CN115340633A - High-toughness carboxylic butyronitrile latex, preparation method thereof and high-toughness gloves - Google Patents
High-toughness carboxylic butyronitrile latex, preparation method thereof and high-toughness gloves Download PDFInfo
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- CN115340633A CN115340633A CN202210835695.XA CN202210835695A CN115340633A CN 115340633 A CN115340633 A CN 115340633A CN 202210835695 A CN202210835695 A CN 202210835695A CN 115340633 A CN115340633 A CN 115340633A
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- 229920000126 latex Polymers 0.000 title claims abstract description 73
- 239000004816 latex Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 title abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 122
- 238000006243 chemical reaction Methods 0.000 claims abstract description 109
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 91
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 54
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000839 emulsion Substances 0.000 claims abstract description 41
- 239000003999 initiator Substances 0.000 claims abstract description 38
- 238000004132 cross linking Methods 0.000 claims abstract description 36
- 238000007872 degassing Methods 0.000 claims abstract description 31
- 239000006185 dispersion Substances 0.000 claims abstract description 29
- 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 abstract description 27
- 150000002825 nitriles Chemical class 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 17
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 8
- FRQQKWGDKVGLFI-UHFFFAOYSA-N 2-methylundecane-2-thiol Chemical compound CCCCCCCCCC(C)(C)S FRQQKWGDKVGLFI-UHFFFAOYSA-N 0.000 claims abstract description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 24
- 239000002270 dispersing agent Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 16
- 238000004945 emulsification Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 13
- 239000003995 emulsifying agent Substances 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 9
- 208000012839 conversion disease Diseases 0.000 claims description 8
- ZDNFTNPFYCKVTB-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,4-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C=C1 ZDNFTNPFYCKVTB-UHFFFAOYSA-N 0.000 claims description 6
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- JZEXORLUKMQOFA-UHFFFAOYSA-N 2-(1-ethoxyethyl)-2-(hydroxymethyl)propane-1,3-diol prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCOC(C)C(CO)(CO)CO JZEXORLUKMQOFA-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229920000459 Nitrile rubber Polymers 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 26
- 239000011258 core-shell material Substances 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 26
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 24
- 239000000047 product Substances 0.000 description 22
- LXAHHHIGZXPRKQ-UHFFFAOYSA-N 5-fluoro-2-methylpyridine Chemical compound CC1=CC=C(F)C=N1 LXAHHHIGZXPRKQ-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 229910001873 dinitrogen Inorganic materials 0.000 description 12
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 12
- 235000017557 sodium bicarbonate Nutrition 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 10
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 7
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 5
- 238000004073 vulcanization Methods 0.000 description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 4
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical group CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- XNINAOUGJUYOQX-UHFFFAOYSA-N 2-cyanobutanoic acid Chemical compound CCC(C#N)C(O)=O XNINAOUGJUYOQX-UHFFFAOYSA-N 0.000 description 3
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 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 description 2
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000002560 nitrile group Chemical group 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 description 2
- 239000005843 Thiram Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 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
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D19/00—Gloves
- A41D19/0055—Plastic or rubber gloves
- A41D19/0058—Three-dimensional gloves
- A41D19/0062—Three-dimensional gloves made of one layer of material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L13/00—Compositions of rubbers containing carboxyl groups
- C08L13/02—Latex
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses high-toughness carboxylic butyronitrile latex, a preparation method thereof and high-toughness gloves, and relates to the technical field of synthetic butyronitrile latex. The preparation method comprises the following steps: pre-emulsifying a first water solvent, a first emulsified dispersion liquid and a mixed monomer, and adding a first initiator to perform a polymerization reaction to obtain a seed emulsion; the mixed monomer comprises butadiene, acrylonitrile, a crosslinking monomer and tert-dodecyl mercaptan; pre-emulsifying a second aqueous solvent, a second emulsified dispersion liquid and a reaction monomer to obtain a monomer pre-emulsified solution; reactive monomers include butadiene, acrylonitrile, methacrylic acid, and tertiary dodecyl mercaptan; and carrying out polymerization reaction on the seed emulsion, the monomer pre-emulsified solution and the second initiator, and degassing after the polymerization is finished. The carboxylated nitrile latex with the core-shell structure can be obtained, the soft part of the outer layer of the carboxylated nitrile latex gives good flexibility to the product, and the cross-linking part of the inner core of the colloidal particle gives good strength to the product, so that the product has good flexibility and strength.
Description
Technical Field
The invention relates to the technical field of synthetic butyronitrile latex, in particular to high-toughness carboxyl butyronitrile latex, a preparation method thereof and high-toughness gloves.
Background
Carboxylated nitrile latex is generally obtained by emulsion polymerization of butadiene, acrylonitrile, methacrylic acid or a fourth functional monomer. Because the carboxylic butyronitrile latex contains nitrile group and carboxyl, the product has high strength, good wear resistance, heat resistance, oil resistance, acid and alkali resistance and weather resistance, thereby having very wide application. The disposable butyronitrile gloves prepared by the carboxylic butyronitrile latex are well received by the market because of good mechanical property and good protection effect. The strength and softness of the gloves can be adjusted by adjusting the content of nitrile groups and carboxyl groups in the carboxylated nitrile latex, but the gloves on the market rarely have the performance of high strength and high flexibility, which greatly limits the application of the gloves in certain fields.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide high-toughness carboxylic butyronitrile latex, a preparation method thereof and high-toughness gloves.
The invention is realized in the following way:
in a first aspect, the present invention provides a method for preparing a high-toughness carboxylated nitrile latex, which comprises:
preparing a seed emulsion: pre-emulsifying a first water solvent, a first emulsified dispersion liquid and a mixed monomer, then adding a first initiator to carry out polymerization reaction, and obtaining a seed emulsion when the reaction conversion rate reaches more than 98%; the mixed monomer comprises 60-70% of butadiene, 25-35% of acrylonitrile, 2-7% of crosslinking monomer and 0.1-0.6% of tert-dodecyl mercaptan by mass percent;
preparation of monomer pre-emulsified solution: pre-emulsifying a second water solvent, a second emulsified dispersion liquid and a reaction monomer to obtain a monomer pre-emulsified solution; the reaction monomer comprises, by mass, 70-80% of butadiene, 15-24% of acrylonitrile, 3-5% of methacrylic acid and 0.5-1% of tert-dodecyl mercaptan;
polymerization reaction: carrying out polymerization reaction on the seed emulsion, the monomer pre-emulsified solution and a second initiator, and adding a termination solution when the conversion rate exceeds 97% to finish the reaction;
degassing treatment: the latex after completion of the polymerization was subjected to degassing treatment.
In alternative embodiments, the crosslinking monomer comprises one or more of divinylbenzene, ethoxytrimethylolpropane triacrylate, diallyl terephthalate, and methylenebisacrylamide.
In an alternative embodiment, the mixed monomers comprise, by mass percent, 63-68% of butadiene, 27-32% of acrylonitrile, 3-6% of a crosslinking monomer, and 0.2-0.5% of tertiary dodecyl mercaptan; the reaction monomer comprises 73-78% of butadiene, 18-24% of acrylonitrile, 3-4% of methacrylic acid and 0.6-0.8% of tert-dodecyl mercaptan in percentage by mass;
preferably, the mixed monomer comprises 64-66% of butadiene, 29-31% of acrylonitrile, 4-5% of crosslinking monomer and 0.2-0.4% of tertiary dodecyl mercaptan by mass percent; the reaction monomer comprises 75-77% of butadiene, 19-21% of acrylonitrile, 3.1-3.5% of methacrylic acid and 0.7-0.8% of tert-dodecyl mercaptan by mass percent.
In an alternative embodiment, the mass ratio of the first water solvent, the first emulsified dispersion, the mixed monomer, and the first initiator is 60 to 120:20-40:100-110:3-8; preferably: 80-100:25-35:100-105:5-7 parts; more preferably from 92 to 97:30-34:102-104:6-7;
preferably, the mass ratio of the reaction monomer, the second emulsion dispersion and the second aqueous solvent is 100-120:30-40:70-110; more preferably 105 to 110:32-38:80-100 parts of; more preferably from 107 to 109:34-36:85-95;
preferably, the first and second aqueous solvents are both desalinated water.
In an alternative embodiment, the first and second emulsion dispersions are the same composition; the mass percent of the emulsified and dispersed components in the first emulsified and dispersed liquid is 8-12%, wherein the emulsified and dispersed components comprise 80-92% of emulsifier, 6-15% of dispersant and 1-5% of electrolyte by mass percent;
preferably, the emulsifying and dispersing component comprises 85-90% of emulsifier, 8-12% of dispersant and 2-4% of electrolyte by mass percentage; more preferably, the emulsifying and dispersing component comprises 86-88% of emulsifying agent, 9-11% of dispersing agent and 3-4% of electrolyte by mass percent;
preferably, the emulsifier comprises one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and fatty alcohol-polyoxyethylene ether;
preferably, the dispersing agent is one or more of a diffusant NF, a diffusant MF and a diffusant NNO;
preferably, the electrolytes are EDTA-disodium and sodium bicarbonate;
preferably, the mass percent of the initiator in the first initiator and the mass percent of the initiator in the second initiator are both 4-6%;
preferably, the initiator is at least one of potassium persulfate, ammonium persulfate and hydrogen peroxide.
In an alternative embodiment, the polymerization reaction comprises: firstly adding the seed emulsion, adding the monomer pre-emulsified solution under the stirring condition, heating to 40-45 ℃, adding the second initiator, and then carrying out the polymerization reaction by adopting segmented temperature control;
preferably, the step-wise temperature control comprises the steps of reacting at 40-45 ℃ for 2.5-3.5 hours, reacting at 46-55 ℃ for 3-8 hours, and finally reacting at 56-65 ℃ for 2.5-3.5 hours.
In an alternative embodiment, the mass ratio of the seed emulsion, the monomer pre-emulsification solution, the second initiator and the termination solution is 10-15:60-80:0.5-1.5:0.05-0.1; preferably from 11 to 13:70-76:0.8-1.2:0.05-0.08; more preferably 11 to 12:73-75:1-1.2:0.05-0.06;
preferably, the mass percent of the terminating agent in the terminating solution is 4-6%;
preferably, the terminating agent comprises at least one of sodium thiram, sodium nitrite, and sodium polysulfide.
In an alternative embodiment, the degassing treatment comprises: heating the latex to 55-60 ℃, keeping the pressure at-0.07 to-0.08 Mpa, degassing, and cooling to 30-35 ℃ after degassing.
In a second aspect, the present invention provides a high toughness carboxylated nitrile latex, which is prepared by the method for preparing the high toughness carboxylated nitrile latex according to any one of the previous embodiments.
In a third aspect, the present invention provides a high strength and high toughness glove made using the high strength and high toughness carboxylated nitrile latex of the previous embodiments.
The invention has the following beneficial effects:
according to the preparation method of the high-strength and high-toughness carboxylic butyronitrile latex, the crosslinking monomer is added into the mixed monomer in the process of preparing the seed latex, the crosslinking monomer can be subjected to crosslinking polymerization with other monomers in the mixed monomer to form the hard core polymer seed latex particle with a crosslinking structure, the mass percentage of butadiene in the mixed monomer is reduced, the polymer seed latex particle is ensured to have more excellent strength, the polymer seed latex particle is used as an initiation active center, the reaction monomer is added, and the polymerization reaction is continuously initiated. The ratio of acrylonitrile monomers is reduced in the reaction process, the ratio of butadiene monomers is improved, and the colloidal particles obtained after the reaction have the characteristics of high ratio of butadiene in the outer rubber molecular chain and good flexibility of the molecular chain, wherein the outer soft part endows the product with good flexibility, and the colloidal particle inner core cross-linking part endows the product with good strength, so that the product has good flexibility and strength simultaneously. And because the inner layer part is harder, the inner layer part is equivalent to a crosslinking point in a vulcanization crosslinking system, and the mechanical property of the product is favorably improved. The colloidal particles have special structures, so that the product has good mechanical properties of high strength and high toughness.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The invention provides a preparation method of high-toughness carboxylic acrylonitrile-butadiene latex, which comprises the following steps:
s1, preparing seed emulsion.
Firstly, nitrogen gas replacement is carried out on the reaction kettle, and after the replacement is finished, the reaction kettle is vacuumized to-0.09 Mpa. The first water solvent, the first emulsified dispersion and the mixed monomer were pre-emulsified for 30 minutes. In the pre-emulsification process, a reaction kettle is heated to 50-65 ℃, then a first initiator is added for polymerization reaction, and when the reaction conversion rate reaches more than 98%, a seed emulsion is obtained.
In the present application, the mass ratio of the first aqueous solvent, the first emulsion dispersion, the mixed monomer, and the first initiator is 60 to 120:20-40:100-110:3-8; preferably: 80-100:25-35:100-105:5-7 parts; more preferably 92 to 97:30-34:102-104:6-7.
Wherein the first aqueous solvent is desalted water.
The mass percentage of the emulsified and dispersed components in the first emulsified and dispersed liquid is 8-12%, wherein the emulsified and dispersed components comprise 80-92% of emulsifier, 6-15% of dispersant and 1-5% of electrolyte according to mass percentage; preferably, the emulsifying and dispersing component comprises 85-90% of emulsifier, 8-12% of dispersant and 2-4% of electrolyte by mass percent; more preferably, the emulsifying and dispersing component comprises 86-88% of emulsifying agent, 9-11% of dispersing agent and 3-4% of electrolyte by mass percent; preferably, the emulsifier includes but is not limited to one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and fatty alcohol-polyoxyethylene ether; the dispersing agent comprises one or more of but not limited to a dispersing agent NF, a dispersing agent MF and a dispersing agent NNO; electrolytes include, but are not limited to, EDTA-disodium and sodium bicarbonate.
The mixed monomer comprises 60-70% of butadiene, 25-35% of acrylonitrile, 2-7% of crosslinking monomer and 0.1-0.6% of tert-dodecyl mercaptan by mass percent; the mixed monomer comprises 63-68% of butadiene, 27-32% of acrylonitrile, 3-6% of crosslinking monomer and 0.2-0.5% of tert-dodecyl mercaptan by mass percent; preferably, the mixed monomers include, by mass percent, 64-66% of butadiene, 29-31% of acrylonitrile, 4-5% of a crosslinking monomer, and 0.2-0.4% of tertiary dodecyl mercaptan. Wherein, the crosslinking monomer includes but is not limited to one or more of divinylbenzene, ethoxy trimethylolpropane triacrylate, diallyl terephthalate and methylene bisacrylamide.
The mass percentage of the initiator in the first initiator is 4-6%; preferably, the initiator is at least one of potassium persulfate, ammonium persulfate, and hydrogen peroxide.
In the application, the crosslinking monomer is added into the mixed monomer, so that the scleromere seed polymer emulsion with a crosslinking structure can be obtained during the polymerization reaction of S1, and the seed emulsion particles are endowed with good structural strength due to crosslinking among rubber molecular chains. Meanwhile, the hardness of the seed polymer latex particle can be adjusted by adjusting the addition amounts of the crosslinking monomer and the acrylonitrile. The amount of crosslinking monomer and acrylonitrile is increased to improve hardness, and the amount of butadiene is increased to improve softness.
S2, preparing a monomer pre-emulsification solution.
And pre-emulsifying the second aqueous solvent, the second emulsified dispersion liquid and the reaction monomer to obtain a monomer pre-emulsified solution. Specifically, adding a reaction monomer into a mixing kettle, continuously adding an emulsifier solution, continuously adding desalted water, starting stirring, and pre-emulsifying for 1 hour to obtain a uniform pre-emulsified solution for later use.
Wherein the mass ratio of the reaction monomer to the second emulsified dispersion to the second water solvent is 100-120:30-40:70-110; preferably 105 to 110:32-38:80-100 parts of; more preferably from 107 to 109:34-36:85-95.
The reaction monomer comprises, by mass, 70-80% of butadiene, 15-24% of acrylonitrile, 3-5% of methacrylic acid and 0.5-1% of tert-dodecyl mercaptan; the reaction monomer comprises 73-78% of butadiene, 18-24% of acrylonitrile, 3-4% of methacrylic acid and 0.6-0.8% of tert-dodecyl mercaptan in percentage by mass; the reaction monomer comprises 75-77% of butadiene, 19-21% of acrylonitrile, 3.1-3.5% of methacrylic acid and 0.7-0.8% of tert-dodecyl mercaptan by mass percent.
The composition of the second emulsion dispersion is the same as the first emulsion dispersion and will not be described further herein. The second aqueous solvent is desalted water.
And S3, carrying out polymerization reaction.
Firstly, nitrogen gas replacement is carried out on the reaction kettle, and after the replacement is finished, the reaction kettle is vacuumized to-0.09 Mpa. And (3) carrying out polymerization reaction on the seed emulsion, the monomer pre-emulsified solution and a second initiator, and adding a termination solution when the conversion rate exceeds 97%, so as to finish the reaction.
Specifically, in the application, the seed emulsion is added firstly, the monomer pre-emulsified solution is added under the stirring condition, the temperature is raised to 40-45 ℃, the second initiator is added, and then the segmented temperature control is adopted for carrying out the polymerization reaction; wherein the mass ratio of the seed emulsion to the monomer pre-emulsified solution to the second initiator to the termination solution is 10-15:60-80:0.5-1.5:0.05-0.1; preferably from 11 to 13:70-76:0.8-1.2:0.05-0.08; more preferably from 11 to 12:73-75:1-1.2:0.05-0.06.
In this application, the seed emulsion (i.e., polymer seed latex particle) with a cross-linked structure prepared in step S1 is used as an initiation active center, and a reaction monomer is added to continue to initiate a polymerization reaction. At the moment, the polymer seed latex particles and the reaction monomer are polymerized to form the carboxylated nitrile latex with the core-shell structure, wherein the cross-linking part of the inner colloidal particle core endows the product with good strength, and the soft part of the outer layer endows the product with good flexibility, so that the product has good flexibility and strength at the same time. Because the proportion of acrylonitrile monomer in the monomer pre-emulsification solution is reduced, and the proportion of butadiene monomer is increased, the proportion of butadiene in the outer rubber molecular chain of colloidal particles obtained after the reaction is finished is high, and the flexibility of the molecular chain is good.
The mass percent of the terminating agent in the terminating solution is 4-6%; the terminating agent includes, but is not limited to, at least one of sodium ferbamate, sodium nitrite, and sodium polysulfide. The mass percent of the initiator in the second initiator is 4-6%; initiators include, but are not limited to, at least one of potassium persulfate, ammonium persulfate, and hydrogen peroxide.
The polymerization reaction is carried out by adopting segmented temperature control, so that the final product quality can be better controlled. Preferably, the stepwise temperature control comprises a reaction at 40-45 ℃ for 2.5-3.5 hours, followed by a reaction at 46-55 ℃ for 3-8 hours, and finally a reaction at 56-65 ℃ for 2.5-3.5 hours.
And S4, degassing.
The latex after completion of the polymerization was subjected to degassing treatment. The degassing treatment comprises the following steps: heating the latex to 55-60 deg.C, maintaining the pressure at-0.07 to-0.08 Mpa, degassing, and cooling to 30-35 deg.C after degassing.
The high-toughness carboxyl butyronitrile latex prepared by the steps is latex particles with a core-shell structure, the outer soft part endows a product with good flexibility, and the inner cross-linking part of the colloidal particles endows the product with good strength, so that the high-toughness glove prepared by the high-toughness carboxyl butyronitrile latex has good flexibility and strength. Therefore, the application field of the gloves is expanded, the production cost is reduced, and the popularization of the labor protection gloves is facilitated.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a high-toughness carboxylated nitrile latex, and a preparation method thereof comprises the following steps:
s1, preparing seed emulsion: firstly, nitrogen gas replacement is carried out on the reaction kettle, and after the replacement is finished, the reaction kettle is vacuumized to-0.09 Mpa. Then 60 parts of desalted water is added into the reaction kettle, and 20 parts of first emulsified dispersion liquid with the mass concentration of 10% is added, wherein the mass percentages of the sodium dodecyl benzene sulfonate, the dispersing agent NF, the EDTA-disodium and the sodium bicarbonate are respectively 80%, 15%, 2.5% and 2.5%; 100 parts of mixed monomer, wherein the mass percent of butadiene, acrylonitrile, divinyl benzene and tert-dodecyl mercaptan is 60%, 33%, 6.4% and 0.6%, respectively, the reaction kettle is started to stir, and pre-emulsification is carried out for 30 minutes. In the pre-emulsification process, a reaction kettle is heated to 50 ℃, 6 parts of prepared first initiator solution is added to initiate polymerization, and when the reaction conversion rate reaches more than 98%, the target seed emulsion is obtained. Cooling to 30-40 deg.C for use.
Preparing an S2 monomer pre-emulsified solution: firstly, 100 parts of reaction monomer is added into a mixing kettle, wherein the mass percentages of butadiene, acrylonitrile, methacrylic acid and tert-dodecyl mercaptan are respectively 70%, 26%, 3% and 1%; then adding 30 parts of second emulsified dispersion liquid with the mass concentration of 10%, wherein the mass percentages of the sodium dodecyl sulfate, the dispersing agent MF, the EDTA-disodium and the sodium bicarbonate are 82%, 13%, 2% and 3% respectively; and continuously adding 70 parts of desalted water, starting stirring, and pre-emulsifying for 1 hour to obtain a uniform pre-emulsified solution for later use.
S3, polymerization reaction: firstly, nitrogen gas replacement is carried out on the reaction kettle, and after the replacement is finished, the reaction kettle is vacuumized to-0.09 Mpa. Firstly, 10 parts of the seed emulsion prepared by the S1 is added into a reaction kettle, and the reaction kettle is started to stir. 60 parts of the monomer pre-emulsified solution prepared in S2 was added with stirring. Heating to 40 ℃ was started, and 0.5 part of a second initiator solution having a mass concentration of 5% was added to start the polymerization reaction. The polymerization adopts the step temperature control, and the reaction lasts for 3 hours at 40 ℃, 8 hours at 46 ℃ and 3 hours at 56 ℃. When the conversion rate exceeded 97%, 0.05 part of a terminator having a mass concentration of 5% was added to terminate the reaction.
S4, degassing: and after the polymerization is finished, transferring the latex into a degassing kettle, heating to 55-60 ℃, keeping the pressure at-0.07 to-0.08 Mpa, and cooling to 30-35 ℃ after the degassing is finished to obtain a target finished product.
Example 2
The embodiment provides a high-toughness carboxylated nitrile latex, and a preparation method thereof comprises the following steps:
s1, preparing seed emulsion: firstly, nitrogen gas replacement is carried out on the reaction kettle, and after the replacement is finished, the reaction kettle is vacuumized to-0.09 Mpa. Then 95 parts of desalted water is added into the reaction kettle, and 32 parts of first emulsified dispersion liquid with the mass concentration of 10% is added, wherein the mass percentages of the sodium dodecyl benzene sulfonate, the dispersing agent NF, the EDTA-disodium and the sodium bicarbonate are respectively 87%, 10%, 1.5% and 1.5%; 103 parts of mixed monomer, wherein the mass percentages of butadiene, acrylonitrile, divinylbenzene and tert-dodecyl mercaptan are 65%, 30%, 4.7% and 0.3%, respectively, the reaction kettle is started to stir, and pre-emulsification is carried out for 30 minutes. In the pre-emulsification process, a reaction kettle is heated to 60 ℃, 6 parts of prepared first initiator solution is added to initiate polymerization, and when the reaction conversion rate reaches more than 98%, the target seed emulsion is obtained. Cooling to 30-40 deg.C for use.
Preparation of S2 monomer pre-emulsified solution: firstly, 108 parts of reaction monomer is added into a mixing kettle, wherein the mass percentages of butadiene, acrylonitrile, methacrylic acid and tert-dodecyl mercaptan are 76%, 20%, 3.3% and 0.7% respectively; then adding 35 parts of second emulsified dispersion liquid with the mass concentration of 10%, wherein the mass percentages of the sodium dodecyl sulfate, the dispersing agent MF, the EDTA-disodium and the sodium bicarbonate are respectively 87%, 10%, 1.5% and 1.5%; and continuously adding 90 parts of desalted water, starting stirring, and pre-emulsifying for 1 hour to obtain a uniform pre-emulsified solution for later use.
S3, polymerization reaction: firstly, nitrogen gas replacement is carried out on the reaction kettle, and after the replacement is finished, the reaction kettle is vacuumized to-0.09 Mpa. Firstly, 12 parts of the seed emulsion prepared by the step S1 is added into a reaction kettle, and the reaction kettle is started to stir. 74 parts of the monomer pre-emulsified solution prepared in S2 was added with stirring. Heating to 40 ℃ was started, and 1.1 parts by mass of a second initiator solution having a concentration of 5% was added to start the polymerization reaction. The polymerization adopts the step temperature control, and the reaction lasts for 3 hours at 43 ℃, 6 hours at 50 ℃ and 3 hours at 61 ℃. When the conversion rate exceeded 97%, 0.05 part of a terminator having a mass concentration of 5% was added to terminate the reaction.
S4, degassing: and transferring the latex into a degassing kettle after polymerization is finished, heating to 55-60 ℃, keeping the pressure at-0.07 to-0.08 Mpa, and cooling to 30-35 ℃ after degassing is finished to obtain the target finished product.
Example 3
The embodiment provides a high-toughness carboxylated nitrile latex, and a preparation method thereof comprises the following steps:
s1, preparing seed emulsion: firstly, nitrogen gas replacement is carried out on the reaction kettle, and after the replacement is finished, the reaction kettle is vacuumized to-0.09 Mpa. Then adding 120 parts of desalted water into the reaction kettle, and then adding 40 parts of first emulsified dispersion liquid with the mass concentration of 10%, wherein the mass percentages of sodium dodecyl benzene sulfonate, a dispersing agent NF, EDTA-disodium and sodium bicarbonate are respectively 92%, 6%, 1% and 1%; 110 parts of mixed monomer, wherein the mass percentages of butadiene, acrylonitrile, divinylbenzene and tert-dodecyl mercaptan are respectively 70%, 25%, 4.4% and 0.6%, and the reaction kettle is started to stir, and pre-emulsification is carried out for 30 minutes. In the pre-emulsification process, the reaction kettle is heated to 60 ℃, 7 parts of the prepared first initiator solution is added to initiate polymerization, and when the reaction conversion rate reaches more than 98%, the target seed emulsion is obtained. Cooling to 30-40 deg.C for use.
Preparation of S2 monomer pre-emulsified solution: adding 120 parts of reaction monomer into a mixing kettle, wherein the mass percentages of butadiene, acrylonitrile, methacrylic acid and tert-dodecyl mercaptan are respectively 80%, 15%, 4% and 1%; then adding 40 parts of second emulsified dispersion liquid with the mass concentration of 10%, wherein the mass percentages of the lauryl sodium sulfate, the dispersing agent MF, the EDTA-disodium and the sodium bicarbonate are respectively 92%, 6%, 1% and 1%; and continuously adding 110 parts of desalted water, starting stirring, and pre-emulsifying for 1 hour to obtain a uniform pre-emulsified solution for later use.
S3, polymerization reaction: firstly, nitrogen gas replacement is carried out on the reaction kettle, and after the replacement is finished, the reaction kettle is vacuumized to-0.09 Mpa. Firstly, 15 parts of the seed emulsion prepared by the step S1 is added into a reaction kettle, and the reaction kettle is started to stir. 80 parts of the monomer pre-emulsified solution prepared in S2 was added with stirring. Heating to 43 ℃ was started, and 1.5 parts by mass of a 5% second initiator solution was added to start the polymerization reaction. The polymerization adopts the step temperature control, and the reaction is carried out for 3 hours at 43 ℃, 3 hours at 55 ℃ and 3 hours at 65 ℃. When the conversion rate exceeded 97%, 0.05 part of a terminator having a mass concentration of 5% was added to terminate the reaction.
S4, degassing: and transferring the latex into a degassing kettle after polymerization is finished, heating to 55-60 ℃, keeping the pressure at-0.07 to-0.08 Mpa, and cooling to 30-35 ℃ after degassing is finished to obtain the target finished product.
Example 4
The embodiment provides a high-toughness carboxylated nitrile latex, and a preparation method thereof comprises the following steps:
s1, preparing seed emulsion: firstly, nitrogen gas replacement is carried out on the reaction kettle, and after the replacement is finished, the reaction kettle is vacuumized to-0.09 Mpa. Then 100 parts of desalted water is added into the reaction kettle, and 35 parts of first emulsified dispersion liquid with the mass concentration of 10% is added, wherein the mass percentages of the sodium dodecyl benzene sulfonate, the dispersing agent NF, the EDTA-disodium and the sodium bicarbonate are respectively 90%, 8%, 1% and 1%; 100 parts of mixed monomer, wherein the mass percentages of butadiene, acrylonitrile, divinylbenzene and tert-dodecyl mercaptan are respectively 68%, 27%, 4.5% and 0.5%, and the reaction kettle is started to stir, and pre-emulsification is carried out for 30 minutes. In the pre-emulsification process, a reaction kettle is heated to 60 ℃, 5 parts of prepared first initiator solution is added to initiate polymerization, and when the reaction conversion rate reaches more than 98%, the target seed emulsion is obtained. Cooling to 30-40 deg.C for use.
Preparation of S2 monomer pre-emulsified solution: firstly, adding 110 parts of reaction monomer into a mixing kettle, wherein the mass percentages of butadiene, acrylonitrile, methacrylic acid and tert-dodecyl mercaptan are 73%, 23%, 3.4% and 0.6% respectively; then 32 parts of second emulsified dispersion liquid with the mass concentration of 10% are added, wherein the mass percentages of the lauryl sodium sulfate, the dispersing agent MF, the EDTA-disodium and the sodium bicarbonate are respectively 90%, 8%, 1% and 1%; continuously adding 100 parts of desalted water, starting stirring, and pre-emulsifying for 1 hour to obtain a uniform pre-emulsified solution for later use.
S3, polymerization reaction: firstly, nitrogen gas replacement is carried out on the reaction kettle, and after the replacement is finished, the reaction kettle is vacuumized to-0.09 Mpa. Firstly, 13 parts of the seed emulsion prepared by the step S1 is added into a reaction kettle, and the reaction kettle is started to stir. 70 parts of the monomer pre-emulsified solution prepared in S2 was added with stirring. Heating to 43 ℃ was started, and 0.8 part of a second initiator solution having a mass concentration of 5% was added to start the polymerization reaction. The polymerization adopts the step temperature control, and the reaction is carried out for 3 hours at 43 ℃, 3 hours at 55 ℃ and 3 hours at 65 ℃. When the conversion rate exceeded 97%, 0.08 part of a terminator having a mass concentration of 5% was added to terminate the reaction.
S4, degassing: and transferring the latex into a degassing kettle after polymerization is finished, heating to 55-60 ℃, keeping the pressure at-0.07 to-0.08 Mpa, and cooling to 30-35 ℃ after degassing is finished to obtain the target finished product.
Example 5
The embodiment provides a high-toughness carboxylated nitrile latex, and a preparation method thereof comprises the following steps:
s1, preparing seed emulsion: firstly, nitrogen gas replacement is carried out on the reaction kettle, and after the replacement is finished, the reaction kettle is vacuumized to-0.09 Mpa. Then 100 parts of desalted water is added into the reaction kettle, and 35 parts of first emulsified dispersion liquid with the mass concentration of 8% are added, wherein the mass percentages of sodium dodecyl benzene sulfonate, a dispersing agent NF, EDTA-disodium and sodium bicarbonate are respectively 90%, 8%, 1% and 1%; 100 parts of mixed monomer, wherein the mass percentages of butadiene, acrylonitrile, diallyl terephthalate, methylene bisacrylamide and tert-dodecyl mercaptan are 68%, 27%, 2%, 2.5% and 0.5%, respectively, the reaction kettle is started to stir, and pre-emulsification is carried out for 30 minutes. In the pre-emulsification process, a reaction kettle is heated to 50 ℃, 5 parts of prepared first initiator solution is added to initiate polymerization, and when the reaction conversion rate reaches more than 98%, the target seed emulsion is obtained. Cooling to 30-40 deg.C for use.
Preparation of S2 monomer pre-emulsified solution: firstly, adding 110 parts of reaction monomer into a mixing kettle, wherein the mass percentages of butadiene, acrylonitrile, methacrylic acid and tert-dodecyl mercaptan are 73%, 23%, 3.4% and 0.6% respectively; then 32 parts of second emulsified dispersion liquid with the mass concentration of 8% are added, wherein the mass percentages of the lauryl sodium sulfate, the dispersing agent MF, the EDTA-disodium and the sodium bicarbonate are respectively 90%, 8%, 1% and 1%; and continuously adding 100 parts of desalted water, starting stirring, and pre-emulsifying for 1 hour to obtain a uniform pre-emulsified solution for later use.
S3, polymerization reaction: firstly, nitrogen gas replacement is carried out on the reaction kettle, and after the replacement is finished, the reaction kettle is vacuumized to-0.09 Mpa. Firstly, 13 parts of the seed emulsion prepared by the step S1 is added into a reaction kettle, and the reaction kettle is started to stir. 70 parts of the monomer pre-emulsified solution prepared in S2 was added with stirring. Heating to 45 ℃ was started, and 0.8 part of a second initiator solution having a mass concentration of 5% was added to start the polymerization reaction. The polymerization adopts the step temperature control, and the reaction is carried out for 3.5 hours at the temperature of 43 ℃, 7 hours at the temperature of 55 ℃ and 2.5 hours at the temperature of 65 ℃. When the conversion rate exceeded 97%, 0.08 part of a terminator having a mass concentration of 6% was added to terminate the reaction.
S4, degassing: and transferring the latex into a degassing kettle after polymerization is finished, heating to 55-60 ℃, keeping the pressure at-0.07 to-0.08 Mpa, and cooling to 30-35 ℃ after degassing is finished to obtain the target finished product.
Example 6
This example is substantially the same as example 5 except that 100 parts of the mixed monomers in the present application, wherein the mass percentages of butadiene, acrylonitrile, ethoxytrimethylolpropane triacrylate, diallyl terephthalate, methylenebisacrylamide, and t-dodecyl mercaptan, were 68%, 25.5%, 2%, and 0.5%, respectively.
Example 7
This example is substantially the same as example 5 except that 100 parts of the mixed monomer in the present application, in which the mass percentages of butadiene, acrylonitrile, divinylbenzene, diallyl terephthalate, methylenebisacrylamide and t-dodecanethiol were 68%, 26.5%, 2%, 1% and 0.5%, respectively, was used.
Comparative example 1
Model number 660 carboxylated nitrile latex manufactured by south emperor chemical industries, ltd.
Comparative example 2
The type HT108 carboxylated nitrile latex is manufactured by Shijiazhuang Hongtai rubber Co.
Comparative example 3
This comparative example is substantially the same as example 1 except that "100 parts of mixed monomers in which the mass percentages of butadiene, acrylonitrile, divinylbenzene and tertiary dodecanethiol are 60%, 33%, 6.4% and 0.6%, respectively" in example 1 was modified as follows: 100 parts of reaction monomer, wherein the components of the reaction monomer are consistent with those of the reaction monomer, namely the mass percentages of butadiene, acrylonitrile, methacrylic acid and tert-dodecyl mercaptan are respectively 70%, 26%, 3% and 1%.
Comparative example 4
This comparative example is essentially the same as example 1, except that: in this comparative example, the polymerization reaction was carried out at 46 ℃ for 14 hours.
Comparative example 5
This comparative example is substantially the same as example 1 except that in this comparative example, the amount of the mixed monomer composition is different, and example 1 is such that the mass percentages of butadiene, acrylonitrile, divinylbenzene and tertiary dodecanethiol are 60%, 33%, 6.4% and 0.6%, respectively; this comparative example is 60% butadiene, 29.4% acrylonitrile, 10% divinylbenzene and 0.6% t-dodecyl mercaptan.
Comparative example 6
This comparative example is substantially the same as example 1 except that in this comparative example, the amount of the mixed monomer composition is different, and example 1 is such that the mass percentages of butadiene, acrylonitrile, divinylbenzene and tertiary dodecanethiol are 60%, 33%, 6.4% and 0.6%, respectively; this comparative example was 65% butadiene, 38% acrylonitrile, 1.4% divinylbenzene and 0.6% tertiary dodecanethiol.
Test examples
The latex in the embodiment and the proportion is prepared according to a disposable glove sample preparation process, the prevulcanization, sample preparation and post-vulcanization processes of the latex sample are completely the same except that the performance of the latex to be evaluated is different, and the single variable of the latex is strictly controlled in the sample preparation process. And after sample preparation is finished, testing indexes such as viscosity, particle size, mechanical property and the like of the sample. Wherein the vulcanization bag is butyronitrile latex type II vulcanization bag of star glove Limited company, and the addition amount is 3 percent of the dry ratio between the grinding material and the butyronitrile latex.
The method for testing each index comprises the following steps:
(1) Viscosity: a model NDJ-5S rotational viscometer is adopted, and 60 revolutions of a 1# rotor are tested under the condition.
(2) Particle size analyzer: the particle size detection is carried out by a Malvern particle size analyzer with the model of Zetasizer Lab according to a standard test method provided by a manufacturer.
(3) And (3) testing mechanical properties: the testing method is implemented by adopting a test machine Co., ltd in the south-Ji time with the model of WDW-10B and according to the relevant requirements of national standard GB/T10213-2006.
See table 1 for test results:
TABLE 1 summary of the results of the Performance test of examples and comparative examples
As can be seen from the above table, comparative examples 1-2 employ the existing carboxylated nitrile latex, which has a combination of properties that is less than optimal as compared to example 1 of the present application. In contrast, in comparative example 3, the mixed monomer is directly replaced by the reactive monomer, and the reactive monomer does not contain the crosslinking monomer (divinylbenzene), so that comparative example 3 cannot form a shell-core structure, and the tensile strength is significantly reduced. In comparative example 4, polymerization reaction is performed at the same temperature, and the reaction can be carried out stably only if the temperature in the early stage of the polymerization reaction needs to be low, while in comparative example 4, the reaction is carried out for 14 hours at 46 ℃, which results in serious esterification of internal colloidal particles and reduced comprehensive performance. It can be seen from the data of comparative example 5 that the amount of the crosslinking monomer is increased, and at this time, the core-shell structure is phase-separated, the core and the shell are easily separated, defects are formed, and the core and the shell are easily broken by the tensile force, so that the elongation at break and the tensile strength of comparative example 5 are significantly lower than those of example 1. It can be seen from the data of comparative example 6 that the use of the crosslinking monomer in a small amount results in less core-shell structure formation and reduced tensile strength, but comparative example 6 has better elongation at break because of better film-forming uniformity. Therefore, the performance index of the latex can be changed within the preferable range of the application by adjusting the feeding proportion and the process parameters, but the performance index is obviously better than that of the comparative example, and the latex has the characteristics of high strength and high toughness.
In summary, in the preparation method of the high-toughness carboxylic acrylonitrile butadiene latex provided by the application, the cross-linking monomer is added into the mixed monomer in the process of preparing the seed latex, and the cross-linking monomer can be cross-linked and polymerized with other monomers in the mixed monomer to form the hard-core polymer seed latex particle with a cross-linking structure, so that the mass percentage of butadiene in the mixed monomer is reduced, the polymer seed latex particle is ensured to have more excellent strength, the polymer seed latex particle is used as an initiation active center, the reaction monomer is added, and the polymerization reaction is continuously initiated. The ratio of acrylonitrile monomers is reduced in the reaction process, the ratio of butadiene monomers is improved, and the colloidal particles obtained after the reaction have the characteristics of high ratio of butadiene in the outer rubber molecular chain and good flexibility of the molecular chain, wherein the outer soft part endows the product with good flexibility, and the colloidal particle inner core cross-linking part endows the product with good strength, so that the product has good flexibility and strength simultaneously. And because the inner layer part is harder, the inner layer part is equivalent to a crosslinking point in a vulcanization crosslinking system, and the mechanical property of the product is favorably improved. The colloidal particles have special structures, so that the product has good mechanical properties of high strength and high toughness.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement 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 preparation method of high-toughness carboxylated nitrile latex is characterized by comprising the following steps:
preparing a seed emulsion: pre-emulsifying a first water solvent, a first emulsified dispersion liquid and a mixed monomer, then adding a first initiator to carry out polymerization reaction, and obtaining a seed emulsion when the reaction conversion rate reaches more than 98%; the mixed monomer comprises 60-70% of butadiene, 25-35% of acrylonitrile, 2-7% of crosslinking monomer and 0.1-0.6% of tert-dodecyl mercaptan by mass percent;
preparation of monomer pre-emulsified solution: pre-emulsifying a second aqueous solvent, a second emulsified dispersion liquid and a reaction monomer to obtain a monomer pre-emulsified solution; the reaction monomer comprises, by mass, 70-80% of butadiene, 15-24% of acrylonitrile, 3-5% of methacrylic acid and 0.5-1% of tert-dodecyl mercaptan;
polymerization reaction: carrying out polymerization reaction on the seed emulsion, the monomer pre-emulsified solution and a second initiator, and adding a termination solution when the conversion rate exceeds 97% to finish the reaction;
degassing treatment: the latex after completion of the polymerization was subjected to degassing treatment.
2. The method for preparing high-toughness carboxylated nitrile latex according to claim 1, wherein the crosslinking monomer comprises one or more of divinylbenzene, ethoxytrimethylolpropane triacrylate, diallyl terephthalate and methylenebisacrylamide.
3. The preparation method of the high-toughness carboxylated nitrile latex according to claim 1, wherein the mixed monomers comprise, by mass, 63-68% of butadiene, 27-32% of acrylonitrile, 3-6% of crosslinking monomer and 0.2-0.5% of tertiary dodecyl mercaptan; the reaction monomer comprises 73-78% of butadiene, 18-24% of acrylonitrile, 3-4% of methacrylic acid and 0.6-0.8% of tert-dodecyl mercaptan in percentage by mass.
4. The preparation method of the high-toughness carboxylated nitrile latex according to claim 1, wherein the mass ratio of the first aqueous solvent to the first emulsified dispersion to the mixed monomer to the first initiator is 60-120:20-40:100-110:3-8;
the mass ratio of the reaction monomer to the second emulsion dispersion to the second water solvent is 100-120:30-40:70-110.
5. The method for preparing high-toughness carboxylated nitrile latex according to claim 1, wherein the first emulsified dispersion and the second emulsified dispersion have the same composition; the mass percent of the emulsified and dispersed components in the first emulsified and dispersed liquid is 8-12%, wherein the emulsified and dispersed components comprise 80-92% of emulsifier, 6-15% of dispersant and 1-5% of electrolyte by mass percent.
6. The method for preparing high-toughness carboxylated nitrile rubber latex according to claim 1, wherein the polymerization reaction comprises: firstly adding the seed emulsion, adding the monomer pre-emulsified solution under the stirring condition, heating to 40-45 ℃, adding the second initiator, and then carrying out the polymerization reaction by adopting segmented temperature control;
the step temperature control comprises the steps of firstly reacting at 40-45 ℃ for 2.5-3.5 hours, then reacting at 46-55 ℃ for 3-8 hours, and finally reacting at 56-65 ℃ for 2.5-3.5 hours.
7. The preparation method of the high-toughness carboxylated nitrile latex according to claim 6, wherein the mass ratio of the seed emulsion to the monomer pre-emulsification solution to the second initiator to the termination solution is 10-15:60-80:0.5-1.5:0.05-0.1; the mass percentage of the terminating agent in the terminating solution is 4-6%.
8. The process for the preparation of the high-toughness carboxylated nitrile latex according to claim 1, wherein the degassing treatment comprises: heating the latex to 55-60 ℃, keeping the pressure at-0.07 to-0.08 Mpa, degassing, and cooling to 30-35 ℃ after degassing.
9. A high-toughness carboxylated nitrile latex, characterized in that it is prepared by the process for preparing the high-toughness carboxylated nitrile latex according to any one of claims 1 to 8.
10. A high-toughness glove, characterized in that it is prepared from the high-toughness carboxylated nitrile latex according to claim 9.
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| KR20210132867A (en) * | 2020-04-28 | 2021-11-05 | 주식회사 엘지화학 | Method for preparing nitrile based copolymer |
| CN113683728A (en) * | 2021-07-02 | 2021-11-23 | 上海昶法新材料有限公司 | Preparation method of carboxylated butyronitrile latex |
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