CN116874685A - Organosilicon acrylic ester emulsion and preparation method thereof - Google Patents
Organosilicon acrylic ester emulsion and preparation method thereof Download PDFInfo
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- CN116874685A CN116874685A CN202310907322.3A CN202310907322A CN116874685A CN 116874685 A CN116874685 A CN 116874685A CN 202310907322 A CN202310907322 A CN 202310907322A CN 116874685 A CN116874685 A CN 116874685A
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- 239000000839 emulsion Substances 0.000 title claims abstract description 193
- -1 acrylic ester Chemical class 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 238000004945 emulsification Methods 0.000 title description 2
- 239000000178 monomer Substances 0.000 claims abstract description 73
- 239000003999 initiator Substances 0.000 claims abstract description 60
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 37
- 239000010703 silicon Substances 0.000 claims abstract description 37
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 229920002545 silicone oil Polymers 0.000 claims abstract description 13
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 90
- 238000006243 chemical reaction Methods 0.000 claims description 71
- 238000003756 stirring Methods 0.000 claims description 58
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 45
- 229920001296 polysiloxane Polymers 0.000 claims description 43
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 26
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 25
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 25
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 25
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 25
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 24
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 14
- 229960002887 deanol Drugs 0.000 claims description 14
- 239000012972 dimethylethanolamine Substances 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 claims description 3
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 claims description 3
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-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
- 238000004321 preservation Methods 0.000 claims description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 3
- 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 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-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
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 2
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture 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
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 238000011534 incubation Methods 0.000 claims 1
- 239000004925 Acrylic resin Substances 0.000 abstract description 8
- 229920000178 Acrylic resin Polymers 0.000 abstract description 6
- 239000003973 paint Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 37
- 239000000463 material Substances 0.000 description 34
- 230000001276 controlling effect Effects 0.000 description 22
- 230000009477 glass transition Effects 0.000 description 15
- 238000001914 filtration Methods 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 238000000576 coating method Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 239000000499 gel Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910002808 Si–O–Si Inorganic materials 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005303 weighing Methods 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
Landscapes
- 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 relates to an organosilicon acrylic ester emulsion and a preparation method thereof, belonging to the technical field of paint. The invention provides an organosilicon acrylic ester emulsion which comprises the following raw materials in parts by mass: 8.58-30.24 parts of organosilicon monomer, 0.34-0.40 part of hydrophilic acrylic monomer, 18.21-21.34 parts of acrylic ester soft monomer, 5.18-6.01 parts of acrylic ester hard monomer, 0.52-0.68 part of crosslinkable acrylic ester monomer, 0.12-0.14 part of initiator, 0.56-0.58 part of emulsifier, 0.34-0.40 part of neutralizer and 26.6-46.98 parts of water; the organic silicon monomer is acrylic ester silicone oil. According to the invention, under the condition of not changing the softness of the acrylic resin, the acrylic silicone oil is introduced, so that the use level of the emulsifier is effectively reduced while the simple and efficient grafting is realized, and the organosilicon content in the emulsion, the hand feeling and the anti-tackiness of the emulsion are obviously improved.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to an organosilicon acrylic ester emulsion and a preparation method thereof.
Background
The polyacrylic resin has a large amount of soft monomers under the condition of low glass transition temperature, so that the polyacrylic resin has high softness and strong adhesive force, but the application field is greatly limited by the high surface viscosity; the polysiloxane in the organosilicon has the lowest glass transition temperature (-123 ℃) in the reported polymer, and the hydrophobic Si-O-Si structure can be hydrolyzed and condensed to form a Si-O-Si cross-linked network during film formation, and is enriched on the surface of the coating after film formation; therefore, the acrylic resin is modified by the organosilicon, so that the hand feeling and the anti-sticking performance can be effectively improved under the condition of not reducing the softness.
In order to effectively increase the content of the organic silicon component, researchers have conducted a great deal of research work from two directions of the organic silicon and the modified resin synthesis process. However, the silicone content of the silicone-acrylate modified resin in the market at present is generally less than 15%, and in this case, the actual content of the silicone is low no matter the silicone is used as a main resin or an auxiliary agent, and the advantage of the modified resin is difficult to effectively display when the silicone-acrylate modified resin is used in comparison with a conventional acrylic resin. In addition, in order to effectively solve the problem of poor compatibility between polysiloxane and polyacrylate components, in the conventional seed emulsion polymerization process, the addition amount of the emulsifier is high, so that not only the hydrophobic property of the organosilicon is affected, but also the polymer content and the substantial content of the organosilicon in the polymer are reduced.
Therefore, how to effectively increase the content of the organic silicon component in the acrylic resin is a technical problem to be solved at present.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide an organosilicon acrylic ester emulsion and a preparation method thereof.
The invention is realized by the following technical scheme:
the organic silicon acrylic ester emulsion comprises the following raw materials in parts by mass: 8.58-30.24 parts of organosilicon monomer, 0.34-0.40 part of hydrophilic acrylic monomer, 18.21-21.34 parts of acrylic ester soft monomer, 5.18-6.01 parts of acrylic ester hard monomer, 0.52-0.68 part of crosslinkable acrylic ester monomer, 0.12-0.14 part of initiator, 0.56-0.58 part of emulsifier, 0.34-0.40 part of neutralizer and 26.6-46.98 parts of water; the organic silicon monomer is acrylic ester silicone oil.
Under the condition of not changing the flexibility of the acrylic resin with low glass transition temperature (Tg= -29.66 ℃), a proper amount of organosilicon monomer is introduced to modify the acrylic resin, and acrylic ester with high reactivity is used as a reactive functional group to carry out copolymerization reaction with other acrylic ester monomers, so that the dosage of a reactive emulsifier is effectively reduced while simple and efficient grafting is carried out; in addition, the organic silicon content in the modified acrylic ester emulsion is obviously improved to 32.4% by utilizing the characteristic of high silicon ratio, so that the hand feeling and the anti-sticking property of the organic silicon acrylic ester emulsion are greatly improved.
As a preferred embodiment of the silicone acrylate emulsion of the present invention, the silicone monomer has a silicon content of not less than 60%.
Preferably, the acrylate-based silicone oil is Silok3823F 5.
As a preferred embodiment of the silicone acrylate emulsion of the present invention, the hydrophilic acrylic monomer includes at least one of acrylic acid and methacrylic acid.
As a preferred embodiment of the silicone acrylate emulsion of the present invention, the acrylate soft monomer includes at least one of methyl acrylate, ethyl acrylate, butyl acrylate, and isooctyl acrylate.
Preferably, the acrylate soft monomer comprises at least one of butyl acrylate and isooctyl acrylate.
As a preferred embodiment of the silicone acrylate emulsion of the present invention, the acrylate hard monomer includes at least one of methyl methacrylate and styrene.
Preferably, the acrylate hard monomer is methyl methacrylate.
As a preferred embodiment of the silicone acrylate emulsion of the present invention, the crosslinkable acrylate monomer includes at least one of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, hydroxybutyl methacrylate, and N-methylolacrylamide.
Preferably, the crosslinkable acrylate monomer includes at least one of hydroxyethyl methacrylate and hydroxybutyl methacrylate.
As a preferred embodiment of the silicone acrylate emulsion of the present invention, the initiator comprises at least one of sodium persulfate, ammonium persulfate, potassium persulfate, and t-butyl hydroperoxide. Preferably, the initiator comprises at least one of potassium persulfate and ammonium persulfate.
As a preferred embodiment of the silicone acrylate emulsion of the present invention, the emulsifier is a reactive emulsifier; preferably, the emulsifier is SR-10.
As a preferred embodiment of the silicone acrylate emulsion of the present invention, the neutralizing agent comprises at least one of triethylamine, dimethylethanolamine, diethylethanolamine, 2-amino-2-methylpropanol.
Preferably, the neutralizing agent comprises at least one of dimethylethanolamine and diethylethanolamine.
The invention further provides a preparation method of the organic silicon acrylic ester emulsion, which comprises the following steps:
(1) Uniformly mixing a first part of water, a first part of emulsifier, a hydrophilic acrylic monomer, an acrylic ester soft monomer, an acrylic ester hard monomer and a crosslinkable acrylic ester monomer to obtain emulsion, and then adding a first part of initiator to uniformly mix to obtain pre-emulsion A; uniformly mixing an organosilicon monomer and a second part of initiator to obtain a pre-emulsion B;
(2) And heating and stirring the second part of water and the second part of emulsifier uniformly, adding the first part of pre-emulsion A as seeds under the condition of heating and stirring, adding the third part of initiator, uniformly mixing, adding the second part of pre-emulsion A, then adding the pre-emulsion B, carrying out heat preservation reaction, cooling, and then adding a neutralizing agent to regulate the pH value, thus obtaining the organosilicon acrylic ester emulsion.
According to the preparation method disclosed by the invention, a post-addition process is adopted, the mixed solution of the organosilicon monomer and a proper amount of initiator is used as the pre-emulsion B, and then the pre-emulsion B is added into an acrylate emulsion reaction system, so that the silicone oil grafting rate can be effectively improved, and the organosilicon acrylate emulsion with better performance can be obtained.
As a preferred embodiment of the preparation method of the silicone acrylate emulsion, in the step (1), the weight part of the first part of water is 8.2-15.8 parts; the weight part of the first part of emulsifier is 0.22-0.25 part; the weight part of the first part of initiator is 0.03-0.05 part; the weight part of the second part of initiator is 0.03-0.05 part.
In the preparation method, water is divided into two parts, an emulsifying agent is divided into two parts, and an initiator is divided into three parts and is respectively added into a reaction system to prepare the organosilicon acrylic ester emulsion.
As a preferred embodiment of the method for preparing a silicone acrylate emulsion of the present invention, in the step (2), the weight part of the first part of the pre-emulsion a is 1.75-2.2 parts.
The invention adopts a seed emulsion polymerization mode, divides the pre-emulsion A into two parts, wherein the first part of the pre-emulsion A is used as seeds, then the rest of the second part of the pre-emulsion A is added, and then the pre-emulsion B is added, thereby improving the grafting rate of the silicone oil.
As a preferred embodiment of the preparation method of the organosilicon acrylic ester emulsion, in the step (2), the temperature of the heat preservation reaction is 80-85 ℃ and the time is 5-8 h.
Preferably, in the step (2), the residual pre-emulsion A and the residual pre-emulsion B are added in a dropwise manner; the time for dripping the second part of pre-emulsion A is 2 hours; the time for dropping the pre-emulsion B was 1h.
The invention has the following beneficial effects: according to the organosilicon acrylic ester emulsion, a seed emulsion polymerization mode is adopted, and a post-addition mode is adopted under the condition of not changing the theoretical glass transition temperature of the emulsion, so that the silicone oil grafting rate of the emulsion is effectively improved to 32.4%, and further the hand feeling and the anti-tackiness of the emulsion are greatly improved.
2) The invention utilizes the high reactivity of the reactive functional group acrylic ester in the organosilicon monomer, optimizes the addition amount and the addition process of the organosilicon, effectively reduces the use amount of the emulsifier, improves the polymer content and the substantial content of the organosilicon in the polymer, and further improves the hand feeling and the anti-sticking property of the organosilicon modified acrylic ester emulsion.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples. It will be appreciated by persons skilled in the art that the specific embodiments described herein are for purposes of illustration only and are not intended to be limiting.
The test methods used in the examples are conventional methods unless otherwise specified; the materials, reagents and the like used, unless otherwise specified, are all commercially available.
Example 1
The organic silicon acrylic ester emulsion comprises the following raw materials in parts by mass: 8.58 parts of organosilicon monomer Silok3823F, 0.35 part of methacrylic acid, 18.57 parts of n-butyl acrylate, 5.22 parts of methyl methacrylate, 0.56 part of hydroxyethyl methacrylate, 0.13 part of initiator ammonium persulfate, 0.58 part of emulsifier SR-10, 0.35 part of neutralizer dimethylethanolamine and 26.98 parts of deionized water.
The preparation method of the organosilicon acrylic ester emulsion comprises the following steps:
(1) 8.2 parts of water and 0.24 part of emulsifier are placed in a flask to be stirred and dissolved, after 10min, 0.35 part of methacrylic acid, 18.57 parts of n-butyl acrylate, 5.22 parts of methyl methacrylate and 0.56 part of hydroxyethyl methacrylate are mixed and added into the flask to be continuously stirred, after 20min, stable white pre-emulsion is formed, and then 0.04 part of ammonium persulfate initiator is added into the flask to be stirred for 10min, so as to obtain pre-emulsion A; adding 8.58 parts of Silok3823F5 organic silicon monomer and 0.03 part of ammonium persulfate initiator into a flask, mixing and stirring to obtain pre-emulsion B;
(2) Adding the rest of 18.78 parts of water and 0.34 part of emulsifier into a reaction kettle, stirring and heating to 80 ℃, adding 1.76 parts of pre-emulsion A as seeds into the reaction kettle under the condition of heating and stirring, adding 0.06 part of mixed solution of ammonium persulfate initiator and water after 5min, firstly dropwise adding the pre-emulsion A into the reaction kettle for the first 2h after 5min, dropwise adding the pre-emulsion B into the reaction kettle after 1h, controlling the material reaction temperature to be 80-85 ℃, controlling the stirring speed to be uniform and stirring the material, keeping the reaction temperature for 2h after the dropwise adding, cooling to room temperature, adding 0.35 part of neutralizer, adjusting the pH of the material to 7, and filtering to obtain the organosilicon acrylic emulsion.
The glass transition temperature of the silicone acrylate emulsion of this example was-29.66 ℃.
Example 2
The organic silicon acrylic ester emulsion comprises the following raw materials in parts by mass: organosilicon monomer Silok3823F 5.17 parts, methacrylic acid 0.35 parts, n-butyl acrylate 18.57 parts, methyl methacrylate 5.22 parts, hydroxyethyl methacrylate 0.56 parts, initiator ammonium persulfate 0.13 parts, emulsifier SR-10.58 parts, neutralizer dimethylethanolamine 0.35 parts and deionized water 33.73 parts.
The preparation method of the organosilicon acrylic ester emulsion comprises the following steps:
(1) 10.56 parts of water and 0.24 part of emulsifier are placed in a flask to be stirred and dissolved, after 10min, 0.35 part of methacrylic acid, 18.57 parts of n-butyl acrylate, 5.22 parts of methyl methacrylate and 0.56 part of hydroxyethyl methacrylate are mixed and added into the flask to be continuously stirred, after 20min, stable white pre-emulsion is formed, and then 0.04 part of ammonium persulfate initiator is added into the flask to be stirred for 10min, so as to obtain pre-emulsion A; 17.17 parts of Silok3823F5 organic silicon monomer and 0.03 part of ammonium persulfate initiator are added into a flask, and mixed, so as to obtain a pre-emulsion B;
(2) Adding the rest of 23.17 parts of water and 0.34 part of emulsifier into a reaction kettle, stirring and heating to 80 ℃, adding 1.84 parts of pre-emulsion A as seeds into the reaction kettle under the condition of heating and stirring, adding 0.06 part of mixed solution of ammonium persulfate initiator and water after 5min, firstly dropwise adding the pre-emulsion A into the reaction kettle for the first 2h after 5min, dropwise adding the pre-emulsion B into the reaction kettle after 1h, controlling the material reaction temperature to be 80-85 ℃, controlling the stirring speed to be uniform and stirring the material, keeping the reaction temperature for 2h after the dropwise adding, cooling to room temperature, adding 0.35 part of neutralizer, adjusting the pH of the material to 7, and filtering to obtain the organosilicon acrylic emulsion.
The glass transition temperature of the silicone acrylate emulsion of this example was-29.66 ℃.
Example 3
The organic silicon acrylic ester emulsion comprises the following raw materials in parts by mass: 30.24 parts of organosilicon monomer Silok3823F, 0.35 part of methacrylic acid, 18.57 parts of n-butyl acrylate, 5.22 parts of methyl methacrylate, 0.56 part of hydroxyethyl methacrylate, 0.13 part of initiator ammonium persulfate, 0.58 part of emulsifier SR-10, 0.35 part of neutralizer dimethylethanolamine and 44 parts of deionized water.
The preparation method of the organosilicon acrylic ester emulsion comprises the following steps:
(1) 14 parts of water and 0.24 part of emulsifier are placed in a flask to be stirred and dissolved, after 10min, 0.35 part of methacrylic acid, 18.57 parts of n-butyl acrylate, 5.22 parts of methyl methacrylate and 0.56 part of hydroxyethyl methacrylate are mixed and added into the flask to be continuously stirred, after 20min, stable white pre-emulsion is formed, and then 0.04 part of ammonium persulfate initiator is added into the flask to be stirred for 10min, so that pre-emulsion A is obtained; adding 30.24 parts of Silok3823F5 organic silicon monomer and 0.03 part of ammonium persulfate initiator into a flask, mixing and stirring to obtain pre-emulsion B;
(2) Adding the rest 30 parts of water and 0.34 part of emulsifier into a reaction kettle, stirring and heating to 80 ℃, taking 1.98 parts of pre-emulsion A as seeds under the condition of heating and stirring, adding mixed solution of 0.06 part of ammonium persulfate initiator and water into the reaction kettle after 5min, firstly dripping the pre-emulsion A into the reaction kettle for the first 2h, then dripping the pre-emulsion B into the reaction kettle for 1h, controlling the material reaction temperature to be 80-85 ℃, controlling the stirring speed to be capable of uniformly stirring the material, keeping the reaction temperature for 2h after the dripping is finished, cooling to room temperature, adding 0.35 part of neutralizer, adjusting the pH of the material to 7, and filtering to obtain the organosilicon acrylic emulsion.
The glass transition temperature of the silicone acrylate emulsion of this example was-29.66 ℃.
Example 4
The organic silicon acrylic ester emulsion comprises the following raw materials in parts by mass: 30.24 parts of organosilicon monomer Silok3823F5, 0.40 part of methacrylic acid, 21.34 parts of n-butyl acrylate, 6.01 parts of methyl methacrylate, 0.68 part of hydroxyethyl methacrylate, 0.14 part of initiator ammonium persulfate, 0.58 part of emulsifier SR-10, 0.40 part of neutralizer dimethylethanolamine and 46.98 parts of deionized water.
The preparation method of the organosilicon acrylic ester emulsion comprises the following steps:
(1) 15.68 parts of water and 0.24 part of emulsifier are placed in a flask to be stirred and dissolved, after 10min, 0.40 part of methacrylic acid, 21.34 parts of n-butyl acrylate, 6.01 parts of methyl methacrylate and 0.68 part of hydroxyethyl methacrylate are mixed and added into the flask to be continuously stirred, after 20min, stable white pre-emulsion is formed, and then 0.05 part of ammonium persulfate initiator is added into the flask to be stirred for 10min, so as to obtain pre-emulsion A; adding 30.24 parts of Silok3823F5 organic silicon monomer and 0.03 part of ammonium persulfate initiator into a flask, mixing and stirring to obtain pre-emulsion B;
(2) Adding 31.3 parts of water and 0.34 part of emulsifier in the balance into a reaction kettle, stirring and heating to 80 ℃, taking 2.17 parts of pre-emulsion A as seeds, adding mixed solution of 0.06 part of ammonium persulfate initiator and water into the reaction kettle under the condition of heating and stirring, dropwise adding the pre-emulsion A into the reaction kettle for 5min, dropwise adding the pre-emulsion B into the reaction kettle for 1h after the first 2h, controlling the material reaction temperature to be 80-85 ℃, controlling the stirring speed to be uniform, stirring the materials, keeping the reaction temperature for 2h after the dropwise adding, cooling to room temperature, adding 0.40 part of neutralizer, adjusting the pH of the materials to 7, and filtering to obtain the organosilicon acrylic emulsion.
The glass transition temperature of the silicone acrylate emulsion of this example was-29.70 ℃.
Example 5
The organic silicon acrylic ester emulsion comprises the following raw materials in parts by mass: 8.58 parts of organosilicon monomer Silok3823F, 0.34 part of methacrylic acid, 18.21 parts of n-butyl acrylate, 5.18 parts of methyl methacrylate, 0.52 part of hydroxyethyl methacrylate, 0.12 part of initiator ammonium persulfate, 0.56 part of emulsifier SR-10, 0.34 part of neutralizer dimethylethanolamine and 26.6 parts of deionized water.
The preparation method of the organosilicon acrylic ester emulsion comprises the following steps:
(1) 8.7 parts of water and 0.23 part of emulsifier are placed in a flask to be stirred and dissolved, after 10min, 0.34 part of methacrylic acid, 18.21 parts of n-butyl acrylate, 5.18 parts of methyl methacrylate and 0.52 part of hydroxyethyl methacrylate are mixed and added into the flask to be continuously stirred, after 20min, stable white pre-emulsion is formed, and then 0.04 part of ammonium persulfate initiator is added into the flask to be stirred for 10min, so as to obtain pre-emulsion A; adding 8.58 parts of Silok3823F5 organic silicon monomer and 0.03 part of ammonium persulfate initiator into a flask, mixing and stirring to obtain pre-emulsion B;
(2) Adding 17.9 parts of water and 0.33 part of emulsifier in the balance into a reaction kettle, stirring and heating to 80 ℃, taking 1.87 parts of pre-emulsion A as seeds under the condition of heating and stirring, adding 0.05 part of mixed solution of ammonium persulfate initiator and water into the reaction kettle after 5min, firstly dropwise adding the pre-emulsion A into the reaction kettle for the first 2h, dropwise adding the pre-emulsion B into the reaction kettle after 1h, controlling the material reaction temperature to be 80-85 ℃, controlling the stirring speed to be uniform, stirring the materials, keeping the reaction temperature for 2h after the dropwise adding, cooling to room temperature, adding 0.34 part of neutralizer, adjusting the pH of the materials to 7, and filtering to obtain the organosilicon acrylic emulsion.
The glass transition temperature of the silicone acrylate emulsion of this example was-29.68 ℃.
Comparative example 1
The organic silicon acrylic ester emulsion comprises the following raw materials in parts by mass: 0.35 part of methacrylic acid, 18.57 parts of n-butyl acrylate, 5.22 parts of methyl methacrylate, 0.56 part of hydroxyethyl methacrylate, 0.13 part of initiator ammonium persulfate, 0.58 part of emulsifier SR-10, 0.35 part of neutralizer dimethylethanolamine and 20.24 parts of deionized water.
The preparation method of the organosilicon acrylic ester emulsion comprises the following steps:
(1) 6.98 parts of water and 0.24 part of emulsifier are placed in a flask to be stirred and dissolved, after 10min, 0.35 part of methacrylic acid, 18.57 parts of n-butyl acrylate, 5.22 parts of methyl methacrylate and 0.56 part of hydroxyethyl methacrylate are mixed and added into the flask to be continuously stirred, after 20min, stable white pre-emulsion is formed, and then 0.04 part of ammonium persulfate initiator is added into the flask to be stirred for 10min, so as to obtain pre-emulsion A;
(2) Adding 13.26 parts of water and 0.34 part of emulsifier into a reaction kettle, stirring and heating to 80 ℃, taking 1.68 parts of pre-emulsion A as seeds under the condition of heating and stirring, adding 0.06 part of mixed solution of ammonium persulfate initiator and water into the reaction kettle after 5min, firstly dropwise adding the pre-emulsion A into the reaction kettle for 3h, controlling the material reaction temperature to 80-85 ℃, controlling the stirring speed to be uniform, stirring the materials, keeping the reaction temperature for 2h after the dropwise adding is finished, cooling to room temperature, adding 0.35 part of neutralizer, regulating the pH of the materials to 7, and filtering to obtain the organosilicon acrylic emulsion.
The glass transition temperature of the silicone acrylate emulsion of this example was-29.66 ℃.
Comparative example 2
The organic silicon acrylic ester emulsion comprises the following raw materials in parts by mass: organosilicon monomer Silok 3825.58, methacrylic acid 0.35, butyl acrylate 18.57, methyl methacrylate 5.22, hydroxyethyl methacrylate 0.56, initiator ammonium persulfate 0.13, emulsifier SR-10.66, neutralizer dimethylethanolamine 0.35 and deionized water 27.04.
The preparation method of the organosilicon acrylic ester emulsion comprises the following steps:
(1) 8.2 parts of water and 0.24 part of emulsifier are placed in a flask to be stirred and dissolved, after 10min, 0.35 part of methacrylic acid, 18.57 parts of n-butyl acrylate, 5.22 parts of methyl methacrylate and 0.56 part of hydroxyethyl methacrylate are mixed and added into the flask to be continuously stirred, after 20min, stable white pre-emulsion is formed, and then 0.04 part of ammonium persulfate initiator is added into the flask to be stirred for 10min, so as to obtain pre-emulsion A; 8.58 parts of Silok3825 organosilicon monomer, 0.03 part of ammonium persulfate initiator and 0.08 part of emulsifier are added into a flask, and mixed and stirred to obtain pre-emulsion B;
(2) Adding the rest of 18.84 parts of water and 0.34 part of emulsifier into a reaction kettle, stirring and heating to 80 ℃, adding 1.76 parts of pre-emulsion A as seeds into the reaction kettle under the condition of heating and stirring, adding 0.06 part of mixed solution of ammonium persulfate initiator and water after 5min, firstly dropwise adding the pre-emulsion A into the reaction kettle for the first 2h after 5min, dropwise adding the pre-emulsion B into the reaction kettle after 1h, controlling the material reaction temperature to be 80-85 ℃, controlling the stirring speed to be uniform and stirring the material, keeping the reaction temperature for 2h after the dropwise adding, cooling to room temperature, adding 0.35 part of neutralizer, adjusting the pH of the material to 7, and filtering to obtain the organosilicon acrylic emulsion.
The glass transition temperature of the silicone acrylate emulsion of this example was-29.66 ℃.
Comparative example 3
The organic silicon acrylic ester emulsion comprises the following raw materials in parts by mass: 30.24 parts of organosilicon monomer Silok3823F, 0.35 part of methacrylic acid, 18.57 parts of n-butyl acrylate, 5.22 parts of methyl methacrylate, 0.56 part of hydroxyethyl methacrylate, 0.13 part of initiator ammonium persulfate, 0.58 part of emulsifier SR-10, 0.35 part of neutralizer dimethylethanolamine and 44 parts of deionized water.
The preparation method of the organosilicon acrylic ester emulsion comprises the following steps:
(1) 14 parts of water and 0.24 part of emulsifier are placed in a flask to be stirred and dissolved, after 10min, 0.35 part of methacrylic acid, 18.57 parts of n-butyl acrylate, 5.22 parts of methyl methacrylate, 0.56 part of hydroxyethyl methacrylate and 30.24 parts of Silok3823F5 organic silicon monomer are mixed and added into the flask to be continuously stirred, after 20min, stable white pre-emulsion is formed, and then 0.07 part of ammonium persulfate initiator is added into the flask to be stirred for 10min, so that pre-emulsion A is obtained;
(2) Adding the rest 30 parts of water and 0.34 part of emulsifier into a reaction kettle, stirring and heating to 80 ℃, taking 1.98 parts of pre-emulsion A as seeds under the condition of heating and stirring, adding mixed solution of 0.06 part of ammonium persulfate initiator and water into the reaction kettle after 5min, firstly dripping the pre-emulsion A into the reaction kettle for the first 2h, then dripping the pre-emulsion B into the reaction kettle for 1h, controlling the material reaction temperature to be 80-85 ℃, controlling the stirring speed to be capable of uniformly stirring the material, keeping the reaction temperature for 2h after the dripping is finished, cooling to room temperature, adding 0.35 part of neutralizer, adjusting the pH of the material to 7, and filtering to obtain the organosilicon acrylic emulsion.
The glass transition temperature of the silicone acrylate emulsion of this example was-29.66 ℃.
Comparative example 4
The organic silicon acrylic ester emulsion comprises the following raw materials in parts by mass: 30.24 parts of organosilicon monomer Silok3823F, 0.35 part of methacrylic acid, 18.57 parts of n-butyl acrylate, 5.22 parts of methyl methacrylate, 0.56 part of hydroxyethyl methacrylate, 0.13 part of initiator ammonium persulfate, 0.58 part of emulsifier SR-10, 0.35 part of neutralizer dimethylethanolamine and 44 parts of deionized water.
The preparation method of the organosilicon acrylic ester emulsion comprises the following steps:
(1) 14 parts of water and 0.24 part of emulsifier are placed in a flask to be stirred and dissolved, after 10min, 0.35 part of methacrylic acid, 18.57 parts of n-butyl acrylate, 5.22 parts of methyl methacrylate and 0.56 part of hydroxyethyl methacrylate are mixed and added into the flask to be continuously stirred, after 20min, stable white pre-emulsion is formed, and then 0.04 part of ammonium persulfate initiator is added into the flask to be stirred for 10min, so that pre-emulsion A is obtained; adding 30.24 parts of Silok3823F5 organic silicon monomer and 0.03 part of ammonium persulfate initiator into a flask, mixing and stirring to obtain pre-emulsion B;
(2) Adding the rest of water and 0.34 part of emulsifier into a reaction kettle, stirring and heating to 80 ℃, taking 1.98 parts of pre-emulsion A as seeds under the condition of heating and stirring, adding mixed solution of 0.06 part of ammonium persulfate initiator and water into the reaction kettle after 5min, simultaneously dropwise adding the rest of pre-emulsion A and pre-emulsion B into the reaction kettle within 3h after 5min, controlling the reaction temperature of materials to be 80-85 ℃, controlling the stirring speed to be capable of uniformly stirring the materials, keeping the reaction temperature for 2h after the dropwise adding is finished, cooling to room temperature, adding 0.35 part of neutralizer to adjust the pH of the materials to 7, and filtering to obtain the organosilicon acrylic emulsion.
The glass transition temperature of the silicone acrylate emulsion of this example was-29.66 ℃.
Comparative example 5
The organic silicon acrylic ester emulsion comprises the following raw materials in parts by mass: silicone monomer Silok3823F 5.44 parts, methacrylic acid 0.35 parts, n-butyl acrylate 18.57 parts, methyl methacrylate 5.22 parts, hydroxyethyl methacrylate 0.56 parts, initiator ammonium persulfate 0.13 parts, emulsifier SR-10.58 parts, neutralizer dimethylethanolamine 0.35 parts and deionized water 25.3 parts.
The preparation method of the organosilicon acrylic ester emulsion comprises the following steps:
(1) Adding 12.59 parts of water and 0.24 part of an emulsifier into a flask, stirring and dissolving, adding 0.35 part of methacrylic acid, 18.57 parts of n-butyl acrylate, 5.22 parts of methyl methacrylate and 0.56 part of hydroxyethyl methacrylate into the flask after 10min, continuously stirring, forming a stable white pre-emulsion after 20min, adding 0.04 part of ammonium persulfate initiator into the flask, and stirring for 10min to obtain a pre-emulsion A; adding 6.44 parts of Silok3823F5 organic silicon monomer and 0.03 part of ammonium persulfate initiator into a flask, mixing and stirring to obtain pre-emulsion B;
(2) Adding the rest of 12.71 parts of water and 0.34 part of emulsifier into a reaction kettle, stirring and heating to 80 ℃, adding 1.64 parts of pre-emulsion A as seeds into the reaction kettle under the condition of heating and stirring, adding 0.06 part of mixed solution of ammonium persulfate initiator and water after 5min, firstly dropwise adding the pre-emulsion A into the reaction kettle for the first 2h after 5min, dropwise adding the pre-emulsion B into the reaction kettle after 1h, controlling the material reaction temperature to be 80-85 ℃, controlling the stirring speed to be uniform and stirring the material, keeping the reaction temperature for 2h after the dropwise adding, cooling to room temperature, adding 0.35 part of neutralizer, adjusting the pH of the material to 7, and filtering to obtain the organosilicon acrylic emulsion.
The glass transition temperature of the silicone acrylate emulsion of this example was-29.66 ℃.
Comparative example 6
The organic silicon acrylic ester emulsion comprises the following raw materials in parts by mass: silicone monomer Silok3823F 5.36.06 parts, methacrylic acid 0.35 parts, n-butyl acrylate 18.57 parts, methyl methacrylate 5.22 parts, hydroxyethyl methacrylate 0.56 parts, initiator ammonium persulfate 0.13 parts, emulsifier SR-10.58 parts, neutralizer dimethylethanolamine 0.35 parts and deionized water 48.57 parts.
The preparation method of the organosilicon acrylic ester emulsion comprises the following steps:
(1) 16.09 parts of water and 0.24 part of emulsifier are placed in a flask to be stirred and dissolved, after 10min, 0.35 part of methacrylic acid, 18.57 parts of n-butyl acrylate, 5.22 parts of methyl methacrylate and 0.56 part of hydroxyethyl methacrylate are mixed and added into the flask to be continuously stirred, after 20min, stable white pre-emulsion is formed, and then 0.04 part of ammonium persulfate initiator is added into the flask to be stirred for 10min, so as to obtain pre-emulsion A; adding 36.06 parts of Silok3823F5 organic silicon monomer and 0.03 part of ammonium persulfate initiator into a flask, mixing and stirring to obtain pre-emulsion B;
(2) Adding 32.48 parts of water and 0.34 part of emulsifier in the balance into a reaction kettle, stirring and heating to 80 ℃, taking 2.01 parts of pre-emulsion A as seeds under the condition of heating and stirring, adding mixed solution of 0.06 part of ammonium persulfate initiator and water into the reaction kettle after 5min, firstly dripping the pre-emulsion A into the reaction kettle for the first 2h, then dripping 1h into the reaction kettle after the pre-emulsion B, controlling the material reaction temperature to be 80-85 ℃, controlling the stirring speed to be capable of uniformly stirring the material, keeping the reaction temperature for 2h after the dripping is finished, cooling to room temperature, adding 0.35 part of neutralizer, adjusting the pH of the material to 7, and filtering to obtain the organosilicon acrylic emulsion.
The glass transition temperature of the silicone acrylate emulsion of this example was-29.66 ℃.
Effect testing
a. Total silicone oil grafting in emulsion
The total mass of the emulsion is recorded as m (g), and the mass of a 200-mesh filter bag which is weighed cleanly is recorded as m 1 (g) Filtering the emulsion, cleaning all residues in the container, placing in a filter bag, repeatedly cleaning, oven drying, weighing and marking the weight as m 2 (g) The emulsion gel fraction N (%) can be calculated as follows:
grafting refers to the reaction of macromolecular chains with appropriate branching or functional side groups by chemical bonds, and the resulting product is referred to as a graft copolymer. Grafting efficiency refers generally to grafting efficiency, both synonymous, grafting efficiency = [ grafted monomer mass/(grafted monomer mass + grafted monomer homopolymer mass) ] ×100%. Similarly, the silicone oil grafting ratio W (%) in the emulsion of the present invention was calculated by: silicone oil grafting = [60% silicone prepolymer mass + silicone monomer mass/all solute mass ] ×100%. Table 1 shows the gel fraction and the graft ratio of the acrylic emulsions of examples and comparative examples of the present invention.
TABLE 1 gel and graft Rate of the Silicone acrylate emulsions of examples and comparative examples
b. Hand feel assessment
The acrylic emulsion is rated by 5 persons as a group, the acrylic emulsion is analyzed from five index angles respectively, the degree increment is rated as I, II, III, IV and V respectively, the I is the worst, and the V is the best. Table 2 shows the hand feel evaluation results of examples of the present invention and comparative examples.
Table 2 hand feel evaluation results for examples and comparative examples
| Slip feeling | Softness and softness | Sense of meat thickness | Strength of | |
| Example 1 | III | Ⅳ | III | Ⅳ |
| Example 2 | Ⅳ | Ⅳ | Ⅳ | Ⅳ |
| Example 3 | Ⅴ | Ⅴ | Ⅴ | Ⅴ |
| Example 4 | Ⅳ | Ⅳ | Ⅳ | Ⅳ |
| Example 5 | III | Ⅳ | III | III |
| Comparative example 1 | Ⅰ | III | Ⅱ | III |
| Comparative example 2 | III | III | III | III |
| Comparative example 3 | Ⅳ | Ⅴ | Ⅳ | Ⅳ |
| Comparative example 4 | Ⅳ | Ⅴ | Ⅳ | Ⅳ |
| Comparative example 5 | Ⅱ | III | Ⅱ | III |
| Comparative example 6 | Ⅳ | Ⅳ | Ⅳ | Ⅳ |
c. Evaluation of surface viscosity
Under normal temperature conditions: lightly pressing the emulsion with hands on the surface layer of the acrylic emulsion, wherein the emulsion is adsorbed in the embodiment 1 and completely separated in 2 s; example 2 adsorbed slightly and completely detached within 1 s; example 3 did not adsorb at all; example 4 adsorbed slightly and completely detached within 1 s; example 5 adsorbed and completely desorbed within 2 s; comparative example 1 is easily adsorbed and does not break away within 2 s; comparative example 2 was slightly adsorbed and did not break away within 1; comparative example 3 was substantially non-adsorbed and detached from comparative example 4; comparative example 5 adsorbed and did not break away within 2 s; comparative example 6 was substantially unadsorbed and released upon removal.
Under the hot sticking resistance test condition: a heat seal tester was set up, temperature t=200 ℃, pressure p=10 MPa, hot press time t=30 s. Two samples of each emulsion were prepared for hot pressing, opened after room temperature and observed for emulsion change, the rating mode is shown in Table 3, and Table 4 shows the results of the hot-tack rating of the examples and comparative examples of the present invention.
TABLE 3 Heat resistance rating method
| Rating of | Rating description |
| 1 | The coating is completely adhered, and the whole piece is peeled off after forced tearing |
| 2 | The coating is seriously sticky and is not formed after being forcibly torn |
| 3 | The coating is seriously sticky, and the coating is partially broken after being torn by force |
| 4 | The coating is slightly sticky and can be torn off with little force, and the coating is not damaged |
| 5 | The coating layers are not adhered at all |
Table 4 results of the heat-resistant adhesive ratings of examples and comparative examples
| Heat resistance rating | |
| Example 1 | 3 |
| Example 2 | 4 |
| Example 3 | 5 |
| Example 4 | 4 |
| Example 5 | 3 |
| Comparative example 1 | 1 |
| Comparative example 2 | 3 |
| Comparative example 3 | 4 |
| Comparative example 4 | 4 |
| Comparative example 5 | 2 |
| Comparative example 6 | 4 |
From the above performance test, it can be seen that the comparative examples 1-3 and comparative example 1 can effectively improve the silicone oil grafting rate and the hand feeling and surface tackiness of the resin in the modified emulsion by gradually increasing the ratio of the silicone monomer under the same process conditions: as can be seen from comparative examples 1-6 and comparative example 2, the amount of reactive emulsifier can be effectively reduced by utilizing the high activity of the acrylate group, and the grafting state of the modified emulsion added with Silok3823F5 is better and the emulsion performance is more ideal when a large amount of silicone oil is grafted; it is known from comparative examples 3 and 4 that the same organosilicon monomer is added, and the post-addition process can more effectively improve the hand feeling and the surface anti-sticking property of the modified resin; as is clear from comparative examples 1 to 3 and comparative examples 5 to 6, too small an amount of the organic silicon added has little effect on the properties of the modified acrylic emulsion, and when too large an amount of the organic silicon added, effective grafting is difficult, the emulsion easily gels and the properties in various aspects are lowered.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The organic silicon acrylic ester emulsion is characterized by comprising the following raw materials in parts by weight: 8.58-30.24 parts of organosilicon monomer, 0.34-0.40 part of hydrophilic acrylic monomer, 18.21-21.34 parts of acrylic ester soft monomer, 5.18-6.01 parts of acrylic ester hard monomer, 0.52-0.68 part of crosslinkable acrylic ester monomer, 0.12-0.14 part of initiator, 0.56-0.58 part of emulsifier, 0.34-0.40 part of neutralizer and 26.6-46.98 parts of water; the organic silicon monomer is acrylic ester silicone oil.
2. The silicone acrylate emulsion according to claim 1, wherein the silicone monomer has a silicon content of not less than 60%.
3. The silicone acrylate emulsion according to claim 1, wherein the silicone monomer is Silok3823F 5.
4. The silicone acrylate emulsion according to claim 1, wherein the emulsifier is a reactive emulsifier.
5. The silicone acrylate emulsion according to claim 1, wherein at least one of the following is satisfied:
(1-1) the hydrophilic acrylic monomer comprises at least one of acrylic acid and methacrylic acid;
(1-2) the acrylate soft monomer comprises at least one of methyl acrylate, ethyl acrylate, butyl acrylate and isooctyl acrylate;
(1-3) the acrylate hard monomer comprises at least one of methyl methacrylate and styrene;
the crosslinkable acrylate monomer according to (1-4) comprises at least one of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, hydroxybutyl methacrylate, and N-methylolacrylamide.
6. The silicone acrylate emulsion according to claim 1, wherein at least one of the following is satisfied:
(2-1) the initiator comprises at least one of sodium persulfate, ammonium persulfate, potassium persulfate and tert-butyl hydroperoxide;
the neutralizing agent of (2-2) comprises at least one of triethylamine, dimethylethanolamine, diethylethanolamine, 2-amino-2-methylpropanol.
7. The method for preparing the organic silicon acrylic ester emulsion according to any one of claims 1 to 6, comprising the following steps:
(1) Uniformly mixing a first part of water, a first part of emulsifier, a hydrophilic acrylic monomer, an acrylic ester soft monomer, an acrylic ester hard monomer and a crosslinkable acrylic ester monomer to obtain emulsion, and then adding a first part of initiator to uniformly mix to obtain pre-emulsion A; uniformly mixing an organosilicon monomer and a second part of initiator to obtain a pre-emulsion B;
(2) And heating and stirring the second part of water and the second part of emulsifier uniformly, adding the first part of pre-emulsion A as seeds under the condition of heating and stirring, adding the third part of initiator, uniformly mixing, adding the second part of pre-emulsion A, then adding the pre-emulsion B, carrying out heat preservation reaction, cooling, and then adding a neutralizing agent to regulate the pH value, thus obtaining the organosilicon acrylic emulsion.
8. The method for preparing a silicone acrylate emulsion according to claim 7, wherein in said step (1), the first part of water is 8.2 to 15.8 parts by weight; the weight part of the first part of emulsifier is 0.22-0.25 part; the weight part of the first part of initiator is 0.03-0.05 part; the weight part of the second part of initiator is 0.03-0.05 part.
9. The method of producing an emulsion of silicone acrylic acid according to claim 7, wherein in the step (2), the weight part of the first part of the pre-emulsion a is 1.75 to 2.2 parts.
10. The method for preparing an emulsion of a silicone acrylate according to claim 7, wherein in the step (2), the temperature of the incubation reaction is 80-85 ℃ for 5-8 hours.
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