CN117467078A - Carboxyl nitrile latex and preparation method and application thereof - Google Patents
Carboxyl nitrile latex and preparation method and application thereof Download PDFInfo
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- CN117467078A CN117467078A CN202210863971.3A CN202210863971A CN117467078A CN 117467078 A CN117467078 A CN 117467078A CN 202210863971 A CN202210863971 A CN 202210863971A CN 117467078 A CN117467078 A CN 117467078A
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- CN
- China
- Prior art keywords
- parts
- emulsifier
- nitrile latex
- carboxylated nitrile
- added
- 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.)
- Pending
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- 239000004816 latex Substances 0.000 title claims abstract description 89
- 229920000126 latex Polymers 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title abstract description 17
- -1 Carboxyl nitrile Chemical class 0.000 title description 12
- 150000002825 nitriles Chemical class 0.000 claims abstract description 47
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 40
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003999 initiator Substances 0.000 claims abstract description 16
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 15
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000002270 dispersing agent Substances 0.000 claims abstract description 14
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 14
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 14
- 125000003147 glycosyl group Chemical group 0.000 claims abstract description 14
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 14
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 14
- 239000012874 anionic emulsifier Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 125000002091 cationic group Chemical group 0.000 claims abstract description 9
- 239000003792 electrolyte Substances 0.000 claims abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 81
- 238000000034 method Methods 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 31
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 3
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 3
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 claims description 2
- 239000012966 redox initiator Substances 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 238000009776 industrial production Methods 0.000 abstract description 6
- 229940123973 Oxygen scavenger Drugs 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 19
- 230000008569 process Effects 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 15
- 238000012360 testing method Methods 0.000 description 14
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 13
- XNINAOUGJUYOQX-UHFFFAOYSA-N 2-cyanobutanoic acid Chemical compound CCC(C#N)C(O)=O XNINAOUGJUYOQX-UHFFFAOYSA-N 0.000 description 12
- 239000012752 auxiliary agent Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- FRQQKWGDKVGLFI-UHFFFAOYSA-N 2-methylundecane-2-thiol Chemical compound CCCCCCCCCC(C)(C)S FRQQKWGDKVGLFI-UHFFFAOYSA-N 0.000 description 10
- 239000000839 emulsion Substances 0.000 description 10
- 239000000499 gel Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 230000000704 physical effect Effects 0.000 description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 239000003945 anionic surfactant Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 5
- 238000006467 substitution reaction Methods 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
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000000693 micelle Substances 0.000 description 3
- 239000012875 nonionic emulsifier Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-isoascorbic acid Chemical compound OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 2
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 235000010350 erythorbic acid Nutrition 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007794 irritation Effects 0.000 description 2
- 229940026239 isoascorbic acid Drugs 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- ODHYIQOBTIWVRZ-UHFFFAOYSA-N n-propan-2-ylhydroxylamine Chemical compound CC(C)NO ODHYIQOBTIWVRZ-UHFFFAOYSA-N 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- LGNQGTFARHLQFB-UHFFFAOYSA-N 1-dodecyl-2-phenoxybenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1OC1=CC=CC=C1 LGNQGTFARHLQFB-UHFFFAOYSA-N 0.000 description 1
- 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 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
- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 1
- QPQKUYVSJWQSDY-CCEZHUSRSA-N 4-(phenylazo)aniline Chemical compound C1=CC(N)=CC=C1\N=N\C1=CC=CC=C1 QPQKUYVSJWQSDY-CCEZHUSRSA-N 0.000 description 1
- QPWHIXUCVYSLML-UHFFFAOYSA-K C(C)(=O)[O-].C(C)(=O)O.C(C)(=O)[O-].C(C)(=O)[O-].[Fe+2].C(CN)N.[Na+] Chemical compound C(C)(=O)[O-].C(C)(=O)O.C(C)(=O)[O-].C(C)(=O)[O-].[Fe+2].C(CN)N.[Na+] QPWHIXUCVYSLML-UHFFFAOYSA-K 0.000 description 1
- YHHRAYNEBXSCTG-UHFFFAOYSA-N C1(C=CC=C1)[Si] Chemical compound C1(C=CC=C1)[Si] YHHRAYNEBXSCTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011499 joint compound Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- HFFLGKNGCAIQMO-UHFFFAOYSA-N trichloroacetaldehyde Chemical compound ClC(Cl)(Cl)C=O HFFLGKNGCAIQMO-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with nitriles
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D19/00—Gloves
- A41D19/0055—Plastic or rubber gloves
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/28—Emulsion polymerisation with the aid of emulsifying agents cationic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Textile Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention provides a carboxylated nitrile latex, a preparation method and application thereof, wherein the carboxylated nitrile latex is prepared from the following raw materials in parts by mass: butadiene, acrylonitrile, methacrylic acid, an emulsifier, a dispersing agent, an electrolyte, ferrous sulfate, a co-reducing agent, a molecular weight regulator, an oxygen scavenger, an initiator and desalted water; wherein the emulsifier is a mixture of an anionic emulsifier and a cationic emulsifier, the anionic emulsifier is sodium dodecyl sulfate, and the cationic emulsifier is a glycosyl gemini cationic surfactant; the mass ratio of the anionic emulsifier to the cationic emulsifier in the emulsifier is 1:0.05 to 0.1. The carboxylated nitrile latex has low gel content and high mechanical stability, and the preparation method is simple and controllable, and is easy for industrial production.
Description
Technical Field
The invention relates to the technical field of latex preparation, in particular to carboxyl butyronitrile latex and a preparation method and application thereof.
Background
The carboxyl butyronitrile latex is a high molecular white emulsion prepared by emulsion polymerization of butadiene, acrylonitrile and unsaturated carboxylic acid, and the molecular chain of the emulsion contains polar nitrile groups and carboxyl groups, so that the performance of the emulsion is superior to that of the common butyronitrile latex, and the mechanical stability, thawing stability, adhesiveness, film forming property, post-processing property and the like of the emulsion are improved. The prepared latex has excellent oil resistance, chemical resistance and wear resistance, good fluidity, high tensile strength and unique adhesive force, and has good compatibility with polar high polymer substances such as starch, casein, vinyl resin, phenolic resin, chloral resin and the like. However, the existing production process of the carboxylated nitrile latex mostly adopts a medium-high temperature method, and the prepared latex product generally has the problems of high gel content, poor film forming property or complex operation, and is not beneficial to industrial production.
As disclosed in chinese patent document CN201510152547.8, a method for preparing the carboxylated nitrile latex for impregnating non-woven fabrics is disclosed, wherein after the polymerization kettle is vacuumized and replaced by nitrogen, desalted water, an emulsifier, a molecular weight regulator, a pH buffer solution, an α, β -ethylenically unsaturated nitrile monomer, a conjugated diene monomer, a C3-C5 ethylenically unsaturated carboxylic acid monomer, cyclopentadienyl silane, perfluoro α, β -ethylenically olefin, and an initiator are added in a continuous feeding manner, wherein the emulsifier is one or more of an anionic emulsifier, a polyoxyethylene ether nonionic emulsifier, and a quaternary ammonium salt amphoteric emulsifier, and the emulsifier is preferably a nonionic emulsifier and/or a quaternary ammonium salt amphoteric emulsifier, and more preferably a nonionic emulsifier and a quaternary ammonium salt amphoteric emulsifier with a mass ratio of 1:1.2-2, and the polymerization reaction is performed at 65 ℃ for 8 hours; cooling to 35 ℃ after the reaction is finished, cooling and discharging after curing for 2 hours, and adding a pH value regulator to adjust the pH value to 8-11 to obtain the carboxyl butyronitrile latex. The technical scheme has the defects or shortages that: the method adopts a high-temperature polymerization method, adopts a continuous feeding process, and has complex operation and great difficulty in industrial implementation.
Chinese patent document CN201510971937.8 discloses a preparation method of carboxylated nitrile latex for high-strength and high-wear-resistance nitrile gloves, which comprises the steps of respectively adding acrylonitrile according to weight ratio: 28-35 parts; butadiene: 60-70 parts; unsaturated carboxylic acid: 2-7 parts; unsaturated carboxylic acid esters: 0-5 parts; reactive emulsifier: 2.5 to 5.0 parts; an electrolyte: 0.1 to 0.5 part; pH buffer: 0.1 to 0.5 part; thiol: 0.5 to 1.5 parts; and (3) an initiator: 0.2 to 0.5 part; deionized water: 110-140 parts. The method is characterized in that a sectional temperature control process is adopted, the temperature is raised to 25-35 ℃ to react for 6-8 hours, the first time of adding the reactive emulsifier and the mercaptan is started, the reaction is continued to be carried out for 4-6 hours when the temperature is raised to 36-40 ℃, the second time of adding the reactive emulsifier and the mercaptan is added, the temperature is raised to 45-60 ℃ to react for 4-6 hours, and when the conversion rate reaches 98%, the reaction is stopped to prepare the carboxylated nitrile latex with the solid content of 43-45%. The technical scheme has the defects or shortages that: the method adopts a medium-high temperature polymerization method and a sectional temperature control process, is complex in operation, high in control difficulty and unfavorable for industrial production, and the gel content is high due to high branching and crosslinking degree of the product.
The Chinese patent document CN202111163259.4 discloses a nitrile latex and a preparation method and application thereof, wherein the nitrile latex is prepared from 78-95 parts by weight of butadiene, 38-55 parts by weight of acrylonitrile, 5-10 parts by weight of acrylic ester, 1-3 parts by weight of N- (hydroxymethyl) acrylamide, 1-5 parts by weight of emulsifying agent, 1-3 parts by weight of initiator, 0.1-2 parts by weight of molecular weight regulator, 0.1-2 parts by weight of pH regulator and 0.5-2 parts by weight of film forming auxiliary agent. The acrylic ester and N- (hydroxymethyl) acrylamide are adopted to modify the nitrile latex in the document, and the acrylic ester has wide adhesiveness and excellent flex resistance and crack growth resistance, so that the prepared nitrile latex has better adhesiveness and strength. Meanwhile, N- (hydroxymethyl) acrylamide is used as an auxiliary material, and the N- (hydroxymethyl) acrylamide has self-crosslinking performance, so that the butyronitrile latex can be rapidly formed into a film, and the yellowing of a film caused by overlong film forming time is prevented. The finally prepared nitrile latex has good adhesiveness and high film forming speed, so that the production and use requirements of the lining glove of the oil-resistant dipped product can be met, and meanwhile, the high strength can meet the long-term use requirements. However, the technical scheme has the defects or shortcomings that: the method adopts a medium-high temperature polymerization method, and the high gel content is caused by high branching and crosslinking degree of the product.
Chinese patent document CN201510679217.4 discloses a preparation method of high-performance carboxylated nitrile latex: the latex adopts emulsion polymerization technology with styrene-butadiene latex as seeds, part of monomers are dripped, butadiene and acrylonitrile are used as main monomers, unsaturated carboxylic acid, multiple double bond crosslinking monomers and other functional monomers are used as auxiliary monomers, a composite emulsifying system is adopted during polymerization, namely, a reactive emulsifier and an anionic emulsifier are compounded, persulfate is used as an initiator, alkyl mercaptan is used as a molecular weight regulator, and other auxiliary agents, the reaction temperature is 40-60 ℃, and the conversion rate is more than 98%. The raw materials added dropwise in the latex production process are dispersed by an ultrasonic homogenizer or a high-pressure homogenizer to form stable miniemulsion of 50-500 nm, and then are added dropwise into a reaction kettle. The final prepared carboxylated nitrile latex has the particle size of 100-120 nm, good latex fluidity, moderate viscosity, excellent mechanical stability and chemical stability, and high toughness and bonding strength. The technical scheme has the following defects: the method adopts a medium-high temperature polymerization method, adopts a continuous dripping process, utilizes seed latex to carry out graft polymerization, has a complex feeding process, and is difficult to realize industrial production.
The Chinese patent document CN201710799349.X discloses a production process of carboxylated nitrile latex, which comprises the following steps: (1) Weighing raw materials including 75-100 parts of deionized water, 1-2 parts of molecular weight regulator, 0.1-0.5 part of pH buffering agent and 3-5 parts of emulsifier, adding the raw materials into a polymerization kettle, stirring for 1-2 hours at the speed of 550-750 r/min at the temperature of 28-45 ℃, and vacuumizing after uniformly mixing; (2) Weighing raw materials including 38-50 parts of butadiene, 20-30 parts of acrylonitrile, 8-15 parts of acrylic acid monomer and 2-5 parts of unsaturated carboxylic acid, adding the raw materials into a polymerization kettle in the step 1, keeping the temperature and the rotating speed in the step 1 unchanged, and stirring for 1-3 hours to obtain emulsion; (3) Slowly heating the emulsion obtained in the step 2 at a speed of 3-5 ℃/min for reaction, adding an initiator and deionized water while heating, controlling the adding flow ratio of the initiator to the deionized water to be 1:6.6-8, and after the reaction temperature is raised to 58-75 ℃, and the initiator and the deionized water are added, carrying out heat preservation reaction until the conversion rate reaches more than 99%, thus obtaining the latex emulsion; (4) And (3) transferring the latex emulsion obtained in the step (3) into a degassing kettle for degassing treatment, adding an auxiliary agent accounting for 1.5-4% of the total amount of the latex emulsion, uniformly dispersing by a high-speed dispersing machine, cooling, and packaging to obtain the required carboxylated nitrile latex. The technical scheme has the defects or shortages that: the method adopts a medium-high temperature polymerization method, the feeding process is complex, and the industrial implementation difficulty is high.
Chinese patent document CN201610140264.6 discloses a carboxylated nitrile latex and a preparation method thereof, comprising the steps of: (1) In the presence of an initiator, at the reaction temperature of 10-25 ℃, contacting acrylonitrile, vinyl unsaturated carboxylic acid monomer and emulsifier in water, wherein the contact condition is that copolymerization reaction occurs to generate a copolymer with the particle diameter of 50-90nm, so as to obtain seed latex; (2) Continuously adding a mixture of acrylonitrile, butadiene and a molecular weight regulator into the seed latex obtained in the step (1) at the reaction temperature of 25-35 ℃, and adding an emulsifier after the addition is finished, and continuously reacting, wherein the emulsifier is sodium dodecyl diphenyl ether sulfonate and/or octyl phenol polyoxyethylene ether; (3) And (3) adding an initiator into the reaction mixture obtained in the step (2) at the reaction temperature of 35-45 ℃ and continuing the reaction to prepare the carboxylated nitrile latex. The technical scheme has the defects or shortages that: the method adopts a high-temperature polymerization method, adopts a continuous feeding process, and has complex operation and great difficulty in industrial implementation.
Disclosure of Invention
The invention aims to solve the technical problem of providing a carboxylated nitrile latex and a preparation method and application thereof, and aims to solve the problems of high gel content or high industrial implementation difficulty in the carboxylated nitrile latex and the preparation method thereof in the prior art.
Therefore, the invention provides the following technical scheme:
the carboxylated nitrile latex comprises the following raw materials in percentage by mass: 64-70 parts of butadiene, 26-33 parts of acrylonitrile, 3.0-6.0 parts of methacrylic acid, 2.5-4.0 parts of emulsifier, 1.0-3.0 parts of dispersing agent, 0.02-0.08 parts of electrolyte, 0.005-0.05 part of ferrous sulfate, 0.02-0.06 part of auxiliary reducing agent, 0.4-1.0 part of molecular weight regulator, 0.005-0.02 part of deoxidizer, 0.04-0.10 part of initiator and 125-140 parts of desalted water;
wherein the emulsifier is a mixture of an anionic emulsifier and a cationic emulsifier, the anionic emulsifier is sodium dodecyl sulfate, and the cationic emulsifier is a glycosyl gemini cationic surfactant;
the mass ratio of the anionic emulsifier to the cationic emulsifier in the emulsifier is 1:0.05 to 0.1.
Optionally, the glycosyl gemini cationic surfactant has the following structural formula:
wherein n=1 to 3, and r is an alkyl group.
Alternatively, R is selected from C12-C14 linear alkyl groups.
Alternatively, R is selected from the group consisting of C12 linear alkyl groups.
The solid content of the nitrile latex is usually 25-30%, and the solid content of the carboxylated nitrile latex for labor protection gloves is usually required to be above 40%. In order to increase the solid content of the latex, the polymerization reaction must be carried out under the conditions of low water ratio and high conversion rate, the reduction of the water ratio inevitably influences the viscosity and pH of the system, the increase of the conversion rate leads to the remarkable increase of the gel content in the later period of the reaction, particularly the solid content reaches a certain degree, the viscosity of the system is increased, and the latex is easy to form paste and lose fluidity. In the preparation process of the high-solid carboxyl-containing nitrile latex, the main means is to synthesize the carboxyl nitrile latex with large particle size and wide distribution in order to reduce the viscosity of the system.
The traditional quaternary ammonium salt type cationic surfactant has strong irritation, and can be separated out due to interaction after being compounded with the anionic surfactant, so that the quaternary ammonium salt type cationic surfactant is disabled and cannot be applied. The glycosyl group double-son cationic surfactant has the advantages that glycosyl groups are introduced into the traditional cationic surfactant, so that the irritation of the glycosyl group double-son cationic surfactant is reduced, the glycosyl group double-son cationic surfactant can be well compounded with the anionic surfactant, and the glycosyl group double-son cationic surfactant can interact with the anionic surfactant to form a joint compound, has higher surface activity, can reduce the critical micelle concentration and the surface tension of an emulsifying agent, and can enable monomers to enter a polymerization place-solubilization micelle more easily, so that the latex particle size is increased, the latex with wide particle size distribution is prepared, smaller particles can be filled in large particle gaps, the accumulation volume of latex particles is increased, and the high-solid-content carboxylated nitrile latex is prepared.
Alternatively, the initiator is a low temperature redox initiator, preferably cumene hydroperoxide and/or diisopropylbenzene hydroperoxide.
Optionally, the electrolyte is any one of sodium carbonate, sodium bicarbonate and sodium pyrophosphate.
The diffusing agent, the auxiliary reducing agent, the molecular weight regulator and the deoxidizing agent can be all known in the technical field, and are not particularly limited. For example, the diffusing agent may be at least one selected from sodium disulfite, dimethyl ketoxime, isoascorbic acid, carbohydrazide, N-isopropylhydroxylamine, etc. The co-reducing agent can be selected from radix Cynanchi Paniculati, etc., and the molecular weight regulator is common regulator for emulsion polymerization, such as tert-dodecyl mercaptan, n-dodecyl mercaptan, etc. The oxygen scavenger may be at least one selected from sodium dithionite, dimethyl ketoxime, isoascorbic acid, carbohydrazide, N-isopropylhydroxylamine, etc.
The invention also provides a preparation method of the carboxylated nitrile latex, which comprises the following steps:
mixing desalted water, an emulsifying agent, a dispersing agent, a molecular weight regulator, an activating agent, a reducing aid, an electrolyte, methacrylic acid and acrylonitrile, adding an deoxidizer and butadiene, controlling the temperature of the system to 8-15 ℃, adding an initiator, performing polymerization reaction at 8-15 ℃, and adding 0.05-0.2 part of a terminator when the polymerization conversion rate reaches 95%, thus obtaining the carboxylated nitrile latex.
Optionally, the method further comprises the step of adjusting the pH of the carboxylated nitrile latex to 8.0-10.0 by using 3-5 wt% KOH solution after adding the terminator.
Alternatively, the terminator may be at least one of sodium nitrite, actinide reagent, p-aminoazobenzene, etc. which are conventional in the art.
The inventor finds that the control of the stability and gel content of the latex is facilitated by controlling the temperature of the polymerization reaction to be 8-15 ℃ aiming at the formula of the carboxylated nitrile latex.
The invention also provides a labor protection glove which is prepared from the carboxylated nitrile latex or the carboxylated nitrile latex prepared by the preparation method of the carboxylated nitrile latex.
Compared with the prior art, the invention has the beneficial effects that:
according to the carboxyl butyronitrile latex, the emulsifier formed by compounding the specific glycosyl Gemini cationic surfactant and the anionic surfactant is introduced in the polymerization process, so that the tradition that the anionic surfactant and the cationic surfactant cannot be shared is broken, the critical micelle concentration and the solution surface tension of the emulsifier are further reduced by the compounded emulsifier, and the emulsification efficiency is improved; the ferrous sulfate activator and other raw materials are combined to be mutually matched, so that the stability and the production efficiency of the latex can be obviously improved. The solid content of the synthesized carboxyl butyronitrile latex is 42.0-44.0%, the viscosity is less than or equal to 60 mPa.S, the particle size is 70-90 nm, the mechanical stability is less than or equal to 0.1%, the gel content is less than 15.0%, the gel content is low, the film forming property, the mechanical stability and the strength are excellent, and the preparation method is simple and controllable, and is easy for industrial production.
Detailed Description
The present invention will be specifically described below by way of examples. It is noted herein that the following examples are given solely for the purpose of illustration and are not to be construed as limiting the scope of the invention, as many insubstantial modifications and variations of the invention will become apparent to those skilled in the art in light of the above disclosure.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Evaluation analysis method:
total solid content: execution Standard SH/T1154-2011
Latex viscosity: implementation standard SH/T1152-2014
pH value: execution Standard SH/T1150-2011
Mechanical stability: execution Standard SH/T1151-2011
Surface tension: implementation standard SH/T1156-2014
Raw gelatin content: implementation standard SH/T1050-91
The existing commercial diffusing agent, auxiliary reducing agent, molecular weight regulator and deoxidizing agent, and commercial or self-made glycosyl Gemini cationic surfactant can meet the technical scheme of the invention, however, for convenience of comparison, the following examples and comparative examples adopt the raw materials purchased by the following manufacturers:
butadiene, which implements GB/T13291-2008 standard, industrial products, purity is more than or equal to 99.5%, lanzhou petrochemical company;
acrylonitrile, GB/T7717.1-2008 standard, industrial products with purity more than or equal to 99.5%, lanzhou petrochemical company;
methacrylic acid, industrial grade, purity > 99%, national pharmaceutical group chemical company, inc;
glycosyl gemini cationic surfactants with different carbon numbers and different glycosyl polymerization degrees are analytically pure with purity more than 99 percent and are available from national pharmaceutical group chemical reagent company;
sodium dodecyl sulfate, industrial product with purity > 96%, lanzhou petrochemical company;
ferrous sulfate, industrial product with purity not less than 98%, lanzhou petrochemical company;
white block: industrial products with purity more than or equal to 98 percent, and Lanzhou petrochemical company;
ethylenediamine tetraacetic acid-iron sodium salt (EDTA-iron sodium salt), industrial products, purity (EDTA on a dry basis) of more than or equal to 97.0%, lanzhou petrochemical company;
tertiary dodecyl mercaptan, imported industrial products with purity more than or equal to 97.3 percent, lanzhou petrochemical company;
dicumyl peroxide, industrial products with purity more than or equal to 80 percent, and Lanzhou petrochemical company;
deoxidizer, industrial product, na 2 S 2 O 4 The content is more than or equal to 85.0 percent, and the Lanzhou petrochemical company.
Example 1
The polymerization was carried out in a 15L stirred autoclave. The addition amount of each monomer auxiliary agent is calculated by weight of each 100 parts of monomer. At the beginning of the polymerization, 136 parts of desalted water, 3 parts of sodium dodecyl sulfate, 0.15 part of C12-glycosyl gemini cationic surfactant (n=2), 1.5 parts of dispersing agent NF, 0.03 part of sodium carbonate, 0.005 part of ferrous sulfate, 0.04 part of white block, 0.5 part of tertiary dodecyl mercaptan, 27 parts of acrylonitrile and 3.0 parts of methacrylic acid are respectively added into a polymerization kettle, after vacuumizing, 0.005 part of deoxidizer is added, the substitution is continued for three times by nitrogen, 70 parts of butadiene is added, when the temperature of the polymerization kettle is reduced to below 15 ℃, 0.06 part of hydrogen peroxide diisopropylbenzene is added, the polymerization reaction is started, the polymerization reaction temperature is controlled to be 8-15 ℃ in the process, dry matters are measured once for 2 hours, 0.05 part of terminator is added when the conversion rate reaches 95.4%, the carboxyl butyronitrile latex is prepared, the PH is adjusted by adding 3wt% of KOH solution, and physical property test is carried out, and the results are shown in Table 1.
Example 2
The polymerization was carried out in a 15L stirred autoclave. The addition amount of each monomer auxiliary agent is calculated by weight of each 100 parts of monomer. At the beginning of the polymerization, 126 parts of desalted water, 3 parts of sodium dodecyl sulfate, 0.3 part of C13-glycosyl gemini cationic surfactant (n=1), 2.0 parts of dispersing agent NF, 0.04 part of sodium bicarbonate, 0.005 part of ferrous sulfate, 0.03 part of white block, 0.55 part of tertiary dodecyl mercaptan, 32 parts of acrylonitrile and 3.0 parts of methacrylic acid are respectively added into a polymerization kettle, after vacuumizing, 0.009 part of deoxidizer is added, the substitution is continued for three times by nitrogen, 65 parts of butadiene is added, when the temperature of the polymerization kettle is reduced to below 15 ℃, 0.06 part of hydrogen peroxide diisopropylbenzene is added, the polymerization reaction is started, the polymerization reaction temperature is controlled to be 8-15 ℃ in the process, dry matters are measured every 2 hours, 0.2 part of terminator is added when the conversion rate reaches 95.2%, the carboxyl butyronitrile latex is prepared, the PH is adjusted by adding 4wt% of KOH solution, and then physical property testing is carried out, and the result is shown in Table 1.
Example 3
The polymerization was carried out in a 15L stirred autoclave. The addition amount of each monomer auxiliary agent is calculated by weight of each 100 parts of monomer. At the beginning of the polymerization, 130 parts of desalted water, 3.2 parts of sodium dodecyl sulfate, 0.2 part of C12-glycosyl gemini cationic surfactant (n=3), 2.5 parts of dispersing agent NF, 0.05 part of sodium carbonate, 0.008 part of ferrous sulfate, 0.02 part of white block, 0.5 part of tertiary dodecyl mercaptan, 29 parts of acrylonitrile and 5.0 parts of methacrylic acid are respectively added into a polymerization kettle, after vacuumizing, 0.01 part of deoxidizer is added, the substitution is continued for three times by nitrogen, 66 parts of butadiene is added, when the temperature of the polymerization kettle is reduced to below 15 ℃, 0.1 part of cumene hydroperoxide is added, the polymerization reaction is started, the polymerization reaction temperature is controlled to be 8-15 ℃ in the process, dry matter is measured every 2 hours, 0.1 part of terminator is added when the conversion rate reaches 95.1%, the carboxylated nitrile latex is prepared, the pH is adjusted by adding 5wt% of KOH solution, and physical property test is carried out, and the results are shown in Table 1.
Example 4
The polymerization was carried out in a 15L stirred autoclave. The addition amount of each monomer auxiliary agent is calculated by weight of each 100 parts of monomer. At the beginning of the polymerization, 140 parts of desalted water, 3.6 parts of sodium dodecyl sulfate, 0.3 part of C14-glycosyl gemini cationic surfactant (n=2), 2.0 parts of dispersing agent NF, 0.05 part of sodium carbonate, 0.01 part of ferrous sulfate, 0.06 part of white block, 0.6 part of tertiary dodecyl mercaptan, 26 parts of acrylonitrile and 6.0 parts of methacrylic acid are respectively added into a polymerization kettle, after vacuumizing, 0.03 part of deoxidizer is added, the mixture is continuously replaced by nitrogen for three times, 68 parts of butadiene is added, when the temperature of the polymerization kettle is reduced to below 15 ℃, 0.08 part of cumene hydroperoxide is added, the polymerization reaction is started, the polymerization reaction temperature is controlled to be 8-15 ℃ in the process, dry matter is measured every 2 hours, 0.1 part of terminator is added when the conversion rate reaches 94.7%, the carboxyl butyronitrile latex is prepared, the pH is adjusted by adding 5wt% of KOH solution, and physical property test is carried out, and the results are shown in Table 1.
Example 5
The polymerization was carried out in a 15L stirred autoclave. The addition amount of each monomer auxiliary agent is calculated by weight of each 100 parts of monomer. At the beginning of the polymerization, 132 parts of desalted water, 2.5 parts of sodium dodecyl sulfate, 0.15 part of C13-glycosyl gemini cationic surfactant (n=3), 2.8 parts of dispersing agent NF, 0.06 part of sodium pyrophosphate, 0.04 part of ferrous sulfate, 0.05 part of white block, 0.8 part of tertiary dodecyl mercaptan, 33 parts of acrylonitrile and 3.0 parts of methacrylic acid are respectively added into a polymerization kettle, after vacuumizing, 0.05 part of deoxidizer is added, the mixture is continuously replaced by nitrogen for three times, 64 parts of butadiene is added, when the temperature of the polymerization kettle is reduced to below 15 ℃, 0.05 part of hydrogen peroxide diisopropylbenzene is added, the polymerization reaction is started, the polymerization reaction temperature is controlled to be 8-15 ℃, dry matters are measured every 2 hours in the process, 0.08 part of terminator is added when the conversion rate reaches 95.1%, the carboxyl butyronitrile latex is prepared, the KOH solution with the concentration of 5wt% is added for regulating the PH, and then the physical property test is carried out, and the results are shown in Table 1.
Comparative example 1
The polymerization was carried out in a 15L stirred autoclave. The addition amount of each monomer auxiliary agent is calculated by weight of each 100 parts of monomer. 136 parts of desalted water, 3 parts of sodium dodecyl sulfate, 1.5 parts of dispersing agent NF, 0.03 part of sodium carbonate, 0.005 part of ferrous sulfate, 0.04 part of white block, 0.5 part of tertiary dodecyl mercaptan, 27 parts of acrylonitrile and 3.0 parts of methacrylic acid are respectively added into a polymerization kettle at the beginning of polymerization reaction, after vacuumizing, 0.005 part of deoxidizer is added, the mixture is continuously replaced by nitrogen for three times, 70 parts of butadiene is added, when the temperature of the polymerization kettle is reduced to below 15 ℃, 0.06 part of dicumyl hydroperoxide is added, the polymerization reaction is started, the polymerization reaction temperature is controlled to be 8-15 ℃ in the process, dry matters are measured every 2 hours, 0.05 part of terminator is added when the conversion rate reaches 92.4%, the carboxyl nitrile latex is prepared, 3wt% KOH solution is added for regulating the PH, and then physical property test is carried out, and the results are shown in Table 1.
Comparative example 2
The polymerization was carried out in a 15L stirred autoclave. The addition amount of each monomer auxiliary agent is calculated by weight of each 100 parts of monomer. At the beginning of the polymerization, 126 parts of desalted water, 3 parts of sodium dodecyl sulfate, 0.6 part of C13-glycosyl gemini cationic surfactant (n=1), 2.0 parts of dispersing agent NF, 0.04 part of sodium bicarbonate, 0.005 part of ferrous sulfate, 0.03 part of white block, 0.55 part of tertiary dodecyl mercaptan, 32 parts of acrylonitrile and 3.0 parts of methacrylic acid are respectively added into a polymerization kettle, after vacuumizing, 0.009 part of deoxidizer is added, the substitution with nitrogen is continued for three times, 65 parts of butadiene is added, when the temperature of the polymerization kettle is reduced to below 15 ℃, 0.06 part of hydrogen peroxide diisopropylbenzene is added, the polymerization reaction is started, the polymerization reaction temperature is controlled to be 8-15 ℃ in the process, dry matters are measured every 2 hours, 0.2 part of terminator is added when the conversion rate reaches 78.2%, carboxyl nitrile latex is prepared, 4wt% of KOH solution is added to adjust the PH, and then physical property test is carried out, and the results are shown in Table 1.
Comparative example 3
The polymerization was carried out in a 15L stirred autoclave. The addition amount of each monomer auxiliary agent is calculated by weight of each 100 parts of monomer. At the beginning of the polymerization, 100 parts of desalted water, 3.2 parts of sodium dodecyl sulfate, 0.2 part of C12-glycosyl gemini cationic surfactant (n=3), 2.5 parts of dispersing agent NF, 0.05 part of sodium carbonate, 0.008 part of ferrous sulfate, 0.02 part of white block, 0.5 part of tertiary dodecyl mercaptan, 29 parts of acrylonitrile and 5.0 parts of methacrylic acid are respectively added into a polymerization kettle, after vacuumizing, 0.01 part of deoxidizer is added, the substitution is continued for three times by nitrogen, 66 parts of butadiene is added, when the temperature of the polymerization kettle is reduced to below 15 ℃, 0.1 part of cumene hydroperoxide is added, the polymerization reaction is started, the polymerization reaction temperature is controlled to be 8-15 ℃ in the process, dry matter is measured every 2 hours, 0.1 part of terminator is added when the conversion rate reaches 85.1%, the carboxyl butyronitrile latex is prepared, the KOH solution with 5 weight percent is added for regulating the PH, and physical property test is carried out, and the results are shown in Table 1.
Comparative example 4
The polymerization was carried out in a 15L stirred autoclave. The addition amount of each monomer auxiliary agent is calculated by weight of each 100 parts of monomer. At the beginning of the polymerization, 140 parts of desalted water, 3.6 parts of sodium dodecyl sulfate, 0.3 part of C14-glycosyl gemini cationic surfactant (n=2), 2.0 parts of dispersing agent NF, 0.05 part of sodium carbonate, 0.01 part of ferrous sulfate, 0.06 part of white block, 0.6 part of tertiary dodecyl mercaptan, 26 parts of acrylonitrile and 6.0 parts of methacrylic acid are respectively added into a polymerization kettle, after vacuumizing, 0.03 part of deoxidizer is added, the mixture is continuously replaced by nitrogen for three times, 68 parts of butadiene is added, when the temperature of the polymerization kettle is reduced to below 25 ℃, 0.08 part of cumene hydroperoxide is added, the polymerization reaction is started, the polymerization reaction temperature is controlled to be 20-25 ℃, dry matter is measured every 2 hours, 0.1 part of terminator is added when the conversion rate reaches 94.7%, the carboxyl butyronitrile latex is prepared, the pH is adjusted by adding 5wt% of KOH solution, and physical property test is carried out, and the results are shown in Table 1.
Table 1 test results
As can be seen from the data in the table, the carboxylated nitrile latex provided by the invention has the advantages of low gel content, excellent film forming property, mechanical stability and strength, simple and controllable preparation method and easiness in industrial production. Specifically, the only difference between comparative example 1 and example 1 is that: the emulsifier in the comparative example 1 is only added with a single anionic emulsifier sodium dodecyl sulfate, other formulation processes are kept unchanged, and test results show that the surface tension of the carboxyl butyronitrile latex emulsion system prepared in the comparative example 1 is increased, the viscosity is increased, the heat dissipation of the polymerization reaction is uneven, more educts are generated during sampling analysis, the total solid content can only reach about 40%, the latex has poor mechanical stability, the coagulation content is greatly increased, and the latex performance is greatly reduced.
The only difference between comparative example 2 and example 2 is that: the amount of C12-glycosyl gemini cationic surfactant used in comparative example 2 was increased to give sodium lauryl sulfate: the dosage ratio of the C12-glycosyl gemini cationic surfactant reaches 1:0.2, other formulation processes remain unchanged, and test results show that the use amount of the cationic surfactant in the comparative example 2 is increased, so that the stability of a polymerization system is reduced, the polymerization reaction is greatly affected, a large amount of colloidal particles are separated out in the reaction process, and the solid content of the latex can only reach about 35%.
The only difference between comparative example 3 and example 3 is that: in comparative example 3, the desalted water consumption is reduced to 100 parts, other formula processes are kept unchanged, and test results show that after the desalted water consumption is reduced to a certain degree, the viscosity of the system is rapidly increased, the stirring and heat dissipation are difficult, the system stability is reduced, the polymerization conversion rate can only reach about 85%, and the latex fluidity is poor.
The only difference between comparative example 4 and example 4 is that: in comparative example 4, the polymerization temperature was increased and controlled to about 20 to 25℃with other formulation techniques maintained, and the test results showed that the polymerization temperature was increased, the polymerization rate was increased, the system stability was deteriorated, and the gel content was greatly increased.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (8)
1. The carboxylated nitrile latex is characterized by comprising the following raw materials in parts by weight: 64-70 parts of butadiene, 26-33 parts of acrylonitrile, 3.0-6.0 parts of methacrylic acid, 2.5-4.0 parts of emulsifier, 1.0-3.0 parts of dispersing agent, 0.02-0.08 parts of electrolyte, 0.005-0.05 part of ferrous sulfate, 0.02-0.06 part of auxiliary reducing agent, 0.4-1.0 part of molecular weight regulator, 0.005-0.02 part of deoxidizer, 0.04-0.10 part of initiator and 125-140 parts of desalted water;
wherein the emulsifier is a mixture of an anionic emulsifier and a cationic emulsifier, the anionic emulsifier is sodium dodecyl sulfate, and the cationic emulsifier is a glycosyl gemini cationic surfactant;
the mass ratio of the anionic emulsifier to the cationic emulsifier in the emulsifier is 1:0.05 to 0.1.
2. The carboxylated nitrile latex according to claim 1, characterized in that the glycosyl gemini cationic surfactant has the formula:
wherein n=1 to 3, and r is an alkyl group.
3. The carboxylated nitrile latex according to claim 2, characterized in that R is chosen from the group consisting of linear alkyl groups of from C12 to C14.
4. A carboxylated nitrile latex according to claim 3 in which R is selected from the group consisting of C12 linear alkyl groups.
5. Carboxylated nitrile latex according to claim 1, in which the initiator is a low temperature redox initiator, preferably cumene hydroperoxide and/or diisopropylbenzene hydroperoxide.
6. The carboxylated nitrile latex according to claim 1, wherein the electrolyte is at least one of sodium carbonate, sodium bicarbonate and sodium pyrophosphate.
7. The process for preparing carboxylated nitrile latex according to any one of claims 1 to 6, characterized in that it comprises the following steps:
in an inert atmosphere, desalted water, an emulsifying agent, a dispersing agent, a molecular weight regulator, an activating agent, a reducing aid, an electrolyte, methacrylic acid and acrylonitrile are mixed, then an deoxidizer and butadiene are added, after the system temperature is controlled to 8-15 ℃, an initiator is added, polymerization reaction is carried out at 8-15 ℃, and when the polymerization conversion rate reaches more than 95%, 0.05-0.2 part of terminator is added, so that the carboxylated nitrile latex is obtained.
8. A labor protection glove prepared from the carboxylated nitrile latex according to any one of claims 1 to 6 or the carboxylated nitrile latex prepared by the method of preparing the carboxylated nitrile latex according to claim 7.
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