CN100398619C - Small grain size rosin ester emulsion preparation method - Google Patents
Small grain size rosin ester emulsion preparation method Download PDFInfo
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- CN100398619C CN100398619C CNB200610037842XA CN200610037842A CN100398619C CN 100398619 C CN100398619 C CN 100398619C CN B200610037842X A CNB200610037842X A CN B200610037842XA CN 200610037842 A CN200610037842 A CN 200610037842A CN 100398619 C CN100398619 C CN 100398619C
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Abstract
The present invention discloses a preparation method for a small grain size rosin ester emulsion. The preparation method comprises the following steps: step one, a rosinyl polyether and strong alkali are mixed accordingly to a mole ratio of 1: (1.2 to 3) and are distillated under reduced pressure, then monochloroacetic acid or moniobromic acid water solution with the mass concentration of 75% to 90% is dropped, and reaction is continuously carried out for 1 to 2h after charging; step two, palmitic acid poly-glucoside is added to be sufficiently stirred at 80 DEG C to 120 DEG C; step three, a rosin ester is heated to 120 DEG C to 160 DEG C, a compound emulsifying agent accounting for 5 to 15% of the mass of the rosin ester is added to be uniformly stirred, a temperature drops to 100 DEG C to 120 DEG C, deionized water is added to be rapidly stirred until the viscosity is smaller than 200 centipoises, phase inversion reaction ends, a stirring is decelerated to make stirring continuously carried out, then the temperature drops to 10 to 25 DEG C, and filtration is carried out. The method of the present invention has the advantages of low cost and environmental protection, an obtained rosin ester emulsion is stable, and the average grain size is smaller than 150 nm.
Description
Technical field
The present invention relates to a kind of preparation method of rosin ester emulsion, relate in particular to a kind of preparation method of small grain size rosin ester emulsion.
Background technology
Rosin is as a kind of reproducible natural resource, and is main as tackifier in tackiness agent and coating.Rosin and rosin ester are a kind of oil-soluble resins, it can only be dissolved in the organic solvent or with organic substance matching and could using.Development along with modern technologies; people are to the attention of environment protection; in industrial circles such as tackiness agent, coating, develop in succession pollution-free, nuisanceless, low-cost, and water-latex type product safe and convenient to use or claim emulsion type products, i.e. " environmental protection " product.After the 1980s, emulsion adhesive and coating warp in the sixth of the twelve Earthly Branches are occupied an leading position in tackiness agent and coatings industry.Rosin ester emulsion can significantly improve the performance of emulsion adhesive and coating, and can reduce tackiness agent and coating cost, is subjected to people's generally attention, the preparation of existing many bibliographical information rosin ester emulsions.The emulsifying agent that U.S.Patent5236624 report adopts negatively charged ion and nonionogenic tenside to be re-dubbed gets 40%～60% the emulsion particle diameter rosin ester emulsion less than 500nm with the continuous emulsification legal system, be used for the Tackified emulsion of water-borne pressure sensitive adhesive; China is also more active to the research of rosin ester emulsion, Wang Zhenhong etc. and Xie Hui etc. adopt fusion anti-phase emulsion process to prepare lowization some rosin ester emulsion respectively, prepared high-softening-point rosin ester emulsion with solvent hydrotropy emulsion process and high pressure-temperature emulsion process, the emulsion-stabilizing performance is better, but residual in the emulsion that makes with solvent hydrotropy emulsion process have an organic solvent partly; Liao Shizhen etc. are that raw material synthetic tensio-active agent is that the small particle size ester gum stability of emulsion of emulsifying agent preparation was above 6 months with rosin.Substantially do not have open but these research contents of Chinese scholar are not all declared relevant patent, especially emulsifying agent.
The size of rosin ester emulsion directly influence emulsion stability and with the intermiscibility of polymer emulsion, the rosin ester emulsion that particle diameter is big has certain stability under normal weather condition, but less stable under mal-condition such as high temperature, low temperature, the transportation and the use of product have been limited, simultaneously relatively poor with the consistency of polymer emulsion, be separated after causing film forming, make film uniformity poor, thereby cause unstable properties.
Summary of the invention
The invention provides the preparation method of a kind of median size less than the small grain size rosin ester emulsion of 150nm, low, the environmental protection of this method cost, it is stable to obtain rosin ester emulsion, and median size is less than 150nm.
The present invention adopts following technical scheme:
A kind of preparation method of small grain size rosin ester emulsion comprises following a few step:
The first step, rosinyl polyether carboxylation's preparation: with rosinyl polyethers and highly basic in molar ratio 1: mix (1.2～3), underpressure distillation, drip mass concentration again and be 75%～90% the aqueous solution, solute in this aqueous solution is a kind of in a Monochloro Acetic Acid or the bromoacetic acid or both mixtures, the mol ratio of the amount of substance of the amount of substance of solute and rosinyl polyethers is (1～2): 1, and reaction 1～2h is continued in the reinforced back that finishes, and obtains rosinyl polyether carboxylic acid salts solution;
Second step, the preparation of Compositional type emulsifying agent: in above-mentioned rosinyl polyether carboxylic acid salts solution, add the Palmic acid poly glucoside, under 80 ℃～120 ℃ conditions, fully stir, obtain the Compositional type emulsifying agent, wherein, rosinyl polyether carboxylation and Palmic acid poly glucoside mass ratio are 10: (1～10);
The 3rd step, the preparation of small grain size rosin ester emulsion: rosin ester is heated to 120 ℃～160 ℃, adds the Compositional type emulsifying agent that accounts for rosin ester quality 5～15%, stir, be cooled to 100 ℃～120 ℃, add 80 ℃～98 ℃ the deionized water that accounts for rosin ester quality 40%-60%, stir fast, to viscosity during less than 200 centipoises, the phase inversion reaction finishes, and reduces stirring velocity and continues to stir, and cools to 10～25 ℃ then, filter, obtain small grain size rosin ester emulsion.
The present invention obtains following technique effect:
1. adopted the novel environmental type compound emulsifying agent of rosinyl polyether carboxylation and Palmic acid poly glucoside blended, biological degradability is good, thereby this preparation method's environmental protection.
2. adopted a kind of novel environmental type emulsifying agent, not only environmental protection, and emulsifying effectiveness is fine, the rosin ester emulsion median size of preparation is less than 150nm, improved product stability and with the consistency of polymer emulsion.
3. adopted a kind of novel environmental type emulsifying agent, good stability, under violent condition (high temperature, low temperature) but long-term storage, simultaneously because the size of particle diameter and polymer emulsion is similar, both consistencies are better, are the emulsion-type tackifier of ideal aqueous adhesive and water-borne coatings.
The present invention is that the green polymeric surface active agent of feedstock production is the Compositional type emulsifying agent with natural resource rosin and natural plant grease palmitinic acid, the rosin ester emulsion median size of preparation is less than 150nm, good stability, under violent condition (high temperature, low temperature) but long-term storage, simultaneously because the size of particle diameter and polymer emulsion is similar, both consistencies are better, are the emulsion-type tackifier of ideal aqueous adhesive and water-borne coatings.
The present invention will be the Compositional type emulsifying agent with the green anionic polymer tensio-active agent rosinyl polyether carboxylation of sylvic acid preparation and the green nonionogenic tenside Palmic acid glucoside for preparing with palmitinic acid, adopt phase conversion method that rosin ester is carried out emulsification, obtain the rosin ester emulsion of median size less than 150nm, the stability of raising product reaches the consistency with polymer emulsion.
Description of drawings
Accompanying drawing 1 is the size distribution figure of the embodiment of the invention 2.
Embodiment
Embodiment 1
A kind of preparation method of small grain size rosin ester emulsion comprises following a few step:
The first step, green anionic polymer tensio-active agent rosinyl polyether carboxylation's preparation: with rosinyl polyethers and highly basic in molar ratio 1: mix (1.2～3), highly basic can be chosen for sodium hydroxide, a kind of in the potassium hydroxide, mol ratio can be chosen for: 1: 1.5,1: 1.8,1: 2.3,1: 2.7, underpressure distillation, the condition of underpressure distillation can be for vacuumizing the 1.0～3.0KPa that reduces pressure, and Heating temperature is: 60～95 ℃, drip mass concentration again and be 75%～90% the aqueous solution, solute in this aqueous solution is a kind of in a Monochloro Acetic Acid or the bromoacetic acid or both mixtures, wherein, the amount of substance of solute (a kind of or both mixtures in a Monochloro Acetic Acid or the bromoacetic acid) and the mol ratio of rosinyl polyethers are (1～2): 1, for example can be chosen for 1.3: 1,1.5: 1,1.75: 1,1.9: 1, the proportioning of mixture can be any proportioning, reaction 1～2h is continued in the reinforced back that finishes, and obtains green anionic polymer tensio-active agent rosinyl polyether carboxylation;
Second step, the preparation of Compositional type emulsifying agent: is 10 with rosinyl polyether carboxylation and Palmic acid poly glucoside by mass ratio: mix (1～10), for example can be chosen for: 10: 1.5,10: 4,10: 6.5,10: 9, under 80 ℃～120 ℃ conditions, fully stir, temperature can be chosen for 90 ℃, 115 ℃, churning time can be 0.5～1 hour, and the emulsion after the stirring stirs fully, promptly obtains the Compositional type emulsifying agent there not being after with 3000 rev/mins of centrifugal 10min layering to think on the whizzer;
The 3rd step, the preparation of small grain size rosin ester emulsion: rosin ester is heated to 120 ℃～160 ℃, temperature can be chosen for 135 ℃, and 144 ℃, 152 ℃, 156 ℃, add the Compositional type emulsifying agent that accounts for rosin ester quality 5～15%, can be chosen for 7.2%, 8%, 11.3%, 12.6,13.5%, stir, be cooled to 100 ℃～120 ℃, temperature can be chosen for 105 ℃, 112 ℃, slowly adds 80 ℃～98 ℃ the deionized water that accounts for rosin ester quality 40%-60%, stir fast (mixing speed can be 3000-5000rpm), begin low speed (800-1000 rev/min) during less than 200 centipoises to viscosity and stir, cool to 10～25 ℃ then, filter (filtering effect: generally all use strainer filtering in laboratory and the production with 200 mesh filter screens, because the used rosin of synthetic rosin ester is not made with extra care, there are a lot of impurity the inside; In addition, the rosin ester (seldom) that does not have emulsification to fall can be attached to filtering out on the filter screen.), obtain small grain size rosin ester emulsion.Small particle size of the present invention is meant that the rosin ester emulsion median size is less than 150nm
The rosin of related rosinyl polyethers, rosinyl polyether carboxylation and rosin ester can be gum resin in the invention process step, also can be starex or wood rosin.
Related rosin ester is meant ester compound that rosin and unit alcohol, dibasic alcohol or polyvalent alcohol generation esterification make or their mixture in the invention process step; Unit alcohol comprises methyl alcohol, ethanol, propyl carbinol or isooctyl alcohol, and dibasic alcohol comprises that ethylene glycol, Diethylene Glycol, glycol ether, triglycol or the polymerization degree are the polyoxyethylene glycol of 1-10, and polyvalent alcohol comprises glycerine, tetramethylolmethane, sorbyl alcohol or sucrose.
In the present embodiment, the rosinyl polyether carboxylation can be rosin alcohol Soxylat A 25-7 carboxylic acid sodium, ester gum polyethenoxy ether carboxylate, pentalyn polyethenoxy ether carboxylate, acrylic acid modified rosin glyceryl ester Soxylat A 25-7, Lewisol 28 Soxylat A 25-7 etc.
In the present embodiment, the related rosinyl polyethers of step 1 is meant the polyether products of rosin, modified rosin, rosinyl oxy-compound or rosinyl nitrogenous compound and oxyethane addition gained; Modified rosin is meant staybelite, nilox resin, maleated rosin, polymerized rosin or acrylic acid modified rosin; The rosinyl oxy-compound is meant the ester class product of rosin alcohol, phenol-modified rosin or rosin and modified rosin and dibasic alcohol or polyvalent alcohol generation part esterification; The rosinyl nitrogenous compound is meant rosinyl acid amides or the rosinyl tetrahydroglyoxaline that rosin and thanomin, diethanolamine or polyamines polyene generation amidate action obtain; The preferred nilox resin Soxylat A 25-7 of rosinyl polyethers, acrylic acid modified rosin Soxylat A 25-7 or acrylic acid modified rosin glyceryl ester Soxylat A 25-7.
In the present embodiment, rosinyl polyethers that step 1 is related and alkaline amount ratio (mol ratio) preferred 1: (1.5～2.0).
In the present embodiment, a kind of in a Monochloro Acetic Acid that step 1 is related or the bromoacetic acid or both amount of substances and with the mol ratio preferred (1～1.4) of rosinyl polyethers: 1.
In this enforcement, the related Palmic acid glucoside of step 2 is meant that the polymerization degree that Palmic acid higher alcohols and glucose generation reaction of guanosine obtain is 1～3 poly glucoside; The Palmic acid higher alcohols are meant the block affixture (oxyethane and propylene oxide total polymerization degree 2-20) of palmityl alcohol, palmitic monoethanolamide, palmitinic acid diglycollic amide, palmitinic acid ethylene oxide adduct (ethylene oxide polymerization degree 1-20), palmitinic acid propylene oxide adduct (propylene oxide polymerization degree 1-20) or palmitinic acid and oxyethane and propylene oxide; Preferred palmitinic acid and ethylene oxide adduct.
In the present embodiment, the rosinyl polyether carboxylation that step 2 is related and the mass ratio of Palmic acid poly glucoside are 10: (1～10), preferred 10: (3～6).
In the present embodiment, the consumption of the Compositional type emulsifying agent that step 3 is related is 5～15%, preferred 8～12% of a rosin ester quality consumption.
The reaction of alleged phase inversion is meant that rosin ester and composite emulsifying agent are after stirring among the present invention, deionized water slowly adds fashionable, just having begun is the water-in-oil-type system, system is very sticking, and viscosity increases gradually, viscosity maximum during to phase inversion, and viscosity reduces suddenly then, system is an oil-in-water-type, and range estimation can obviously be seen.
The preparation of embodiment 2 small particle size methyl esters of rosin (viscous liquid) emulsions
(the ethylene oxide polymerization degree is 10 with 100.0g nilox resin Soxylat A 25-7, hydroxyl mole number 0.152mol) and 9.15g (0.229mol) sodium hydroxide put into reactor, vacuumize the 2.0KPa that reduces pressure, be heated to 85 ℃, the Monochloro Acetic Acid aqueous solution 21.5g (0.182mol) of dropping 80%, reinforced finishing continues reaction 1.5h, promptly gets nilox resin Soxylat A 25-7 carboxylic acid sodium.The solution and the 4g palmitinic acid Soxylat A 25-7 poly glucoside (the ethylene oxide polymerization degree is 10) that will contain 10g nilox resin Soxylat A 25-7 carboxylic acid sodium fully stir 0.5h under 100 ℃ of conditions, promptly get methyl esters of rosin emulsification Compositional type emulsifying agent; With 140g methyl esters of rosin (viscous liquid, acid number is less than 10mg/g (KOH)) be added in the reactor, be heated to 120 ℃, above-mentioned Compositional type emulsifying agent is added, stir 1h, when temperature is reduced to 105 ℃, slowly be added dropwise to 90 ℃ deionized water 126g, this moment high-speed stirring, rotating speed can be 3000 rev/mins, treat that phase inversion finishes after, stirring at low speed, rotating speed can be 800～1000 rev/mins, cooling is rapidly filtered and is promptly got the methyl esters of rosin emulsion that oyster white has obvious blue fluorescence, measures solid content (55 ± 2) %, median size is less than 100nm, and viscosity is less than 400mPas.
The preparation of embodiment 3 small particle size flexalyns (50 ℃ of softening temperatures) emulsion
(the ethylene oxide polymerization degree is 10 with 100.0g acrylic acid modified rosin Soxylat A 25-7, hydroxyl mole number 0.166mol) and 13.28g (0.332mol) sodium hydroxide put into reactor, vacuumize the 2.0KPa that reduces pressure, be heated to 90 ℃, the Monochloro Acetic Acid aqueous solution 23.6g (0.2mol) of dropping 80%, reinforced finishing continues reaction 1.5h, promptly gets acrylic acid modified rosin Soxylat A 25-7 carboxylic acid sodium.The solution and the 5g palmitinic acid Soxylat A 25-7 poly glucoside (the ethylene oxide polymerization degree is 10) that will contain 10g acrylic acid modified rosin Soxylat A 25-7 carboxylic acid sodium mix, under 100 ℃ of conditions, fully stir 0.5h, promptly get flexalyn emulsification Compositional type emulsifying agent; With 150g flexalyn (thick semisolid, acid number is less than 20mg/g (KOH), 50 ℃ of softening temperatures) be added in the reactor, be heated to 130 ℃, above-mentioned Compositional type emulsifying agent is added, stir 1h, when temperature is reduced to 110 ℃, slowly be added dropwise to 95 ℃ deionized water 152g, at this moment high-speed stirring, after treating that phase inversion finishes, stirring at low speed is lowered the temperature rapidly, filters promptly to get the flexalyn emulsion that oyster white has obvious blue fluorescence, measures solid content (52 ± 2) %, median size is less than 50nm, and viscosity is less than 300mPas.
The preparation of embodiment 4 small particle size ester gums (85 ℃ of softening temperatures) emulsion
(the ethylene oxide polymerization degree is 10 with 100.0g acrylic acid modified rosin glyceryl ester Soxylat A 25-7, hydroxyl mole number 0.127mol) and 10.16g (0.254mol) sodium hydroxide put into reactor, vacuumize the 2.0KPa that reduces pressure, be heated to 90 ℃, the Monochloro Acetic Acid aqueous solution 18.0g (0.152mol) of dropping 80%, reinforced finishing continues reaction 1.5h, promptly gets acrylic acid modified rosin glyceryl ester Soxylat A 25-7 carboxylic acid sodium.The solution and the 5g palmitinic acid Soxylat A 25-7 poly glucoside (the ethylene oxide polymerization degree is 10) that will contain 10g acrylic acid modified rosin glyceryl ester Soxylat A 25-7 carboxylic acid sodium mix, under 100 ℃ of conditions, fully stir 0.5h, promptly get ester gum emulsification Compositional type emulsifying agent; With 150g ester gum (crisp shape solid, acid number is less than 10mg/g (KOH), 85 ℃ of softening temperatures) be added in the reactor, be heated to 140 ℃, above-mentioned Compositional type emulsifying agent is added, stir 1h, when temperature is reduced to 115 ℃, slowly be added dropwise to 95 ℃ deionized water 165g, this moment high-speed stirring, suddenly diminish to system viscosity, then phase inversion finishes, and stirring at low speed is lowered the temperature rapidly, filter and promptly get the ester gum emulsion that oyster white has obvious blue fluorescence, measure solid content (50 ± 2) %, median size is less than 150nm, and viscosity is less than 200mPas.
The preparation of embodiment 5 small particle size rosin ethylene glycol and mixed esters of pentaerythritol (80 ℃ of softening temperatures) emulsion
The Compositional type emulsifying agent prepares with embodiment 3. 150.0g rosin ethylene glycol and mixed esters of pentaerythritol (crisp shape solid, acid number is less than 10mg/g (KOH), 80 ℃ of softening temperatures) be added in the reactor, be heated to 140 ℃, above-mentioned Compositional type emulsifying agent is added, stir 1h, when temperature is reduced to 115 ℃, slowly be added dropwise to 95 ℃ deionized water 152g, this moment, high-speed stirring diminished suddenly to system viscosity, and then phase inversion finishes, stirring at low speed, cooling is rapidly filtered and is promptly got rosin ethylene glycol and the mixed esters of pentaerythritol emulsion that oyster white has obvious blue fluorescence, measures solid content (52 ± 2) %, median size is less than 150nm, and viscosity is less than 200mPas.
The present invention measures size distribution and adopts surveying instrument to be: typed Mastersiver 2000, MalvernCompany, Made in England. (the Mastersiver 2000 type particle size analyzers of Britain Ma Erwen company).Measuring method: under the room temperature (under 25 degrees centigrade), in 2000ml beaker (tap water of 1600m is housed), add the sample emulsion about 2 grams, stir, measure under less than 10% situation in shading density through the rotor of 2000 rev/mins of rotating speeds.
The small particle size rosin milk that the present invention obtains is under 25 ℃, and steady time was greater than 6 months.
The small particle size rosin milk consistency that the present invention obtains: with Emulsion acrylic resin, ethylene-vinyl acetate emulsion, vinyl acetate copolymer, nature rubber latex, vinylbenzene-Ding divinyl rubber latex, nitrile-Ding two rubber latexs, neoprene latexs etc. can be held mutually.
Claims (7)
1. the preparation method of a small grain size rosin ester emulsion is characterized in that comprising following a few step:
The first step, rosinyl polyether carboxylation's preparation: with rosinyl polyethers and highly basic in molar ratio 1: mix (1.2～3), underpressure distillation, drip mass concentration again and be 75%～90% the aqueous solution, solute in this aqueous solution is a kind of in a Monochloro Acetic Acid or the bromoacetic acid or both mixtures, the mol ratio of the amount of substance of solute and rosinyl polyethers is (1～2): 1, and reaction 1～2h is continued in the reinforced back that finishes, and obtains rosinyl polyether carboxylic acid salts solution;
Second step, the preparation of Compositional type emulsifying agent: in above-mentioned rosinyl polyether carboxylic acid salts solution, add the Palmic acid poly glucoside, under 80 ℃～120 ℃ conditions, fully stir, obtain the Compositional type emulsifying agent, wherein, rosinyl polyether carboxylation and Palmic acid poly glucoside mass ratio are 10: (1～10);
The 3rd step, the preparation of small grain size rosin ester emulsion: rosin ester is heated to 120 ℃～160 ℃, add the Compositional type emulsifying agent that accounts for rosin ester quality 5～15%, stir, be cooled to 100 ℃～120 ℃, add 80 ℃～98 ℃ the deionized water that accounts for rosin ester quality 40%-60%, stir with 3000-5000 rev/min speed, to viscosity during less than 200 centipoises, the phase inversion reaction finishes, and rotating speed is reduced to 800-1000 rev/min continues to stir, and cools to 10～25 ℃ then, filter, obtain small grain size rosin ester emulsion.
2. the preparation method of small grain size rosin ester emulsion according to claim 1, the raw material rosin that it is characterized in that rosinyl polyethers, rosinyl polyether carboxylation and rosin ester is the one or more kinds of mixtures in gum resin, starex and the wood rosin, and the proportioning of mixture can be any proportioning.
3. the preparation method of small grain size rosin ester emulsion according to claim 1 is characterized in that rosinyl polyethers and alkaline mol ratio are 1: (1.5～2.0).
4. the preparation method of small grain size rosin ester emulsion according to claim 1 is characterized in that a kind of or both amount of substances in a Monochloro Acetic Acid or the bromoacetic acid and is (1～1.4) with the mol ratio of rosinyl polyethers: 1.
5. the preparation method of small grain size rosin ester emulsion according to claim 1 is characterized in that the Palmic acid poly glucoside is the affixture of palmitinic acid and oxyethane.
6. the preparation method of small grain size rosin ester emulsion according to claim 1, the mass ratio that it is characterized in that rosinyl polyether carboxylation and Palmic acid poly glucoside is 10: (3～6).
7. the preparation method of small grain size rosin ester emulsion according to claim 1, the consumption that it is characterized in that the Compositional type emulsifying agent is 8～12% of a rosin ester quality consumption.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3966654A (en) * | 1973-08-06 | 1976-06-29 | Hercules Incorporated | Stable rosin dispersions |
| US4199369A (en) * | 1975-11-17 | 1980-04-22 | Hercules Incorporated | Aqueous fortified rosin dispersions |
| CN1168912A (en) * | 1996-06-14 | 1997-12-31 | 安徽省化工研究院 | Temp. phase transformation art for all-free dispersion rosin size |
| CN1202554A (en) * | 1997-06-18 | 1998-12-23 | 杭州市化工研究所 | Rosin series neutral glueing agent and its preparing method |
| CN1310201A (en) * | 2000-08-08 | 2001-08-29 | 杭州化工研究所职工技术协会 | Low foaming dispersed rosin size |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3966654A (en) * | 1973-08-06 | 1976-06-29 | Hercules Incorporated | Stable rosin dispersions |
| US4199369A (en) * | 1975-11-17 | 1980-04-22 | Hercules Incorporated | Aqueous fortified rosin dispersions |
| CN1168912A (en) * | 1996-06-14 | 1997-12-31 | 安徽省化工研究院 | Temp. phase transformation art for all-free dispersion rosin size |
| CN1202554A (en) * | 1997-06-18 | 1998-12-23 | 杭州市化工研究所 | Rosin series neutral glueing agent and its preparing method |
| CN1310201A (en) * | 2000-08-08 | 2001-08-29 | 杭州化工研究所职工技术协会 | Low foaming dispersed rosin size |
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