CN102174780B - Self-emulsifying alkenyl succinic anhydride sizing agent and preparation method thereof - Google Patents
Self-emulsifying alkenyl succinic anhydride sizing agent and preparation method thereof Download PDFInfo
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- CN102174780B CN102174780B CN 201110061783 CN201110061783A CN102174780B CN 102174780 B CN102174780 B CN 102174780B CN 201110061783 CN201110061783 CN 201110061783 CN 201110061783 A CN201110061783 A CN 201110061783A CN 102174780 B CN102174780 B CN 102174780B
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Abstract
The invention relates to a sizing agent in the paper making field, in particular to a self-emulsifying alkenyl succinic anhydride sizing agent and a preparation method thereof; the self-emulsification alkenyl succinic anhydride sizing agent comprises nanometer titanium dioxide and alkenyl succinic anhydride. The nanometer titanium dioxide is hydrophilic, the particle diameter is smaller than 100 nm and the water content is smaller than 1%. The weight ratio of the nanometer titanium dioxide to the alkenyl succinic anhydride is 1:(20-1000). The preparation method comprises the step of adding the nanometer titanium dioxide into the alkenyl succinic anhydride under a stirring condition, wherein stirring speed preferably is 50-1000 r/m and stirring time is 1-30 min. The invention has the advantages that the preparation method is simple, fewer stabilizing agents are consumed and no any surfactants are added; and the prepared alkenyl succinic anhydride sizing agent nearly has no water, therefore no hydrolysis is generated, the transportation and storage are convenient, the onsite emulsifying and internal sizing are convenient, and the sizing efficiency is high.
Description
Technical field
The present invention relates to the sizing agent in the field of papermaking, be specifically related to a kind of self-emulsifying type alkenyl succinic anhydride sizing agent, also relate to its preparation method.
Background technology
Alkenyl succinic anhydride (being called for short ASA) is a kind of papermaking neutral sizing agent commonly used, have reactivity height, applying glue pH value scope wide, with alkaline filler and advantages such as aluminium salt compatibility is good, paper strength height, be applicable to that various paper and cardboard especially need in the machine slaking and contain the high yield pulp of a large amount of anion chaff interferences and the applying glue of paper that secondary stock is manufactured paper with pulp and cardboard.Yet alkenyl succinic anhydride is met the water electrode facile hydrolysis, and its hydrolysate not only reduces the applying glue efficient of alkenyl succinic anhydride, also forms problems such as deposition easily, influences the normal operation of paper machine.Therefore, alkenyl succinic anhydride need be in the on-the-spot emulsification of applying glue, and emulsion should be used as early as possible.Mainly be to utilize cationic starch and low-molecular-weight surfactant that alkenyl succinic anhydride is carried out emulsification at present.Yet, the starch consumption is big, need to re-use after first gelatinization, the cooling, the emulsifying process complexity, operating technology to the workman is had relatively high expectations, and surfactant also brings certain adverse effect to applying glue, as causes bubble-related issues, reduction sizability etc., has influenced the extensive use of alkenyl succinic anhydride sizing agent.Though utilize synthetic polymer and other natural polysaccharides and derivative emulsification alkenyl succinic anhydride thereof can exempt gelatinization and process for cooling, but still have that the emulsifying agent consumption is big, needs are synthetic with prepare deficiencies such as emulsifier special and prepared alkenyl succinic anhydride emulsion valid density are low.Reported to utilize to have the method for surface-active synthetic high polymer emulsifying agent emulsification alkenyl succinic anhydride as " Chinese papermaking " the 1st phase in 2007 article of the 11st page, but the mass ratio that needs at least to reach with alkenyl succinic anhydride is the amount of 1:1, could obtain the alkenyl succinic anhydride emulsion of suitable applying glue efficient; The 22nd page of " Chinese paper industry " the 4th phase in 2009 reported the technology of utilizing benzene emulsion copolymer emulsification alkenyl succinic anhydride, the mass fraction of emulsifying agent can be down to 20%, but need adapted retention agent and stabilizing agent could obtain to stablize preferably and sizing efficiency.
US Patent No. 6284099 has disclosed a kind of method of utilizing bentonite, cataloid and low quantity of surfactant to stablize alkenyl succinic anhydride emulsion, has reduced the consumption of surfactant.Publication number is that the Chinese patent of CN 101333789 discloses a kind of bentonite and hydrotalcite of utilizing and unites use, the method that is used for emulsification and stable alkenyl succinic anhydride, this emulsifying process can avoid using surfactant and fully thus to the adverse effect of alkenyl succinic anhydride applying glue, and can prepare the higher alkenyl succinic anhydride emulsion of effective content.China Patent No. is that 200910020447.4 patent of invention has disclosed a kind of method of utilizing montmorillonite/shitosan/ammoniacal liquor to stablize alkenyl succinic anhydride emulsion, and gained emulsion liquid-drop diameter is little, applying glue efficient height.Yet, these solia particles of stablizing alkenyl succinic anhydride emulsion all have higher hydrophily, need could to obtain stable emulsion by means of other assistants emulsification together/stablize alkenyl succinic anhydride, therefore, the emulsification of alkenyl succinic anhydride still needs higher technology.
US Patent No. 4040900 has disclosed a kind of mode of utilizing the direct emulsification alkenyl succinic anhydride of moisture in the slurry: in advance the basic ether of emulsifying agent polyethylene glycol oxide alkane (virtue) is directly mixed with alkenyl succinic anhydride, directly add mixture in the slurry again, utilize the slurry mixing device with the direct emulsification of alkenyl succinic anhydride, avoided the caused hydrolysis of preparation alkenyl succinic anhydride emulsion fully, but still use the exhibiting high surface activating agent as emulsifying agent, and the size components instability need be mixed emulsifying agent with alkenyl succinic anhydride at the scene.US Patent No. 6444024 has disclosed a kind of preparation method of moisture free alkenyl succinic anhydride sizing agent, this method is to utilize alpha-olefin and α, the copolymer of β-unsaturated dicarboxylic or derivatives thereof is as emulsifying agent, with the alkenyl succinic anhydride blend and 80 ℃ of maintenances at least 2 hours, obtain water-free paper-making sizing component, this size components just can obtain alkenyl succinic anhydride emulsion type sizing agent before use directly with water and milkization.This alkenyl succinic anhydride sizing agent has farthest been simplified the on-the-spot emulsifying technology of alkenyl succinic anhydride, but needs the special-purpose emulsifying agent of preparation, and emulsifying agent need heat with mixing of alkenyl succinic anhydride and carries out.
Summary of the invention
The present invention is directed to the deficiency of existing alkenyl succinic anhydride emulsifying technology and sizing agent component, provide a kind of nano-titania particle that utilizes as the self-emulsifying type alkenyl succinic anhydride sizing agent of stabilizing agent, this sizing agent does not contain surfactant, preparation is simple, convenient, both joined in the paper stock after the dilutable water emulsification, carry out plasm-glue-blending, can directly join in the paper stock again, after utilizing the direct emulsification of moisture in the paper stock, carry out plasm-glue-blending, can farthest reduce the hydrolysis of alkenyl succinic anhydride, improve the applying glue efficient of alkenyl succinic anhydride.
The present invention is achieved by the following technical solutions:
Nano titanium oxide is distributed in the alkenyl succinic anhydride, and agitation as appropriate obtains self-emulsifying type alkenyl succinic anhydride sizing agent.This self-emulsifying type alkenyl succinic anhydride sizing agent is under agitation mixed with a certain amount of water, can obtain stable alkenyl succinic anhydride emulsion sizing agent, be used for the plasm-glue-blending of paper; This self-emulsifying type alkenyl succinic anhydride sizing agent also can under agitation directly be added in the paper stock, directly carries out plasm-glue-blending.
Alkenyl succinic anhydride involved in the present invention is the various alkenyl succinic anhydride industrial products for paper-making sizing without emulsification that exist with liquid form under the normal temperature, in order to improve applying glue efficient, preferably do not add the alkenyl succinic anhydride industrial products of surfactant.
Nano titanium oxide involved in the present invention refer to any primary particle sizes less than 100 nm and moisture less than 1% synthesis of nano titania powder, comprise various industrial nano titanium dioxide products.As emulsification and the stabilizing agent in the self-emulsifying type alkenyl succinic anhydride sizing agent, generally to control in the scope of 1:20～1000 with the part by weight of alkenyl succinic anhydride, preferred proportion is 1:50～250.
Self-emulsifying type alkenyl succinic anhydride sizing agent involved in the present invention prepares in the scheme, agitation as appropriate refers to make the agitaion that nano titanium oxide is dispersed in to be provided in the liquid alkenyl succinic anhydride, can be provided by any stirring and shearing equipment, general 50 ~ 1000 rev/mins of mixing speed, mixing time 1～30 minute.
In the emulsification scheme of self-emulsifying type alkenyl succinic anhydride sizing agent involved in the present invention, self-emulsifying type alkenyl succinic anhydride sizing agent is under agitation mixed with a certain amount of water, but both under agitation water was added in the self-emulsifying type alkenyl succinic anhydride sizing agent, also can be under agitation self-emulsifying type alkenyl succinic anhydride sizing agent to be added in the water, but preferred scheme be that water is added in the self-emulsifying type alkenyl succinic anhydride sizing agent.The part by weight of wherein controlling the agent of self-emulsifying type alkenyl succinic anhydride and water is 1:1～50, and preferred ratio is 1:2～10.Related mechanical agitation can be provided by any stirring and shearing equipment, general 500 ~ 10000 rev/mins of mixing speed, mixing time 2～20 minutes.
In the emulsification scheme of self-emulsifying type alkenyl succinic anhydride sizing agent involved in the present invention, under agitation directly be added in the paper stock self-emulsifying type alkenyl succinic anhydride sizing agent, referring to self-emulsifying type alkenyl succinic anhydride sizing agent is added to provide the equipment entrance of certain mechanical shearing effect place, as before being added to pressurized screen, the porch of fan pump porch and head box pulp distributor etc.
The invention has the beneficial effects as follows: preparation technology is simple, stabilizing agent dosage is few, do not need to add any surfactant, almost there is not moisture in the prepared self-emulsifying type alkenyl succinic anhydride sizing agent, thereby hydrolysis can not take place, transportation and storage are convenient, and on-the-spot emulsification and plasm-glue-blending are convenient, applying glue efficient height.
The specific embodiment
The invention will be further described below in conjunction with specific embodiment, do not constitute any limitation of the invention.Except other indicates, all umbers among the embodiment are all in weight portion.
Embodiment 1
With 0.1 part of commodity nano titanium oxide (primary particle diameter 18 nm, anatase, hydrophilic, moisture is less than 1%) under 50 rev/mins stirring, be distributed in 100 parts of commodity alkenyl succinic anhydrides that do not contain surfactant of oily, stirred 30 minutes, and obtained self-emulsifying type alkenyl succinic anhydride sizing agent; Get 100 parts of deionized waters under 5000 rev/mins mixing speed, in the above-mentioned 100 parts of self-emulsifying type alkenyl succinic anhydride sizing agents of disposable adding, stirred 5 minutes, obtain solid content and be about 50% alkenyl succinic anhydride emulsion type sizing agent.
Get 100 parts of beating degrees and be about 42
oThe poplar BTMP of SR adds in 9900 parts of water, after defiberizing machine is discongested, adds 1 part of above-mentioned sizing agent, mixes the back and forms paper stock, and copy the about 60g/m of formulation amount by quick kayser method sheet forming apparatus
2Handsheet, and behind 105 ℃ of dry 10min, utilizing liquid osmosis (GB/T5405-2002) to record the handsheet degree of sizing is 123s.
Embodiment 2
With 0.16 part of commodity nano titanium oxide (primary particle sizes 18 nm, anatase, hydrophilic) under 100 rev/mins stirring, be distributed in 100 parts of commodity alkenyl succinic anhydrides that do not contain surfactant of oily, stirred 25 minutes, and obtained self-emulsifying type alkenyl succinic anhydride sizing agent; Get 500 parts of deionized waters under 10000 rev/mins mixing speed, in the above-mentioned 100 parts of alkenyl succinic anhydride sizing agents of disposable adding, stirred 3 minutes, obtain solid content and be about 16.7% alkenyl succinic anhydride emulsion type sizing agent.
Get 100 parts of beating degrees and be about 42
oThe poplar BTMP of SR adds in 9900 parts of water, after defiberizing machine is discongested, adds 3 parts of above-mentioned sizing agents, mixes the back and forms paper stock, and copy the about 60g/m of formulation amount by quick kayser method sheet forming apparatus
2Handsheet, and behind 105 ℃ of dry 10min, utilizing liquid osmosis (GB/T5405-2002) to record the handsheet degree of sizing is 128s.
Embodiment 3
With 0.4 part of commodity nano titanium oxide (primary particle sizes 25nm, anatase: rutile ≈ 3:1, hydrophilic) under 250 rev/mins stirring, be distributed in 100 parts of commodity alkenyl succinic anhydrides that contain low quantity of surfactant of oily, stirred 20 minutes, and obtained self-emulsifying type alkenyl succinic anhydride sizing agent; Get 700 parts of deionized waters under 500 rev/mins mixing speed, in the above-mentioned 100 parts of self-emulsifying type alkenyl succinic anhydride sizing agents of disposable adding, stir 20 clocks, obtain solid content and be about 12.5% alkenyl succinic anhydride emulsion type sizing agent.
Get 100 parts of beating degrees and be about 42
oThe poplar BTMP of SR adds in 9900 parts of water, after defiberizing machine is discongested, adds 3 parts of above-mentioned sizing agents, mixes the back and forms paper stock, and copy the about 60g/m of formulation amount by quick kayser method sheet forming apparatus
2Handsheet, and behind 105 ℃ of dry 10min, utilizing liquid osmosis (GB/T5405-2002) to record the handsheet degree of sizing is 43s.
Embodiment 4
With 0.6 part of commodity nano titanium oxide (primary particle sizes 25nm, anatase: rutile ≈ 3:1, hydrophilic) under 300 rev/mins stirring, be distributed in 100 parts of commodity alkenyl succinic anhydrides that do not contain surfactant of oily, stirred 15 minutes, and obtained self-emulsifying type alkenyl succinic anhydride sizing agent; Get 400 parts of deionized waters under 1500 rev/mins mixing speed, in the above-mentioned 100 parts of self-emulsifying type alkenyl succinic anhydride sizing agents of disposable adding, stir 15 clocks, obtain solid content and be about 20% alkenyl succinic anhydride emulsion type sizing agent.
Get 100 parts of beating degrees and be about 42
oThe poplar BTMP of SR adds in 9900 parts of water, after defiberizing machine is discongested, adds 2 parts of above-mentioned sizing agents, mixes the back and forms paper stock, and copy the about 60g/m of formulation amount by quick kayser method sheet forming apparatus
2Handsheet, and behind 105 ℃ of dry 10min, utilizing liquid osmosis (GB/T5405-2002) to record the handsheet degree of sizing is 93s.
Embodiment 5
With 1 part of commodity nano titanium oxide (primary particle sizes 25 nm, rutile, hydrophilic) under 500 rev/mins stirring, be distributed in 99 parts of commodity alkenyl succinic anhydrides that do not contain surfactant of oily, stirred 15 minutes, and obtained self-emulsifying type alkenyl succinic anhydride sizing agent; Get 200 parts of deionized waters under 7500 rev/mins mixing speed, in the above-mentioned 100 parts of self-emulsifying type alkenyl succinic anhydride sizing agents of disposable adding, stirred 5 minutes, obtain solid content and be about 33.3% alkenyl succinic anhydride emulsion type sizing agent.
Get 100 parts of beating degrees and be about 42
oThe poplar BTMP of SR adds in 9900 parts of water, after defiberizing machine is discongested, adds 1 part of above-mentioned sizing agent, mixes the back and forms paper stock, and copy the about 60g/m of formulation amount by quick kayser method sheet forming apparatus
2Handsheet, and behind 105 ℃ of dry 10min, utilizing liquid osmosis (GB/T5405-2002) to record the handsheet degree of sizing is 55s.
Embodiment 6
With 2 parts of commodity nano titanium oxides (primary particle sizes 50 nm, anatase, hydrophilic)) under 750 rev/mins stirring, be distributed in 98 parts of commodity alkenyl succinic anhydrides that do not contain surfactant of oily, stirred 10 minutes, and obtained self-emulsifying type alkenyl succinic anhydride sizing agent; Get 2000 parts of deionized waters under 2000 rev/mins mixing speed, in the above-mentioned 100 parts of self-emulsifying type alkenyl succinic anhydride sizing agents of disposable adding, stir 10 clocks, obtain solid content and be about 5% alkenyl succinic anhydride emulsion type sizing agent.
Get 100 parts of beating degrees and be about 42
oThe poplar BTMP of SR adds in 9900 parts of water, after defiberizing machine is discongested, adds 8 parts of above-mentioned sizing agents, mixes the back and forms paper stock, and copy the about 60g/m of formulation amount by quick kayser method sheet forming apparatus
2Handsheet, and behind 105 ℃ of dry 10min, utilizing liquid osmosis (GB/T5405-2002) to record the handsheet degree of sizing is 93s.
Embodiment 7
With 2.5 parts of commodity nano titanium oxides (primary particle sizes 80 nm, anatase titanium dioxide) under 1000 rev/mins stirring, be distributed in 97.5 parts of commodity alkenyl succinic anhydrides that contain low quantity of surfactant of oily, stirred 1 minute, obtain self-emulsifying type alkenyl succinic anhydride sizing agent; Get 1000 parts of deionized waters under 8000 rev/mins mixing speed, in the above-mentioned 100 parts of self-emulsifying type alkenyl succinic anhydride sizing agents of disposable adding, stir 2 clocks, obtain solid content and be about 10% alkenyl succinic anhydride emulsion type sizing agent.
Get 100 parts of beating degrees and be about 42
oThe poplar BTMP of SR adds in 9900 parts of water, after defiberizing machine is discongested, adds 5 parts of above-mentioned sizing agents, mixes the back and forms paper stock, and copy the about 60g/m of formulation amount by quick kayser method sheet forming apparatus
2Handsheet, and behind 105 ℃ of dry 10min, utilizing liquid osmosis (GB/T5405-2002) to record the handsheet degree of sizing is 87s.
Embodiment 8
5 parts of commodity nano titanium oxides (P25) under 1000 rev/mins stirring, are distributed in 95 parts of commodity alkenyl succinic anhydrides that do not contain surfactant of oily, stirred 2 minutes, obtain self-emulsifying type alkenyl succinic anhydride sizing agent; Get 5000 parts of deionized waters under 10000 rev/mins mixing speed, in the above-mentioned 100 parts of self-emulsifying type alkenyl succinic anhydride sizing agents of disposable adding, stir 3 clocks, obtain solid content and be about 2% alkenyl succinic anhydride emulsion type sizing agent.
Get 100 parts of beating degrees and be about 42
oThe poplar BTMP of SR adds in 9900 parts of water, after defiberizing machine is discongested, adds 20 parts of above-mentioned sizing agents, mixes the back and forms paper stock, and copy the about 60g/m of formulation amount by quick kayser method sheet forming apparatus
2Handsheet, and behind 105 ℃ of dry 10min, utilizing liquid osmosis (GB/T5405-2002) to record the handsheet degree of sizing is 89s.
Embodiment 9
With 4 parts of commodity nano titanium oxide (primary particle sizes 25nm, anatase: rutile ≈ 3:1, hydrophilic) under 500 rev/mins stirring, is distributed in 96 parts of commodity alkenyl succinic anhydrides that do not contain surfactant of oily, stirred 10 minutes, and obtained self-emulsifying type alkenyl succinic anhydride sizing agent.
Get 100 parts and be about 42
oThe poplar BTMP of SR adds in 9900 parts of water, after defiberizing machine is discongested, add above-mentioned 0.5 part self-emulsifying type alkenyl succinic anhydride sizing agent, under 2000 rev/mins speed, stirred 10 minutes, mix with paper stock, and copy the about 60g/m of formulation amount by quick kayser method sheet forming apparatus
2Handsheet, and behind 105 ℃ of dry 10min, utilizing liquid osmosis (GB/T5405-2002) to record the handsheet degree of sizing is 104s.
Embodiment 10
With 3 parts of commodity nano titanium oxide (primary particle sizes 25nm, anatase: rutile ≈ 3:1, hydrophilic) under 750 rev/mins stirring, is distributed in 97 parts of commodity alkenyl succinic anhydrides that do not contain surfactant of oily, stirred 8 minutes, and obtained self-emulsifying type alkenyl succinic anhydride sizing agent.
Get 100 parts and be about 42
oThe poplar BTMP of SR adds in 900 parts of water, after defiberizing machine is discongested, add above-mentioned 0.5 part self-emulsifying type alkenyl succinic anhydride sizing agent, under 5000 rev/mins speed, stirred 5 minutes, mix with paper stock, add 9000 parts of water diluted slurries afterwards, and copy the about 60g/m of formulation amount by quick kayser method sheet forming apparatus
2Handsheet, and behind 105 ℃ of dry 10min, utilizing liquid osmosis (GB/T5405-2002) to record the handsheet degree of sizing is 129s.
Claims (8)
1. a self-emulsifying type alkenyl succinic anhydride sizing agent is characterized in that being made up of nano titanium oxide and alkenyl succinic anhydride, and the weight ratio of nano titanium oxide and alkenyl succinic anhydride is 1:20～1000.
2. self-emulsifying type alkenyl succinic anhydride sizing agent according to claim 1 is characterized in that nano titanium oxide is hydrophilic, granularity less than 100 nm and moisture less than 1%.
3. self-emulsifying type alkenyl succinic anhydride sizing agent according to claim 1, the weight ratio that it is characterized in that nano titanium oxide and alkenyl succinic anhydride is 1:50～250.
4. self-emulsifying type alkenyl succinic anhydride sizing agent according to claim 1 is characterized in that self-emulsifying type alkenyl succinic anhydride sizing agent mixed with water being made into emulsion and joining in the paper pulp again or directly join in the paper pulp and use.
5. self-emulsifying type alkenyl succinic anhydride sizing agent according to claim 4, it is characterized in that under stirring water is added in the self-emulsifying type alkenyl succinic anhydride sizing agent or with self-emulsifying type alkenyl succinic anhydride sizing agent and be added in the water, the weight ratio of self-emulsifying type alkenyl succinic anhydride sizing agent and water is 1:1～50.
6. self-emulsifying type alkenyl succinic anhydride sizing agent according to claim 5, it is characterized in that under stirring, water being added in the self-emulsifying type alkenyl succinic anhydride sizing agent, the weight ratio of self-emulsifying type alkenyl succinic anhydride sizing agent and water is 1:2～10,500～10000 rev/mins of mixing speeds, mixing time 2～20 minutes.
7. the preparation method of the described self-emulsifying type alkenyl succinic anhydride of claim 1 sizing agent is characterized in that under stirring nano titanium oxide being joined in the alkenyl succinic anhydride.
8. preparation method according to claim 7 is characterized in that mixing speed is 50 ~ 1000 rev/mins, mixing time 1～30 minute.
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| CN102493272B (en) * | 2011-11-18 | 2014-07-16 | 山东轻工业学院 | ASA emulsion sizing agent and preparation method thereof |
| CN102493273B (en) * | 2011-11-19 | 2014-02-12 | 山东轻工业学院 | Alkenyl succinic anhydride emulsion sizing agent and its preparation method |
| CN103790072B (en) * | 2014-02-18 | 2016-01-20 | 齐鲁工业大学 | A kind of fluorescence ASA glue used in paper-making and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101864690A (en) * | 2002-10-24 | 2010-10-20 | 斯派克特拉-科特公司 | Coating compositions comprising alkyl ketene dimers and alkyl succinic anhydrides for use in paper making |
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| CN101864690A (en) * | 2002-10-24 | 2010-10-20 | 斯派克特拉-科特公司 | Coating compositions comprising alkyl ketene dimers and alkyl succinic anhydrides for use in paper making |
Non-Patent Citations (2)
| Title |
|---|
| 赵振环等.preparation of Nano-TiO2 stabilized ASA emulsion and its sizing behavior on BCTMP.《Research Progress in Paper Industry and Biorefinery，4thISETPP》.华南理工大学出版社,2010,1645-1648. |
| 赵振环等.preparation of Nano-TiO2 stabilized ASA emulsion and its sizing behavior on BCTMP.《Research Progress in Paper Industry and Biorefinery,4thISETPP》.华南理工大学出版社,2010,1645-1648. * |
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