CN111040351A - Organic silicon nano zinc oxide double-modified acrylate emulsion and preparation method thereof - Google Patents
Organic silicon nano zinc oxide double-modified acrylate emulsion and preparation method thereof Download PDFInfo
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- CN111040351A CN111040351A CN201911380692.6A CN201911380692A CN111040351A CN 111040351 A CN111040351 A CN 111040351A CN 201911380692 A CN201911380692 A CN 201911380692A CN 111040351 A CN111040351 A CN 111040351A
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 58
- 239000000839 emulsion Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 9
- 239000010703 silicon Substances 0.000 title claims abstract description 9
- -1 zinc oxide double-modified acrylate Chemical class 0.000 title claims abstract description 7
- 238000004945 emulsification Methods 0.000 title description 2
- 239000000178 monomer Substances 0.000 claims abstract description 52
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000003999 initiator Substances 0.000 claims abstract description 29
- 239000008367 deionised water Substances 0.000 claims abstract description 26
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 26
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 16
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 13
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 13
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 11
- 239000006172 buffering agent Substances 0.000 claims abstract description 7
- 230000000977 initiatory effect Effects 0.000 claims abstract description 7
- 239000008267 milk Substances 0.000 claims abstract description 7
- 210000004080 milk Anatomy 0.000 claims abstract description 7
- 235000013336 milk Nutrition 0.000 claims abstract description 7
- 230000033116 oxidation-reduction process Effects 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 31
- SMFFOCYRDBWPIA-UHFFFAOYSA-N N.[O-2].[Zn+2] Chemical compound N.[O-2].[Zn+2] SMFFOCYRDBWPIA-UHFFFAOYSA-N 0.000 claims description 18
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 16
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 239000000872 buffer Substances 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- 235000010352 sodium erythorbate Nutrition 0.000 claims description 4
- 239000004320 sodium erythorbate Substances 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- RBWSWDPRDBEWCR-RKJRWTFHSA-N sodium;(2r)-2-[(2r)-3,4-dihydroxy-5-oxo-2h-furan-2-yl]-2-hydroxyethanolate Chemical compound [Na+].[O-]C[C@@H](O)[C@H]1OC(=O)C(O)=C1O RBWSWDPRDBEWCR-RKJRWTFHSA-N 0.000 claims description 4
- LTIUDPOSFOYSKA-UHFFFAOYSA-N 2-ethenyl-2,4,4,6,6,8,8-heptamethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C=C)O[Si](C)(C)O1 LTIUDPOSFOYSKA-UHFFFAOYSA-N 0.000 claims description 3
- GMGYYSMUGVAJHJ-UHFFFAOYSA-N C=C.CCO[SiH](OCC)OCC Chemical compound C=C.CCO[SiH](OCC)OCC GMGYYSMUGVAJHJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- NELRINSZCVVEAD-UHFFFAOYSA-N chloro-ethenyl-methylsilane Chemical compound C[SiH](Cl)C=C NELRINSZCVVEAD-UHFFFAOYSA-N 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 claims description 3
- 239000005050 vinyl trichlorosilane Substances 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
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 9
- 229910002808 Si–O–Si Inorganic materials 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 2
- 229920002994 synthetic fiber Polymers 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 42
- 239000000203 mixture Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000004383 yellowing Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 102100026735 Coagulation factor VIII Human genes 0.000 description 3
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- XTAARPJDFFXHGH-GRPBBMKTSA-N [(5s,8r,9s,10s,13s,14s,17s)-10,13-dimethyl-3-oxo-1,2,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydrocyclopenta[a]phenanthren-17-yl] propanoate Chemical compound C([C@@H]1CC2)C(=O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H](OC(=O)CC)[C@@]2(C)CC1 XTAARPJDFFXHGH-GRPBBMKTSA-N 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical compound [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses an organic silicon nano zinc oxide double-modified acrylate emulsion and a preparation method thereof, relating to the technical field of polymer synthetic materials. The emulsion is prepared from the following raw materials in parts by mass: 100-200 parts of acrylate monomer, 10-40 parts of vinyl organosilicon monomer, 6-10 parts of emulsifier, 3-10 parts of initiator, 2-6 parts of reducing agent, 1-3 parts of buffering agent, 4-10 parts of ammonia water, 2-6 parts of nano zinc oxide and a proper amount of deionized water; the preparation method comprises the following steps: preparing milk, initiating polymerization, oxidation reduction and modification of nano zinc oxide. According to the invention, vinyl organosilicon monomers and acrylic monomers are firstly subjected to free radical polymerization, Si-O-Si is introduced into polymer molecular chains, then nano zinc oxide is dissolved in ammonia water, the dispersibility of the nano zinc oxide is improved, the nano zinc oxide is added into a polymer and the PH is adjusted, and the nano zinc oxide is filled into a composite material, so that the composite material has excellent heat resistance, water resistance, mechanical properties and other properties.
Description
Technical Field
The invention relates to the technical field of polymer synthetic materials, in particular to an organic silicon nano zinc oxide double-modified acrylate emulsion and a preparation method thereof.
Background
The acrylic ester emulsion has excellent weather resistance, film forming property and caking property, is widely applied in the fields of coatings, adhesives and the like, and has the defects of poor water resistance, wear resistance, mechanical property and the like. The vinyl organosilicon monomer contains Si-O-Si bonds, and has the advantages of excellent flexibility, water resistance, good air permeability and the like. The acrylate and vinyl organosilicon monomers are subjected to emulsion polymerization modification, so that the acrylate and vinyl organosilicon monomers have the excellent performances of both, and have important significance in the use of polymer materials.
The nanometer zinc oxide belongs to semiconductor material, and has the advantages of good chemical stability, strong ultraviolet absorption capacity, thermal property, antistatic property and the like. However, the nano zinc oxide is easy to agglomerate in the polymer and has poor compatibility, thereby limiting the application of the nano material in the polymer. Therefore, it is important to research how to effectively improve various properties of the polymer material by adding the nano material into the polymer emulsion by a suitable and effective method.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides an organosilicon nano zinc oxide double modified acrylate emulsion and a preparation method thereof, and the prepared modified acrylic emulsion has excellent heat resistance, water resistance, mechanical properties and the like.
The invention provides an organic silicon nano zinc oxide double-modified acrylate emulsion which is prepared from the following raw materials in parts by weight: 100-200 parts of acrylate monomer, 10-40 parts of vinyl organosilicon monomer, 6-10 parts of emulsifier, 3-10 parts of initiator, 2-6 parts of reducing agent, 1-3 parts of buffering agent, 4-10 parts of ammonia water, 2-6 parts of nano zinc oxide and a proper amount of deionized water.
Preferably, the acrylate monomer includes a main monomer and a functional monomer; the main monomer is the combination of any two or more of butyl acrylate, ethyl acrylate and methyl methacrylate and any one or more of acrylic acid, methacrylic acid and acrylonitrile; the functional monomer is any one or more of hydroxyethyl acrylate and N-hydroxymethyl acrylamide.
Preferably, the vinyl organosilicon monomer is any one of ethylene triethoxysilane, methyl vinyl chlorosilane, vinyl trichlorosilane and vinyl heptamethylcyclotetrasiloxane.
Preferably, the emulsifier is a combination of one of sodium dodecyl sulfate and sodium dodecyl benzene sulfonate and an emulsifier OP-10;
preferably, the initiator is any one of ammonium persulfate, potassium persulfate and sodium persulfate;
preferably, the reducing agent is any one of N, N-dimethyl-3-hydroxy-3- (2-thiophene) -1-propylamine and sodium erythorbate;
the buffer is any one of sodium bicarbonate and ammonium bicarbonate;
preferably, the mass concentration of the ammonia water is 10-30%;
preferably, the nano zinc oxide is rod-shaped nano zinc oxide, and the particle size is 30-60 nm.
The invention also provides a preparation method of the organic silicon nano zinc oxide double modified acrylate emulsion, which comprises the following steps:
s1, milk making: adding an emulsifier and a buffering agent into a proper amount of deionized water, adding an acrylate monomer and a vinyl organosilicon monomer under stirring to form a milky white state, and stirring to obtain an emulsified mixed monomer solution; adding an initiator into deionized water, and stirring to prepare an initiator solution;
s2, initiating polymerization: dropwise adding an initiator solution into the emulsified mixed monomer solution for emulsion polymerization, and then carrying out heat preservation reaction;
s3, oxidation reduction: cooling the reaction system in the S2, and dropwise adding a reducing agent to eliminate residual monomers in the reaction system;
s4, modifying the nano zinc oxide: adjusting the pH value of ammonia water by using deionized water, heating, adding nano zinc oxide into the ammonia water, stirring to obtain a nano zinc oxide ammonia water solution, dropwise adding the nano zinc oxide ammonia water solution into the emulsion, adjusting the pH value of the system to 8-9, and stirring for reaction to obtain the nano zinc oxide ammonia water solution.
Preferably, in S1, the initiator is added to deionized water, and stirred to prepare an initiator solution with a mass concentration of 10-30%.
Preferably, in S2, the initiator solution is dripped into the emulsified mixed monomer solution for emulsion polymerization, the dripping time is 2-4h, the dripping temperature is 75-85 ℃, and the reaction is carried out for 30-60min after the dripping is finished.
Preferably, in S3, the reaction system in S2 is cooled to 60-70 ℃, a reducing agent is dripped for 30-60min, and residual monomers in the reaction system are eliminated.
Preferably, in S4, deionized water is used for adjusting the pH value of ammonia water to 8-9, the temperature is raised to 50-60 ℃, and nano zinc oxide is added into the ammonia water.
Has the advantages that: the vinyl organic silicon monomer and the nano zinc oxide are adopted to carry out double modification on the acrylate emulsion, firstly, the vinyl organic silicon monomer and the acrylic monomer are subjected to free radical polymerization, Si-O-Si is introduced into a polymer molecular chain, then the nano zinc oxide is dissolved in ammonia water, the dispersibility of the nano zinc oxide is improved, the nano zinc oxide is added into a polymer and the PH is adjusted, and the nano zinc oxide is filled into a composite material, so that the acrylate emulsion has excellent heat resistance, water resistance, mechanical property and the like.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
An organosilicon nano zinc oxide double modified acrylate emulsion, the preparation method comprises the following steps:
s1, milk making: adding 4 parts of SDS (sodium dodecyl sulfate) emulsifier, 2 parts of OP-10 and 2 parts of sodium bicarbonate serving as a buffering agent into 220 parts of deionized water, adding 70 parts of BA, 40 parts of EA, 10 parts of MMA, 5 parts of AN, 8 parts of AA, 12 parts of HEMA, 3 parts of N-MAM and 15 parts of vinyl trichlorosilane in a milky state, and quickly stirring for 20min to obtain AN emulsified mixed monomer solution; adding 3 parts of initiator potassium persulfate into 8 parts of deionized water, and stirring to prepare an initiator solution;
s2, initiating polymerization: dropwise adding an initiator solution into the emulsified mixed monomer solution for emulsion polymerization, wherein the dropwise adding time is 2 hours, the dropwise adding temperature is 75 ℃, and after dropwise adding, carrying out heat preservation reaction for 30 min;
s3, oxidation reduction: cooling the reaction system in the S2 to 60 ℃, dropwise adding 2 parts of reducing agent DHTP for 30min, and eliminating residual monomers in the reaction system;
s4, modifying the nano zinc oxide: adding 10 parts of 10% ammonia water into 20 parts of deionized water, stirring and mixing, heating to 50 ℃, adding 6 parts of nano zinc oxide into the mixture, stirring for 60min to obtain a nano zinc oxide ammonia water solution, dropwise adding the nano zinc oxide ammonia water solution into the emulsion, adjusting the pH value of the system to 8, and stirring for reaction to obtain the nano zinc oxide ammonia water solution.
Example 2
An organosilicon nano zinc oxide double modified acrylate emulsion, the preparation method comprises the following steps:
s1, milk making: adding 7 parts of emulsifier sodium dodecyl benzene sulfonate, 3 parts of emulsifier OP-10 and 3 parts of buffering agent ammonium bicarbonate into 270 parts of deionized water, adding 60 parts of BA, 40 parts of EA, 20 parts of MMA, 15 parts of MAA, 16 parts of HEMA, 1 part of N-MAM and 25 parts of ethylene triethoxysilane when stirring to be in a milky white state, and quickly stirring for 30min to obtain an emulsified mixed monomer solution; adding 7 parts of initiator ammonium persulfate into 25 parts of deionized water, and stirring to prepare an initiator solution;
s2, initiating polymerization: dropwise adding an initiator solution into the emulsified mixed monomer solution for emulsion polymerization, wherein the dropwise adding time is 4 hours, the dropwise adding temperature is 85 ℃, and after dropwise adding, carrying out heat preservation reaction for 60 min;
s3, oxidation reduction: cooling the reaction system in the S2 to 70 ℃, and dropwise adding 6 parts of reducing agent sodium erythorbate for 60min to eliminate residual monomers in the reaction system;
s4, modifying the nano zinc oxide: adding 4 parts of 30% ammonia water into 10 parts of deionized water, stirring and mixing, heating to 60 ℃, adding 2 parts of nano zinc oxide into the mixture, stirring for 60min to obtain a nano zinc oxide ammonia water solution, dropwise adding the nano zinc oxide ammonia water solution into the emulsion, adjusting the pH value of the system to 9, and stirring for reaction to obtain the nano zinc oxide ammonia water solution.
Example 3
An organosilicon nano zinc oxide double modified acrylate emulsion, the preparation method comprises the following steps:
s1, milk making: adding 5 parts of emulsifier sodium dodecyl benzene sulfonate, 2 parts of emulsifier OP-10 and 2 parts of buffer sodium bicarbonate into 300 parts of deionized water, adding 40 parts of BA, 20 parts of EA, 90 parts of MMA, 20 parts of MAA, 10 parts of HEMA, 4 parts of N-MAM and 40 parts of methyl vinyl chlorosilane into the mixture under the condition of stirring the mixture into milk white, and quickly stirring the mixture for 25min to obtain an emulsified mixed monomer solution; adding 4 parts of initiator sodium persulfate into 12 parts of deionized water, and stirring to prepare an initiator solution;
s2, initiating polymerization: dropwise adding the initiator solution into the emulsified mixed monomer solution for emulsion polymerization, wherein the dropwise adding time is 2.5h, the dropwise adding temperature is 80 ℃, and after the dropwise adding is finished, carrying out heat preservation reaction for 40 min;
s3, oxidation reduction: cooling the reaction system in the S2 to 65 ℃, and dropwise adding 3 parts of reducing agent sodium erythorbate for 40min to eliminate residual monomers in the reaction system;
s4, modifying the nano zinc oxide: adding 6 parts of 20% ammonia water into 8 parts of deionized water, stirring and mixing, heating to 55 ℃, adding 3 parts of nano zinc oxide into the mixture, stirring for 60min to obtain a nano zinc oxide ammonia water solution, dropwise adding the nano zinc oxide ammonia water solution into the emulsion, adjusting the pH value of the system to 8.5, and stirring for reaction to obtain the nano zinc oxide ammonia water solution.
Example 4
An organosilicon nano zinc oxide double modified acrylate emulsion, the preparation method comprises the following steps:
s1, milk making: adding 6 parts of emulsifier SDS, 3 parts of emulsifier OP-10 and 2 parts of buffer ammonium bicarbonate into 240 parts of deionized water, adding 40 parts of BA, 20 parts of EA, 100 parts of MMA, 10 parts of AA, 8 parts of N-MAM and 35 parts of vinyl heptamethylcyclotetrasiloxane under stirring to form milky white, and quickly stirring for 30min to obtain an emulsified mixed monomer solution; adding 4 parts of initiator sodium persulfate into 15 parts of deionized water, and stirring to prepare an initiator solution;
s2, initiating polymerization: dropwise adding an initiator solution into the emulsified mixed monomer solution for emulsion polymerization, wherein the dropwise adding time is 3 hours, the dropwise adding temperature is 80 ℃, and after the dropwise adding is finished, the heat preservation reaction is carried out for 50 min;
s3, oxidation reduction: cooling the reaction system in S2 to 65 ℃, dropwise adding 3 parts of reducing agent DHTP for 50min, and eliminating residual monomers in the reaction system;
s4, modifying the nano zinc oxide: adding 4 parts of 30% ammonia water into 10 parts of deionized water, stirring and mixing, heating to 60 ℃, adding 2 parts of nano zinc oxide into the mixture, stirring for 60min to obtain a nano zinc oxide ammonia water solution, dropwise adding the nano zinc oxide ammonia water solution into the emulsion, adjusting the pH value of the system to 8.5, and stirring for reaction to obtain the nano zinc oxide ammonia water solution.
Comparative example
Compared with the embodiment 4, the difference is that the nano zinc oxide is dispersed in water in S4, and the pH of the system is adjusted to 8.5 by 10% sodium hydroxide solution, and the rest is unchanged; the specific step S4 is: dispersing 2 parts of nano zinc oxide in 14 parts of deionized water, stirring for 60min to obtain a nano zinc oxide aqueous solution, dropwise adding the nano zinc oxide aqueous solution into the emulsion, adjusting the pH of the system to 8.5 by adopting a 10% sodium hydroxide solution, and stirring for reaction to obtain the nano zinc oxide emulsion.
The modified acrylate emulsions prepared in examples 1 to 4 of the present invention and comparative example were tested for their properties, and the results are shown in Table 1.
And (3) testing items: a. tensile strength: testing according to GB/T1040-92
b. Testing the aging resistance of the adhesive film: coating a proper amount of the emulsion on a tetrafluoro plate, forming a film for 48 hours at the room temperature of 25 ℃, and then continuously drying for 12 hours in a drying oven at the temperature of 60 ℃. The film is cut into 20X20cm and is placed under an ultraviolet lamp for irradiation for 120h, and the appearance phenomena of crack, yellowing and the like of the adhesive film are taken as the investigation indexes.
c. And (3) testing water resistance: coating the emulsion on a tetrafluoro plate, forming a film for 48 hours at the room temperature of 25 ℃, and continuously drying for 12 hours in a drying oven at the temperature of 60 ℃. The coating film was cut into 5cm × 5cm samples, weighed (W1), soaked in distilled water for 24 hours, taken out, surface water was removed by suction with filter paper, and weighed (W2). The water absorption calculation formula is as follows: water absorption rate was (W2-W1)/W1 × 100%.
TABLE 1 data for performance testing in examples 1-4 and comparative examples
| Item | Tensile strength/MPa | Aging resistance | Water absorption rate |
| Example 1 | 6MPa | No yellowing and crack | 8％ |
| Example 2 | 5MPa | Slight yellowing and no crack | 10％ |
| Example 3 | 8MPa | No yellowing and crack | 11％ |
| Example 4 | 9MPa | No yellowing and crack | 9％ |
| Comparative example | 2MPa | Partial yellowing and cracking | 15％ |
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. The organic silicon nano zinc oxide double-modified acrylate emulsion is characterized by being prepared from the following raw materials in parts by mass: 100-200 parts of acrylate monomer, 10-40 parts of vinyl organosilicon monomer, 6-10 parts of emulsifier, 3-10 parts of initiator, 2-6 parts of reducing agent, 1-3 parts of buffering agent, 4-10 parts of ammonia water, 2-6 parts of nano zinc oxide and a proper amount of deionized water.
2. The silicone nano zinc oxide double modified acrylate emulsion of claim 1 wherein the acrylate monomers comprise a main monomer and a functional monomer; the main monomer is the combination of any two or more of butyl acrylate, ethyl acrylate and methyl methacrylate and any one or more of acrylic acid, methacrylic acid and acrylonitrile; the functional monomer is any one or more of hydroxyethyl acrylate and N-hydroxymethyl acrylamide.
3. The organosilicon nano-zinc oxide double modified acrylate emulsion according to claim 1 or 2, wherein the vinyl organosilicon monomer is any one of ethylene triethoxysilane, methyl vinyl chlorosilane, vinyl trichlorosilane, and vinyl heptamethylcyclotetrasiloxane.
4. The organosilicon nano zinc oxide double modified acrylate emulsion according to any one of claims 1 to 3, wherein the emulsifier is a combination of one of sodium dodecyl sulfate and sodium dodecyl benzene sulfonate and an emulsifier OP-10;
preferably, the initiator is any one of ammonium persulfate, potassium persulfate and sodium persulfate;
preferably, the reducing agent is any one of N, N-dimethyl-3-hydroxy-3- (2-thiophene) -1-propylamine and sodium erythorbate;
the buffer is any one of sodium bicarbonate and ammonium bicarbonate.
5. The organosilicon nano-zinc oxide double modified acrylate emulsion according to any one of claims 1 to 4, wherein the mass concentration of the ammonia water is 10 to 30%;
preferably, the nano zinc oxide is rod-shaped nano zinc oxide, and the particle size is 30-60 nm.
6. The preparation method of the organosilicon nano zinc oxide double modified acrylate emulsion based on any one of claims 1 to 5 is characterized by comprising the following steps:
s1, milk making: adding an emulsifier and a buffering agent into a proper amount of deionized water, adding an acrylate monomer and a vinyl organosilicon monomer under stirring to form a milky white state, and stirring to obtain an emulsified mixed monomer solution; adding an initiator into deionized water, and stirring to prepare an initiator solution;
s2, initiating polymerization: dropwise adding an initiator solution into the emulsified mixed monomer solution for emulsion polymerization, and then carrying out heat preservation reaction;
s3, oxidation reduction: cooling the reaction system in the S2, and dropwise adding a reducing agent to eliminate residual monomers in the reaction system;
s4, modifying the nano zinc oxide: adjusting the pH value of ammonia water by using deionized water, heating, adding nano zinc oxide into the ammonia water, stirring to obtain a nano zinc oxide ammonia water solution, dropwise adding the nano zinc oxide ammonia water solution into the emulsion, adjusting the pH value of the system to 8-9, and stirring for reaction to obtain the nano zinc oxide ammonia water solution.
7. The method for preparing the organosilicon nano-zinc oxide double modified acrylate emulsion according to claim 6, wherein in S1, the initiator is added into deionized water, and stirring is carried out to prepare an initiator solution with a mass concentration of 10-30%.
8. The preparation method of the organosilicon nano-zinc oxide double modified acrylate emulsion according to claim 6 or 7, characterized in that in S2, the initiator solution is dripped into the emulsified mixed monomer solution for emulsion polymerization, the dripping time is 2-4h, the dripping temperature is 75-85 ℃, and the reaction is carried out for 30-60min after the dripping.
9. The method for preparing the organosilicon nano-zinc oxide double modified acrylate emulsion according to any one of claims 6 to 8, wherein in S3, the reaction system in S2 is cooled to 60 to 70 ℃, a reducing agent is added dropwise for 30 to 60min, and residual monomers in the reaction system are eliminated.
10. The method for preparing the organosilicon nano-zinc oxide double modified acrylate emulsion according to any one of claims 6 to 9, wherein in S4, deionized water is used to adjust the pH of ammonia water to 8-9, the temperature is raised to 50-60 ℃, and nano-zinc oxide is added into the ammonia water.
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