CN118005855A - Nitrile latex, preparation method thereof, hydrogenated nitrile rubber latex, nitrile latex composition and nitrile latex vulcanized rubber - Google Patents
Nitrile latex, preparation method thereof, hydrogenated nitrile rubber latex, nitrile latex composition and nitrile latex vulcanized rubber Download PDFInfo
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- CN118005855A CN118005855A CN202211394084.2A CN202211394084A CN118005855A CN 118005855 A CN118005855 A CN 118005855A CN 202211394084 A CN202211394084 A CN 202211394084A CN 118005855 A CN118005855 A CN 118005855A
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- 229920000126 latex Polymers 0.000 title claims abstract description 175
- 239000004816 latex Substances 0.000 title claims abstract description 172
- 150000002825 nitriles Chemical class 0.000 title claims abstract description 125
- 229920000459 Nitrile rubber Polymers 0.000 title claims abstract description 85
- 239000000203 mixture Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000004636 vulcanized rubber Substances 0.000 title abstract description 16
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 136
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 103
- 229920001577 copolymer Polymers 0.000 claims abstract description 81
- 239000002245 particle Substances 0.000 claims abstract description 57
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 196
- 238000006243 chemical reaction Methods 0.000 claims description 101
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000003995 emulsifying agent Substances 0.000 claims description 21
- ZIWRUEGECALFST-UHFFFAOYSA-M sodium 4-(4-dodecoxysulfonylphenoxy)benzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCOS(=O)(=O)c1ccc(Oc2ccc(cc2)S([O-])(=O)=O)cc1 ZIWRUEGECALFST-UHFFFAOYSA-M 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 7
- 239000003607 modifier Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000004073 vulcanization Methods 0.000 claims description 3
- 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 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 229940096992 potassium oleate Drugs 0.000 claims description 2
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- HLPHHOLZSKWDAK-UHFFFAOYSA-M sodium;formaldehyde;naphthalene-1-sulfonate Chemical compound [Na+].O=C.C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HLPHHOLZSKWDAK-UHFFFAOYSA-M 0.000 claims description 2
- 150000001356 alkyl thiols Chemical class 0.000 claims 2
- 229920003051 synthetic elastomer Polymers 0.000 abstract description 2
- 239000005061 synthetic rubber Substances 0.000 abstract description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 26
- 238000006116 polymerization reaction Methods 0.000 description 26
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 22
- 229920001971 elastomer Polymers 0.000 description 19
- 239000005060 rubber Substances 0.000 description 19
- 239000007787 solid Substances 0.000 description 19
- 238000012360 testing method Methods 0.000 description 15
- 239000003638 chemical reducing agent Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 238000005070 sampling Methods 0.000 description 14
- 239000007800 oxidant agent Substances 0.000 description 13
- 239000001103 potassium chloride Substances 0.000 description 13
- 235000011164 potassium chloride Nutrition 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- FRQQKWGDKVGLFI-UHFFFAOYSA-N 2-methylundecane-2-thiol Chemical compound CCCCCCCCCC(C)(C)S FRQQKWGDKVGLFI-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000001590 oxidative effect Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000002738 chelating agent Substances 0.000 description 7
- -1 alkyl mercaptan Chemical compound 0.000 description 6
- 239000011790 ferrous sulphate Substances 0.000 description 6
- 235000003891 ferrous sulphate Nutrition 0.000 description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 6
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 5
- SPTHWAJJMLCAQF-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 125000002560 nitrile group Chemical group 0.000 description 3
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- UWSAIOMORQUEHN-UHFFFAOYSA-L sodium;2-[2-[carboxylatomethyl(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetate;iron(5+) Chemical compound [Na+].[Fe+5].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O UWSAIOMORQUEHN-UHFFFAOYSA-L 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- QZKRHPLGUJDVAR-UHFFFAOYSA-K EDTA trisodium salt Chemical compound [Na+].[Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O QZKRHPLGUJDVAR-UHFFFAOYSA-K 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- YNHLTFFFFZOFBO-UHFFFAOYSA-N OO.C1=CC=CC=2C3=CC=CC=C3C=CC12 Chemical compound OO.C1=CC=CC=2C3=CC=CC=C3C=CC12 YNHLTFFFFZOFBO-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229960005066 trisodium edetate Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the field of synthetic rubber, and discloses a nitrile rubber latex and a preparation method thereof, hydrogenated nitrile rubber latex, a nitrile rubber latex composition and nitrile rubber latex vulcanized rubber. A double-layer structure at least sequentially comprising an inner layer and an outer layer along the direction from the center to the outer surface of the nitrile rubber particles in the nitrile latex; wherein the inner layer is provided by a copolymer A, and the content of bound acrylonitrile is more than or equal to 33wt% and the content of bound isoprene is more than 10wt% and less than 20wt% based on the total weight of the copolymer A; the outer layer is provided by a copolymer B, and the content of bound acrylonitrile is more than or equal to 33 weight percent and the content of bound isoprene is more than 5 weight percent based on the total weight of the copolymer A and the copolymer B. The nitrile rubber particles in the nitrile rubber latex have a double-layer structure, and the content of the combined nitrile in the nitrile rubber latex product is more than or equal to 33wt%, so that the nitrile rubber latex has excellent oil resistance and provides good elongation at break and stress at definite elongation.
Description
Technical Field
The invention relates to the field of synthetic rubber, in particular to a nitrile latex and a preparation method thereof, hydrogenated nitrile rubber latex, a nitrile latex composition and nitrile latex vulcanized rubber.
Background
Butadiene-acrylonitrile copolymer rubber, namely nitrile rubber for short, is a random copolymer of butadiene and acrylonitrile formed by emulsion polymerization, and has excellent oil resistance, excellent wear resistance, excellent solvent resistance and excellent heat resistance in a wider temperature range because the molecular structure of the polymer contains polar groups of nitrile groups and unsaturated double bonds. Nitrile rubber has two application forms, one is emulsion polymerization to obtain emulsion, and is called nitrile latex for short, and is often used for producing gloves, latex products, adhesives and the like. The other is emulsion polymerization, which is demulsified and dried to give a solid form, commonly known as nitrile rubber. Rubber rings, rubber mats, rubber tubes, rubber belts, foamed products and the like are produced after mixing with carbon black and the like and vulcanization.
The emulsion-form nitrile latex is mainly used for gloves, and compared with gloves produced by other materials, the glove produced by the nitrile latex has excellent protective performance, can prevent oily molecules from invading, and is due to unique performance of polar nitrile groups in the molecular weight of the nitrile rubber. The higher the nitrile group content (bound nitrile content), the better its oil resistance and the better the barrier properties provided. Generally, 5 different grades can be classified according to the mass fraction of bound nitriles in the molecular chain, low nitrile (< 25%), medium nitrile (26% -30%), medium high nitrile (31% -32%), high nitrile (33% -45%) and ultrahigh nitrile (45% -53%). Among them, high nitrile and ultra-high nitrile grades have excellent oil resistance.
Nitrile latex gloves can be broadly classified into two classes, one class containing a fabric liner, and the performance requirements of such gloves on nitrile latex are primarily oil resistance, usually ensured by increasing the level of bound nitrile, for example, high nitrile and ultra high nitrile grade nitrile latex can be used. The other type is a lining-free, i.e., thin glove, commonly used in the medical, inspection, and electronics fields. The glove not only requires the nitrile latex to have good oil resistance, but also requires the nitrile latex to have good elasticity, and is not easy to damage due to stretching deformation in the wearing process and the using process, namely, the nitrile latex is required to have high elongation at break and stretching stress. The high nitrile and ultra-high nitrile grade nitrile latex has a high polar group content in the molecular chain, which reduces the elasticity and is generally unsatisfactory. In order to achieve both elasticity and thin glove production, medium and high nitrile grade nitrile latex is commonly used, but at the same time, certain oil resistance, i.e. protection capability, is sacrificed.
At present, relatively few researches are carried out in this aspect, and how to simultaneously improve the oil resistance, the elongation at break and the stretching stress of the nitrile latex is rarely reported in the prior art.
Disclosure of Invention
The invention aims to solve the problems of poor oil resistance, elongation at break and stress at definite elongation of the prior art, and provides a nitrile rubber latex, a preparation method thereof, hydrogenated nitrile rubber latex, a nitrile rubber composition and nitrile rubber vulcanized rubber.
In order to achieve the above object, a first aspect of the present invention provides a nitrile latex, wherein a double layer structure comprising at least an inner layer and an outer layer in this order along a direction from a center to an outer surface of nitrile rubber particles in the nitrile latex;
wherein the inner layer is provided by a copolymer A, and the content of bound acrylonitrile is more than or equal to 33wt% and the content of bound isoprene is more than 10wt% and less than 20wt% based on the total weight of the copolymer A;
The outer layer is provided by a copolymer B, and the content of bound acrylonitrile is more than or equal to 33 weight percent and the content of bound isoprene is more than 5 weight percent based on the total weight of the copolymer A and the copolymer B.
The second aspect of the invention provides a preparation method of nitrile latex, wherein the method comprises the following steps:
s1, carrying out a first reaction on acrylonitrile A, butadiene A, a molecular weight regulator A, isoprene and an emulsifier in water in the presence of an initiator to obtain a latex A containing nitrile rubber particles A, wherein the nitrile rubber particles A contain an inner layer provided by a copolymer A;
s2, adding acrylonitrile B, butadiene B, a molecular weight regulator A and vinyl unsaturated carboxylic acid into the latex A for a second reaction to obtain latex B containing nitrile rubber particles B, wherein the latex B sequentially comprises an inner layer provided by a copolymer A and an outer layer provided by the copolymer B along the direction from the center of the nitrile rubber particles B to the outer surface;
Wherein the conditions of the first reaction are such that the content of bound acrylonitrile is not less than 33wt% and the content of bound isoprene is more than 10wt% and less than 20wt% of the copolymer A obtained in the first reaction; the diameter of the nitrile rubber particles A in the latex A is 50-100nm;
The conditions of the second reaction are such that a copolymer B is obtained in the second reaction, the content of bound acrylonitrile is more than or equal to 33wt% and the content of bound isoprene is more than 5wt% based on the total weight of the copolymer A and the copolymer B; the diameter of the nitrile rubber particles B in the latex B is 100-150nm.
In a third aspect, the present invention provides a nitrile latex prepared by the above-described preparation method.
In a fourth aspect, the present invention provides a hydrogenated nitrile rubber latex, wherein the hydrogenated nitrile rubber latex is prepared by hydrogenation of the nitrile rubber latex.
In a fifth aspect, the present invention provides a nitrile latex composition, wherein the nitrile latex composition comprises the nitrile latex described above.
The sixth aspect of the invention provides a nitrile latex vulcanized rubber, wherein the nitrile latex vulcanized rubber is prepared by mixing and vulcanizing the nitrile latex composition.
Through the technical scheme, the nitrile latex and the preparation method thereof, the hydrogenated nitrile rubber latex, the nitrile latex composition and the nitrile latex vulcanized rubber have the following beneficial effects:
The nitrile latex provided by the invention has a double-layer structure, the combined nitrile of the nitrile latex is more than 33wt%, and the nitrile latex has excellent oil resistance, meanwhile, by introducing isoprene comonomer, the particle structure in the latex is controlled, and the reaction temperature of each stage is controlled, so that the nitrile latex has a special structure and lower gel content, and therefore, the vulcanized rubber of the nitrile latex keeps better elongation at break and obvious stretching stress, and is particularly suitable for producing thin gloves.
According to the preparation method of the nitrile latex, provided by the invention, the polymerization monomers are fed step by step and polymerized step by step, and the specific particle diameter and the specific acrylonitrile combination amount are obtained in each stage by controlling the reaction conditions of each stage, so that the nitrile latex vulcanized rubber has excellent oil resistance, elongation at break and stretching stress, and the composition and structure of the polymer can be controlled by the method, thereby being beneficial to large-scale industrial stable production.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
As described above, the first aspect of the present invention provides a nitrile latex, wherein a double layer structure comprising at least an inner layer and an outer layer in this order is provided in a direction from the center to the outer surface of nitrile rubber particles in the nitrile latex;
wherein the inner layer is provided by a copolymer A, and the content of bound acrylonitrile is more than or equal to 33wt% and the content of bound isoprene is more than 10wt% and less than 20wt% based on the total weight of the copolymer A;
The outer layer is provided by a copolymer B, and the content of bound acrylonitrile is more than or equal to 33 weight percent and the content of bound isoprene is more than 5 weight percent based on the total weight of the copolymer A and the copolymer B.
The nitrile rubber particles in the nitrile latex provided by the invention have a double-layer structure, comprise the copolymer A and the copolymer B with the combined acrylonitrile content, and contain isoprene structural units in a molecular chain structure, and the special structures can further enable the nitrile latex to have excellent oil resistance, elongation at break and stretching stress at the same time.
According to the invention, the content of bound acrylonitrile is 33-40% by weight and the content of bound isoprene is 10-20% by weight, based on the total weight of the copolymer A.
According to the invention, the content of bound acrylonitrile is 33-40 wt.% and the content of bound isoprene is 5-10 wt.%, based on the total weight of the copolymer A and the copolymer B.
According to the invention, the diameter of the inner layer is 50-100nm, and the sum of the diameters of the inner layer and the outer layer is 100-150nm; preferably, the diameter of the inner layer is 61-91nm, and the sum of the diameters of the inner layer and the outer layer is 120-148nm.
According to the invention, the copolymer B also comprises structural units provided by ethylenically unsaturated carboxylic acids; preferably, the content of bound ethylenically unsaturated carboxylic acid is more than 2wt%, preferably from 2 to 5wt%, based on the total weight of the copolymer a and the copolymer B.
According to the invention, the content of insolubles in chlorobenzene is less than 1% by weight, preferably less than 0.5% by weight, based on the total weight of nitrile rubber particles in the nitrile latex.
The second aspect of the invention provides a preparation method of nitrile latex, wherein the method comprises the following steps:
s1, carrying out a first reaction on acrylonitrile A, butadiene A, a molecular weight regulator A, isoprene and an emulsifier in water in the presence of an initiator to obtain a latex A containing nitrile rubber particles A, wherein the nitrile rubber particles A contain an inner layer provided by a copolymer A;
s2, adding acrylonitrile B, butadiene B, a molecular weight regulator A and vinyl unsaturated carboxylic acid into the latex A for a second reaction to obtain latex B containing nitrile rubber particles B, wherein the latex B sequentially comprises an inner layer provided by a copolymer A and an outer layer provided by the copolymer B along the direction from the center of the nitrile rubber particles B to the outer surface;
Wherein the conditions of the first reaction are such that the content of bound acrylonitrile is not less than 33wt% and the content of bound isoprene is more than 10wt% and less than 20wt% of the copolymer A obtained in the first reaction; the diameter of the nitrile rubber particles A in the latex A is 50-100nm;
The conditions of the second reaction are such that a copolymer B is obtained in the second reaction, the content of bound acrylonitrile is more than or equal to 33wt% and the content of bound isoprene is more than 5wt% based on the total weight of the copolymer A and the copolymer B; the diameter of the nitrile rubber particles B in the latex B is 100-150nm.
In the invention, the content of the combined nitrile in the nitrile latex product is more than or equal to 33wt% through condition control, and the nitrile latex belongs to high nitrile grade, thereby ensuring the oil resistance of the product.
Further, by introducing isoprene comonomer, feeding step by step, controlling the timing and dosage of feeding distribution, controlling the reaction conditions of each stage and the like, the nitrile latex with a special structure is obtained, and the structural characteristics are as follows:
(1) The molecular chain structure contains isoprene structural units, and the total content of isoprene is more than 5 wt%;
(2) The butyronitrile latex particles have a two-layer structure, wherein the inner layer contains relatively high isoprene binding capacity which is more than 10wt%; the outer layer structure contains a carboxyl structure and transitional isoprene structural units;
(3) Has a lower gel content, the gel content is less than 1wt%.
These special structures in turn enable the nitrile latex vulcanizates obtained to have excellent elongation at break and tensile stress.
Therefore, the nitrile latex obtained by the invention has excellent oil resistance, elongation at break and tensile stress.
According to the invention, in the first reaction, the acrylonitrile A is used in an amount of 36 to 43wt%, the butadiene A is used in an amount of 57 to 64wt%, and the isoprene is used in an amount of 12 to 25wt%, based on the total weight of the acrylonitrile A and the butadiene A; preferably, the acrylonitrile A is used in an amount of 39 to 43wt%, the butadiene A is used in an amount of 57 to 61wt% and the isoprene is used in an amount of 18 to 25wt%, based on the total weight of acrylonitrile A and butadiene A.
According to the invention, in the second reaction, the acrylonitrile B is used in an amount of 33 to 43% by weight, preferably 36 to 43% by weight, based on the total weight of acrylonitrile B and butadiene B. Further, in the second reaction, the material is added in batches and dropwise. The batch addition may be divided into two, three or more times. Preferably, the dropping speed is such that the material is added within 1-5 hours, preferably within 3-5 hours.
Further, in the second reaction, the amount of butadiene B is 57 to 67% by weight and the amount of the ethylenically unsaturated carboxylic acid is 3 to 8% by weight based on the total weight of acrylonitrile B and butadiene B.
In the invention, the method further comprises the following steps: after the first reaction, a small amount of latex A was taken, and the solid content of latex A was tested, thereby calculating the conversion. After breaking a portion of latex a, dry gel tests were obtained for bound acrylonitrile, bound butadiene, and bound isoprene.
In the invention, the method further comprises the following steps: after the second reaction, a small amount of latex B was taken, the solids content of latex B was tested, and the total conversion was calculated. After breaking a portion of latex B, the dry gel test end products were obtained with bound acrylonitrile, bound butadiene, bound isoprene and bound carboxyl units.
In the present invention, it is to be noted that, according to the reaction process, after the second reaction, the bound acrylonitrile content of the copolymer mixture obtained by the first reaction and the second reaction is sampled and tested.
According to the present invention, in step S2, preferably, when the total monomer conversion reaches 40 to 60%, acrylonitrile B, butadiene B, a molecular weight regulator A, and a vinyl unsaturated carboxylic acid are added to perform a second reaction, thereby obtaining a nitrile latex product.
According to the invention, the initiator is used in an amount of 0.1 to 0.5% by weight, based on the total weight of acrylonitrile and butadiene.
According to the invention, the emulsifier is used in an amount of 1.5 to 6% by weight, based on the total weight of acrylonitrile and butadiene.
According to the invention, the first molecular weight regulator is used in an amount of 0.2 to 0.5% by weight and the second molecular weight regulator is used in an amount of 0.2 to 0.5% by weight, based on the total weight of acrylonitrile and butadiene.
In the present invention, the initiator is a redox initiator, wherein the oxidizing agent is selected from oxidizing agents conventional in the art, for example, the oxidizing agent is selected from at least one of dicumyl peroxide, cumene hydroperoxide, p-menthane hydroperoxide, phenanthrene hydroperoxide, potassium persulfate, sodium persulfate and ammonium persulfate, preferably cumene hydroperoxide and/or potassium persulfate. In the present invention, the reducing agent is selected from reducing agents conventional in the art, for example, the reducing agent is selected from at least one of ferrous sulfate, ferric sodium ethylenediamine tetraacetate, ethylenediamine, triethanolamine, sodium formaldehyde sulfoxylate, preferably at least one of ferrous sulfate, ferric sodium ethylenediamine tetraacetate and sodium formaldehyde sulfoxylate. In the invention, the amount of the initiator is 0.1 to 0.5 weight percent based on the total addition amount of butadiene and acrylonitrile, wherein the amount of the oxidant is 0.05 to 0.2 weight percent, and the amount of the reducing agent is 0.1 to 0.5 weight percent.
In the present invention, the emulsifier is selected from emulsifiers conventional in the art, for example, the emulsifier is selected from at least two of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium dodecyl diphenyl ether disulfonate, octyl polyoxyethylene ether, potassium oleate, sodium naphthalene sulfonate formaldehyde condensate.
In the invention, the amount of the emulsifier is 1.5 to 6 weight percent based on the total addition amount of butadiene and acrylonitrile; further, the emulsifier is used in an amount of 3 to 8wt% based on the total weight of acrylonitrile and butadiene.
In the present invention, the first molecular weight modifier and the second molecular weight modifier are both selected from alkyl mercaptan molecular weight modifiers conventional in the art, for example, the molecular weight modifiers are selected from alkyl mercaptans having 8 to 16 carbon atoms, preferably n-dodecyl mercaptan and/or t-dodecyl mercaptan.
In the invention, the amount of the first molecular weight regulator is 0.2-0.5wt% and the amount of the second molecular weight regulator is 0.2-0.5wt% based on the total amount of butadiene and acrylonitrile added.
In the present invention, in order to overcome oxygen inhibition, it is preferable that the contacting is performed in an inert atmosphere. The inert atmosphere refers to any gas or gas mixture that does not chemically react with the reactants and reaction products, such as nitrogen, helium, and one or more of the group zero gases of the periodic table. The inert atmosphere may be maintained by introducing into the polymerization system any one of the gases or gas mixtures described above that do not react chemically with the reactants and products.
In the present invention, the amount of the water is not particularly limited as long as the polymerization reaction can be favorably performed. From the end use point of view, the water is preferably used in an amount of 100 to 150 parts by weight based on 100 parts by weight of the total weight of acrylonitrile and butadiene. Typically, water will contain some metal ions, such as Mg 2+、Ca2+、Fe3 +、Fe2+, which are difficult to completely avoid even with treated deionized water, and which will affect the progress of the polymerization reaction, and therefore, preferably, the process of the present invention further comprises adding a chelating agent to the contact reaction system in step (1). The chelating agent typically has a central ion of one salt-forming group and a complexing group; the central ion and the complexing group are capable of reacting with the metal cation to entrap the metal ion within the chelator, thereby preventing the metal ion from functioning. The kind and amount of the chelating agent are well known to those skilled in the art, and for example, the chelating agent may be selected from one or more of disodium edetate, trisodium edetate and tetrasodium edetate; generally, the chelating agent is used in an amount of 0.01 to 0.03wt% based on the water mass.
In the present invention, in order to promote the stabilization of the emulsion reaction, an electrolyte may be added to the emulsion system in an amount of a kind and an amount well known to those skilled in the art, for example, sodium bicarbonate, potassium carbonate, potassium chloride, etc.
According to the invention, the conditions of the first reaction include: the first reaction temperature is 0 to 40 ℃, preferably 0 to 15 ℃, more preferably 0 to 8 ℃. Lower reaction temperatures favor lower gel content products. The reaction time is 2-5h.
According to the invention, the conditions of the second reaction include: the second reaction temperature is 0 to 40 ℃, preferably 0 to 15 ℃, more preferably 0 to 8 ℃. Lower reaction temperatures favor lower gel content products. The reaction time is 3-10h.
In a third aspect, the present invention provides a nitrile latex prepared by the preparation method described above.
In the present invention, the nitrile latex has an insoluble content of less than 1wt%, preferably less than 0.5wt%, in chlorobenzene.
In the present invention, the nitrile latex is produced by the above method, the dispersion medium is water, and the solid content is not particularly limited. From the viewpoint of application, it is preferably 40 to 60% by weight. In general, the latex can be directly prepared by the above method, and the solid content is controlled by the monomer addition amount, the water addition amount and the polymerization degree, and the control method is a known method. In addition, a method of dilution with water or concentration with water may be employed, and the concentration method may be a common method of distillation, centrifugation, or the like. According to the application requirements, various auxiliary agents such as a stabilizer, a viscosity regulator, a pH regulator, an agglomerating agent and the like can be added after the copolymer latex provided by the invention is prepared by the method, and the auxiliary agents are reported in the published materials and are not repeated.
In a fourth aspect, the present invention provides a hydrogenated nitrile rubber latex, wherein the hydrogenated nitrile rubber latex is prepared by hydrogenation of the nitrile rubber latex described above.
In the invention, the hydrogenated nitrile rubber is prepared by hydrogenation of the nitrile latex. The hydrogenation method is reported in the published materials and is not repeated. The prepared hydrogenated nitrile rubber can maintain the original better oil resistance, and can also obviously improve the weather resistance and chemical resistance of the rubber. The hydrogenated nitrile rubber can be added with reinforcing agents, vulcanizing agents, accelerators, anti-aging agents and the like, or other high polymer materials can be used together to form a composition, and the composition can be vulcanized to obtain the hydrogenated nitrile rubber vulcanized rubber, which are all known methods and are reported in the published materials.
In a fifth aspect, the present invention provides a nitrile latex composition, wherein the nitrile latex composition comprises the nitrile latex described above and/or the hydrogenated nitrile rubber latex described above.
The sixth aspect of the invention provides a nitrile latex vulcanized rubber, wherein the nitrile latex vulcanized rubber is prepared by mixing and vulcanizing the nitrile latex composition.
The present invention will be described in detail by examples.
In the following examples and comparative examples:
The bound nitrile content is measured as follows: flocculating the rubber latex, washing and drying to obtain solid rubber, dissolving the solid rubber with deuterated chloroform, and testing by adopting a nuclear magnetic hydrogen spectrum;
The diameter of the nitrile rubber particles is directly tested by adopting a particle diameter photometer;
The insoluble content in chlorobenzene was measured as follows: the latex is flocculated, washed and dried to obtain solid rubber, and the solid rubber is tested by referring to SH/T1050-2014, wherein only toluene in the standard is replaced by chlorobenzene, and other conditions and methods are unchanged;
elongation at break and stretching stress of the vulcanized rubber are measured according to national standard GT/T528-2009;
the oil resistance of the vulcanizate was determined according to method I in SH/T1159-2010.
The raw materials used in the examples and comparative examples are all commercially available.
Example 1
Step 1, 2000g of deionized water, 0.6g of ethylene diamine tetraacetic acid tetrasodium salt (chelating agent), 320g of acrylonitrile A, 6g of tertiary dodecyl mercaptan (molecular weight regulator), 50g of sodium dodecyl diphenyl ether disulfonate (emulsifying agent), 20g of octyl polyoxyethylene ether-10 (emulsifying agent), 8g of potassium chloride (electrolyte), 1.0g of ferrous sulfate (initiator-reducing agent) and 6.0g of formaldehyde sodium sulfoxylate (initiator-reducing agent) are added into a 10L polymerization kettle, stirring and mixing are started, vacuum pumping and nitrogen filling are carried out for three times, then the temperature is kept constant to 5 ℃, 490g of butadiene A and 160g of isoprene are added, and finally 2.5g of hydrogen peroxide diisopropylbenzene (initiator-oxidizing agent) are added for constant temperature reaction for 5 hours. After the end of the first reaction, a latex A containing nitrile rubber particles A containing an inner layer provided by copolymer A was obtained, the polymerization conversion was 45.2% by sampling test, latex A was 35.5% by weight with nitrile, 51.2% by weight with butadiene and 13.3% by weight with isoprene.
And step 2, uniformly adding 400g of pre-mixed acrylonitrile B, 700g of butadiene B, 6g of tertiary dodecyl mercaptan (molecular weight regulator), 15g of sodium dodecyl diphenyl ether disulfonate, 45g of methacrylic acid and 1000g of deionized water through a diaphragm metering pump, wherein the adding speed is 400g/h. The reaction was continued for 5 hours after the addition was completed. After the completion of the second reaction, a latex B containing nitrile rubber particles B was obtained, comprising, in order from the center to the outer surface of the nitrile rubber particles B, an inner layer provided by a copolymer A and an outer layer provided by a copolymer B, and the solid content was 40.9%, the polymerization conversion was 95.9%, the latex B was 34.3% by weight in combination with nitrile, 56.4% by weight in combination with butadiene, 7.2% by weight in combination with isoprene and 2.1% by weight in combination with methacrylic acid, by sampling test. The insoluble content of chlorobenzene was 0.33% by weight, based on the total weight of rubber in the nitrile latex.
In addition, the diameters of the inner layer, the inner layer and the outer layer are shown in Table 1.
In the above reaction, the amount of acrylonitrile A in step 1 was 39.5% by weight, the amount of butadiene A was 60.5% by weight, and the amount of isoprene was 19.8% by weight, based on the total weight of acrylonitrile A and butadiene A. The amount of acrylonitrile B in step 2 was 36.4% by weight, the amount of butadiene B was 63.6% by weight, and the amount of methacrylic acid was 4.1% by weight, based on the total weight of acrylonitrile B and butadiene B. Based on the total weight of butadiene and acrylonitrile, the amount of the oxidant is 0.13wt%, the amount of the reducing agent is 0.37wt%, the amount of the emulsifier is 4.5wt%, the amount of the potassium chloride is 0.42wt%, the amount of the first molecular weight regulator is 0.31wt%, and the amount of the second molecular weight regulator is 0.31wt%.
Example 2
Step 1, 2000g of deionized water, 0.6g of ethylene diamine tetraacetic acid tetrasodium salt, 320g of acrylonitrile A, 6g of tertiary dodecyl mercaptan, 50g of sodium dodecyl diphenyl ether disulfonate, 20g of octyl polyoxyethylene ether-10, 8g of potassium chloride, 1.0g of ferrous sulfate and 6.0g of formaldehyde sodium sulfoxylate are added into a 10L polymerization kettle, stirring and mixing are started uniformly, vacuum pumping and nitrogen filling are carried out for three times, then the temperature is kept to 5 ℃, 460g of butadiene A and 190g of isoprene are added, and finally 2.5g of hydrogen peroxide diisopropylbenzene are added, and the reaction is carried out for 5 hours at the constant temperature. After the end of the first reaction, a latex A containing nitrile rubber particles A containing an inner layer provided by copolymer A was obtained, the polymerization conversion was measured to be 42.7% by weight, the latex A was 36.1% by weight with nitrile, 47.3% by weight with butadiene and 16.6% by weight with isoprene.
And step 2, uniformly adding 400g of pre-mixed acrylonitrile B, 700g of butadiene B, 6g of tertiary dodecyl mercaptan, 15g of sodium dodecyl diphenyl ether disulfonate, 45g of methacrylic acid and 1000g of deionized water through a diaphragm metering pump, wherein the adding speed is 400g/h. The reaction was continued for 5 hours after the addition was completed. After the completion of the second reaction, a latex B containing nitrile rubber particles B was obtained, comprising, in order from the center to the outer surface of the nitrile rubber particles B, an inner layer provided by a copolymer A and an outer layer provided by a copolymer B, and the solid content was 40.2%, the polymerization conversion was 94.3%, the latex B was 34.5% by weight in combination with nitrile, 54.6% by weight in combination with butadiene, 8.9% by weight in combination with isoprene and 2.0% by weight in combination with methacrylic acid, by sampling test. The insoluble content of chlorobenzene was 0.38% by weight, based on the total weight of rubber in the nitrile latex.
In addition, the diameters of the inner layer, the inner layer and the outer layer are shown in Table 1.
In the above reaction, the amount of acrylonitrile A in step 1 was 41.0% by weight, the amount of butadiene A was 59.0% by weight, and the amount of isoprene was 24.4% by weight, based on the total weight of acrylonitrile A and butadiene A. The amount of acrylonitrile B in step 2 was 36.4% by weight, the amount of butadiene B was 63.6% by weight, and the amount of methacrylic acid was 4.1% by weight, based on the total weight of acrylonitrile B and butadiene B. Based on the total weight of butadiene and acrylonitrile, the amount of the oxidant is 0.13wt%, the amount of the reducing agent is 0.37wt%, the amount of the emulsifier is 4.5wt%, the amount of the potassium chloride is 0.43wt%, the amount of the first molecular weight regulator is 0.32wt%, and the amount of the second molecular weight regulator is 0.32wt%.
Example 3
Step 1, 2000g of deionized water, 0.6g of ethylene diamine tetraacetic acid tetrasodium salt, 320g of acrylonitrile A, 6g of tertiary dodecyl mercaptan, 50g of sodium dodecyl diphenyl ether disulfonate, 20g of octyl polyoxyethylene ether-10, 8g of potassium chloride, 1.0g of ferrous sulfate and 6.0g of formaldehyde sodium sulfoxylate are added into a 10L polymerization kettle, stirring and mixing are started uniformly, vacuum pumping and nitrogen filling are carried out for three times, then the temperature is kept to 5 ℃, 540g of butadiene A and 110g of isoprene are added, and finally 2.5g of hydrogen peroxide diisopropylbenzene are added, and the reaction is carried out for 5 hours at the constant temperature. After the end of the first reaction, a latex A containing nitrile rubber particles A containing an inner layer provided by copolymer A was obtained, the polymerization conversion was measured to be 51.9%, the latex A was 34.3% by weight in combination with nitrile, 54.9% by weight in combination with butadiene and 10.8% by weight in combination with isoprene.
And step 2, uniformly adding 400g of pre-mixed acrylonitrile B, 700g of butadiene B, 6g of tertiary dodecyl mercaptan, 15g of sodium dodecyl diphenyl ether disulfonate, 45g of methacrylic acid and 1000g of deionized water through a diaphragm metering pump, wherein the adding speed is 400g/h. The reaction was continued for 5 hours after the addition was completed. After the completion of the second reaction, a latex B containing nitrile rubber particles B was obtained, comprising, in order from the center to the outer surface of the nitrile rubber particles B, an inner layer provided by a copolymer A and an outer layer provided by a copolymer B, and the solid content was 41.7% and the polymerization conversion was 97.8% by sampling test, and the latex B was 34.1% by weight in combination with nitrile, 58.8% by weight in combination with butadiene, 5.1% by weight in combination with isoprene and 2.0% by weight in combination with methacrylic acid. The insoluble content of chlorobenzene was 0.49% by weight, based on the total weight of rubber in the nitrile latex.
In addition, the diameters of the inner layer, the inner layer and the outer layer are shown in Table 1.
In the above reaction, the amount of acrylonitrile A in step 1 was 37.2% by weight, the amount of butadiene A was 62.8% by weight, and the amount of isoprene was 12.8% by weight, based on the total weight of acrylonitrile A and butadiene A. The amount of acrylonitrile B in step 2 was 36.4% by weight, the amount of butadiene B was 63.6% by weight, and the amount of methacrylic acid was 4.1% by weight, based on the total weight of acrylonitrile B and butadiene B. Based on the total weight of butadiene and acrylonitrile, the amount of the oxidant is 0.13wt%, the amount of the reducing agent is 0.36wt%, the amount of the emulsifier is 4.3wt%, the amount of the potassium chloride is 0.41wt%, the amount of the first molecular weight regulator is 0.31wt%, and the amount of the second molecular weight regulator is 0.31wt%.
Example 4
Step 1, the same as in example 1. After the end of the first reaction, a latex A containing nitrile rubber particles A containing an inner layer provided by copolymer A was obtained, the polymerization conversion was 45.1% by sampling test, latex A was 35.4% by weight with nitrile, 51.1% by weight with butadiene and 13.5% by weight with isoprene.
Step 2, heating to 15 ℃, and adding 400g of acrylonitrile B, 700g of butadiene B, 6g of tertiary dodecyl mercaptan, 15g of sodium dodecyl diphenyl ether disulfonate, 45g of methacrylic acid and 1000g of deionized water which are mixed in advance at a constant speed through a diaphragm metering pump, wherein the adding speed is 400g/h. The reaction was continued for 3 hours after the addition was completed. After the completion of the second reaction, a latex B containing nitrile rubber particles B was obtained, comprising, in order from the center to the outer surface of the nitrile rubber particles B, an inner layer provided by a copolymer A and an outer layer provided by a copolymer B, and the solid content was 42.3%, the polymerization conversion was 99.2%, the latex B was 34.0% by weight in combination with nitrile, 54.5% by weight in combination with butadiene, 9.4% by weight in combination with isoprene and 2.1% by weight in combination with methacrylic acid, by sampling test. The insoluble content of chlorobenzene was 0.86wt% based on the total weight of rubber in the nitrile latex.
In addition, the diameters of the inner layer, the inner layer and the outer layer are shown in Table 1.
In the above reaction, the amount of acrylonitrile A in step 1 was 39.5% by weight, the amount of butadiene A was 60.5% by weight, and the amount of isoprene was 19.8% by weight, based on the total weight of acrylonitrile A and butadiene A. The amount of acrylonitrile B in step 2 was 36.4% by weight, the amount of butadiene B was 63.6% by weight, and the amount of methacrylic acid was 4.1% by weight, based on the total weight of acrylonitrile B and butadiene B. Based on the total weight of butadiene and acrylonitrile, the amount of the oxidant is 0.13wt%, the amount of the reducing agent is 0.37wt%, the amount of the emulsifier is 4.5wt%, the amount of the potassium chloride is 0.42wt%, the amount of the first molecular weight regulator is 0.31wt%, and the amount of the second molecular weight regulator is 0.31wt%.
Example 5
Step 1, the same as in example 1. After the end of the first reaction, a latex A containing nitrile rubber particles A containing an inner layer provided by copolymer A was obtained, the polymerization conversion was 44.8% by sampling, latex A was 35.6% by weight with nitrile, 51.3% by weight with butadiene and 13.1% by weight with isoprene.
And step 2, uniformly adding 400g of pre-mixed acrylonitrile B, 700g of butadiene B, 6g of tertiary dodecyl mercaptan, 15g of sodium dodecyl diphenyl ether disulfonate, 80g of methacrylic acid and 1000g of deionized water through a diaphragm metering pump, wherein the adding speed is 400g/h. The reaction was continued for 5 hours after the addition was completed. After the completion of the second reaction, a latex B containing nitrile rubber particles B was obtained, which in turn comprised an inner layer provided by copolymer A and an outer layer provided by copolymer B in the direction from the center to the outer surface of the nitrile rubber particles B, and which had a solids content of 41.1%, a polymerization conversion of 95.5%, a nitrile-bonded content of 33.7% by weight, a butadiene-bonded content of 55.6% by weight, an isoprene-bonded content of 7.2% by weight and a methacrylic acid-bonded content of 3.5% by weight, as measured by sampling. The insoluble content of chlorobenzene was 0.56% by weight, based on the total weight of rubber in the nitrile latex.
In addition, the diameters of the inner layer, the inner layer and the outer layer are shown in Table 1.
In the above reaction, the amount of acrylonitrile A in step 1 was 39.5% by weight, the amount of butadiene A was 60.5% by weight, and the amount of isoprene was 19.8% by weight, based on the total weight of acrylonitrile A and butadiene A. The amount of acrylonitrile B in step 2 was 36.4% by weight, the amount of butadiene B was 63.6% by weight, and the amount of methacrylic acid was 7.3% by weight, based on the total weight of acrylonitrile B and butadiene B. Based on the total weight of butadiene and acrylonitrile, the amount of the oxidant is 0.13wt%, the amount of the reducing agent is 0.37wt%, the amount of the emulsifier is 4.5wt%, the amount of the potassium chloride is 0.42wt%, the amount of the first molecular weight regulator is 0.31wt%, and the amount of the second molecular weight regulator is 0.31wt%.
Example 6
Step 1, 2000g of deionized water, 0.6g of ethylene diamine tetraacetic acid tetrasodium salt, 290g of acrylonitrile A, 6g of tertiary dodecyl mercaptan, 50g of sodium dodecyl diphenyl ether disulfonate, 20g of octyl polyoxyethylene ether-10, 8g of potassium chloride, 1.0g of ferrous sulfate and 6.0g of formaldehyde sodium sulfoxylate are added into a 10L polymerization kettle, stirring and mixing are started uniformly, vacuum pumping and nitrogen filling are carried out for three times, then the temperature is kept to 5 ℃, 490g of butadiene A and 110g of isoprene are added, and finally 2.5g of hydrogen peroxide diisopropylbenzene are added, and the reaction is carried out for 5 hours at the constant temperature. After the end of the first reaction, a latex A containing nitrile rubber particles A containing an inner layer provided by copolymer A was obtained, the polymerization conversion was 43.5% by sampling test, latex A was 33.1% by weight with nitrile, 55.2% by weight with butadiene and 11.7% by weight with isoprene.
And step 2, uniformly adding 360g of pre-mixed acrylonitrile B, 700g of butadiene B, 6g of tertiary dodecyl mercaptan, 15g of sodium dodecyl diphenyl ether disulfonate, 45g of methacrylic acid and 1000g of deionized water through a diaphragm metering pump, wherein the adding speed is 400g/h. The reaction was continued for 5 hours after the addition was completed. After the completion of the second reaction, a latex B containing nitrile rubber particles B was obtained, comprising, in order from the center to the outer surface of the nitrile rubber particles B, an inner layer provided by a copolymer A and an outer layer provided by a copolymer B, and the solid content was 41.3%, the polymerization conversion was 97.1%, the latex B was 33.1% by weight in combination with nitrile, 59.3% by weight in combination with butadiene, 5.4% by weight in combination with isoprene and 2.2% by weight in combination with methacrylic acid, by sampling test. The insoluble content of chlorobenzene was 0.76% by weight, based on the total weight of rubber in the nitrile latex.
In addition, the diameters of the inner layer, the inner layer and the outer layer are shown in Table 1.
In the above reaction, the amount of acrylonitrile A in step 1 was 37.2% by weight, the amount of butadiene A was 62.8% by weight, and the amount of isoprene was 14.1% by weight, based on the total weight of acrylonitrile A and butadiene A. Based on the total weight of acrylonitrile B and butadiene B, the acrylonitrile B amount in step 2 was 34.0wt%, the butadiene B amount was 66.0wt% and the methacrylic acid amount was 4.2wt%. Based on the total weight of butadiene and acrylonitrile, the amount of the oxidant is 0.14wt%, the amount of the reducing agent is 0.38wt%, the amount of the emulsifier is 4.6wt%, the amount of the potassium chloride is 0.43wt%, the amount of the first molecular weight regulator is 0.33wt%, and the amount of the second molecular weight regulator is 0.33wt%.
Comparative example 1
The procedure and the amounts of each charged were the same as in example 1 except that the amount of isoprene charged in the first step was changed from 160g to 75g.
After the end of the first reaction, a latex A containing nitrile rubber particles A containing an inner layer provided by copolymer A was obtained, the polymerization conversion was 55.4% by sampling test, 39.3% by weight of nitrile-bound butadiene, 53.1% by weight of isoprene-bound isoprene.
After the completion of the second reaction, a latex B containing nitrile rubber particles B was obtained, comprising, in order from the center to the outer surface of the nitrile rubber particles B, an inner layer provided by a copolymer A and an outer layer provided by a copolymer B, and the solid content was 41.7% and the polymerization conversion was 97.9% by sampling test, and the latex B was 35.7% by weight in combination with nitrile, 58.6% by weight in combination with butadiene, 3.5% by weight in combination with isoprene and 2.2% by weight in combination with methacrylic acid. The insoluble content of chlorobenzene was 0.42% by weight, based on the total weight of rubber in the nitrile latex.
In addition, the diameters of the inner layer, the inner layer and the outer layer are shown in Table 1.
In the above reaction, the amount of acrylonitrile A in step 1 was 39.5% by weight, the amount of butadiene A was 60.5% by weight, and the amount of isoprene was 9.3% by weight, based on the total weight of acrylonitrile A and butadiene A. The amount of acrylonitrile B in step2 was 36.4% by weight, the amount of butadiene B was 63.6% by weight, and the amount of methacrylic acid was 4.1% by weight, based on the total weight of acrylonitrile B and butadiene B. Based on the total weight of butadiene and acrylonitrile, the amount of the oxidant is 0.13wt%, the amount of the reducing agent is 0.37wt%, the amount of the emulsifier is 4.5wt%, the amount of the potassium chloride is 0.42wt%, the amount of the first molecular weight regulator is 0.31wt%, and the amount of the second molecular weight regulator is 0.31wt%.
Comparative example 2
The procedure and the amounts of each charged were the same as in example 1 except that the amount of isoprene charged in the first step was changed from 160g to 250g.
After the end of the first reaction, a latex A containing nitrile rubber particles A containing an inner layer provided by copolymer A was obtained, the polymerization conversion was 40.2% by sampling, latex A was 33.4% by weight with nitrile, 44.2% by weight with butadiene and 22.4% by weight with isoprene.
After the completion of the second reaction, a latex B containing nitrile rubber particles B was obtained, comprising, in order from the center to the outer surface of the nitrile rubber particles B, an inner layer provided by a copolymer A and an outer layer provided by a copolymer B, and the solid content was 41.1%, the polymerization conversion was 94.2%, the latex B was 33.2% by weight in combination with nitrile, 53.7% by weight in combination with butadiene, 11.1% by weight in combination with isoprene and 2.0% by weight in combination with methacrylic acid, by sampling test. The insoluble content of chlorobenzene was 1.27% by weight, based on the total weight of rubber in the nitrile latex.
In addition, the diameters of the inner layer, the inner layer and the outer layer are shown in Table 1.
In the above reaction, the amount of acrylonitrile A in step 1 was 39.5% by weight, the amount of butadiene A was 60.5% by weight, and the amount of isoprene was 30.3% by weight, based on the total weight of acrylonitrile A and butadiene A. The amount of acrylonitrile B in step 2 was 36.4% by weight, the amount of butadiene B was 63.6% by weight, and the amount of methacrylic acid was 4.1% by weight, based on the total weight of acrylonitrile B and butadiene B. Based on the total weight of butadiene and acrylonitrile, the amount of the oxidant is 0.13wt%, the amount of the reducing agent is 0.37wt%, the amount of the emulsifier is 4.5wt%, the amount of the potassium chloride is 0.42wt%, the amount of the first molecular weight regulator is 0.31wt%, and the amount of the second molecular weight regulator is 0.31wt%.
Comparative example 3
The procedure and the amounts of each material added were the same as in example 1, except that all materials were added at once before the reaction was started, and were not subdivided into two steps.
The final product had a solids content of 42.1%, a polymerization conversion of 98.7%, 34.1% by weight of bound nitrile, 56.3% by weight of bound butadiene, 7.5% by weight of bound isoprene and 2.1% by weight of bound methacrylic acid. The insoluble content of chlorobenzene was 3.47% by weight, based on the total weight of rubber in the nitrile latex.
In addition, the diameters of the inner and outer layers are shown in Table 1.
TABLE 1
| Sample numbering | Particle size of inner layer/nm | Particle size of inner layer and outer layer/nm |
| Example 1 | 68 | 133 |
| Example 2 | 61 | 126 |
| Example 3 | 91 | 141 |
| Example 4 | 70 | 148 |
| Example 5 | 65 | 128 |
| Example 6 | 64 | 145 |
| Comparative example 1 | 104 | 144 |
| Comparative example 2 | 60 | 128 |
| Comparative example 3 | / | 146 |
Test case
Preparation of vulcanized rubber
The latices obtained in examples and comparative examples were diluted to a solid content of 40wt%, and then pH was adjusted to 9 with aqueous ammonia, followed by mixing according to the formulation, and vulcanization was carried out at 110 to 120℃for 20 minutes to obtain a film, and the elongation at break, elongation stress and oil resistance of the vulcanized rubber were measured and the results are shown in Table 2.
The formula is as follows: 100 parts of latex, 2 parts of zinc oxide, 0.5 part of sulfur, 0.3 part of accelerator BZ, 0.5 part of anti-aging agent and 2 parts of titanium dioxide.
TABLE 2
| Sample numbering | Swelling degree/% | 300% Stress/MPa | Elongation at break/% |
| Example 1 | 18.4 | 6.41 | 592 |
| Example 2 | 19.5 | 7.64 | 566 |
| Example 3 | 18.7 | 6.11 | 619 |
| Example 4 | 21.3 | 6.24 | 570 |
| Example 5 | 20.2 | 6.86 | 606 |
| Example 6 | 21.5 | 6.51 | 625 |
| Comparative example 1 | 21.7 | 2.23 | 433 |
| Comparative example 2 | 25.4 | 8.04 | 341 |
| Comparative example 3 | 36.4 | 2.23 | 384 |
As can be seen from Table 2, the nitrile latices provided in examples 1-6 of the present invention combine lower swelling, higher tensile stress and higher elongation at break. Therefore, the nitrile latex provided by the invention has excellent oil resistance and mechanical property, and can meet the application requirements of thin gloves.
In addition, the Isoprene (IP) content of comparative example 1 is low, and the mechanical property is not improved sufficiently; the Isoprene (IP) content of comparative 2 is too high and thus the strength is large, but the hardness is high, resulting in insufficient elongation.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (14)
1. A nitrile latex, characterized by comprising at least a bilayer structure of an inner layer and an outer layer in sequence along the direction from the center to the outer surface of nitrile rubber particles in the nitrile latex;
wherein the inner layer is provided by a copolymer A, and the content of bound acrylonitrile is more than or equal to 33wt% and the content of bound isoprene is more than 10wt% and less than 20wt% based on the total weight of the copolymer A;
The outer layer is provided by a copolymer B, and the content of bound acrylonitrile is more than or equal to 33 weight percent and the content of bound isoprene is more than 5 weight percent based on the total weight of the copolymer A and the copolymer B.
2. The nitrile latex according to claim 1, wherein the content of bound acrylonitrile is 33-40wt% and the content of bound isoprene is 10-20wt%, based on the total weight of the copolymer a;
And/or, the content of bound acrylonitrile is 33-40wt% and the content of bound isoprene is 5-10wt%, based on the total weight of the copolymer A and the copolymer B.
3. The nitrile latex of claim 1, wherein the diameter of the inner layer is 50-100nm and the sum of the diameters of the inner and outer layers is 100-150nm.
4. The nitrile latex according to any of claims 1-3, wherein said copolymer B further comprises structural units provided by ethylenically unsaturated carboxylic acids;
Preferably, the content of bound ethylenically unsaturated carboxylic acid is more than 2wt%, preferably from 2 to 5wt%, based on the total weight of the copolymer a and the copolymer B.
5. The nitrile latex according to any of claims 1-4, wherein the content of insolubles in chlorobenzene is less than 1 wt.%, preferably less than 0.5 wt.%, based on the total weight of nitrile rubber particles in the nitrile latex.
6. A method for preparing a nitrile latex, which is characterized by comprising the following steps:
s1, carrying out a first reaction on acrylonitrile A, butadiene A, a molecular weight regulator A, isoprene and an emulsifier in water in the presence of an initiator to obtain a latex A containing nitrile rubber particles A, wherein the nitrile rubber particles A contain an inner layer provided by a copolymer A;
s2, adding acrylonitrile B, butadiene B, a molecular weight regulator A and vinyl unsaturated carboxylic acid into the latex A for a second reaction to obtain latex B containing nitrile rubber particles B, wherein the latex B sequentially comprises an inner layer provided by a copolymer A and an outer layer provided by the copolymer B along the direction from the center of the nitrile rubber particles B to the outer surface;
Wherein the conditions of the first reaction are such that the content of bound acrylonitrile is not less than 33wt% and the content of bound isoprene is more than 10wt% and less than 20wt% of the copolymer A obtained in the first reaction; the diameter of the nitrile rubber particles A in the latex A is 50-100nm;
The conditions of the second reaction are such that a copolymer B is obtained in the second reaction, the content of bound acrylonitrile is more than or equal to 33wt% and the content of bound isoprene is more than 5wt% based on the total weight of the copolymer A and the copolymer B; the diameter of the nitrile rubber particles B in the latex B is 100-150nm.
7. The production method according to claim 6, wherein in the first reaction, the acrylonitrile A is used in an amount of 36 to 43wt%, the butadiene A is used in an amount of 57 to 64wt%, and the isoprene is used in an amount of 12 to 25wt%, based on the total weight of acrylonitrile A and butadiene A;
in the second reaction, the amount of acrylonitrile B is 33 to 43wt%, the amount of butadiene B is 57 to 67wt%, and the amount of vinyl unsaturated carboxylic acid is 3 to 8wt%, based on the total weight of acrylonitrile B and butadiene B.
8. The preparation method according to claim 6 or 7, wherein the initiator is used in an amount of 0.1 to 0.5wt% based on the total weight of acrylonitrile and butadiene;
The amount of the emulsifier is 1.5-6wt% based on the total weight of the acrylonitrile and the butadiene;
the first molecular weight regulator is used in an amount of 0.2 to 0.5wt% and the second molecular weight regulator is used in an amount of 0.2 to 0.5wt% based on the total weight of acrylonitrile and butadiene.
9. The production method according to any one of claims 6 to 8, wherein the conditions of the first reaction include: the first reaction temperature is 0-40 ℃ and the reaction time is 2-5h;
The conditions of the second reaction include: the second reaction temperature is 0-40 ℃ and the reaction time is 3-10h.
10. The production method according to any one of claims 6 to 9, wherein the first molecular weight modifier and the second molecular weight modifier are each selected from an alkyl thiol-based molecular weight modifier; preferably, each is independently selected from the group consisting of alkyl thiols of C 8-C16; more preferably n-dodecyl mercaptan and/or t-dodecyl mercaptan;
Preferably, the emulsifier is selected from at least two of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium dodecyl diphenyl ether disulfonate, octyl polyoxyethylene ether, potassium oleate, and sodium naphthalene sulfonate formaldehyde condensate.
11. A nitrile latex produced by the production process according to any one of claims 6 to 10.
12. A hydrogenated nitrile rubber latex, characterized in that it is obtained by hydrogenation of the nitrile rubber latex according to any one of claims 1 to 5 and 11.
13. A nitrile latex composition, characterized in that it comprises the nitrile latex according to any one of claims 1 to 5 and 11 and/or the hydrogenated nitrile rubber latex according to claim 12.
14. A nitrile latex vulcanizate, wherein the nitrile latex vulcanizate is prepared from the nitrile latex composition of claim 13 by mixing and vulcanization.
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