CN1427018A - High stability corboxylic latex - Google Patents
High stability corboxylic latex Download PDFInfo
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- CN1427018A CN1427018A CN 01144355 CN01144355A CN1427018A CN 1427018 A CN1427018 A CN 1427018A CN 01144355 CN01144355 CN 01144355 CN 01144355 A CN01144355 A CN 01144355A CN 1427018 A CN1427018 A CN 1427018A
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Abstract
A high-stability carboxylatex is a 5 or more than 5membered copolymer containing aliphatic conjugated diolefine, aromatic vinyl compound, vinyl unsaturated carboxylic acid, unsaturated amide, acrylate and/or acrylonitrile. During its polymerization, an anionic emulsifier and a non-ionic emulsifier are used. Its advantages are high stability, and proper viscosity and granularity.
Description
Technical field
The present invention relates to a kind of carboxyl copolymer, particularly a kind of high stability, the carboxyl copolymer that viscosity and particle diameter are suitable.
Background technology
Carboxylate latex is widely used in the bonding and the dipping of paper coating, on-woven fiber.Along with the improvement and the development of latex application art technology, also more and more higher to the performance requriements of latex, especially require latex to have excellent Technological adaptability.As the paper latex for coating of surface covered greater than 900m/min, require latex that good pigment, filler consistency are arranged, can prepare the coating of high solids content (solid content＞65%), under high shear forces, institute joins coating and should have excellent flowability, water-retentivity and mechanical stability, to adapt to the successional processing requirement of high-speed coating.The most important performance of associated latex then is mechanical stability, chemical stability and particle diameter.
Previous patent is when synthesizing carboxylate latex, use the composite emulsifying system of more a spot of anionic emulsifier and nonionic emulsifying agent, use relatively large water-soluble monomer or use the unsaturated acyl amine monomers, yet these methods can not be prepared mechanical stability and the suitable latex of chemical stability excellence, particle diameter and viscosity.A kind of quaternary or the above carboxylic styrene butadiene latex of quaternary are provided as CN-1208737, use the unsaturated amides of 1-2wt%, compound emulsifying agent 0.3～1.5wt% that anionic emulsifier and nonionic emulsifying agent constitute, and 1 part of anionic emulsifier of every use need be used 0.5～3 part nonionic emulsifying agent, but the latex particle size of preparing like this is bigger, tend to occur some problems in application process, tackify is serious during as preparation coating, can't prepare high solids coatings; The coating water-retentivity is relatively poor in coating process, can't implement the continuity coating.
Summary of the invention
The purpose of this invention is to provide the suitable carboxylate latex of a kind of mechanical stability and chemical stability excellence, particle diameter and viscosity.
In order to finish above-mentioned purpose, polymerization single polymerization monomer of the present invention 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 2～25% and/or vinyl cyanide 1～10wt%, wherein the aliphatics conjugated diene comprises divinyl, isoprene and their mixture.Aromatic ethenyl compound comprises the mixture of vinylbenzene and alpha-methyl styrene; The vinyl unsaturated carboxylic acid comprises vinylformic acid, methylene-succinic acid and their mixture; Unsaturated amides comprises acrylamide, n-methylolacrylamide and their mixture; Acrylate comprises methyl methacrylate, methyl acrylate and their mixture.
Simultaneously, the present invention has adopted compound emulsifying agent, i.e. anionic emulsifier and nonionic emulsifying agent when polymerization.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.The emulsifying agent consumption is 1.6～2.5wt% (is 100wt% in the monomer total amount), and wherein anionic emulsifier and nonionic emulsifying agent amount ratio are 4～6: 1, and be bigger than the consumption among the CN1208737.The emulsifying agent consumption increases, and causes viscosity of latex to increase, and can change by the ionogen consumption and adjust.But when the ionogen consumption was excessive, the salt in the latex system was too much, can make the latex particle breakdown of emulsion, thereby reduced the stability of latex.
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, and initiator can once add also and can add in batches.Polymerization temperature is preferably between 30～80 ℃.The adding mode of unsaturated amides can be that disposable adding also can add in batches, and emulsifying agent equally also can once add or add in batches, and monomeric adding mode is disposable, adding or adding continuously in batches.
The characteristics of the carboxylate latex that high stability of the present invention, particle diameter and viscosity are suitable are:
(1). latex is for containing the aliphatics conjugated diene, aromatic ethenyl compound, vinyl unsaturated carboxylic acid, the carboxyl copolymer more than five yuan or five yuan of unsaturated amides, acrylate and/or acrylonitrile monemer.
(2). adopted compound emulsifying agent to make when latex is polymerization, compound emulsifying agent is negatively charged ion and nonionic emulsifying agent, and usage ratio is certain.
(3). this latex adopts the emulsifying agent and the ionogen of more amount to make, and has suitable particle diameter and viscosity, and the mechanical stability of latex and chemical stability excellence can satisfy the processing requirement of high-speed coating.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1 (is 100wt% in the total monomer add-on):
The 10L polymerization reactor at first vacuumizes, use nitrogen replacement again, vacuum tightness reaches-during 0.10MPa, the adding water yield is 60wt%, sodium lauryl sulphate 1.0wt%, the oxyethane adduct number is 10 polyoxyethylene phenolic group in ninth of the ten Heavenly Stems ether 0.35wt%, Repone K 0.08wt%, sodium bicarbonate 0.2wt%, vinylbenzene 12wt%, tert-dodecyl mercaptan 0.3wt%, vinylformic acid 2wt%, methylene-succinic acid 1wt%, methyl methacrylate 3wt%, n-methylolacrylamide 1wt%, divinyl 10wt% begins to stir and be warmed up to 65 ℃ then, behind the adding initiator ammonium persulfate 1.5wt%, with water 40% and residual monomers and emulsifying agent promptly: sodium lauryl sulphate 0.6wt%, Sodium dodecylbenzene sulfonate 0.1wt%, tert-dodecyl mercaptan 0.2wt%, vinylbenzene 34wt%, divinyl 25wt%, polyase 13 hour after the mixture of methyl methacrylate 12wt% added continuously in 6 hours, polymerisation conversion reaches more than 98%, with in the potassium hydroxide and the pH value of latex, the pH value is to deviate from residual monomer at 8 ± 0.5 o'clock, and it the results are shown in Table 2.
Embodiment 2 (is 100wt% in the total monomer add-on)
The 10L polymerization reactor at first vacuumizes, use nitrogen replacement again, vacuum tightness reaches-during 0.10MPa, add entry 100wt%, sodium lauryl sulphate 1.8wt%, the oxyethane adduct number is 10 polyoxyethylene phenolic group in ninth of the ten Heavenly Stems ether 0.35wt%, Repone K 0.1wt%, sodium bicarbonate 0.2wt%, vinylbenzene 39wt%, tert-dodecyl mercaptan 0.5wt%, vinylformic acid 3wt%, methyl methacrylate 17wt%, acrylamide 1wt%, divinyl 40wt% begins to stir and be warmed up to 60 ℃ then, adds initiator ammonium persulfate 1.6wt% polyreaction 8 hours, transformation efficiency reaches more than 98%, with in the potassium hydroxide and the pH value of latex, the pH value is to deviate from residual monomer at 8 ± 0.5 o'clock, and it the results are shown in Table 2.
Embodiment 3 (is 100wt% in the total monomer add-on)
The 10L polymerization reactor at first vacuumizes, use nitrogen replacement again, vacuum tightness reaches-during 0.10MPa, the adding water yield is 80wt%, sodium stearyl sulfate 1.0wt%, the oxyethane adduct number is 20 polyoxyethylene phenolic group in ninth of the ten Heavenly Stems ether 0.2wt%, the oxyethane adduct number is 10 polyoxyethylene octyl group ester 0.1wt%, Repone K 0.1wt%, sodium bicarbonate 0.2wt%, alpha-methyl styrene 15wt%, tert-dodecyl mercaptan 0.3wt%, vinylformic acid 2.5wt%, vinyl cyanide 10wt%, acrylamide 0.5wt%, divinyl 10wt% begins to stir and be warmed up to 65 ℃ then, add initiator ammonium persulfate 1wt%, keep polyreaction and add entry 20wt% after 3 hours continuously, sodium stearyl sulfate 0.5wt%, hexadecyl benzene sulfonic acid sodium salt 0.1wt%, tert-dodecyl mercaptan 0.2wt%, ammonium persulphate 0.5wt%, vinylbenzene 32wt%, the mixture of divinyl 30wt% continues polymerization 6 hours, polymerisation conversion reaches more than 98%, with in the potassium hydroxide and the pH value of latex, the pH value is to deviate from residual monomer at 8 ± 0.5 o'clock, and it the results are shown in Table 2.
Embodiment 4,5,6,7 adopts the polymerization process of embodiment 1 to obtain respectively, and the add-on of monomer and emulsifying agent sees Table 1, and the physical index of the latex that records sees Table 2.
Comparative Examples 1,2,3,4 adopts the polymerization process of embodiment 1 to obtain respectively, and the add-on of monomer and emulsifying agent sees Table 1, and the physical index of the latex that records sees Table 2.
Table 1 embodiment 1-7 and comparative example 1-8 monomer and emulsifier type and add-on
| Latex | Embodiment | Comparative example | |||||||||||||
| ????1 | ????2 | ????3 | ????4 | ????5 | ????6 | ????7 | ????1 | ????2 | ????3 | ????4 | ????5 | ????6 | ????7 | ??8 | |
| Styrene AMS butadiene-isoprene methyl methacrylate methyl acrylate acrylic acid itaconic acid maleic acid acrylonitrile acrylamide NMA | ????46 ????- ????35 ????- ????15 ????- ????2 ????1 ????- ????- ????1 | ????39 ????- ????40 ????- ????17 ????- ????3 ????- ????- ????- ????1 ????- | ????32 ????15 ????40 ????- ????- ????- ????2.5 ????- ????- ????10 ????0.5 ????- | ????30 ????- ????50 ????- ????- ????10 ????3 ????- ????- ????5 ????- ????2 | ????51 ????- ????- ????40 ????5 ????- ????1 ????2 ????- ????- ????- ????1 | ????55 ????- ????38 ????- ????- ????- ????- ????- ????3 ????3 ????1 ????- | ????56.5 ????- ????30 ????- ????10 ????- ????2.5 ????- ????- ????- ????0.5 ????0.5 | ????40 ????- ????46 ????- ????10 ????- ????3 ????- ????- ????- ????1 ????- | ????54 ????- ????37. ????5 ????- ????- ????- ????2.5 ????- ????- ????5 ????- ????1 | ????30 ????- ????56 ????- ????5 ????- ????3 ????- ????- ????5 ????- ????1 | ????36 ????- ????50 ????- ????- ????- ????3 ????- ????- ????10 ????- ????1 | ????58 ????- ????38 ????- ????- ????- ????3 ????- ????- ????- ????1 ????- | ????45 ????- ????35 ????- ????10 ????- ????3.5 ????- ????- ????3 ????1.5 ????2 | ????55 ????- ????34 ????- ????8 ????- ????3 ????- ????- ????- ????- ????- | ??50 ??- ??40 ??- ??- ??- ??2.6 ??- ??- ??7 ??- ??0.4 |
| Lauryl sodium sulfate sodium stearyl sulfate neopelex cetyl benzene sulfonic acid sodium salt nonyl phenolic group polyethenoxy ether sodium sulfate, (ethoxymer distribution is 10) octyl group phenolic group polyethenoxy ether sodium sulfate, (ethoxymer distribution is 18) octyl group phenolic group APEO, (ethoxymer distribution 10) octyl group phenolic group APEO, (ethoxymer distribution 20) polyoxyethylene octyl group ester, (ethoxymer distribution is 10) polyoxyethylene butyl ester, (ethoxymer distribution is 16) | ????1.6 ????- ????0.1 ????- ????- ????- ????0.35 ????- ????- ????- | ????1.8 ????- ????- ????- ????- ????- ????0.35 ????- ????- ????- | ????- ????1.5 ????- ????0.1 ????- ????- ????- ????0.2 ????0.1 ????- | ????1.4 ????- ????- ????- ????0.3 ????- ????0.3 ????- ????- ????- | ????- ????1.3 ????- ????- ????- ????0.3 ????- ????0.35 ????- ????- | ????1.6 ????- ????0.1 ????- ????- ????- ????0.2 ????- ????- ????0.2 | ????1.7 ????- ????- ????0.2 ????- ????- ????- ????- ????0.4 ????- | ????2 ????- ????- ????- ????- ????- ????- ????- ????- ????- | ????1.5 ????- ????- ????- ????- ????- ????0.2 ????- ????- ????- | ????1.25 ????- ????- ????- ????- ????- ????0.25 ????- ????- ????- | ????2.5 ????- ????- ????- ????- ????- ????0.5 ????- ????- ????- | ????1.6 ????- ????- ????- ????- ????- ????0.3 ????- ????- ????- | ????1.8 ????- ????- ????- ????- ????- ????0.3 ????- ????- ????- | ????1.7 ????- ????- ????- ????- ????- ????0.3 ????- ????- ????- | ??1.8 ??- ??- ??- ??- ??- ??0.25 ??- ??- ??- |
The physical index contrast of table 2 embodiment 1-7 and comparative example 1-8 gained latex
Latex performance *: use the SH/T1152-92 method to measure viscosity of latex, the SH/T1151-92 method is measured mechanical stability, the SH/T1608-95 method is measured chemical stability, the SH/T1150-92 method is measured the pH value, the SH/T1153-92 method is measured macroscopical gel, uses the AUTOSIZER IIC type particle diameter instrument of Britain to survey the equal particle diameter of Z.
| The latex performance * | Embodiment | Comparative example | |||||||||||||
| ??1 | ????2 | ????3 | ????4 | ????5 | ????6 | ????7 | ????1 | ????2 | ????3 | ????4 | ????5 | ????6 | ????7 | ????8 | |
| Viscosity/mPa.s | ??105 | ????128 | ????82 | ????93 | ????112 | ????95 | ????135 | ????83 | ????102 | ????88 | ????305 | ????132 | ????313 | ????90 | ????108 |
| Mechanical stability/% | ??0.03 | ????0.04 | ????0.02 | ????0.05 | ????0.02 | ????0.01 | ????0.01 | ????0.08 | ????0.11 | ????0.24 | ????0.01 | ????0.06 | ????0.03 | ????0.04 | ????0.07 |
| Chemical stability/% | ??0.001 | ????0.005 | ????0.003 | ????0.010 | ????0.007 | ????0.001 | ????0.003 | ????15.3 | ????8.2 | ????5.7 | ????0.003 | ????0.008 | ????0.005 | ????10.9 | ????8.6 |
| PH value | ??7.85 | ????8.01 | ????7.62 | ????7.50 | ????8.10 | ????7.93 | ????7.80 | ????7.95 | ????7.60 | ????7.75 | ????7.83 | ????8.12 | ????8.02 | ????7.74 | ????8.01 |
| Particle diameter/nm | ??106.1 | ????131.1 | ????115.3 | ????122.4 | ????130.7 | ????105.8 | ????118.6 | ????121.5 | ????133.5 | ????195.0 | ????97.8 | ????183.3 | ????130.5 | ????127.6 | ????118.3 |
| Macroscopic view gel/% | ??0.005 | ????0.008 | ????0.002 | ????0.007 | ????0.006 | ????0.003 | ????0.001 | ????0.010 | ????0.030 | ????0.100 | ????0.001 | ????0.006 | ????0.004 | ????0.008 | ????0.005 |
Claims (8)
1. high stability corboxylic latex, monomer comprises the aliphatics conjugated diene, aromatic ethenyl compound, the 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 2～25% and/or vinyl cyanide 1～10wt%, and latex has adopted compound emulsifying agent when polymerization, in the monomer total amount is 100wt%, and consumption is 1.6～2.5wt%, and wherein the amount ratio of anionic emulsifier and nonionic emulsifying agent is 4～6: 1.
2. carboxylate latex according to claim 1 is characterized in that the aliphatics conjugated diene comprises divinyl, isoprene.
3. carboxylate latex according to claim 1 is characterized in that aromatic ethenyl compound comprises the mixture of vinylbenzene and alpha-methyl styrene.
4. carboxylate latex according to claim 1 is characterized in that the vinyl unsaturated carboxylic acid comprises vinylformic acid, methylene-succinic acid and their mixture.
5. carboxylate latex according to claim 1 is characterized in that unsaturated amides comprises acrylamide, n-methylolacrylamide and their mixture.
6. carboxylate latex according to claim 1 is characterized in that acrylate comprises methyl methacrylate, methyl acrylate and their mixture.
7. 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.
8. carboxylate latex according to claim 1 and 2 is characterized in that 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 |
|---|---|---|---|
| CNB011443553A CN1175014C (en) | 2001-12-17 | 2001-12-17 | High stability corboxylic latex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011443553A CN1175014C (en) | 2001-12-17 | 2001-12-17 | High stability corboxylic latex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1427018A true CN1427018A (en) | 2003-07-02 |
| CN1175014C CN1175014C (en) | 2004-11-10 |
Family
ID=4677504
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011443553A Expired - Fee Related CN1175014C (en) | 2001-12-17 | 2001-12-17 | High stability corboxylic latex |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1175014C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101638454B (en) * | 2008-07-31 | 2012-07-04 | 于景东 | Modified pyridine styrene butadiene rubber latex and synthesis method and application thereof |
| CN103626936A (en) * | 2013-12-18 | 2014-03-12 | 上海强盛化工有限公司 | Water-resistant and high temperature-resistant polymer latex and preparation method thereof |
| CN103694410A (en) * | 2013-12-18 | 2014-04-02 | 上海强盛化工有限公司 | Production method of carboxylic butadiene acrylonitrile latex |
| CN111138581A (en) * | 2020-01-17 | 2020-05-12 | 日照广大建筑材料有限公司 | Isoprene latex and preparation method thereof |
| CN113388063A (en) * | 2021-08-04 | 2021-09-14 | 福建亮晶晶新材料有限公司 | Preparation method of polymer latex for papermaking |
| CN113416576A (en) * | 2021-06-30 | 2021-09-21 | 长江大学 | Compound demulsifier and application thereof |
| WO2023227369A1 (en) * | 2022-05-27 | 2023-11-30 | Basf Se | The use of an aqueous dispersion of a polymer p as a polymeric binder in electrode slurry composition for anodes of secondary batteries |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101307117B (en) * | 2008-05-01 | 2010-07-14 | 中国石油兰州石油化工公司 | Method for synthesizing acrylic ester-acrylonitrile emulsion for making asbestos or nonasbestos sheets |
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2001
- 2001-12-17 CN CNB011443553A patent/CN1175014C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101638454B (en) * | 2008-07-31 | 2012-07-04 | 于景东 | Modified pyridine styrene butadiene rubber latex and synthesis method and application thereof |
| CN103626936A (en) * | 2013-12-18 | 2014-03-12 | 上海强盛化工有限公司 | Water-resistant and high temperature-resistant polymer latex and preparation method thereof |
| CN103694410A (en) * | 2013-12-18 | 2014-04-02 | 上海强盛化工有限公司 | Production method of carboxylic butadiene acrylonitrile latex |
| CN103694410B (en) * | 2013-12-18 | 2017-04-26 | 上海强盛化工有限公司 | Production method of carboxylic butadiene acrylonitrile latex |
| CN111138581A (en) * | 2020-01-17 | 2020-05-12 | 日照广大建筑材料有限公司 | Isoprene latex and preparation method thereof |
| CN111138581B (en) * | 2020-01-17 | 2022-05-06 | 日照广大建筑材料有限公司 | Isoprene latex and preparation method thereof |
| CN113416576A (en) * | 2021-06-30 | 2021-09-21 | 长江大学 | Compound demulsifier and application thereof |
| CN113416576B (en) * | 2021-06-30 | 2022-09-30 | 长江大学 | Compound demulsifier and application thereof |
| CN113388063A (en) * | 2021-08-04 | 2021-09-14 | 福建亮晶晶新材料有限公司 | Preparation method of polymer latex for papermaking |
| WO2023227369A1 (en) * | 2022-05-27 | 2023-11-30 | Basf Se | The use of an aqueous dispersion of a polymer p as a polymeric binder in electrode slurry composition for anodes of secondary batteries |
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| Publication number | Publication date |
|---|---|
| CN1175014C (en) | 2004-11-10 |
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