CN116410617A - Surface modified glass bead composite filler and preparation method and application thereof - Google Patents
Surface modified glass bead composite filler and preparation method and application thereof Download PDFInfo
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- CN116410617A CN116410617A CN202310223505.3A CN202310223505A CN116410617A CN 116410617 A CN116410617 A CN 116410617A CN 202310223505 A CN202310223505 A CN 202310223505A CN 116410617 A CN116410617 A CN 116410617A
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- modified glass
- glass bead
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- 239000011521 glass Substances 0.000 title claims abstract description 106
- 239000011324 bead Substances 0.000 title claims abstract description 104
- 239000002131 composite material Substances 0.000 title claims abstract description 85
- 239000000945 filler Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims abstract description 59
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 59
- 238000001035 drying Methods 0.000 claims abstract description 30
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 30
- 229920001971 elastomer Polymers 0.000 claims abstract description 27
- 239000000806 elastomer Substances 0.000 claims abstract description 25
- 238000005406 washing Methods 0.000 claims abstract description 16
- 239000004111 Potassium silicate Substances 0.000 claims abstract description 15
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052913 potassium silicate Inorganic materials 0.000 claims abstract description 15
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004094 surface-active agent Substances 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 230000032683 aging Effects 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 47
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000006185 dispersion Substances 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 14
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 239000012046 mixed solvent Substances 0.000 claims description 10
- 238000004108 freeze drying Methods 0.000 claims description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000001914 filtration Methods 0.000 abstract 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 21
- 238000003756 stirring Methods 0.000 description 18
- 230000004048 modification Effects 0.000 description 13
- 238000012986 modification Methods 0.000 description 13
- 238000001291 vacuum drying Methods 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 238000001132 ultrasonic dispersion Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
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- 230000000694 effects Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 238000002715 modification method Methods 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010559 graft polymerization reaction Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- KVFIJIWMDBAGDP-UHFFFAOYSA-N ethylpyrazine Chemical compound CCC1=CN=CC=N1 KVFIJIWMDBAGDP-UHFFFAOYSA-N 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000012213 gelatinous substance Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000000707 layer-by-layer assembly Methods 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
- C08K7/20—Glass
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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- 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
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- 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
- C08L2207/04—Thermoplastic elastomer
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a surface modified glass bead composite filler, and a preparation method and application thereof, and belongs to the technical field of polymer composite materials. The preparation method of the surface modified glass bead composite filler comprises the steps of taking glass beads as raw materials, treating the raw materials through a pretreatment agent aqueous solution, treating the raw materials through a surfactant, forming gel with potassium silicate water glass, aging the gel, filtering, washing and drying the gel to obtain the surface modified glass bead composite filler. The surface modified glass bead composite filler can greatly enhance the interfacial binding force between the polymer and the glass beads. The invention also provides application of the surface modified glass bead composite filler in preparing a thermoplastic polyurethane elastomer composite material, and the prepared thermoplastic polyurethane elastomer composite material has the characteristics of heat resistance, excellent mechanical property and the like, and has high application value and wide application prospect.
Description
Technical Field
The invention belongs to the technical field of polymer composite materials, in particular relates to a surface modified glass bead composite filler, a preparation method and application thereof, and particularly relates to application of the surface modified glass bead in preparation of a thermoplastic polyurethane elastomer composite material.
Background
Thermoplastic polyurethane elastomers (TPU) are a class of elastomers between rubber and plastic, and as a typical multi-block linear polymer, consist of two parts, a "hard segment" and a "soft segment". Compared with traditional materials such as rubber and plastic, the TPU is widely applied to the fields of wires and cables, daily necessities, medical treatment, automobiles and the like due to the advantages of excellent processability, high molding speed, high raw material utilization rate and environment friendliness and reusability. But TPU also has the obvious disadvantages of lower tensile strength, uncontrollable deformation recovery and poor heat resistance, and the performance decreases rapidly with increasing temperature. At present, people mainly prepare TPU composite materials by a simple and easy blending modification method by taking inorganic materials as reinforcing phases and TPU as continuous phases. The use of inorganic materials can significantly improve the modulus, strength and heat resistance of the TPU.
The glass bead (HGB) is a specially processed glass bead with smooth surface, has smaller density and granularity of 100-500 μm. Has the characteristics of high compressive strength, high melting point, high resistivity, low heat conductivity coefficient, heat shrinkage rate and the like, and is a novel inorganic nonmetallic material with wide application and excellent performance which is developed in recent years. In addition, the composite material also has excellent properties of insulation, self-lubrication, sound insulation, fire resistance, corrosion resistance, radiation protection, no toxicity and the like. Can be directly filled in most types of thermosetting and thermoplastic resin products, thereby reducing the weight of the products, lowering the cost, eliminating the internal stress of the products and enhancing the weather resistance.
But the incorporation of HGB into the polymer melt is relatively difficult due to its smooth surface. Therefore, in practical application, the HGB is generally subjected to surface modification, and the combination of the HGB subjected to surface modification and the polymer melt is tighter, so that the HGB has very important significance for improving the performance of the glass microsphere filled composite material product.
In the prior art, the methods for modifying the HGB surface include surface chemical modification, surface coating modification, surface graft polymerization modification and the like. The surface chemical modification refers to changing the surface structure and state of particles through chemical adsorption or chemical reaction between the surface modifier and the particle surface, so as to achieve the purpose of surface modification. The surface coating modification is a method for coating/coating the surfaces of inorganic particles by using inorganic matters or organic matters to achieve modification, and is carried out by coating physical coating, chemical coating and simple chemical reaction or precipitation phenomenon. The chemical coating is to carry out surface coating modification on the inorganic powder by utilizing functional group reaction, free radical reaction, sol adsorption and the like, thereby improving the dispersibility, compatibility and the like of the inorganic powder in the high polymer and having wider use value. The physical coating is to use a surfactant, a water-soluble or oil-soluble polymer compound and the like to carry out film coating treatment on the surface of the powder to achieve the aim of surface modification, thereby improving the cementing capacity, strength, temperature resistance and the like of the inorganic powder. The surface graft polymerization modification is mainly to coat a layer of polymer on the surface of the filler by using raw materials such as monomers, an initiator and the like by adopting an in-situ polymerization method. Reactive points are introduced on the surfaces of the hollow glass beads and then react with functional groups to realize the modification effect.
Although the proposed modification methods improve the binding properties of the HGB to the polymer melt to some extent, there is still room for further improvement.
Disclosure of Invention
Aiming at the technical problems, the invention aims to provide a surface modified glass bead composite filler, a preparation method and application thereof, which further improve the interfacial binding force between a thermoplastic polyurethane elastomer and glass beads and further improve the performance of the thermoplastic polyurethane elastomer composite material.
The technical scheme adopted by the invention for solving the technical problems is as follows.
The invention provides a preparation method of a surface modified glass bead composite filler, which comprises the following steps:
firstly, treating glass beads (HGB) in a pretreatment agent aqueous solution for 1.2-1.8 hours, washing with deionized water (DI) until the pH value is neutral, washing with ethanol, and drying to obtain pretreated glass beads;
the pretreatment agent is one of citric acid and sodium hydroxide;
dispersing the pretreated glass beads in a mixed solvent, adding a surfactant, and reacting at 75-85 ℃ for 80-100 min to obtain surface modified glass beads;
the mass ratio of the pretreated glass beads to the surfactant is 0.1:0.45-0.47;
dispersing the surface modified glass beads in deionized water to obtain a surface modified glass bead dispersion liquid;
uniformly mixing potassium silicate water glass and surface modified glass bead dispersion liquid, adding Sodium Dodecyl Benzene Sulfonate (SDBS), reacting for 23-25 min, dropwise adding dilute hydrochloric acid at 0-5 ℃, and reacting for more than 5h after the dropwise adding is finished to form gel-like substances, thereby obtaining surface modified glass bead gel;
the mass ratio of the potassium silicate water glass to the surface modified glass bead dispersion liquid to the sodium dodecyl benzene sulfonate to the dilute hydrochloric acid is 1:4-6:0.008-0.012:2.4-2.6;
and fifthly, aging the surface modified glass bead gel for 9-11 hours, and performing suction filtration, washing and drying to obtain the surface modified glass bead composite filler.
Preferably, in the first step, the density of the glass beads is 1.8-2.0 g/cm 3 The average particle size is 30-32 mu m.
Preferably, in the first step, the concentration of the pretreatment aqueous solution is 0.4-0.6 mol/L.
Preferably, in the first step, the washing is performed 3 to 4 times with ethanol.
Preferably, in the first step, the drying device is an oven.
Preferably, in the second step, the ratio of the pretreated glass beads to the mixed solvent is 0.1 g:180-220 mL.
Preferably, in the second step, the mixed solvent is a mixture of water and absolute ethyl alcohol in a volume ratio of 3:1.
Preferably, in step two, the reaction is carried out under continuous stirring.
Preferably, in the second step, the surfactant is one of cetyltrimethylammonium chloride, cetyltrimethylammonium bromide and sodium dodecyl benzene sulfonate.
Preferably, in the third step, the mass ratio of the surface modified glass beads to the deionized water is 1:1100-1300.
Preferably, in the third step, the dispersing mode is ultrasonic, the dispersing equipment is an ultrasonic cleaner, the dispersing temperature is 23-27 ℃, and the dispersing time is 25-35 min.
Preferably, in the fourth step, the modulus of the potassium silicate water glass is 3.3.
Preferably, in the fourth step, the concentration of the dilute hydrochloric acid is 0.8-1.2 mol/L.
Preferably, in the fifth step, the drying is freeze drying.
Preferably, in the fifth step, the deionized water is washed for 4 to 6 times.
The invention also provides the surface modified glass bead composite filler prepared by the preparation method of the surface modified glass bead composite filler.
The invention also provides application of the surface modified glass bead composite filler in preparation of thermoplastic polyurethane elastomer composite materials.
Preferably, dispersing the surface modified glass bead composite filler into an organic solvent, uniformly mixing the surface modified glass bead composite filler with a thermoplastic polyurethane elastomer at 70-90 ℃, defoaming and drying to obtain a thermoplastic polyurethane elastomer composite material;
the mass ratio of the surface modified glass bead composite filler to the thermoplastic polyurethane elastomer is 0.025-0.2:10.
More preferably, the organic solvent is N, N-Dimethylformamide (DMF).
More preferably, the thermoplastic polyurethane elastomer is of the WHT-1195 type.
More preferably, the uniform mixing is performed by stirring for 4 hours.
More preferably, the defoaming and drying equipment is a vacuum drying oven.
More preferably, the temperature of the drying is 80 ℃.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention relates to a preparation method of a surface modified glass bead composite filler, which takes HGB as a raw material, pretreats the HGB surface by citric acid (or sodium hydroxide) to improve the reactivity, improves the hydrophilic interface by a surfactant, and deposits a layer of nano silicon dioxide particles (SiO) on the pretreated HGB surface by electrostatic self-assembly by taking potassium silicate water glass as the raw material 2 ) Preparing the surface modified glass bead composite filler (HGB@SiO) 2 ) The interfacial binding force between the polymer and the glass beads is greatly enhanced.
2. The TPU composite material prepared by the surface modified glass bead composite filler has the characteristics of heat resistance, excellent mechanical property and the like, and has high application value and wide application prospect.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments 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 other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a scanning electron microscope image of the pretreated glass beads prepared in example 1 of the present invention;
FIG. 2 shows CTAB-HGB@SiO prepared in example 1 of the invention 2 Scanning electron microscope pictures of the composite filler.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below, but it is to be understood that these descriptions are merely intended to illustrate further features and advantages of the invention, and are not limiting of the claims of the invention.
The preparation method of the surface modified glass bead composite filler comprises the following steps:
firstly, treating glass beads in a pretreatment agent aqueous solution for 1.2-1.8 hours, washing with deionized water until the pH value is neutral, washing with ethanol, and drying to obtain pretreated glass beads;
dispersing the pretreated glass beads in a mixed solvent, adding a surfactant, and reacting for 80-100 min at 75-85 ℃ to promote the surfactant to be fully adsorbed and dispersed on the surfaces of the pretreated glass beads so as to obtain the surface modified glass beads;
dispersing the surface modified glass beads in deionized water to obtain a surface modified glass bead dispersion liquid;
uniformly mixing potassium silicate water glass and surface modified glass bead dispersion liquid, adding sodium dodecyl benzene sulfonate, reacting for 23-25 min at 0-5 ℃, dropwise adding dilute hydrochloric acid at the constant temperature of 0-5 ℃, and reacting for more than 5h after dropwise adding to form gel-like substances to obtain surface modified glass bead gel;
and fifthly, aging the surface modified glass bead gel for 9-11 hours, and performing suction filtration, washing and drying to obtain the surface modified glass bead composite filler.
In the first step, the pretreatment agent is one of citric acid and sodium hydroxide, and the surface of the glass beads is pretreated by the pretreatment agent to improve the reactivity of the glass beads. Preferably, the glass beads are treated in an aqueous pretreatment solution for 1.5 hours. The density of the glass beads is 1.8g/cm 3 ～2.0g/cm 3 Preferably 1.9g/cm 3 The average particle size is 30 to 32. Mu.m, preferably 31. Mu.m. However, it should be noted that other glass beads known to those skilled in the art are suitable for use in the present invention. The concentration of the aqueous pretreatment solution is preferably 0.4mol/L to 0.6mol/L, more preferably 0.5mol/L. However, other concentrations that allow for surface etching of glass microspheres are also suitable for use in the present invention. The ethanol washing is not particularly limited, and preferably 3 to 4 times of washing with ethanol. The drying apparatus is usually an oven, but other drying apparatuses are also applicable to the present invention, and can be used to achieve a drying effect.
In the above technical scheme, in the second step, the mass ratio of the pretreated glass beads to the surfactant is 0.1:0.45-0.47, preferably 0.1:0.464. The ratio of the pretreated glass beads to the mixed solvent is preferably 0.1 g:180-220 mL, more preferably 0.1g:200mL; the mixed solvent is preferably a mixture of water and absolute ethanol in a volume ratio of 3:1, and the water is preferably deionized water. However, the mixed solvent is only a solvent, and other solvents and proportions capable of achieving the above effect may be used. The reaction is preferably carried out with continuous stirring, the stirring speed being set according to the actual requirements. The surfactant is preferably one of cetyltrimethylammonium chloride, cetyltrimethylammonium bromide and sodium dodecyl benzene sulfonate. Preferably at 75 to 85 deg.c for 90min.
In the above technical scheme, in the third step, the mass ratio of the surface modified glass beads to the deionized water is preferably 1:1100-1300, more preferably 1:1200. However, deionized water only plays a role of a solvent, and other ratios capable of achieving the effect are also possible. Preferably, the dispersing mode is ultrasonic, the dispersing equipment is an ultrasonic cleaner, the dispersing temperature is 23-27 ℃, preferably 25 ℃, and the dispersing time is 25-35 min, preferably 30min. However, other ways, devices, temperatures, and times for achieving dispersion are also possible.
In the above technical solution, in the fourth step, the modulus of the potassium silicate water glass is preferably 3.3. The concentration of the dilute hydrochloric acid is preferably 1mol/L. The mass ratio of the potassium silicate water glass to the surface modified glass bead dispersion liquid to the sodium dodecyl benzene sulfonate to the dilute hydrochloric acid is 1:4-6:0.008-0.012:2.4-2.6, and is preferably 1:5:0.01:2.5.
In the fifth aspect, the drying is preferably freeze-drying, but it should be noted that other drying methods may be used. Deionized water is typically washed 5 times.
The surface modified glass bead composite filler prepared by the preparation method of the surface modified glass bead composite filler can be applied to preparation of thermoplastic polyurethane elastomer composite materials. The application method is not particularly limited, and is similar to the application of the surface modified glass beads in the prior art in preparing the thermoplastic polyurethane elastomer composite material. Dispersing the surface modified glass bead composite filler into an organic solvent, uniformly mixing the surface modified glass bead composite filler with a thermoplastic polyurethane elastomer at 70-90 ℃ and preferably 80 ℃, pouring the mixture into a mold, defoaming and drying the mixture to obtain a thermoplastic polyurethane elastomer composite material; wherein, the mass ratio of the surface modified glass bead composite filler to the thermoplastic polyurethane elastomer is (0.025-0.2) 10; the organic solvent is preferably N, N-Dimethylformamide (DMF); the thermoplastic polyurethane elastomer is preferably of the WHT-1195 type; the mode of uniform mixing is preferably stirring, and the time is preferably 4 hours; the equipment for defoaming and drying is preferably a vacuum drying oven; the temperature of drying is preferably 80 ℃.
The terms used in the present invention generally have meanings commonly understood by those of ordinary skill in the art unless otherwise indicated. In order to enable those skilled in the art to better understand the technical solutions of the present invention, the present invention will be described in further detail with reference to examples.
In the following examples, various processes and methods, which are not described in detail, are conventional methods well known in the art. Materials, reagents, devices, instruments, equipment and the like used in the examples described below are commercially available unless otherwise specified.
The invention is further illustrated below with reference to examples.
Example 1
Step one, glass beads (HGB) (density 1.9 g/cm) 3 Average particle size of 31 μm) was added to a 0.5mol/L aqueous NaOH solution, treated for 1.5 hours under mechanical stirring, washed with deionized water to neutral pH, washed with ethanol 3 to 4 times, and dried in an oven to give a pretreated HGB.
Step two, putting 0.1g of pretreated HGB into a mixed solution of 150ml of water and 50ml of absolute ethyl alcohol, ultrasonically dispersing the three materials in a three-mouth bottle for 5min, then adding 0.464g of Cetyl Trimethyl Ammonium Bromide (CTAB), and mechanically stirring at 80 ℃ for 90min to obtain the CTAB-HGB.
Step three, mixing 0.5g of CTAB-HGB with 600g of deionized water, and placing the obtained mixed solution in an ultrasonic cleaner for ultrasonic dispersion, wherein the ultrasonic temperature is 25 ℃ and the ultrasonic time is 30min to obtain CTAB-HGB dispersion;
mixing potassium silicate water glass with the modulus of 3.3 and CTAB-HGB dispersion liquid according to the mass ratio of 1:5 to obtain a mixed solution, adding Sodium Dodecyl Benzene Sulfonate (SDBS), mixing and stirring for 25min, keeping the temperature at 0-5 ℃, adding 1mol/L dilute hydrochloric acid, dropwise adding and stirring the potassium silicate water glass and the dilute hydrochloric acid according to the mass ratio of 1:2.5, reacting for 5h after the dropwise adding is completed to form a gel-like substance, and obtaining CTAB-HGB@SiO 2 Gel;
step five, CTAB-HGB@SiO 2 Standing and aging the gel for 10 hours, performing reduced pressure suction filtration by a suction filter, washing with deionized water for 5 times, and freeze-drying in a freeze-drying box to obtain CTAB-HGB@SiO 2 And (3) a composite filler.
Step six, 0.025g CTAB-HGB@SiO 2 Adding the composite filler into 100ml of N, N-Dimethylformamide (DMF), performing ultrasonic dispersion for 20min, heating to 80deg.C, dissolving 10g TPU (WHT-1195 type) into the dispersion, stirring at high speed (500 r/min) for 4 hr, and standingPutting into a mould, defoaming in a vacuum drying oven at 80 ℃, and drying to obtain CTAB-HGB@SiO 2 TPU composite.
Example 2
0.05g of CTAB-HGB@SiO prepared in example 1 2 Adding the composite filler into 100ml of N, N-Dimethylformamide (DMF), performing ultrasonic dispersion for 20min, heating to 80 ℃, dissolving 10g of TPU (WHT-1195 type) into the dispersion liquid, stirring at high speed (500 r/min) for 4h, placing into a mould, placing into a vacuum drying oven at 80 ℃ for deaeration, and drying to obtain CTAB-HGB@SiO 2 TPU composite.
Example 3
0.1g of CTAB-HGB@SiO prepared in example 1 2 Adding the composite filler into 100ml of N, N-Dimethylformamide (DMF), performing ultrasonic dispersion for 20min, heating to 80 ℃, dissolving 10g of TPU (WHT-1195 type) into the dispersion liquid, stirring at high speed (500 r/min) for 4h, placing into a mould, placing into a vacuum drying oven at 80 ℃ for deaeration, and drying to obtain CTAB-HGB@SiO 2 TPU composite.
Example 4
0.2g of CTAB-HGB@SiO prepared in example 1 2 Adding the composite filler into 100ml of N, N-Dimethylformamide (DMF), performing ultrasonic dispersion for 20min, heating to 80 ℃, dissolving 10g of TPU (WHT-1195 type) into the dispersion liquid, stirring at high speed (500 r/min) for 4h, placing into a mould, placing into a vacuum drying oven at 80 ℃ for deaeration, and drying to obtain CTAB-HGB@SiO 2 TPU composite.
Comparative example 1
100ml of N, N-Dimethylformamide (DMF) is measured, then heated to 80 ℃, 10g of TPU (WHT-1195 type) is dissolved in the dispersion liquid, stirred for 4 hours at high speed (500 r/min), placed in a mould, and placed in a vacuum drying oven at 80 ℃ for deaeration and drying, thus obtaining the TPU material.
Comparative example 2
0.05g of glass beads (HGB) (density 1.9 g/cm) 3 31 μm average particle size) was added to 100ml of N, N-Dimethylformamide (DMF), sonicated for 20min, then heated to 80℃and 10g of TPU (WHT-1195 type) was dissolved in the dispersion, stirred at high speed (500 r/min) for 4h, and put into a moldIn the device, the mixture is placed in a vacuum drying oven at 80 ℃ for deaeration and drying, and the HGB/TPU composite material is obtained.
Comparative example 3
Step one, glass beads (HGB) (density 1.9 g/cm) 3 Average particle size of 31 μm) was added to a 0.5mol/L aqueous NaOH solution, treated for 1.5 hours under mechanical stirring, washed with deionized water to neutral pH, washed with ethanol 3 to 4 times, and dried in an oven to give a pretreated HGB.
Step two, 0.1g of pretreated HGB is put into a mixed solution of 150ml of water and 50ml of absolute ethyl alcohol, and the three are dispersed in a three-mouth bottle for 5min by ultrasonic. Then 0.464g cetyl trimethylammonium bromide (CTAB) was added. Mechanical stirring is carried out for 90min at 80 ℃ to obtain CTAB-HGB.
Adding 0.05g of CTAB-HGB into 100ml of N, N-Dimethylformamide (DMF), performing ultrasonic dispersion for 20min, heating to 80 ℃, dissolving 10g of TPU (WHT-1195 type) into the dispersion liquid, stirring at high speed (500 r/min) for 4h, putting into a mould, putting into a vacuum drying oven at 80 ℃ for defoaming, and drying to obtain the CTAB-HGB/TPU composite material.
Comparative example 4
Step one, glass beads (HGB) (density 1.9 g/cm) 3 Average particle size of 31 μm) was added to a 0.5mol/L aqueous NaOH solution, treated for 1.5 hours under mechanical stirring, washed with deionized water to neutral pH, washed with ethanol 3 to 4 times, and dried in an oven to give a pretreated HGB.
Step two, mixing 0.5g of pretreated HGB with 600g of deionized water, and placing the obtained mixed solution in an ultrasonic cleaner for ultrasonic dispersion, wherein the ultrasonic temperature is 25 ℃, and the ultrasonic time is 30min to obtain HGB dispersion;
mixing potassium silicate water glass with the modulus of 3.3 and HGB dispersion liquid according to the mass ratio of 1:5 to obtain a mixed solution, adding Sodium Dodecyl Benzene Sulfonate (SDBS), mixing and stirring for 25min, keeping the temperature at 0-5 ℃, adding 1mol/L dilute hydrochloric acid, dropwise adding and stirring, reacting for 5h after dropwise adding is completed, and forming the finished productGel-like material to obtain HGB@SiO 2 Gel;
step four, HGB@SiO 2 Standing and aging the gel for 10 hours, performing reduced pressure suction filtration by a suction filter, washing with deionized water for 5 times, and freeze-drying in a freeze-drying box to obtain HGB@SiO 2 And (3) a composite filler.
Step five, 0.05g HGB@SiO 2 Adding the composite filler into 100ml of N, N-Dimethylformamide (DMF), performing ultrasonic dispersion for 20min, heating to 80 ℃, dissolving 10g of TPU (WHT-1195 type) into the dispersion liquid, stirring at high speed (500 r/min) for 4h, placing into a mould, placing into a vacuum drying oven at 80 ℃ for defoaming, and drying to obtain HGB@SiO 2 TPU composite.
Comparative example 5
Step one, glass beads (HGB) (density 1.9 g/cm) 3 Average particle size of 31 μm) was added to a 0.5mol/L aqueous NaOH solution, treated for 1.5 hours under mechanical stirring, washed with deionized water to neutral pH, washed with ethanol 3 to 4 times, and dried in an oven to give a pretreated HGB.
Step two, mixing 0.5g of pretreated HGB with 600g of deionized water, and placing the obtained mixed solution in an ultrasonic cleaner for ultrasonic dispersion, wherein the ultrasonic temperature is 25 ℃, and the ultrasonic time is 30min to obtain HGB dispersion;
step three, mixing potassium silicate water glass with the modulus of 3.3 and HGB dispersion liquid according to the mass ratio of 1:5 to obtain a mixed solution, keeping the temperature between 0 and 5 ℃, adding 1mol/L dilute hydrochloric acid, dropwise adding and stirring the mixture, and reacting for 5 hours after the dropwise adding is completed to form a gelatinous substance, thereby obtaining the HGB@SiO 2 Gel;
step four, HGB@SiO 2 Standing and aging the gel for 10 hours, performing reduced pressure suction filtration by a suction filter, washing with deionized water for 5 times, and freeze-drying in a freeze-drying box to obtain HGB@SiO 2 And (3) a composite filler.
Step five, 0.05g HGB@SiO 2 Adding the composite filler into 100ml of N, N-Dimethylformamide (DMF), performing ultrasonic dispersion for 20min, heating to 80deg.C, dissolving 10g TPU (WHT-1195 type) into the dispersion, stirring at high speed (500 r/min) for 4 hr, and addingIn a mould, putting the mould in a vacuum drying oven at 80 ℃ for defoaming and drying to obtain HGB@SiO 2 TPU composite.
TABLE 1 Properties of TPU composite
Note that: t (T) 10 : temperature at which 10% of the TPU mass is lost.
As can be seen from examples 1 to 4 and comparative example 1 in Table 1, when CTAB-HGB@SiO 2 When the addition amount of the composite filler is less than 0.5 percent (100 parts by mass of TPU), the reinforcing effect of the composite filler on the TPU is obvious. When the addition amount is 0.5%, the tensile strength can reach 56.3MPa, and the elongation at break can reach 720.5%. With the increase of the addition amount of the composite filler, the mechanical property of the modified TPU is reduced to a certain extent, even lower than that of the pure TPU, and the composite filler is possibly poor in uniformity and dispersity in the TPU matrix with the increase of the addition amount, so that a certain agglomeration phenomenon occurs, and the material is more easily broken due to the local stress concentration.
From a comparison of comparative examples 2 to 5 and example 2, it is apparent that CTAB-HGB@SiO 2 The reinforcing effect of the composite filler on TPU is most obvious, which shows that CTAB-HGB@SiO 2 The modification method of the composite filler is efficient and practical. Example 2 increases the initial degradation temperature of the TPU by 8.9 ℃ compared to comparative example 1, because the complex morphology of the surface of the glass beads is tightly bonded to the TPU matrix, isolating heat and oxygen ingress, and delaying the release of volatile degradation products.
It is apparent that the above embodiments are merely examples for clarity of illustration and are not limiting examples. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. The preparation method of the surface modified glass bead composite filler is characterized by comprising the following steps:
firstly, treating glass beads in a pretreatment agent aqueous solution for 1.2-1.8 hours, washing with deionized water until the pH value is neutral, washing with ethanol, and drying to obtain pretreated glass beads;
the pretreatment agent is one of citric acid and sodium hydroxide;
dispersing the pretreated glass beads in a mixed solvent, adding a surfactant, and reacting at 75-85 ℃ for 80-100 min to obtain surface modified glass beads;
the mass ratio of the pretreated glass beads to the surfactant is 0.1:0.45-0.47;
dispersing the surface modified glass beads in deionized water to obtain a surface modified glass bead dispersion liquid;
uniformly mixing potassium silicate water glass and surface modified glass bead dispersion liquid, adding sodium dodecyl benzene sulfonate, reacting for 23-25 min, dropwise adding dilute hydrochloric acid at 0-5 ℃, and reacting for more than 5h after the dropwise adding is finished to form gel-like substances, thereby obtaining surface modified glass bead gel;
the mass ratio of the potassium silicate water glass to the surface modified glass bead dispersion liquid to the sodium dodecyl benzene sulfonate to the dilute hydrochloric acid is 1:4-6:0.008-0.012:2.4-2.6;
and fifthly, aging the surface modified glass bead gel for 9-11 hours, and performing suction filtration, washing and drying to obtain the surface modified glass bead composite filler.
2. The method for preparing a surface-modified glass bead composite filler according to claim 1, wherein in the first step,
the density of the glass beads is 1.8-2.0 g/cm 3 The average granularity is 30-32 mu m;
the concentration of the pretreatment agent aqueous solution is 0.4-0.6 mol/L.
3. The method for preparing a surface-modified glass bead composite filler according to claim 1, wherein in the second step,
the ratio of the pretreated glass beads to the mixed solvent is 0.1 g:180-220 mL;
the mixed solvent is a mixture of water and absolute ethyl alcohol in a volume ratio of 3:1;
the surfactant is one of cetyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide and sodium dodecyl benzene sulfonate.
4. The method for preparing a surface-modified glass bead composite filler according to claim 1, wherein in the third step,
the mass ratio of the surface modified glass beads to the deionized water is 1:1100-1300;
the dispersion mode is ultrasonic, the dispersion temperature is 23-27 ℃, and the dispersion time is 25-35 min.
5. The method for preparing a surface-modified glass bead composite filler according to claim 1, wherein in the fourth step,
the modulus of the potassium silicate water glass is 3.3;
the concentration of the dilute hydrochloric acid is 0.8-1.2 mol/L.
6. The method for preparing a surface-modified glass bead composite filler according to claim 1, wherein in the fifth step, the drying is freeze drying.
7. The surface-modified glass bead composite filler prepared by the method for preparing a surface-modified glass bead composite filler according to any one of claims 1 to 6.
8. The use of the surface modified glass bead composite filler of claim 7 in the preparation of thermoplastic polyurethane elastomer composites.
9. The application of the surface modified glass bead composite filler in preparing thermoplastic polyurethane elastomer composite materials, which is characterized in that the surface modified glass bead composite filler is dispersed in an organic solvent, uniformly mixed with the thermoplastic polyurethane elastomer at 70-90 ℃, defoamed and dried to obtain the thermoplastic polyurethane elastomer composite materials;
the mass ratio of the surface modified glass bead composite filler to the thermoplastic polyurethane elastomer is 0.025-0.2:10.
10. The use of the surface modified glass bead composite filler according to claim 9 for preparing thermoplastic polyurethane elastomer composite materials, wherein,
the thermoplastic polyurethane elastomer is WHT-1195 type;
the organic solvent is N, N-dimethylformamide.
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| CN117467350B (en) * | 2023-11-27 | 2024-08-30 | 国网山东省电力公司电力科学研究院 | Hydrophobic wear-resistant insulating paint for composite insulating bird cover and preparation method thereof |
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