CN116023701B - High-temperature-resistant yellowing-resistant thermal expansion foaming microsphere and preparation method thereof - Google Patents
High-temperature-resistant yellowing-resistant thermal expansion foaming microsphere and preparation method thereof Download PDFInfo
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- 239000004005 microsphere Substances 0.000 title claims abstract description 69
- 238000005187 foaming Methods 0.000 title claims abstract description 48
- 238000004383 yellowing Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- -1 siloxane compound Chemical class 0.000 claims abstract description 49
- 239000000178 monomer Substances 0.000 claims abstract description 35
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000725 suspension Substances 0.000 claims abstract description 20
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 16
- 239000011257 shell material Substances 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 239000004088 foaming agent Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 229920001296 polysiloxane Polymers 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 229910052708 sodium Inorganic materials 0.000 claims description 13
- 239000011734 sodium Substances 0.000 claims description 13
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 239000006260 foam Substances 0.000 claims description 5
- 229910000077 silane Inorganic materials 0.000 claims description 5
- 239000011162 core material Chemical class 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- WQPMYSHJKXVTME-UHFFFAOYSA-N 3-hydroxypropane-1-sulfonic acid Chemical compound OCCCS(O)(=O)=O WQPMYSHJKXVTME-UHFFFAOYSA-N 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- DTPCFIHYWYONMD-UHFFFAOYSA-N decaethylene glycol Polymers OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO DTPCFIHYWYONMD-UHFFFAOYSA-N 0.000 claims description 3
- 239000012933 diacyl peroxide Substances 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- RYPYDIHMPGBBJN-UHFFFAOYSA-M sodium;2-methyl-1-(prop-2-enoylamino)propane-1-sulfonate Chemical compound [Na+].CC(C)C(S([O-])(=O)=O)NC(=O)C=C RYPYDIHMPGBBJN-UHFFFAOYSA-M 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 6
- 239000003921 oil Substances 0.000 description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000004604 Blowing Agent Substances 0.000 description 4
- 229920000103 Expandable microsphere Polymers 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- NOBYOEQUFMGXBP-UHFFFAOYSA-N (4-tert-butylcyclohexyl) (4-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CC(C(C)(C)C)CCC1OC(=O)OOC(=O)OC1CCC(C(C)(C)C)CC1 NOBYOEQUFMGXBP-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000003094 microcapsule Substances 0.000 description 2
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- YSUMQPFWYXSLJV-UHFFFAOYSA-N [Na].CC(CS(=O)(=O)O)C.C(C=C)(=O)N Chemical compound [Na].CC(CS(=O)(=O)O)C.C(C=C)(=O)N YSUMQPFWYXSLJV-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- QPMJENKZJUFOON-PLNGDYQASA-N ethyl (z)-3-chloro-2-cyano-4,4,4-trifluorobut-2-enoate Chemical compound CCOC(=O)C(\C#N)=C(/Cl)C(F)(F)F QPMJENKZJUFOON-PLNGDYQASA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Abstract
The application relates to the technical field of thermal expansion materials, in particular to a high-temperature-resistant yellowing-resistant thermal expansion foaming microsphere and a preparation method thereof. The application provides a preparation method of high-temperature-resistant yellowing-resistant thermal expansion foaming microspheres, which comprises the following steps: mixing silica sol, a reactive anionic surfactant and water to obtain a water phase; mixing a monomer, an acrylic modified siloxane compound, an initiator and a foaming agent to obtain an oil phase; adding the oil phase into the water phase, and heating for reaction to obtain a suspension solution; washing, filtering and drying the suspension solution to obtain the thermal expansion foaming microsphere. According to the preparation method provided by the application, the reactive anionic surfactant is introduced to improve the reaction stability of the suspension, the acrylic modified siloxane compound is used as the shell material of the foaming microsphere, the heat resistance and yellowing resistance of the shell material are improved through the heat resistance and flexibility of the organosilicon group, the initial foaming temperature of the prepared foaming microsphere can reach 225 ℃, and the maximum expansion temperature can reach 265 ℃.
Description
Technical Field
The application relates to the technical field of materials, in particular to a high-temperature-resistant yellowing-resistant thermal expansion foaming microsphere and a preparation method thereof.
Background
The heat expansion type foaming microsphere is a microcapsule sphere structure composed of a shell and a core material, wherein the shell is composed of an airtight thermoplastic high polymer, the core material is hydrocarbon, the boiling point of the hydrocarbon is smaller than the glass transition temperature of the polymer shell, after the polymer shell is heated to a certain temperature, the polymer shell is softened, the low-boiling hydrocarbon serves as a foaming agent, and the expansion of the microcapsule is increased due to the internal vapor pressure generated by gasification. The temperature at which the thermally expandable microspheres begin to expand is referred to as the initial expansion temperature T onset The temperature at which maximum expansion is reached is called T max 。
The heat-expandable expanded microspheres have a certain heat-resistant range, and when heat treatment is performed at a relatively high temperature or for a long time, the expanded microspheres shrink due to air leakage, and good heat expansion performance cannot be obtained. When the foaming microsphere is used in some materials such as thermoplastic plastics, rubber or thermoplastic elastomer which need high-temperature operation processing, the initial expansion temperature of the microsphere is required to be higher, so that a better foaming effect is achieved. In order to improve the heat resistance of heat-expandable microspheres, patent CN111701546A discloses a yellowing-resistant high-temperature-resistant expandable microsphere, a preparation method and application thereof, wherein nitrile monomers, amide-containing monomers, double-bond carboxyl-containing monomers and acrylic ester monomers are used as a shell material system, organic acid or organic anhydride is added in the later stage of microsphere polymerization reaction for further crosslinking to improve the heat resistance and yellowing resistance, the initial expansion temperature of the obtained expandable microsphere is less than 150 ℃, the maximum expansion temperature is less than 200 ℃, and the material with higher requirement on the initial expansion temperature cannot be met.
Based on the above analysis, it is necessary to provide a thermally expandable expanded microsphere having a high initial expansion temperature and excellent yellowing resistance.
Disclosure of Invention
The embodiment of the application provides a preparation method of a high-temperature-resistant yellowing-resistant thermal expansion foaming microsphere, which aims to solve the problem that the initial expansion temperature of the foaming microsphere is low in the prior art.
The application provides a preparation method of high-temperature-resistant yellowing-resistant thermal expansion foaming microspheres, which comprises the following steps:
step S101, mixing silica sol, a reactive anionic surfactant and water to obtain a water phase;
step S102, mixing a monomer, an acrylic modified siloxane compound, an initiator and a foaming agent to obtain an oil phase; wherein the reactive anionic surfactant has at least one vinyl group and the acrylic-modified silicone compound has at least two vinyl groups;
step S103, adding the oil phase into the water phase, stirring at a certain speed until the particle size reaches a proper value, heating to a certain temperature in a closed container, and reacting for 10-20 h to obtain a suspension solution;
and step S104, washing, filtering and drying the suspension solution to obtain the thermal expansion foaming microsphere.
In some embodiments, the acrylic-modified siloxane compound has a molecular weight of 1000 to 1500.
In some embodiments, the acrylic-modified silicone compound is selected from any one of a multifunctional acrylic-modified silicone compound, a difunctional acrylic-modified silicone compound, or a mixture of both.
In some embodiments, the multifunctional acrylic-modified siloxane compound has the structural formula:
wherein the general structural formula of R isb has a value of 3 to 6. The application relates to a multifunctional group CThe value of a in the structural formula of the enoate modified siloxane compound is not limited as long as the total molecular weight is ensured not to exceed 1500.
In some embodiments, the difunctional acrylic modified siloxane compound has the structural formula:
wherein the general structural formula of R isThe application does not limit the value of c in the structural formula of the difunctional acrylic modified siloxane compound, so long as the total molecular weight is ensured not to exceed 1500.
In some embodiments, the multifunctional acrylic-modified siloxane compound and the difunctional acrylic-modified siloxane compound are both prepared by reacting an alcoholic hydroxyl silicone with acrylic acid.
In some embodiments, when the multifunctional acrylic-modified siloxane compound and the difunctional acrylic-modified siloxane compound are used simultaneously, the mixing mass ratio of the multifunctional acrylic-modified siloxane compound to the difunctional acrylic-modified siloxane compound is 3:1 to 1:1.
In some embodiments, the silica sol is selected from an acidic nanosilica sol or a silane modified silica sol. The acidic or silane modified nano silica sol has better stability on oil phase liquid drops, and can provide a stabilizing protective layer on the surfaces of the oil phase liquid drops.
In some embodiments, the silica sol is used in an amount of 5% to 10% by mass of the total mass of monomer, silicone prepolymer, initiator and blowing agent.
In some embodiments, the reactive anionic surfactant is selected from any one or more of sodium vinyl alkyl sulfonate, sodium allyl hydroxypropyl sulfonate, sodium acrylamido-2-methylpropane sulfonate, and ammonium 1-allyloxy-3- (4-nonylphenol) -2-propanolate polyoxyethylene (10) ether sulfate.
In some preferred embodiments, the reactive anionic surfactant is sodium vinyl alkyl sulfonate, which has higher reactivity when the sodium vinyl alkyl sulfonate participates in copolymerization.
In some embodiments, the reactive anionic surfactant is present in an amount of 0.5% to 1% by mass of the total mass of monomer, silicone prepolymer, initiator and blowing agent.
In some embodiments, the monomer is selected from acrylate monomers, acrylic monomers, or acrylonitrile monomers
In some preferred embodiments, the monomer is selected from methyl methacrylate, methacrylic acid, or methacrylonitrile type monomers. Further, the monomer is methacrylonitrile monomer and a mixture thereof.
In some embodiments, the foaming agent is selected from any one or more of n-hexane, n-pentane and n-heptane.
In some embodiments, the initiator is selected from any one or more of peroxyesters, dialkyl peroxides, peroxydicarbonates, diacyl peroxides, or azo compounds.
In some preferred embodiments, the initiator is selected from the group consisting of highly reactive azobisisoheptonitrile or di (4-t-butylcyclohexyl) peroxydicarbonate.
In some embodiments, the initiator is used in an amount of 1% to 5% by mass of the total mass of the monomer and the silicone prepolymer.
In some embodiments, the mass ratio of the monomer to the acrylic-modified siloxane compound is from 7:3 to 9:1.
In a second aspect, the application provides the high-temperature-resistant yellowing-resistant thermal expansion foaming microsphere prepared by the preparation method, wherein the shell material of the high-temperature-resistant yellowing-resistant thermal expansion foaming microsphere is a polymer generated by the reaction of a monomer and an acrylic modified siloxane compound, and the core material of the high-temperature-resistant yellowing-resistant thermal expansion foaming microsphere is a foaming agent; wherein the acrylic-modified siloxane compound has at least two vinyl groups.
In some embodiments, the acrylic-modified siloxane compound has a molecular weight of 1000 to 1500.
In some embodiments, the acrylic-modified silicone compound is selected from any one of a multifunctional acrylic-modified silicone compound, a difunctional acrylic-modified silicone compound, or a mixture of both.
In some embodiments, when the multifunctional acrylic-modified siloxane compound and the difunctional acrylic-modified siloxane compound are used simultaneously, the mass ratio of the multifunctional acrylic-modified siloxane compound to the difunctional acrylic-modified siloxane compound is 3:1 to 1:1.
In some embodiments, the silica sol is selected from an acidic nanosilica sol or a silane modified silica sol. The acidic or silane modified nano silica sol has better stability on oil phase liquid drops, and can provide a stabilizing protective layer on the surfaces of the oil phase liquid drops.
In some embodiments, the silica sol is used in an amount of 5% to 10% by mass of the total mass of monomer, silicone prepolymer, initiator and blowing agent.
In some embodiments, the reactive anionic surfactant is selected from any one or more of sodium vinyl alkyl sulfonate, sodium allyl hydroxypropyl sulfonate, sodium acrylamido-2-methylpropane sulfonate, and ammonium 1-allyloxy-3- (4-nonylphenol) -2-propanolate polyoxyethylene (10) ether sulfate.
In some preferred embodiments, the reactive anionic surfactant is sodium vinyl alkyl sulfonate, which has higher reactivity when the sodium vinyl alkyl sulfonate participates in copolymerization.
In some embodiments, the reactive anionic surfactant is present in an amount of 0.5% to 1% by mass of the total mass of monomer, silicone prepolymer, initiator and blowing agent.
In some embodiments, the monomer is selected from the group consisting of an acrylic monomer, and an acrylonitrile monomer.
In some preferred embodiments, the monomer is selected from any one or more of methyl methacrylate, methacrylic acid, or methacrylonitrile. Further, the monomer is methacrylonitrile or a mixture thereof.
In some embodiments, the initiator is selected from any one or more of peroxyesters, dialkyl peroxides, peroxydicarbonates, diacyl peroxides, or azo compounds.
In some preferred embodiments, the initiator is selected from the group consisting of highly reactive azobisisoheptonitrile or di (4-t-butylcyclohexyl) peroxydicarbonate.
In some embodiments, the initiator is used in an amount of 1% to 5% by mass of the total mass of the monomer and the silicone prepolymer.
In some embodiments, the mass ratio of the monomer to the acrylic-modified siloxane compound is from 7:3 to 9:1.
The foaming microsphere takes the reactant of the acrylic modified siloxane compound and the monomer as the shell material, the organosilicon group improves the high temperature resistance and flexibility of the shell material, and the vinyl double bond can improve the crosslinking degree in the reaction process, so that the strength of the shell material at high temperature is further improved.
The technical scheme provided by the application has the beneficial effects that:
1. according to the preparation method provided by the application, the acrylic modified siloxane compound is introduced as the shell material of the foaming microsphere, the heat resistance and yellowing resistance of the shell material are improved through the heat resistance and flexibility of the organosilicon group, the initial foaming temperature of the prepared foaming microsphere can reach 225 ℃, and the highest expansion temperature can reach 265 ℃;
2. according to the preparation method provided by the application, the reactive anionic surfactant is introduced into the water phase to serve as the suspension aid of silicon dioxide, so that emulsion drops can be prevented from coalescing and stabilized, the controllability of microsphere particle size is improved, and the obtained foamed microsphere is uniform in particle size and has good expansion rate;
3. the method provided by the application does not need to additionally add a cross-linking agent, use a combination of metal ions, oligomers and a polymerization inhibitor in the preparation process, has a simple process, does not need complex post-treatment, and is beneficial to industrial preparation.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a macroscopic view of the thermally expanded microspheres prepared according to example 1 of the present application;
FIG. 2 is a macroscopic view of the thermally expanded foam microsphere prepared in example 1 of the present application after being heated at 265 ℃;
FIG. 3 is an SEM image of thermally expanded foam microspheres prepared according to example 1 of the present application;
FIG. 4 is an SEM image of the thermally expanded foam microsphere prepared in example 1 of the present application after heating at 265 ℃.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more apparent, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
The embodiment of the application provides a preparation method of a high-temperature-resistant yellowing-resistant thermal expansion foaming microsphere, which can solve the problem that the initial expansion temperature of the foaming microsphere is low in the prior art.
The embodiment of the application provides a preparation method of a high-temperature-resistant yellowing-resistant thermal expansion foaming microsphere, which comprises the following steps:
step S101, uniformly mixing silica sol, a reactive anionic surfactant and water to obtain a water phase;
step S102, uniformly mixing a monomer, an acrylic modified siloxane compound, an initiator and a foaming agent to obtain an oil phase;
step S103, adding the oil phase into the water phase, stirring at a certain speed until the particle size reaches a proper value, heating to a certain temperature in a closed container, and reacting for 10-20 h to obtain a suspension solution;
and step S104, washing, filtering and drying the suspension solution to obtain the thermal expansion foaming microsphere.
Wherein the acrylic-modified silicone compound has at least two vinyl groups, and the acrylic-modified silicone compound is any one of or a mixture of multifunctional acrylic-modified silicone compounds or difunctional acrylic-modified silicone compounds.
The structural formula of the multifunctional acrylic modified siloxane compound is shown as the formula (I):
formula (I):
in the formula (I), the general structural formula of R isb has a value of 3 to 6.
The structural formula of the difunctional acrylic modified siloxane compound is shown as a formula (II):
formula (II):
in the formula (II), the general structural formula of R is
The high temperature resistant yellowing resistant thermal expansion resistant foaming microsphere and the preparation method thereof provided by the application are described in detail below by combining examples and comparative examples.
Example 1:
example 1 provides a method for preparing high temperature resistant yellowing resistant thermal expansion foaming microsphere, comprising the following steps:
(1) Weighing 20g of acidic silica sol (30% of solid content), 0.5g of sodium vinyl alkyl sulfonate and 160g of water, and uniformly stirring to obtain a water phase solution;
(2) 39.2g of methacrylonitrile, 11.2g of methyl methacrylate, 5.6g of methacrylic acid, 18g of a multifunctional acrylic modified siloxane compound (a=6, b=3) with a molecular weight of 1122, 6g of a difunctional acrylic modified siloxane compound (c=9) with a molecular weight of 1024, 20g of n-hexane and 0.8g of azobisisoheptonitrile are weighed and stirred uniformly to obtain an oil phase;
(3) Adding the oil phase into the water phase at room temperature, stirring for 20 minutes in a closed container at a rotating speed of 500rpm to form a stable suspension solution, and slowly heating to 55 ℃ to react for 20 hours;
(4) Washing, filtering and drying the obtained suspension solution to obtain the thermal expansion foaming microsphere powder.
The macroscopic view of the expanded microsphere prepared in example 1 is shown in FIG. 1, the macroscopic view of the expanded microsphere heated at 265 ℃ is shown in FIG. 2, and as can be seen from FIG. 2, the expanded microsphere prepared in example 1 does not turn yellow and still remains white.
SEM images of the expanded microspheres prepared in example 1 are shown in fig. 3, and SEM images after heating at 265 ℃ are shown in fig. 4.
The size of the expanded microspheres prepared in example 1 is: d50 The expanded microsphere has an initial expansion temperature of 225 ℃ and a maximum expansion temperature of 265 ℃ and an expansion ratio of 30-40 times, and does not yellow after complete expansion, wherein the expansion temperature is 13.2 mu m, d90=19.8 mu m and the span is 1.35.
Comparative example 1:
comparative example 1 provides a method for preparing thermally expanded foam microspheres comprising the steps of:
(1) Weighing 20g of acidic silica sol (30% of solid content), 0.5g of sodium vinyl alkyl sulfonate and 160g of water, and uniformly stirring to obtain a water phase solution;
(2) 56g of methacrylonitrile, 16g of methyl methacrylate, 8g of methacrylic acid, 20g of n-hexane and 0.8g of azodiisoheptanenitrile are weighed and stirred uniformly to obtain an oil phase;
(3) Adding the oil phase into the water phase at room temperature, stirring for 20 minutes in a closed container at a rotating speed of 500rpm to form a stable suspension solution, and slowly heating to 55 ℃ to react for 20 hours;
(4) The obtained suspension solution was washed, filtered and dried to obtain pale yellow powder.
The pale yellow powder obtained in comparative example 1 did not have foaming properties, indicating that the obtained linear-structure shell material was poor in air tightness and could not be foamed without introducing the acrylic-modified silicone compound.
It can be seen from comparative example 1 and example 1 that the addition of the multifunctional acrylic-modified silicone compound and the difunctional acrylic-modified silicone compound during the preparation process can improve the foaming properties of the microspheres and possess a higher initial expansion temperature and maximum expansion temperature.
Comparative example 2:
comparative example 2 provides a method for preparing thermally expanded microspheres comprising the steps of:
(1) Weighing 20g of acidic silica sol (30% solid content) and 160g of water, and uniformly stirring to obtain a water phase solution;
(2) 39.2g of methacrylonitrile, 11.2g of methyl methacrylate, 5.6g of methacrylic acid, 18g of a multifunctional acrylic modified siloxane compound (a=6, b=3) with a molecular weight of 1122, 6g of a difunctional acrylic modified siloxane compound (c=9) with a molecular weight of 1024, 20g of n-hexane and 0.8g of azobisisoheptonitrile are weighed and stirred uniformly to obtain an oil phase;
(3) Adding the oil phase into the water phase at room temperature, stirring for 20 minutes in a closed container at a rotating speed of 500rpm to form a stable suspension solution, and slowly heating to 55 ℃ to react for 20 hours;
(4) Washing, filtering and drying the obtained suspension solution to obtain the thermal expansion foaming microsphere powder.
The size of the expanded microspheres prepared in comparative example 2 was: d50 =20.7 μm, d90=50.8 μm, span 2.75, the initial expansion temperature of the expanded microsphere is 210 ℃, the maximum expansion temperature is 230 ℃, and the expansion ratio is 10-20 times.
As can be seen from comparative example 2 and example 1, the addition of the reactive anionic surfactant during the preparation process is favorable for obtaining the foaming microsphere with uniform particle size and high expansion ratio.
Example 2:
example 2 provides a method for preparing high temperature resistant yellowing resistant thermal expansion foaming microsphere, comprising the following steps:
(1) Weighing 20g of acidic silica sol (30% of solid content), 0.5g of acrylamide-2-methylpropanesulfonic acid sodium and 160g of water, and uniformly stirring to obtain a water phase solution;
(2) 47.6g of methacrylonitrile, 13.6g of methyl methacrylate, 6.8g of methacrylic acid, 7g of a multifunctional acrylic modified siloxane compound (a=7, b=4) with a molecular weight of 1368, 5g of a difunctional acrylic modified siloxane compound with a molecular weight of 1320 (c=13), 20g of n-hexane and 0.8g of azodiisoheptanenitrile are weighed and stirred uniformly to obtain an oil phase;
(3) Adding the oil phase into the water phase at room temperature, stirring for 20 minutes in a closed container at a rotating speed of 500rpm to form a stable suspension solution, and slowly heating to 55 ℃ to react for 20 hours;
(4) Washing, filtering and drying the obtained suspension solution to obtain the thermal expansion foaming microsphere powder.
The size of the expanded microspheres prepared in example 2 was: d50 The initial expansion temperature of the foaming microsphere is 220 ℃, the maximum expansion temperature is 260 ℃, the expansion multiplying power is 40-50 times, and the foaming microsphere does not yellow after complete expansion, wherein the expansion multiplying power is 14.9 mu m, d90=20.5 mu m and the span is 1.31.
Example 3:
example 3 provides a method for preparing high temperature resistant yellowing resistant thermal expansion foaming microsphere, comprising the following steps:
(1) Weighing 20g of acidic silica sol (30% of solid content), 0.5g of sodium vinyl alkyl sulfonate and 160g of water, and uniformly stirring to obtain a water phase solution;
(2) 50.4g of methacrylonitrile, 14.4g of methyl methacrylate, 7.2g of methacrylic acid, 4g (a=5, b=5) of a polyfunctional acrylic modified siloxane compound with a molecular weight of 1392, 4g (c=11) of a difunctional acrylic modified siloxane compound with a molecular weight of 1172, 15g of n-hexane and 0.8g of azobisisoheptonitrile are weighed and stirred uniformly to obtain an oil phase;
(3) Adding the oil phase into the water phase at room temperature, stirring for 20 minutes in a closed container at a rotating speed of 500rpm to form a stable suspension solution, and slowly heating to 55 ℃ to react for 20 hours;
(4) Washing, filtering and drying the obtained suspension solution to obtain the thermal expansion foaming microsphere powder.
The size of the expanded microspheres prepared in example 3 is: d50 The expanded microsphere has an initial expansion temperature of 210 ℃ and a maximum expansion temperature of 245 ℃ and an expansion ratio of 40-50 times, and does not yellow after complete expansion, wherein the expansion temperature is 11.2 mu m, d90=17.3 mu m and the span is 1.38.
In the description of the present specification, reference to the terms "one embodiment/manner," "some embodiments/manner," "example," "a particular example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment/manner or example is included in at least one embodiment/manner or example of the application. In this specification, the schematic representations of the above terms are not necessarily for the same embodiment/manner or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments/modes or examples. Furthermore, the various embodiments/modes or examples described in this specification and the features of the various embodiments/modes or examples can be combined and combined by persons skilled in the art without contradiction.
It should be noted that in the present application, relational terms such as "first" and "second" and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element. In the present application, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically specified otherwise.
The foregoing is only a specific embodiment of the application to enable those skilled in the art to understand or practice the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (6)
1. The preparation method of the high-temperature-resistant yellowing-resistant thermal expansion foaming microsphere is characterized by comprising the following steps of:
mixing silica sol, a reactive anionic surfactant and water to obtain a water phase;
mixing a monomer, an acrylic modified siloxane compound, an initiator and a foaming agent to obtain an oil phase;
adding the oil phase into the water phase, and heating for reaction to obtain a suspension solution;
washing, filtering and drying the suspension solution to obtain the thermal expansion foaming microsphere;
wherein the reactive anionic surfactant has at least one vinyl group, and is selected from any one or more of sodium vinyl alkyl sulfonate, sodium allyl hydroxypropyl sulfonate, sodium acrylamido-2-methylpropanesulfonate and ammonium 1-allyloxy-3- (4-nonylphenol) -2-propanol polyoxyethylene (10) ether sulfate;
the acrylic modified siloxane compound has at least two vinyl groups, and any one or the mixture of two of the multifunctional acrylic modified siloxane compounds and the difunctional acrylic modified siloxane compounds is selected; the structural formula of the multifunctional acrylic modified siloxane compound is shown as follows:
wherein the structural general formula of R isb has a value of 3-6; the structural formula of the difunctional acrylic modified siloxane compound is shown as follows:
wherein the structural general formula of R is
2. The method for producing a heat-expandable foam microsphere resistant to high temperature and yellowing according to claim 1, wherein the molecular weight of the acrylic modified silicone compound is 1000 to 1500.
3. The method for preparing the high-temperature-resistant yellowing-resistant thermal expansion foaming microsphere according to claim 1, wherein the silica sol is acid nano silica sol or silane modified silica sol.
4. The method for preparing the high-temperature-resistant yellowing-resistant thermal expansion foaming microsphere according to claim 1, wherein the monomer is selected from acrylic ester monomers, acrylic acid monomers or acrylonitrile monomers.
5. The method for preparing the high-temperature-resistant yellowing-resistant thermal expansion foaming microsphere according to claim 1, wherein the initiator is any one or more of peroxyester, dialkyl peroxide, peroxydicarbonate, diacyl peroxide or azo compound.
6. The high-temperature-resistant yellowing-resistant thermal expansion foaming microsphere prepared by the preparation method of any one of claims 1 to 5, wherein a shell material of the high-temperature-resistant yellowing-resistant thermal expansion foaming microsphere is a polymer generated by reaction of a monomer and an acrylic modified siloxane compound, and a core material of the high-temperature-resistant yellowing-resistant thermal expansion foaming microsphere is a foaming agent; wherein the reactive anionic surfactant has at least one vinyl group and the acrylic-modified silicone compound has at least two vinyl groups.
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