CN1692976A - Cationic dispersion rosin size - Google Patents
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- CN1692976A CN1692976A CN200510043569.7A CN200510043569A CN1692976A CN 1692976 A CN1692976 A CN 1692976A CN 200510043569 A CN200510043569 A CN 200510043569A CN 1692976 A CN1692976 A CN 1692976A
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Abstract
A dispersed cationic rosin gum used in making paper is prepared through emulsifying the rosin gum by composite cationic emulsifying-dispersing agent and high-temp ordinary-pressure reverse conversion process. Said composite cationic emulsifying-dispersing agent contains proportionally non-ionic amphiphilic polymer emulsion and cationic quaternary ammonium salt type surfactant or water-solule cationic polymer. Its advantage is high stability.
Description
(1) technical field under
The present invention relates to a kind of papermaking internal sizing agent, particularly a kind of cationic dispersion rosin size.
(2) background technology
Papermaking rosiny main component is a resinous acid, and hydrophobic group is partially hydrogenated phenanthrene ring, and hydrophilic group is a carboxyl.In order to improve rosin and interfibrous bonding force, also often utilize toxilic acid (acid anhydride) or fumaric acid to the rosin addition, form maleated rosin or rich horse rosin that each hydrogenation phenanthrene ring has three carboxyls.Therefore, the rosin based sizing agent itself is electronegativity, fine with the consistency of anionic polymer or tensio-active agent, utilize anion surfactant and the polymkeric substance can be with comparalive ease with its melts emulsification, the negatively charged ion dispersion rosin size that emulsion cooling back forms is also more stable.But because paper pulp fiber itself has negative charge, having the dispersion rosin size of positive charge can be directly and fiber-reactive and anchoring on the fiber, its retention and applying glue efficient height, sizing agent consumption are few, and can reduce addition of aluminum sulfate and improve applying glue pH value, thereby be the important development direction of neutral rosin sizing agent.Yet, cationic emulsifier is easy to destroy with being electronegative rosin generation static neutralizing effect the stability of rosin milk, make that the preparation difficulty of cationic dispersion rosin size is bigger, utilize general cats product to be difficult to prepare stable cationic dispersion rosin size.Increase thus that dosage of surfactant also can reduce rosin applying glue efficient with produce foam.
U.S. Pat 4,943, disclosed a kind of preparation method of cationic dispersion rosin size in 608, promptly utilize cation polymer emulsifier emulsification rosin, disclosed emulsifying agent is by methyl methacrylate, t-butyl styrene or alpha-methyl styrene, N-(dimethylaminopropyl) acrylamide, vinyl acetate copolymerized forming, this emulsifying agent is the cationic polymers that has uncle's amino, obtains positive charge after this cationic polymers further reacts through acidifying with acetic acid or with methyl iodide.U.S. Pat 5,438, disclosed the another kind of cationic polyacrylamide emulsifying agent that contains hydrophobic group in 087, this cationic emulsifier in fact also is a kind of tertiary amines cationic polymers by dimethylaminoethyl methacrylate, acrylamide, styrene copolymerized acquisition.Among the Chinese patent CN1109489A, utilize petroleum resin to react down at 200-210 ℃ with maleic anhydride earlier, resultant reacts under same temperature with the diethylin propylene diamine again, the gained resultant reacts down at 200-210 ℃ with chloroethanol again, make cation dispersing agent, utilize this dispersion agent under the high-pressure emulsification condition, to prepare cationic dispersion rosin size.In U.S. Pat 5,846, in 308, utilize the mixture that has positive charge that diallyl dimethyl ammoniumchloride and sodium lignosulfonate form mixes with fortified rosin in being dissolved in methyl chloride twice of back through homogenizer with rosin solution emulsification, with acquisition cationic dispersion rosin size after the methyl chloride evaporation.U.S. Pat 6,042, the cationic dispersion rosin size technology of preparing disclosed in 691 are then utilized daiamid one polymine, one epoxy chloropropane and polyoxyethylene glycol emulsification rosin, and with the sulfuric acid adjust pH to 2-3.5, emulsion need be through high-pressure homogeneous processing.U.S. Pat 6,369,119 disclosed cationic dispersion rosin size technologies of preparing then are earlier with after the saponification of part rosin, adding obtains cationic dispersion rosin size through the starch emulsification rosin of degraded, or with fused rosin with will through the degraded high substitution value starch, through the dispersion of high pressure homogenisers, obtain cationic dispersion rosin size.
Cationic dispersion rosin size preparation method disclosed in the above patent, the general macromolecule cation polymer emulsification rosin that adopts, relatively poor with the rosiny consistency, need be at emulsification rosin under the strong acidic condition, to reduce the ionization of carboxyl in the rosin, be difficult for forming stable rosin milk; Perhaps need emulsification system through high-pressure homogeneous processing, facility investment is higher; Utilize the alkaline purification technology that rosin is partly-hydrolysed, then reduced the free rosin content of rosin sizing agent, be unfavorable for improving rosiny applying glue efficient.
(3) summary of the invention
The present invention is in order to overcome the deficiency of above technology, and a kind of good stability, cationic dispersion rosin size that applying glue efficient is high are provided.
The present invention realizes by following measure:
Cationic dispersion rosin size of the present invention, utilize high-temperature pressure to reverse technology, make after by composite cation emulsification and dispersion agent the emulsification of rosin based sizing agent, it is characterized in that: described composite cation emulsification and dispersion agent comprise following composition, account for the non-ionic amphiphilic polymer emulsion of cationic dispersion rosin size weight 2-30% and account for the quaternary amines cats product of cationic dispersion rosin size weight 0.5-20% or the cationic water-soluble polymer of middle high charge density.
Cationic dispersion rosin size of the present invention, related rosin based sizing agent comprises rosin, various modified rosin, ester gum or its mixture, is generally the mixture of rosin and ester gum or the mixture of rosin, modified rosin and ester gum.Modified rosin mainly refers to toxilic acid or the maleic anhydride modified maleated rosin or the rich horse rosin of fumaric acid modification.
Cationic dispersion rosin size of the present invention, related non-ionic amphiphilic polymer emulsion is formed through emulsion copolymerization by lipophilicity thiazolinyl class monomer, wetting ability thiazolinyl class monomer.Used lipophilicity thiazolinyl class monomer is vinylbenzene, vinyl toluene, butylstyrene, butyl acrylate, methyl acrylate, methyl methacrylate etc., and the most frequently used is vinylbenzene, butyl acrylate or its mixture.Used wetting ability thiazolinyl class monomer is acrylamide, Methacrylamide and other alkyl acrylamide, and commonly used is acrylamide.Wherein the part by weight of lipophilicity monomer and hydrophilic monomer is 2: 1-1: 2, and the most frequently used is 1: 1.Non-ionic amphiphilic polymer emulsion add-on (calculating by other material outside dewatering) generally accounts for the 2-30% of cationic dispersion rosin size weight, and amount commonly used is 5-20%, and the most frequently used amount is 10-15%.
Cationic dispersion rosin size of the present invention, related quaternary amines cats product comprise one or more of dodecyl benzyl dimethyl ammonium chloride, palmityl trimethyl ammonium chloride, cetyl trimethylammonium bromide, octadecyl trimethyl ammonium chloride.These cats products can use separately, also can be used, and preferably are used, and are better than respectively independent Use Limitation fruit when being used with palmityl trimethyl ammonium chloride or brometo de amonio as dodecyl benzyl dimethyl ammonium chloride.According to institute's emulsive rosin components difference, both weight ratios can be 4: 1-1: change between 2, be preferably in 2: 1-1: between 1.Total add-on of cats product is generally the 0.5-20% that accounts for cationic dispersion rosin size weight, 1-10% preferably, and that the most frequently used is 1-5%.
Among the preparation method of cationic dispersion rosin size of the present invention, related cationic polymers, it can be the cationic polymers of various middle high charge densities, be the cationic monomer proportion greater than 30% cationic polyacrylamide, diallyl dimethyl ammoniumchloride, polymine, polymine-epoxy chloropropane, polymeric amide polyamines-epoxy chloropropane, but preferably polymeric amide polyamines-epoxy chloropropane, polymine or polymine-epoxy chloropropane, the most frequently used is polymeric amide polyamines-epoxy chloropropane.The general polymeric amide polyamines-epoxy chloropropane as wet strength agent for papermaking or sizing synergist sale just can satisfy the requirement of this invention.Add-on is generally the 0.5-20% of cationic dispersion rosin size, 1-10% preferably, and the most frequently used amount is between 2-5%.
Among the preparation method of cationic dispersion rosin size of the present invention, related rosin normal pressure reverses emulsifying process, be meant under 140-200 ℃ the fusion of rosin based sizing agent, add while stirring by non-ionic amphiphilic polymer emulsion and cats product or composite composite cation emulsification and the dispersion agent of cationic polymers, form water-in-oil emulsion, afterwards, improve stirring velocity, add and be preheated to 80-100 ℃ hot water, make phase reversal of emulsion, form emulsion oil-in-water, cooling forms cationic dispersion rosin size.
Need to prove, because positively charged ion composite emulsifying and dispersion agent are water dispersion, if portion is bigger in rosiny emulsification, then in the adition process of composite emulsifying and dispersion agent, just begun phase inversion, therefore, when utilizing the technology of the present invention to prepare cationic dispersion rosin size,, also be normal if phase inversion occurs early.
Also the partial cation polymkeric substance can be added in the phase inversion water as stablizer in the preparation, also can add part cold water in the emulsion behind the phase inversion, to improve speed of cooling.
In the technology of preparing of cationic dispersion rosin size of the present invention, the non-ionic amphiphilic polymer emulsion that contains oleophilic group and hydrophilic group simultaneously has extraordinary consistency with the rosin based sizing agent that has negative charge, utilizing normal pressure to reverse technology is easy to rosin emulsification, and also very good with the consistency of cats product or cationic water-soluble polymer, the cationic dispersion rosin size of preparation has good stability; The cationic dispersion rosin size of above-mentioned preparation has higher applying glue efficient.
(4) embodiment
Following example technology according to the present invention provides, and is used to illustrate the present invention, unless indicate in appending claims, does not constitute any limitation of the invention.Unless otherwise, all umbers are all by weight in the example.
Example one: the preparation of non-ionic amphiphilic polymer emulsion
Latex A: with 40 share liquid paraffins, 30 share butyl acrylates and 30 share acrylamides add in the reactor, add 1.4 share cetyl trimethylammonium bromides again, 1.4 share dodecylbenzyl ammonium chloride, 1.4 share Sorbitol Powder fatty acid ester (SPAN-80), 1.4 share polyoxyethylene nonylphenol ether (OP-10) and 0.4 share urea, start agitator and add 204 share deionized waters, heating simultaneously heats up, treat temperature rise to 75-80 ℃ and be incubated 30min after, the ammonium persulphate that 0.8 share is dissolved in the 80 share water adds in the reactor, and at 3-4 hour postcooling of 75-80 ℃ of following reaction, blowing obtains about 391 shares of non-ionic amphiphilic polymer emulsion A.
Emulsion B: the preparation method of non-ionic amphiphilic polymer emulsion B is identical with latex A, just replaces 30 share butyl acrylates with 30 share butylstyrenes.
Emulsion C: the preparation method of non-ionic amphiphilic polymer emulsion C is identical with latex A, just replaces 30 share butyl acrylates with 24 share vinyl toluenes, 6 share methyl methacrylates.
Emulsion D: the preparation method of non-ionic amphiphilic polymer emulsion D is identical with latex A, just replaces 30 share butyl acrylates with 15 share vinylbenzene, 15 share butyl acrylates.
Emulsion E: the preparation method of non-ionic amphiphilic polymer emulsion E is identical with latex A, just replaces 30 share butyl acrylates with 5 share vinylbenzene, 25 share butyl acrylates.
Emulsion F: the preparation method of non-ionic amphiphilic polymer emulsion F is identical with latex A, just replaces 30 share butyl acrylates with 8 share vinylbenzene, 12 share methyl acrylates, and the amount of acrylamide is increased to 40 shares.
Emulsion G: the preparation method of non-ionic amphiphilic polymer emulsion G is identical with latex A, just replaces 30 share butyl acrylates with 15 share vinylbenzene, 25 share butyl acrylates, and the amount of acrylamide is reduced to 20 shares.
Example two: the preparation of cationic dispersion rosin size
Cationic dispersion rosin size A: 18 share non-ionic amphiphilic polymer emulsion A and 0.75 share cetyl trimethylammonium bromide, 0.75 share dodecylbenzyl ammonium chloride are mixed, and it is standby to form composite cation emulsification and dispersant A.With 18 share one-level rosin and 12 share ester gums in reactor in 160-200 ℃ of following heating and melting, add composite cation emulsification and dispersant A, after composite emulsifying and dispersion agent adding finish, improve stirring velocity to the 800-1500rpm, begin to add phase inversion water 54 shares, the temperature of phase inversion water should be controlled at 90-95 ℃, after phase inversion finishes, continue to stir 5 minutes, sizing material is cooled to below 40 ℃, obtain oyster white cationic dispersion rosin size A, solid content is about 35%, does not see demixing phenomenon through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size B: 18 share non-ionic amphiphilic polymer emulsion B and 0.75 share cetyl trimethylammonium bromide, 0.75 share dodecylbenzyl ammonium chloride are mixed, form composite cation emulsification and dispersant B.With composite cation emulsification and the dispersant A among composite cation emulsification and the dispersant B replacement cationic dispersion rosin size A preparation technology, other preparation technology with cationic dispersion rosin size A is identical, can obtain cationic dispersion rosin size B, solid content is about 35%, does not see demixing phenomenon through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size C: same, 18 share non-ionic amphiphilic polymer emulsion C and 0.75 share cetyl trimethylammonium bromide, 0.75 share dodecylbenzyl ammonium chloride are mixed, form composite cation emulsification and dispersing agent C.With composite cation emulsification and the dispersant B among composite cation emulsification and the dispersing agent C replacement cationic dispersion rosin size B preparation technology, other preparation technology with cationic dispersion rosin size B is identical, can obtain cationic dispersion rosin size C, solid content is about 35%, does not see demixing phenomenon through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size D: same, 18 share non-ionic amphiphilic polymer emulsion D and 0.75 share cetyl trimethylammonium bromide, 0.75 share dodecylbenzyl ammonium chloride are mixed, form composite cation emulsification and dispersion agent D.With composite cation emulsification and the dispersing agent C among composite cation emulsification and the dispersion agent D replacement cationic dispersion rosin size C preparation technology, other preparation technology with cationic dispersion rosin size C is identical, can obtain cationic dispersion rosin size D, solid content is about 35%, does not see demixing phenomenon through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size E: same, 18 share non-ionic amphiphilic polymer emulsion E and 0.75 share cetyl trimethylammonium bromide, 0.75 share dodecylbenzyl ammonium chloride are mixed, form composite cation emulsification and dispersion agent E.With composite cation emulsification and the dispersion agent D among the composite cation emulsifying agent E replacement cationic dispersion rosin size D preparation technology, other preparation technology with cationic dispersion rosin size D is identical, can obtain cationic dispersion rosin size E, solid content is about 35%, does not see demixing phenomenon through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size F: same, 18 share non-ionic amphiphilic polymer emulsion F and 0.75 share cetyl trimethylammonium bromide, 0.75 share dodecylbenzyl ammonium chloride are mixed, form composite cation emulsification and dispersion agent F.With composite cation emulsification and the dispersion agent E among composite cation emulsification and the dispersion agent F replacement cationic dispersion rosin size E preparation technology, other preparation technology with cationic dispersion rosin size E is identical, can obtain cationic dispersion rosin size F, solid content is about 35%, does not see demixing phenomenon through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size G: same, 18 share non-ionic amphiphilic polymer emulsion G and 0.75 share cetyl trimethylammonium bromide, 0.75 share dodecylbenzyl ammonium chloride are mixed, form composite cation emulsification and dispersion agent G.With composite cation emulsification and the dispersion agent F among composite cation emulsification and the dispersion agent G replacement cationic dispersion rosin size F preparation technology, other preparation technology with cationic dispersion rosin size F is identical, can obtain cationic dispersion rosin size G, solid content is about 35%, does not see demixing phenomenon through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size D
1: .40 share non-ionic amphiphilic polymer emulsion D and 0.1 share cetyl trimethylammonium bromide, 0.1 share dodecylbenzyl ammonium chloride are mixed, form composite cation emulsification and dispersion agent D
1With composite cation emulsification and dispersion agent D
1Replace composite cation emulsification and dispersion agent D, replace original 54 phase inversion water with 33 share phase inversion water, other condition is identical with cationic dispersion rosin size D, can obtain cationic dispersion rosin size D
1, solid content is about 35%, through the centrifugal 30min of 4000rpm, does not see demixing phenomenon.
Cationic dispersion rosin size D
2: 18 share non-ionic amphiphilic polymer emulsion D and 0.3 share cetyl trimethylammonium bromide, 0.3 share dodecylbenzyl ammonium chloride are mixed, form composite cation emulsification and dispersion agent D
2With composite cation emulsification and dispersion agent D
2Replace composite cation emulsification and dispersion agent D, other condition is identical with cationic dispersion rosin size D, can obtain cationic dispersion rosin size D
2, solid content is about 35%, does not see demixing phenomenon through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size D
3: 18 share non-ionic amphiphilic polymer emulsion D and 0.4 share cetyl trimethylammonium bromide, 0.8 share dodecylbenzyl ammonium chloride are mixed, form composite cation emulsification and dispersion agent D
3With composite cation emulsification and dispersion agent D
3Replace composite cation emulsification and dispersion agent D, other condition is identical with cationic dispersion rosin size D, can obtain cationic dispersion rosin size D
3, solid content is about 35%, does not see demixing phenomenon through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size D
4: 18 share non-ionic amphiphilic polymer emulsion D and 0.4 share cetyl trimethylammonium bromide, 1.6 share dodecylbenzyl ammonium chlorides are mixed, form composite cation emulsification and dispersion agent D
4With composite cation emulsification and dispersion agent D
4Replace composite cation emulsification and dispersion agent D, other condition is identical with cationic dispersion rosin size D, can obtain cationic dispersion rosin size D
4, solid content is about 35%, does not see demixing phenomenon through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size D
5: 18 share non-ionic amphiphilic polymer emulsion D and 1 share cetyl trimethylammonium bromide, 0.5 share dodecylbenzyl ammonium chloride are mixed, form composite cation emulsification and dispersion agent D
5With composite cation emulsification and dispersion agent D
5Replace composite cation emulsification and dispersion agent D, other condition is identical with cationic dispersion rosin size D, can obtain cationic dispersion rosin size D
5, solid content is about 35%, does not see demixing phenomenon through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size D
6: 18 share non-ionic amphiphilic polymer emulsion D and 2 share cetyl trimethylammonium bromides are mixed, form composite cation emulsification and dispersion agent D
6With composite cation emulsification and dispersion agent D
6Replace composite cation emulsification and dispersion agent D, other condition is identical with cationic dispersion rosin size D, can obtain cationic dispersion rosin size D
6, solid content is about 35%, does not see demixing phenomenon through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size D
7: 18 share non-ionic amphiphilic polymer emulsion D and 2 share dodecylbenzyl ammonium chlorides are mixed, form composite cation emulsification and dispersion agent D
7With composite cation emulsification and dispersion agent D
7Replace composite cation emulsification and dispersion agent D, other preparation technology with cationic dispersion rosin size D is identical, can obtain cationic dispersion rosin size D
7, solid content is about 35%, does not see demixing phenomenon through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size D
8: 18 share non-ionic amphiphilic polymer emulsion D and 2 share octadecyl trimethyl ammonium chloride are mixed, form composite cation emulsification and dispersion agent D
8With composite cation emulsification and dispersion agent D
8Replace composite cation emulsification and dispersion agent D, other condition is identical with cationic dispersion rosin size D, can obtain cationic dispersion rosin size D
8, solid content is about 35%, does not see demixing phenomenon through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size D
9: 18 share non-ionic amphiphilic polymer emulsion D and 1 share octadecyl trimethyl ammonium chloride, 1 share dodecylbenzyl ammonium chloride are mixed, form composite cation emulsification and dispersion agent D
9With composite cation emulsification and dispersion agent D
9Replace composite cation emulsification and dispersion agent D, other preparation technology with cationic dispersion rosin size D is identical, can obtain cationic dispersion rosin size D
9, solid content is about 35%, does not see demixing phenomenon through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size D
10: 4 share non-ionic amphiphilic polymer emulsion D and 4 share octadecyl trimethyl ammonium chloride, 4 share dodecylbenzyl ammonium chlorides, 15 share water are mixed, form composite cation emulsification and dispersion agent D
10With composite cation emulsification and dispersion agent D
10Replace composite cation emulsification and dispersion agent D, other condition is identical with cationic dispersion rosin size D, can obtain cationic dispersion rosin size D
10, solid content is about 35%, does not see demixing phenomenon through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size D
11: 18 share non-ionic amphiphilic polymer emulsion D and 0.5 share cetyl trimethylammonium bromide, 0.5 share dodecylbenzyl ammonium chloride are mixed, form composite cation emulsification and dispersion agent D
11Three grades of rosin of 15 shares, 12 shares, 15% maleated rosin, 3 share ester gums in 160-200 ℃ of following heating and melting, are added composite cation emulsification and dispersion agent D
11, other preparation technology with cationic dispersion rosin size D is identical, can obtain cationic dispersion rosin size D
11, solid content is about 35%, does not see demixing phenomenon through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size D
12: 18 share non-ionic amphiphilic polymer emulsion D and 0.8 share cetyl trimethylammonium bromide, 0.8 share dodecylbenzyl ammonium chloride are mixed, form composite cation emulsification and dispersion agent D
12Three grades of rosin of 30 shares in 140-160 ℃ of following heating and melting, are added composite cation emulsification and dispersion agent D
12, other preparation technology with cationic dispersion rosin size D is identical, can obtain cationic dispersion rosin size D
12, solid content is about 35%, does not see demixing phenomenon through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size D
13: 20 share non-ionic amphiphilic polymer emulsion D and 10 share polymeric amide polyamines-epoxy chloropropane (concentration 12.5% is in the aqueous solution) are mixed, form positively charged ion composite emulsifying and dispersion agent D
13With positively charged ion composite emulsifying and dispersion agent D
13Replace positively charged ion composite emulsifying and dispersion agent D, and the phase inversion water yield is reduced to 45 shares, other preparation technology with cationic dispersion rosin size D is identical, can obtain cationic dispersion rosin size D
13, solid content is about 35%, does not see demixing phenomenon through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size D
14: 10 share non-ionic amphiphilic polymer emulsion D and 30 share polymeric amide polyamines-epoxy chloropropane (concentration 12.5% is in the aqueous solution) are mixed, form positively charged ion composite emulsifying and dispersion agent D
14With positively charged ion composite emulsifying and dispersion agent D
14Replace positively charged ion composite emulsifying and dispersion agent D, and the phase inversion water yield is reduced to 44 shares, other preparation technology with cationic dispersion rosin size D is identical, can obtain cationic dispersion rosin size D
14, solid content is about 35%, does not see demixing phenomenon through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size D
15: 25 share non-ionic amphiphilic polymer emulsion D and 6 share polymeric amide polyamines-epoxy chloropropane (concentration 12.5% is in the aqueous solution) are mixed, form positively charged ion composite emulsifying and dispersion agent D
15With positively charged ion composite emulsifying and dispersion agent D
15Replace positively charged ion composite emulsifying and dispersion agent D, and the phase inversion water yield is reduced to 46 shares, other preparation technology with cationic dispersion rosin size D is identical, can obtain cationic dispersion rosin size D
15, solid content is about 35%, does not see demixing phenomenon through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size D
16: the non-ionic amphiphilic polymer emulsion D and the 2 share polymeric amide polyamines-epoxy chloropropane (concentration 12.5% is in the aqueous solution) of 40 shares are mixed, form positively charged ion composite emulsifying and dispersion agent D
16With positively charged ion composite emulsifying and dispersion agent D
16Replace positively charged ion composite emulsifying and dispersion agent D, and the phase inversion water yield is reduced to 45 shares, other preparation technology with cationic dispersion rosin size D is identical, can obtain cationic dispersion rosin size D
16, solid content is about 35%, does not see demixing phenomenon through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size D
17: 20 share non-ionic amphiphilic polymer emulsion D and 8 share polymeric amide polyamines-epoxy chloropropane (concentration 12.5% is in the aqueous solution) are mixed, form positively charged ion composite emulsifying and dispersion agent D
17With positively charged ion composite emulsifying and dispersion agent D
17Replace positively charged ion composite emulsifying and dispersion agent D
11, and the phase inversion water yield is reduced to 46 shares, other and cationic dispersion rosin size D
11Preparation technology identical, can obtain cationic dispersion rosin size D
17, solid content is about 35%, does not see demixing phenomenon through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size D
18: 18 share non-ionic amphiphilic polymer emulsion D and 10 share polymeric amide polyamines-epoxy chloropropane (concentration 12.5% is in the aqueous solution) are mixed, form positively charged ion composite emulsifying and dispersion agent D
18With positively charged ion composite emulsifying and dispersion agent D
18Replace positively charged ion composite emulsifying and dispersion agent D
12, and the phase inversion water yield is reduced to 45 shares, other and cationic dispersion rosin size D
12Preparation technology identical, can obtain cationic dispersion rosin size D
18, solid content is about 35%, does not see demixing phenomenon through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size D
19: with the non-ionic amphiphilic polymer emulsion D and 2 shares of 20 shares be dissolved in the cation ionization degree 35% in the 20 share deionized waters in advance, the cationic polyacrylamide of molecular weight 400,000 mixes, and forms positively charged ion composite emulsifying and dispersion agent D
19With positively charged ion composite emulsifying and dispersion agent D
19Replace positively charged ion composite emulsifying and dispersion agent D, and the phase inversion water yield is reduced to 35 shares, other preparation technology with cationic dispersion rosin size D is identical, can obtain cationic dispersion rosin size D
19, solid content is about 35%, does not see demixing phenomenon through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size D
20: the diallyl dimethyl ammoniumchloride of the non-ionic amphiphilic polymer emulsion D of 20 shares and 10 share concentration 20%, molecular weight 250,000 is mixed, form positively charged ion composite emulsifying and dispersion agent D
20With positively charged ion composite emulsifying and dispersion agent D
20Replace positively charged ion composite emulsifying and dispersion agent D, and the phase inversion water yield is reduced to 47 shares, other preparation technology with cationic dispersion rosin size D is identical, can obtain cationic dispersion rosin size D
20, solid content is about 35%, does not see demixing phenomenon through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size D
21: the polyethylene imonium of the non-ionic amphiphilic polymer emulsion D of 20 shares and 10 share concentration 15%, molecular weight 500,000 is mixed, form positively charged ion composite emulsifying and dispersion agent D
21With positively charged ion composite emulsifying and dispersion agent D
21Replace positively charged ion composite emulsifying and dispersion agent D, and the phase inversion water yield is reduced to 45 shares, other preparation technology with cationic dispersion rosin size D is identical, can obtain cationic dispersion rosin size D
21, solid content is about 35%, does not see demixing phenomenon through the centrifugal 30min of 4000rpm.
Example three: the glue blending function of cationic dispersion rosin size
Chemical Straw Pulp after defiberizing machine is discongested, is added 20% talcum powder, after mixing, be diluted to 1% concentration, obtain paper stock.
Get the paper stock of 750 share concentration 1%, add the Tai-Ace S 150 (Al of 0.15 share
2(SO
4)
318H
2O, below identical), after mixing, cationic dispersion rosin size A (the concentration 35% that adds 0.15 share again, in weight in wet base, below identical), on handshcet former, copy sheet, drying, utilize liquid infiltration method (Stockigt method) to measure the degree of sizing of cationic dispersion rosin size A applying glue handsheet, degree of sizing is 6s.
Get 750 share paper stocks, repeat said process, just cationic dispersion rosin size A is changed to cationic dispersion rosin size B, and utilize the liquid infiltration method to measure the degree of sizing of cationic dispersion rosin size B applying glue handsheet, degree of sizing is 8s.
Get 750 share paper stocks, repeat said process, just cationic dispersion rosin size B is changed to cationic dispersion rosin size C, obtain the handsheet of cationic dispersion rosin size C applying glue, and utilize the liquid infiltration method to measure its degree of sizing, degree of sizing is 9s.
Get 750 share paper stocks, repeat said process, just cationic dispersion rosin size C is changed to cationic dispersion rosin size D, obtains the handsheet of cationic dispersion rosin size D applying glue, and utilizes the liquid infiltration method to measure its degree of sizing, and degree of sizing is 13s.
Get 750 share paper stocks, add the Tai-Ace S 150 of 0.15 share, the cationic dispersion rosin size D and the 0.003 share cationic polyacrylamide (cation ionization degree about 10% of 0.15 share successively, molecular weight 8,000,000, below identical), on handshcet former, copy sheet, drying, utilize the degree of sizing of liquid infiltration method mensuration with the paper of cationic polyacrylamide retention, cationic dispersion rosin size B applying glue, degree of sizing is 35s.
Get 750 share paper stocks, add the Tai-Ace S 150 of 0.15 share, cationic dispersion rosin size D, 0.003 share cationic polyacrylamide and the 0.03 share modified alta-mud of 0.15 share successively, on handshcet former, copy sheet, drying, utilize the degree of sizing of liquid infiltration method mensuration with the paper of cationic polyacrylamide/modified alta-mud Microparticle Retention System retention, cationic dispersion rosin size B applying glue, degree of sizing is 67s.
Get 750 share paper stocks, add the Tai-Ace S 150 of 0.15 share, after mixing, add the cationic dispersion rosin size D of 0.15 share
1, on handshcet former, copy sheet, drying, obtain cationic dispersion rosin size D
1The handsheet of applying glue utilizes the liquid infiltration method to measure its degree of sizing, and degree of sizing is 14s.
Get 750 share paper stocks, add the Tai-Ace S 150 of 0.15 share, after mixing, add the cationic dispersion rosin size D of 0.15 share
2, on handshcet former, copy sheet, drying, obtain cationic dispersion rosin size D
2The handsheet of applying glue utilizes the liquid infiltration method to measure its degree of sizing, and degree of sizing is 11s.
Get 750 share paper stocks, add the Tai-Ace S 150 of 0.15 share, after mixing, add the cationic dispersion rosin size D of 0.15 share
3, on handshcet former, copy sheet, drying, obtain cationic dispersion rosin size D
3The handsheet of applying glue utilizes the liquid infiltration method to measure its degree of sizing, and degree of sizing is 12s.
Get 750 share paper stocks, add the Tai-Ace S 150 of 0.15 share, after mixing, add the cationic dispersion rosin size D of 0.15 share
4, on handshcet former, copy sheet, drying, obtain cationic dispersion rosin size D
4The handsheet of applying glue utilizes the liquid infiltration method to measure its degree of sizing, and degree of sizing is 9s.
Get 750 share paper stocks, add the Tai-Ace S 150 of 0.15 share, after mixing, add the cationic dispersion rosin size D of 0.15 share
5, on handshcet former, copy sheet, drying, obtain cationic dispersion rosin size D
5The handsheet of applying glue utilizes the liquid infiltration method to measure its degree of sizing, and degree of sizing is 7s.
Get 750 share paper stocks, add the Tai-Ace S 150 of 0.15 share, after mixing, add the cationic dispersion rosin size D of 0.15 share
6, on handshcet former, copy sheet, drying, obtain cationic dispersion rosin size D
6The handsheet of applying glue utilizes the liquid infiltration method to measure its degree of sizing, and degree of sizing is 6s.
Get 750 share paper stocks, add the Tai-Ace S 150 of 0.15 share, after mixing, add the cationic dispersion rosin size D of 0.15 share
7, on handshcet former, copy sheet, drying, obtain cationic dispersion rosin size D
7The handsheet of applying glue utilizes the liquid infiltration method to measure its degree of sizing, and degree of sizing is 8s.
Get 750 share paper stocks, add the Tai-Ace S 150 of 0.15 share, after mixing, add the cationic dispersion rosin size D of 0.15 share
8, on handshcet former, copy sheet, drying, obtain cationic dispersion rosin size D
8The handsheet of applying glue utilizes the liquid infiltration method to measure its degree of sizing, and degree of sizing is 6s.
Get 750 share paper stocks, add the Tai-Ace S 150 of 0.15 share, after mixing, add the cationic dispersion rosin size D of 0.15 share
9, on handshcet former, copy sheet, drying, obtain cationic dispersion rosin size D
9The handsheet of applying glue utilizes the liquid infiltration method to measure its degree of sizing, and degree of sizing is 7s.
Get 750 share paper stocks, add the Tai-Ace S 150 of 0.15 share, after mixing, add the cationic dispersion rosin size D of 0.15 share
10, on handshcet former, copy sheet, drying, obtain cationic dispersion rosin size D
10The handsheet of applying glue utilizes the liquid infiltration method to measure its degree of sizing, and degree of sizing is 2s.
Get 750 share paper stocks, add the Tai-Ace S 150 of 0.15 share, after mixing, add the cationic dispersion rosin size D of 0.15 share
11, on handshcet former, copy sheet, drying, obtain cationic dispersion rosin size D
11The handsheet of applying glue utilizes the liquid infiltration method to measure its degree of sizing, and degree of sizing is 16s.
Get 750 share paper stocks, add the Tai-Ace S 150 of 0.15 share, after mixing, add the cationic dispersion rosin size D of 0.15 share
12, on handshcet former, copy sheet, drying, obtain cationic dispersion rosin size D
12The handsheet of applying glue utilizes the liquid infiltration method to measure its degree of sizing, and degree of sizing is 5s.
Get 750 share paper stocks, add the Tai-Ace S 150 of 0.15 share, after mixing, add the cationic dispersion rosin size D of 0.15 share
13, on handshcet former, copy sheet, drying, obtain cationic dispersion rosin size D
13The handsheet of applying glue utilizes the liquid infiltration method to measure its degree of sizing, and degree of sizing is 65s.
Get 750 share paper stocks, add the Tai-Ace S 150 of 0.15 share, after mixing, add the cationic dispersion rosin size D of 0.15 share
13, after mixing, add 0.0015 share cationic polyacrylamide again, on handshcet former, copy sheet, drying, obtain cationic dispersion rosin size D
13The handsheet of applying glue, cationic polyacrylamide retention utilizes the liquid infiltration method to measure its degree of sizing, and degree of sizing is 102s.
Get 750 share paper stocks, add the Tai-Ace S 150 of 0.15 share, after mixing, add the cationic dispersion rosin size D of 0.15 share
14, on handshcet former, copy sheet, drying, obtain cationic dispersion rosin size D
14The handsheet of applying glue utilizes the liquid infiltration method to measure its degree of sizing, and degree of sizing is 43s.
Get 750 share paper stocks, add the Tai-Ace S 150 of 0.15 share, after mixing, add the cationic dispersion rosin size D of 0.15 share
15, on handshcet former, copy sheet, drying, obtain cationic dispersion rosin size D
15The handsheet of applying glue utilizes the liquid infiltration method to measure its degree of sizing, and degree of sizing is 57s.
Get 750 share paper stocks, add the Tai-Ace S 150 of 0.15 share, after mixing, add the cationic dispersion rosin size D of 0.15 share
16, on handshcet former, copy sheet, drying, obtain cationic dispersion rosin size D
16The handsheet of applying glue utilizes the liquid infiltration method to measure its degree of sizing, and degree of sizing is 58s.
Get 750 share paper stocks, add the Tai-Ace S 150 of 0.15 share, after mixing, add the cationic dispersion rosin size D of 0.15 share
17, on handshcet former, copy sheet, drying, obtain cationic dispersion rosin size D
17The handsheet of applying glue utilizes the liquid infiltration method to measure its degree of sizing, and degree of sizing is 57s.
Get 750 share paper stocks, add the Tai-Ace S 150 of 0.15 share, after mixing, add the cationic dispersion rosin size D of 0.15 share
18, on handshcet former, copy sheet, drying, obtain cationic dispersion rosin size D
18The handsheet of applying glue utilizes the liquid infiltration method to measure its degree of sizing, and degree of sizing is 32s.
Get 750 share paper stocks, add the Tai-Ace S 150 of 0.15 share, after mixing, add the cationic dispersion rosin size D of 0.15 share
19, on handshcet former, copy sheet, drying, obtain cationic dispersion rosin size D
19The handsheet of applying glue utilizes the liquid infiltration method to measure its degree of sizing, and degree of sizing is 21s.
Get 750 share paper stocks, add the Tai-Ace S 150 of 0.15 share, after mixing, add the cationic dispersion rosin size D of 0.15 share
20, on handshcet former, copy sheet, drying, obtain cationic dispersion rosin size D
20The handsheet of applying glue utilizes the liquid infiltration method to measure its degree of sizing, and degree of sizing is 15s.
Get 750 share paper stocks, add the Tai-Ace S 150 of 0.15 share, after mixing, add the cationic dispersion rosin size D of 0.15 share
21, on handshcet former, copy sheet, drying, obtain cationic dispersion rosin size D
21The handsheet of applying glue utilizes the liquid infiltration method to measure its degree of sizing, and degree of sizing is 28s.
Get 750 share paper stocks, add the Tai-Ace S 150 of 0.15 share, after mixing, add the cationic dispersion rosin size E of 0.15 share, on handshcet former, copy sheet, drying, obtain the handsheet of cationic dispersion rosin size E applying glue, utilize the liquid infiltration method to measure its degree of sizing, degree of sizing is 10s.
Get 750 share paper stocks, add the Tai-Ace S 150 of 0.15 share, after mixing, add the cationic dispersion rosin size F of 0.15 share, on handshcet former, copy sheet, drying, obtain the handsheet of cationic dispersion rosin size F applying glue, utilize the liquid infiltration method to measure its degree of sizing, degree of sizing is 7s.
Get 750 share paper stocks, add the Tai-Ace S 150 of 0.15 share, after mixing, add the cationic dispersion rosin size G of 0.15 share, on handshcet former, copy sheet, drying, obtain the handsheet of cationic dispersion rosin size G applying glue, utilize the liquid infiltration method to measure its degree of sizing, degree of sizing is 9s.
Claims (7)
1. cationic dispersion rosin size, utilize high-temperature pressure to reverse technology, make after by composite cation emulsification and dispersion agent the emulsification of rosin based sizing agent, it is characterized in that: described composite cation emulsification and dispersion agent comprise following composition, account for the non-ionic amphiphilic polymer emulsion of cationic dispersion rosin size weight 2-30% and account for the quaternary amines cats product of cationic dispersion rosin size weight 0.5-20% or the cationic water-soluble polymer of middle high charge density.
2. cationic dispersion rosin size according to claim 1 is characterized in that: described non-ionic amphiphilic polymer emulsion by lipophilicity thiazolinyl class monomer and wetting ability thiazolinyl class monomer with 2: 1-1: 2 weight ratio forms through letex polymerization; Described quaternary amines cats product is one or more of dodecyl dimethyl benzyl ammonium halide, cetyl trimethyl ammonium halide or octadecyl trimethyl ammonium chloride; The cationic water-soluble polymer of high charge density is one or more of cationic polyacrylamide, diallyl dimethyl ammoniumchloride, polymeric amide polyamines-epoxy chloropropane, polymine-epoxy chloropropane or polymine in described.
3. cationic dispersion rosin size according to claim 2 is characterized in that: described lipophilicity thiazolinyl class monomer is one or more of vinylbenzene, vinyl toluene, butylstyrene, butyl acrylate, methyl acrylate or methyl methacrylate; Described wetting ability thiazolinyl class monomer is one or more of acrylamide, Methacrylamide or alkyl acrylamide; The weight ratio of lipophilicity vinyl monomer and wetting ability vinyl monomer is 1: 1; Add-on accounts for the 5-20% of cationic dispersion rosin size weight.
4. cationic dispersion rosin size according to claim 3 is characterized in that: described non-ionic amphiphilic polymer emulsion accounts for the 10-15% of cationic dispersion rosin size weight.
5. cationic dispersion rosin size according to claim 1 and 2, it is characterized in that: described cats product is the mixture of dodecyl dimethyl benzyl ammonium halide and cetyl trimethyl ammonium halide, both weight ratios are 4: 1-1: between 2, add-on accounts for the 1-10% of cationic dispersion rosin size weight; Described cationic water-soluble polymer is one or more of polymeric amide polyamines-epoxy chloropropane, polymine-epoxy chloropropane or polymine, and add-on accounts for the 1-10% of cationic dispersion rosin size weight.
6. cationic dispersion rosin size according to claim 1 and 2 is characterized in that: described cats product accounts for the 1-5% of cationic dispersion rosin size weight; Described cationic water-soluble polymer accounts for the 2-5% of cationic dispersion rosin size weight.
7. cationic dispersion rosin size according to claim 1, it is characterized in that: described high-temperature pressure reverses technology and is meant under 140-200 ℃ the rosin sizing agent fusion, add composite cation emulsification and dispersion agent while stirring, form water-in-oil emulsion, afterwards, improve stirring velocity, add and be preheated to 80-100 ℃ hot water, make phase reversal of emulsion, form O/w emulsion, cooling forms cationic dispersion rosin size.
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| CNB2005100435697A CN1295014C (en) | 2005-05-23 | 2005-05-23 | Cationic dispersion rosin size |
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|---|---|---|---|
| CNB2005100435697A CN1295014C (en) | 2005-05-23 | 2005-05-23 | Cationic dispersion rosin size |
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| CN1692976A true CN1692976A (en) | 2005-11-09 |
| CN1295014C CN1295014C (en) | 2007-01-17 |
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|---|---|---|---|
| CNB2005100435697A Expired - Fee Related CN1295014C (en) | 2005-05-23 | 2005-05-23 | Cationic dispersion rosin size |
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| CN (1) | CN1295014C (en) |
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| CN102261014A (en) * | 2010-05-28 | 2011-11-30 | 荒川化学工业株式会社 | Rosin emulsion sizing agent and paper obtained by using the sizing agnet |
| CN103628356A (en) * | 2013-11-27 | 2014-03-12 | 杭州杭化哈利玛化工有限公司 | Novel cationic rosin sizing agent and application thereof |
| CN103806334A (en) * | 2014-02-20 | 2014-05-21 | 如东南天农科化工有限公司 | Process for preparing cationic rosin size |
| CN106283870A (en) * | 2016-08-29 | 2017-01-04 | 上海东升新材料有限公司 | A kind of preparation method of cationic rosin size |
| CN106283850A (en) * | 2016-08-29 | 2017-01-04 | 上海东升新材料有限公司 | A kind of Reaction Cationic Rosin Sizing and preparation method thereof |
| CN106279533A (en) * | 2016-08-29 | 2017-01-04 | 上海东升新材料有限公司 | A kind of cationic rosin size emulsifying agent and preparation method thereof |
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| JP2002173889A (en) * | 2000-12-08 | 2002-06-21 | Kindai Kagaku Kogyo Kk | Dispersant for cation-type rosin emulsion sizing agent |
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