CN108396589A - A kind of cationic rosin size emulsifier and preparation method thereof - Google Patents
A kind of cationic rosin size emulsifier and preparation method thereof Download PDFInfo
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- CN108396589A CN108396589A CN201810116364.4A CN201810116364A CN108396589A CN 108396589 A CN108396589 A CN 108396589A CN 201810116364 A CN201810116364 A CN 201810116364A CN 108396589 A CN108396589 A CN 108396589A
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/16—Sizing or water-repelling agents
Abstract
A kind of cationic rosin size emulsifier of present invention offer and preparation method thereof, including the following raw material are made：Dimethylaminoethyl methacrylate, styrene, chitosan, glacial acetic acid, water, acrylic acid, acrylamide, sodium potassium tartrate tetrahydrate, initiator.Obtained emulsifier stability is good, directly rosin can be emulsified using the emulsifier, emulsifier is few, effect is good, at low cost, and the size emulsion liquid particles obtained after emulsification can reach nanoscale, stable quality, can long-time stable storage (5 50 DEG C)；Obtained gum rosin lotion is applied to sizing after emulsification, and other glue sizing auxiliary agent dosages are few, and sizing agent dosage is few, effect is good, at low cost, and sized paper is made to have certain antibiotic and sterilizing effect, paper durability good.
Description
Technical field
The present invention relates to a kind of cationic rosin size emulsifiers and preparation method thereof, belong to emulsifier preparing technical field.
Background technology
Cationic rosin size is one kind of paper internal sizing agent, is mainly used for improving the water-resistance of paper.Cationic pine
Balosam is directed to for anion gum rosin.Anion gum rosin is domestic traditional paper sizing agent, usually by dedicated
Gum rosin emulsion is made in anion size emulsion agent high temperature emulsification rosin, and the usual solid content 50% of anion gum rosin is left
It is right；Cationic rosin size is then that gum rosin emulsion is made by dedicated cationic rosin size emulsifier high temperature emulsification rosin, sun
The usual solid content 25% or so of ion gum rosin, sizing efficiency is better than anion gum rosin, and cost is relative to anion rosin
Glue reduces by 40%.Currently, cationic rosin size emulsifier relies primarily on import or is monopolized by corporation with foreign capital.
Currently, in the prior art about the report of cationic rosin size emulsifier.Such as, Chinese patent literature
CN103628356A discloses a kind of novel cation rosin sizing agent and its application on paper making additive, the sizing agent each group
Part parts by weight be：Mixed emulsifier 3~15, modified rosin resin 15~40, emulsion stabilizer 5~30 add water to make always to contain
Gu amount is 30~80%；Wherein mixed emulsifier is by cationic acrylic macromolecule emulsifier, modified polyamide ring
Oxygen chloropropane resin and low molecular weight cationic emulsifier are made；The cationic acrylic macromolecule emulsifier is by following each
Component is made：Initiator, acetic acid, styrene, cationic monomer, alkyl carbon number be 1-8 alkyl acrylate in one kind or
Several, alkyl carbon number is one or more of alkyl methacrylate of 1-8, lauryl mercaptan and water；But the breast of the invention
Agent stability is not good enough, and sizing agent dosage is big when sizing, and while being glued uses numerous emulsifiers and stabilizer, prepares and sizing
Cost is higher.
For another example, Chinese patent literature CN106279533A discloses a kind of preparation method of cationic rosin size emulsifier,
Include the following steps：Surfactant is added in reaction kettle, deionized water is then added, is heated up；It is added at one time cation
Monomer solution, monomer solution and initiator solution；Deionized water, adjustment solid content are 35% to obtain the final product.The invention is using standing water
Polymerisation in solution, production technology is easy, and production efficiency is high, but the emulsion-stabilizing that the emulsifier rosin prepared by the invention obtains
Property it is not good enough, and while emulsifying rosin need to use other auxiliary agents, it is big to emulsify dosage of high cost；Meanwhile aqueous solution polymerization is stood, easily produce
Raw agglomeration, easily causes runaway reaction.
Invention content
In view of the deficienciess of the prior art, the present invention provides a kind of cationic rosin size emulsifier, which stablizes
Property is good, can directly be emulsified to rosin using the emulsifier, emulsifier is few, effect is good, at low cost, is obtained after emulsification
Size emulsion liquid particles can reach nanoscale, and stable quality can long-time stable storage (- 5-50 DEG C)；It is obtained after emulsification
Gum rosin lotion is applied to sizing, and other glue sizing auxiliary agent dosages are few, and sizing agent dosage is few, effect is good, at low cost, and makes sized paper
Opening has certain antibiotic and sterilizing effect, paper durability good.
The present invention also provides the preparation methods of above-mentioned cationic rosin size emulsifier, and this method device therefor is simple, operation
Step is simple, at low cost.
Technical scheme is as follows：
A kind of cationic rosin size emulsifier, including the raw material of following parts by weight are made：
30-80 parts of dimethylaminoethyl methacrylate, 10-35 parts of styrene, 0.5-3 parts of chitosan, glacial acetic acid
100-180 parts, 100-750 parts of water, 3-10 parts of acrylic acid, 50-75 parts of acrylamide, 2-10 parts of sodium potassium tartrate tetrahydrate, initiator 1-6
Part.
According to currently preferred, the cationic rosin size emulsifier, including the raw material of following parts by weight are made：
60-70 parts of dimethylaminoethyl methacrylate, 20-25 parts of styrene, 2 parts of chitosan, glacial acetic acid 120-150
Part, 200-500 parts of water, 5-8 parts of acrylic acid, 60-70 parts of acrylamide, 5-8 parts of sodium potassium tartrate tetrahydrate, 2-6 parts of initiator.
According to currently preferred, the weight average molecular weight of the chitosan is 15-30 ten thousand, deacetylation 50-99%.
According to currently preferred, the initiator is one kind in potassium peroxydisulfate, ammonium persulfate or sodium peroxydisulfate.
According to currently preferred, the cationic rosin size emulsifier is light yellow transparent liquid, solid content 25-
35wt%, pH 3-5, the viscosity at 25 DEG C is 15-60 centipoises.
The preparation method of above-mentioned cationic rosin size emulsifier, including step：
Under protective gas atmosphere, by dimethylaminoethyl methacrylate, styrene, chitosan, glacial acetic acid, water,
Acrylic acid, acrylamide and sodium potassium tartrate tetrahydrate are uniformly mixed, and obtain mixed liquor；Initiator is added, 70-90 DEG C is stirred to react 1-5h,
Obtain reaction solution；Water is added, 85-110 DEG C of distillation 0.5-3h adds water and adjust solid content, obtain size emulsion agent.
According to currently preferred, the protective gas is one kind in nitrogen, helium or argon gas.
According to currently preferred, the quality of the protective gas be dimethylaminoethyl methacrylate, styrene,
The 1-3% of chitosan, glacial acetic acid, water, acrylic acid, acrylamide, sodium potassium tartrate tetrahydrate and initiator raw material gross mass.
According to currently preferred, when the mixeding liquid temperature is 40-60 DEG C, the 50-70% of initiator gross mass is added,
It is stirred to react 0.5-3h in 70-90 DEG C；Then remaining initiator is added, the reaction was continued 0.5-2h.
According to currently preferred, the stir speed (S.S.) is 150-190 revs/min.
According to currently preferred, the solid content for mending the system that adds water to is 25-40wt%.
Application of the above-mentioned cationic rosin size emulsifier in emulsifying rosin.
The technical characterstic and advantageous effect of the present invention：
1, in the present invention, dimethylaminoethyl methacrylate, styrene are polymerized monomers, and acrylamide is cation
Monomer；Acrylic acid is promoter, can not only be dissolved in water, but also can be dissolved in styrene and dimethylamine second
Fat, thus reaction can be made to be easy to carry out, while it can adjust polymers obtained molecular weight；Chitosan is nontoxic, green
Colouring stabilizer, one side can stablize reaction rate, avoid generating sudden and violent poly- phenomenon, on the other hand can make product cationic degree
It improves, stability improves, and extends the storage time of product, and product is made to have certain antibiotic and sterilizing effect；Glacial acetic acid controls
Reacting liquid pH value；Sodium potassium tartrate tetrahydrate is conditioning agent and complexing agent, adjusts orientation reaction, prevents metal ion disturbance, make product more
Stablize；Initiator is then used for initiation reaction and control reaction rate.
2, the method that the present invention uses emulsion polymerization, dimethylaminoethyl methacrylate, styrene and acrylamide
Three kinds of monomers are copolymerized；The emulsifier of specific structure and ingredient of the present invention, each raw material play synergistic effect；The present invention's
Emulsifier can directly emulsify rosin, and emulsifier is few, effect is good, at low cost, and the emulsifier of the present invention has
Antibiotic and sterilizing acts on, and storage stability is good；It can reach and receive using the size emulsion liquid particles obtained after emulsifier of the present invention
Meter level (size emulsion liquid particles average diameter be 0.1-1 micron), and with antibiotic and sterilizing effect, stable quality, when can be long
Between storage-stable (- 5-50 DEG C)；And due to the cationic of chitosan, can help to capture the anionic trash in paper pulp,
The dosage that auxiliary air sizing agent such as aluminum sulfate can be reduced when thus applied to sizing, makes sizing efficiency greatly improve, sizing agent dosage
It is few, sizing cost is reduced, while sized paper being made to have certain antibiotic and sterilizing effect, paper durability good.
3, various raw materials are easy to get in preparation method of the present invention, and equipment is simple, and technological requirement is low, at low cost；Point of initiator
Section is added, and can control reaction rate, and reaction can be made thorough, toxic component is avoided to remain.
Specific implementation mode
The present invention is further elaborated with reference to embodiment, but institute's protection domain of the present invention is without being limited thereto.
Raw material in embodiment without specified otherwise is regular market purchase product；Experimental method described in following embodiments,
Unless otherwise specified, it is conventional method.
Embodiment 1
A kind of preparation method of cationic rosin size emulsifier, including step：
To be passed through 15kg nitrogen in reaction kettle, be added 70kg dimethylamine second fat, 20kg styrene,
2kg chitosans (weight average molecular weight is 200,000, deacetylation 80%), 130kg glacial acetic acid, 450kg deionized waters, 5kg propylene
Acid, 60kg acrylamides and 6kg potassium tartrates are uniformly mixed, and rotating speed is scheduled on 170 revs/min, when temperature in the kettle is raised to 50 DEG C
3kg potassium peroxydisulfates are added, when temperature in the kettle reaches 80 DEG C, clock reaction 2h adds 2kg potassium peroxydisulfates, continues then at 80 DEG C
1h is reacted, reaction solution is obtained.It mends again and adds water to solid content to 35wt%, 102 DEG C of reaction distillation 1h.It is cooled to room temperature, blowing is added
Water to solid content is 30wt%, and transparence size emulsion agent is made.
Cationic rosin size emulsifier manufactured in the present embodiment is light yellow transparent liquid, solid content 30wt%, pH=3-
4,50 centipoise of viscosity (25 DEG C), room temperature preservation, steady in a long-term (self-control is modern to the utmost to place 8 years, still effectively, no layering and precipitating
Phenomenon).
Embodiment 2
A kind of preparation method of cationic rosin size emulsifier, including step：
To be passed through 24kg nitrogen in reaction kettle, be added 60kg dimethylamine second fat, 25kg styrene,
2kg chitosans (weight average molecular weight is 150,000, deacetylation 90%), 120kg glacial acetic acid, 500kg deionized waters, 8kg propylene
Acid, 70kg acrylamides and 5kg potassium tartrates are uniformly mixed, and rotating speed is scheduled on 150 revs/min, when temperature in the kettle is raised to 40 DEG C
3kg potassium peroxydisulfates are added, when temperature in the kettle reaches 90 DEG C, clock reaction 2h adds 3kg potassium peroxydisulfates, continues then at 90 DEG C
1h is reacted, reaction solution is obtained.Water is added again adjusts solid content to 30wt%, 110 DEG C of reaction distillation 1h.It is cooled to room temperature, blowing, mends
It is 25wt% to add water to solid content, and transparence size emulsion agent is made.
Cationic rosin size emulsifier manufactured in the present embodiment is light yellow transparent liquid, solid content 25wt%, pH=3-
4,40 centipoise of viscosity (25 DEG C), room temperature preservation, steady in a long-term (self-control is modern to the utmost to place 8 years, still effectively, no layering and precipitating
Phenomenon).
Embodiment 3
A kind of preparation method of cationic rosin size emulsifier, including step：
To be passed through 15kg nitrogen in reaction kettle, be added 65kg dimethylamine second fat, 23kg styrene,
2kg chitosans (weight average molecular weight is 300,000, deacetylation 95%), 150kg glacial acetic acid, 200kg deionized waters, 6kg propylene
Acid, 65kg acrylamides and 8kg potassium tartrates are uniformly mixed, and rotating speed is scheduled on 190 revs/min, when temperature in the kettle is raised to 60 DEG C
1.2kg potassium peroxydisulfates are added, when temperature in the kettle reaches 70 DEG C, clock reaction 2h adds 0.8kg potassium peroxydisulfates, then at 70 DEG C
The reaction was continued 2h, obtains reaction solution.Water is added again adjusts solid content to 40wt%, 90 DEG C of reaction distillation 2h.It is cooled to room temperature, puts
Material, it is 35wt% that benefit, which adds water to solid content, and transparence size emulsion agent is made.
Cationic rosin size emulsifier manufactured in the present embodiment is light yellow transparent liquid, solid content 35wt%, pH=3-
4,60 centipoise of viscosity (25 DEG C), room temperature preservation, steady in a long-term (self-control is modern to the utmost to place 8 years, still effectively, no layering and precipitating
Phenomenon).
Comparative example 1
A kind of preparation method of cationic rosin size emulsifier, as described in Example 1, except that：Chitosan is not added with,
The solid content of cationic rosin size emulsifier is adjusted to 30wt%, other conditions are consistent with embodiment 1.
This comparative example cationic rosin size emulsifier pH=4-5,30 centipoise of viscosity (25 DEG C), room temperature preservation have for 1 month
There is phenomena such as layering, precipitation in effect after 1 month.
By this comparative example it is found that chitosan has great influence, breast prepared by the present invention to the stability of final emulsifier
Agent stability is preferable.
Comparative example 2
A kind of preparation method of cationic rosin size emulsifier, as described in Example 1, except that：The weight of chitosan
Average molecular weight is 100,000, adjusts the solid content of cationic rosin size emulsifier to 30wt%, other conditions are consistent with embodiment 1.
This comparative example cationic rosin size emulsifier pH=3-4,40 centipoise of viscosity (25 DEG C), room temperature preservation have for 6 months
There is phenomena such as layering, precipitation in effect after 6 months.
By this comparative example it is found that the molecular weight of chitosan has great influence, the present invention to the stability of final emulsifier
The emulsifier stability prepared using the chitosan of specified molecular weight as raw material is preferable.
Comparative example 3
A kind of preparation method of cationic rosin size emulsifier, as described in Example 1, except that：The weight of chitosan
Average molecular weight is 400,000, adjusts the solid content of cationic rosin size emulsifier to 30wt%, other conditions are consistent with embodiment 1.
This comparative example cationic rosin size emulsifier pH=3-4,80 centipoise of viscosity (25 DEG C), room temperature preservation, 1 year is effectively, and 1
Occurs phenomena such as layering, precipitation after year.
By this comparative example it is found that the molecular weight of chitosan has great influence, the present invention to the stability of final emulsifier
The emulsifier stability prepared using the chitosan of specified molecular weight as raw material is preferable；And the Weight-average molecular of this comparative example chitosan
Amount is higher than 300,000, and chitosan is poorly soluble, and production difficulty is big, and product stability also declines.
Comparative example 4
A kind of preparation method of cationic rosin size emulsifier, as described in Example 1, except that：It is added without winestone
Sour potassium sodium adjusts the solid content of cationic rosin size emulsifier to 30wt%, and other conditions are consistent with embodiment 1.
This comparative example cationic rosin size emulsifier pH=3-4,40 centipoise of viscosity (25 DEG C), room temperature preservation have for 6 months
There is phenomena such as layering, precipitation in effect after 6 months.
By this comparative example it is found that sodium potassium tartrate tetrahydrate acts synergistically as conditioning agent and complexing agent and other raw materials, to final
The stability tool of emulsifier has a certain impact.
Comparative example 5
A kind of preparation method of cationic rosin size emulsifier, as described in Example 1, except that：It is added without propylene
Amide adjusts the solid content of cationic rosin size emulsifier to 30wt%, and other conditions are consistent with embodiment 1.
This comparative example cationic rosin size emulsifier pH=3-4,30 centipoise of viscosity (25 DEG C), room temperature preservation have for 6 months
There is phenomena such as separation, precipitation in effect after 6 months.
By this comparative example it is found that acrylamide monomer structure has important influence to the stability of final emulsifier.
Comparative example 6
A kind of preparation method of cationic rosin size emulsifier, as described in Example 1, except that：It is added without propylene
Acid adjusts the solid content of cationic rosin size emulsifier to 30wt%, and other conditions are consistent with embodiment 1.
This comparative example cationic rosin size emulsifier pH=4-5,35 centipoise of viscosity (25 DEG C), room temperature preservation have for 3 months
There is phenomena such as layering, precipitation in effect after 3 months.
By this comparative example it is found that while acrylic acid is as promoter, the synergistic effect with other raw materials also can be to final
The stability of emulsifier has an impact.
Test example 1
Rosin fusing is heated up to 180 DEG C, embodiment 1, comparative example 1-6 and commercially available emulsifier are heated to 90 DEG C,
Deionized water is heated to 95 DEG C, by rosin：Emulsifier：Deionized water quality ratio is 200：50：750 mixing, it is equal to be passed through high pressure
Matter machine, at a temperature of 120 DEG C, homogeneous under 12000rpm rotating speeds, continuous discharge；Cold water cools down, and is cooled to 40 degree hereinafter, warm water tune
Solid content 25wt% is saved, cationic rosin emulsion is prepared, stands and preserves.
The above-mentioned cationic rosin emulsion that is prepared stablize at size emulsion liquid particles average diameter and 25 DEG C
Property test, measurement result is as shown in the table：
1 cationic rosin emulsion performance test of table
As shown in Table 1, the specific raw material of the present invention forms, and has mutual synergistic effect between heterogeneity so that this
The emulsifier of invention is applied to emulsification rosin and shows preferable effect, and it is less to emulsify dosage.
Test example 2
Cationic rosin emulsion in test example 1 is subjected to sizing test by the prior art, copy paper condition is：Pure wood
Slurry, starches dense 11wt%, addition of aluminum sulfate 1.5wt% (dosage of aluminum sulfate accounts for the percentage of the quality of pure wood pulp), pH6.8, tries
Testing the cationic rosin emulsion dosage 0.8wt% that is obtained in example 1, (cationic rosin emulsion accounts for the percentage of pure pulp quality
Than), it is as shown in the table to measure degree of sizing：
The test of 2 degree of sizing of table (Cobb value methods, 25 DEG C, normal pressure, g/m2)
| Test | Embodiment 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | It is commercially available |
| Hygroscopicity value | 13.5 | 13.8 | 13.7 | 13.8 | 13.6 | 13.6 | 13.6 | 15.3 |
As shown in Table 2, emulsifier of the invention is applied to after emulsifying and being glued relative to comparative example and commercially available emulsification
Agent has good sizing efficiency.
Claims (10)
1. a kind of cationic rosin size emulsifier, including the raw material of following parts by weight are made：
30-80 parts of dimethylaminoethyl methacrylate, 10-35 parts of styrene, 0.5-3 parts of chitosan, glacial acetic acid 100-180
Part, 100-750 parts of water, 3-10 parts of acrylic acid, 50-75 parts of acrylamide, 2-10 parts of sodium potassium tartrate tetrahydrate, 1-6 parts of initiator.
2. cationic rosin size emulsifier according to claim 1, which is characterized in that the cationic rosin size emulsification
Agent, including the raw material of following parts by weight are made：
60-70 parts of dimethylaminoethyl methacrylate, 20-25 parts of styrene, 2 parts of chitosan, 120-150 parts of glacial acetic acid,
200-500 parts of water, 5-8 parts of acrylic acid, 60-70 parts of acrylamide, 5-8 parts of sodium potassium tartrate tetrahydrate, 2-6 parts of initiator.
3. cationic rosin size emulsifier according to claim 1, which is characterized in that the weight average molecular weight of the chitosan
For 15-30 ten thousand, deacetylation 50-99%.
4. cationic rosin size emulsifier according to claim 1, which is characterized in that the initiator be potassium peroxydisulfate,
One kind in ammonium persulfate or sodium peroxydisulfate.
5. cationic rosin size emulsifier according to claim 1, which is characterized in that the cationic rosin size emulsifier
For light yellow transparent liquid, solid content 25-35wt%, pH 3-5, the viscosity at 25 DEG C is 15-60 centipoises.
6. the preparation method of cationic rosin size emulsifier as described in any one in claim 1-5, including step：
Under protective gas atmosphere, by dimethylaminoethyl methacrylate, styrene, chitosan, glacial acetic acid, water, propylene
Acid, acrylamide and sodium potassium tartrate tetrahydrate are uniformly mixed, and obtain mixed liquor；Initiator is added, 70-90 DEG C is stirred to react 1-5h, obtains instead
Answer liquid；Water is added, 85-110 DEG C of distillation 0.5-3h adds water and adjust solid content, obtain size emulsion agent.
7. the preparation method of cationic rosin size emulsifier according to claim 6, which is characterized in that the protective gas
Quality be dimethylaminoethyl methacrylate, styrene, chitosan, glacial acetic acid, water, acrylic acid, acrylamide, winestone
The 1-3% of sour potassium sodium and initiator raw material gross mass.
8. the preparation method of cationic rosin size emulsifier according to claim 6, which is characterized in that the mixed liquor temperature
When degree is 40-60 DEG C, the 50-70% of initiator gross mass is added, 0.5-3h is stirred to react in 70-90 DEG C；Then it adds surplus
Remaining initiator, the reaction was continued 0.5-2h.
9. the preparation method of cationic rosin size emulsifier according to claim 6, which is characterized in that the stir speed (S.S.)
It is 150-190 revs/min.
10. the preparation method of cationic rosin size emulsifier according to claim 6, which is characterized in that described to add water
Solid content to system is 25-40wt%.
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Cited By (4)
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| CN111118948A (en) * | 2019-12-25 | 2020-05-08 | 上海东升新材料有限公司 | Cationic rosin size and preparation method thereof |
| CN114573755A (en) * | 2022-05-05 | 2022-06-03 | 山东奥赛新材料有限公司 | Preparation method of cationic emulsifier for rosin size |
| CN115746201A (en) * | 2022-11-30 | 2023-03-07 | 上海昶法新材料有限公司 | Synthesis method of chlorine-free cationic rosin size emulsifier |
| CN115746201B (en) * | 2022-11-30 | 2024-05-10 | 上海昶法新材料有限公司 | Synthetic method of chlorine-free cationic rosin size emulsifier |
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| 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 |
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| US5853542A (en) * | 1995-09-11 | 1998-12-29 | Hercules Incorporated | Method of sizing paper using a sizing agent and a polymeric enhancer and paper produced thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111118948A (en) * | 2019-12-25 | 2020-05-08 | 上海东升新材料有限公司 | Cationic rosin size and preparation method thereof |
| CN114573755A (en) * | 2022-05-05 | 2022-06-03 | 山东奥赛新材料有限公司 | Preparation method of cationic emulsifier for rosin size |
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| CN115746201A (en) * | 2022-11-30 | 2023-03-07 | 上海昶法新材料有限公司 | Synthesis method of chlorine-free cationic rosin size emulsifier |
| CN115746201B (en) * | 2022-11-30 | 2024-05-10 | 上海昶法新材料有限公司 | Synthetic method of chlorine-free cationic rosin size emulsifier |
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| CN108396589B (en) | 2020-09-04 |
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