CN105801767A - Preparing method for paint rheolytic moisture holding regulator - Google Patents
Preparing method for paint rheolytic moisture holding regulator Download PDFInfo
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- CN105801767A CN105801767A CN201610190085.3A CN201610190085A CN105801767A CN 105801767 A CN105801767 A CN 105801767A CN 201610190085 A CN201610190085 A CN 201610190085A CN 105801767 A CN105801767 A CN 105801767A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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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
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Paper (AREA)
Abstract
The invention belongs to the field of papermaking additives and relates to a regulator, in particular to a preparing method for a paint rheolytic moisture holding regulator.According to the rheolytic moisture holding regulator related in the method, hydrophobic groups are introduced on molecules of a common polymer and are associated, and meanwhile the hydrophobic groups can also adsorb emulsion particles and pigment particles.A net structure formed by associating the molecules is firm, and good paint thickening and moisture holding performance is achieved.
Description
Technical field
The invention belongs to paper making additive field, relate to regulator, the preparation method particularly relating to a kind of coating rheology water conservation regulator.
Background technology
Water-retaining property is an important key property of coating, and coating behavior in service is had important impact.The coating that water-retaining property is bad, the moisture in coating is too fast to body paper transfer, and under pressure, moisture is easy to discharge from coating, and this causes that coating filter cake solidified with regard to fast thickening before entering scraper nip, thus causing that serious scratch phenomenon occurs；Adhesive in coating also moves in body paper with the absorption of water, thus reducing the surface strength of coating, causes the coating paper dry linting when printing and delamination problems, and when body paper absorbability and air permeability are bigger, this problem can be more serious.
Water-retaining agent can control water-retaining property and the rheological characteristic of coating, and the performability of coating, coating weight control and the optical-mechanical performance etc. becoming paper are all played an important role by this.Water-retaining agent can improve the water retention property of coating, controls the fluidity of free water in coating, reduces the migration to base paper, facilitate coating to be evenly distributed, and high-solid-content paint is even more important by this.
CMC is as thickening water-retaining agent, and paper industry obtains and applies earlier at home, and CMC forms network structure by the absorption in surface of pigments in coating, thus improving painting work performability and coating water retention.But CMC also shows that weak point as water-retaining agent.It is mainly manifested in:
Also interacting between 1.CMC and styrene-butadiene latex, this effect is easily caused the generation of flocculation, reduces the stability of latex；
The water retention property of 2.CMC is extremely sensitive to ambient temperature, and the water retention property containing CMC coating, with the rising of temperature and dramatic decrease, is unfavorable for the stability that coatings operates；
3.CMC is as promoting limited for water-retaining agent to coating water retention；
4.CMC chance Ca salt does not precipitate but can cause coating viscosity reduction, and meeting the heavy metal salts such as aluminum, ferrum, silver can precipitate；
5.CMC viscosity is significantly high, to the thickening power of coating it is also obvious that the operation viscosity of coating is wayward；
When 6.CMC boils, CMC contacts with water, and local easily expands in bulk, and becomes gelatinous-like masses, need to ensure that sufficient swollen dissolves during a large amount of preparation.
So novel coating for paper thickening stream becomes water conservation system and arises at the historic moment with regard to this, to adapt to the requirement of coating technique development, but the performance of more existing water conservation regulators less ideal, and its key is exactly in its production method.
Summary of the invention
The problem that the present invention is directed to above-mentioned water conservation regulator, the preparation method devising a kind of coating rheology water conservation regulator.
In order to achieve the above object, the technical solution used in the present invention is, the preparation method that the present invention devises a kind of coating rheology water conservation regulator, is made up of the material of following mass parts,
Hydrophilic monomer+hydrophobic monomer 100 parts
Surfactant 5-15 part
Initiator 0.01-0.05 part
Cross-linking agent 0.01-0.05 part
Emulsifying agent 0.1-0.8 part
250 parts of water
Wherein:
With the weight of monomer mixture for 100%, described hydrophilic monomer accounts for 30 ~ 60%, and hydrophobic monomer accounts for 40 ~ 70%.
Specifically include following steps:
A, add water, emulsifying agent, cross-linking agent in a kettle., stir；
B, addition monomer mixture, stirring, pre-emulsion is prepared when 40 ~ 50 DEG C；
C, adding water, emulsifying agent in a kettle., stir, be warming up between 75 ~ 85 DEG C under 40 ~ 50 DEG C of conditions, dropping part pre-emulsion and initiator solution, time for adding is 30min, is added dropwise to complete follow-up continuation of insurance temperature and reacts 30min again, prepares seed emulsion；
D, reactor seed emulsion in add surfactant, stirring is warming up to 70 ~ 80 DEG C, the remaining pre-emulsion of dropping and initiator solution, and time for adding is 30min, after being added dropwise to complete, insulation reaction 1 ~ 3h；
E, it is cooled to room temperature, filters and prepare finished product.
As preferably, described hydrophilic monomer is made up of acrylic acid, methacrylic acid and itaconic acid, described acrylic acid: methacrylic acid: itaconic acid is 5:4:1.
As preferably, described hydrophobic monomer is one or more of butyl acrylate, hydroxyethyl methylacrylate, methyl methacrylate, 2-methyl methacrylate and ethyl 2-methacrylate.
As preferably, described surfactant is the modified function monomer containing hydrophobic group, and described modified function monomer is docosyl polyoxyethylenated alcohol methacrylate.
As preferably, described initiator is Ammonium persulfate..
As preferably, described cross-linking agent is diallyl phthalate.
As preferably, described emulsifying agent is methacrylic acid hydroxide sodium dimercaptosulphanatein.
Compared with prior art, advantages of the present invention and good effect are in that,
The stream mentioned in the present invention becomes water conservation regulator and introduces hydrophobic group on the molecule of plain edition polymer, associate between these hydrophobic groups, meanwhile, hydrophobic group can also adsorb emulsion particle and granules of pigments, the network structure ratio that this molecular association is formed is stronger, has good coating thickening water retention property.
Below from structure, the mechanism of action, on the comparison of coating property and the advantage affecting four aspects specifically once present invention on paper performance.
1, structure comparison
With a large amount of carboxyls in products molecule chain of the present invention, be a class with hydrophilic polymer be key, become water conservation regulator at end or side chain with the parental type stream of hydrophobic group.Hydrophobic group and other particles, by associating and adsorption, form the association network structure with big hydrodynamic volume, are connected to different continuous phase or dispersion particle；It is connected to the aqueous solution in system and other auxiliary agents further through hydrogen bond action, had both enhanced low sheraing structural viscosity, improved the water retention property of coating, and changed again the flow behavior of coating；This network structure can be destroyed under the impact of high shear force and produce shear thinning phenomenon, reduces high sheared apparent viscosity, makes high-speed coating have more excellent operability.Traditional water-retaining agent adds in coating, mainly through mutually associating between carboxylic group and pigment particles, latex particle, it is achieved the thickening water conservation to coating.
The structure difference of table 1 present invention and tradition water-retaining agent
2, the mechanism of action compares
Stream becomes the stream change water conservation mechanism of water conservation regulator and is broadly divided into four parts: volumetric expansion effect, strand winding effect, association, adsorption by hydrogen bond effect.
(1) volumetric expansion effect
Resultant current become water conservation regulator by alkali and after, due to the repulsive interaction of ion, result in the stretching, extension of the expansion of polymer and structure.Swollen by the heavy polymer of aquation, occupies the space of solution, result in the rising of solution viscosity.
(2) strand winding effect
Along with the rising of polymer concentration, there occurs the physical entanglement between polymer molecular chain, which enhance stream and become water retaining efficiency.
(3) association
Can mutually associate between hydrophobic group on polymer, thus causing the raising of viscosity.These hydrophobic group are equally possible to be produced to associate with the latex particle in coating, surfactant and pigment particles, thus improving viscosity.
(4) adsorption by hydrogen bond effect
Hydrogen bonded effect can occur to become between water conservation regulator and solution at stream, it is also possible to occurs to become between water conservation regulator and additive at stream.Stream becomes water conservation regulator molecule can also be adsorbed on surface of pigments by hydrogen bonded, so all further increases the water retention property of coating.
Table 2 present invention compares with the mechanism of action of tradition water-retaining agent
3, the impact on coating property
(1) high and low shear viscosity range of accommodation widely；
Can load by flexible coating machine scraper, improve the runnability of coating machine；
(2) water retention value range of accommodation widely；
Promote coating rheology water retention property, improve coating service ability；
(3) thickening efficiency is high；
Thickening effect is that (such as CMC) 3 times, consumption is the 1/3 of CMC or less to tradition thickening agent, has good economy；
(4) coating solids is improved；
CMC thickening efficiency is low, and addition is big.Due to the solid content of CMC steaming and decocting in advance to 11%, therefore cause that the solid content of whole coating cannot raise.Using product of the present invention instead, owing to thickening efficiency is high, addition is few, it is possible to improve coating solids.
4, the impact on paper performance
Improve the quality of paper, such as performances such as better smoothness, glossiness, coating covering and less coating infiltrations；Reduce adhesive to migrate, improve paper printing uniformity；Trace problem is scraped in the coating solving to occur in scraper for coating.
Except above-mentioned four aspects, also having some other advantage, concrete advantage is as follows:
(1) liquid, directly adds, easy to use, saves equipment investment and preparation expense；And CMC needs steaming and decocting in advance, increase equipment investment；
(2) there is microbial stability, it is not necessary to antibacterial；
(3) good stability；
(4) there is good rheological characteristic and resistance to settling, and reduce syneresis, it is possible to be compatible with organic or inorganic pigment.
In sum, product of the present invention compares learn with tradition water-retaining agent:
(1) make the viscosity/rheology that coating reaches to need to meet feeding (scraper, roll-type, spraying), storage and the characteristic suspended.
(2) improved paper quality, can be had the performances such as the covering of better smoothness, glossiness, coating and less coating infiltration.
(3) coating property can be improved；Such as improve water-retaining property, and coating evaporation rate, coating set speed, coating layer thickness etc..
(4) reduce binder migration, improve printing uniformity.
(5) present invention is used can also to reduce cost (liquid replaces expensive raw material).
Detailed description of the invention
In order to be more clearly understood that the above-mentioned purpose of the present invention, feature and advantage, below in conjunction with embodiment, the present invention will be further described.It should be noted that when not conflicting, embodiments herein and the feature in embodiment can be mutually combined.
Elaborate a lot of detail in the following description so that fully understanding the present invention, but, the present invention can also adopt and be different from other modes described here and implement, and therefore, the present invention is not limited to the restriction of the specific embodiment of description described below.
The outstanding feature of the present invention is described in the concrete application two in coating from the concrete preparation method of coating rheology water conservation regulator and the coating rheology water conservation regulator prepared by the preparation method the present invention below.
One, coating rheology water conservation regulator preparation method
Embodiment 1
Hydrophilic monomer+hydrophobic monomer 100 parts
8 parts of surfactant
Initiator 0.01 part
Cross-linking agent 0.01 part
Emulsifying agent 0.1 part
250 parts of water
Wherein:
With the weight of monomer mixture for 100%, described hydrophilic monomer accounts for 30%, and hydrophobic monomer accounts for 70%.
Hydrophilic monomer: acrylic acid: methacrylic acid: itaconic acid is 5:4:1；
Hydrophobic monomer: one or more of butyl acrylate, hydroxyethyl methylacrylate, methyl methacrylate, 2-methyl methacrylate and ethyl 2-methacrylate；
Surfactant: the modified function monomer containing hydrophobic group, docosyl polyoxyethylenated alcohol methacrylate；
Initiator: Ammonium persulfate.
Cross-linking agent: diallyl phthalate
Emulsifying agent: methacrylic acid hydroxide sodium dimercaptosulphanatein
Specifically include following steps:
A, add water, emulsifying agent, cross-linking agent in a kettle., stir；
B, addition monomer mixture, stirring, pre-emulsion is prepared when 40 DEG C；
C, adding water, emulsifying agent in a kettle., stir, be warming up between 85 DEG C under 40 DEG C of conditions, dropping part pre-emulsion and initiator solution, time for adding is 30min, is added dropwise to complete follow-up continuation of insurance temperature and reacts 30min again, prepares seed emulsion；
D, reactor seed emulsion in add surfactant, stirring is warming up to 75 DEG C, the remaining pre-emulsion of dropping and initiator solution, and time for adding is 30min, after being added dropwise to complete, insulation reaction 2h；
E, it is cooled to room temperature, filters and prepare finished product.
Embodiment 2
Hydrophilic monomer+hydrophobic monomer 100 parts
12 parts of surfactant
Initiator 0.02 part
Cross-linking agent 0.02 part
Emulsifying agent 0.2 part
250 parts of water
Wherein:
With the weight of monomer mixture for 100%, described hydrophilic monomer accounts for 50%, and hydrophobic monomer accounts for 50%.
Hydrophilic monomer: acrylic acid: methacrylic acid: itaconic acid is 5:4:1；
Hydrophobic monomer: one or more of butyl acrylate, hydroxyethyl methylacrylate, methyl methacrylate, 2-methyl methacrylate and ethyl 2-methacrylate；
Surfactant: the modified function monomer containing hydrophobic group, docosyl polyoxyethylenated alcohol methacrylate；
Initiator: Ammonium persulfate.
Cross-linking agent: diallyl phthalate
Emulsifying agent: methacrylic acid hydroxide sodium dimercaptosulphanatein
Specifically include following steps:
A, add water, emulsifying agent, cross-linking agent in a kettle., stir；
B, addition monomer mixture, stirring, pre-emulsion is prepared when 45 DEG C；
C, adding water, emulsifying agent in a kettle., stir, be warming up between 85 DEG C under 45 DEG C of conditions, dropping part pre-emulsion and initiator solution, time for adding is 30min, is added dropwise to complete follow-up continuation of insurance temperature and reacts 30min again, prepares seed emulsion；
D, reactor seed emulsion in add surfactant, stirring is warming up to 80 DEG C, the remaining pre-emulsion of dropping and initiator solution, and time for adding is 30min, after being added dropwise to complete, insulation reaction 2h；
E, it is cooled to room temperature, filters and prepare finished product.
Embodiment 3
Hydrophilic monomer+hydrophobic monomer 100 parts
15 parts of surfactant
Initiator 0.04 part
Cross-linking agent 0.04 part
Emulsifying agent 0.3 part
250 parts of water
Wherein:
With the weight of monomer mixture for 100%, described hydrophilic monomer accounts for 60%, and hydrophobic monomer accounts for 40%.
Hydrophilic monomer: acrylic acid: methacrylic acid: itaconic acid is 5:4:1；
Hydrophobic monomer: one or more of butyl acrylate, hydroxyethyl methylacrylate, methyl methacrylate, 2-methyl methacrylate and ethyl 2-methacrylate；
Surfactant: the modified function monomer containing hydrophobic group, docosyl polyoxyethylenated alcohol methacrylate；
Initiator: Ammonium persulfate.
Cross-linking agent: diallyl phthalate
Emulsifying agent: methacrylic acid hydroxide sodium dimercaptosulphanatein
Specifically include following steps:
A, add water, emulsifying agent, cross-linking agent in a kettle., stir；
B, addition monomer mixture, stirring, pre-emulsion is prepared when 50 DEG C；
C, adding water, emulsifying agent in a kettle., stir, be warming up between 80 DEG C under 50 DEG C of conditions, dropping part pre-emulsion and initiator solution, time for adding is 30min, is added dropwise to complete follow-up continuation of insurance temperature and reacts 30min again, prepares seed emulsion；
D, reactor seed emulsion in add surfactant, stirring is warming up to 80 DEG C, the remaining pre-emulsion of dropping and initiator solution, and time for adding is 30min, after being added dropwise to complete, insulation reaction 2h；
E, it is cooled to room temperature, filters and prepare finished product.
It is as shown in the table that stream prepared by embodiment becomes water conservation regulator performance indications
Two, the coating rheology water conservation regulator concrete application test in coating
According to following table, formulation for coating material carries out coating.
China clay is first dispersed into emulsion, and solid content is 70%；Dispersant dosage is the 0.05% of china clay oven-dry weight, and high speed dispersion 10 minutes also keeps the stirring whirlpool of certain depth；China clay is mixed with the calcium carbonate emulsion that solid content is 75%, high speed dispersion 5 minutes；The over dry ratio of china clay and calcium carbonate is 15:85；Add carboxylic styrene butadiene latex；And it is fully dispersed；The addition of latex: over dry pigment 10%；Add other auxiliary agents, be stirred mixing under the low speed, use 10% sodium hydrate aqueous solution to be regulated between 8 ~ 9 by the pH value of coating, be eventually adding suitable quantity of water by solid for coating containing being adjusted to 68%；Design two groups of experiments and become the performance of water conservation regulator to compare this stream.
It is different that coating 1 is distinctive in that with coating 2 stream becomes water conservation regulator, and in coating 1, water-retaining agent agent is carboxymethyl cellulose, and it is embodiment product that the stream in coating 2 becomes water conservation regulator.
Note: calcium carbonate and china clay totally 100 parts, all the other chemicals are relative to 100 parts of over dry pigment.It is 8～9 that stream becomes the pH value adjusting product system before water conservation regulator adds, and dilutes by the ratios with water of 1:2, under stirring at low speed, is slowly added to the product after dilution.
2, coating property test
The coating 1 using tradition water-retaining agent preparation is identical with coating other formula of 2(coating of embodiment product configuration) performance indications contrast, as shown in the table:
Can be seen that from list data, stream becomes under the water conservation regulator addition consumption into tradition water-retaining agent 1/3, and product of the present invention has a good thickening effect, and flows change water conservation regulator and form network structure in coating, reduce the flowing of water in coating to a certain extent, improve coating water retention energy.
3. Paper Coating test
Bodystock paper is lain on coating machine, take appropriate coating on art base paper, carry out primary coat, the coating of topcoating twice.Coating weight is 12g/m2.Coated paper is put into ripening 20min in 105 DEG C of baking ovens, then paper is carried out press polish.Equilibrium water conten 24h in climatic chamber put into by paper after press polish.
4. paper performance test
Pattern is detected, and index is as shown in the table:
List data can improve the uniformity of coating it can be seen that stream becomes water conservation regulator, improves paper covering performance and glossiness.The glossiness and the smoothness that become paper increase, and the surface strength of one-tenth paper is constant or slightly improves.
The above; it it is only presently preferred embodiments of the present invention; it is not the restriction that the present invention is made other form; the Equivalent embodiments that any those skilled in the art were changed or be modified as equivalent variations possibly also with the technology contents of the disclosure above is applied to other field; but it is every without departing from technical solution of the present invention content; according to any simple modification, equivalent variations and remodeling that above example is made by the technical spirit of the present invention, still fall within the protection domain of technical solution of the present invention.
Claims (7)
1. the preparation method of a coating rheology water conservation regulator, it is characterised in that be made up of the material of following mass parts:
Hydrophilic monomer+hydrophobic monomer 100 parts
Surfactant 5-15 part
Initiator 0.01-0.05 part
Cross-linking agent 0.01-0.05 part
Emulsifying agent 0.1-0.8 part
250 parts of water
Wherein:
With the weight of monomer mixture for 100%, described hydrophilic monomer accounts for 30 ~ 60%, and hydrophobic monomer accounts for 40 ~ 70%；
Specifically include following steps:
A, add water, emulsifying agent, cross-linking agent in a kettle., stir；
B, addition monomer mixture, stirring, pre-emulsion is prepared when 40 ~ 50 DEG C；
C, adding water, emulsifying agent in a kettle., stir, be warming up between 75 ~ 85 DEG C under 40 ~ 50 DEG C of conditions, dropping part pre-emulsion and initiator solution, time for adding is 30min, is added dropwise to complete follow-up continuation of insurance temperature and reacts 30min again, prepares seed emulsion；
D, reactor seed emulsion in add surfactant, stirring is warming up to 70 ~ 80 DEG C, the remaining pre-emulsion of dropping and initiator solution, and time for adding is 30min, after being added dropwise to complete, insulation reaction 1 ~ 3h；
E, it is cooled to room temperature, filters and prepare finished product.
2. the preparation method of a kind of coating rheology water conservation regulator according to claim 1, it is characterised in that described hydrophilic monomer is made up of acrylic acid, methacrylic acid and itaconic acid, described acrylic acid: methacrylic acid: itaconic acid is 5:4:1.
3. the preparation method of a kind of coating rheology water conservation regulator according to claim 2, it is characterized in that, described hydrophobic monomer is one or more of butyl acrylate, hydroxyethyl methylacrylate, methyl methacrylate, 2-methyl methacrylate and ethyl 2-methacrylate.
4. the preparation method of a kind of coating rheology water conservation regulator according to claim 3, it is characterized in that, described surfactant is the modified function monomer containing hydrophobic group, and described modified function monomer is docosyl polyoxyethylenated alcohol methacrylate.
5. the preparation method of a kind of coating rheology water conservation regulator according to claim 4, it is characterised in that described initiator is Ammonium persulfate..
6. the preparation method of a kind of coating rheology water conservation regulator according to claim 5, it is characterised in that described cross-linking agent is diallyl phthalate.
7. the preparation method of a kind of coating rheology water conservation regulator according to claim 6, it is characterised in that described emulsifying agent is methacrylic acid hydroxide sodium dimercaptosulphanatein.
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| CN201610190085.3A CN105801767A (en) | 2016-03-30 | 2016-03-30 | Preparing method for paint rheolytic moisture holding regulator |
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| CN201610190085.3A CN105801767A (en) | 2016-03-30 | 2016-03-30 | Preparing method for paint rheolytic moisture holding regulator |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101787231A (en) * | 2010-01-27 | 2010-07-28 | 济南大学 | Hydrophobic modified associative thickener and preparation method thereof |
| CN102492103A (en) * | 2011-12-07 | 2012-06-13 | 深圳市瑞成科讯实业有限公司 | Tackifying polymer and preparation method thereof |
| CN102558936A (en) * | 2011-12-23 | 2012-07-11 | 深圳市瑞成科讯实业有限公司 | Thickener system and preparation method of thickener |
| CN102675951A (en) * | 2012-05-22 | 2012-09-19 | 济南大学 | Water-repellent modified association thickening agent and preparation method thereof |
| CN103980441A (en) * | 2014-05-19 | 2014-08-13 | 上海正欧实业有限公司 | Associated thickening agent generated by rheologic and modified monomer and preparation method of associated thickening agent |
-
2016
- 2016-03-30 CN CN201610190085.3A patent/CN105801767A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101787231A (en) * | 2010-01-27 | 2010-07-28 | 济南大学 | Hydrophobic modified associative thickener and preparation method thereof |
| CN102492103A (en) * | 2011-12-07 | 2012-06-13 | 深圳市瑞成科讯实业有限公司 | Tackifying polymer and preparation method thereof |
| CN102558936A (en) * | 2011-12-23 | 2012-07-11 | 深圳市瑞成科讯实业有限公司 | Thickener system and preparation method of thickener |
| CN102675951A (en) * | 2012-05-22 | 2012-09-19 | 济南大学 | Water-repellent modified association thickening agent and preparation method thereof |
| CN103980441A (en) * | 2014-05-19 | 2014-08-13 | 上海正欧实业有限公司 | Associated thickening agent generated by rheologic and modified monomer and preparation method of associated thickening agent |
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