CN109071886A - 用于浸渍成型的胶乳组合物,以及由其制备的成型制品 - Google Patents
用于浸渍成型的胶乳组合物,以及由其制备的成型制品 Download PDFInfo
- Publication number
- CN109071886A CN109071886A CN201780027059.1A CN201780027059A CN109071886A CN 109071886 A CN109071886 A CN 109071886A CN 201780027059 A CN201780027059 A CN 201780027059A CN 109071886 A CN109071886 A CN 109071886A
- Authority
- CN
- China
- Prior art keywords
- dip forming
- weight
- latex composition
- monomer
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004816 latex Substances 0.000 title claims abstract description 69
- 229920000126 latex Polymers 0.000 title claims abstract description 69
- 239000000203 mixture Substances 0.000 title claims abstract description 68
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000178 monomer Substances 0.000 claims description 63
- 239000002253 acid Substances 0.000 claims description 55
- 229920001577 copolymer Polymers 0.000 claims description 43
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 39
- -1 fumaric acid nitrile Chemical class 0.000 claims description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 21
- 150000002825 nitriles Chemical class 0.000 claims description 21
- 239000005864 Sulphur Substances 0.000 claims description 18
- 239000000839 emulsion Substances 0.000 claims description 15
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 11
- 150000001993 dienes Chemical class 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 8
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 8
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Natural products OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 5
- 230000009477 glass transition Effects 0.000 claims description 5
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 239000001530 fumaric acid Substances 0.000 claims description 4
- 230000036541 health Effects 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- 239000011976 maleic acid Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 2
- UTOVMEACOLCUCK-SNAWJCMRSA-N (e)-4-butoxy-4-oxobut-2-enoic acid Chemical compound CCCCOC(=O)\C=C\C(O)=O UTOVMEACOLCUCK-SNAWJCMRSA-N 0.000 claims description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- ICKPUFPXUBGDLV-UHFFFAOYSA-N 2-methyl-3-methylidenebutanedinitrile Chemical compound N#CC(C)C(=C)C#N ICKPUFPXUBGDLV-UHFFFAOYSA-N 0.000 claims description 2
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 claims description 2
- IGLWCQMNTGCUBB-UHFFFAOYSA-N 3-methylidenepent-1-ene Chemical compound CCC(=C)C=C IGLWCQMNTGCUBB-UHFFFAOYSA-N 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 2
- NVKHKMBMLSFNNU-UHFFFAOYSA-N C=CC1=CC=CC=C1.[S] Chemical compound C=CC1=CC=CC=C1.[S] NVKHKMBMLSFNNU-UHFFFAOYSA-N 0.000 claims 1
- UTOVMEACOLCUCK-PLNGDYQASA-N butyl maleate Chemical compound CCCCOC(=O)\C=C/C(O)=O UTOVMEACOLCUCK-PLNGDYQASA-N 0.000 claims 1
- 238000007689 inspection Methods 0.000 claims 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 11
- 230000000704 physical effect Effects 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 230000032683 aging Effects 0.000 description 8
- 239000003995 emulsifying agent Substances 0.000 description 8
- 239000000701 coagulant Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 210000004243 sweat Anatomy 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- 230000010148 water-pollination Effects 0.000 description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 244000043261 Hevea brasiliensis Species 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 229920003052 natural elastomer Polymers 0.000 description 3
- 229920001194 natural rubber Polymers 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003002 pH adjusting agent Substances 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000000908 ammonium hydroxide Substances 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
- 239000003945 anionic surfactant Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- BHIWKHZACMWKOJ-UHFFFAOYSA-N methyl isobutyrate Chemical compound COC(=O)C(C)C BHIWKHZACMWKOJ-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 150000008117 polysulfides Polymers 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
- 235000019394 potassium persulphate Nutrition 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- 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
- WDDOJLCUVINMPG-UHFFFAOYSA-N 1-cyanopropyl prop-2-enoate 2-methylprop-2-enoic acid Chemical compound C(C=C)(=O)OC(CC)C#N.C(C(=C)C)(=O)O WDDOJLCUVINMPG-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- PDTKWRNJZXHERV-UHFFFAOYSA-N 2-ethenylpyridine;pyridine Chemical compound C1=CC=NC=C1.C=CC1=CC=CC=N1 PDTKWRNJZXHERV-UHFFFAOYSA-N 0.000 description 1
- TVWBTVJBDFTVOW-UHFFFAOYSA-N 2-methyl-1-(2-methylpropylperoxy)propane Chemical compound CC(C)COOCC(C)C TVWBTVJBDFTVOW-UHFFFAOYSA-N 0.000 description 1
- OVWSIXLZDZQCSI-UHFFFAOYSA-N 2-methylprop-2-enoic acid oxalonitrile Chemical compound C(C(=C)C)(=O)O.N#CC#N OVWSIXLZDZQCSI-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- BODRLKRKPXBDBN-UHFFFAOYSA-N 3,5,5-Trimethyl-1-hexanol Chemical compound OCCC(C)CC(C)(C)C BODRLKRKPXBDBN-UHFFFAOYSA-N 0.000 description 1
- DUJMVKJJUANUMQ-UHFFFAOYSA-N 4-methylpentanenitrile Chemical compound CC(C)CCC#N DUJMVKJJUANUMQ-UHFFFAOYSA-N 0.000 description 1
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- MUPIEMDDBGZNRU-UHFFFAOYSA-N C(C)(C)C(=O)O.C(C)(C)(C)OO Chemical compound C(C)(C)C(=O)O.C(C)(C)(C)OO MUPIEMDDBGZNRU-UHFFFAOYSA-N 0.000 description 1
- MGHOFXHSTBMUFT-UHFFFAOYSA-N C(C=C)(=O)OCCCC#N.CC(C(=O)O)=C Chemical compound C(C=C)(=O)OCCCC#N.CC(C(=O)O)=C MGHOFXHSTBMUFT-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- YNENYVYNANJKGV-UHFFFAOYSA-N N-(dihydroxymethyl)-N-methylprop-2-enamide Chemical compound C(C=C)(=O)N(C(O)O)C YNENYVYNANJKGV-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910020275 Na2Sx Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 229940123973 Oxygen scavenger Drugs 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
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- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
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- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种用于浸渍成型的胶乳组合物和由其制备的成型制品,更具体地,所述组合物使用具有亲水性的多硫化钠,从而能够制备具有慢的脱水收缩,优异的拉伸强度、伸长率和应力特性,以及优异的耐汗性,并且佩戴时感觉优异的浸渍成型制品。
Description
技术领域
本申请要求基于2016年09月9日提交的韩国专利申请No.10-2016-0116102的优先权的权益,该申请的全部内容通过引用并入本说明书中。
本发明涉及一种用于浸渍成型的胶乳组合物,以及由其制备的成型制品,所述用于浸渍成型的胶乳组合物通过使用具有亲水性能的多硫化钠作为硫化剂,可以用于制备具有温和的脱水收缩、优异的拉伸强度、伸长率和模量特性、以及优异的对汗液的耐久性的浸渍成型制品。
背景技术
在各种日常生活,例如家务、食品工业、电子工业、医学领域中使用的一次性橡胶手套是通过天然橡胶或腈类共聚物胶乳的浸渍成型而制成的。近年来,由于天然橡胶的过敏和其不稳定的供需的问题,腈手套在一次性手套市场中引起关注。
在替代天然橡胶手套的腈手套市场中,近年来,在手套制造中的加工性能的改善和在手套使用中的耐久性已经成为重要的部分。因此,旨在改善脱水收缩时间以改善手套生产的加工性能,并且生产不硬但是不易撕裂以改善耐用性和佩戴感受的手套。
特别是,手套的佩戴感受与模量值密切相关。也就是说,存在的问题是模量越小佩戴感受越高,但是手套本身的物理性能(拉伸强度、伸长率和模量)越低。另外,存在的问题是,当手套长时间佩戴时发生手套由于汗液而变性或撕裂。因此,迫切需要开发一种通过改善耐久性在人类长时间使用中没有问题的产品。
另一方面,在使用腈类共聚物胶乳生产成型制品中,硫化剂用于交联。根据腈胶乳的组成、分子分布状态、结构等适当选择硫化剂。
诸如粉末硫、不溶性硫、析出硫和胶体硫的硫被用作代表性的硫化剂,并且为了促进它,使用氧化锌、氧化镁、氧化铅(PbO)等。
将腈类共聚物制备为水分散液型的胶乳,以确保混合物均匀混合并且不发生析出。在胶乳中,腈类共聚物通过作为硫化剂的硫彼此交联,此时,当硫渗透到胶乳粒子中时顺利发生交联。此外,使用硫的交联需要老化较长时间。此时,当胶乳的稳定性低时,在表面上形成膜或发生聚集,并且当老化工艺不充分时,变得难以均匀地混合胶乳和配合剂。
为了制备诸如普通手套等的产品,在制备腈类胶乳之后,混合诸如包括硫化剂的各种添加剂的配合剂。此时,由于硫化剂的含量直接影响模量,因此胶乳的稳定性也应该被认为非常重要。
[现有技术文献]
(专利文献1)韩国专利公开No.2010-0066005,“橡胶组合物和使用其制备的橡胶手套”
发明内容
技术问题
作为解决上述问题的各种研究的结果,本发明的发明人证实,当将具有亲水性的多硫化钠作为硫化剂与羧酸改性的腈类共聚物胶乳混合并使用所得混合物进行浸渍成型时,可以制备具有温和的脱水收缩,优异的与拉伸强度、伸长率和模量有关的物理性能,改善的对汗液的耐久性,通过降低模量而改善的佩戴感受的浸渍成型制品,从而完成了本发明。
因此,本发明的一个目的是提供一种包含羧酸改性的腈类共聚物胶乳和多硫化钠的用于浸渍成型的胶乳组合物。
此外,本发明的另一目的是提供一种通过由所述用于浸渍成型的胶乳组合物制备而具有温和的脱水收缩、优异的物理性能和对汗液的耐久性的浸渍成型制品。
技术方案
为了实现上述目的,本发明提供用于浸渍成型的胶乳组合物,其特征在于,包含由共轭二烯类单体、烯属不饱和腈单体和烯属不饱和酸单体共聚而成的羧酸改性的腈类共聚物胶乳,以及多硫化钠。
此时,用于浸渍成型的胶乳组合物的特征在于,基于100重量份的羧酸改性的腈类共聚物,包含0.1重量份至5重量份的多硫化钠。
此外,本发明提供一种浸渍成型制品,其特征在于,通过使上述用于浸渍成型的胶乳组合物浸渍成型而制备。
有益效果
根据本发明的用于浸渍成型的胶乳组合物通过使用具有亲水性的多硫化钠作为硫化剂,并因此在浸渍成型过程中实现温和的脱水收缩而改善加工性能。
特别是,与使用常规硫作为硫化剂的产品相比,通过使用多硫化钠而交联的浸渍成型制品不仅具有相同或更高的拉伸强度、伸长率和模量,而且还改善对汗液的耐久性。另外,浸渍成型制品的模量低于使用常规硫的产品的模量,因此当佩戴在人体上时可以提供良好的使用感受。
浸渍成型制品可以容易地应用于需要其的工业,例如检查手套、避孕套、医用导管、工业手套、家用手套和保健产品。
具体实施方式
在下文中,将更详细地描述本发明以帮助理解本发明。
应当理解,在说明书和权利要求书中使用的词语或术语不应该被解释为限于常用词典中定义的含义,并且基于发明人可以适当地定义词语或术语的含义以最好地描述本发明的原则,词语或术语应该被解释为具有与本发明的技术思想一致的含义和概念。
用于浸渍成型的胶乳组合物
本发明提出一种包含羧酸改性的腈类共聚物胶乳的用于浸渍成型的胶乳组合物,其中,使用具有优异的亲水性的多硫化钠代替硫作为硫化剂。
多硫化钠也称为聚硫橡胶,是通过将硫(S8)加入到强碱性水溶液中而制备的亲水性硫化剂,表示为Na2Sx(x=2至5)。在多硫化钠水溶液中,硫离子化以形成多硫阴离子,例如二硫阴离子(S2 2-)、三硫阴离子(S3 2-)、四硫阴离子(S4 2-)和五硫阴离子(S5 2-)。
更具体地,当多硫化钠溶解在水溶液中时,其末端离子化成S阴离子和Na阳离子,如下面的式(1)所示,并且多硫化钠的分子结构中具有通过-S-S-键连接的结构:
[式1]
此时,S阴离子与羧酸改性的腈类共聚物反应,通过-S-S-结构进行交联反应。
多硫化钠水溶液由于比现有的硫化剂(S8)更亲水,因此混合时具有与羧酸改性的腈类共聚物均匀混合的优点。多硫化钠易于进入由存在于多硫化物两端的Na阳离子形成亲水性和疏水性的内外边界的胶乳内部,因此使得羧酸改性的腈类共聚物交联更顺利。
利用多硫化钠水溶液交联与常规硫(S8)粉末交联相同,因此与常规硫化剂相比,可以生产具有相同或更高的拉伸强度和伸长率的浸渍成型制品。另外,参考与在300%和500%下的模量有关的数据,与使用硫粉末的浸渍成型制品相比,根据本发明的浸渍成型制品具有低的模量(参见表1和表2),并且由于其优异的弹性性能,在人体上具有良好的使用感受。另外,可以确保优异的对汗液的耐久性的优点。
在本发明中对多硫化钠水溶液的制备没有特别限制,可以通过本领域已知的方法制备。例如,所述水溶液通过将硫化钠溶解在蒸馏水中以制备强碱性水溶液,然后加入硫(S8)粉末[Macromol.Rapid Commun.2015,36,1103-1107]来制备。此时,考虑到水溶液中硫的沉淀,优选多硫化钠溶液的浓度为5重量%至20重量%。
以固含量计算,相对于100重量份的羧酸改性的腈类共聚物胶乳,这种多硫化钠以0.1重量份至5重量份,优选以0.5重量份至1重量份的量使用。如果多硫化钠的含量小于上述范围,则不能确保上述效果。相反,如果超过上述范围,则发生脱水收缩,并且由于过度固化而使物理性能劣化,并且制备具有坚硬的佩戴感受的浸渍成型制品。因此,多硫化钠在上述范围内适当使用。
多硫化钠以添加到羧酸改性的腈类共聚物的胶乳中的方式来使用。
在下文中,将更详细地描述本发明中公开的羧酸改性的腈类共聚物。
正如已经提及的,羧酸改性的腈类共聚物是由共轭二烯类单体、烯属不饱和腈单体和烯属不饱和酸单体共聚而成的共聚物。
首先,共轭二烯类单体是构成根据本发明的羧酸改性的腈类共聚物的单体。其具体实例包括选自1,3-丁二烯、2,3-二甲基-1,3-丁二烯、2-乙基-1,3-丁二烯、1,3-戊二烯和异戊二烯中的至少一种。其中,优选1,3-丁二烯和异戊二烯,最优选使用1,3-丁二烯。
基于构成羧酸改性的腈类共聚物的全部单体的总重量为100重量%,共轭二烯类单体的含量可以为40重量%至89重量%,优选为45重量%至80重量%,更优选为50重量%至78重量%。如果所述含量小于上述范围,则浸渍成型制品***并且佩戴感受劣化。相反,如果超过上述范围,则浸渍成型制品的耐油性劣化并且拉伸强度降低。
作为构成根据本发明的羧酸改性的腈类共聚物的其它单体,烯属不饱和腈单体是选自丙烯腈、甲基丙烯腈、富马酸腈、α-氯腈和α-氰乙基丙烯腈中的至少一种。其中,优选丙烯腈和甲基丙烯腈,最优选使用丙烯腈。
基于构成羧酸改性的腈类共聚物的全部单体的总重量为100重量%,烯属不饱和腈单体的含量可以为10重量%至50重量%,优选为15重量%至45重量%,更优选为25重量%至45重量%。如果所述含量小于上述范围,则浸渍成型制品的耐油性劣化并且拉伸强度降低。相反,如果超过上述范围,则浸渍成型制品***并且佩戴感受劣化。
此外,作为构成根据本发明的羧酸改性的腈类共聚物的其它单体,烯属不饱和酸单体是包含选自羧基、磺酸基和酸酐基中的至少一种酸性基团的烯属不饱和酸单体。烯属不饱和酸单体包括,例如,诸如丙烯酸、甲基丙烯酸、衣康酸、马来酸或富马酸的烯属不饱和羧酸单体;诸如马来酸酐和柠康酸酐的多羧酸酐;诸如苯乙烯磺酸的烯属不饱和磺酸单体;诸如富马酸单丁酯、马来酸单丁酯和马来酸单-2-羟基丙酯的烯属不饱和多羧酸偏酯单体。其中,特别优选甲基丙烯酸。这些烯属不饱和酸单体可以以碱金属盐或铵盐等的形式使用。
基于构成羧酸改性的腈类共聚物的全部单体的总重量为100重量%,烯属不饱和酸单体的含量可以为0.1重量%至10重量%,优选为0.5重量%至9重量%,更优选为1重量%至8重量%。如果所述含量小于上述范围,则浸渍成型制品的拉伸强度降低。相反,如果超过上述范围,则浸渍成型制品***并且佩戴感受劣化。
根据本发明的羧酸改性的腈类共聚物还可以选择性地包含能够与烯属不饱和腈单体和烯属不饱和酸单体共聚的其它烯属不饱和单体。
可共聚的烯属不饱和单体可以包括选自以下中的至少一种:包括苯乙烯、烷基苯乙烯和乙烯基萘的乙烯基芳香族单体;包括氟代乙基乙烯基醚的氟代烷基乙烯基醚;包括(甲基)丙烯酰胺、N-羟甲基(甲基)丙烯酰胺、N,N-二羟甲基(甲基)丙烯酰胺、N-甲氧基甲基(甲基)丙烯酰胺和N-丙氧基甲基(甲基)丙烯酰胺的烯属不饱和酰胺单体;包括乙烯基吡啶、乙烯基降冰片烯、二环戊二烯和1,4-己二烯的非共轭二烯单体;包括(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸三氟乙酯、(甲基)丙烯酸四氟丙酯、马来酸二丁酯、富马酸二丁酯、马来酸二乙酯、(甲基)丙烯酸甲氧基甲酯、(甲基)丙烯酸乙氧基乙酯、(甲基)丙烯酸甲氧基乙氧基乙酯、(甲基)丙烯酸氰基甲酯、(甲基)丙烯酸2-氰基乙酯、(甲基)丙烯酸1-氰基丙酯、(甲基)丙烯酸2-乙基-6-氰基己酯、(甲基)丙烯酸3-氰基丙酯、(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯、(甲基)丙烯酸缩水甘油酯和(甲基)丙烯酸二甲基氨乙酯的烯属不饱和羧酸酯单体。
基于构成羧酸改性的腈类共聚物的全部单体的总重量为100重量%,所述烯属不饱和腈单体和可与其共聚的其它烯属不饱和单体可以以0.001重量%至20重量%的量使用。如果所述含量超过20重量%,则柔软的佩戴感受和拉伸强度之间的平衡不适合。因此,所述含量在上述范围内适当选择。
正如已经提及的,本发明的羧酸改性的腈类共聚物胶乳可以通过向构成羧酸改性的腈类共聚物的单体中加入乳化剂、聚合引发剂、或分子量调节剂通过乳液聚合来制备。
具体地,羧酸改性的腈类共聚物胶乳通过包括以下步骤来制备:
步骤(a):将共轭二烯类单体、烯属不饱和腈单体和烯属不饱和酸单体、乳化剂、聚合引发剂和去离子水添加到聚合反应器中;
步骤(b):进行乳液聚合;以及
步骤(c):结束聚合。
在步骤(a)中,共轭二烯类单体、烯属不饱和腈单体、烯属不饱和酸单体、乳化剂和聚合引发剂可以一次性或连续地添加到聚合反应器中。另外,各个组分可以一次性添加到聚合反应器中,或者将它们中的一些含量添加到聚合反应器中然后可以将剩余的含量再次连续地添加到聚合反应器中。
对乳化剂没有特别限制,但是可以使用阴离子表面活性剂、非离子表面活性剂、阳离子表面活性剂和两性表面活性剂作为乳化剂。其中,特别优选使用选自烷基苯磺酸盐、脂肪族磺酸盐、高级醇的硫酸酯盐、α-烯烃磺酸盐和烷基醚硫酸酯盐中的阴离子表面活性剂。
此时,基于100重量份的构成羧酸改性的腈类共聚物的单体,乳化剂以0.3重量份至10重量份,优选为0.8重量份至8重量份,更优选为1.5重量份至6重量份的量使用。如果所述含量小于上述范围,则聚合时的稳定性降低。相反,如果超过上述范围,则存在由于产生大量泡沫而难以制备浸渍成型制品的问题。
对聚合引发剂没有特别限制,但是可以具体地使用自由基引发剂。自由基引发剂可以包括选自以下中的至少一种:无机过氧化物,如过硫酸钠、过硫酸钾、过硫酸铵、过磷酸钾和过氧化氢;有机过氧化物,如叔丁基过氧化物、过氧化氢异丙苯、萜烷过氧化氢、二叔丁基过氧化物、叔丁基异丙苯基过氧化物、过氧化乙酰、异丁基过氧化物、过氧化辛酰、过氧化二苯甲酰、过氧化3,5,5-三甲基己醇和叔丁基过氧化异丁酸酯;偶氮二异丁腈,偶氮双-2,4-二甲基戊腈、偶氮双环己烷甲腈和偶氮二异丁酸甲酯。在这些自由基引发剂中,更优选无机过氧化物,特别优选过硫酸盐。
基于100重量份的构成羧酸改性的腈类共聚物的全部单体,聚合引发剂以0.01重量份至2重量份,优选0.02重量份至1.5重量份的量使用。如果所述含量小于上述范围,则聚合速率降低,因此难以生产最终产品。相反,如果超过上述范围,则聚合速率太快而不能控制聚合。
对活化剂没有特别限制并且可以使用本领域通常已知的活化剂。其实例可以包括选自甲醛次硫酸氢钠、乙二胺四乙酸钠、硫酸亚铁、葡萄糖、焦磷酸钠和亚硫酸钠中的至少一种。
对分子量调节剂没有特别限制,例如,可以包括α-甲基苯乙烯二聚体;硫醇,如叔十二烷基硫醇、正十二烷基硫醇和辛基硫醇;卤代烃,如四氯化碳、二氯甲烷和二溴甲烷;以及含硫化合物,如二硫化四乙基秋兰姆、二硫化双亚戊基秋兰姆和二硫化二异丙基黄原酸酯(diisopropyl xanthogen disulfide)。这些分子量调节剂可以单独使用或两种或更多种组合使用。其中,优选硫醇,更优选使用叔十二烷基硫醇。
使用的分子量调节剂的量根据其种类而变化,但是基于100重量份的构成羧酸改性的腈类共聚物的全部单体,可以优选为0.1重量份至2.0重量份,优选为0.2重量份至1.5重量份,更优选为0.3重量份至1.0重量份。如果所述含量小于上述范围,则浸渍成型制品的物理性能显著劣化。相反,如果超过上述范围,则存在聚合稳定性降低的问题。
此外,当然可以根据需要添加少量的诸如螯合剂、分散剂、pH调节剂、脱氧剂、粒径调节剂、抗老化剂和氧清除剂的物质。
对构成羧酸改性的腈类共聚物的单体混合物的添加方法没有特别限制,可以是以下中的任意方法:将单体混合物一次性全部添加到聚合反应器中的方法、将单体混合物连续添加到聚合反应器中的方法、将部分的单体混合物添加到聚合反应器中并且将剩余的单体连续添加到聚合反应器中的方法。
在步骤(b)中,乳液聚合过程中的聚合温度通常可以为10℃至90℃,优选为20℃至80℃,更优选为25℃至75℃,但是没有特别限制。
在步骤(c)中,聚合反应结束时的转化率可以为85%以上,优选为88%至99.9%,更优选为90%至99%。停止聚合后,除去未反应的单体,调节固体含量和pH,得到用于浸渍成型的羧酸改性的腈类共聚物胶乳。
羧酸改性的腈类共聚物胶乳的玻璃化转变温度为-30℃至-10℃。如果所述胶乳的玻璃化转变温度低于上述范围,拉伸强度显著降低或由于手套的粘性使佩戴感受劣化。相反,如果高于上述范围,则在浸渍成型制品中产生裂纹,这是不期望的。玻璃化转变温度可以通过控制共轭二烯单体的含量来调节,并且可以通过差示扫描量热法来测量。
羧酸改性的腈类共聚物胶乳的平均粒径可以为100nm至500nm,优选为150nm至250nm。如果用于浸渍成型的胶乳的粒径在上述范围内,则可以提高制备的浸渍成型制品的拉伸强度。此时,可以通过控制乳化剂的种类和含量来调节用于浸渍成型的胶乳的粒径,并且粒径可以通过激光(Laser Scattering Analyzer,Nicomp)测量。
将通过上述步骤制备的羧酸改性的腈类共聚物胶乳与具有亲水性的多硫化钠的水溶液混合以制备用于浸渍成型的胶乳组合物。
多硫化钠的水溶液可以一次性添加到胶乳中或分批数次添加。
根据需要,可以向所述用于浸渍成型的胶乳组合物中加入预定量的诸如抗老化剂、抗氧化剂、防腐剂、抗菌剂、润湿剂、增稠剂、分散剂、颜料、染料、填料、增强剂和pH调节剂的各种添加剂。
根据本发明的用于浸渍成型的胶乳组合物具有10重量%至40重量%,优选15重量%至35重量%,更优选15重量%至30重量%的固体浓度。如果所述浓度太低,则胶乳组合物的输送效率会降低。如果太高,则固体浓度会导致粘度增加,并且会引起诸如储存稳定性等的问题。因此,浓度在上述范围内适当调节。
用于浸渍成型的胶乳组合物的pH可以是8至12,优选是9至11,更优选是9.3至10.5。如果pH超出上述范围,则用于浸渍成型的胶乳组合物的稳定性会劣化。
此时,当制备用于浸渍成型的胶乳时,通过添加一定量的pH调节剂,可以调节用于浸渍成型的胶乳组合物的pH。作为pH调节剂,可以使用1%至5%的氢氧化钾水溶液或1%至5%的氨水。
浸渍成型制品
此外,本发明提供一种由所述用于浸渍成型的胶乳组合物制备的浸渍成型制品。
对根据本发明的一个实施方案的浸渍成型制品没有特别限制并且可以通过本领域公知的方法来制备,例如,可以通过使用直接浸渍法、阳极凝固浸渍法、Teague凝固浸渍法等来制备。优选地,可以使用阳极凝固浸渍法。在使用阳极凝固浸渍法生产浸渍成型制品的情况下,具有可以生产具有均匀厚度的浸渍成型制品的优点。
作为具体实例,浸渍成型制品可以通过包括以下步骤来制备:
将用于浸渍成型的手形模具浸入到凝固剂溶液中并使凝固剂粘附到用于浸渍成型的模具表面(步骤a);
将其表面粘附有凝固剂的浸渍成型模具浸入用于浸渍成型的胶乳组合物中以形成浸渍成型层(步骤b);以及
对浸渍成型层进行热处理以使胶乳树脂交联(步骤c)。
步骤(a)是将凝固剂粘附到用于浸渍成型的手形模具的表面上的步骤,并且没有特别限制,但是可以通过将用于浸渍成型的模具浸入凝固剂溶液中至少一分钟并取出模具然后在70℃至150℃下干燥来进行。
凝固剂溶液是凝固剂溶解在水、醇或它们的混合物中的溶液,并且通常可以包含5重量%至50重量%的凝固剂,优选10重量%至40重量%的凝固剂。
对上述凝固剂没有特别限制,例如,包括金属卤化物,例如氯化钡、氯化钙、氯化镁、氯化锌和氯化铝;硝酸盐,例如硝酸钡、硝酸钙和硝酸锌;乙酸盐,例如乙酸钡、乙酸钙和乙酸锌;以及硫酸盐,例如硫酸钙、硫酸镁和硫酸铝。优选氯化钙、硝酸钙和它们的组合。
步骤(b)是在粘附有凝固剂的用于浸渍成型的模具上形成根据本发明的用于浸渍成型的胶乳组合物的浸渍成型层的步骤,并且在步骤(b)中,浸渍成型层可以通过将粘附有凝固剂的用于浸渍成型的模具浸入用于浸渍成型的胶乳组合物中至少一分钟并且取出模具来形成。
步骤(c)是通过使胶乳树脂交联到浸渍成型层上来得到浸渍成型制品的步骤,并且可以通过对浸渍成型层热处理来进行。
对热处理没有特别限制,但是可以通过,例如,在70℃至150℃下进行1分钟至10分钟第一热处理然后在100℃至180℃下进行5分钟到30分钟第二热处理来进行。
在热处理过程中,首先从浸渍成型层蒸发水组分,并通过交联使浸渍成型层的胶乳树脂硬化,从而得到浸渍成型制品。
对浸渍成型制品没有特别限制并且可以应用于各种胶乳工业,例如,可以应用于选自检查手套、避孕套、医用导管、工业手套、医用手套、家用手套、工业手套和保健产品中的至少一种成型制品。
在下文中,将提供优选实施例以更好地理解本发明。对于本领域技术人员显而易见的是,提供以下实施例仅用于说明本发明,并且在本发明的范围和技术范围内可以进行各种修改和改变。这些修改和改变意在落入所附权利要求书的范围内。
实施例
实施例1:用于浸渍成型的胶乳组合物和浸渍成型制品的制备
(羧酸改性的腈类共聚物胶乳的制备)
将装备有搅拌器、温度计、冷凝器和氮气入口并配置成连续加入单体、乳化剂和聚合引发剂的10L的高压反应器用氮气置换。此后,相对于100重量份的25重量%的丙烯腈、70重量%的1,4-丁二烯和5重量%的甲基丙烯酸的单体混合物,向高压反应器中加入2.5重量份的烷基苯磺酸钠、0.5重量份的叔十二烷基硫醇和140重量份的离子交换水,并将温度升高至48℃。
在升高温度后,加入0.25重量份的作为聚合引发剂的过硫酸钾。当转化率达到95%时,通过加入0.1重量份的二甲基二硫代氨基甲酸钠结束聚合。通过除臭工艺除去未反应的单体,加入氨水、抗氧化剂和消泡剂,得到固体浓度为45%且pH为8.3的羧化丙烯腈-丁二烯类共聚物胶乳。
作为分析所述胶乳的结果,玻璃化转变温度为-10℃,平均粒径为110nm。
(用于浸渍成型的组合物的制备)
向100重量份的制备的羧酸改性的腈类共聚物胶乳中,加入10%浓度的亲水性多硫化钠的溶液(多硫化钠)以制备混合物。
向该混合物中加入氢氧化钾溶液和适量的二次蒸馏水以得到固体浓度为25%且pH为10.0的用于浸渍成型的组合物。
(浸渍成型制品的制备)
通过混合18重量份的硝酸钙、87.5重量份的蒸馏水和0.5重量份的润湿剂(澳大利亚Huntsman Corporation生产的Teric 320)制备凝固剂溶液。将手形陶瓷模具浸入该溶液中10秒钟,取出,然后在80℃下干燥4分钟,使凝固剂粘附在手形模具上。
接下来,将涂覆有凝固剂的模具浸入用于浸渍成型的组合物中10秒钟,拉起,在80℃下干燥2分钟,并浸入水或温水中1分钟。之后,使其在120℃下交联20分钟。将交联后的浸渍成型层从手形模具取下,得到手套形状的浸渍成型制品。该浸渍成型制品的物理性能显示在表1和表2中。
为了确认脱水收缩时间,将涂覆有凝固剂的模具浸入上述用于浸渍成型的组合物中10秒钟然后拉起,在120℃下干燥6分钟,并浸入水或温水中3分钟。当在120℃下干燥6分钟时,检查水滴滴落的时间以确认脱水收缩时间。脱水收缩时间示在下面的表1和表2中。
实施例2:用于浸渍成型的胶乳组合物和浸渍成型制品的制备
除了以0.7重量份的比例使用亲水性多硫化钠以外,以与实施例1中相同的方式制备用于浸渍成型的胶乳组合物,并且使用其制备手套形状的浸渍成型制品。
实施例3:用于浸渍成型的胶乳组合物和浸渍成型制品的制备
除了以1.0重量份的比例使用亲水性多硫化钠以外,以与实施例1中相同的方式制备用于浸渍成型的胶乳组合物,并且使用其制备手套形状的浸渍成型制品。
比较例1:用于浸渍成型的胶乳组合物和浸渍成型制品的制备
除了使用1重量份的硫化剂(硫)代替亲水性多硫化钠以外,以与实施例1中相同的方式制备用于浸渍成型的胶乳组合物,并且使用其制备手套形状的浸渍成型制品。
实验例1:评价浸渍成型制品的物理性能
测量在上述实施例和比较例中制备的浸渍成型制品的物理性能。在将用于浸渍成型的胶乳组合物老化1天和3天之后,测量下面的物理性能,结果显示在下面的表1和表2中。
(1)拉伸强度、伸长率,以及在300%和500%下的模量(MPa)
根据EN 455-2,由得到的浸渍成型制品制备哑铃形试样。随后,以500mm/min的拉伸速率拉伸试样,测量在300%和500%的伸长率下的模量、断裂拉伸强度和断裂伸长率。
(2)耐久性
在制备用于测量浸渍成型制品在25℃下的耐久性的溶液之后,该溶液由16重量份的氯化钠、16重量份的乳酸、3.2重量份的尿素和64.8重量份的水组成,将腈橡胶手套试样***耐久性测量装置中,将试样反复拉伸至其初始长度的2倍然后释放(拉伸至多2倍,还原至少1倍),并且测量直至发生破裂的次数。此时,次数越大表示耐久性越好。
(3)脱水收缩
当在120℃下干燥6分钟时,检查水滴滴落的时间,确定脱水收缩时间。此时,脱水收缩时间越长表示加工性能越好。
表1
老化1天
表2
老化3天
表1和表2的结果表明,在根据本发明使用多硫化钠作为硫化剂的实施例1至3中,拉伸强度、模量和伸长率等于或高于使用硫的比较例1的拉伸强度、模量和伸长率,脱水收缩时间也更长。
然而,可以看出,对于在特定的300%和500%下的模量(即模量)值,与比较例1相比,实施例1至3的浸渍成型制品整体上略低,因此可以产生良好的使用感受。此外,耐久性非常优异。
此外,比较用于浸渍成型的组合物老化1天和3天后得到的表1和表2的数值,可以看出,在老化1天的情况下,实施例的数值优于比较例的数值,但是在老化3天后,实施例和比较例的数值具有类似的结果。这些结果表明,与硫相比,根据本发明的多硫化钠可以迅速和快速地引起交联,这是因为多硫化钠由于其高的亲水性而更快速地渗透到羧酸改性的腈类胶乳中。
工业实用性
根据本发明的用于浸渍成型的胶乳组合物可以用于制备胶乳制品,例如,诸如各种工业和家用手套的保健产品。
Claims (11)
1.一种用于浸渍成型的胶乳组合物,包含:由共轭二烯类单体、烯属不饱和腈单体和烯属不饱和酸单体共聚而成的羧酸改性的腈类共聚物胶乳;以及多硫化钠。
2.根据权利要求1所述的用于浸渍成型的胶乳组合物,其特征在于,基于100重量份的羧酸改性的腈类共聚物,所述用于浸渍成型的胶乳组合物包含0.1重量份至5重量份的多硫化钠。
3.根据权利要求1所述的用于浸渍成型的胶乳组合物,其特征在于,多硫化钠以浓度为5重量%至20重量%的水溶液来使用。
4.根据权利要求1所述的用于浸渍成型的胶乳组合物,其特征在于,所述羧酸改性的腈类共聚物胶乳的玻璃化转变温度为-30℃至-10℃,平均粒径为100nm至500nm以上。
5.根据权利要求1所述的用于浸渍成型的胶乳组合物,其特征在于,基于总和为100重量%的所述单体,所述羧酸改性的腈类共聚物由40重量%至89重量%的共轭二烯类单体、10重量%至50重量%的烯属不饱和腈单体和0.1重量%至10重量%的烯属不饱和酸单体共聚而成。
6.根据权利要求1所述的用于浸渍成型的胶乳组合物,其特征在于,所述共轭二烯类单体是选自1,3-丁二烯、2,3-二甲基-1,3-丁二烯、2-乙基-1,3-丁二烯、1,3-戊二烯和异戊二烯中的至少一种。
7.根据权利要求1所述的用于浸渍成型的胶乳组合物,其特征在于,所述烯属不饱和腈单体是选自丙烯腈、甲基丙烯腈、富马酸腈、α-氯腈和α-氰乙基丙烯腈中的至少一种。
8.根据权利要求1所述的用于浸渍成型的胶乳组合物,其特征在于,所述烯属不饱和酸单体是选自丙烯酸、甲基丙烯酸、衣康酸、马来酸、富马酸、马来酸酐、柠康酸酐、苯乙烯磺酸、富马酸单丁酯、马来酸单丁酯和马来酸单-2-羟基丙酯中的至少一种。
9.根据权利要求1所述的用于浸渍成型的胶乳组合物,其特征在于,所述羧酸改性的腈类共聚物与另外添加的作为共聚单体的烯属不饱和单体共聚。
10.一种浸渍成型制品,其特征在于,通过使权利要求1至9中任意一项所述的用于浸渍成型的胶乳组合物浸渍成型来制备。
11.根据权利要求10所述的浸渍成型制品,其特征在于,所述浸渍成型制品是选自检查手套、避孕套、医用导管、工业手套、医用手套、家用手套、工业手套和保健产品中的至少一种。
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MY194631A (en) | 2022-12-08 |
CN109071886B (zh) | 2020-10-02 |
US20190127507A1 (en) | 2019-05-02 |
EP3412718A1 (en) | 2018-12-12 |
EP3412718A4 (en) | 2019-06-05 |
EP3412718B1 (en) | 2019-11-27 |
US10858469B2 (en) | 2020-12-08 |
JP2019510108A (ja) | 2019-04-11 |
JP6893217B2 (ja) | 2021-06-23 |
KR20180028606A (ko) | 2018-03-19 |
KR102081766B1 (ko) | 2020-02-26 |
WO2018048122A1 (ko) | 2018-03-15 |
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