CN117567688A - Butyronitrile emulsion and synthesis method and application thereof - Google Patents
Butyronitrile emulsion and synthesis method and application thereof Download PDFInfo
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- CN117567688A CN117567688A CN202410051977.XA CN202410051977A CN117567688A CN 117567688 A CN117567688 A CN 117567688A CN 202410051977 A CN202410051977 A CN 202410051977A CN 117567688 A CN117567688 A CN 117567688A
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- deionized water
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- 239000000839 emulsion Substances 0.000 title claims abstract description 53
- 238000001308 synthesis method Methods 0.000 title claims abstract description 10
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 title abstract description 11
- 238000004945 emulsification Methods 0.000 title description 2
- 229920002545 silicone oil Polymers 0.000 claims abstract description 62
- 239000004014 plasticizer Substances 0.000 claims abstract description 54
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000008367 deionised water Substances 0.000 claims abstract description 50
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000011259 mixed solution Substances 0.000 claims abstract description 28
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000010703 silicon Substances 0.000 claims abstract description 20
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 20
- 150000001733 carboxylic acid esters Chemical class 0.000 claims abstract description 19
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- 239000002270 dispersing agent Substances 0.000 claims abstract description 10
- 239000003792 electrolyte Substances 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 239000006174 pH buffer Substances 0.000 claims abstract description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 9
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- 238000011049 filling Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 36
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 33
- 150000002825 nitriles Chemical class 0.000 claims description 31
- 238000002360 preparation method Methods 0.000 claims description 24
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 21
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 21
- 235000019797 dipotassium phosphate Nutrition 0.000 claims description 21
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 21
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 21
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 21
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 claims description 21
- YUWNCXAPBJINHX-UHFFFAOYSA-N 2-methylprop-2-enoic acid trimethylsilane Chemical compound C(C(=C)C)(=O)O.C[SiH](C)C YUWNCXAPBJINHX-UHFFFAOYSA-N 0.000 claims description 17
- 230000000844 anti-bacterial effect Effects 0.000 claims description 16
- 239000003963 antioxidant agent Substances 0.000 claims description 16
- 239000003899 bactericide agent Substances 0.000 claims description 16
- 239000002518 antifoaming agent Substances 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 230000003078 antioxidant effect Effects 0.000 claims description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 14
- KZOJQMWTKJDSQJ-UHFFFAOYSA-M sodium;2,3-dibutylnaphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S([O-])(=O)=O)=C(CCCC)C(CCCC)=CC2=C1 KZOJQMWTKJDSQJ-UHFFFAOYSA-M 0.000 claims description 12
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 9
- 230000001681 protective effect Effects 0.000 claims description 9
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- -1 methylene dinaphthyl Chemical group 0.000 claims description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 4
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 229940096992 potassium oleate Drugs 0.000 claims description 3
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 3
- 229940083575 sodium dodecyl sulfate Drugs 0.000 claims description 3
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 3
- GCNLRNBDDUYJMP-UHFFFAOYSA-M sodium;2-methylnaphthalene-1-sulfonate Chemical compound [Na+].C1=CC=CC2=C(S([O-])(=O)=O)C(C)=CC=C21 GCNLRNBDDUYJMP-UHFFFAOYSA-M 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 3
- 238000009849 vacuum degassing Methods 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 2
- DUYAAUVXQSMXQP-UHFFFAOYSA-N ethanethioic S-acid Chemical compound CC(S)=O DUYAAUVXQSMXQP-UHFFFAOYSA-N 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 22
- 239000003921 oil Substances 0.000 abstract description 15
- 239000002245 particle Substances 0.000 abstract description 9
- 230000001808 coupling effect Effects 0.000 abstract description 4
- 229920000126 latex Polymers 0.000 abstract description 3
- 239000004816 latex Substances 0.000 abstract description 3
- 229920002521 macromolecule Polymers 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 30
- 239000000243 solution Substances 0.000 description 20
- FRQQKWGDKVGLFI-UHFFFAOYSA-N 2-methylundecane-2-thiol Chemical compound CCCCCCCCCC(C)(C)S FRQQKWGDKVGLFI-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 14
- PGQNYIRJCLTTOJ-UHFFFAOYSA-N trimethylsilyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)O[Si](C)(C)C PGQNYIRJCLTTOJ-UHFFFAOYSA-N 0.000 description 14
- 238000007598 dipping method Methods 0.000 description 11
- 229920000459 Nitrile rubber Polymers 0.000 description 8
- 239000000178 monomer Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- NNIYQNKSQADOLJ-UHFFFAOYSA-N FC(F)=C(F)[Si] Chemical group FC(F)=C(F)[Si] NNIYQNKSQADOLJ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 229920000715 Mucilage Polymers 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000011787 zinc oxide Substances 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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with nitriles
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a butyronitrile emulsion, a synthesis method and application thereof, and relates to the technical field of labor protection latex. The synthesis method comprises the following steps: mixing deionized water, electrolyte, pH buffer, dispersing agent, emulsifying agent and silicone oil plasticizer to form emulsified mixed liquid; mixing deionized water, the emulsified mixed solution, mercaptan, acrylonitrile, unsaturated carboxylic acid and silicon-containing unsaturated carboxylic acid ester, starting stirring, filling nitrogen, vacuumizing, repeatedly replacing for multiple times, adding butadiene, starting heating to 35-45 ℃, adding an initiator, and starting polymerization reaction; when the conversion rate reaches over 96%, ammonia water is added to adjust the pH value to 6-8, a terminator is added to stop the reaction. The invention can improve the flexibility of the macromolecule, and can simultaneously distribute the silicone oil plasticizer into colloidal particles in the synthesis process by utilizing the coupling effect, thereby improving the softness and comfort of the prepared glove and ensuring excellent low temperature resistance under the premise of oil resistance, wear resistance and wear resistance.
Description
Technical Field
The invention relates to the technical field of latex for labor protection, in particular to a butyronitrile emulsion and a synthesis method and application thereof.
Background
With the development of society and the importance of people to labor protection, various work activities basically wear gloves, and the protective gloves are generally used for protecting hands of people in special labor occasions, for example: low temperature environments, oil exposure environments, corrosive operations, and/or protection from frictional damage. In some cases, various protection requirements exist, which require that the protective glove should meet the protection requirements at the same time.
The surface layer of the protective glove is usually made of natural latex or nitrile rubber. Wherein, the natural latex can be well applied at low temperature; however, natural latex is not oil-resistant and has poor wear resistance.
The glass transition temperature of the nitrile rubber is about minus 25 ℃, the glass transition temperature of the vulcanized nitrile rubber is about minus 10 ℃, the temperature of the vulcanized nitrile rubber is lower than the glass transition temperature of the nitrile rubber in high latitude areas such as northeast, the glove has hard hand feeling, becomes fragile and is easy to break, and cannot be used.
Therefore, the prior art has performance limitations no matter the natural latex or the nitrile rubber, and cannot widely meet the protection requirements of complex labor occasions.
Chinese patent application CN 108395595A discloses a preparation method of low temperature resistant butyronitrile protective glove and used butyronitrile mucilage, the method reduces the crosslinking density by adjusting the dosage of crosslinking agent, zinc oxide and the like, further, plasticizer is added to reduce intermolecular acting force, increase intermolecular movement and reduce glass transition temperature, so that the low temperature resistance of the product is better, and the oil resistance, wear resistance and wear resistance of the butyronitrile glove are improved. Solves the defects of the nitrile rubber from the rear end.
In the current market, the existing latex needs to be adjusted at the rear end to improve the defect of the nitrile rubber, and the cost, the performance and the customer experience cannot be well balanced.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a butyronitrile emulsion and a synthesis method and application thereof.
The invention is realized in the following way:
in a first aspect, the invention provides a method for synthesizing a nitrile emulsion, comprising:
mixing deionized water, electrolyte, pH buffer, dispersing agent, emulsifying agent and silicone oil plasticizer to form emulsified mixed liquid;
mixing deionized water, the emulsified mixed solution, mercaptan, acrylonitrile, unsaturated carboxylic acid and silicon-containing unsaturated carboxylic acid ester, starting stirring, filling nitrogen, vacuumizing, repeatedly replacing for multiple times, adding butadiene, starting heating to 35-45 ℃, adding an initiator, and starting polymerization reaction;
when the conversion rate reaches over 96%, ammonia water is added to adjust the pH value to 6-8, a terminator is added to stop the reaction.
In an optional embodiment, the weight portion ratio of the materials in the forming of the emulsified mixture is as follows: 30-90 parts of deionized water, 0.1-0.5 part of electrolyte, 0.1-0.5 part of pH buffer, 0.1-0.5 part of dispersing agent, 2.5-4 parts of emulsifying agent and 2-6 parts of silicone oil plasticizer.
In an alternative embodiment, the materials in the step of polymerization are mixed in parts by weight: 40-110 parts of deionized water, 0.3-0.9 part of mercaptan, 25-40 parts of acrylonitrile, 2-8 parts of unsaturated carboxylic acid, 1-6 parts of silicon-containing unsaturated carboxylic acid ester, 46-72 parts of butadiene and 0.1-0.3 part of initiator.
In an alternative embodiment, the silicone oil plasticizer comprises a combination of one or more of carboxy silicone oil, methyl silicone oil, and fluoro silicone oil.
In alternative embodiments, the silicon-containing unsaturated carboxylic acid ester comprises a combination of one or more of trimethylsilane methacrylate, gamma-methacryloxypropyl trimethoxysilane, and alpha-methacryloxymethyl trimethylsilane.
In an alternative embodiment, the material in forming the emulsified mixture further comprises at least one of features (1) -feature (4):
characteristic (1): the electrolyte comprises one or more of potassium chloride, potassium pyrophosphate and sodium pyrophosphate;
feature (2): the pH buffer comprises a combination of one or more of sodium bicarbonate, potassium carbonate, and potassium hydrogen phosphate;
feature (3): the dispersing agent comprises one or more of sodium methylene dinaphthyl sulfonate, sodium methyl naphthalene sulfonate and sodium dibutyl naphthalene sulfonate;
feature (4): the emulsifier comprises one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, potassium oleate and sodium naphthalene sulfonate.
In an alternative embodiment, the mass further comprises at least one of the features (5) -feature (7) in the step of polymerizing:
feature (5): the mercaptans include a combination of one or more of t-dodecyl mercaptan and isopropyl dithiobis methylthiocarboxylate;
feature (6): the unsaturated carboxylic acid includes a combination of one or more of acrylic acid and methacrylic acid.
Feature (7): the initiator comprises a combination of one or more of potassium persulfate and ammonium persulfate.
In an alternative embodiment, after stopping the reaction, an antifoaming agent is added, and after dilution, vacuum degassing is performed to the desired solids content, and antioxidants and bactericides are added.
In a second aspect, the present invention provides a nitrile emulsion prepared by the synthesis method of the nitrile emulsion according to the previous embodiment.
In a third aspect, the present invention provides the use of the nitrile emulsion according to the previous embodiments for the preparation of protective gloves.
The invention has the following beneficial effects:
according to the synthesis method of the butyronitrile emulsion, silicone oil plasticizer is introduced in the preparation of the emulsion mixed liquid, and silicon-containing unsaturated carboxylic acid ester is introduced as a fourth monomer in the polymerization reaction stage, so that quaternary copolymerization is realized, and the silicon-containing unsaturated carboxylic acid ester is introduced, so that the flexibility of a polymer can be improved; the unsaturated carboxylic ester containing silicon can distribute silicone oil plasticizer into colloidal particles in the synthesis process by utilizing the coupling effect, so that the problem that the conventional plasticizer is difficult to permeate into the colloidal particles is solved, meanwhile, the glove prepared from the nitrile emulsion is soft and comfortable, oil resistance, wear resistance and low temperature resistance are ensured, the problem that the glove is cold-resistant, oil-resistant and cannot be used at low temperature is solved, and the nitrile emulsion can be widely applied to the preparation of protective gloves.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The invention provides a synthesis method of a butyronitrile emulsion, which comprises the following steps:
s1, preparing an emulsified mixed solution.
Deionized water, electrolyte, pH buffer, dispersing agent, emulsifying agent and silicone oil plasticizer are mixed to form emulsified mixed liquid. Wherein, the weight portion ratio of the materials is: 30-90 parts of deionized water, 0.1-0.5 part of electrolyte, 0.1-0.5 part of pH buffer, 0.1-0.5 part of dispersing agent, 2.5-4 parts of emulsifying agent and 2-6 parts of silicone oil plasticizer.
Electrolytes include, but are not limited to, combinations of one or more of potassium chloride, potassium pyrophosphate, and sodium pyrophosphate; pH buffers include, but are not limited to, combinations of one or more of sodium bicarbonate, potassium carbonate, and potassium hydrogen phosphate; the dispersant includes, but is not limited to, a combination of one or more of sodium methylenedinaphthyl sulfonate, sodium methylnaphthalene sulfonate, and sodium dibutylnaphthalene sulfonate; emulsifiers include, but are not limited to, one or more combinations of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, potassium oleate, and sodium naphthalene sulfonate. Silicone oil plasticizers include, but are not limited to, combinations of one or more of carboxy silicone oil, methyl silicone oil, and fluoro silicone oil.
S2, polymerization reaction.
Mixing deionized water, emulsified mixed solution, mercaptan, acrylonitrile, unsaturated carboxylic acid and silicon-containing unsaturated carboxylic acid ester, starting stirring, charging nitrogen, vacuumizing, repeatedly replacing for multiple times, adding butadiene, starting heating to 35-45 ℃, adding an initiator, and starting polymerization reaction; wherein, the weight portion ratio of the materials is: 40-110 parts of deionized water, 0.3-0.9 part of mercaptan, 25-40 parts of acrylonitrile, 2-8 parts of unsaturated carboxylic acid, 1-6 parts of silicon-containing unsaturated carboxylic acid ester, 46-72 parts of butadiene and 0.1-0.3 part of initiator.
Mercaptans include, but are not limited to, combinations of one or more of t-dodecyl mercaptan and isopropyl dithiobis (methylthio) carboxylate; unsaturated carboxylic acids include, but are not limited to, combinations of one or more of acrylic acid and methacrylic acid; silicon-containing unsaturated carboxylic acid esters include, but are not limited to, trimethylsilane methacrylate, gamma-methacryloxypropyl trimethoxysilane, and alpha-methacryloxymethyl trimethylsilane; the initiator includes, but is not limited to, a combination of one or more of potassium persulfate and ammonium persulfate.
S3, post-processing.
When the conversion rate reaches over 96%, ammonia water is added to adjust the pH value to 6-8, a terminator is added to stop the reaction. After stopping the reaction, adding an antifoaming agent, diluting, vacuum degassing to the required solid content, and adding an antioxidant and a bactericide. The terminators, defoamers, antioxidants and bactericides used in this step are all conventional choices in the art and the amounts thereof are also conventional choices in the art and are not described in detail herein.
In the invention, silicone oil plasticizer is introduced in the stage of preparing emulsion mixed liquid, and simultaneously silicon-containing unsaturated carboxylic ester is introduced in the polymerization reaction stage as a fourth monomer, so that quaternary copolymerization is realized, and the introduction of silicon-containing unsaturated carboxylic ester can improve the flexibility of the polymer; the unsaturated carboxylic ester containing silicon can distribute silicone oil plasticizer into colloidal particles in the synthesis process by utilizing the coupling effect, so that the problem that the conventional plasticizer is difficult to permeate into the colloidal particles is solved, meanwhile, the glove prepared from the nitrile emulsion is soft and comfortable, oil resistance, wear resistance and low temperature resistance are ensured, the problem that the glove is cold-resistant, oil-resistant and cannot be used at low temperature is solved, and the nitrile emulsion can be widely applied to the preparation of protective gloves.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
(1) Adding 35kg of deionized water, 0.15kg of potassium pyrophosphate, 0.12kg of potassium hydrogen phosphate, 0.17kg of dibutyl sodium naphthalene sulfonate, 1.86kg of sodium dodecyl benzene sulfonate and 2.04kg of silicone oil plasticizer (carboxyl silicone oil) into an emulsifier preparation kettle, and stirring for 20-25min until the mixture is transparent and uniform to form an emulsified mixed solution for later use.
(2) Adding 44kg of deionized water into a reaction kettle, adding the prepared emulsion mixed solution, sequentially adding 0.35kg of tertiary dodecyl mercaptan, 17.46kg of acrylonitrile, 2.91kg of methacrylic acid and 1.75kg of trimethyl silane methacrylate, starting stirring, charging nitrogen, vacuumizing, repeatedly replacing for three times, adding 36.08kg of butadiene, starting heating to 39 ℃, adding 8.54kg of potassium persulfate solution (1.5%), and starting the reaction.
(3) When the conversion rate reaches over 96%, ammonia water is added to adjust the pH value to about 7, a terminator is added, a defoaming agent is added, the mixture is diluted and then vacuum deaerated to the required solid content, and a certain amount of antioxidant and bactericide are added to prepare the finished product.
(4) And then preparing gloves according to a gum dipping glove process, and evaluating relevant performances.
The amounts of all the components in this example were determined according to the specific reactor (150 kg), and the amounts were calculated according to parts by weight, wherein 58.33 parts of deionized water, 0.25 part of potassium pyrophosphate, 0.20 part of potassium hydrogen phosphate, 0.28 part of sodium dibutylnaphthalene sulfonate, 3.10 parts of sodium dodecylbenzene sulfonate, and 3.40 parts of silicone oil plasticizer (carboxyl silicone oil) in the step (1), each 0.6kg by weight. 73.33 parts of deionized water, 0.58 part of tertiary dodecyl mercaptan, 29.10 parts of acrylonitrile, 4.85 parts of methacrylic acid, 2.92 parts of trimethylsilyl methacrylate, 60.13 parts of butadiene and 0.21 part of potassium persulfate in the step (2), wherein the potassium persulfate is added in a potassium persulfate solution with the concentration of 1.5 percent in the addition process, and each weight part is 0.6kg.
Example 2
(1) 22.98kg of deionized water, 0.06kg of potassium pyrophosphate, 0.06kg of potassium hydrogen phosphate, 0.06kg of dibutyl sodium naphthalene sulfonate, 1.50kg of sodium dodecyl benzene sulfonate and 1.20kg of silicone oil plasticizer (methyl silicone oil) are added into an emulsifier preparation kettle, and the mixture is stirred for 20-25min until the mixture is transparent and uniform to form an emulsified mixed solution for standby.
(2) Adding 60kg of deionized water into a reaction kettle, adding the prepared emulsion mixed solution, sequentially adding 0.18kg of tertiary dodecyl mercaptan, 15kg of acrylonitrile, 1.20kg of methacrylic acid and 0.60kg of trimethyl silane methacrylate, starting stirring, charging nitrogen, vacuumizing, repeatedly replacing for three times, adding 43.12kg of butadiene, starting heating to 39 ℃, adding 4kg of potassium persulfate solution (1.5%), and starting the reaction.
(3) When the conversion rate reaches over 96%, ammonia water is added to adjust the pH value to about 7, a terminator is added, a defoaming agent is added, the mixture is diluted and then vacuum deaerated to the required solid content, and a certain amount of antioxidant and bactericide are added to prepare the finished product.
(4) And then preparing gloves according to a gum dipping glove process, and evaluating relevant performances.
The amounts of all the components in this example were determined according to the specific reactor (150 kg), and were calculated according to parts by weight, wherein 38.3 parts of deionized water, 0.1 part of potassium pyrophosphate, 0.1 part of potassium hydrogen phosphate, 0.1 part of sodium dibutylnaphthalene sulfonate, 2.5 parts of sodium dodecylbenzene sulfonate, and 2 parts of silicone oil plasticizer (carboxyl silicone oil), each 0.6kg by weight were used in step (1). In the step (2), 100 parts of deionized water, 0.3 part of tertiary dodecyl mercaptan, 25 parts of acrylonitrile, 2 parts of methacrylic acid, 1 part of trimethylsilane methacrylate, 71.87 parts of butadiene and 0.1 part of potassium persulfate, wherein the weight of each part is 0.6kg, and the potassium persulfate is added in a potassium persulfate solution with the concentration of 1.5% in the adding process.
Example 3
(1) 50.4kg of deionized water, 0.28kg of potassium pyrophosphate, 0.28kg of potassium hydrogen phosphate, 0.28kg of dibutyl sodium naphthalene sulfonate, 2.24kg of sodium dodecyl benzene sulfonate and 3.36kg of silicone oil plasticizer (fluorosilicone oil) are added into an emulsifier preparation kettle, and stirring is carried out for 20-25min until the mixture is transparent and uniform to form an emulsified mixed solution for standby.
(2) Feeding a polymerization kettle, adding 24kg of deionized water into the reaction kettle, adding the prepared emulsion mixed solution, sequentially adding 0.50kg of tertiary dodecyl mercaptan, 22.4kg of acrylonitrile, 4.48kg of methacrylic acid and 3.36kg of trimethyl silane methacrylate, starting stirring, charging nitrogen, vacuumizing, repeatedly replacing for three times, adding 25.76kg of butadiene, starting heating to 39 ℃, adding 11.2kg of potassium persulfate solution (1.5%), and starting the reaction.
(3) When the conversion rate reaches over 96%, ammonia water is added to adjust the pH value to about 7, a terminator is added, a defoaming agent is added, the mixture is diluted and then vacuum deaerated to the required solid content, and a certain amount of antioxidant and bactericide are added to prepare the finished product.
(4) And then preparing gloves according to a gum dipping glove process, and evaluating relevant performances.
The amounts of all the components in this example were determined according to the specific reactor (150 kg), and the amounts were calculated according to parts by weight, wherein 90 parts of deionized water, 0.5 part of potassium pyrophosphate, 0.5 part of potassium hydrogen phosphate, 0.5 part of sodium dibutylnaphthalene sulfonate, 4 parts of sodium dodecylbenzene sulfonate, and 6 parts of silicone oil plasticizer (carboxyl silicone oil) in the step (1), each 0.56kg by weight. In the step (2), 42.86 parts of deionized water, 0.89 part of tertiary dodecyl mercaptan, 40 parts of acrylonitrile, 8 parts of methacrylic acid, 6 parts of trimethylsilyl methacrylate, 46 parts of butadiene and 0.3 part of potassium persulfate, wherein the potassium persulfate is added in a potassium persulfate solution with the concentration of 1.5 percent in the adding process, and each weight part is 0.56kg.
Example 4
(1) 28kg of deionized water, 0.15kg of potassium pyrophosphate, 0.12kg of potassium hydrogen phosphate, 0.18kg of dibutyl sodium naphthalene sulfonate, 1.89kg of sodium dodecyl benzene sulfonate and 1.2kg of silicone oil plasticizer (carboxyl silicone oil) are added into an emulsifier preparation kettle, and the mixture is stirred for 20 to 25 minutes until the mixture is transparent and uniform to form an emulsified mixed solution for standby.
(2) Feeding a polymerization kettle, adding 50kg of deionized water into the reaction kettle, adding the prepared emulsion mixed solution, sequentially adding 0.35kg of tertiary dodecyl mercaptan, 17.70kg of acrylonitrile, 2.95kg of methacrylic acid and 0.6kg of trimethyl silane methacrylate, starting stirring, charging nitrogen, vacuumizing, repeatedly replacing for three times, adding 37.76kg of butadiene, starting heating to 39 ℃, adding 8.8 kg of potassium persulfate solution (1.5%), and starting the reaction.
(3) When the conversion rate reaches over 96%, ammonia water is added to adjust the pH value to about 7, a terminator is added, a defoaming agent is added, the mixture is diluted and then vacuum deaerated to the required solid content, and a certain amount of antioxidant and bactericide are added to prepare the finished product.
(4) And then preparing gloves according to a gum dipping glove process, and evaluating relevant performances.
The amounts of all the components in this example were determined according to the specific reactor (150 kg), and were calculated according to parts by weight, wherein 46.67 parts of deionized water, 0.25 parts of potassium pyrophosphate, 0.2 parts of potassium hydrogen phosphate, 0.3 parts of sodium dibutylnaphthalene sulfonate, 3.15 parts of sodium dodecylbenzene sulfonate, and 2 parts of silicone oil plasticizer (carboxyl silicone oil), each 0.6kg by weight were used in step (1). 83.33 parts of deionized water, 0.58 part of tertiary dodecyl mercaptan, 29.5 parts of acrylonitrile, 4.92 parts of methacrylic acid, 1 part of trimethylsilyl methacrylate, 62.93 parts of butadiene and 0.22 part of potassium persulfate in the step (2), wherein the potassium persulfate is added in a potassium persulfate solution with the concentration of 1.5 percent in the adding process, and each weight part is 0.6kg.
Example 5
(1) 46kg of deionized water, 0.14kg of potassium pyrophosphate, 0.11kg of potassium hydrogen phosphate, 0.17kg of dibutyl sodium naphthalene sulfonate, 1.82kg of sodium dodecyl benzene sulfonate and 3.41kg of silicone oil plasticizer (carboxyl silicone oil) are added into an emulsifier preparation kettle, and the mixture is stirred for 20 to 25 minutes until the mixture is transparent and uniform to form an emulsified mixed solution for standby.
(2) Adding 33kg of deionized water into a reaction kettle, adding the prepared emulsion mixed solution, sequentially adding 0.34kg of tertiary dodecyl mercaptan, 17.06kg of acrylonitrile, 2.84kg of methacrylic acid and 3.41kg of trimethyl silane methacrylate, starting stirring, charging nitrogen, vacuumizing, repeatedly replacing for three times, adding 33.56kg of butadiene, starting heating to 39 ℃, adding 8.35kg of potassium persulfate solution (1.5%), and starting the reaction.
(3) When the conversion rate reaches over 96%, ammonia water is added to adjust the pH value to about 7, a terminator is added, a defoaming agent is added, the mixture is diluted and then vacuum deaerated to the required solid content, and a certain amount of antioxidant and bactericide are added to prepare the finished product.
(4) And then preparing gloves according to a gum dipping glove process, and evaluating relevant performances.
The amounts of all the components in this example were determined according to the specific reactor (150 kg), and were calculated according to parts by weight, wherein 76.67 parts of deionized water, 0.23 part of potassium pyrophosphate, 0.18 part of potassium hydrogen phosphate, 0.28 part of sodium dibutylnaphthalene sulfonate, 3.03 parts of sodium dodecylbenzene sulfonate, and 5.68 parts of silicone oil plasticizer (carboxyl silicone oil) were used in the step (1), each 0.6kg by weight. In the step (2), 55 parts of deionized water, 0.57 part of tertiary dodecyl mercaptan, 28.43 parts of acrylonitrile, 4.73 parts of methacrylic acid, 5.68 parts of trimethylsilyl methacrylate, 55.93 parts of butadiene and 0.21 part of potassium persulfate, wherein the weight of each part is 0.6kg, and the potassium persulfate is added in a potassium persulfate solution with the concentration of 1.5 percent in the adding process.
Example 6
(1) 28kg of deionized water, 0.15kg of potassium pyrophosphate, 0.12kg of potassium hydrogen phosphate, 0.18kg of dibutyl sodium naphthalene sulfonate, 1.89kg of sodium dodecyl benzene sulfonate and 1.18kg of silicone oil plasticizer (carboxyl silicone oil) are added into an emulsifier preparation kettle, and the mixture is stirred for 20 to 25 minutes until the mixture is transparent and uniform to form an emulsified mixed solution for standby.
(2) Feeding a polymerization kettle, adding 50kg of deionized water into the reaction kettle, adding the prepared emulsion mixed solution, sequentially adding 0.35kg of tertiary dodecyl mercaptan, 17.70kg of acrylonitrile, 2.95kg of methacrylic acid and 3.54kg of trimethyl silane methacrylate, starting stirring, charging nitrogen, vacuumizing, repeatedly replacing for three times, adding 34.81kg of butadiene, starting heating to 39 ℃, adding 8.65kg of potassium persulfate solution (1.5%), and starting the reaction.
(3) When the conversion rate reaches over 96%, ammonia water is added to adjust the pH value to about 7, a terminator is added, a defoaming agent is added, the mixture is diluted and then vacuum deaerated to the required solid content, and a certain amount of antioxidant and bactericide are added to prepare the finished product.
(4) And then preparing gloves according to a gum dipping glove process, and evaluating relevant performances.
The amounts of all the components in this example were determined according to the specific reactor (150 kg), and were calculated according to parts by weight, wherein 47.46 parts of deionized water, 0.25 parts of potassium pyrophosphate, 0.2 parts of potassium hydrogen phosphate, 0.31 parts of sodium dibutylnaphthalene sulfonate, 3.2 parts of sodium dodecylbenzene sulfonate, and 2 parts of silicone oil plasticizer (carboxyl silicone oil) in step (1), each 0.59kg by weight.
84.75 parts of deionized water, 0.59 part of tertiary dodecyl mercaptan, 30 parts of acrylonitrile, 5 parts of methacrylic acid, 6 parts of trimethylsilyl methacrylate, 59 parts of butadiene and 0.22 part of potassium persulfate in the step (2), wherein the potassium persulfate is added in a potassium persulfate solution with the concentration of 1.5% in the addition process.
Comparative example 1
The comparative example provides a nitrile emulsion without silicone oil plasticizer and trimethylsilyl methacrylate, which is prepared by the following steps:
(1) Adding 19kg of deionized water, 0.15kg of potassium pyrophosphate, 0.12kg of potassium hydrogen phosphate, 0.18kg of dibutyl sodium naphthalene sulfonate, 1.92kg of sodium dodecyl benzene sulfonate and 0kg of silicone oil plasticizer into an emulsifier preparation kettle, and stirring for 20-25min until the mixture is transparent and uniform to form an emulsified mixed solution for later use.
(2) Feeding a polymerization kettle, adding 59kg of deionized water into the reaction kettle, adding the prepared emulsion mixed solution, sequentially adding 0.36kg of tertiary dodecyl mercaptan, 18.04kg of acrylonitrile, 3.01kg of methacrylic acid and 0kg of trimethyl silane methacrylate, starting stirring, charging nitrogen, vacuumizing, repeatedly replacing for three times, adding 39.09kg of butadiene, starting heating to 39 ℃, adding 8.82kg of potassium persulfate solution (1.5%), and starting the reaction.
(3) When the conversion rate reaches over 96%, ammonia water is added to adjust the pH value to about 7, a terminator is added, a defoaming agent is added, the mixture is diluted and then vacuum deaerated to the required solid content, and a certain amount of antioxidant and bactericide are added to prepare the finished product.
(4) And then preparing gloves according to a gum dipping glove process, and evaluating relevant performances.
Comparative example 2
The comparative example provides a nitrile emulsion to which a silicone oil plasticizer is not added, but trimethylsilane methacrylate is added, and the specific preparation method is as follows:
(1) Preparing an emulsifier, adding 19.22kg of deionized water, 0.15kg of potassium pyrophosphate, 0.12kg of potassium hydrogen phosphate, 0.18kg of sodium dibutyl naphthalene sulfonate, 1.92kg of sodium dodecyl benzene sulfonate and 0kg of silicone oil plasticizer into an emulsifier preparation kettle, and stirring for 20-25min until the mixture is transparent and uniform to form an emulsified mixed solution for later use.
(2) Feeding a polymerization kettle, adding 59kg of deionized water into the reaction kettle, adding the prepared emulsion mixed solution, sequentially adding 0.36kg of tertiary dodecyl mercaptan, 18kg of acrylonitrile, 3.01kg of methacrylic acid and 1.80kg of trimethyl silane methacrylate, starting stirring, charging nitrogen, vacuumizing, repeatedly replacing for three times, adding 37.28kg of butadiene, starting heating to 39 ℃, adding 8.82kg of potassium persulfate solution (1.5%), and starting the reaction.
(3) When the conversion rate reaches over 96%, ammonia water is added to adjust the pH value to about 7, a terminator is added, a defoaming agent is added, the mixture is diluted and then vacuum deaerated to the required solid content, and a certain amount of antioxidant and bactericide are added to prepare the finished product.
(4) And then preparing gloves according to a gum dipping glove process, and evaluating relevant performances.
Comparative example 3
The comparative example provides a nitrile emulsion to which trimethylsilyl methacrylate was not added but silicone oil plasticizer was added, which was prepared as follows:
(1) Preparing an emulsifier, adding 35kg of deionized water, 0.15kg of potassium pyrophosphate, 0.12kg of potassium hydrogen phosphate, 0.17kg of sodium dibutyl naphthalene sulfonate, 1.86kg of sodium dodecyl benzene sulfonate and 2.04kg of silicone oil plasticizer into an emulsifier preparation kettle, and stirring for 20-25min until the mixture is transparent and uniform to form an emulsified mixed solution for later use.
(2) Adding 44kg of deionized water into a reaction kettle, adding the prepared emulsion mixed solution, sequentially adding 0.35kg of tertiary dodecyl mercaptan, 17.46kg of acrylonitrile, 2.91kg of methacrylic acid and 0kg of trimethyl silane methacrylate, starting stirring, charging nitrogen, vacuumizing, repeatedly replacing for three times, adding 37.82kg of butadiene, starting heating to 39 ℃, adding 8.54kg of potassium persulfate solution (1.5%), and starting reacting.
(3) When the conversion rate reaches over 96%, ammonia water is added to adjust the pH value to about 7, a terminator is added, a defoaming agent is added, the mixture is diluted and then vacuum deaerated to the required solid content, and a certain amount of antioxidant and bactericide are added to prepare the finished product.
(4) And then preparing gloves according to a gum dipping glove process, and evaluating relevant performances.
Comparative example 4
The comparative example provides a nitrile emulsion to which a silicone oil plasticizer and trimethylsilyl methacrylate are added, but the node of addition is after the polymerization reaction is completed, and the specific preparation method is as follows:
(1) Preparing an emulsifier, adding 35kg of deionized water, 0.15kg of potassium pyrophosphate, 0.12kg of potassium hydrogen phosphate, 0.17kg of sodium dibutyl naphthalene sulfonate, 1.86kg of sodium dodecyl benzene sulfonate and 0kg of silicone oil plasticizer into an emulsifier preparation kettle, and stirring for 20-25min until the mixture is transparent and uniform to form an emulsified mixed solution for later use.
(2) Adding 44kg of deionized water into a reaction kettle, adding the prepared emulsion mixed solution, sequentially adding 0.35kg of tertiary dodecyl mercaptan, 17.46kg of acrylonitrile, 2.91kg of methacrylic acid and 0kg of trimethyl silane methacrylate, starting stirring, charging nitrogen, vacuumizing, repeatedly replacing for three times, adding 36.08kg of butadiene, starting heating to 39 ℃, adding 8.54kg of potassium persulfate solution (1.5%), and starting the reaction.
(3) When the conversion rate reaches over 96%, ammonia water is added to adjust the pH value to about 7, a terminator is added, a defoaming agent is added, the mixture is diluted and then vacuum deaerated to the required solid content, a certain amount of antioxidant and bactericide are added, then 1.75kg of trimethylsilane methacrylate and 2.04kg of silicone oil plasticizer are added, and the mixture is stirred uniformly to obtain the finished product.
(4) And then preparing gloves according to a gum dipping glove process, and evaluating relevant performances.
Comparative example 5
The comparative example provides a butyronitrile emulsion, the added plasticizer of which is di (2-ethylhexyl) phthalate, and the specific preparation method is as follows:
(1) Adding 35kg of deionized water, 0.15kg of potassium pyrophosphate, 0.12kg of potassium hydrogen phosphate, 0.17kg of dibutyl sodium naphthalene sulfonate, 1.86kg of sodium dodecyl benzene sulfonate and 2.04kg of plasticizer (di (2-ethylhexyl) phthalate) into an emulsifier preparation kettle, and stirring for 20-25min until the mixture is transparent and uniform to form an emulsified mixture for later use.
(2) Adding 44kg of deionized water into a reaction kettle, adding the prepared emulsion mixed solution, sequentially adding 0.35kg of tertiary dodecyl mercaptan, 17.46kg of acrylonitrile, 2.91kg of methacrylic acid and 1.75kg of trimethyl silane methacrylate, starting stirring, charging nitrogen, vacuumizing, repeatedly replacing for three times, adding 36.08kg of butadiene, starting heating to 39 ℃, adding 8.54kg of potassium persulfate solution (1.5%), and starting the reaction.
(3) When the conversion rate reaches over 96%, ammonia water is added to adjust the pH value to about 7, a terminator is added, a defoaming agent is added, the mixture is diluted and then vacuum deaerated to the required solid content, and a certain amount of antioxidant and bactericide are added to prepare the finished product.
Comparative example 6
The comparative example provides a nitrile emulsion, the added fourth monomer is trifluoro vinyl silane, and the specific preparation method is as follows:
(1) Adding 35kg of deionized water, 0.15kg of potassium pyrophosphate, 0.12kg of potassium hydrogen phosphate, 0.17kg of dibutyl sodium naphthalene sulfonate, 1.86kg of sodium dodecyl benzene sulfonate and 2.04kg of silicone oil plasticizer (carboxyl silicone oil) into an emulsifier preparation kettle, and stirring for 20-25min until the mixture is transparent and uniform to form an emulsified mixed solution for later use.
(2) Adding 44kg of deionized water into a reaction kettle, adding the prepared emulsion mixed solution, sequentially adding 0.35kg of tertiary dodecyl mercaptan, 17.46kg of acrylonitrile, 2.91kg of methacrylic acid and 1.75kg of trifluoro vinyl silane, starting stirring, charging nitrogen, vacuumizing, repeatedly replacing three times, adding 36.08kg of butadiene, starting heating to 39 ℃, adding 8.54kg of potassium persulfate solution (1.5%) and starting reaction.
(3) When the conversion rate reaches over 96%, ammonia water is added to adjust the pH value to about 7, a terminator is added, a defoaming agent is added, the mixture is diluted and then vacuum deaerated to the required solid content, and a certain amount of antioxidant and bactericide are added to prepare the finished product.
(4) And then preparing gloves according to a gum dipping glove process, and evaluating relevant performances.
Experimental example 1
The nitrile emulsions prepared in examples 1 to 6 and comparative examples 1 to 6 were subjected to performance test, wherein the oil resistance and solvent resistance were tested according to the test method for liquid resistance of vulcanized rubber GB1690-1992, and the oil used for the oil resistance test was ASTM 1# oil; solvent resistance test the solvent used was isooctane, n-hexane.
The test results are shown in Table 1.
TABLE 1 statistical tables of performance measurements of nitrile emulsions obtained in different examples
Experimental example two
The performance of the dipped gloves prepared from the nitrile emulsions prepared in examples 1 to 6 and comparative examples 1 to 6 described above was tested in the mechanical protection standard EN388 (industrial glove protection european standard). And (3) testing the low temperature resistance, wherein the nitrile glove is used after being placed at the temperature of minus 10 ℃ for 4 hours, the hand feeling is judged, and the nitrile glove is used after being placed at the temperature of minus 25 ℃ for 4 hours, and the hand feeling is judged.
The test results are shown in Table 2.
TABLE 2 statistical table of performance measurements of dipped gloves obtained from different examples
As can be seen from the above table, the ratio of the extracted soluble substances of the gum-dipped gloves prepared in examples 1 to 6 of the present invention is significantly lower than that of comparative examples 1 to 6, which fully proves that the examples of the present application are more completely reacted and the extraction rates of the plasticizer and the small molecular substances are lower, and at the same time, the change rate of the tensile properties of the gum-dipped gloves prepared in examples 1 to 6 is also significantly lower than that of comparative examples 1 to 6, which proves that examples 1 to 6 have better tensile properties. Further, the gloves of examples 1-6 all achieved 4131, whereas comparative examples 1-6 only achieved 4121, wherein EN388 was a test of abrasion resistance, cut resistance, tear resistance and puncture resistance of the glove and showed a rating thereof, and comparing the data of examples 1-6 and comparative examples 1-6, it can be seen that the major advantage of examples 1-6 over comparative examples 1-6 is better tear resistance, which further embodies that examples 1-6 have more excellent tensile properties. Further, it can be seen that the low temperature resistance of the dipped gloves prepared in examples 1 to 6 of the present invention is significantly better than that of comparative examples 1 to 6, wherein comparative example 1 omits both the silicone oil plasticizer and the trimethylsilyl methacrylate, and the low temperature resistance is the worst, while comparative example 2 omits only the silicone oil plasticizer, and at this time, the addition of trimethylsilyl methacrylate can improve the softness, and comparative example 3 omits only the trimethylsilyl methacrylate, and although comparative example 3 adds the silicone oil plasticizer, it is difficult for the silicone oil plasticizer to penetrate into the colloidal particles due to the lack of trimethylsilyl methacrylate, and thus the hand feel of comparative example 2 used after 4 hours at-10 ℃ is better than that of comparative example 3. In comparative example 4, though the silicone oil plasticizer and the trimethylsilyl methacrylate are added at the same time, they are added after the polymerization reaction is completed, and the trimethylsilyl methacrylate is not quaternary copolymerized with other monomers due to the difference of the added nodes, and the silicone oil plasticizer cannot be effectively distributed in the colloidal particles in the synthesis process, so that the low temperature resistance is still poor. The plasticizer selected in comparative example 5 does not contain silicon, and at this time, a certain effect of improving flexibility can be obtained, but the effect is weaker than that of comparative example 3 in which the silicone-based plasticizer is added alone. The fourth monomer selected in comparative example 6 was not within the scope of the present invention, and at this time, the reaction system was unstable, the viscosity of the final product was high, the mechanical stability was poor, and the glove effect was also poor.
In summary, according to the synthetic method of the nitrile emulsion, silicone oil plasticizer is introduced in the preparation of the emulsion mixture, and silicon-containing unsaturated carboxylic acid ester is introduced in the polymerization reaction stage as a fourth monomer, so that quaternary copolymerization is realized, and the introduction of the silicon-containing unsaturated carboxylic acid ester can improve the flexibility of the polymer; the unsaturated carboxylic ester containing silicon can distribute silicone oil plasticizer into colloidal particles in the synthesis process by utilizing the coupling effect, so that the problem that the conventional plasticizer is difficult to permeate into the colloidal particles is solved, meanwhile, the glove prepared from the nitrile emulsion is soft and comfortable, oil resistance, wear resistance and low temperature resistance are ensured, the problem that the glove is cold-resistant, oil-resistant and cannot be used at low temperature is solved, and the nitrile emulsion can be widely applied to the preparation of protective gloves.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for synthesizing a nitrile emulsion, which is characterized by comprising the following steps:
mixing deionized water, electrolyte, pH buffer, dispersing agent, emulsifying agent and silicone oil plasticizer to form emulsified mixed liquid;
mixing deionized water, the emulsified mixed solution, mercaptan, acrylonitrile, unsaturated carboxylic acid and silicon-containing unsaturated carboxylic acid ester, starting stirring, filling nitrogen, vacuumizing, repeatedly replacing for multiple times, adding butadiene, starting heating to 35-45 ℃, adding an initiator, and starting polymerization reaction;
when the conversion rate reaches over 96%, ammonia water is added to adjust the pH value to 6-8, a terminator is added to stop the reaction.
2. The method for synthesizing the nitrile emulsion according to claim 1, wherein the mixture ratio of the materials in the emulsion mixture is as follows in parts by weight: 30-90 parts of deionized water, 0.1-0.5 part of electrolyte, 0.1-0.5 part of pH buffer, 0.1-0.5 part of dispersing agent, 2.5-4 parts of emulsifying agent and 2-6 parts of silicone oil plasticizer.
3. The method for synthesizing the nitrile emulsion according to claim 1, wherein in the step of polymerization reaction, the materials are mixed according to the parts by weight: 40-110 parts of deionized water, 0.3-0.9 part of mercaptan, 25-40 parts of acrylonitrile, 2-8 parts of unsaturated carboxylic acid, 1-6 parts of silicon-containing unsaturated carboxylic acid ester, 46-72 parts of butadiene and 0.1-0.3 part of initiator.
4. The method for synthesizing a nitrile emulsion according to claim 1, wherein the silicone oil plasticizer comprises one or more of carboxyl silicone oil, methyl silicone oil and fluoro silicone oil.
5. The method of synthesizing a nitrile emulsion of claim 1, wherein the silicon-containing unsaturated carboxylic acid ester comprises a combination of one or more of trimethylsilane methacrylate, gamma-methacryloxypropyl trimethoxysilane, and alpha-methacryloxymethyl trimethylsilane.
6. The method of synthesizing a nitrile emulsion according to any one of claims 1 to 5, characterized in that the material in forming the emulsified mixture further comprises at least one of the characteristics (1) - (4):
characteristic (1): the electrolyte comprises one or more of potassium chloride, potassium pyrophosphate and sodium pyrophosphate;
feature (2): the pH buffer comprises a combination of one or more of sodium bicarbonate, potassium carbonate, and potassium hydrogen phosphate;
feature (3): the dispersing agent comprises one or more of sodium methylene dinaphthyl sulfonate, sodium methyl naphthalene sulfonate and sodium dibutyl naphthalene sulfonate;
feature (4): the emulsifier comprises one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, potassium oleate and sodium naphthalene sulfonate.
7. The method of synthesis of nitrile emulsions according to any one of claims 1 to 5, wherein the material further comprises at least one of features (5) -feature (7) during the step of polymerizing:
feature (5): the mercaptans include a combination of one or more of t-dodecyl mercaptan and isopropyl dithiobis methylthiocarboxylate;
feature (6): the unsaturated carboxylic acid comprises a combination of one or more of acrylic acid and methacrylic acid;
feature (7): the initiator comprises a combination of one or more of potassium persulfate and ammonium persulfate.
8. The method according to any one of claims 1 to 5, further comprising adding an antifoaming agent after stopping the reaction, diluting, vacuum degassing to a desired solid content, and adding an antioxidant and a bactericide.
9. A nitrile emulsion prepared by the synthesis method of the nitrile emulsion according to any one of claims 1-8.
10. Use of the nitrile emulsion according to claim 9 for the preparation of protective gloves.
Priority Applications (1)
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