CN117069886A - Biological enzyme catalyzed aqueous acrylic ester emulsion and preparation method thereof - Google Patents
Biological enzyme catalyzed aqueous acrylic ester emulsion and preparation method thereof Download PDFInfo
- Publication number
- CN117069886A CN117069886A CN202311079730.0A CN202311079730A CN117069886A CN 117069886 A CN117069886 A CN 117069886A CN 202311079730 A CN202311079730 A CN 202311079730A CN 117069886 A CN117069886 A CN 117069886A
- Authority
- CN
- China
- Prior art keywords
- parts
- emulsion
- enzyme
- bio
- emulsifier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000839 emulsion Substances 0.000 title claims abstract description 114
- -1 acrylic ester Chemical class 0.000 title claims abstract description 34
- 108090000790 Enzymes Proteins 0.000 title claims abstract description 21
- 102000004190 Enzymes Human genes 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 238000004945 emulsification Methods 0.000 title description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 239000012874 anionic emulsifier Substances 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 239000007800 oxidant agent Substances 0.000 claims abstract description 12
- 239000000080 wetting agent Substances 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 11
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 7
- 239000012875 nonionic emulsifier Substances 0.000 claims abstract description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 7
- 239000006172 buffering agent Substances 0.000 claims abstract description 5
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 5
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 23
- 108010001336 Horseradish Peroxidase Proteins 0.000 claims description 21
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical group CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 16
- 239000003995 emulsifying agent Substances 0.000 claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 239000011734 sodium Substances 0.000 claims description 14
- 229910052708 sodium Inorganic materials 0.000 claims description 14
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 12
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000013530 defoamer Substances 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical group [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 claims description 2
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000872 buffer Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000002480 mineral oil Substances 0.000 claims description 2
- 235000010446 mineral oil Nutrition 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 9
- 150000002500 ions Chemical class 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 230000032683 aging Effects 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- RZXLPPRPEOUENN-UHFFFAOYSA-N Chlorfenson Chemical compound C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C=C1 RZXLPPRPEOUENN-UHFFFAOYSA-N 0.000 description 10
- 239000003999 initiator Substances 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- 230000000977 initiatory effect Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 2
- 240000003291 Armoracia rusticana Species 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 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 description 1
- 235000011330 Armoracia rusticana Nutrition 0.000 description 1
- 102000003886 Glycoproteins Human genes 0.000 description 1
- 108090000288 Glycoproteins Proteins 0.000 description 1
- 108010044467 Isoenzymes Proteins 0.000 description 1
- 102000003992 Peroxidases Human genes 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007863 gel particle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 108040007629 peroxidase activity proteins Proteins 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Classifications
-
- 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
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
-
- 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
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (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
- C08F4/00—Polymerisation catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention provides a biological enzyme catalysis aqueous acrylic ester emulsion and a preparation method thereof, wherein the biological enzyme catalysis aqueous acrylic ester emulsion comprises the following components in parts by weight: 80 to 200 parts of vinyl monomer, 0.2 to 2.4 parts of reactive anionic emulsifier, 0.1 to 1.2 parts of reactive nonionic emulsifier, 0.5 to 3 parts of anionic emulsifier, 0.003 to 0.05 part of biological enzyme, 0.01 to 0.3 part of oxidant, 0.02 to 0.6 part of reducing agent, 0.01 to 0.06 part of defoaming agent, 0.01 to 0.05 part of wetting agent, 100 to 300 parts of deionized water, 0.2 to 6 parts of buffering agent and 0.2 to 7 parts of pH regulator. According to the bio-enzyme catalyzed aqueous acrylate emulsion and the preparation method thereof, the aqueous acrylate emulsion polymerization is initiated by adopting an HRP enzyme catalysis technology, the raw material source is environment-friendly, the HRP enzyme has no corrosiveness and strong oxidability, the storage and transportation performances are safer, the preparation process can be initiated at low temperature, the energy consumption is low, the ion content in the emulsion polymerization is effectively reduced, the water resistance and ageing resistance of the aqueous acrylate emulsion after film formation are improved, and a more environment-friendly and safe technical route is provided for the industrial production of the emulsion.
Description
Technical Field
The invention relates to the technical field of a method for preparing aqueous acrylic ester emulsion, in particular to a biological enzyme catalysis aqueous acrylic ester emulsion and a preparation method thereof.
Background
At present, in the industrial production of acrylic ester emulsion, two main types of traditional initiators can be used for emulsion polymerization, one type is a thermal decomposition initiator such as sodium persulfate, ammonium persulfate and the like, the other type is a redox system initiator such as a potassium persulfate-ferrous chloride system, a potassium persulfate-sodium bisulfite system and the like, and the two types of initiator systems have low cost and mature use technology process and are favored by the market.
However, during the emulsion production process, as the polymerization proceeds, the conventional initiator is decomposed and generates a large amount of ions, which remain in the emulsion. The existence of a large amount of ions can have adverse effects on the water resistance, ageing resistance and other properties of the emulsion after the emulsion is dried to form a film. In addition, for acrylate emulsion polymerization, the proper initiation temperature of persulfate is usually high, the energy consumption is high, and the cost is not neglected for industrial production. Meanwhile, the persulfate initiator is a strong oxidative solid and is easy to explode when being subjected to high heat or impact, and has certain danger in the transportation and storage processes.
Horseradish peroxidase (HRP) is a widely used peroxidase preparation with a high content, commercialized earlier, and exists in the tubers of horseradish plants. HRP enzyme is not a pure enzyme preparation, but a glycoprotein complex enzyme consisting of multiple isoenzymes in horseradish roots. The HRP enzyme provides a novel technical direction in the field of preparing green and safe aqueous acrylate emulsion.
Disclosure of Invention
The invention aims to disclose a biological enzyme catalyzed aqueous acrylic ester emulsion, which adopts an HRP enzyme catalysis technology to initiate aqueous acrylic ester emulsion polymerization, has the advantages of environment-friendly raw material source, no corrosiveness and strong oxidizing property of HRP enzyme, safer storage and transportation property, low energy consumption, effective reduction of ion content in emulsion polymerization, improvement of water resistance and aging resistance of aqueous acrylic ester emulsion after film formation, and provides a more environment-friendly and safer technical route for emulsion industrial production.
In order to achieve the aim, the invention provides a bio-enzyme catalyzed aqueous acrylic ester emulsion which comprises the following components in parts by weight: 80 to 200 parts of vinyl monomer, 0.2 to 2.4 parts of reactive anionic emulsifier, 0.1 to 1.2 parts of reactive nonionic emulsifier, 0.5 to 3 parts of anionic emulsifier, 0.003 to 0.05 part of biological enzyme, 0.01 to 0.3 part of oxidant, 0.02 to 0.6 part of reducing agent, 0.01 to 0.06 part of defoaming agent, 0.01 to 0.05 part of wetting agent, 100 to 300 parts of deionized water, 0.2 to 6 parts of buffering agent and 0.2 to 7 parts of pH regulator.
In some embodiments, the vinyl-based monomer is one or more of a (meth) acrylate or (meth) acrylic acid or (meth) styrene containing a vinyl functional group.
In some embodiments, the reactive anionic emulsifier is sodium allyl ether sulfonate; the reactive nonionic emulsifier is allyloxy nonylphenoxypropanol polyoxyethylene ether; the anionic emulsifier is one or more of sodium lauryl sulfate or ethoxylated alkylphenol sulfate.
In some embodiments, the biological enzyme is horseradish peroxidase HRP.
In some embodiments, the oxidizing agent is a 30% strength hydrogen peroxide solution; the reducing agent is acetylacetone; the defoamer is one or more of mineral oil or polyether modified organic silicon; the wetting agent is dioctyl sodium sulfonate; the buffer is disodium hydrogen phosphate or sodium bicarbonate; the pH regulator is ammonia water or 2-amino-2-methyl-1-propanol.
The invention also aims to disclose a preparation method of the aqueous acrylic ester emulsion catalyzed by biological enzyme, which adopts an HRP enzyme catalysis technology to initiate the polymerization of the aqueous acrylic ester emulsion, has the advantages of environment-friendly raw material source, no corrosiveness and strong oxidizing property of the HRP enzyme, safer storage and transportation property, low energy consumption in the preparation process, effective reduction of ion content in emulsion polymerization, improvement of water resistance and ageing resistance of the aqueous acrylic ester emulsion after film formation, and provides a more environment-friendly and safer technical route for the industrial production of the emulsion.
In order to achieve the above purpose, the invention provides a preparation method of a bio-enzyme catalyzed aqueous acrylic ester emulsion, which comprises the following steps:
(1) adding 0.1-1.8 parts of reactive anionic emulsifier, 0.1-0.8 part of reactive nonionic emulsifier, 0.5-2.4 parts of anionic emulsifier and 0.003-0.05 part of HRP enzyme into 50-150 parts of deionized water, and stirring to obtain an emulsifier aqueous solution; adding 80-200 parts of acrylate monomer, 1-6 parts of acrylic acid monomer and 0.02-0.6 part of reducing agent into the obtained emulsifier aqueous solution, and stirring for 40-45 min to obtain pre-emulsion A;
(2) adding the rest of emulsifying agent, 0.2-6 parts of buffering agent and 50-110 parts of deionized water into a four-neck flask, uniformly dissolving, heating to 40-45 ℃, injecting 1-10% by weight of pre-emulsion A prepared in the step (1) and 10-20% by weight of oxidizing agent, and reacting for 40-60 min to prepare seed emulsion B;
(3) after the heat preservation reaction is finished, the residual pre-emulsion A and the residual oxidant are simultaneously dripped into the seed emulsion B, the dripping time of the pre-emulsion is 3-4 h, the dripping time of the oxidant is 50-60 min, the temperature is controlled at 40-45 ℃, after the dripping is finished, the heat preservation is carried out for 2h, and then the temperature is reduced to 30 ℃;
(4) when the temperature is reduced to below 30 ℃, 0.2-7 parts of pH regulator is added, the pH is regulated to 7-7.5, then 0.01-0.06 parts of defoamer and 0.01-0.05 parts of wetting agent are added, the mixture is stirred for 20-30 min until the emulsion is uniform, and the mixture is filtered and discharged, thus obtaining the bio-enzyme catalyzed aqueous acrylate emulsion.
In some embodiments, in step (1), the stirring speed is 800 to 2000r/min, and in steps (2) to (4), the stirring speed is 150 to 200r/min.
Compared with the prior art, the invention has the beneficial effects that: according to the bio-enzyme catalyzed aqueous acrylate emulsion and the preparation method thereof, the aqueous acrylate emulsion polymerization is initiated by adopting an HRP enzyme catalysis technology, the raw material source is environment-friendly, the HRP enzyme has no corrosiveness and strong oxidability, the storage and transportation performances are safer, the preparation process can be initiated at low temperature, the energy consumption is low, the ion content in the emulsion polymerization is effectively reduced, the water resistance and ageing resistance of the aqueous acrylate emulsion after film formation are improved, and a more environment-friendly and safe technical route is provided for the industrial production of the emulsion.
Detailed Description
The present invention will be described in detail with reference to the following embodiments, but it should be understood that these embodiments are not limiting, and functional, method, or structural equivalents and alternatives thereof by those skilled in the art are within the scope of the present invention.
Example 1
The embodiment discloses a bio-enzyme catalyzed aqueous acrylic ester emulsion and a preparation method thereof, comprising the following steps:
(1) adding 0.6g of sodium allylpolyoxyethylene ether sulfonate, 0.2g of allyloxy nonylphenoxypropanol polyoxyethylene ether, 1.4g of sodium lauryl sulfate and 0.008 part of HRP enzyme into 80g of deionized water, and stirring to obtain an emulsifier aqueous solution; in the aqueous emulsifier solution obtained, 48g of butyl acrylate, 62g of isooctyl acrylate, 2.1g of methacrylic acid, 2.3g of hydroxybutyl acrylate, 3.2g of methyl acrylate and 0.1g of acetylacetone were stirred at a speed of 1500r/min for 15min to obtain a pre-emulsion A.
(2) Adding 0.1g of sodium allyl polyoxyethylene ether sulfonate, 0.3g of sodium lauryl sulfate, 1.2 parts of disodium hydrogen phosphate and 60 parts of deionized water into a four-neck flask, stirring for dissolution, wherein the stirring speed is 180r/min, introducing nitrogen for deoxidization, heating to 45 ℃, injecting 4% by weight of pre-emulsion A prepared in the step (1) and 0.1g of hydrogen peroxide solution, and reacting for 50min to prepare the seed emulsion B.
(3) After the heat preservation reaction is finished, the residual pre-emulsion A and 0.3g of hydrogen peroxide solution are simultaneously dripped into the seed emulsion B, the dripping time of the pre-emulsion is 4 hours, the dripping time of the hydrogen peroxide solution is 50 minutes, and the temperature is controlled at 45 ℃. After the dripping is finished, the temperature is kept for 2 hours, and then the temperature is reduced by 30 ℃.
(4) When the temperature is reduced to below 30 ℃, ammonia water is added to adjust the pH value to 7-7.5, then 0.02 part of defoamer and 0.01 part of wetting agent are added, the mixture is stirred for 20min until the emulsion is uniform, and the mixture is filtered and discharged, thus obtaining the bio-enzyme catalytic aqueous acrylate emulsion.
Example 2
The embodiment discloses a bio-enzyme catalyzed aqueous acrylic ester emulsion and a preparation method thereof, comprising the following steps:
(1) adding 0.4g of sodium allylpolyoxyethylene ether sulfonate, 0.2g of allyloxy nonylphenoxypropanol polyoxyethylene ether, 1.8g of sodium lauryl sulfate and 0.012 part of HRP enzyme into 80g of deionized water, and stirring to obtain an emulsifier aqueous solution; in the aqueous emulsifier solution obtained, 48g of butyl acrylate, 12g of isooctyl acrylate, 1.5g of acrylic acid, 2.3g of hydroxybutyl acrylate, 34.1g of methyl methacrylate, 20g of styrene and 0.15g of acetylacetone were stirred at a speed of 1500r/min for 15min to prepare a pre-emulsion A.
(2) Adding 0.1g of sodium allyl polyoxyethylene ether sulfonate, 0.3g of sodium lauryl sulfate, 1.2 parts of disodium hydrogen phosphate and 60 parts of deionized water into a four-neck flask, stirring for dissolution, wherein the stirring speed is 180r/min, introducing nitrogen for deoxidization, heating to 45 ℃, injecting 4% by weight of pre-emulsion A prepared in the step (1) and 0.1g of hydrogen peroxide solution, and reacting for 50min to prepare the seed emulsion B.
(3) After the heat preservation reaction is finished, the residual pre-emulsion A and 0.3g of hydrogen peroxide solution are simultaneously dripped into the seed emulsion B, the dripping time of the pre-emulsion is 4 hours, the dripping time of the hydrogen peroxide solution is 50 minutes, and the temperature is controlled at 45 ℃. After the dripping is finished, the temperature is kept for 2 hours, and then the temperature is reduced by 30 ℃.
(4) When the temperature is reduced to below 30 ℃, ammonia water is added to adjust the pH value to 7-7.5, then 0.02 part of defoamer and 0.01 part of wetting agent are added, the mixture is stirred for 20min until the emulsion is uniform, and the mixture is filtered and discharged, thus obtaining the bio-enzyme catalytic aqueous acrylate emulsion.
Example 3
The embodiment discloses a bio-enzyme catalyzed aqueous acrylic ester emulsion and a preparation method thereof, comprising the following steps:
(1) adding 0.6g of sodium allylpolyoxyethylene ether sulfonate, 0.2g of allyloxy nonylphenoxy propanol polyoxyethylene ether, 1.6g of ethoxylated alkylphenol sodium sulfate and 0.008 part of HRP enzyme into 80g of deionized water, and stirring to obtain an emulsifier aqueous solution; in the aqueous emulsifier solution obtained, 80g of butyl acrylate, 1.2g of acrylic acid, 2.1g of hydroxyethyl acrylate, 34.3g of methyl methacrylate and 0.1g of acetylacetone were stirred at a speed of 1500r/min for 15min to obtain a pre-emulsion A.
(2) Adding 0.1g of sodium allyl polyoxyethylene ether sulfonate, 0.3g of ethoxylated alkyl phenol sodium sulfate, 1.2 parts of disodium hydrogen phosphate and 60 parts of deionized water into a four-neck flask, stirring and dissolving, wherein the stirring speed is 180r/min, introducing nitrogen to deoxidize and heating to 45 ℃, injecting 4% by weight of pre-emulsion A prepared in the step (1) and 0.1g of hydrogen peroxide solution, and reacting for 50min to prepare the seed emulsion B.
(3) After the heat preservation reaction is finished, the residual pre-emulsion A and 0.3g of hydrogen peroxide solution are simultaneously dripped into the seed emulsion B, the dripping time of the pre-emulsion is 4 hours, the dripping time of the hydrogen peroxide solution is 50 minutes, and the temperature is controlled at 45 ℃. After the dripping is finished, the temperature is kept for 2 hours, and then the temperature is reduced by 30 ℃.
(4) When the temperature is reduced to below 30 ℃, ammonia water is added to adjust the pH value to 7-7.5, then 0.02 part of defoamer and 0.01 part of wetting agent are added, the mixture is stirred for 20min until the emulsion is uniform, and the mixture is filtered and discharged, thus obtaining the bio-enzyme catalytic aqueous acrylate emulsion.
Example 4
The embodiment discloses a bio-enzyme catalyzed aqueous acrylic ester emulsion and a preparation method thereof, comprising the following steps:
(1) adding 0.4g of sodium allylpolyoxyethylene ether sulfonate, 0.2g of allyloxy nonylphenoxy propanol polyoxyethylene ether, 1.2g of ethoxylated alkylphenol sodium sulfate and 0.012 part of HRP enzyme into 80g of deionized water, and stirring to obtain an emulsifier aqueous solution; in the aqueous emulsifier solution obtained, 85g of butyl acrylate, 1.2g of acrylic acid, 2.1g of hydroxyethyl acrylate, 24.3g of methyl methacrylate, 5g of glycidyl methacrylate and 0.15g of acetylacetone were stirred at a speed of 1500r/min for 15min to obtain a pre-emulsion A.
(2) Adding 0.1g of sodium allyl polyoxyethylene ether sulfonate, 0.3g of ethoxylated alkyl phenol sodium sulfate, 1.2 parts of disodium hydrogen phosphate and 60 parts of deionized water into a four-neck flask, stirring and dissolving, wherein the stirring speed is 180r/min, introducing nitrogen to deoxidize and heating to 45 ℃, injecting 4% by weight of pre-emulsion A prepared in the step (1) and 0.1g of hydrogen peroxide solution, and reacting for 50min to prepare the seed emulsion B.
(3) After the heat preservation reaction is finished, the residual pre-emulsion A and 0.3g of hydrogen peroxide solution are simultaneously dripped into the seed emulsion B, the dripping time of the pre-emulsion is 4 hours, the dripping time of the hydrogen peroxide solution is 50 minutes, and the temperature is controlled at 45 ℃. After the dripping is finished, the temperature is kept for 2 hours, and then the temperature is reduced by 30 ℃.
(4) When the temperature is reduced to below 30 ℃, ammonia water is added to adjust the pH value to 7-7.5, then 0.02 part of defoamer and 0.01 part of wetting agent are added, the mixture is stirred for 20min until the emulsion is uniform, and the mixture is filtered and discharged, thus obtaining the bio-enzyme catalytic aqueous acrylate emulsion.
The HRP enzyme alone does not have the property of catalyzing synthesis and must be added with H 2 O 2 Beta-diketones such as acetylacetone (ACAC) as oxidizing agents and reducing substrates]As an initiator, an enzyme redox catalytic system is formed, so that active free radicals can be generated and polymerization of monomers can be initiated.
Comparative example
(1) Adding 0.4g of sodium allylpolyoxyethylene ether sulfonate, 0.2g of allyloxy nonylphenoxy propanol polyoxyethylene ether and 1.2g of ethoxylated alkylphenol sodium sulfate into 80g of deionized water, and stirring to obtain an emulsifier aqueous solution; in the obtained aqueous emulsifier solution, 85g of butyl acrylate, 1.2g of acrylic acid, 2.1g of hydroxyethyl acrylate, 24.3g of methyl methacrylate and 5g of glycidyl methacrylate were stirred at a speed of 1500r/min for 15min to obtain a pre-emulsion A, and then 0.6g of ammonium persulfate was added to the pre-emulsion and stirred uniformly for use.
(2) Adding 0.1g of sodium allyl polyoxyethylene ether sulfonate, 0.3g of ethoxylated alkyl phenol sodium sulfate, 0.2 part of ammonium persulfate and 60 parts of deionized water into a four-neck flask, stirring for dissolution, wherein the stirring speed is 180r/min, introducing nitrogen for deoxidization, heating to 82 ℃, injecting 4% by weight of pre-emulsion A prepared in the step (1), and reacting for 30min to prepare seed emulsion B.
(3) After the heat preservation reaction is finished, the residual pre-emulsion A and the seed emulsion B are simultaneously dripped into the seed emulsion B, the pre-emulsion is dripped for 2 hours, and the temperature is controlled at 82 ℃. After the dripping is finished, the temperature is kept for 2 hours, and then the temperature is reduced by 50 ℃.
(4) When the temperature is reduced to below 50 ℃, ammonia water is added to adjust the pH value to 7-7.5, then 0.02 part of defoamer and 0.01 part of wetting agent are added, the mixture is stirred for 20 minutes until the emulsion is uniform, and the mixture is filtered and discharged to obtain the traditional acrylate emulsion.
The testing method comprises the following steps:
the emulsion state is visually detected;
emulsion gel amount: filtering by adopting a 200-mesh filter screen, and drying gel particles to constant weight for weighing;
emulsion solids content: emulsion solids contentM1 is the mass of the dried sample, and M0 is the mass of the emulsion before drying;
monomer conversion: monomer conversionS1 is the actual solid content of the emulsion, S0 is the actual solid content of the emulsion;
emulsion particle size: testing by using a Markov laser particle sizer;
waterproof performance, coating the emulsion on a 25-um PET substrate by using a 20-um silk stick, drying at 80 ℃ for 5min, coating a release film, and curing for 24h in a 50 ℃ oven. After curing, the film is put into warm water for 3 hours, and the whitening state of the film is observed and recorded.
The test results obtained are given in the following table:
from the results of examples and comparative examples, the gel amount, emulsion solid content, monomer conversion rate and particle size of the acrylate emulsion prepared by the HRP enzyme catalytic system of the invention are not much different from those of the acrylate emulsion prepared by the traditional initiator; in terms of water resistance, the HRP enzyme initiation system can generate less ions, so that the water resistance of the emulsion after film formation is obviously improved. Therefore, the HRP enzyme has good technical and technological base in the aspect of replacing the traditional initiation system, and a more green and efficient technical route is provided for the field of synthesizing the aqueous acrylic ester emulsion.
According to the bio-enzyme catalyzed aqueous acrylic ester emulsion and the preparation method thereof, the sources of the raw materials of the initiation system are green and environment-friendly, and compared with the traditional persulfate initiator, the bio-enzyme catalyzed aqueous acrylic ester emulsion has no corrosiveness and strong oxidizing property, and has safer storage and transportation property. In addition, the traditional initiator has higher initiation temperature, long heating time and higher energy consumption, and the biological enzyme initiation system is adopted, the preparation process can be initiated at low temperature, the energy consumption is lower, ions are not generated in the polymerization process, and the water resistance and ageing resistance of the emulsion after film formation are improved. Therefore, the biological enzyme high-efficiency catalytic system introduced by the invention provides a new technology and process route for preparing the aqueous acrylic ester emulsion.
The above list of detailed descriptions is only specific to practical embodiments of the present invention, and they are not intended to limit the scope of the present invention, and all equivalent embodiments or modifications that do not depart from the spirit of the present invention should be included in the scope of the present invention.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (7)
1. The bio-enzyme catalyzed aqueous acrylic ester emulsion is characterized by comprising the following components in parts by weight: 80 to 200 parts of vinyl monomer, 0.2 to 2.4 parts of reactive anionic emulsifier, 0.1 to 1.2 parts of reactive nonionic emulsifier, 0.5 to 3 parts of anionic emulsifier, 0.003 to 0.05 part of biological enzyme, 0.01 to 0.3 part of oxidant, 0.02 to 0.6 part of reducing agent, 0.01 to 0.06 part of defoaming agent, 0.01 to 0.05 part of wetting agent, 100 to 300 parts of deionized water, 0.2 to 6 parts of buffering agent and 0.2 to 7 parts of pH regulator.
2. The aqueous acrylate emulsion catalyzed by biological enzymes according to claim 1 wherein the vinyl monomer is one or more of (meth) acrylate or (meth) acrylic acid or (meth) styrene containing vinyl functionality.
3. The bio-enzyme catalyzed aqueous acrylate emulsion according to claim 1 wherein the reactive anionic emulsifier is sodium allyl ether sulfonate; the reactive nonionic emulsifier is allyloxy nonylphenoxypropanol polyoxyethylene ether; the anionic emulsifier is one or more of sodium lauryl sulfate or ethoxylated alkylphenol sulfate.
4. The bio-enzyme catalyzed aqueous acrylate emulsion according to claim 1 wherein the bio-enzyme is horseradish peroxidase HRP.
5. The aqueous acrylate emulsion catalyzed by biological enzymes according to claim 1 wherein the oxidizer is a 30% hydrogen peroxide solution; the reducing agent is acetylacetone; the defoamer is one or more of mineral oil or polyether modified organic silicon; the wetting agent is dioctyl sodium sulfonate; the buffer is disodium hydrogen phosphate or sodium bicarbonate; the pH regulator is ammonia water or 2-amino-2-methyl-1-propanol.
6. A method for preparing the bio-enzyme catalyzed aqueous acrylate emulsion according to any one of claims 1 to 5, comprising the steps of:
(1) adding 0.1-1.8 parts of reactive anionic emulsifier, 0.1-0.8 part of reactive nonionic emulsifier, 0.5-2.4 parts of anionic emulsifier and 0.003-0.05 part of HRP enzyme into 50-150 parts of deionized water, and stirring to obtain an emulsifier aqueous solution; adding 80-200 parts of acrylate monomer, 1-6 parts of acrylic acid monomer and 0.02-0.6 part of reducing agent into the obtained emulsifier aqueous solution, and stirring for 40-45 min to obtain pre-emulsion A;
(2) adding the rest of emulsifying agent, 0.2-6 parts of buffering agent and 50-110 parts of deionized water into a four-neck flask, uniformly dissolving, heating to 40-45 ℃, injecting 1-10% by weight of pre-emulsion A prepared in the step (1) and 10-20% by weight of oxidizing agent, and reacting for 40-60 min to prepare seed emulsion B;
(3) after the heat preservation reaction is finished, the residual pre-emulsion A and the residual oxidant are simultaneously dripped into the seed emulsion B, the dripping time of the pre-emulsion is 3-4 h, the dripping time of the oxidant is 50-60 min, the temperature is controlled at 40-45 ℃, after the dripping is finished, the heat preservation is carried out for 2h, and then the temperature is reduced to 30 ℃;
(4) when the temperature is reduced to below 30 ℃, 0.2-7 parts of pH regulator is added, the pH is regulated to 7-7.5, then 0.01-0.06 parts of defoamer and 0.01-0.05 parts of wetting agent are added, the mixture is stirred for 20-30 min until the emulsion is uniform, and the mixture is filtered and discharged, thus obtaining the bio-enzyme catalyzed aqueous acrylate emulsion.
7. The method for producing a bio-enzyme catalyzed aqueous acrylate emulsion according to claim 6, wherein in the step (1), the stirring speed is 800 to 2000r/min, and in the steps (2) to (4), the stirring speed is 150 to 200r/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311079730.0A CN117069886A (en) | 2023-08-25 | 2023-08-25 | Biological enzyme catalyzed aqueous acrylic ester emulsion and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311079730.0A CN117069886A (en) | 2023-08-25 | 2023-08-25 | Biological enzyme catalyzed aqueous acrylic ester emulsion and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117069886A true CN117069886A (en) | 2023-11-17 |
Family
ID=88716792
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311079730.0A Pending CN117069886A (en) | 2023-08-25 | 2023-08-25 | Biological enzyme catalyzed aqueous acrylic ester emulsion and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117069886A (en) |
-
2023
- 2023-08-25 CN CN202311079730.0A patent/CN117069886A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9688601B2 (en) | Process for preparing (meth)acrylates | |
| CN104448156B (en) | A kind of room temperature preparation method of high-efficiency polycarboxylic acid water reducer | |
| CN103980432B (en) | Containing polycarboxylate water-reducer and its preparation method of modified soluble acrylate | |
| CN111234564B (en) | Environment-friendly flame retardant and intumescent fire-retardant coating prepared from same | |
| CN113831448A (en) | Pure acrylic emulsion, raw material composition thereof, preparation method and application thereof | |
| CN111995717A (en) | High-performance polycarboxylate superplasticizer, preparation method thereof and concrete | |
| CN113667050A (en) | Crosslinking monomer, crosslinking polycarboxylate superplasticizer and preparation method | |
| CN114656587A (en) | Emulsion polymer with low coagulator content, and preparation method and application thereof | |
| CN117069886A (en) | Biological enzyme catalyzed aqueous acrylic ester emulsion and preparation method thereof | |
| CN108034015B (en) | Preparation method of polyvinyl chloride | |
| CN113754822A (en) | Modified tertiary vinegar emulsion of non-protective adhesive system and preparation method thereof | |
| CN1329469C (en) | Modified urea formaldehyde binding agent and its preparation method | |
| CN106046243A (en) | Environment-friendly high-solid-content PVC (Polyvinyl Chloride) floor glue emulsion and preparation method thereof | |
| CN110790875A (en) | Organic silicon modified acrylic emulsion adhesive and preparation method thereof | |
| CN102924735B (en) | Method for preparing modified lignosulfonate high-performance water reducing agent | |
| CN114573759A (en) | Self-crosslinking styrene-acrylic emulsion for producing waterproof wood strip lines and preparation method thereof | |
| JP2002527540A (en) | Redox polymerization method | |
| CN108912261B (en) | Flame-retardant acrylate miniemulsion and preparation method thereof | |
| KR100569219B1 (en) | Method of reducing the content of residual monomers in emulsion polymers | |
| CN116178234B (en) | Preparation method of solvent type peroxy-2-ethylhexyl tert-butyl carbonate | |
| CN114044857B (en) | Preparation method of polyacrylate aqueous dispersion with carboxyl-rich surface, dispersion and application of polyacrylate aqueous dispersion | |
| CN108793810A (en) | A kind of preparation method of polycarboxylate water-reducer | |
| CN1333299A (en) | Process for preparing acrylic ester elastic emulsion | |
| CN114230710A (en) | Low-odor pure silicone acrylate acrylic emulsion and preparation method thereof | |
| CN114409857B (en) | Graphene oxide monomer, high-workability polycarboxylate superplasticizer and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |