CN116120575B - Silicon dioxide graft polymer and preparation method and application thereof - Google Patents
Silicon dioxide graft polymer and preparation method and application thereof Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 229
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 98
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 61
- 229920000578 graft copolymer Polymers 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 15
- BNXXLUYQVWEFLC-UHFFFAOYSA-N oxiran-2-ylmethyl 2-bromo-2-methylpropanoate Chemical compound CC(C)(Br)C(=O)OCC1CO1 BNXXLUYQVWEFLC-UHFFFAOYSA-N 0.000 claims abstract description 9
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- 239000002131 composite material Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 17
- 238000005299 abrasion Methods 0.000 claims description 14
- 235000019441 ethanol Nutrition 0.000 claims description 13
- 239000000725 suspension Substances 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- -1 bromoisobutyric acid glycidyl ester modified silicon dioxide Chemical class 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 13
- 229920001610 polycaprolactone Polymers 0.000 description 12
- 239000010410 layer Substances 0.000 description 11
- 239000004632 polycaprolactone Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 239000006087 Silane Coupling Agent Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000010559 graft polymerization reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- GNGSQLYNLOIDAU-UHFFFAOYSA-N C(C(C)C)(=O)Br.[Br] Chemical compound C(C(C)C)(=O)Br.[Br] GNGSQLYNLOIDAU-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- UURSXESKOOOTOV-UHFFFAOYSA-N dec-5-ene Chemical compound CCCCC=CCCCC UURSXESKOOOTOV-UHFFFAOYSA-N 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular 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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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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
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Silicon Polymers (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a silicon dioxide graft polymer and a preparation method and application thereof, wherein the preparation method comprises the following steps: adding bromoisobutyric acid glycidyl ester into modified nano silicon dioxide to react; adding sodium methoxide solution under the condition of nitrogen, and reacting to obtain deprotonated nano silicon dioxide grafts; then adding glycidol for polymerization under nitrogen, and reacting for 30-60min at 100-135 ℃; further adding caprolactone under the condition of nitrogen, introducing nitrogen at 80-100 ℃ and adding 10-20mg of stannous iso-octoate, and reacting for 5-10 hours. According to the invention, the polyglycidyl is grafted on the surface of the silicon dioxide, so that the reaction rate is improved, and the addition amount does not need to be strictly controlled. The caprolactone has more sites for reaction in the grafting process, and the caprolactone coated by the outer layer has good compactness. The silicon dioxide grafted polymer prepared by the invention not only can enhance the compatibility with TPE, EVA, POE, OBC and other materials, but also can further improve the wear resistance, hardness and tensile strength.
Description
Technical Field
The invention belongs to the field of silicon dioxide composite materials, and particularly relates to a silicon dioxide graft polymer and a preparation method and application thereof.
Background
Nanosilica composites have found wide application in recent years, the range of which involves: plastics, rubber, biological probes, paints, and the like. When nano silicon dioxide is added into plastic or rubber, the wear resistance, tensile strength and tear resistance are obviously improved. The current preparation method of the silicon dioxide comprises a dry method and a wet method, the dry method comprises a gas phase method and an electric arc method, the wet method comprises a precipitation method, a gel method and a microemulsion method, the production process of the dry method is high in cost and high in energy consumption, the preparation method is complex, the current main flow method for preparing the silicon dioxide is stober methods, however, the silicon dioxide is easy to agglomerate, advanced modification treatment is needed, so far, the modification method of the silicon dioxide is quite a lot, the modification of the high polymer on the silicon dioxide is divided into two types of physical modification and chemical modification, the physical modification is carried out, the bonding capability is weaker, the stability is poorer, and the stable silicon dioxide hybrid material can be obtained through the reaction of the functional group on the surface of the silicon dioxide and the high polymer. Mathieu et al studied the living polymerization process of caprolactone monomers on the surface of nano SiO 2 particles. Silicon dioxide is treated by a silane coupling agent, and then caprolactone is grafted directly. At present, most of the silicon dioxide is pretreated by adopting a silane coupling agent, and grafting is directly carried out on the silane coupling agent. The method has lower requirements on conditions and fewer steps, but the method has limited hydroxyl number, and the later grafted product has poor dispersibility and lower value in practical application.
Disclosure of Invention
The invention aims to provide a silicon dioxide graft polymer, and a preparation method and application thereof. Aiming at the problem of long time consumption, the invention makes the experiment simpler and more convenient, and realizes mass preparation in a short time; aiming at the problems of grafting density and dispersibility, the creative method adopts the method of firstly treating glycidol and then grafting caprolactone, thereby leading the dispersibility of silicon dioxide in plastics and rubber to be better.
A method for preparing a silica graft polymer comprising the steps of:
(1) Preparing nano silicon dioxide particles;
(2) Modifying the nano silicon dioxide particles;
(3) Preparing bromoisobutyric acid glycidyl ester;
(4) Adding the modified nano silicon dioxide in the step (2) into a container, adding tetrahydrofuran, carrying out ultrasonic treatment for 30-60min, adding bromoisobutyric acid glycidyl ester, stirring at room temperature, heating to 40-60 ℃, reacting for 16-24h, centrifuging, separating, cleaning and drying to obtain bromoisobutyric acid glycidyl ester modified silicon dioxide;
(5) Adding the bromoisobutyric acid glycidyl ester modified silicon dioxide obtained in the step (4) into a container, adding a mixed solvent, heating to 70-80 ℃ for reaction for 10-12h, then adding a sodium methoxide solution under the condition of nitrogen, stirring for 4-6 h under the condition of 70-80 ℃, centrifuging and washing the obtained suspension, and drying to obtain the deprotonated nano silicon dioxide graft.
(6) Adding the deprotonated nano-silica graft obtained in the step (5) into a container, and adding glycidol for polymerization under the condition of nitrogen, wherein the mass ratio of the deprotonated nano-silica graft to the glycidol is 1:10-100, reacting for 30-60min at 100-135 ℃, adding distilled water to terminate the reaction after the reaction is finished, and cleaning the reaction product with water and ethanol to obtain a polymer product intermediate;
(7) Adding the polymer product intermediate obtained in the step (3) into a container, and adding caprolactone under the condition of nitrogen, wherein the mass ratio of the polymer to the caprolactone is 1:20-50, introducing nitrogen at 80-100 ℃ and adding 10-20mg of stannous iso-octoate, reacting for 5-10 hours, adding tetrahydrofuran to terminate the reaction after the reaction is finished, centrifuging the suspension, and washing with tetrahydrofuran to obtain the product of the silica graft polymer.
Stannous iso-octoate may be replaced with TBD (1, 5-triazidinicyclo (4, 0) dec-5-ene).
Preferably, the preparation method of the nano silica particles in the step (1) comprises the following steps: absolute ethyl alcohol, ammonia water and deionized water are added into a bottle A and stirred for 3-4 hours, tetraethoxysilane and ethanol are added into a bottle B and stirred for 3-4 hours, the solution in the bottle B is transferred to the bottle A and stirred for 12 hours at room temperature, and a milky suspension is obtained, centrifuged and washed.
More preferably, the step (1) further comprises adding ammonia water, hydrogen peroxide and distilled water into the milky suspension obtained in the step (1) according to the volume ratio of 1:1:5, carrying out ultrasonic treatment for 2-3 hours, stirring for 30-60 minutes at 70-80 ℃, centrifuging to obtain a solid, washing with water and drying.
Preferably, the modification of the nano-silica particles of step (2) comprises: adding the nano silicon dioxide particles obtained in the step (1) into toluene, ultrasonically cleaning for 30-60 minutes to obtain kh550 (3-aminopropyl triethoxysilane) with the mass fraction of 4.5%, stirring for 2-3 hours at the temperature of 80-100 ℃, centrifuging, separating, cleaning and vacuum drying.
Preferably, the mixed solvent in the step (5) is a mixed solution of ethanol and water in a volume ratio of 2:8.
The silica graft polymer obtained by the preparation method is prepared.
The application of the silicon dioxide graft polymer is used as a wear-resistant material or an additive of the wear-resistant material.
A wear resistant material comprising the above silica graft polymer.
Preferably, the abrasion resistant material is a composite of one or more of TPE, EVA, POE and OBC with a silica graft polymer. The silicon dioxide graft polymer is added into plastics and rubber, and the abrasion resistance is tested, so that the abrasion resistance is obviously improved. The method aims at the problem of uneven dispersion of silica nanoparticles in materials such as rubber, and provides a solution, and the preparation of the silica graft polymer is realized by a simple method, so that the silica has better dispersibility in the materials such as rubber, and the industrial application of the silica is possible.
The preparation method of the wear-resistant material comprises the steps of heating and melting one or more materials of TPE, EVA, POE and OBC on an electric furnace, and then adding 1-5% of silicon dioxide grafted polymer.
The method is characterized in that the method comprises the steps of preparing the polymer with the caprolactone as the outermost layer, and then preparing the polymer with the caprolactone as the outermost layer.
According to the invention, the silicon dioxide is subjected to chemical modification to prepare the silicon dioxide graft with good performance, the surface of the silicon dioxide is provided with hydroxyl groups, and the graft polymerization can be carried out on the surface of the silicon dioxide by a grafting method, so that the dispersibility of the silicon dioxide is improved. The grafting of caprolactone on the surface of silicon dioxide increases the dispersibility and the dispersion speed along with the increase of the polymerization density, and in order to enlarge the grafting density of caprolactone, the invention firstly grafts polyglycidyl on the surface of silicon dioxide, increases the reaction site and then realizes the grafting polymerization of caprolactone.
According to the invention, the surface of silicon dioxide is directly treated by glycidol, and the graft polymerization of polycaprolactone is carried out on the polyglycidyl to form a block copolymer of the polyglycidyl and the polycaprolactone. So that the dispersibility of the nano silicon dioxide is improved well.
Compared with the prior art, the invention has the following advantages:
(1) The preparation method is simple, and can be used for mass preparation with low cost in a short time. According to the invention, glycidol is grafted on the surface of silicon dioxide in an anionic polymerization mode, so that the reaction rate can be greatly improved, and excessive addition can be realized in the process of adding potassium alkoxide and glycidol, thereby being convenient for industrial application. The potassium alkoxide is removed in excess with methanol after deprotonation. The amount of glycidol used here is not particularly precisely required since self-polymerization occurs in the case of an excess amount of glycidol and the number of hydroxyl groups on the silica is not defined.
(2) The density of the grafted caprolactone is high, the dispersibility is greatly improved, and the polyglycidyl increases the number of hydroxyl groups, so that more sites of the caprolactone can react in the grafting process, and the compactness of the caprolactone wrapped by the outer layer is good.
(3) The silicon dioxide grafted polymer not only can enhance the compatibility with materials such as TPE, EVA, POE, OBC and the like, but also can further improve the wear resistance, hardness and tensile strength, and has better effect than that of independently adding SiO 2.
Drawings
FIG. 1 is a synthetic flow diagram of a silica graft polymer of the present invention;
FIG. 2 is a nuclear magnetic resonance spectrum of the synthetic glycidyl bromoisobutyrate of the present invention;
FIG. 3 is an EDS spectroscopy of the synthesized SiO 2 -1 of the present invention;
FIG. 4 is an SEM image of SiO 2 -1 (left panel), siO 2 -3 (middle panel), siO 2 -4 (right panel) synthesized according to the present invention;
FIG. 5 is a TEM image of the synthesized SiO 2 -1 of the present invention;
FIG. 6 is a thermogravimetric diagram of SiO 2-1、SiO2 -3 and SiO 2 -4 synthesized according to the present invention;
FIG. 7 is a stress strain graph, wherein the upper panel is the stress strain graph of a SiO 2/TPE composite and the lower panel is the stress strain graph of two composites of SiO 2 -4/TPE.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings, for the purpose of making the objects, technical solutions and advantages of the present invention more apparent.
Example 1
The preparation method of the silicon dioxide grafted polymer takes the silicon dioxide dispersibility as a background, the silicon dioxide surface is provided with hydroxyl groups, the silicon dioxide surface is grafted with a glycidyl polymer in a grafting from mode, more hydroxyl groups are obtained after the glycidyl grafting is successful, and then a large amount of hydroxyl groups of the polyglycidyl are used for grafting polycaprolactone to form the grafted polymer of the polyglycidyl and polycaprolactone blocks, and the preparation method comprises the following steps:
(1) 350ml of absolute ethyl alcohol, 75ml of ammonia water and 215ml of deionized water are added into a bottle A and stirred for 3 hours, 45ml of tetraethoxysilane and 315ml of ethanol are added into a bottle B and stirred for 3 hours, the solution in the bottle B is transferred to the bottle A and stirred for 12 hours at room temperature, a milky suspension is obtained, and the suspension is centrifuged and washed with ethanol to obtain nano silica particles. To increase the hydroxyl groups on the silica surface, the obtained silica was added to RCA cleaning solution (ammonia water, hydrogen peroxide and distilled water were mixed in a ratio of 1:1:5) and sonicated for several hours, stirred at 75 ℃ for 45 minutes, centrifuged to obtain a solid, which was washed with water and dried to obtain nano silica particles (abbreviated as SO 2 -1).
(2) 10G of nano silica particles SO 2 -1 are weighed, added into 60ml of toluene, and subjected to ultrasonic treatment by an ultrasonic cleaner for 40min to obtain a suspension of silica, and kh550 (3-aminopropyl triethoxysilane) with the mass fraction of 4.5% is added and stirred at the temperature of 90 ℃ for 150min. After the reaction is completed, the mixture is separated by a centrifugal machine, washed by ethanol for 5 times, and dried for 8 hours in a vacuum drying oven at 100 ℃ to obtain modified silicon dioxide (abbreviated as SiO 2 -2).
(3) Methylene chloride (50 ml), glycidol (14.8 g), triethylamine (21 g) were added to the flask, and the flask was placed in an ice-water bath. Bromine isobutyryl bromide (45 g) was added to 50ml of methylene chloride, and the mixture was slowly dropped into a flask and stirred for 8 hours, after the completion of the reaction, the mixture was washed with distilled water to neutrality, and after the methylene chloride was removed by a rotary evaporator, glycidyl bromoisobutyrate was obtained by distillation under reduced pressure.
(4) Adding modified silicon dioxide (SiO 2 -2) into a flask, adding 70ml of dry tetrahydrofuran, carrying out ultrasonic treatment for 30min, adding 2.53g of bromoisobutyric acid glycidyl ester, stirring for 1h at room temperature, heating to 50 ℃, reacting for 18h, separating by a centrifuge after the reaction is finished, washing the solid by ethanol, removing the ethanol by a rotary evaporator, and carrying out vacuum drying to obtain the bromoisobutyric acid glycidyl ester modified silicon dioxide. Adding the obtained solid into a flask, adding a mixed solution (2:8) of ethanol and water into the flask, heating to 80 ℃ for reaction for 12 hours to obtain halogenated alkyl hydroxylated silicon dioxide graft
(5) 1G of the above halogenated alkyl hydroxylated silica graft was added to a flask, 5ml of sodium methoxide solution was added under nitrogen, and stirred at 70℃for 4 hours, and the resulting suspension was centrifuged and washed with methanol and toluene, and dried to obtain a deprotonated nanosilica graft. It was added to a flask, and glycidol was added under nitrogen to polymerize, and reacted at 125℃for 50 minutes, after the completion of the reaction, distilled water was added to terminate the reaction, and it was washed with water and ethanol and dried to obtain a silica-grafted polyglycidyl product (SiO 2 -3).
(6) The obtained polymer (SiO 2 -3) was charged into a flask, 10ml of caprolactone was added into the flask under nitrogen, 16mg of stannous octoate was added under nitrogen at 95℃to react for 7 hours, tetrahydrofuran was added to terminate the reaction after the reaction was completed, and the suspension was centrifuged and washed 3 times with tetrahydrofuran to obtain a silica graft polymer (SiO 2 -4).
Example 2
Preparation of a composite of TPE, EVA, POE, OBC and a silica graft polymer (SiO 2 -4) comprising: heating and melting one or more of TPE, EVA, POE and OBC materials on an electric furnace, and adding the nano silicon dioxide obtained in the step (1) of the example 1 and the silicon dioxide graft polymer (SiO 2 -HPG-PCL) obtained in the step (4) into the four materials according to the weight percentage of about 2% of the four materials to form a composite material.
Characterization of Performance
1. Characterization of the silica graft Polymer Properties of example 1
As shown in FIG. 2, the present invention results in the synthesis of glycidyl bromoisobutyrate.
From fig. 3 it can be seen that the ratio of Si to O is 2:1, demonstrates the successful synthesis of silica.
By comparing FIG. 4, the silicon dioxide in the middle graph of FIG. 4 is coated with a layer of polymer, which proves that glycidol is effectively grafted on the surface of the silicon dioxide, and the right graph of FIG. 4 shows that the silicon dioxide grafted polymer synthesized by the invention is coated with a layer of polymer on the outer layer of the silicon dioxide, and the silicon dioxide is not agglomerated and is uniformly dispersed on a copper mesh.
FIG. 6 is a thermogram of SiO 2-1、SiO2 -3 and silica graft polymer SiO 2 -4, with mass loss of mainly adsorbed water at 0℃to 200℃and mass loss of mainly hydroxyl groups on silica and polymer at 200℃to 800℃and with mass loss of SiO 2-1、SiO2-3、SiO2 -4 at 200℃to 800℃accounting for 4.1%, 4.6% and 6.2% of the total weight, respectively, demonstrating that the thickness of the polymer layer is increasing, demonstrating successful synthesis of SiO 2 -3 and SiO 2 -4.
The invention needs to protect the method of grafting polymerization by caprolactone on the basis of directly adopting glycidol treatment to increase the number of hydroxyl groups on the surface of the silicon dioxide and omitting a silane coupling agent when the dispersibility of the silicon dioxide is improved. The silicon dioxide graft prepared by the method is simple to operate, has no particularly strict requirement on the addition amount of reactants, is easy for large-scale production and is applied to industrialization. The grafting density of caprolactone is well improved by the branching reaction of caprolactone after hyperbranched polymerization.
2. Abrasion resistance test of composite containing silica graft Polymer of example 2
The resulting composite material was subjected to abrasion resistance test by pressing it with a weight of 50g against 500 mesh sandpaper at a speed of 2cm/s and by comparing the abrasion resistance before and after the addition of the step nano silica particles SiO 2 -1 synthesized in example 1 and the silica graft polymer SiO 2 -4, and the results are shown in tables 1 to 4. From tables 1 to 4, it can be seen that silica has an effect of enhancing the abrasion resistance of the material, and the abrasion resistance enhancement of the silica graft polymer of the present invention is more remarkable. It can be seen that the abrasion resistance of the invention after the graft polymerization of silica is further improved.
Table 1 results of abrasion resistance test of the composite materials formed from the silica graft polymer of the present invention and TPE
TABLE 2 abrasion resistance test results of composite materials formed from the silica graft polymers of the invention and EVA
TABLE 3 abrasion resistance test results of composite materials of the silica graft polymers of the invention and POE
TABLE 4 abrasion resistance test results of composite materials formed from the silica graft polymers of the invention and OBC
3. Hardness test of composite containing silica graft Polymer of example 2
The composite material prepared in example 2 was tested for hardness by a Shore durometer and the results are shown in tables 5-8, with further improvement in hardness when the silica graft polymer was added to plastic or rubber.
TABLE 5 hardness test results of the composite materials formed from the silica graft polymers of the invention and TPE
TABLE 6 hardness test results of the composite materials formed from the silica graft polymers of the invention and EVA
TABLE 7 hardness test results of composite materials of the silica graft polymers of the invention and POE
4. Tensile Strength test of composite containing silica graft Polymer of example 2
The composite material prepared in the example 2 is subjected to a tensile strength test, and the tensile strength of SiO 2/TPE is 2.06MPa and the elongation at break is 400% as shown in FIG. 7; the tensile strength of SiO 2 -4/TPE is 3.06MPa, the elongation at break is 480%, and the comparison shows that the composite material formed by the product SiO 2- 4 obtained by the invention has better mechanical properties.
Comparative example 1
Unlike example 1, the following is: the silica nano-particles are firstly treated by a coupling agent, polycaprolactone is grafted on the hydroxyl of the coupling agent, and finally polyglycidyl is grafted. The inner layer is formed by a block copolymer of which the outer layer is formed by polyglycidyl. The polycaprolactone of the inner layer is of a linear structure, the number of hydroxyl groups of the polycaprolactone is limited, the grafting density is lower than that of the polycaprolactone of the inner layer in example 1, the grafting efficiency is lower, and a compact polymer protective layer is difficult to form, so that the dispersibility of the polycaprolactone is poor. And the time consumption is long, the amount of the coupling agent during the reaction is required to be very accurate, the operation difficulty is increased, and the method is not beneficial to industrialized production and application.
Because of the limited number of hydroxyl groups on the silica surface, there is a difference in the density of the silica re-grafted polycaprolactone and polyglycidyl first treated and then grafted polycaprolactone polymers treated directly with a silane coupling agent. If the silane coupling agent is added in an excessive amount during the hydrolysis process, the reaction between the bodies occurs, and the silane coupling agent adheres to the surface of the silicon dioxide, thereby affecting the grafting rate of the surface of the silicon dioxide.
Claims (7)
1. A method for preparing a silica graft polymer, comprising the steps of:
(1) Preparing nano silicon dioxide particles: adding absolute ethyl alcohol, ammonia water and deionized water into a bottle A, stirring for 3-4h, adding tetraethoxysilane and ethanol into a bottle B, stirring for 3-4h, transferring the solution in the bottle B to the bottle A, stirring for 12h at room temperature to obtain milky suspension, centrifuging and washing; adding ammonia water, hydrogen peroxide and distilled water into the obtained milky suspension according to the volume ratio of 1:1:5, ultrasonically treating for 2-3 hours, stirring for 30-60 minutes at 70-80 ℃, centrifuging to obtain a solid, washing with water and drying;
(2) Modifying the nano silicon dioxide particles: adding the nano silicon dioxide particles obtained in the step (1) into toluene, ultrasonically cleaning for 30-60 minutes, adding kh550 with the mass fraction of 4.5%, stirring for 2-3 hours at the temperature of 80-100 ℃, centrifuging, separating, cleaning and vacuum drying;
(3) Preparing bromoisobutyric acid glycidyl ester;
(4) Adding the modified nano silicon dioxide in the step (2) into a container, adding tetrahydrofuran, carrying out ultrasonic treatment for 30-60min, adding bromoisobutyric acid glycidyl ester, stirring at room temperature, heating to 40-60 ℃, reacting for 16-24h, centrifuging, separating, cleaning and drying to obtain bromoisobutyric acid glycidyl ester modified silicon dioxide;
(5) Adding the solid obtained in the step (4) into a container, adding a mixed solvent, heating to 70-80 ℃ for reaction for 10-12h, then adding a sodium methoxide solution under the condition of nitrogen, stirring for 4-6 h under the condition of 70-80 ℃, centrifuging and washing the obtained suspension, and drying to obtain the deprotonated nano silicon dioxide graft;
(6) Adding the deprotonated nano-silica graft obtained in the step (5) into a container, and adding glycidol for polymerization under the condition of nitrogen, wherein the mass ratio of the deprotonated nano-silica graft to the glycidol is 1:10-100, reacting for 30-60min at 100-135 ℃, adding distilled water to terminate the reaction after the reaction is finished, and cleaning the reaction product with water and ethanol to obtain a polymer product intermediate;
(7) Adding the polymer product intermediate obtained in the step (3) into a container, and adding caprolactone under the condition of nitrogen, wherein the mass ratio of the polymer to the caprolactone is 1:20-50, introducing nitrogen at 80-100 ℃ and adding 10-20mg of stannous iso-octoate, reacting for 5-10 hours, adding tetrahydrofuran to terminate the reaction after the reaction is finished, centrifuging the suspension, and washing with tetrahydrofuran to obtain the product of the silica graft polymer.
2. The method according to claim 1, wherein the mixed solvent in the step (5) is a mixed solution of ethanol and water in a volume ratio of 2:8.
3. A silica graft polymer obtainable by the process according to claim 1 or 2.
4. Use of a silica graft polymer according to claim 3 for abrasion resistant materials.
5. A wear resistant material comprising the silica graft polymer of claim 3.
6. The wear resistant material of claim 5 wherein said wear resistant material is a composite of one or more of TPE, EVA, POE and OBC and a silica grafted polymer.
7. The method of claim 6, comprising melting one or more of TPE, EVA, POE and OBC by heating on an electric furnace and adding 1-5% silica graft polymer.
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| CN102399376A (en) * | 2010-09-09 | 2012-04-04 | 中国科学院化学研究所 | Silicon dioxide with organic functional molecules grafted on surface, preparation method thereof, and purpose thereof |
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