CN1128765A - Aqueous high molecular emulsion - Google Patents
Aqueous high molecular emulsion Download PDFInfo
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- CN1128765A CN1128765A CN 95101526 CN95101526A CN1128765A CN 1128765 A CN1128765 A CN 1128765A CN 95101526 CN95101526 CN 95101526 CN 95101526 A CN95101526 A CN 95101526A CN 1128765 A CN1128765 A CN 1128765A
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Abstract
Alkyl methylol amine, alkyl thiol and 2-phenyl propylene as chain transfer agent, through mixing and emulsified polymerization the polymer emulsion is prepd.. The monomers are: monoethylene aromatic, aliphatic conjugated diene, non-saturated ethylene carboxylic acid, non-saturated sofonic acid and sulfonate, non-saturated thiamine, non-saturated ethylene alkyl ester and ethylene cyanide monomer.
Description
The present invention relates to a kind of aqueous high molecular emulsion, it is by monovinylidene aromatic monomer, and aliphatic conjugated diene monomers and unsaturated ethylene carboxylic acid monomer copolymerization form, and have high-intensity bounding force.Be widely used in the coating processing of the white pigment of paper and paperboard surface.
For the latex of the coating processing and other fields of the white pigment that is applied to paper and paperboard surface, need it to have good dried stripper-resistance, wet stripper-resistance, optical property and post-treatment characteristic, the smell of any discomfort can not be arranged.
As everyone knows, cross-linking density in the high molecular emulsion, it is so-called toluene insoluble composition, can influence the balancing effect of above-mentioned these character, it can be easy to be controlled by chain-transfer agent, as alkyl sulfhydryl or Organohalogen compounds (tetracol phenixin, chloroform) etc., but alkyl sulfide alcohols chain-transfer agent has foreign odor usually, and the Organohalogen compounds chain-transfer agent then can cause global environmental issue.
Therefore, the object of the present invention is to provide a kind of latex, it can improve the foreign odor that is produced because of use alkyl sulfide alcohols chain-transfer agent and solve the caused environmental issue of organic fontanelle compound.
Latex of the present invention is being widely used in paper and the paperboard surface pigment application adds man-hour, uses as the aqueous high molecular caking agent.
High molecular emulsion of the present invention is to utilize known emulsion polymerization method and adopt at least a chain-transfer agent synthetic, is 100% in whole monomeric gross weights, and employed monomer comprises:
(a) monovinylidene aromatic monomer (monovinylidene aromatic monomers), for example: vinylbenzene, alpha-methyl styrene, neighbour-vinyl toluene, p-methylstyrene, neighbour, right-dimethyl styrene, neighbour, right-diethylbenzene ethene, dichlorostyrene, Vinylstyrene, 4-3 level-butylstyrene, monochloro vinylbenzene and Vinyl toluene etc.; Because factors such as obtaining property, price, usability are preferably vinylbenzene and Vinyl toluene, wherein with vinylbenzene for most preferably; Its consumption accounts for the 20%-79.5% of whole monomeric gross weights, is preferably 25%-75%, if it is too strong to surpass 79.5% o'clock latex rigidity, makes bond strength die down, if be lower than 20% rigidity deficiency;
(b) aliphatic conjugated diene monomers (aliphaticconjugated diene monomers), from 4 to 9 of its carbonatomss, for example: 1,3-butadiene, 2-methyl isophthalic acid, 3-divinyl, 2,3-dimethyl-1,3-divinyl, pentadiene, 2-neo-pentyl-1,3-butadiene and other analogues, as: 2-chloro-1,3-divinyl and 2-cyano group-1,3-butadiene etc.; More than various monomers its special performance is respectively arranged, but because factors such as price and obtaining property, 1,3-butadiene is most preferred; Its consumption accounts for the 20%-70% of whole monomeric gross weights, is preferably 30%-60%, if be lower than the bounding force deficiency of 20% o'clock latex, if it is poor to surpass the water-resistant capacity of 70% latex, bounding force also can be not enough simultaneously;
(c) unsaturated ethylene carboxylic acid monomer (ethylenically unsaturated carboxylic acid monomers), can with the organic acid of other monomer copolymerizables, for example: vinylformic acid, methacrylic acid, butylene-[1]-acid, 3-phenylallene-[2]-acid, suitable-butene dioic acid, the methyne Succinic Acid, instead-butene dioic acid etc., perhaps unsaturated ethylene sulfonic acid monomer (ethylenically unsaturated sulfonic acid monomers) is as vinylformic acid-2-sulfonic acid ethyl ester, methacrylic acid-2-sulfonic acid propyl ester, 2-acrylamide-2-methyl propane sulfonic acid, styrene sulfonic acid, methacrylic sulfonic acid etc., the alkaline metal salt of above-mentioned acid or ammonium salt also can use; Total consumption of unsaturated ethylene olefinic carboxylic acid and unsaturated ethylene sulfonic acid accounts for the 0.5%-10% of whole monomeric gross weights, if be lower than 0.5%, then the mechanical stability of latex is bad, the mixed stability of pigment is also poor, if surpass 10%, then the viscosity of latex is too high, and is not suitable for actually operating, and its consumption is preferably the 1%-8% of whole monomeric gross weights;
(d) ethylenic unsaturation amides monomer (ethylenically unsaturated amide monomers), for example: acrylamide, Methacrylamide, N-hydroxymethyl acrylamide and N-butoxymethyl acrylamide etc., its whole consumptions account for the 0%-10% of whole monomeric gross weights, add this monomeric purpose and be for the mechanical stability that improves latex and the mixed stability of pigment, its preferred amounts is 0%-8%;
(e) ethylenic unsaturation alkyl ester monomer (ethylenically unsaturated alkylester monomers), its consumption accounts for the 0%-30% of whole monomeric gross weights, be preferably 0%-20%, can use the acrylic acid hydroxy alkyl ester that contains 2 to 8 carbon atoms, for example: vinylformic acid-2-hydroxyl ethyl ester, vinylformic acid-3-hydroxypropyl acrylate, vinylformic acid-4-hydroxy butyl ester, 2-hydroxyethyl methacrylate, methacrylic acid-3-hydroxypropyl acrylate, methacrylic acid-4-hydroxy butyl ester, and alkyl acrylic (methacrylic acid) alkyl ester that contains 1 to 18 carbon atom is for example: methyl acrylate, ethyl propenoate, methyl methacrylate, ethyl acrylate, propyl acrylate, butyl methacrylate, isopropyl methacrylate, phenyl methacrylate, methacrylic acid chloroethene ester, the methacrylic cyclohexyl, the acrylic acid epoxy propyl ester, glytidyl methacrylate etc.;
(f) thiazolinyl nitrile monomer (ethylenic nitrile monomers), for example: vinyl cyanide, methacrylonitrile, propylene dichloride nitrile etc., its consumption accounts for the 0%-20% of whole monomeric gross weights, is preferably 0%-15%.
The employed chain-transfer agent of latex of the present invention must contain: (a) alkyl methylol alkane; (b) alkyl sulfhydryl; (c) at least a in the 2-phenyl propylene binary, promptly, in building-up process, be used alone respectively or two kinds and two or more mixtures, its total usage quantity accounts for 0.05% to 10% of whole monomeric gross weights, and wherein alkyl methylol amine weight percent accounts for 5% to 70% of chain-transfer agent total amount.
Alkyl methylol amine is the one-level amine, and its structure is as follows:
N≤5 X+Y+Z=3
Alkyl methylol amine is the alkaline water soluble molecule, during 20 ℃ of temperature, its pKa value is between 6 to 12, most preferably between 7 to 11, and volatility is low, during 20 ℃ of temperature, vapour pressure is lower than 1 mmhg, is preferably to be lower than 0.5 mmhg, and the carbonatoms of alkyl preferably is less than or equal to 3, for example: Tutofusin tris, 1,1-dihydroxymethyl ethylamine, 1-methyl isophthalic acid-hydroxymethyl ethyl amine, 1-methyl isophthalic acid-methylol propyl group amine, 1,1-dihydroxymethyl propyl group amine.
It is 5 to 12 compound that alkyl sulfhydryl (alkylthiol) can be carbonatoms, be that 12 compound is comparatively preferred wherein with carbonatoms, as: lauryl mercaptan, a positive lauryl mercaptan, 4-normal-butyl octyl mercaptan, dodecyl-6-mercaptan, 3 grades-lauryl mercaptan, also can be the Thiovanic acid derivative, for example: thioglycollic acid-2-ethyl hexyl ester, three-(alpha mercaptoacetic acid methylene radical ester) propane, also can be the β-Qiu Jibingsuan derivative, for example: 3-thiohydracrylic acid-2-ethylhexyl, 3-thiohydracrylic acid-3-methoxyl group butyl ester, three-(β-Thiovanic acid methylene radical ester) propane.
2-phenyl propylene binary (2-phenyl propylene dimer) for example can be: 2, and 4-phenylbenzene-4-methyl-1-pentene, 2,4-phenylbenzene-4-methyl-2-amylene.
The chain-transfer agent consumption accounts for 0.05% to 10% of whole monomeric gross weights, is preferably 0.1% to 7%, makes its toluene insoluble composition that can control latex in 45% to 90% scope.If it is poor to be lower than 45% dried peel strength, vacuum packaging is poor, if it is poor to surpass 90% moisture-resistant stripping strength.
High-performance water-based latex of the present invention adopts the emulsion polymerization method preparation, monomer under agitation is emulsified in aqueous phase equably, wherein also contain and to produce initiator and the emulsifying agent that free radical takes place with initiation reaction, to initiator type without limits, commonly used have an organo-peroxide, as: 3 grades of butylhydroperoxides, propyloxy phenyl base hydrogen peroxide; Or azo-compound, as: 2, the two isobutyl-nitriles of 2-azo; Or inorganic oversulfated thing, as: Potassium Persulphate, Sodium Persulfate, ammonium persulphate all can.The also available oxidation-reduction mode of above-mentioned initiator, with reductive agent and usefulness, as: S-WAT, ferrous sulfate etc.Initiator amount accounts for the 0.05%-3% of whole monomeric gross weights, is preferably 0.1%-2%.
Emulsifying agent can be according to the level of the claimed range of latex particle diameter and the suitable emulsification degree that can reach, on consumption and kind, be allowed a choice, usually emulsion polymerization can be selected anionic, non-ionic type, amphoteric and cationic emulsifier for use, generally uses one or both or two or more mixtures at least.
The example of typical anionic emulsifier is: as alkylsulfonate, alkylbenzene sulfonate, sulfonic group succsinic acid alkyl diester, poly-ethanol alkyl sulfonated bodies or alkylaryl ether sulfonated bodies, fatty acid soaps.Commonly used have Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, sulfonic group succsinic acid-n-octadecyl ester disodium, a sulfonic group-dodecylphenyl ether disodium etc.
Typical nonionic emulsifier is: as polyethylene glycol alkyl ether, polyoxyethylene glycol alkane worker phenolic ether, lipid acid sorb ester, polyethylene glycol fatty acid sorb ester etc.
Typical amphoteric emulsifying agent is: as the sweet nitronic acid derivative of N-trialkyl, amino acid derivative.The derivative that lauryl glycine, octadecyl glycine or the like are arranged, N-lauryl-two (amido ethyl) glycine, octadecyl-two (amido ethyl) glycine commonly used.
Typical cationic emulsifier is the derivative of fatty acid group alkylammonium salt and 4 grades of ammonium salts, and commonly used have 4 grades of ammonium muriates of dodecyl-trimethylammonium, 4 grades of ammonium muriates of octadecyl-trimethylammonium.
The consumption of emulsifying agent accounts for the 0.05-5% of whole monomeric gross weights, is preferably 0.1%-3%.If be lower than 0.05%, the poor stability when polyreaction can cause that a large amount of coagulums produce, and because of the emulsion particle subnumber that generates very little with particle diameter cause greatly coated paper (cardboard) when promptly brushing anti-stripping property relatively poor; If surpass the poor water resistance of 5% macromolecule latex glued membrane, and have blistered problem in coating preparation or circulation time.The median size of amount control latex of utilizing emulsifying agent simultaneously is 0.05 micron to 0.5 micron scope.
Can add alkali, sequestrant, solvent, plasticizer and the ionogen etc. that those of ordinary skill in the art knows when the emulsion polymerization according to specific purpose in addition.
In reactor, carry out the monomer of emulsion polymerization reaction, can be in the presence of emulsifying agent and initiator, heat be heated and begin the reaction, form latex particle, temperature of reaction can be chosen between 5 ℃-100 ℃, be preferably between 30 ℃-95 ℃, the addition manner of monomer and raw material also has many kinds, can adopt continous way interpolation, monomer gradation interpolation, full dose to mix single interpolation etc., polyreaction is performed until productive rate according to selected temperature and reaches set objective, add suitable medicine then and slough residual monomer, and be concentrated into needed solids content scope.
Aqueous high molecular emulsion of the present invention can be used as the coating of paper and cardboard with the caking agent in the coating, and generally speaking, coating contains caking agent, white pigment and other chemical assistant with coating.
In the coating of the present invention, in the white pigment dry weight is 100%, the relative dry weight of its various tackiness agents is 5%-30%, the relative dry weight of chemical assistant is 0.1%-5%, and tackiness agent can use single latex or latex and help glue to use with, and latex wherein of the present invention accounts for the 20%-100% of tackiness agent gross dry weight.
White pigment is, for example: kaolin, lime carbonate, aluminium hydroxide, titanium white, barium sulfate, Sha Dingbai, mica powder, and pigment dyestuff as polystyrene, phenol resin.
To help glue can be natural or the synthetic tackiness agent as lactic casein, soybean protein, starch, carboxy methyl cellulose, sodiun alginate, SBR latex, MBR latex, polyvinyl alcohol, PVAc latex and acrylate copolymer latex.Auxiliary agent comprises dispersion agent, viscosity modifier, dyestuff, whitening agent, lubricant, emulsifying agent, anti-hydrated agent, pH regulator agent, defoamer and sanitas etc.
Coating of the present invention adds man-hour being used for the coating of blank sheet of paper and paperboard surface, is applicable to various coating machine, as the scraper type coating machine, roll rumble formula coating machine, rod coater and air-blade type coating machine etc.
The comparative descriptions of embodiments of the invention and comparative example as after, but the present invention is not restricted to this.Synthesizing of water based emulsion
Embodiment 1-21
The deionized water of 100 weight parts is joined in the reactor, and various raw material monomers, emulsifying agent, chain-transfer agent and initiator add at twice, and the each add-on (all representing with weight part) of various components and emulsifying agent, chain-transfer agent and initiator is listed in the table 1.When synthetic; each component that will add is for the first time joined in the reactor by the amount shown in the table 1; and with the nitrogen replacement air so that nitrogen protection to be provided, then 85 ℃ of down reactions 1 hour, again in 5 hours; constant speed is added the various monomeric mixture and the chain-transfer agent that will add for the second time continuously; the amount that adds sees Table 1, adds the emulsifying agent as shown in table 1 and the aqueous solution of initiator simultaneously continuously in 6 hours, after this; reacted about 16 hours of total overall reaction time more about 9 hours.When transformation efficiency reaches 97% when above, pH value to 8 is adjusted with sodium hydroxide in the cooling back, removes the unreacted residual monomer then, and mixture is concentrated into its solids content is 48%, and the median size of latex particle is between 0.12 to 0.2 micron.
Comparative example a-g
Carrying out compound experiment according to the step identical with above embodiment, is that employed feed composition and add-on are shown in Table 2.
The smell test
Latex is applied on the slide the about 20g/m of unit surface glue spread with spreading rod
2, the sample that is cut into 3cm * 6cm size places in the vial, and with bottle cap sealing, heating is 30 minutes in 120 ℃ baking oven, tests its smell with nose thereafter.Oder levels comparation and assessment method is as follows:
Zero: do not have
△: light
X: dense
The toluene insoluble composition measurement
Make the polymeric membrane of 0.3 mm thick with the synthetic latex, accurately take by weighing the film of 0.4g, place the airtight bottle that includes 100 milliliters of toluene, vibration is 6 hours in 30 ℃ of homothermic water-baths, thereafter with 100 strainer filterings, oven dry filtrate calculates the solids per-cent heavy with respect to film in the filtrate, this is the solvable composition of toluene, and the toluene insoluble composition then is 100% to deduct the solvable composition of toluene.
Experimental example
With the embodiment of the invention and comparative example institute synthetic latex, being modulated into solids component with the proportioning shown in the table 3 is 60% coating, and adjusts pH value to 9 with ammonium hydroxide, and its range of viscosities is at 1000-2500cps.
Table 3
| Composition | The dry weight ratio |
| One-level carclazyte (* 1) | ????70 |
| Calcination china clay (* 2) | ????10 |
| Lime carbonate (* 3) | ????20 |
| Dispersion agent (* 4) | ????0.3 |
| Anti-hydrated agent (* 5) | ????0.4 |
| Carboxymethyl cellulose rope (* 6) | ????1 |
| Latex | ????18 |
(* 1) UW-90 is Engelhard Mineral ﹠amp; The product of chemicals.
(* 2) Ansilex-93 is Engelhard Mineral ﹠amp; The chemicals product.
(* 3) TP-222H is an Okutama Kogyo Ltd. product.
(* 4) Aron T-40 is Toa Gosei Co, the Ltd. product.
(* 5) Surmirez 636 is Sumitomo Chemical Co, the Ltd. product.
(* 6) Cellogen-7A is a Daiichi Kogyo Ltd. product.
Being coated with worker's rod with Meyer, the various coating of embodiment and comparative example are evenly coated basic weight is 300g/m
2The white board body paper on, its glue spread is controlled at 17 ± 0.5g/m
2, insert immediately in 120 ℃ the ventilated drying oven, after dry 30 seconds, be 90kg/cm again with the line pressure, temperature is 130 ℃ rolling press press polish, and pattern is placed 20 ℃, the postevaluation in following 24 hours of 65% relative humidity, its result is shown in table 4 and table 5.
Do peel strength (dry pick)
Use the printing ink of high viscosity, repeatedly print paper with RI printing trier (Akira Seisakusho label), shelled phenomenon to paper and taken place, shelled degree with the visual method evaluation then, adopt 5 method comparation and assessment, 5 is best, and 1 for the poorest.
Wet peel strength (wet pick)
The coating pattern is wetting with wet cotton rumble earlier, re-uses the ink printing of RI printing trier with suitable viscosity, makes paper shell phenomenon and takes place, and has shelled degree with the visual method evaluation then, adopts 5 method comparation and assessment, and 5 is best, and 1 for the poorest.
Vacuum packaging (Blister packability)
Use the Arakawa BlisterNo.11 reagent that diluted, be applied on the cardboard that has printed, on cardboard, its hot pressing condition is 120 ℃ * 5 seconds with the hot pressing of PVC diaphragm, and pressure is 2Kg/cm
2, with hand PVC sheet and cardboard are peeled off then, check the degree of breaking at two interfaces, adopt 5 method comparation and assessment, 5 is best, 1 for the poorest.
Embodiment described in the present invention is as the reference of describing content of the present invention, is not to be used for limiting the present invention.
Table 1
| Embodiment | |||||||
| The latex numbering | ????1 | ????2 | ????3 | ????4 | ????5 | ????6 | ????7 |
| The monomer amount ratio is styrene butadiene methyl methacrylate acrylonitrile methine succinic acid fumaric acid methacrylic acid acrylic acid acrylamide methacrylic acid for the first time/for the second time | 9.5/44 ??5/27 ??2/3 ??1/4 1.5/ ???/2 ??1/ | ?8.5/43.5 ???6/29 ???2/1 ????/3 ???2/ ????/1 ????/1.5 ?1.5/ ????/1 | ???8/38 ???8/32 ????/3 ????/5 ???1/5 ?1.5/ ????/2 ?1.5/ | ?6.5/40.5 ??10/30 ???1/5 ?0.5/3 ?1.5/ ????/1 ?0.5/0.5 | ???7/42.5 ???8/32 ???2/3 ????/0.5 ???1/ ???1/ ????/2 ???1/ | ???9/45 ?7.5/30 ???2/2.5 ???1/ ?0.5/2 ???/0.5 | ?6.5/40 ??10/32 ???1/2.5 ???1/2.5 ?1.5/ ????/2 ????/1 |
| The chain-transfer agent 3 grades-dodecyl first time/second time mercaptan 1-methyl-(methylol)-ethylamine 1,1-two (methylol)-ethylamine 2-phenyl propylene binary | 0.2/0.2 0.3/0.1 0.4/ | 0.15/0.4 ?0.2/0.4 ?0.1/0.3 | 0.12/0.36 ?0.4/0.1 ?0.3/0.4 | ?0.1/0.42 ?0.6/ ?0.1/0.2 | ?0.3/0.2 ?0.2/0.4 ?0.3/0.1 | ?0.2/0.4 ?0.2/0.4 ?0.5/ | 0.15/0.3 ?0.7/0.2 ?0.3/ |
| The emulsifying agent dialkyl group Phenylsulfonic acid Na first time/second time ten | 0.2/0.5 | ?0.2/0.5 | ?0.2/0.5 | ?0.2/0.5 | ?0.2/0.5 | ?0.2/0.5 | ?0.2/0.5 |
| The initiator Potassium Persulphate first time/second time | 0.5/0.5 | ?0.5/0.5 | ?0.5/0.5 | ?0.5/0.5 | ?0.5/0.5 | ?0.5/0.5 | ?0.5/0.5 |
| Embodiment | |||||||
| The latex numbering | ????8 | ????9 | ????10 | ????11 | ????12 | ????13 | ????14 |
| The monomer amount ratio is styrene butadiene methyl methacrylate acrylonitrile methine succinic acid fumaric acid methacrylic acid acrylic acid acrylamide methacrylic acid for the first time/for the second time | ?9.5/41 ???6/31 ???2/5 ?1.5/ ????/2 ????/1 ???1/ | ?6.5/42.5 ???7/30 ???1/0.5 ???2/5 ?1.5/ ????/2 ???2/ | ???7/44 ?7.5/28 ?2.5/2.5 ?0.5/3 ???1/ ???1/2.5 ?0.5/ | ????7/42.5 ????7/28 ????1/3.5 ????2/4 ????2/ ?????/0?5 ?????/1.5 ????1/ | ???7/42.5 ?8.5/28 ???1/3.5 ?0.5/4 ???2/ ????/0.5 ????/1.5 ???1/ | ???7/38.5 ??10/30 ???3/4.5 ???1/ ???1/2 ???3/ | ???4/46 ???5/30 ???1/2.5 ?2.5/4 ???1/ ?1.5/1.5 ????/0.5 ???1/0.5 |
| The chain-transfer agent 3 grades-dodecyl first time/second time mercaptan 1-methyl-(methylol)-ethylamine 1,1-two (methylol)-ethylamine 2-phenyl propylene binary | ?0.1/0.2 ?0.9/1.0 ?0.4/ | 0.15/0.6 ?0.4/0?3 ?0.1/0.3 | ?0.2/0?4 ?0.3/0.1 ?0.2/0.3 | 0.14/0.4 ?0.3/0.2 ????/0.2 | 0.15/0.4 ?0.2/0.1 ?0.2/0.1 | 0.25/0.6 ?0.1/0.3 ?0.35/0.4 | 0.06/0.4 ?0.1/04 ?0.3/0.3 |
| The emulsifying agent dialkyl group Phenylsulfonic acid Na first time/second time ten | ?0.2/0.5 | ?0.2/0.5 | ?0.2/0.5 | ?0.2/0.5 | ?0.2/0.5 | ?0.2/0.5 | ?0.2/0.5 |
| The initiator Potassium Persulphate first time/second time | ?0.5/0.5 | ?0.5/0.5 | ?0.5/0.5 | ?0.5/0.5 | ?0.5/0.5 | ?0.5/0.5 | ?0.5/0.5 |
| Embodiment | |||||||
| The latex numbering | ????15 | ????16 | ????17 | ????18 | ????19 | ????20 | ????21 |
| The monomer amount ratio is styrene butadiene methyl methacrylate acrylonitrile methine succinic acid fumaric acid methacrylic acid acrylic acid acrylamide methacrylic acid for the first time/for the second time | ????5/41.5 ????8/31 ????4/5.5 ??1.5/ ????1/ ?????/2 ??0.5/ | ???5/40.5 ?7.5/30 ???2/3 ???1/5 ?0.5/ ?0.5/ ?1.5/1.5 ???2/ | ?2.5/41 ???3/40 ???1/4 ???2/3 ???1/ ?0.5/ ????/2 | 10.5/28.5 ??12/30 ???5/10 ?1.5/ ???1/0.5 ????/1 | ?8.5/43.5 ?4.5/28 ???3/3 ???2/4 ????/1 ?0.5/ ?0.5/ ???1/ ????/0.5 | ?4.5/47 ???3/33 ???5/3 ????/1 ???1/ ????/0.5 ???1/ ?0.5/0.5 | ???7/32.5 ???7/40 ???1/2.5 ???2/3 ????/0.5 ???1/ ???1/0.5 ???1/1 |
| The chain-transfer agent 3 grades-dodecyl first time/second time mercaptan 1-methyl-(methylol)-ethylamine 1,1-two (methylol)-ethylamine 2-phenyl propylene binary | 0.16/0.7 ?0.2/0.3 ?0.4/ | 0.12/0.6 ?0.1/0.4 ?0.3/0.3 | 0.03/0.6 ????/0.5 ????/0.5 | ?0.2/0.6 ?0.3/0.3 ?0.24/0.36 | ?0.1/0.65 ????/0.6 ????/0.45 | 0.06/0.7 ?0.1/0.3 0.34/0.32 | 0.12/0.64 ?0.1/0.5 ?0.1/0.6 |
| The emulsifying agent dialkyl group Phenylsulfonic acid Na first time/second time ten | ?0.2/0.5 | ?0.2/0.5 | ?0.2/0.5 | ?0.2/0.5 | ?0.2/0.5 | ?0.2/0.5 | ?0.2/0.5 |
| The initiator Potassium Persulphate first time/second time | ?0.5/0.5 | ?0.5/0.5 | ?0.5/0.5 | ?0.5/0.5 | ?0.5/0.5 | ?0.5/0.5 | ?0.5/0.5 |
| Comparative example | |||||||
| The latex numbering | ????a | ????b | ????c | ????d | ????e | ????f | ????g |
| The monomer amount ratio is styrene butadiene methyl methacrylate acrylonitrile methine succinic acid fumaric acid methacrylic acid acrylic acid acrylamide methacrylic acid for the first time/for the second time | ???6/30 ???7/28 ???2/18 ???3/2.5 ???2/ ????/1.5 | ??7/27.5 ??6/28 ??5/16 ???/7 ??1/ ????/0.5 ?0.5/1 ?0.5/ | ???1/30.5 ??10/33 ???2/3 ????/7 ???1/ ???1/ ????/1 ????/0.5 | 12.5/59 ???3/12 ???2/3 ???1/4 ?1.5/2 | ?3.5/8.5 12.5/60 ?2.5/2.5 ????/7 ?1.5/ ????/?2 | ?3.5/39 ?8.5/32 ?3.5/5.5 ???2/1 ?0.5/ ????/1 ???1/1.5 ???1/ | ?6.5/42.5 ???7/30 ???2/0.5 ???1/5 ?1.5/ ????/2 ???2/ |
| The chain-transfer agent 3 grades-dodecyl first time/second time mercaptan 1-methyl isophthalic acid-(methylol)-ethylamine tetracol phenixin 2-phenyl propylene binary | 0.14/ ?1.4/1.4 ?0.6/0.5 | ?0.5/1.5 ????/0.2 | ?0.4/ ?0.5/0.8 ?0.1/0.2 | ?0.1/0.36 ????/0.1 ????/0.2 | 0.15/1.2 ????/0.3 | ?0.1/0.7 ?0.1/ ????/1.2 | ?0.1/0.4 |
| The emulsifying agent dialkyl group Phenylsulfonic acid Na first time/second time ten | ?0.2/0.5 | ?0.2/0.5 | ?0.2/0.5 | ?0.2/0.5 | ?0.2/0.5 | ?0.2/0.5 | ?0.2/0.5 |
| The initiator Potassium Persulphate first time/second time | ?0.5/0.5 | ?0.5/0.5 | ?0.5/0.5 | ?0.5/0.5 | ?0.5/0.5 | ?0.5/0.5 | ?0.5/0.5 |
| The latex numbering | Smell | Toluene insoluble composition (%) | Dried peel strength (counting) | Wet peel strength (counting) | Vacuum packaging (counting) |
| ????1 | ???○ | ????78 | ????4 | ????4 | ????5 |
| ????2 | ???○ | ????83.6 | ????5 | ????4.5 | ????5 |
| ????3 | ???○ | ????84 | ????5 | ????4 | ????5 |
| ????4 | ???○ | ????76.7 | ????5 | ????4 | ????5 |
| ????5 | ???○ | ????61.5 | ????4 | ????4.5 | ????4 |
| ????6 | ???○ | ????74.5 | ????4.5 | ????5 | ????4.5 |
| ????7 | ???○ | ????69.9 | ????5 | ????5 | ????5 |
| ????8 | ???○ | ????53.5 | ????4 | ????5 | ????5 |
| ????9 | ???○ | ????78.3 | ????4.5 | ????4 | ????5 |
| ????10 | ???○ | ????79.3 | ????4.5 | ????4 | ????5 |
| ????11 | ???○ | ????85.9 | ????5 | ????4 | ????5 |
| The latex numbering | Smell | Toluene insoluble composition (%) | Dried peel strength (counting) | Wet peel strength (counting) | Vacuum packaging (counting) |
| ????12 | ???○ | ????82.1 | ????5 | ????4 | ????5 |
| ????13 | ???○ | ????66.1 | ????4 | ????4 | ????4.5 |
| ????14 | ???○ | ????79.3 | ????5 | ????4 | ????5 |
| ????15 | ???○ | ????55.2 | ????4.5 | ????5 | ????4 |
| ????16 | ???○ | ????64.1 | ????4.5 | ????5 | ????5 |
| ????17 | ???○ | ????73.4 | ????5 | ????4 | ????5 |
| ????18 | ???○ | ????54.3 | ????3.5 | ????5 | ????4 |
| ????19 | ???○ | ????72.8 | ????4.5 | ????4 | ????5 |
| ????20 | ???○ | ????62.8 | ????4 | ????4.5 | ????5 |
| ????21 | ???○ | ????78.2 | ????5 | ????4.5 | ????5 |
| The latex numbering | Smell | Toluene insoluble composition (%) | Dried peel strength (counting) | Wet peel strength (counting) | Vacuum packaging (counting) |
| ????a | ????○ | ????76.4 | ????4 | ????4 | ????3 |
| ????b | ????○ | ????92 | ????4.5 | ????3 | ????3.5 |
| ????c | ????○ | ????85 | ????4 | ????3 | ????4 |
| ????d | ????○ | ????80.4 | ????3.5 | ????2.5 | ????2 |
| ????e | ????△ | ????43.4 | ????3 | ????2.5 | ????3 |
| ????f | ????○ | ????88.5 | ????4.5 | ????3 | ????4 |
| ????g | ????○ | ????85.1 | ????4 | ????4 | ????3.5 |
Claims (12)
1, a kind of employing emulsion polymerization method is used chain-transfer agent synthetic aqueous high molecular emulsion, and the whole monomeric gross weight that adopts during in synthetic described high molecular emulsion is 100%, and described monomer comprises:
(a) monovinylidene aromatic monomer accounts for the 20%-79.5% of whole monomeric gross weights;
(b) aliphatic conjugated diene monomers accounts for the 20%-70% of whole monomeric gross weights;
(c) ethylenic unsaturation yl carboxylic acid monomer and unsaturated sulfonic acid and acid anhydrides thereof or salt, its consumption accounts for the 0.5%-15% of whole monomeric gross weights;
(d) unsaturated thiazolinyl amide monomer accounts for the 0%-10% of whole monomeric gross weights;
(e) unsaturated thiazolinyl alkyl ester monomer accounts for the 0%-30% of whole monomeric gross weights;
(f) thiazolinyl nitrile monomer accounts for the 0%-20% of whole monomeric gross weights.
2, aqueous high molecular emulsion as claimed in claim 1, wherein:
Described single alkenylene base aromatic monomer is vinylbenzene, alpha-methyl styrene, Vinyl toluene, monochloro vinylbenzene;
Described aliphatic conjugated diene monomers is 1,3-butadiene, halogenation divinyl;
Described ethylenic unsaturation yl carboxylic acid monomer and unsaturated sulfonic acid and acid anhydrides thereof or salt are vinylformic acid, methacrylic acid, butylene-[1]-acid, 3-phenylallene-[2]-acid, methyne Succinic Acid, anti--butene dioic acid, suitable-butene dioic acid, styrene sulfonic acid, 2-methyl isophthalic acid-propene sulfonic acid, 2-acrylamide-2-methyl-propene sulfonic acid;
Described unsaturated thiazolinyl amide monomer is acrylamide, Methacrylamide, N hydroxymethyl acrylamide;
Described unsaturated thiazolinyl alkyl ester monomer is methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl acrylate, vinylformic acid-2-hydroxyl ethyl ester, vinylformic acid-3-hydroxypropyl acrylate, vinylformic acid-4-hydroxy butyl ester, 2-hydroxyethyl methacrylate, methacrylic acid-3-hydroxypropyl acrylate, acrylic acid epoxy propyl ester, glytidyl methacrylate; And
Described thiazolinyl nitrile monomer is vinyl cyanide, methacrylonitrile, propylene dichloride nitrile.
3, aqueous high molecular emulsion as claimed in claim 1, wherein, the median size of described latex is from 0.05 micron to 0.5 micron.
4, aqueous high molecular emulsion as claimed in claim 1, wherein, described chain-transfer agent is: (a) alkyl methylol amine; (b) alkyl sulfhydryl; And (c) at least a or two or two or more mixture in the 2-phenyl propylene binary, its consumption is 100% in whole monomeric gross weights, is 0.05% to 10%, wherein alkyl methylol amine weight accounts for 5% to 70% of chain-transfer agent total amount.
5, aqueous high molecular emulsion as claimed in claim 4, wherein, described chain-transfer agent is: alkyl methylol amine, it is the following one-level amine of general formula:
N≤5 X+Y+Z=3
When 20 ℃ of temperature, its pKa value is between 6 to 12, and its vapour pressure is lower than 1 mmhg.
6, aqueous high molecular emulsion as claimed in claim 5, wherein, the vapour pressure of described alkyl methylol amine when 20 ℃ of temperature is lower than 0.5 mmhg, and the carbonatoms of alkyl is less than or equal to 3.
7, aqueous high molecular emulsion as claimed in claim 6, wherein, described alkyl methylol amine is tri methylol amino methane, 1,1-dihydroxymethyl ethylamine, 1-methyl isophthalic acid-hydroxymethyl ethyl amine, 1-methyl isophthalic acid-methylol propyl group amine, 1,1-dihydroxymethyl propyl group amine.
8, aqueous high molecular emulsion as claimed in claim 4, wherein, described chain-transfer agent is an alkyl sulfhydryl, comprise lauryl mercaptan, a positive lauryl mercaptan, 4-normal-butyl-octyl mercaptan, dodecyl-6-mercaptan, 3 grades-lauryl mercaptan, thioglycollic acid-2-ethylhexyl, three-(α-thioglycollic acid methylene radical ester) propane, 3-thiohydroxy propylene-2-ethylhexyl, 3-thiohydroxy propionic acid-3-methoxyl group butyl ester, three-(β-thioglycollic acid methylene radical ester) propane, 2,4-phenylbenzene-4-methyl-1-pentene, 2,4-phenylbenzene-4-methyl-2-amylene.
9, aqueous high molecular emulsion as claimed in claim 4, wherein, described chain-transfer agent is a 2-phenyl propylene binary, comprises 2,4-phenylbenzene-4-methyl-1-pentene, 2,4-phenylbenzene-4-methyl-2-amylene.
10, aqueous high molecular emulsion as claimed in claim 1, wherein, the toluene insoluble composition of described latex is between 45%-90%.
11, a kind ofly add the aqueous white pigment coating in man-hour, contain as blank sheet of paper or white board surface coated:
(a) pigment and auxiliary agent;
(b) aqueous high molecular emulsion as claimed in claim 1.
12, aqueous white pigment coating as claimed in claim 11 wherein, is 100 weight parts in the dry weight of described white pigment coating, and the consumption of described aqueous high molecular emulsion is 1%-30%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95101526 CN1128765A (en) | 1995-02-09 | 1995-02-09 | Aqueous high molecular emulsion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95101526 CN1128765A (en) | 1995-02-09 | 1995-02-09 | Aqueous high molecular emulsion |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1128765A true CN1128765A (en) | 1996-08-14 |
Family
ID=5073956
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 95101526 Pending CN1128765A (en) | 1995-02-09 | 1995-02-09 | Aqueous high molecular emulsion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1128765A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003046066A1 (en) | 2001-11-26 | 2003-06-05 | Societe De Technologie Michelin | Rubber composition for running tread and method for obtaining same |
| CN104109211A (en) * | 2013-04-19 | 2014-10-22 | 中国石油化工股份有限公司 | Chain transferring agent, and preparation method and application thereof |
| CN104109210A (en) * | 2013-04-19 | 2014-10-22 | 中国石油化工股份有限公司 | Chain transferring agent, and preparation method and application thereof |
| US11965080B2 (en) | 2019-10-07 | 2024-04-23 | Lg Chem, Ltd. | Method of preparing carboxylic acid-modified nitrile-based copolymer latex |
-
1995
- 1995-02-09 CN CN 95101526 patent/CN1128765A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003046066A1 (en) | 2001-11-26 | 2003-06-05 | Societe De Technologie Michelin | Rubber composition for running tread and method for obtaining same |
| CN104109211A (en) * | 2013-04-19 | 2014-10-22 | 中国石油化工股份有限公司 | Chain transferring agent, and preparation method and application thereof |
| CN104109210A (en) * | 2013-04-19 | 2014-10-22 | 中国石油化工股份有限公司 | Chain transferring agent, and preparation method and application thereof |
| CN104109211B (en) * | 2013-04-19 | 2016-02-24 | 中国石油化工股份有限公司 | A kind of chain-transfer agent and its preparation method and application |
| CN104109210B (en) * | 2013-04-19 | 2016-03-30 | 中国石油化工股份有限公司 | A kind of chain-transfer agent and its preparation method and application |
| US11965080B2 (en) | 2019-10-07 | 2024-04-23 | Lg Chem, Ltd. | Method of preparing carboxylic acid-modified nitrile-based copolymer latex |
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