CN105732878A - Core-shell type emulsion with PTFE as core and preparing method thereof - Google Patents
Core-shell type emulsion with PTFE as core and preparing method thereof Download PDFInfo
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- 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
- C08F2/00—Processes of polymerisation
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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Abstract
The invention discloses core-shell type emulsion with PTFE as a core and a preparing method thereof. PTFE dispersion liquid and deionized water are added into a three-necked flask with a constant-pressure dropping funnel and a spherical condenser pipe according to mass parts to be stirred evenly and heated in nitrogen so that seed emulsion can be obtained; mixed monomer is dropped through the constant-pressure dropping funnel, the total amount of monomer is 10-1,000 according to mass parts, swelling is conducted, then, initiator is added for initiating polymerization, reaction is conducted for 24 h, filtering is conducted, ammonium hydroxide is used for adjusting the pH value of the solution after cooling, and the core-shell type emulsion with PTFE as the core is obtained. The level of the adhesive force of an emulsion coating and a rubber surface can reach 4B, and the adhesive force is improved remarkably; contact angle and water absorption test results of emulsion rubber films show that the contact angle of the emulsion latex films can reach 117.94 degrees, the water absorption can be as low as 9.62wt%, and the hydrophobicity of the emulsion latex film is good through comprehensive analysis.
Description
Technical field
The invention belongs to technical field of polymer materials, particularly relate to a kind of with PTFE Structure of Core/shell Emulsion being core and preparation method thereof.
Background technology
Politef (PTFE) has the features such as heat-resisting, weatherability, resistance to chemical attack and surface tension be little, bond energy mainly due to the C-F key in politef is high and stable, molecule is screw type configuration, and C-C main chain is covered by the fluorine atom that volume is bigger completely.Big quantity research shows: add PTFE in composite and material list can be made to reveal the thermostability of excellence, chemical resistance and hydro-oleophobicity etc..Politef is in equal extensive application in field such as modern architecture, perforated membrane, optics, microelectronics and waterproof material, ultralow dielectric substance and coating.But, politef is poor with the compatibility of other macromolecular materials and surface adhesion force.Surface modification is to improve the important channel of PTFE interface compatibility, method of modifying includes: surface emissivity, high-energy irradiation, surface grafting etc., but these methods all need higher chemism or by high work input, modified technical costs is significantly high, it is difficult to realize industrialization.In order to improve the compatibility and the adhesive force of politef and other macromolecular materials, existing document is pointed out, with PTFE for core, with traditional polymer for shell, cladding PTFE prepares core-shell type complex particle (J.Appl.Polym.Sci, 1998,68,185；Macromolecules2009,42,3518-3524).The preparation method of application number a kind of core-shell polymer being seed with PTFE latex particle that has been the patent report of 201310730597.0, polytetrafluoroethyldispersion dispersion is adopted to prepare seed emulsion and carry out seeded emulsion polymerization with monomer, obtain the Structure of Core/shell Emulsion of stability and good dispersion, but the method is conventional emulsion polymerization, causes that the performance of emulsion film significantly reduces because emulsifying agent occurs to migrate in emulsion film forming process.
Existing polytetrafluoroethylmodified modified method can not improve the adhesive force of tetrafluoroethene coating and rubber surface effectively.
Summary of the invention
It is an object of the invention to provide a kind of with PTFE Structure of Core/shell Emulsion being core and preparation method thereof, it is intended to the problem effectively improving tetrafluoroethene coating and the adhesive force of rubber surface.
The present invention is achieved in that a kind of preparation method with the PTFE Structure of Core/shell Emulsion being core, described be core with politef the preparation method of Structure of Core/shell Emulsion comprise the following steps:
Equipped with constant pressure funnel, spherical condensation tube three-neck flask according to mass parts add polytetrafluoroethyldispersion dispersion: 0～100 mass parts and deionized water: 50～900 mass parts, stir, in nitrogen atmosphere heat, it is thus achieved that seed emulsion；
Mix monomer is dripped by the low liquid funnel 1 of constant voltage, according to mass parts monomer total amount: 10～100 mass parts, swelling, the initiator being subsequently adding initiator 0.01～3 mass parts causes polymerization, reaction, filter, regulate solution ph with ammonia after cooling, it is thus achieved that the Structure of Core/shell Emulsion being core with politef.
Further, described in stir, rotating speed is 250～400rpm, heats to reaction temperature 70～90 DEG C, it is thus achieved that seed emulsion in nitrogen atmosphere.
Further, described swelling 5～20min, it is subsequently adding initiator 0.01～3 mass parts initiator and causes polymerization, react 24h.
Further, solution ph is regulated to 7～8 with ammonia after described cooling.
Another object of the present invention is to provide a kind of described Structure of Core/shell Emulsion being core with politef prepared with the preparation method of the PTFE Structure of Core/shell Emulsion being core, include according to mass parts with the Structure of Core/shell Emulsion that politef is core: polytetrafluoroethyldispersion dispersion: 0～100 mass parts；Monomer total amount: 10～100 mass parts；Deionized water: 50～900 mass parts；Initiator: 0.01～3 mass parts.
Further, described mix monomer is made up of soft monomer and hard monomer, and soft, hard monomer mixes with the mass ratio of 1: 0.5～1: 2.
Further, described soft monomer is the one in butyl acrylate, ethyl acrylate, Isooctyl acrylate monomer；Hard monomer is the one in methyl methacrylate, styrene, acrylonitrile, acrylic acid methyl ester., vinylacetate.
Further, described initiator is the one in potassium peroxydisulfate, Ammonium persulfate., sodium peroxydisulfate, azodiisobutyronitrile, Ammonium persulfate. or potassium and sodium sulfite or ammonium redox system.
Another object of the present invention is to provide a kind of described reaction unit used with the preparation method of the PTFE Structure of Core/shell Emulsion being core, described reaction unit includes: constant pressure funnel, spherical condensation tube, three-neck flask, stirring paddle, heating in water bath；
Described constant pressure funnel and spherical condensation tube are arranged on the both sides of three-neck flask, and the centre of three-neck flask is equipped with stirring paddle, and three-neck flask is placed in heating in water bath.
The present invention adopts the method for semicontinuous swelling Soap free cationic emulision to prepare with the PTFE Structure of Core/shell Emulsion being core, according to this emulsion coating of ASTMD3359-02 standard testing and rubber surface adhesive force grade, finding that this emulsion coating adhesive force grade can reach 4B, adhesive force improves notable；Contact angle and the water absorption rate test result of emulsion film show, its contact angle can reach 117.94 ° and water absorption rate can be low to 9.62wt%, and comprehensive analysis show that the hydrophobicity of this latex film is better.Method convenient and efficient proposed by the invention, the emulsion conversion ratio of preparation is high, avoids the adverse effect that product is brought by emulsifying agent, it is possible to obtain the pure latex particle that monodispersity is good simultaneously.The combination property of this Structure of Core/shell Emulsion and latex film highlights, and contributes to expanding further the application of politef.The present invention proposes a kind of preparation method with the PTFE Structure of Core/shell Emulsion being core, by to the selection of shell polymerization single polymerization monomer and regulation and control soft, hard monomer ratio, effectively improve the adhesive force of PTFE and rubber, broader practice prospect is opened with rubber combined for politef, significant simultaneously for the application expanding fluoro coatings aspect.Various embodiments of the present invention all successfully can be prepared with the PTFE Structure of Core/shell Emulsion being core by semicontinuous swelling Soap free cationic emulision method, and this emulsion coating is high with the adhesive force grade of rubber, the content increasing PTFE can improve each combination property of this emulsion film, such as hydrophobicity and thermostability, can expand PTFE building, chemical industry, electric appliance and electronic industry, mechanical industry, aerospace industries, household supplies the extensive use of every field.
Accompanying drawing explanation
Fig. 1 be the embodiment of the present invention provide with the preparation method flow chart of the PTFE Structure of Core/shell Emulsion being core.
Fig. 2 be the embodiment of the present invention provide with the reaction unit schematic diagram of the PTFE Structure of Core/shell Emulsion being core；
In figure: 1, constant pressure funnel；2, spherical condensation tube；3, three-neck flask；4, stirring paddle；5, heating in water bath.
Fig. 3 be the embodiment of the present invention provide with the building-up process schematic diagram of the PTFE Structure of Core/shell Emulsion being core.
Fig. 4 be the embodiment of the present invention provide with the PTFE Structure of Core/shell Emulsion grain structure schematic diagram being core.
Fig. 5 is the transmission electron microscope picture of the emulsion particle of the embodiment 1 that the embodiment of the present invention provides.
Fig. 6 is the transmission electron microscope picture of the emulsion particle of the embodiment 2 that the embodiment of the present invention provides.
Fig. 7 is the transmission electron microscope picture of the emulsion particle of the embodiment 3 that the embodiment of the present invention provides.
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein is only in order to explain the present invention, is not intended to limit the present invention.
Below in conjunction with accompanying drawing, the application principle of the present invention is explained in detail.
Including according to mass parts with the PTFE Structure of Core/shell Emulsion being core of the embodiment of the present invention: polytetrafluoroethyldispersion dispersion: 0～100 mass parts；Monomer total amount: 10～100 mass parts；Deionized water: 50～900 mass parts；Initiator: 0.01～3 mass parts.
Described mix monomer is made up of soft monomer and hard monomer, and soft, hard monomer mixes with the mass ratio of 1: 0.5～1: 2；Soft monomer is the one in butyl acrylate, ethyl acrylate, Isooctyl acrylate monomer；Hard monomer is the one in methyl methacrylate, styrene, acrylonitrile, acrylic acid methyl ester., vinylacetate.
Described initiator is the one in potassium peroxydisulfate, Ammonium persulfate., sodium peroxydisulfate, azodiisobutyronitrile, Ammonium persulfate. or potassium and sodium sulfite or ammonium redox system.
As it is shown in figure 1, the preparation method with the PTFE Structure of Core/shell Emulsion being core of the embodiment of the present invention comprises the following steps:
S101: the preparation of seed emulsion: equipped with constant pressure funnel 1, spherical condensation tube 2 three-neck flask 3 according to mass parts add polytetrafluoroethyldispersion dispersion: 0～100 mass parts and deionized water: 50～900 mass parts, stir, rotating speed is 250～400rpm, nitrogen atmosphere heats to reaction temperature 70～90 DEG C, it is thus achieved that seed emulsion；
S102: with the preparation of the Structure of Core/shell Emulsion that politef is core: drip mix monomer by the low liquid funnel 1 of constant voltage, according to mass parts monomer total amount: 10～100 mass parts, swelling 5～20min, the initiator being subsequently adding initiator 0.01～3 mass parts causes polymerization, reaction 24h, filter, regulate solution ph to 7～8 with ammonia after cooling, it is thus achieved that the Structure of Core/shell Emulsion being core with politef.
As in figure 2 it is shown, the reaction unit with the PTFE Structure of Core/shell Emulsion being core of the embodiment of the present invention specifically includes that constant pressure funnel 1, spherical condensation tube 2, three-neck flask 3, stirring paddle 4, heating in water bath 5.
Constant pressure funnel 1 and spherical condensation tube 2 are arranged on the both sides of three-neck flask 3, and the centre of three-neck flask 3 is equipped with stirring paddle 4, and three-neck flask 3 is placed in heating in water bath 5.
Below in conjunction with specific embodiment, the application principle of the present invention is explained in detail.
The polytetrafluoroethyldispersion dispersion trade mark used by following case is DF-302.
Embodiment 1:
Taking 12g polytetrafluoroethyldispersion dispersion (particle diameter 240nm, solid content 57wt%) and 120g deionized water mix homogeneously in 250ml three-neck flask 3, mixing speed is 300rpm, passes into nitrogen simultaneously, heats to reaction temperature 75 DEG C, it is thus achieved that seed emulsion；Take each 8g of MMA and BA, constitute mix monomer, it is added drop-wise in three-neck flask 3 by constant pressure funnel 1, drip off in 30min, swelling 15min, add potassium persulfate solution (0.12gKPS is dissolved in 10g deionized water) and cause polymerization, reaction 24h, with 100 order nylon net filters after having reacted, regulate solution ph to 7～8 with ammonia after cooling, prepare hud typed PTFE-P (MMA-BA) emulsion.
Fig. 5 is the emulsion particle of embodiment 1 TEM figure after phosphotungstic acid dyes, it can be clearly seen that this emulsion particle has nucleocapsid structure, wherein black part is PTFE core, and light-colored part is P (MMA-BA) shell, emulsion particle size is homogeneous, and PTFE granule is wrapped by completely.Table 1 is the test result of the composition and ratio with the PTFE Structure of Core/shell Emulsion glued membrane being core and adhesive force grade.In conjunction with Fig. 5 with table 1 it can be seen that embodiment 1 successfully prepares hud typed PTFE-P (MMA-BA) emulsion, and the adhesive force grade of this emulsion coating and nitrile rubber (NBR) reaches 4B, illustrates that adhesive force is good.Table 2 is that the contact angle of hud typed PTFE-P (MMA-BA) emulsion film and water absorption rate are with PTFE changes of contents relation, increase along with PTFE content, the contact angle of emulsion film increases, and water absorption rate reduces, and illustrates that the hydrophobicity of this emulsion film improves along with the increase of PTFE content.
Embodiment 2:
Taking 12g polytetrafluoroethyldispersion dispersion (particle diameter 240nm, solid content 57wt%) and 120g deionized water mix homogeneously in 250ml three-neck flask 3, mixing speed is 300rpm, passes into nitrogen simultaneously, heats to reaction temperature 75 DEG C, it is thus achieved that seed emulsion；Take 8.7gMMA and 7.3gBA and constitute mix monomer, it is added drop-wise in three-neck flask 3 by constant pressure funnel 1, drip off in 30min, swelling 15min, add potassium persulfate solution (0.12gKPS is dissolved in 10g deionized water) and cause polymerization, react 24h, with 100 order nylon net filters after having reacted, regulate solution ph to 7～8 with ammonia after cooling, prepare hud typed PTFE-P (MMA-BA) emulsion.
Fig. 6 is the emulsion particle of embodiment 2 TEM figure after phosphotungstic acid dyes, it can be clearly seen that this emulsion particle has nucleocapsid structure, wherein black part is PTFE core, and light-colored part is P (MMA-BA) shell, emulsion particle size is homogeneous, and PTFE granule is wrapped by completely.In conjunction with Fig. 6 and Biao 1 it is apparent that embodiment 2 successfully prepares hud typed PTFE-P (MMA-BA) emulsion, and the adhesive force grade of this emulsion coating and nitrile rubber (NBR) reaches 3B, illustrates that adhesive force is good.
Embodiment 3:
Taking 12g polytetrafluoroethyldispersion dispersion (particle diameter 240nm, solid content 57wt%) and 120g deionized water mix homogeneously in 250ml three-neck flask 3, mixing speed is 300rpm, passes into nitrogen simultaneously, heats to reaction temperature 75 DEG C, it is thus achieved that seed emulsion；Take 7.3g styrene (St) and 8.7g butyl acrylate (BA) constitutes mix monomer, it is added drop-wise in three-neck flask 3 by constant pressure funnel 1, drip off in 30min, swelling 15min, add potassium persulfate solution (0.24gKPS is dissolved in 10g deionized water) and cause polymerization, react 24h, with 100 order nylon net filters after having reacted, regulate solution ph to 7～8 with ammonia after cooling, prepare hud typed PTFE-P (St-BA) emulsion.
Fig. 7 is the emulsion particle of embodiment 3 TEM figure after phosphotungstic acid dyes, it can be seen that emulsion particle size is homogeneous, and PTFE granule is wrapped by completely.In conjunction with Fig. 7 and Biao 1 it is apparent that embodiment 3 successfully prepares hud typed PTFE-P (St-BA) emulsion, and the adhesive force grade of this emulsion coating and nitrile rubber (NBR) reaches 4B, illustrates that adhesive force is good.
Table 1 is with the adhesive force grade of the PTFE Structure of Core/shell Emulsion glued membrane being core
| Sample | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Polytetrafluoroethylene teflon soliquoid | 12g | 12g | 12g |
| Methyl methacrylate | 8.0g | 8.7g | 0 |
| Butyl acrylate | 8.0g | 7.3g | 8.7g |
| Styrene | 0 | 0 | 7.3g |
| Soft or hard monomer ratio | 1∶1 | 1∶1.2 | 1.2∶1 |
| Adhesive force grade | 4B | 3B | 4B |
Note: adhesive force test establishing criteria ASTMD3359-02,25 DEG C, 1atm.
The contact angle of table 2 hud typed PTFE-P (MMA-BA) emulsion film and water absorption rate
| Sample | PTFE weight/mass percentage composition (%) | Contact angle (°) | Water absorption rate (%) |
| S1 | 0 | 79.7° | 40.0% |
| S2 | 10% | 83.5° | 25.7% |
| S3 | 20% | 84.6° | 28.2% |
| S4 | 30% | 92.6° | 19.4% |
| S5 | 40% | 95.9° | 20.0% |
| S6 | 50% | 102.4° | 9.2% |
| S7 | 60% | 117.9° | 9.6% |
Note: contact angle test condition 25 DEG C, 1atm.
Associative list 1, table 2 and Fig. 5-Fig. 7 can be seen that, various embodiments of the present invention all successfully can be prepared with the PTFE Structure of Core/shell Emulsion being core by semicontinuous swelling Soap free cationic emulision method, and this emulsion coating is high in the surface adhesion force grade of rubber, the content increasing PTFE can improve the hydrophobicity of this emulsion film, it is possible to expands the politef extensive use in paint field.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all any amendment, equivalent replacement and improvement etc. made within the spirit and principles in the present invention, should be included within protection scope of the present invention.
Claims (9)
1. one kind with the preparation method of the PTFE Structure of Core/shell Emulsion being core, it is characterised in that described be core with politef the preparation method of Structure of Core/shell Emulsion comprise the following steps:
The preparation of seed emulsion: equipped with constant pressure funnel, spherical condensation tube three-neck flask according to mass parts add polytetrafluoroethyldispersion dispersion: 0～100 mass parts and deionized water: 50～900 mass parts, stir, nitrogen atmosphere heats, it is thus achieved that seed emulsion；
Preparation with the Structure of Core/shell Emulsion that politef is core: drip mix monomer by constant pressure funnel, according to mass parts monomer total amount: 10～100 mass parts, swelling, the initiator being subsequently adding initiator 0.01～3 mass parts causes polymerization, reaction, filter, regulate solution ph with ammonia after cooling, it is thus achieved that the Structure of Core/shell Emulsion being core with politef.
2. the preparation method with the PTFE Structure of Core/shell Emulsion being core as claimed in claim 1, it is characterised in that described in stir, rotating speed is 250～400rpm, heats to reaction temperature 70～90 DEG C, it is thus achieved that seed emulsion in nitrogen atmosphere.
3., as claimed in claim 1 with the preparation method of the PTFE Structure of Core/shell Emulsion being core, it is characterised in that described swelling 5～20min, the initiator being subsequently adding 0.01～3 mass parts causes polymerization, reacts 24h.
4. as claimed in claim 1 with the preparation method of the PTFE Structure of Core/shell Emulsion being core, it is characterised in that regulate solution ph to 7～8 with ammonia after described cooling.
5. the Structure of Core/shell Emulsion being core with politef prepared with the preparation method of the PTFE Structure of Core/shell Emulsion being core as claimed in claim 1, it is characterized in that, described be core with politef Structure of Core/shell Emulsion include according to mass parts: polytetrafluoroethyldispersion dispersion: 0～100 mass parts；Monomer total amount: 10～100 mass parts；Deionized water: 50～900 mass parts；Initiator: 0.01～3 mass parts.
6. as claimed in claim 5 with the PTFE Structure of Core/shell Emulsion being core, it is characterised in that described monomer is made up of soft monomer and hard monomer, and soft, hard monomer mixes with the mass ratio of 1: 0.5～1: 2.
7. as claimed in claim 6 with the PTFE Structure of Core/shell Emulsion being core, it is characterised in that described soft monomer is the one in butyl acrylate, ethyl acrylate, Isooctyl acrylate monomer；Hard monomer is the one in methyl methacrylate, styrene, acrylonitrile, acrylic acid methyl ester., vinylacetate.
8. as claimed in claim 5 with the PTFE Structure of Core/shell Emulsion being core, it is characterised in that described initiator is the one in potassium peroxydisulfate, Ammonium persulfate., sodium peroxydisulfate, azodiisobutyronitrile, Ammonium persulfate. or potassium and sodium sulfite or ammonium redox system.
9. the reaction unit used with the preparation method of the PTFE Structure of Core/shell Emulsion being core as claimed in claim 1, it is characterised in that described reaction unit includes: constant pressure funnel, spherical condensation tube, three-neck flask, stirring paddle, heating in water bath；
Described constant pressure funnel and spherical condensation tube are arranged on the both sides of three-neck flask, and the centre of three-neck flask is equipped with stirring paddle, and three-neck flask is placed in heating in water bath.
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| CN108047374A (en) * | 2018-01-23 | 2018-05-18 | 河北工业大学 | The preparation method of pressure-sensitive adhesive polytetrafluoroethyl/ne /ne polypropylene esters of gallic acid core-shell emulsion |
| CN110183580A (en) * | 2019-05-16 | 2019-08-30 | 北京点域科技有限公司 | A kind of non-sticky type coating and preparation method thereof |
| CN110743473A (en) * | 2019-10-22 | 2020-02-04 | 中国科学院兰州化学物理研究所 | Preparation method of polytetrafluoroethylene @ phenolic resin core-shell composite particles |
| CN111286047A (en) * | 2020-02-14 | 2020-06-16 | 中国科学院兰州化学物理研究所 | Polytetrafluoroethylene-based core-shell nanocomposite and preparation method and application thereof |
| CN112062979A (en) * | 2020-09-07 | 2020-12-11 | 清华大学 | Organic-inorganic core-shell structure self-lubricating composite material and preparation method thereof |
| CN112280062A (en) * | 2020-10-15 | 2021-01-29 | 西南科技大学 | Hydrophobic low-density high-strength polystyrene microsphere and preparation method thereof |
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