CN1075818C - High stability carboxy styrene butadiene rubber latex - Google Patents
High stability carboxy styrene butadiene rubber latex Download PDFInfo
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- CN1075818C CN1075818C CN97113379A CN97113379A CN1075818C CN 1075818 C CN1075818 C CN 1075818C CN 97113379 A CN97113379 A CN 97113379A CN 97113379 A CN97113379 A CN 97113379A CN 1075818 C CN1075818 C CN 1075818C
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- 229920000126 latex Polymers 0.000 title claims abstract description 55
- 239000004816 latex Substances 0.000 title claims abstract description 55
- FDYSSWYQRTVFIS-UHFFFAOYSA-N buta-1,3-diene 3-phenylprop-2-enoic acid Chemical compound C=CC=C.C(=O)(O)C=CC1=CC=CC=C1 FDYSSWYQRTVFIS-UHFFFAOYSA-N 0.000 title abstract 3
- 229920003048 styrene butadiene rubber Polymers 0.000 title abstract 3
- 239000000178 monomer Substances 0.000 claims abstract description 24
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 23
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 15
- 150000001408 amides Chemical class 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- -1 ethenyl compound 15 Chemical compound 0.000 claims description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 11
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 239000012874 anionic emulsifier Substances 0.000 claims description 6
- 150000007942 carboxylates Chemical class 0.000 claims description 6
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 6
- 235000011152 sodium sulphate Nutrition 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- 150000001993 dienes Chemical class 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 4
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims 1
- 229940077388 benzenesulfonate Drugs 0.000 claims 1
- 229940125758 compound 15 Drugs 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 14
- 239000003513 alkali Substances 0.000 abstract description 2
- 229920001577 copolymer Polymers 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 125000000129 anionic group Chemical group 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- 238000003756 stirring Methods 0.000 description 10
- 239000003999 initiator Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 4
- 239000004141 Sodium laurylsulphate Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 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 description 2
- 125000006353 oxyethylene group Chemical group 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- HXWKXAOJVMQTCT-UHFFFAOYSA-M S(=O)(=O)([O-])O.C(CCCCCCCCCCC)[Na].S(=O)(=O)(OCCCCCCCCCCCCCCCCCC)O.[Na+] Chemical compound S(=O)(=O)([O-])O.C(CCCCCCCCCCC)[Na].S(=O)(=O)(OCCCCCCCCCCCCCCCCCC)O.[Na+] HXWKXAOJVMQTCT-UHFFFAOYSA-M 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- VLLYOYVKQDKAHN-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene Chemical compound C=CC=C.CC(=C)C=C VLLYOYVKQDKAHN-UHFFFAOYSA-N 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 125000001400 nonyl 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])C([H])([H])[H] 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- NWZBFJYXRGSRGD-UHFFFAOYSA-M sodium;octadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCOS([O-])(=O)=O NWZBFJYXRGSRGD-UHFFFAOYSA-M 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
Abstract
The present invention provides a high stability carboxy styrene butadiene rubber latex which is a quaternary or more than quaternary copolymer containing unsaturated amide monomers. A compound emulsifying agent, i.e. an anionic emulsifying agent and a nonionic emulsifying agent, is used for polymerization. The high stability carboxy styrene butadiene rubber latex prepared by the method has the advantages of proper latex viscosity and good stability under an acidic or alkali condition , particularly chemical stability.
Description
The present invention relates to a kind of carboxylate latex, particularly a kind of carboxyl butylbenzene copolymer latex with high stability.
Carboxylate latex is widely used in the dipping and the bonding of paper coating, on-woven fiber, and is in application process, also more and more higher to the performance requriements of latex.Along with the improvement and the development of latex application art technology, require latex to have good technology suitability, wherein, stability (comprising mechanical stability and chemical stability) is the most important.
Previous patent is when synthesizing carboxylate latex, use the unsaturated acyl amine monomers, or use the compound system of anionic emulsifier and nonionic emulsifying agent, perhaps in latex, add emulsifying agent, yet these methods can not be prepared high stability, particularly the latex of chemical stability excellence.Also have some to adopt and use relatively large vinyl unsaturated carboxylic acid, the method of unsaturated amides or emulsifying agent improves its stability, as JP61-63795 unsaturated amides add-on is 1.5～6wt%, but the latex of preparing like this, in application process, tend to occur some problems, as: in the paper coating, dope viscosity increases, tackify; In the non-woven fabrics dipping, latex thermo-sensitivity reduces, and has increased product cost.
The purpose of this invention is to provide a kind of adaptation different application technology, under acid, alkali condition, all have the carboxylate latex of excellent stability.
In order to finish above-mentioned purpose, the polymerization single polymerization monomer of high stability corboxylic latex of the present invention consists of: C
4～C
5Aliphatics conjugated diene 10～80wt%, C
8～C
9Aromatic vinyl monomer 15～85wt%, C
4～C
7Acrylate monomer 0～25wt%, vinyl cyanide 0～10wt%, C
3～C
5Vinyl unsaturated carboxylic acid 1～5wt%, C
3～C
4Unsaturated acyl amine monomers 0.5～3wt%, wherein the aliphatics conjugated diene comprises divinyl, isoprene, aromatic vinyl monomer comprises vinylbenzene, the mixture of vinylbenzene and alpha-methyl styrene, the vinyl unsaturated carboxylic acid comprises vinylformic acid, methacrylic acid, methylene-succinic acid and their mixture, acrylic ester monomer comprises methyl methacrylate, methyl acrylate, ethyl propenoate and butyl acrylate and their mixture, the unsaturated acyl amine monomers comprises acrylamide, Methacrylamide, n-methylolacrylamide and their mixture.
Adopted compound emulsifying agent anionic emulsifier and nonionic emulsifying agent when simultaneously, high stability corboxylic latex of the present invention is polymerization and made.Anionic emulsifier comprises C
8～C
20Sodium alkyl sulfate, C
8～C
20Alkyl benzene sulphonate (ABS) is received, C
8～C
20Alkaryl polyethers sodium sulfate and their mixture; Nonionic emulsifying agent comprises: the oxyethane adduct number is 8～20 polyoxyethylene phenolic group ether or oxyethane, and adduct number is 5～20 polyoxyethylene C
2～C
15Fatty ester and their mixture.The emulsifying agent consumption is 0.3～1.5wt% (is 100wt% in the monomer total amount), and the anionic emulsifier that wherein every use is 1 part need be used 0.5～3 part nonionic emulsifying agent.
In the letex polymerization of latex of the present invention, initiator can be thermal initiator such as ammonium persulphate, Potassium Persulphate or redox initiator such as persulphate and sodium bisulfite, polymerization temperature is preferably between 30～80 ℃, the adding mode of unsaturated amides can be that disposable adding is also to add in batches, emulsifying agent equally also can disposable adding or is added in batches, monomeric adding mode be disposable, add in batches or add continuously.
The characteristics of high stability corboxylic latex of the present invention are:
1. this latex is quaternary or the above multipolymer of quaternary that contains unsaturated acyl amine monomers, vinyl unsaturated carboxylic acid;
Adopted compound emulsifying agent to make when 2. this latex is polymerization, compound emulsifying agent is negatively charged ion and nonionic emulsifying agent, and usage ratio is certain;
3. this latex adopts vinyl unsaturated carboxylic acid, unsaturated amides, the emulsifying agent consumption of low amount to make, this latex has suitable viscosity, in the wide region of pH=4～9, not only mechanical stability is good and chemical stability is also very excellent for latex, can adapt to the requirement of different application technology.
High stability corboxylic latex of the present invention has suitable viscosity of latex, no matter under acidity or alkaline condition, all has advantages of excellent stability, particularly chemical stability.
Embodiment 1 (is 100wt% in the total monomer add-on)
In the 10L polymerization reactor, the adding water yield is 90wt%, sodium lauryl sulphate 0.2wt%, oxyethane adduct number are 10 polyoxyethylene octylphenol ether 0.3wt%, vinylformic acid 1wt%, vinylbenzene 10wt%, divinyl 10wt%, acrylamide 0.6wt%, potassium hydroxide 0.2wt%, tert-dodecyl mercaptan 0.3wt%, stir also and be warming up to 60 ℃, add initiator potassium persulfate 0.4wt%, carry out adding entry 10% continuously behind the polyase 13 hour, sodium lauryl sulphate 0.2wt%, the oxyethane adduct number is 10 polyoxyethylene octylphenol ether 0.1wt%, vinylformic acid 2wt%, acrylamide 0.4wt%, vinylbenzene 20wt%, the mixture of divinyl 56wt% continues polymerization 8 hours, and transformation efficiency reaches more than 98%, uses in the potassium hydroxide and the pH value of latex, the pH value is respectively 4,7, deviate from residual monomer at 9 o'clock, obtain three kinds of different latex of pH value, use the SH/T1152-92 method to measure viscosity of latex, and use the SH/T1151-92 method to measure mechanical stability respectively, use 5ml, 10%CaCl
2The measured in solution chemical stability, it the results are shown in Table 2.
Embodiment 2 (is 100wt% in the total monomer add-on)
In the 10L polymerization reactor, add entry 100wt%, sodium stearyl sulfate 0.2wt%, Sodium dodecylbenzene sulfonate 0.2wt%, the oxyethylene adduct number is 10 polyoxyethylene octylphenol ether 0.4wt%, vinylformic acid 2wt%, vinylbenzene 20wt%, alpha-methyl styrene 10wt%, divinyl 67wt%, Methacrylamide 1wt%, potassium hydroxide 0.4wt%, tert-dodecyl mercaptan 0.35wt% stirs and is warming up to 60 ℃, adds initiator potassium persulfate 0.4wt% polymerization 9 hours, transformation efficiency reaches 98% when above, with in the potassium hydroxide and the pH value of latex, the pH value is respectively 4,7, deviate from residual monomer at 9 o'clock, and obtained three kinds of different latex of pH value, use the SH/T1152-92 method to measure viscosity of latex, and use the SH/T1151-92 method to measure mechanical stability respectively, use 5ml, 10%CaCl
2The measured in solution chemical stability, it the results are shown in Table 2.
Embodiment 3 (is 100wt% in the total monomer add-on)
In the 10L polymerization reactor, add entry 60wt%, sodium lauryl sulphate 0.1wt%, the oxyethylene adduct number is 10 octyl group phenolic group polyethenoxy ether sodium sulfate 0.1wt%, vinylformic acid 1wt%, isoprene 20wt%, vinylbenzene 10wt%, Methacrylamide 0.5wt%, potassium hydroxide 0.2wt%, tert-dodecyl mercaptan 0.1wt%, stirring also is warming up to 60 ℃, after adding initiator potassium persulfate 0.8wt%, with water 40wt% and residual monomers and emulsifying agent promptly: sodium lauryl sulphate 0.2wt%, the oxyethane adduct number is 10 octyl group phenolic group polyethenoxy ether sodium sulfate 0.2wt%, polyoxyethylene octylphenol ether (the oxyethane adduct number is 20) 0.2wt%, polyoxyethylene octyl group ester 0.2wt%, methylene-succinic acid 2wt%, isoprene 46wt%, vinylbenzene 20wt%, polymerization was 4 hours after the mixture of n-methylolacrylamide 0.5wt% added in 6 hours continuously, transformation efficiency reaches more than 98%, with in the potassium hydroxide and the pH value of latex, the pH value is respectively 4,7, deviate from residual monomer at 9 o'clock, and obtained three kinds of different latex of pH value, use the SH/T1152-92 method to measure viscosity of latex, and use the SH/T1151-92 method to measure mechanical stability respectively, use 5ml, 10%CaCl
2The measured in solution chemical stability, it the results are shown in Table 2.
Embodiment 4,5,6,7,8
Adopting the polymerization process of embodiment 2 to obtain pH respectively is 4,7,9 latex, and the add-on of monomer and emulsifying agent sees Table 1, and mechanical stability, the chemical stability of the latex that records see Table 2.
Comparative example 1,2,3,4,5
Adopt the polymerization process of embodiment 2, obtain pH respectively and be 4,7,9 latex, the add-on of monomer and emulsifying agent sees Table 1, and mechanical stability, the chemical stability of the latex that records see Table 2.
The mechanical stability measuring method is as follows:
Sample viscosity must be below 200mPas before the test.
In water-bath, latex is transferred to 25 ± 3 ℃, takes by weighing 5.0g latex after via hole diameter 180 ± 15 μ m stainless steel filtering nets filter and place a container (high 127mm, internal diameter 58 ± 2mm), adding 1ml sodium pyrophosphate solution (10%), 2.5g light calcium carbonate.
In latex, add two defoamers; regulate rotating speed to 14000 ± 200r/min; after stirring 30min; shut down, latex and stirring are left, down the careful wiping of the coagulum on stirring rod and the rotating disk; wash in the container with soap lye (the pH value is 10 5% potassium oleate solution); the latex that will contain coagulum (not comprising wall of container top skinning) washes in the strainer of weighing (being accurate to 0.1mg) carefully, and repetitive scrubbing is in washings till the no oyster white.Strainer is placed 100 ± 2 ℃ baking oven, and oven dry is weighed.
High speed machine stability is represented by following formula:
In the formula: m
1-coagulum quality, (g);
m
0-sample dry glue quality, (g).
The chemical stability measuring method is as follows:
Take by weighing 200 ± 0.1g latex constant temperature to 25 ℃ and through the sample of 120 μ m net filtrations in the 250ml beaker, add 10% calcium chloride solution 5ml while stirring, not contact stirring rod and wall of cup is advisable, in 20～30 second time, added, continue to stir 5min, whole process rotating speed is controlled at 300 ± 50r/min.Filter with 180 ± 10 μ m mesh screens of weighing in advance then, simultaneously the latex water on the stirring rod is washed to beaker, add in the lump in the mesh screen, the thorough drip washing of water will fill coagulative mesh screen in 120 ℃ of baking oven inner drying 30min.To room temperature, weighing is accurately to 0.2mg at the moisture eliminator internal cooling.
Chemical stability is calculated as follows:
In the formula: m
1-coagulum quality, (g);
m
0-sample dry glue quality, (g).
Table 1
| Latex is formed (wt%) | Embodiment | Comparative example | ||||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 1 | 2 | 3 | 4 | 5 | ||
| Monomer (%) | Styrene AMS butadiene-isoprene methyl methacrylate butyl acrylate acrylic acid methacrylic acid itaconic acid acrylonitrile acrylamide Methacrylamide NMA | 30 - 66 - - - 3 - - - 1 - - | 20 10 67 - - - 2 - - - - 1 - | 30 - - 66 - - 1 - 2 - - 0.5 0.5 | 28 - 67 - - - 1 2 - - 2 - - | 60 - 36 - - - - 1 1.5 - 1 - 0.5 | 60 - 30.5 - - - 2 0.5 - 5 1 - 1 | 60 - 20 - 15 - 2 - 1 - - - 2 | 30 - 56 - - 10 2 - 0.5 - 0.5 1 - | 30 - 65.5 - - - 2 - - - 1.5 1 - | 30 - 65 - - - 3 - - - 2 - - | 50 - 47 - - - 2.6 - - - 0.4 - - | 50 - 44 - - - 2.5 - - - 1.5 - 2.0 | 50 - 47.5 - - - 2.5 - - - - - - |
| Emulsifying agent (%) | Lauryl sodium sulfate sodium stearyl sulfate neopelex cetyl benzene sulfonic acid sodium salt octyl group phenolic group polyethenoxy ether sodium sulfate I, (ethoxymer distribution is 10) nonyl phenolic group polyethenoxy ether sodium sulfate II, (ethoxymer distribution is 18) polyoxyethylene octylphenol ether I, (ethoxymer distribution is 10) polyoxyethylene octylphenol ether II, (ethoxymer distribution is 20) polyoxyethylene octyl group ester I, (ethoxymer distribution is 10) polyoxyethylene butyl fat II, (ethoxymer distribution is 16) | 0.4 - - - - - 0.4 - - - | - 0.2 0.2 - - - 0.4 - - - | 0.3 - - - 0.3 - - 0.2 0.2 - | 0.8 - - - - 0.2 - 0.5 - - | - 0.4 - - 0.1 - 0.5 - - 0.3 | - - 0.4 - - - - - - 0.3 | 0.4 - - 0.2 - - - - 0.4 - | - - 0.5 - - - 0.4 - - - | 1.4 - - - - - - - - - | 1.0 - - - - - 0.4 - - - | 0.6 - - - - - 0.6 - - - | 1.2 - - - - - 0.8 - - - | 0.6 - - - - - 0.6 - - - |
Table 2
| The latex performance | Embodiment | Comparative example | |||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 1 | 2 | 3 | 4 | 5 | |
| Viscosity (mPa.s) | 80 | 72 | 140 | 90 | 130 | 120 | 147 | 98 | 124 | 110 | 86 | 368 | 94 |
| Mechanical stability (%) * | |||||||||||||
| pH=4 | 0.05 | 0.02 | 0.07 | 0.08 | 0.06 | 0.04 | 0.04 | 0.07 | 0.12 | 0.09 | 0.21 | 0.03 | 0.32 |
| pH=7 | 0.03 | 0.00 | 0.04 | 0.06 | 0.00 | 0.04 | 0.03 | 0.04 | 0.06 | 0.05 | 0.07 | 0.03 | 0.35 |
| pH=9 | 0.03 | 0.00 | 0.00 | 0.04 | 0.02 | 0.00 | 0.02 | 0.04 | 0.05 | 0.05 | - | 0.04 | 0.28 |
| Chemical stability (%) ** | |||||||||||||
| pH=4 | 0.004 | 0.005 | 0.004 | 0.004 | 0.006 | 0.004 | 0.006 | 0.005 | - | 20.4 | 20.0 | 0.040 | 17.6 |
| pH=7 | 0.004 | 0.003 | 0.006 | 0.003 | 0.006 | 0.007 | 0.005 | 0.005 | 15.4 | 16.0 | 18.0 | 0.040 | 15.4 |
| pH=9 | 0.007 | 0.003 | 0.004 | 0.006 | - | 0.005 | 0.005 | 0.004 | 18.2 | 17.4 | 15.6 | 0.045 | 15.8 |
*: numerical value is low more, shows that mechanical stability is high more.
*: numerical value is low more, shows that chemical stability is high more.
Claims (3)
1. high stability corboxylic latex, monomer comprises the aliphatics conjugated diene, aromatic ethenyl compound vinyl unsaturated carboxylic acid, unsaturated amides is characterized in that polymerization single polymerization monomer consists of: C
4～C
5Aliphatics conjugated diene 10～80wt%, C
8～C
9Aromatic ethenyl compound 15～85wt%, C
3～C
5Vinyl unsaturated carboxylic acid 1～5wt%, C
3～C
4Unsaturated amides 0.5～3wt%, C
4～C
7Acrylate 0～25wt%, vinyl cyanide 0～10wt%, and latex has adopted compound emulsifying agent when polymerization, in the monomer total amount is 100wt%, consumption is 0.3～1.5wt%, wherein every use 1 weight part anionic emulsifier need be used the nonionic emulsifying agent of 0.5～3 weight part, and latex has chemical stability under the condition of pH 〉=4.
2. carboxylate latex according to claim 1 is characterized in that the aliphatics conjugated diene comprises divinyl, isoprene; Aromatic ethenyl compound comprises the mixture of vinylbenzene, vinylbenzene and alpha-methyl styrene; The vinyl unsaturated carboxylic acid comprises vinylformic acid, methacrylic acid, methylene-succinic acid and their mixture; Unsaturated amides comprises acrylamide, Methacrylamide, n-methylolacrylamide and their mixtures; Acrylate comprises methyl methacrylate, methyl acrylate, ethyl propenoate, butyl acrylate and their mixture.
3. carboxylate latex according to claim 1 and 2 is characterized in that anionic emulsifier comprises C
8～C
20Sodium alkyl sulfate, C
8～C
20Sodium alkyl benzene sulfonate, C
8～C
20Alkaryl polyethers sodium sulfate and their mixture; Nonionic emulsifying agent comprises that the oxyethane adduct number is that 8～20 polyoxyethylene phenolic group ether, oxyethane adduct number are 5～20 polyoxyethylene C
2～C
15Fatty ester and their mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97113379A CN1075818C (en) | 1997-08-14 | 1997-08-14 | High stability carboxy styrene butadiene rubber latex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97113379A CN1075818C (en) | 1997-08-14 | 1997-08-14 | High stability carboxy styrene butadiene rubber latex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1208737A CN1208737A (en) | 1999-02-24 |
| CN1075818C true CN1075818C (en) | 2001-12-05 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97113379A Expired - Fee Related CN1075818C (en) | 1997-08-14 | 1997-08-14 | High stability carboxy styrene butadiene rubber latex |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101759825B (en) * | 2003-11-24 | 2011-12-07 | 中国石油天然气集团公司 | Carboxylated styrene-butadiene rubber latex special for oil and gas field cementing well |
| CN1295261C (en) * | 2004-03-01 | 2007-01-17 | 吉林市大宇化工有限公司 | Styrene butadiene rubber sodium type polymer and its preparation method |
| CN100429249C (en) * | 2005-07-07 | 2008-10-29 | 中国石油天然气集团公司 | Technology for preparing carboxyl butylbenzene latex |
| CN100429246C (en) * | 2006-07-04 | 2008-10-29 | 中国石油天然气集团公司 | Preparation method of new type latex |
| DE112011105263T5 (en) * | 2011-05-19 | 2014-04-30 | Lembaga Getah Malaysia | Method of quantitative measurement of mechanical stability time (MST) of latex suspensions and apparatus for use in the method |
| CN103044623B (en) * | 2011-10-17 | 2016-09-07 | 中国石油天然气股份有限公司 | A kind of covering and the application in prepared by powdered rubber thereof |
| CN106699971A (en) * | 2016-11-30 | 2017-05-24 | 杭州蓝诚新材料有限公司 | Environment-friendly carboxylic butadiene-styrene latex for papermaking and preparation method thereof |
| CN107034728A (en) * | 2017-05-02 | 2017-08-11 | 广东麦可瑞化工科技有限公司 | A kind of paper water resistant anti-blushing agent |
| CN111269348A (en) * | 2020-01-19 | 2020-06-12 | 杭州龙驹合成材料有限公司 | Super-soft carboxylic styrene-butadiene latex for building and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61268709A (en) * | 1985-05-23 | 1986-11-28 | Japan Synthetic Rubber Co Ltd | Production of copolymer latex |
-
1997
- 1997-08-14 CN CN97113379A patent/CN1075818C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61268709A (en) * | 1985-05-23 | 1986-11-28 | Japan Synthetic Rubber Co Ltd | Production of copolymer latex |
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| Publication number | Publication date |
|---|---|
| CN1208737A (en) | 1999-02-24 |
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