CN109866298A - A kind of paraffinic base Pickering lotion and preparation method thereof containing hydridization montmorillonite - Google Patents
A kind of paraffinic base Pickering lotion and preparation method thereof containing hydridization montmorillonite Download PDFInfo
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Abstract
The present invention relates to waterproofing wood agent fields, more particularly to a kind of paraffinic base Pickering lotion and preparation method thereof containing hydridization montmorillonite, it prepares and contains hydridization montmorillonite in the raw material of lotion, the hydridization montmorillonite is made after being modified by silane, small molecular alcohol and esters of silicon acis to montmorillonite.In lotion prepared by the present invention, hydridization montmorillonite can be adsorbed on paraffin/water interface, play the role of stable emulsion, can be under the premise of guaranteeing stability of emulsion, dosage of surfactant is reduced, to reduce negative effect of the surfactant to emulsion water-proof effect.
Description
Technical field
The present invention relates to waterproofing wood agent fields, and in particular to a kind of waterproofing wood agent containing hydridization montmorillonite.
Background technique
Main component cellulose, hemicellulose and the lignin of wood cell wall contain a large amount of hydroxyl, these hydroxyls are led
Cause timber that there is stronger moisture absorption (water) property, it is biggish with the variation generation of moisture content or ambient humidity so as to cause timber size
Variation, i.e. dimensional instability.Finally, the problems such as causing the drying shrinkage bulking and strain cracking of timber, and to other property of timber
It can cause different degrees of influence.The defect problem for having researcher to claim 90% or more timber is all related with moisture.Therefore, in timber
In processing, waterproofing agent is often used to improve the waterproofness of timber.
Paraffin is a kind of stronger organic substance of hydrophobicity, it can be distributed by physisorption reaches in wood
The purpose of waterproof.However, solid paraffin is not soluble in water and organic solvent, it is at normal temperature solid-state.It is needed for treating of wood
Carried out under high temperature fused state, complex treatment process and processing material in be not easy to be evenly distributed, thus influence timber waterproof effect
Fruit.In order to overcome defect existing for above-mentioned paraffin water repellent, emulsion paraffin water repellent is a kind of preferable selection.Using paraffin as base
Paraffin is dispersed in water phase by material under the action of emulsifier in the form of short grained, forms the paraffinic base of uniform system
Pickering lotion.By impregnating paraffinic base Pickering lotion, processing material in the drying process, divide by the grease phase of lotion
From, promote paraffin be evenly distributed in processing material in, to improve the hydrophobicity of timber.CN 103862538 discloses a kind of base
In the paraffin series waterproofing agent of natural surfactant, using natural Surfactants Alkyl and sapn as emulsifier, with solid
Body paraffin and water are raw material, prepare paraffin series waterproofing wood agent, product is nontoxic, environmentally friendly, inexpensive, can be obviously improved timber
Hydrophobic performance and dimensional stability.CN 104526805 discloses a kind of nonionic paraffinic base Pickering used for wood modification
The preparation method of lotion, using fatty alcohol ether polyoxyethylene nonionic surfactant as emulsifier, in conjunction with macromolecule film former,
Without assistant for emulsifying agent, using inversed phase emulsification, once plus water, small, the stable paraffinic base Pickering lotion of partial size, institute is made
The paraffinic base Pickering lotion obtained can be compounded with acidic liquid and be compounded simultaneously with akaline liquid, can be used for enhancing reality
Timber, the waterproof of wood-based plate, humidity resistance, reduce their moisture absorption and deformation.
Although traditional paraffinic base Pickering lotion improves significant effect to the hydrophobicity of timber, in lotion
In preparation process, in order to obtain comparatively ideal emulsifying effectiveness and lower partial size, need to be added more surfactant.It is to rear
There is no positive effects for the improvement of continuous wood performance, or even can influence the raising of waterproof performance to a certain extent, and part
There are certain pollutions to environment for the surfactant of toxic effect.For this solution it is required that reducing paraffin as far as possible
The content of surfactant in waterproofing agent.In addition, the combustion heat value of paraffin is 43MJ/kg, it is 3.6 times of timber, by paraffin
The timber of processing often more easy firing；And traditional paraffinic base Pickering lotion processing also can not effectively improve timber
Mechanical property can not accomplish " one multiple-effect ".
Summary of the invention
The paraffinic base Pickering lotion containing hydridization montmorillonite that the object of the present invention is to provide a kind of, is mainly improved
Place is containing hydridization montmorillonite in the raw material for prepare lotion, and the hydridization montmorillonite is by silane, small molecular alcohol and esters of silicon acis pair
Montmorillonite is made after being modified.
Hydridization montmorillonite is added in paraffinic base Pickering lotion, montmorillonite solid particle is with absorption after hydridization
Form is adsorbed on paraffin surface, and compared with surfactant, the dosage of hydridization montmorillonite is lower, and the hydrophilic group of this material
Group is fewer, can fully play the waterproof action of paraffin, in turn in the case that the dosage of surfactant is less in lotion
Ideally waterproof is realized in the case where paraffin dosage is less.
Preferably, the preparation method of the hydridization montmorillonite is to mix silane, esters of silicon acis, small molecular alcohol, montmorillonite and water
Close, gone after mixing well moisture removal to get.
As preferred mode of operation, the preparation method that the hydridization suffers de- soil is, 30 after above-mentioned material is mixed
2-10 hour is stirred with the speed of 2000-6000rpm under the conditions of DEG C -60 DEG C.
Preferably, the silane, esters of silicon acis, small molecular alcohol and the mass ratio of montmorillonite are 1~2:12~50:12~50:3
~10.
Preferably, the silane is γ-aminopropyltrimethoxysilane, gamma-aminopropyl-triethoxy-silane, γ-shrink
Glycerol ether oxygen propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane, vinyltriethoxysilane
Or one or more of vinyl three (beta-methoxy ethyoxyl) silane；
Preferably, the esters of silicon acis is one in methyl orthosilicate, ethyl orthosilicate, positive silicic acid propyl ester or butyl silicate
Kind is several；
Preferably, the montmorillonite is one or more of sodium-based montmorillonite, calcium-base montmorillonite or organo montmorillonite, excellent
Select sodium-based montmorillonite.
Preferably, the small molecular alcohol is one or more of methanol, ethyl alcohol, normal propyl alcohol or isopropanol, preferred alcohol.
Preferably, prepare further includes that paraffin, low hlb are non-ionic in the raw material of the paraffinic base Pickering lotion
Surfactant and high hlb nonionic surface active agent.
Preferably, the paraffin is atoleine or solid paraffin, preferably 5# atoleine or 50# solid paraffin；
Preferably, the low hlb nonionic surface active agent is propylene glycol monostearate, glycerol monostearate
Ester, polyoxypropylene stearate, tetraethylene glycol monostearate, polyoxyethylene dioleate, sorbitan monooleate or
One or more of sorbitan monooleate, preferably sorbitan monooleate or anhydrous sorbitol list oleic acid
Ester；
Preferably, the high hlb nonionic surface active agent is polyoxyl 40 stearate, polyoxyethylene 16
Alkylol, polyoxyethylene 20 sorbitan monooleate, Vinlub 73 or polyoxyethylene methyl glucoside half
One or more of oleate, preferably polyoxyl 40 stearate or Vinlub 73.
Preferably, when the dosage of water is 1L, preparing in the raw material of the paraffinic base Pickering lotion includes that hydridization is covered
De- soil 10~80g, 200~700g of paraffin, 10~50g of low hlb nonionic surface active agent and the non-ionic table of high hlb
Face 10~40g of activating agent.
It is further preferred that preparing in the raw material of the paraffinic base Pickering lotion when the dosage of water is 1L and including
Hydridization 50~70g of montmorillonite, 400~500g of paraffin, 20~32g of low hlb nonionic surface active agent and high hlb it is non-from
15~25g of subtype surfactant；
Preferably, in above scheme, the low hlb nonionic surface active agent is propylene glycol monostearate, loses
Water sorbitol monooleate or polyoxyethylene dioleate；The high hlb nonionic surface active agent is polyoxyethylene list
Stearate, half oleate of polyoxyethylene methyl glucoside or polyoxyethylene 20 sorbitan monooleate.
The present invention also protects the preparation method of paraffinic base Pickering lotion of the present invention, includes the following steps:
1) under the conditions of 70 DEG C -95 DEG C, the hydridization montmorillonite and paraffin are mixed, and it is non-that low hlb is added thereto
Ionic surfactant and high hlb nonionic surface active agent stir 10- with the speed of 5000rpm-10000rpm
Colostric fluid is completed in 20min, preparation；
2) by colostric fluid by high pressure homogenizer carry out high-pressure homogeneous, homogenization pressure 40MPa-80MPa, homogeneous 1-2 times,
Hydridization montmorillonite is made and stablizes paraffinic base Pickering lotion timber.
The invention has the following beneficial effects:
1) it has selected to stablize paraffinic base Pickering lotion waterproofing wood agent using hydridization montmorillonite in the present invention, obtain
To partial size small (< 250nm), the high and efficient waterproofing wood agent of stability, which is free of harmful chemical, safety collar
It protects.
2) in waterproofing agent prepared by the present invention, hydridization montmorillonite can be adsorbed on paraffin/water interface, played and stablized cream
The effect of liquid can reduce dosage of surfactant, to reduce surfactant under the premise of guaranteeing stability of emulsion
Negative effect to emulsion water-proof effect.
3) since hydridization montmorillonite has thermal stability and rigidity, stablize paraffinic base using present invention preparation hydridization montmorillonite
Pickering lotion waterproofing wood agent handles timber, can also significantly improve the flame retardant property and mechanical property of timber, realizes
" one multiple-effect ".The waterproofing agent can be applied to the waterproof and dampproof equal fields of wood-based plate.
Detailed description of the invention
For Fig. 1 TEM-EDX as a result, Fig. 1 a is reference examples 2, Fig. 1 b and Fig. 1 c are the result of embodiment 2.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
Embodiment 1
The present embodiment is related to a kind of paraffinic base Pickering lotion containing hydridization montmorillonite.
The hydridization montmorillonite is prepared by the following method:
9g γ-aminopropyltrimethoxysilane, 150g methyl orthosilicate, 150g methanol and 40g sodium-based montmorillonite are dispersed
In 400g water, 2 hours are stirred with the speed of 2000rpm under the conditions of 30 DEG C, then it is dried, obtained hydridization and cover
De- soil 56g.
Prepare includes hydridization montmorillonite 56g, 60# solid paraffin 400g, propylene glycol monostearate in the raw material of the lotion
Ester 25g, ethylene oxide monostearate 17g.
The method for preparing the lotion includes the following steps:
1) under conditions of 70 DEG C, the hydridization montmorillonite of aforementioned preparation and 400g60# solid paraffin are mixed, and thereto
25g propylene glycol monostearate, 17g polyoxyl 40 stearate and 800g water is added, with the speed of 5000rpm, stirring
Colostric fluid is completed in 10min, preparation.
2) colostric fluid is subjected to high-pressure homogeneous, homogenization pressure 40MPa by high pressure homogenizer, homogeneous 1 time to get.
Embodiment 2
The present embodiment is related to a kind of paraffinic base Pickering lotion containing hydridization montmorillonite.
The hydridization montmorillonite is prepared by the following method:
6g gamma-aminopropyl-triethoxy-silane, 80g ethyl orthosilicate, 80g ethyl alcohol and 20g sodium-based montmorillonite are dispersed in
In 300g water, 4 hours are stirred with the speed of 3000rpm under the conditions of 40 DEG C, then it is dried, it is de- to obtain hydridization illiteracy
Native 32g.
Prepare includes above-mentioned hydridization montmorillonite 32g, 50# solid paraffin 240g, anhydrous sorbitol in the raw material of the lotion
Monoleate 12g, polyoxyl 40 stearate 10g.
The method for preparing the lotion includes the following steps:
1) under conditions of 75 DEG C, the hydridization montmorillonite of aforementioned preparation and 240g 50# solid paraffin are mixed, and to its
Middle addition 12g sorbitan monooleate, 10g polyoxyl 40 stearate and 600g water are stirred with the speed of 7000rpm
20min is mixed, colostric fluid is completed in preparation.
2) colostric fluid is subjected to high-pressure homogeneous, homogenization pressure 60MPa by high pressure homogenizer, homogeneous 2 times to get.
Embodiment 3
The present embodiment is related to a kind of paraffinic base Pickering lotion containing hydridization montmorillonite.
The hydridization montmorillonite is prepared by the following method:
By 1g γ-glycidyl ether oxygen propyl trimethoxy silicane, 50g positive silicic acid propyl ester, 50g normal propyl alcohol and 10g calcium base
Montmorillonite is dispersed in 100g water, stirs 6 hours under the conditions of 50 DEG C with the speed of 4000rpm, then it is dried,
Obtain hydridization montmorillonite 14g.
Prepare includes above-mentioned hydridization montmorillonite 14g, 15# atoleine 100g, polyoxyethylene two in the raw material of the lotion
Oleate 5g, half oleate 3g of polyoxyethylene methyl glucoside.
The method for preparing the lotion includes the following steps:
1) under the conditions of 85 DEG C, the hydridization montmorillonite of aforementioned preparation and 100g 15# atoleine are mixed, and thereto
5g polyoxyethylene dioleate, half oleate of 3g polyoxyethylene methyl glucoside and 200g water is added, with the speed of 60000rpm
Degree, stirs 15min, and colostric fluid is completed in preparation.
2) colostric fluid is subjected to high-pressure homogeneous, homogenization pressure 80MPa by high pressure homogenizer, homogeneous 1 time to get.
Embodiment 4
The present embodiment is related to a kind of paraffinic base Pickering lotion containing hydridization montmorillonite.
The hydridization montmorillonite is prepared by the following method:
10g vinyltriethoxysilane, 200g butyl silicate, 200g isopropanol and 50g organo montmorillonite are dispersed
In 500g water, 10 hours are stirred with the speed of 6000rpm under the conditions of 60 DEG C, then it is dried, obtains hydridization
Montmorillonite 72g.
Prepare includes above-mentioned hydridization montmorillonite 72g, 5# atoleine 500g, anhydrous sorbitol list in the raw material of the lotion
Oleate 30g, polyoxyethylene 20 sorbitan monooleate 20g；
The method for preparing the lotion includes the following steps:
1) under the conditions of 95 DEG C, the hydridization montmorillonite of aforementioned preparation and 500g5# atoleine are mixed, and added thereto
Enter 30g sorbitan monooleate, 20g polyoxyethylene 20 sorbitan monooleate and 1000g water, with the speed of 10000rpm
Degree, stirs 20min, and colostric fluid is completed in preparation.
2) colostric fluid is subjected to high-pressure homogeneous, homogenization pressure 70MPa by high pressure homogenizer, homogeneous 2 times to get.
Reference examples 1
This comparative example is related to a kind of lotion, and compared with Example 1, difference is, does not add hydridization illiteracy in the lotion
De- soil, preparation method include the following steps:
Under conditions of 75 DEG C, by 240g 50# solid paraffin, 12g sorbitan monooleate, 10g polyoxyethylene list
Stearate and the mixing of 600g water stir 20min with the speed of 7000rpm, and colostric fluid is completed in preparation.By colostric fluid through excessively high
It presses homogenizer to carry out high-pressure homogeneous, homogenization pressure 60MPa, homogeneous 2 times, paraffinic base Pickering lotion timber lotion is made.
Reference examples 2
This comparative example is related to a kind of lotion, and compared with Example 1, difference is, does not add hydridization illiteracy in the lotion
De- soil, preparation method include the following steps:
Under conditions of 75 DEG C, by 240g 50# solid paraffin, 30g sorbitan monooleate, 20g polyoxyethylene list
Stearate and the mixing of 600g water stir 20min with the speed of 7000rpm, and colostric fluid is completed in preparation.By colostric fluid through excessively high
It presses homogenizer to carry out high-pressure homogeneous, homogenization pressure 60MPa, homogeneous 2 times, paraffinic base Pickering lotion timber lotion is made.
Experimental example 1
From detecting in terms of appearance, average grain diameter, centrifugal stability, storage stability 4, lotion timber in embodiment processed is newborn
Liquid.Average grain diameter is measured using Delsa Nano c-type laser particle analyzer.The measurement method of centrifugal stability is to take respectively
Lotion timber lotion used in embodiment 1-4 and reference examples 1-2 paraffinic base Pickering lotion each 10g of timber lotion, are put into
30min is centrifuged with the revolving speed of 3000r/min in centrifuge, observes emulsion intercalation method.It is every that the results are shown in Table 1:
Table 1
The result shows that the partial size of all embodiments is between 180nm-250nm, and centrifugal stability, storage stability
Keep good.1 stability of reference examples of hydridization montmorillonite is not added significantly lower than other embodiments, is only improved surfactant and contains
Amount, as shown in reference examples 2, can be only achieved preferable stability and lower partial size.
Experimental example 2
Situation is adsorbed in paraffin/water termination using TEM-EDX observation hydridization montmorillonite.Before observation, appropriate embodiment 2 is taken to make
The standby agent of lotion waterproofing wood and 2 paraffinic base Pickering lotion waterproofing wood agent of reference examples, drips in the copper mesh containing carbon film
On.After equal moisture evaporation, absorption situation of the hydridization montmorillonite around drop is observed.As a result as shown in Figure 1.
Emulsion droplet integrally distribution spherical in shape, it is (right in the prior paraffin base Pickering lotion for not adding hydridization montmorillonite
As usual 2, Fig. 1 a) in, have no that droplet surface has hydridization montmorillonite absorption.But the agent of lotion waterproofing wood (embodiment 2, Fig. 1 b and
Fig. 1 c) droplet surface has apparent " black " solid substance, and energy-spectrum scanning Fig. 1 c shows that " black " substance is containing Si element
Hydridization montmorillonite particle.Illustrate that hydridization montmorillonite particle can be adsorbed in droplet surface, improves liquid using solid particle film layer
Mechanical barrier and electrostatic repulsion between drop, increase emulsion intercalation method.
Experimental example 3
By lotion waterproofing wood agent used in embodiment 1-4 and 2 paraffinic base Pickering lotion waterproofing wood of reference examples
It is 2% that agent is diluted to solid content respectively, and subsequent impregnation Cathay poplar, Cathay poplar is having a size of 20mm × 20mm × 20mm.Processing method
Are as follows: timber is placed in immersion can and is first vacuum-treated, vacuum degree is -0.9MPa, vacuum 30min, then stops vacuum simultaneously
The lotion diluted, and the 60min that pressurizes under conditions of 2MPa are added into impregnating autoclave.It, will be wooden after the completion of vacuum pressed dipping
Material takes out from impregnating autoclave, and it is dry to carry out gas.In addition, taking untreated Cathay poplar as blank group.
Then, with reference to GB/T 1934.1-2009 " Method for determination of the water absorption of wood ", the water imbibition of timber for 24 hours is measured；Ginseng
GB/T 1934.2-2009 " Method for determination of the swelling of wood " is examined, the cubical expansivity for 24 hours of timber is measured；Referring to GB
1936.1-1991 " Method for determination of the modulus of elasticity in static bending of wood " and GB 1936.2 " bending strength of wood experimental method ", measurement wood
The Deflection Modulus of Elasticity and bending strength of material；Referring to GB/T2406.2-2009, " plastics oxygen index method measures burning behavior the 2nd
Part: room temperature test " measurement timber oxygen index (OI).The results are shown in Table 2.
The physical and mechanical property of 2 embodiment of table and reference examples processing medium density fibre board (MDF)
The result shows that handling timber using lotion waterproofing wood agent prepared by the present invention, the suction of timber can be significantly reduced
Aqueous and cubical expansivity shows good hydrophobicity and dimensional stability, and effect, which is better than, does not add hydridization montmorillonite
Prior paraffin base Pickering lotion (reference examples 2).The prior paraffin base Pickering lotion of hydridization montmorillonite is not added
(reference examples 2) can not improve the mechanical properties such as the bending strength of timber, elasticity modulus, or even can reduce the oxygen index (OI) of timber, make
Timber is more inflammable.And the agent of lotion waterproofing wood can then be obviously improved the mechanical property and flame retardant property of timber.
Although above having used general explanation, specific embodiment and test, the present invention is made to retouch in detail
It states, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed
Range.
Claims (10)
1. a kind of paraffinic base Pickering lotion containing hydridization montmorillonite, which is characterized in that in the raw material for preparing the lotion
Containing hydridization montmorillonite, the hydridization montmorillonite is made after being modified by silane, small molecular alcohol and esters of silicon acis to montmorillonite.
2. paraffinic base Pickering lotion according to claim 1, which is characterized in that the preparation of the hydridization montmorillonite
Method be by silane, esters of silicon acis, small molecular alcohol, montmorillonite and water mix, gone after mixing well moisture removal to get；
Preferably, the silane, esters of silicon acis, small molecular alcohol and the mass ratio of montmorillonite be 1~2:12~50:12~50:3~
10。
3. paraffinic base Pickering lotion according to claim 1 or 2, which is characterized in that the silane is γ-ammonia third
Base trimethoxy silane, gamma-aminopropyl-triethoxy-silane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-(methyl
Acryloyl-oxy) in propyl trimethoxy silicane, vinyltriethoxysilane or vinyl three (beta-methoxy ethyoxyl) silane
One or more, preferably γ-aminopropyltrimethoxysilane or gamma-aminopropyl-triethoxy-silane.
4. described in any item paraffinic base Pickering lotions according to claim 1~3, which is characterized in that the esters of silicon acis is
One or more of methyl orthosilicate, ethyl orthosilicate, positive silicic acid propyl ester or butyl silicate.
5. paraffinic base Pickering lotion according to any one of claims 1 to 4, which is characterized in that the montmorillonite is
One or more of sodium-based montmorillonite, calcium-base montmorillonite or organo montmorillonite；
And/or the small molecular alcohol is one or more of methanol, ethyl alcohol, normal propyl alcohol or isopropanol, preferred alcohol.
6. described in any item paraffinic base Pickering lotions according to claim 1~5, which is characterized in that prepare the paraffin
It further include paraffin, low hlb nonionic surface active agent and high hlb nonionic surface active agent in the raw material of lotion.
7. described in any item paraffinic base Pickering lotions according to claim 1~6, which is characterized in that the paraffin is liquid
Body paraffin or solid paraffin, preferably 5# atoleine or 50# solid paraffin；
And/or the low hlb nonionic surface active agent is propylene glycol monostearate, glycerin monostearate, polyoxy
Propylene stearate, tetraethylene glycol monostearate, polyoxyethylene dioleate, sorbitan monooleate or Sorbitan
One or more of alcohol monoleate, preferably sorbitan monooleate and sorbitan monooleate；
And/or the high hlb nonionic surface active agent is polyoxyl 40 stearate, polyoxyethylene cetyl base
Alcohol, half oleic acid of polyoxyethylene 20 sorbitan monooleate, Vinlub 73 or polyoxyethylene methyl glucoside
One or more of ester, preferably polyoxyl 40 stearate or Vinlub 73.
8. described in any item paraffinic base Pickering lotions according to claim 1~7, which is characterized in that when the dosage of water is
When 1L, prepare in the raw material of the paraffinic base Pickering lotion include 10~80g of hydridization montmorillonite, 200~700g of paraffin,
10~40g of 10~50g of low hlb nonionic surface active agent and high hlb nonionic surface active agent.
9. described in any item paraffinic base Pickering lotions according to claim 1~7, which is characterized in that when the dosage of water is
When 1L, prepare in the raw material of the paraffinic base Pickering lotion include 50~70g of hydridization montmorillonite, 400~500g of paraffin,
15~25g of 20~32g of low hlb nonionic surface active agent and high hlb nonionic surface active agent.
10. the preparation method of any one of the claim 1~9 paraffinic base Pickering lotion, which is characterized in that including such as
Lower step:
1) under the conditions of 70 DEG C -95 DEG C, the hydridization montmorillonite and paraffin are mixed, and low hlb nonionic is added thereto
Type surfactant and high hlb nonionic surface active agent stir 10- with the speed of 5000rpm-10000rpm
Colostric fluid is completed in 20min, preparation；
2) colostric fluid is subjected to high-pressure homogeneous, homogenization pressure 40MPa-80MPa by high pressure homogenizer, homogeneous 1-2 times is made
The paraffinic base Pickering lotion.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111087538A (en) * | 2020-01-02 | 2020-05-01 | 中国科学院长春应用化学研究所 | W/O emulsion and preparation method thereof, polymer particles and preparation method thereof |
| CN112157770A (en) * | 2020-10-15 | 2021-01-01 | 南京林业大学 | Environment-friendly type bamboo wood mildew-proof treatment method |
| CN114395387A (en) * | 2022-03-15 | 2022-04-26 | 西南石油大学 | Water-in-oil in-situ emulsified nano oil displacement agent with high phase transition point and application thereof |
| CN115414262A (en) * | 2022-07-19 | 2022-12-02 | 江苏诺兴生物科技有限公司 | Epsilon-polylysine Pickering emulsion and preparation method and application thereof |
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