CN1295014C - Cationic dispersion rosin size - Google Patents
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- CN1295014C CN1295014C CNB2005100435697A CN200510043569A CN1295014C CN 1295014 C CN1295014 C CN 1295014C CN B2005100435697 A CNB2005100435697 A CN B2005100435697A CN 200510043569 A CN200510043569 A CN 200510043569A CN 1295014 C CN1295014 C CN 1295014C
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Abstract
The present invention relates to cationic dispersion rosin size for papermaking. To overcome the defects of low cationic dispersion rosin size stability and sizing efficiency existing in the prior art, the cationic dispersion rosin size provided by the present invention is prepared by that a compound cationic emulsion and dispersing agent is used to emulsionize rosin sizing agents by a high-temperature ordinary-pressure reverse technology. The compound cationic emulsion and dispersing agent comprises the components of non-ion amphiphilic polymer emulsion accounting for 2 to 30 wt% of the cationic dispersion rosin size, and a quaternay amine cationic surface active agent or a medium-high charge density cationic water-soluble polymer which accounts for 0.5 to 20 wt% of the cationic dispersion rosin size. The cationic dispersion rosin size prepared by the present invention has high stability and sizing efficiency.
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
The main component of papermaking rosin is a resin acid, and hydrophobic group is partially hydrogenated phenanthrene ring, and hydrophilic group is a carboxyl.In order to improve rosin and interfibrous adhesion, also often utilize maleic acid (acid anhydride) or fumaric acid to the rosin addition, form maleic rosin or rich horse rosin that each hydrogenation phenanthrene ring has three carboxyls.Therefore, the rosin based sizing agent itself is elecrtonegativity, fine with the compatibility of anionic polymer or surfactant, utilize anion surfactant and the polymer can be with comparalive ease with its fused mass emulsification, the anion dispersion rosin size that emulsion cooling back forms is also more stable.But because paper pulp fiber itself has negative electrical 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 neutralization the stability of rosin milk, make that the preparation difficulty of cationic dispersion rosin size is bigger, utilize general cationic surfactant 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 AMS, N-(dimethylaminopropyl) acrylamide, vinyl acetate copolymerized forming, this emulsifying agent is the cationic polymer that has uncle's amino, obtains positive charge after this cationic polymer further reacts through acidifying with acetic acid or with iodomethane.U.S. Pat 5,438, disclosed the another kind of PAMC emulsifying agent that contains hydrophobic group in 087, this cationic emulsifier in fact also is a kind of tertiary amines cationic polymer by dimethylaminoethyl methacrylate, acrylamide, styrene copolymerized acquisition.Among the Chinese patent CN1109489A, utilize Petropols to react down at 200-210 ℃ with maleic anhydride earlier, product reacts under same temperature with the lignocaine propylene diamine again, the gained product reacts down at 200-210 ℃ with chlorethanol again, make cation dispersing agent, utilize this dispersant under the high-pressure emulsification condition, to prepare cationic dispersion rosin size.In U.S. Pat 5,846, in 308, utilize the compound that has positive charge that diallyl dimethyl ammoniumchloride and sodium lignosulfonate form mixes with fortified rosin in being dissolved in chloromethane twice of back through homogenizer with rosin solution emulsification, with acquisition cationic dispersion rosin size after the chloromethane evaporation.U.S. Pat 6,042, the cationic dispersion rosin size technology of preparing disclosed in 691 are then utilized daiamid-polymine-epoxychloropropane and polyethylene 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 the rosin of fusion with will be through the high substituted degree starch of degraded, 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 compatibility of rosin, 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, equipment investment is higher; Utilize the alkali treatment technology that rosin is partly-hydrolysed, then reduced the free rosin content of rosin sizing agent, be unfavorable for improving the applying glue efficient of rosin.
(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 dispersant the emulsification of rosin based sizing agent, it is characterized in that: described composite cation emulsification and dispersant 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 cationic surfactant 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 maleic acid or the maleic anhydride modified maleic 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 lipophile thiazolinyl class monomer, hydrophily thiazolinyl class monomer.Used lipophile thiazolinyl class monomer is styrene, methyl styrene, butylstyrene, butyl acrylate, methyl acrylate, methyl methacrylate etc., and the most frequently used is styrene, butyl acrylate or its mixture.Used hydrophily thiazolinyl class monomer is acrylamide, Methacrylamide and other alkyl acrylamide, and commonly used is acrylamide.Wherein the part by weight of lipophile monomer and hydrophilic monomer is 2: 1-1: 2, and the most frequently used is 1: 1.Non-ionic amphiphilic polymer emulsion addition (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 cationic surfactant comprise one or more of dodecyl benzyl dimethyl ammonium chloride, hexadecyltrimethylammonium chloride, softex kw, OTAC.These cationic surfactants can use separately, also can be used, and preferably are used, and are better than respectively independent Use Limitation fruit when being used with hexadecyltrimethylammonium chloride or ammonium bromide as dodecyl benzyl dimethyl ammonium chloride.According to the rosin components difference of institute's emulsification, both weight ratios can be 4: 1-1: change between 2, be preferably in 2: 1-1: between 1.Total addition of cationic surfactant 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 polymer, it can be the cationic polymer of various middle high charge densities, be the cationic monomer proportion greater than 30% PAMC, diallyl dimethyl ammoniumchloride, polymine, polymine-epoxychloropropane, polyamide polyamines-epoxychloropropane, but preferably polyamide polyamines-epoxychloropropane, polymine or polymine-epoxychloropropane, the most frequently used is polyamide polyamines-epoxychloropropane.The general polyamide polyamines-epoxychloropropane as wet strength agent for papermaking or sizing synergist sale just can satisfy the requirement of this invention.Addition 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 cationic surfactant or composite composite cation emulsification and the dispersant of cationic polymer, form water-in-oil emulsion, afterwards, improve mixing speed, add and be preheated to 80-100 ℃ hot water, make emulsion inverse, form emulsion oil-in-water, cooling forms cationic dispersion rosin size.
Need to prove, because cation composite emulsifying and dispersant are aqueous dispersion, if portion is bigger in the emulsification of rosin, then in the adition process of composite emulsifying and dispersant, 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 polymer can be added in the phase inversion water as stabilizing agent in the preparation, also can add part cold water in the emulsion behind the phase inversion, to improve cooling velocity.
In the technology of preparing of cationic dispersion rosin size of the present invention, the non-ionic amphiphilic polymer emulsion that contains lipophilic group and hydrophilic group simultaneously has extraordinary compatibility with the rosin based sizing agent that has negative electrical charge, utilizing normal pressure to reverse technology is easy to rosin emulsification, and also very good with the compatibility of cationic surfactant 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) specific 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 softex kws again, 1.4 share dodecylbenzyl ammonium chloride, 1.4 share D-sorbite fatty acid ester (SPAN-80), 1.4 share NPE (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 persulfate that 0.8 share is dissolved in the 80 share water adds in the reactor, and 75-80 ℃ of reaction cooling after 3-4 hour down, 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 methyl styrenes, 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 styrene, 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 styrene, 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 styrene, 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 styrene, 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 softex kw, 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 dispersant adding finish, improve mixing speed 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 milky cationic dispersion rosin size A, solid content is about 35%, does not see lamination through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size B: 18 share non-ionic amphiphilic polymer emulsion B and 0.75 share softex kw, 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 lamination through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size C: same, 18 share non-ionic amphiphilic polymer emulsion C and 0.75 share softex kw, 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 lamination through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size D: same, 18 share non-ionic amphiphilic polymer emulsion D and 0.75 share softex kw, 0.75 share dodecylbenzyl ammonium chloride are mixed, form composite cation emulsification and dispersant D.With composite cation emulsification and the dispersing agent C among composite cation emulsification and the dispersant 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 lamination through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size E: same, 18 share non-ionic amphiphilic polymer emulsion E and 0.75 share softex kw, 0.75 share dodecylbenzyl ammonium chloride are mixed, form composite cation emulsification and dispersant E.With composite cation emulsification and the dispersant 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 lamination through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size F: same, 18 share non-ionic amphiphilic polymer emulsion F and 0.75 share softex kw, 0.75 share dodecylbenzyl ammonium chloride are mixed, form composite cation emulsification and dispersant F.With composite cation emulsification and the dispersant E among composite cation emulsification and the dispersant 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 lamination through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size G: same, 18 share non-ionic amphiphilic polymer emulsion G and 0.75 share softex kw, 0.75 share dodecylbenzyl ammonium chloride are mixed, form composite cation emulsification and dispersant G.With composite cation emulsification and the dispersant F among composite cation emulsification and the dispersant 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 lamination through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size D
1: .40 share non-ionic amphiphilic polymer emulsion D and 0.1 share softex kw, 0.1 share dodecylbenzyl ammonium chloride are mixed, form composite cation emulsification and dispersant D
1With composite cation emulsification and dispersant D
1Replace composite cation emulsification and dispersant 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 lamination.
Cationic dispersion rosin size D
2: 18 share non-ionic amphiphilic polymer emulsion D and 0.3 share softex kw, 0.3 share dodecylbenzyl ammonium chloride are mixed, form composite cation emulsification and dispersant D
2With composite cation emulsification and dispersant D
2Replace composite cation emulsification and dispersant 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 lamination through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size D
3: 18 share non-ionic amphiphilic polymer emulsion D and 0.4 share softex kw, 0.8 share dodecylbenzyl ammonium chloride are mixed, form composite cation emulsification and dispersant D
3With composite cation emulsification and dispersant D
3Replace composite cation emulsification and dispersant 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 lamination through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size D
4: 18 share non-ionic amphiphilic polymer emulsion D and 0.4 share softex kw, 1.6 share dodecylbenzyl ammonium chlorides are mixed, form composite cation emulsification and dispersant D
4With composite cation emulsification and dispersant D
4Replace composite cation emulsification and dispersant 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 lamination through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size D
5: 18 share non-ionic amphiphilic polymer emulsion D and 1 share softex kw, 0.5 share dodecylbenzyl ammonium chloride are mixed, form composite cation emulsification and dispersant D
5With composite cation emulsification and dispersant D
5Replace composite cation emulsification and dispersant 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 lamination through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size D
6: 18 share non-ionic amphiphilic polymer emulsion D and 2 share softex kws are mixed, form composite cation emulsification and dispersant D
6With composite cation emulsification and dispersant D
6Replace composite cation emulsification and dispersant 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 lamination 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 dispersant D
7With composite cation emulsification and dispersant D
7Replace composite cation emulsification and dispersant 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 lamination through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size D
8: 18 share non-ionic amphiphilic polymer emulsion D and 2 share OTACs are mixed, form composite cation emulsification and dispersant D
8With composite cation emulsification and dispersant D
8Replace composite cation emulsification and dispersant 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 lamination through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size D
9: 18 share non-ionic amphiphilic polymer emulsion D and 1 share OTAC, 1 share dodecylbenzyl ammonium chloride are mixed, form composite cation emulsification and dispersant D
9With composite cation emulsification and dispersant D
9Replace composite cation emulsification and dispersant 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 lamination through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size D
10: 4 share non-ionic amphiphilic polymer emulsion D and 4 share OTACs, 4 share dodecylbenzyl ammonium chlorides, 15 share water are mixed, form composite cation emulsification and dispersant D
10With composite cation emulsification and dispersant D
10Replace composite cation emulsification and dispersant 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 lamination through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size D
11: 18 share non-ionic amphiphilic polymer emulsion D and 0.5 share softex kw, 0.5 share dodecylbenzyl ammonium chloride are mixed, form composite cation emulsification and dispersant D
11Three grades of rosin of 15 shares, 12 shares, 15% maleic rosin, 3 share ester gums in 160-200 ℃ of following heating and melting, are added composite cation emulsification and dispersant 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 lamination through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size D
12: 18 share non-ionic amphiphilic polymer emulsion D and 0.8 share softex kw, 0.8 share dodecylbenzyl ammonium chloride are mixed, form composite cation emulsification and dispersant D
12Three grades of rosin of 30 shares in 140-160 ℃ of following heating and melting, are added composite cation emulsification and dispersant 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 lamination through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size D
13: 20 share non-ionic amphiphilic polymer emulsion D and 10 share polyamide polyamines-epoxychloropropane (concentration 12.5% is in the aqueous solution) are mixed, form cation composite emulsifying and dispersant D
13With cation composite emulsifying and dispersant D
13Replace cation composite emulsifying and dispersant 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 lamination through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size D
14: 10 share non-ionic amphiphilic polymer emulsion D and 30 share polyamide polyamines-epoxychloropropane (concentration 12.5% is in the aqueous solution) are mixed, form cation composite emulsifying and dispersant D
14With cation composite emulsifying and dispersant D
14Replace cation composite emulsifying and dispersant 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 lamination through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size D
15: 25 share non-ionic amphiphilic polymer emulsion D and 6 share polyamide polyamines-epoxychloropropane (concentration 12.5% is in the aqueous solution) are mixed, form cation composite emulsifying and dispersant D
15With cation composite emulsifying and dispersant D
15Replace cation composite emulsifying and dispersant 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 lamination through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size D
16: the non-ionic amphiphilic polymer emulsion D and the 2 share polyamide polyamines-epoxychloropropane (concentration 12.5% is in the aqueous solution) of 40 shares are mixed, form cation composite emulsifying and dispersant D
16With cation composite emulsifying and dispersant D
16Replace cation composite emulsifying and dispersant 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 lamination through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size D
17: 20 share non-ionic amphiphilic polymer emulsion D and 8 share polyamide polyamines-epoxychloropropane (concentration 12.5% is in the aqueous solution) are mixed, form cation composite emulsifying and dispersant D
17With cation composite emulsifying and dispersant D
17Replace cation composite emulsifying and dispersant 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 lamination through the centrifugal 30min of 4000rpm.
Cationic dispersion rosin size D
18: 18 share non-ionic amphiphilic polymer emulsion D and 10 share polyamide polyamines-epoxychloropropane (concentration 12.5% is in the aqueous solution) are mixed, form cation composite emulsifying and dispersant D
18With cation composite emulsifying and dispersant D
18Replace cation composite emulsifying and dispersant 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 lamination 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 PAMC of molecular weight 400,000 mixes, and forms cation composite emulsifying and dispersant D
19With cation composite emulsifying and dispersant D
19Replace cation composite emulsifying and dispersant 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 lamination 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 cation composite emulsifying and dispersant D
20With cation composite emulsifying and dispersant D
20Replace cation composite emulsifying and dispersant 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 lamination 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 cation composite emulsifying and dispersant D
21With cation composite emulsifying and dispersant D
21Replace cation composite emulsifying and dispersant 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 lamination 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 aluminum sulfate (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 osmosis (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 osmosis 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 osmosis 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 osmosis to measure its degree of sizing, and degree of sizing is 13s.
Get 750 share paper stocks, add the aluminum sulfate of 0.15 share, the cationic dispersion rosin size D and the 0.003 share PAMC (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 osmosis mensuration with the paper of PAMC retention, cationic dispersion rosin size B applying glue, degree of sizing is 35s.
Get 750 share paper stocks, add the aluminum sulfate of 0.15 share, cationic dispersion rosin size D, 0.003 share PAMC 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 osmosis mensuration with the paper of PAMC/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 aluminum sulfate 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 osmosis to measure its degree of sizing, and degree of sizing is 14s.
Get 750 share paper stocks, add the aluminum sulfate 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 osmosis to measure its degree of sizing, and degree of sizing is 11s.
Get 750 share paper stocks, add the aluminum sulfate 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 osmosis to measure its degree of sizing, and degree of sizing is 12s.
Get 750 share paper stocks, add the aluminum sulfate 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 osmosis to measure its degree of sizing, and degree of sizing is 9s.
Get 750 share paper stocks, add the aluminum sulfate 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 osmosis to measure its degree of sizing, and degree of sizing is 7s.
Get 750 share paper stocks, add the aluminum sulfate 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 osmosis to measure its degree of sizing, and degree of sizing is 6s.
Get 750 share paper stocks, add the aluminum sulfate 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 osmosis to measure its degree of sizing, and degree of sizing is 8s.
Get 750 share paper stocks, add the aluminum sulfate 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 osmosis to measure its degree of sizing, and degree of sizing is 6s.
Get 750 share paper stocks, add the aluminum sulfate 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 osmosis to measure its degree of sizing, and degree of sizing is 7s.
Get 750 share paper stocks, add the aluminum sulfate 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 osmosis to measure its degree of sizing, and degree of sizing is 2s.
Get 750 share paper stocks, add the aluminum sulfate 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 osmosis to measure its degree of sizing, and degree of sizing is 16s.
Get 750 share paper stocks, add the aluminum sulfate 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 osmosis to measure its degree of sizing, and degree of sizing is 5s.
Get 750 share paper stocks, add the aluminum sulfate 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 osmosis to measure its degree of sizing, and degree of sizing is 65s.
Get 750 share paper stocks, add the aluminum sulfate of 0.15 share, after mixing, add the cationic dispersion rosin size D of 0.15 share
13, after mixing, add 0.0015 share PAMC again, on handshcet former, copy sheet, drying, obtain cationic dispersion rosin size D
13The handsheet of applying glue, PAMC retention utilizes the liquid osmosis to measure its degree of sizing, and degree of sizing is 102s.
Get 750 share paper stocks, add the aluminum sulfate 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 osmosis to measure its degree of sizing, and degree of sizing is 43s.
Get 750 share paper stocks, add the aluminum sulfate 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 osmosis to measure its degree of sizing, and degree of sizing is 57s.
Get 750 share paper stocks, add the aluminum sulfate 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 osmosis to measure its degree of sizing, and degree of sizing is 58s.
Get 750 share paper stocks, add the aluminum sulfate 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 osmosis to measure its degree of sizing, and degree of sizing is 57s.
Get 750 share paper stocks, add the aluminum sulfate 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 osmosis to measure its degree of sizing, and degree of sizing is 32s.
Get 750 share paper stocks, add the aluminum sulfate 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 osmosis to measure its degree of sizing, and degree of sizing is 21s.
Get 750 share paper stocks, add the aluminum sulfate 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 osmosis to measure its degree of sizing, and degree of sizing is 15s.
Get 750 share paper stocks, add the aluminum sulfate 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 osmosis to measure its degree of sizing, and degree of sizing is 28s.
Get 750 share paper stocks, add the aluminum sulfate 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 osmosis to measure its degree of sizing, degree of sizing is 10s.
Get 750 share paper stocks, add the aluminum sulfate 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 osmosis to measure its degree of sizing, degree of sizing is 7s.
Get 750 share paper stocks, add the aluminum sulfate 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 osmosis to measure its degree of sizing, degree of sizing is 9s.
Claims (5)
1. cationic dispersion rosin size utilizes high-temperature pressure to reverse technology, makes after with the emulsification of rosin based sizing agent by composite cation emulsification and dispersant, it is characterized in that:
Described composite cation emulsification and dispersant comprise following composition, account for the non-ionic amphiphilic polymer emulsion of cationic dispersion rosin size weight 2-30% and account for quaternary amines cationic surfactant or the cationic water-soluble polymer of cationic dispersion rosin size weight 0.5-20%;
Described non-ionic amphiphilic polymer emulsion by lipophile thiazolinyl class monomer and hydrophily thiazolinyl class monomer with 2: 1-1: 2 weight ratio forms through emulsion polymerisation; Described quaternary amines cationic surfactant is one or more of dodecyl dimethyl benzyl ammonium halide, cetyl trimethyl ammonium halide or OTAC; Described cationic water-soluble polymer is one or more of PAMC, diallyl dimethyl ammoniumchloride, polyamide polyamines-epoxychloropropane, polymine-epoxychloropropane or polymine;
Described lipophile thiazolinyl class monomer is one or more of styrene, methyl styrene, butylstyrene, butyl acrylate, methyl acrylate or methyl methacrylate; Described hydrophily thiazolinyl class monomer is one or more of acrylamide, Methacrylamide or alkyl acrylamide.
2. cationic dispersion rosin size according to claim 1 is characterized in that: the weight ratio of described lipophile vinyl monomer and hydrophily vinyl monomer is 1: 1; Described non-ionic amphiphilic polymer emulsion accounts for the 10-15% of cationic dispersion rosin size weight.
3. cationic dispersion rosin size according to claim 1 and 2, it is characterized in that: described cationic surfactant is the mixture of dodecyl dimethyl benzyl ammonium halide and cetyl trimethyl ammonium halide, both weight ratios are 4: 1-1: between 2, addition accounts for the 1-10% of cationic dispersion rosin size weight; Described cationic water-soluble polymer is one or more of polyamide polyamines-epoxychloropropane, polymine-epoxychloropropane or polymine, and addition accounts for the 1-10% of cationic dispersion rosin size weight.
4. cationic dispersion rosin size according to claim 1 and 2 is characterized in that: described cationic surfactant 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.
5. 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 dispersant while stirring, form water-in-oil emulsion, afterwards, improve mixing speed, add and be preheated to 80-100 ℃ hot water, make emulsion inverse, form O/w emulsion, cooling forms cationic dispersion rosin size.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100435697A CN1295014C (en) | 2005-05-23 | 2005-05-23 | Cationic dispersion rosin size |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100435697A CN1295014C (en) | 2005-05-23 | 2005-05-23 | Cationic dispersion rosin size |
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| CN1692976A CN1692976A (en) | 2005-11-09 |
| CN1295014C true CN1295014C (en) | 2007-01-17 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2005100435697A Expired - Fee Related CN1295014C (en) | 2005-05-23 | 2005-05-23 | Cationic dispersion rosin size |
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Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102261014B (en) * | 2010-05-28 | 2015-03-25 | 荒川化学工业株式会社 | Rosin emulsion sizing agent and paper obtained by using the sizing agent |
| CN103628356B (en) * | 2013-11-27 | 2015-10-28 | 杭州杭化哈利玛化工有限公司 | A kind of novel cation 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 |
| CN107236093A (en) * | 2016-03-29 | 2017-10-10 | 上海东升新材料有限公司 | A kind of preparation method for being used to produce the Shuangzi emulsifying agent of 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 |
| CN106279533B (en) * | 2016-08-29 | 2018-06-19 | 上海东升新材料有限公司 | A kind of cationic rosin size emulsifier and preparation method thereof |
| CN106758498B (en) * | 2016-12-21 | 2018-02-13 | 南昌市龙然实业有限公司 | Water resistant oil resistant Cationic dispersed rosin size |
| CN107034729A (en) * | 2017-02-22 | 2017-08-11 | 镇江市天亿化工研究设计院有限公司 | A kind of cation colophony size |
| CN106948217A (en) * | 2017-02-22 | 2017-07-14 | 镇江市天亿化工研究设计院有限公司 | A kind of preparation method of cation colophony size |
| CN111808560B (en) * | 2019-12-31 | 2021-05-11 | 河南省科学院高新技术研究中心 | Multifunctional easy-to-alkali-wash adhesive and preparation method thereof |
| CN111073003B (en) * | 2020-01-11 | 2022-07-19 | 山东奥赛新材料有限公司 | Environment-friendly chlorine-free high-strength wet strength agent and preparation method thereof |
| CN115142296B (en) * | 2022-07-25 | 2023-09-26 | 济宁明升新材料有限公司 | Method for preparing low-cost high-dispersion cationic sizing agent by replacing rosin |
| CN115305743A (en) * | 2022-08-19 | 2022-11-08 | 上海昶法新材料有限公司 | Cation dispersed rosin sizing agent and preparation method thereof |
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| US5438087A (en) * | 1989-12-28 | 1995-08-01 | Japan Pmc Corporation | Paper sizing composition |
| CN1109489A (en) * | 1994-03-30 | 1995-10-04 | 近代化学工业株式会社 | Method for preparation of disperser used in glue applying agent and aqueous emulsion |
| CN1184185A (en) * | 1997-12-03 | 1998-06-10 | 中国科学院广州化学研究所 | preparation of sizing synergist |
| JP2002173889A (en) * | 2000-12-08 | 2002-06-21 | Kindai Kagaku Kogyo Kk | Dispersant for cation-type rosin emulsion sizing agent |
| CN1544755A (en) * | 2003-11-28 | 2004-11-10 | 中国林业科学研究院林产化学工业研究 | Cationic gum rosin sizing agent emulsion and method for preparing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5438087A (en) * | 1989-12-28 | 1995-08-01 | Japan Pmc Corporation | Paper sizing composition |
| CN1109489A (en) * | 1994-03-30 | 1995-10-04 | 近代化学工业株式会社 | Method for preparation of disperser used in glue applying agent and aqueous emulsion |
| CN1184185A (en) * | 1997-12-03 | 1998-06-10 | 中国科学院广州化学研究所 | preparation of sizing synergist |
| JP2002173889A (en) * | 2000-12-08 | 2002-06-21 | Kindai Kagaku Kogyo Kk | Dispersant for cation-type rosin emulsion sizing agent |
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| CN1692976A (en) | 2005-11-09 |
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