nanotube is selected to be mixed with 0.3g of methoxy PEG silane with molecular weight of 5000, 100mL of absolute ethyl alcohol is added, ultrasonic treatment is carried out for 30min for dispersion, then magnetic stirring is carried out for 12h at 80 ℃, and after centrifugal washing and drying, the modified halloysite nanotube is obtained.
Example 1
The preparation method of the modified halloysite nanotube reinforced PVB material comprises the following steps:
1) Feeding 25g of polyvinyl alcohol, 200g of deionized water and 0.05g of antioxidant, stirring at a high speed after the feeding is finished, heating to 95 ℃, and preserving heat for 1h to completely dissolve the polyvinyl alcohol; in this example, the antioxidant is stearyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate; in this example, the stirring speed was 600rpm;
2) Cooling to 25deg.C, adding 0.05g of emulsifier, adding 0.15g of modified halloysite nanotube, homogenizing and emulsifying for 1 hr, adding 14.7mL of n-butyraldehyde, continuously cooling to 10deg.C, adding 20.63mL of hydrochloric acid (hydrochloric acid concentration is 5wt%) and maintaining the temperature unchanged for 1 hr; in this embodiment, the emulsifier is diisooctyl succinate sodium sulfonate;
3) Heating to 70 ℃ at constant speed, preserving heat for 2 hours, adding sodium hydroxide to adjust pH=4, maintaining for 1 hour, washing, adding sodium hydroxide to adjust pH=13 into a washed sample, magnetically stirring for 2 hours, washing to be neutral, and centrifugally drying. And redissolving the dried sample into an ethanol solvent, stirring for 2 hours, pouring into a self-made mold, and drying in a 50 ℃ oven for standby.
Example 2
The preparation method of the modified halloysite nanotube reinforced PVB material comprises the following steps:
1) Feeding 25g of polyvinyl alcohol, 200g of deionized water and 0.05g of antioxidant, stirring at a stirring speed of 600rpm after the feeding is finished, heating to 95 ℃, and preserving heat for 1.5h to completely dissolve the polyvinyl alcohol; in this example, the antioxidant is stearyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate; the stirring speed is 500rpm-800rpm
2) Cooling to 25deg.C, adding 0.05g of emulsifier, adding 0.15g of modified halloysite nanotube (same as in example 1), homogenizing and emulsifying for 1 hr, adding 14.7mL of n-butyraldehyde, continuously cooling to 15deg.C, adding 20.63mL of hydrochloric acid (hydrochloric acid concentration is 5wt%) and maintaining the temperature unchanged for 1 hr; in this embodiment, the emulsifier is diisooctyl succinate sodium sulfonate;
3) Heating to 70 ℃ at constant speed, preserving heat for 2 hours, adding sodium hydroxide to adjust PH=4, maintaining for 1 hour, washing with water, adding sodium hydroxide to adjust PH=13 into a washed sample, magnetically stirring for 2 hours, washing with water to be neutral, and centrifugally drying. And redissolving the dried sample into an ethanol solvent, stirring for 2 hours, pouring into a self-made mold, and drying in a 50 ℃ oven for standby.
Example 3
The preparation method of the modified halloysite nanotube reinforced PVB material comprises the following steps:
1) Feeding 25g of polyvinyl alcohol, 200g of deionized water and 0.05g of antioxidant, stirring at a stirring speed of 600rpm after the feeding is finished, heating to 95 ℃, and preserving heat for 2 hours to completely dissolve the polyvinyl alcohol; in this example, the antioxidant is stearyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate;
2) Cooling to 25deg.C, adding 0.05g of emulsifier, adding 0.15g of modified halloysite nanotube, homogenizing and emulsifying for 1.5 hr, adding 14.7mL of n-butyraldehyde, continuously cooling to 20deg.C, adding 20.63mL of hydrochloric acid (hydrochloric acid concentration is 5wt%) and maintaining the temperature for 1 hr; in this embodiment, the emulsifier is diisooctyl succinate sodium sulfonate;
3) Heating to 70 ℃ at constant speed, preserving heat for 2 hours, adding sodium hydroxide to adjust PH=4, maintaining for 1 hour, washing, adding sodium hydroxide to adjust PH=13 into a washed sample, magnetically stirring for 1.5 hours, washing to be neutral, and centrifuging and drying. And redissolving the dried sample into an ethanol solvent, stirring for 2 hours, pouring into a self-made mold, and drying in a 50 ℃ oven for standby.
Example 4
The preparation method of the modified halloysite nanotube reinforced PVB material comprises the following steps:
1) Feeding 25g of polyvinyl alcohol, 200g of deionized water and 0.05g of antioxidant, stirring at a stirring speed of 600rpm after the feeding is finished, heating to 95 ℃, and preserving heat for 2 hours to completely dissolve the polyvinyl alcohol; in this example, the antioxidant is stearyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate;
2) Cooling to 25deg.C, adding 0.05g of emulsifier, adding 0.15g of modified halloysite nanotube, homogenizing and emulsifying for 1 hr, adding 14.7mL of n-butyraldehyde, continuously cooling to 10deg.C, adding 20.63mL of hydrochloric acid (hydrochloric acid concentration is 5wt%) and maintaining the temperature unchanged for 1 hr; in this embodiment, the emulsifier is diisooctyl succinate sodium sulfonate;
3) Heating to 70 ℃ at constant speed, preserving heat for 2 hours, adding sodium hydroxide to adjust PH=4, maintaining for 1 hour, washing, adding sodium hydroxide to adjust PH=13 into a washed sample, magnetically stirring for 1.5 hours, washing to be neutral, and centrifuging and drying. And redissolving the dried sample into an ethanol solvent, stirring for 2 hours, pouring into a self-made mold, and drying in a 50 ℃ oven for standby.
Example 5
The preparation method of the modified halloysite nanotube reinforced PVB material comprises the following steps:
1) Feeding 25g of polyvinyl alcohol, 180g of deionized water and 0.02g of antioxidant, stirring at a stirring speed of 500rpm after the feeding is finished, heating to 95 ℃, and preserving heat for 1h to completely dissolve the polyvinyl alcohol; in this example, the antioxidant is tris (2, 4-di-t-butylphenyl) phosphite;
2) Cooling to 22 ℃, adding 0.02g of emulsifier, adding 0.12g of modified halloysite nanotube, homogenizing and emulsifying for 1h, adding 12mL of n-butyraldehyde, continuously cooling to 10 ℃, adding 18mL of hydrochloric acid (the concentration of hydrochloric acid is 5 wt%), and keeping the temperature unchanged for 1h; in this embodiment, the emulsifier is diisooctyl succinate sodium sulfonate;
3) Heating to 68 ℃ at constant speed, preserving heat for 2 hours, adding sodium hydroxide to adjust PH=4, maintaining for 1 hour, washing with water, adding sodium hydroxide to adjust PH=13 into a washed sample, magnetically stirring for 1.5 hours, washing with water to be neutral, and centrifugally drying. And redissolving the dried sample into an ethanol solvent, stirring for 2 hours, pouring into a self-made mold, and drying in a 45 ℃ oven for standby.
Example 6
The preparation method of the modified halloysite nanotube reinforced PVB material comprises the following steps:
1) Feeding 25g of polyvinyl alcohol, 220g of deionized water and 0.1g of antioxidant, stirring at a stirring speed of 800rpm after the feeding is finished, heating to 90 ℃, and preserving heat for 1h to completely dissolve the polyvinyl alcohol; in this example, the antioxidant is tetrakis [ beta- (3.5-di-tert-butyl, 4-hydroxyphenyl) propionate ] pentaerythritol;
2) Cooling to 26 ℃, adding 0.1g of emulsifier, adding 0.16g of modified halloysite nanotube, homogenizing and emulsifying for 1h, adding 16mL of n-butyraldehyde, continuously cooling to 10 ℃, adding 22mL of hydrochloric acid (the concentration of hydrochloric acid is 8 wt%), and keeping the temperature unchanged for 1h; in this embodiment, the emulsifier is diisooctyl succinate sodium sulfonate;
3) Heating to 70 ℃ at constant speed, preserving heat for 1.5h, adding sodium hydroxide to adjust the PH=4, maintaining for 1.5h, washing, adding sodium hydroxide to adjust the PH=13 into a washed sample, magnetically stirring for 1.5h, washing to be neutral, and centrifugally drying. And redissolving the dried sample into an ethanol solvent, stirring for 1.5h, pouring into a self-made mold, and drying in a 55 ℃ oven for standby.
Performance test:
the films prepared in examples 1-6 were tested for thickness, and the resulting films were between 0.15 and 0.25mm thick.
The infrared spectrum test results of the halloysite nanotube HNTs and the modified halloysite nanotube m-HNTs are shown in figure 1.
FIG. 1 is a chart showing the infrared absorption spectra of HNTs and m-HNTs in the examples of the present invention, as can be seen from FIG. 1, the characteristic peak is 3697cm for the infrared spectrum of halloysite nanotubes -1 And 3622 cm -1 Stretching vibration of hydroxyl group at peak value of 910 cm -1 Bending vibration belonging to hydroxyl group, peak at 538 cm -1 And 1035 cm -1 Respectively corresponding to the bending vibration peak of Al-O-Si and the stretching vibration peak of Si-O-Si, for the infrared spectrum of m-HNTs, 3435 cm -1 Is mainly from the hydroxyl vibration peak in the adsorbed water, 2873 and 2873 cm -1 Where a new absorption peak band is present corresponding to the symmetrical and asymmetrical tensile vibration absorption bands of alkyl C-H due toStructural characteristic peaks on the main chain of the modifier indicate successful modification of halloysite nanotubes.
As can be seen from FIG. 2a, the halloysite nanotube has a hollow tubular structure, the tube length is about 500nm, and the tube diameter is about 20 nm. The halloysite nanotubes are in a single tube dispersed state, and a layer of polymer is uniformly coated on the outside of the tube in the TEM image of m-HNTs in FIG. 2b, which shows that the modifier has been successfully grafted on the surface of the halloysite nanotubes.
In fig. 3, mechanical properties of unmodified Halloysite Nanotubes (HNTs) and modified halloysite nanotubes (m-HNTs) in-situ reinforced PVB are shown, and as the content of the inorganic filler halloysite nanotubes increases, the tensile strength of the composite material increases, and when the content reaches a certain level, the tensile strength starts to decrease. And compared with HNTs, the addition of m-HNTs improves the tensile strength of the composite material, and reduces the reduction of the elongation at break. When the percentage content of the m-HNTs filler in the polyvinyl alcohol is 0.60%, the overall mechanical property of the composite material is optimal, the tensile strength is 82.39MPa, and the mechanical property of the PVB material can be better enhanced by the modified halloysite nanotube compared with the pure PVB material by 33.5%.
Fig. 4 is a graph of melt index comparisons of modified halloysite nanotube-reinforced PVB composites. From the figure, it can be seen that the unmodified halloysite nanotubes as inorganic filler reduce the melt index of the PVB composite material, so that the processing fluidity of the PVB composite material is poor, and the processing fluidity of the PVB composite material is improved after the PVB composite material is modified, and the melt index reaches 2.8g/10min at the addition amount of 0.60%.
As can be seen from FIG. 5, after m-HNTs are introduced in situ, the prepared m-HNTs-PVB composite film has good shielding effect on 250-380nm ultraviolet light along with the increase of filler content. The prepared PVB film has better transmittance in a visible light region, and the transmittance in the visible light region reaches 90 percent, which is not much different from the PVB produced in the industry.
Fig. 6 is a graph showing the transparency effect of the m-HNTs-PVB composite, and as shown in fig. 6, graphs a and b are respectively composite films prepared by in-situ polymerization of unmodified halloysite nanotubes and modified halloysite nanotubes, and it is apparent from the graph that the transparency difference between the two films is not large, and the following marks can be clearly observed through the films.
Claims (9)
1. The preparation method of the modified halloysite nanotube reinforced PVB material is characterized by comprising the following steps of:
1) Stirring polyvinyl alcohol, water and an antioxidant at a high speed, heating to 90-95 ℃, and preserving heat for 1-2h to completely dissolve the polyvinyl alcohol; the weight ratio of the polyvinyl alcohol to the water to the antioxidant is 25 g: (180-220) g: (0.02-0.1) g; the stirring speed is 500rpm-800rpm;
2) Cooling the system to 22-26 ℃, adding an emulsifying agent and a modified halloysite nanotube for homogenizing and emulsifying for 1-1.5h, adding n-butyraldehyde, continuously cooling to 10-20 ℃, adding a proper amount of hydrochloric acid, and keeping the temperature unchanged for 1-1.5h; the dosage ratio of the emulsifier, the modified halloysite nanotube, the n-butyraldehyde, the hydrochloric acid and the polyvinyl alcohol is (0.02-0.1) g: (0.12-0.16) g: (12-16) ml: (18-22) ml:25g;
3) Heating the system to 68-70 ℃ at constant speed, preserving heat for 1.5-2h, adding sodium hydroxide to adjust pH=4, maintaining for 1-1.5h, washing, adding sodium hydroxide to adjust pH=13 into the washed sample, magnetically stirring for 1.5-2h, washing to neutrality, centrifuging and drying to obtain the product.
2. The method of claim 1, further comprising forming the PVB material of step 4) into a film material: redissolving the dried sample obtained in the step 3) into an ethanol solvent, stirring for 1.5-2h, pouring into a self-made mold, and drying in a drying oven at 45-55 ℃ for standby.
3. The method of any one of claims 1-2, wherein the modified halloysite nanotubes are derived from methoxy PEG silane modified halloysite.
4. A method of preparing a modified halloysite nanotube reinforced PVB material according to claim 3, wherein the modification method comprises: mixing 1g of halloysite with 0.3g-0.5g of methoxy PEG silane, adding 100-120mL of absolute ethyl alcohol, performing ultrasonic treatment for 30-35min for dispersion, stirring at 75-80 ℃ for 12-14h, and performing centrifugal washing and drying to obtain the product.
5. The method for preparing a modified halloysite nanotube reinforced PVB material according to claim 1, wherein in the step 1), the antioxidant is one or a mixture of more than two of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate stearyl alcohol, tri (2, 4-di-tert-butylphenyl) phosphite and tetra [ beta- (3, 5-di-tert-butyl, 4-hydroxyphenyl) propionate ] pentaerythritol.
6. The method for preparing a modified halloysite nanotube reinforced PVB material according to claim 1, wherein in the step 2), the emulsifier is diisooctyl sodium sulfosuccinate.
7. The method of claim 1, wherein in step 2), the concentration of hydrochloric acid is between 5 and 8 weight percent.
8. A modified halloysite nanotube reinforced PVB material prepared by the method of any one of claims 4-7.
9. The use of the modified halloysite nanotube reinforced PVB material of claim 8 in laminated safety glass.
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