CN110437473A - A kind of polymer powder surface treatment method - Google Patents

A kind of polymer powder surface treatment method Download PDF

Info

Publication number
CN110437473A
CN110437473A CN201910762541.0A CN201910762541A CN110437473A CN 110437473 A CN110437473 A CN 110437473A CN 201910762541 A CN201910762541 A CN 201910762541A CN 110437473 A CN110437473 A CN 110437473A
Authority
CN
China
Prior art keywords
powder
mass parts
polymer powder
polymer
mol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201910762541.0A
Other languages
Chinese (zh)
Other versions
CN110437473B (en
Inventor
杨杰
黄岐善
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wanhua Chemical Group Co Ltd
Original Assignee
Shanghai Wan Hua Ke Ju Chemical Technology Development Co Ltd
Wanhua Chemical Group Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Wan Hua Ke Ju Chemical Technology Development Co Ltd, Wanhua Chemical Group Co Ltd filed Critical Shanghai Wan Hua Ke Ju Chemical Technology Development Co Ltd
Priority to CN201910762541.0A priority Critical patent/CN110437473B/en
Publication of CN110437473A publication Critical patent/CN110437473A/en
Application granted granted Critical
Publication of CN110437473B publication Critical patent/CN110437473B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/12Powdering or granulating
    • C08J3/126Polymer particles coated by polymer, e.g. core shell structures
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10Homopolymers or copolymers of propene
    • C08J2323/12Polypropene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2369/00Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2401/00Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2401/08Cellulose derivatives
    • C08J2401/26Cellulose ethers
    • C08J2401/28Alkyl ethers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2405/00Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
    • C08J2405/16Cyclodextrin; Derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2429/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2429/02Homopolymers or copolymers of unsaturated alcohols
    • C08J2429/04Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2439/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
    • C08J2439/04Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C08J2439/06Homopolymers or copolymers of N-vinyl-pyrrolidones
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/25Process efficiency

Landscapes

  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Cosmetics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to a kind of surface treatments of polymer powder, using polymer powder as raw material, the following steps are included: step 1: water-soluble polymer, aqueous media, defoaming agent, optional amido cyclodextrine derivatives being heated and are uniformly mixed, processing solution is obtained, the number-average molecular weight of the water-soluble polymer is 20000g/mol~150000g/mol;Step 2: both polymer powder, processing solution mixed processing being uniformly mixed, obtain the solidliquid mixture containing powder;Step 3: step 2 gained mixture is separated by solid-liquid separation, is dried, the powders of thermoplastic polymers that obtains that treated.Absorption by water-soluble polymer to powder high surface energy region reduces powder roughness, is not necessarily to high temperature high pressure process, and method is simple and safe.Treated, and powder can be used for powdery paints, 3D printing, cosmetics, additive, medicine and other fields.

Description

A kind of polymer powder surface treatment method
Technical field
The invention belongs to polymer powder technical fields, and in particular to a kind of polymer powder surface treatment method, the party The powder of method preparation can be used for the technical fields such as powdery paints, 3D printing.
Background technique
The development of Modern High-Tech and new material industry, the technological progress of conventional industries and product up-gradation require many polymerizations Powder raw material.Since powder granularity is thin, large specific surface area, surface particle number are more, and surface particle and phase suffered by the particle of inside Interreaction force is different, in addition mechanical force activation or mechanochemical treatment in powder preparation process, so that the particle of powder surface Than it, internal particle has higher energy (surface energy) and activity.Therefore the surface nature of powder determines the special of powder Performance, such as sintering temperature is low and sintered body intensity is high, filler reinforcement performance is good and the property such as unique dispersibility, rheological characteristic Energy.
The method for preparing polymer powder mainly has cryogenic mechanical comminuting method and solvent precipitation.Cryogenic mechanical comminuting method benefit There is this characteristic of brittle temperature with high molecular material, be ground into micron-sized powder under cryogenic.Common is poly- Object material such as polystyrene, polypropylene, polycarbonate, polyolefin, ethylene-vinyl acetate resin, polyamide etc. is closed to be ok Dusty material is prepared using cryogenic mechanical comminuting method.The advantages of low-temperature grinding method is that technical process is simple, it is continuous to be able to carry out The production of change, but the grain shape prepared is disorderly and unsystematic, and particle diameter distribution is also wider, and powder also wants screened processing sometimes, no Qualified powder will also carry out multiple reprocessing.
Powder shape, surface energy, mobility are the key that polymer powder applications.Such as in selective laser sintering, The model various aspects of performance of spherical powder sintering is all improved.And according to Frenkel model (Viscous Flow of Crystalline Bodies under the Action of Surface Tension.The Journal of Physics, 1945.9 (5): p.385-391.), the surface tension of powder is also to improve one of the key of sintering character.
At present, it has been reported that the processing method on some polymer powder surfaces.Such as CN108407299A discloses one The method of kind irregular polymer powder sphering, heating make polymer powder form melt drop and under the action of interfacial tension Retraction occurs spontaneously to realize the sphering of irregular polymer powder.It is poly- for high temperature due to being influenced by medium boiling point Object powder is closed to be difficult to be effectively treated.CN107022100A discloses a kind of polymer powder end for powder bed fusion method Reason method, the hydrophobic material of polymer powder alkane, alkene and its mixture.The coating of lyophobic dust can reduce Surface tension influences to be sintered.CN106633114A discloses a kind of spheronization process of polyether-ether-ketone 3D printing powder, uses convolution Device is so that polyetheretherketonematerials materials are washed away in fluid flowing.But this method is stringent to requiring in equipment and operation, and process needs phase Answer solvent.
To sum up, the processing to polymer powder surface in the prior art, concentrates on the spheroidising to powder, plays improvement The purpose of flowing, does not regulate and control surface characteristic;On the other hand it is limited to different dusty materials, needs to use high temperature or special molten Agent just can be carried out processing.General processing method easy to operate has value to powder application is expanded.
Summary of the invention
In view of the above-mentioned problems of the prior art, the polymer powder good the object of the present invention is to provide a kind of operability Last surface treatment method, absorption of the present invention by water-soluble polymer in powder high surface energy region, realizes the table to powder Surface treatment, is not necessarily to high temperature high pressure process, and method is simple and safe.
The purpose of the present invention is realized by the following technical scheme, wherein the raw material parts is unless otherwise specified, it is quality Part.
One aspect of the present invention provides a kind of polymer powder surface treatment method comprising following steps:
Step 1: water-soluble polymer, aqueous media, defoaming agent, optional amido cyclodextrine derivatives heating mixing is equal It is even, obtain processing solution;Heating mixing temperature is 60~95 DEG C;
Step 2: both polymer powder, processing solution mixed processing being uniformly mixed, it is mixed to obtain the solid-liquid containing powder Close object;The mixed processing time is 10min~60min, preferably 15~30min;Mixed processing temperature is 25~50 DEG C;
Step 3: step 2 gained mixture is separated by solid-liquid separation, is dried, the polymer powder that obtains that treated;Solid-liquid Separation is carried out by modes such as the screen to filtrate or centrifuge separations;Drying mode is chosen as vacuum drying or constant pressure and dry etc., excellent It is selected as being dried in vacuo;Drying temperature is 60~100 DEG C, preferably 70~90 DEG C;Drying time is 1~5h.
In the method for the invention, the dosage of various components are as follows:
Polymer powder: 2~50 mass parts, preferably 10~20 mass parts;
Water-soluble polymer: 0.4~5 mass parts, preferably 0.8~2 mass parts;
Aqueous media: 100 mass parts;
Amido cyclodextrine derivatives: 0~2 mass parts;
Defoaming agent: 0.01~0.1 mass parts;
Wherein, the number-average molecular weight of the water-soluble polymer is 20000g/mol~150000g/mol, preferably 50000g/mol~120000g/mol.
In method of the invention, the aqueous media is the aqueous solution of water, small molecular alcohol and/or ether;The small molecule The molecular weight of alcohol or ether is less than 200g/mol, is selected from methanol, ethyl alcohol, ethylene glycol, tetrahydrofuran, dioxane, ethylene glycol list first One of ether, ethylene glycol monoethyl ether, ethylene glycol ether are a variety of, preferably methanol, ethyl alcohol, one in ethylene glycol monoethyl ether Kind is a variety of;Small molecular alcohol and/or ether account for 0wt%~8wt% of aqueous media, preferably 1wt%~5wt%.
In method of the invention, the particle size range of the polymer powder is 10~300 μm, preferably 50~150 μm.Institute Stating polymer powder is powders of thermoplastic polymers, and the thermoplastic polymer can be selected from thermoplastic polyurethane elastomer, polyamides Amine, polyvinyl chloride, polycarbonate, polyester, polyether-ether-ketone, polyphenylene sulfide, polyphenylene oxide, polypropylene, preferred thermoplastic polyurethane bullet Property body, polypropylene;Polymer powder can come from crushing and processing etc..
In method of the invention, the number-average molecular weight of the water-soluble polymer be 20000g/mol~150000g/mol, Preferably 50000g/mol~120000g/mol is selected from polyvinyl alcohol, hydroxypropyl cellulose, hydroxyethyl cellulose, poly- propionyl Amine, polyvinylpyrrolidone, polyethylene oxide are preferably selected from polyvinyl alcohol, hydroxyethyl cellulose.Wherein, the polyvinyl alcohol Alcoholysis degree range is 85%~95%;The hydroxypropyl cellulose, hydroxyethyl cellulose, the viscosity range of 2wt% aqueous solution For 50~400mPa.s.Water-soluble polymer generates a small amount of inhale by the intermolecular force with powder (micron level) surface It is attached, especially to the sharpened areas absorption of powder surface (having higher surface energy here, be more also easy to produce absorption), realize to powder The package on surface reduces powder surface roughness.
In method of the invention, the defoaming agent is one of Polyether Modified Polysiloxanes Defoaming Agent, organic silicon defoamer Or it is a variety of, such as Bi Ke chemistry BYK-019, BYK-024.
In method of the invention, the amido cyclodextrine derivatives are 6- substitutions, and structural formula is as follows:
Wherein, substituent R is the linear alkylene of 2~6 carbon atoms;The cyclodextrin is selected from alpha-cyclodextrin, β-ring paste Essence and gamma-cyclodextrin.
The preparation method of the amido cyclodextrine derivatives can refer to the document report of CN104031179B and severe winter blueness (" preparation of several cyclodextrine derivatives and host-guest interaction are studied ", 2016, University Of Science and Technology Of Tianjin), the structure cyclodextrin With partial hydrophilicity, it can play the role of adjusting viscosity, on the other hand the cyclodextrin composition after drying can reunite on surface, rise To barrier, the effect of lubrication powder.
The second aspect of the invention provides the polymer powder handled according to the above method.
The third aspect of the invention provides the polymer powder handled according to the above method in powdery paints, 3D The purposes of printing, cosmetics, additive, medicine etc..
The invention has the following advantages:
(1) by absorption of the water-soluble polymer to polymer powder high surface energy region, powder roughness can be reduced, Without high temperature high pressure process, method simple general-purpose.
(2) surface characteristic for passing through the adjustable polymer powder of water-soluble polymer, improves the application effect of powder.
(3) this method is applied widely, is not limited by type of polymer, and it is smaller on the influence of the property of material itself.
Detailed description of the invention
FIG. 1 to FIG. 7 is respectively the electron scanning micrograph of Examples 1 to 7;
Fig. 8~Fig. 9 is respectively the electron scanning micrograph of comparative example 1~2.
Specific embodiment
Below by way of specific embodiment, the present invention is described in further detail, but this should not be interpreted as to the present invention Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Performance test:
Powder morphology: scanning electron microscope is used.
Powder diameter distribution: it is measured using BT-9300ST type laser fineness gage.
Powder flowbility: Britain Fu Ruiman FT4 powder rheometry is used.
Raw material sources in embodiment:
Polyvinyl alcohol, Shandong You Suo Chemical Industry Science Co., Ltd
Defoaming agent BYK-019, BYK-024: Bi Ke chemical technology seeks advice from (Shanghai) Co., Ltd.
Polypropylene powder: deep cooling crush self-control
Polycarbonate powder: self-control is crushed
Thermoplastic polyurethane powder: deep cooling crush self-control
Polyvinylpyrrolidone: Sinopharm Chemical Reagent Co., Ltd.
Hydroxyethyl cellulose: Sinopharm Chemical Reagent Co., Ltd.
Beta-cyclodextrin: Sinopharm Chemical Reagent Co., Ltd.
Sodium hydroxide: Sinopharm Chemical Reagent Co., Ltd.
Paratoluensulfonyl chloride: Sinopharm Chemical Reagent Co., Ltd.
Potassium carbonate: Sinopharm Chemical Reagent Co., Ltd.
Ethylenediamine: Sinopharm Chemical Reagent Co., Ltd.
Dimethylformamide: Sinopharm Chemical Reagent Co., Ltd.
Acetone: Sinopharm Chemical Reagent Co., Ltd.
Embodiment 1
30g beta-cyclodextrin is dissolved in 600ml deionized water, is added 18g NaOH solution (0.75mol/L), is plunderred under ice bath Reaction 30min is mixed, 6g paratoluensulfonyl chloride is added portionwise, temperature control continues to be stirred to react 5h at 0-5 DEG C, filters faint yellow White precipitate is precipitated with the hydrochloric acid tune pH to 6-7 of 2mol/L in clear solution, and refrigerated overnight is filtered and recrystallized twice, dry Obtain 6-OTs- β-CD.
It takes 0.83g potassium carbonate and 2ml ethylenediamine in 100ml three neck round bottom flask, 15ml DMF is added as solvent, room 6-OTs- β-CD the 7.8g for being dissolved in 15ml DMF is added after the lower stirring 2h of temperature, is warming up to 80 DEG C, stirred under nitrogen atmosphere reaction 24h.It pours into 200ml acetone and is precipitated after reaction solution is cooling, obtain light yellow solid ethylenediamine base-β-ring paste after filtering drying Essence.
By 100 mass parts water, 2 mass parts ethylenediamine group-beta-cyclodextrins, (number-average molecular weight is 1 mass parts polyvinyl alcohol 50000g/mol, alcoholysis degree 85%), the defoaming agent BYK-019 of 0.1 mass parts is heated at 95 DEG C to be uniformly mixed, and is obtained everywhere Manage solution;
By the D of 10 mass parts50=50 μm of polypropylene powder is mixed with aforementioned processing solution, and the mixed processing at 25 DEG C 15min is dried in vacuo 2h at 100 DEG C, obtains polymer microballoon powder after being then separated by solid-liquid separation using sieve.
Embodiment 2
By 100 mass parts aqueous medias (methanol aqueous solution of 1wt%), 0.4 mass fraction average molecular weight is 150000g/ The polyvinylpyrrolidone of mol, the defoaming agent BYK-019 of 0.01 mass parts is heated at 90 DEG C to be uniformly mixed, and obtains handling molten Liquid;
By the D of 2 mass parts50=300 μm of thermoplastic polyurethane powder is mixed with aforementioned processing solution, and is mixed at 35 DEG C Processing 10min is closed, after separating using centrifugal solid-liquid, 4.5h is dried in vacuo at 60 DEG C, obtains polymer microballoon powder.
Embodiment 3
By 100 mass parts aqueous medias (ethanol water of 8wt%), 5 mass parts hydroxyethyl cellulose (number-average molecular weights 20000g/mol, its 2wt% aqueous solution viscosity be 50mPa.s), the defoaming agent BYK-024 of 0.1 mass parts is heated at 60 DEG C It is uniformly mixed, obtains processing solution;
By the D of 50 mass parts50=10 μm of thermoplastic polyurethane powder is mixed with aforementioned processing solution, and is mixed at 50 DEG C Processing 60min is closed, after being separated by solid-liquid separation using sieve, the constant pressure and dry 2h at 90 DEG C obtains polymer microballoon powder.
Embodiment 4
By 100 mass parts aqueous medias (the ethylene glycol monoethyl ether aqueous solution of 2wt%), (number is equal for 0.8 mass parts polyvinyl alcohol Molecular weight is 120000g/mol, alcoholysis degree 90%), it is equal that the defoaming agent BYK-024 of 0.05 mass parts heats mixing at 80 DEG C It is even, obtain processing solution;
By the D of 20 mass parts50=150 μm of polypropylene powder is mixed with aforementioned processing solution, and at 40 DEG C at mixing 30min is managed, after separating using centrifugal solid-liquid, 4h is dried in vacuo at 80 DEG C, obtains polymer microballoon powder.
Embodiment 5
By 100 mass parts aqueous medias (aqueous tetrahydrofuran solution of 6wt%), (number is equal for 1 mass parts polyvinylpyrrolidone Molecular weight is 100000g/mol), the defoaming agent BYK-019 of 0.05 mass parts is heated at 90 DEG C to be uniformly mixed, and obtains handling molten Liquid;
By the D of 30 mass parts50=300 μm of thermoplastic polyurethane powder is mixed with aforementioned processing solution, and at 50 DEG C Mixed processing 40min after being separated using centrifugal solid-liquid, is dried in vacuo 4h at 70 DEG C, obtains polymer microballoon powder.
Embodiment 6
By 100 mass parts aqueous medias (ethanol water of 5wt%), hydroxyethyl cellulose (the equal molecule of number of 2 mass parts Amount is 400mPa.s in the viscosity of 77000g/mol, its 2wt% aqueous solution), the defoaming agent BYK-024 of 0.1 mass parts is at 95 DEG C Lower heating is uniformly mixed, and obtains processing solution;
By the D of 40 mass parts50=10 μm of thermoplastic polyurethane powder is mixed with aforementioned processing solution, and is mixed at 35 DEG C Processing 50min is closed, after being separated by solid-liquid separation using sieve, 5h is dried in vacuo at 60 DEG C, obtains polymer microballoon powder.
Embodiment 7
By 100 mass parts water, 3 mass parts polyvinyl alcohol (number-average molecular weight 130000g/mol, alcoholysis degree 95%), The defoaming agent BYK-019 of 0.05 mass parts is heated at 80 DEG C to be uniformly mixed, and processing solution is obtained;
By the D of 25 mass parts50=200 μm of polycarbonate powder is mixed with aforementioned processing solution, and is mixed at 40 DEG C 60min is handled, after being separated by solid-liquid separation using sieve, 1h is dried in vacuo at 100 DEG C, obtains polymer microballoon powder.
Comparative example 1
Commercially available thermoplastic polyurethane powder FS 1092A-TPU.
Comparative example 2
Commercial polypropylene powder Luvosint 8824WT.
The powder property before and after the processing of 1 embodiment and comparative example of table

Claims (10)

1. a kind of polymer powder processing method comprising following steps:
Step 1: water-soluble polymer, aqueous media, defoaming agent, optional amido cyclodextrine derivatives are heated and are uniformly mixed, Obtain processing solution;
Preferably, the number-average molecular weight of the water-soluble polymer is 20000g/mol~150000g/mol, more preferably 50000g/mol~120000g/mol;
Step 2: both polymer powder, processing solution mixed processing being uniformly mixed, obtain the solid-liquid mixing containing powder Object;
Step 3: step 2 gained mixture is separated by solid-liquid separation, is dried, the polymer powder that obtains that treated.
2. processing method according to claim 1, which is characterized in that the dosage of various components are as follows:
Polymer powder: 2~50 mass parts, preferably 10~20 mass parts;
Water-soluble polymer: 0.4~5 mass parts, preferably 0.8~2 mass parts;
Aqueous media: 100 mass parts;
Amido cyclodextrine derivatives: 0~2 mass parts;
Defoaming agent: 0.01~0.1 mass parts.
3. processing method according to claim 1 or 2, which is characterized in that the aqueous media be water, small molecular alcohol and/ Or the aqueous solution of ether;The molecular weight of the small molecular alcohol or ether be less than 200g/mol, be preferably selected from methanol, ethyl alcohol, ethylene glycol, One of tetrahydrofuran, dioxane, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether are a variety of, further Preferably one of methanol, ethyl alcohol, ethylene glycol monoethyl ether or a variety of;
Small molecular alcohol and/or ether account for 0wt%~8wt% of aqueous media, preferably 1wt%~5wt%.
4. processing method according to claim 1-3, which is characterized in that the particle size range of the polymer powder It is 10~300 μm, preferably 50~150 μm;
The polymer powder is powders of thermoplastic polymers, selected from thermoplastic polyurethane elastomer, polyamide, polyvinyl chloride, Polycarbonate, polyester, polyether-ether-ketone, polyphenylene sulfide, polyphenylene oxide, polypropylene, preferred thermoplastic polyurethane elastomer, polypropylene.
5. processing method according to claim 1-4, which is characterized in that the water-soluble polymer is selected from poly- second Enol, hydroxypropyl cellulose, hydroxyethyl cellulose, poly- propionamide, polyvinylpyrrolidone, polyethylene oxide, preferably poly- second Enol, hydroxyethyl cellulose;
Wherein, the polyvinyl alcohol alcoholysis degree range is 85%~95%;The hydroxypropyl cellulose, hydroxyethyl cellulose, The viscosity range of 2wt% aqueous solution is 50~400mPa.s.
6. processing method according to claim 1-5, which is characterized in that the defoaming agent is selected from polyether-modified Organic silicon defoamer, organic silicon defoamer, preferably Bi Ke chemistry BYK-019, BYK-024.
7. processing method according to claim 1-6, which is characterized in that the amido cyclodextrine derivatives are 6- Position replaces, and structural formula is as follows:
Wherein, substituent R is the linear alkylene of 2~6 carbon atoms;The cyclodextrin be selected from alpha-cyclodextrin, beta-cyclodextrin and Gamma-cyclodextrin.
8. processing method according to claim 1-7, which is characterized in that heat mixing temperature described in step 1 It is 60~95 DEG C;
And/or: mixed processing time described in step 2 is 10min~60min, preferably 15~30min;Mixed processing temperature It is 25~50 DEG C;
And/or: drying temperature described in step 3 is 60~100 DEG C, preferably 70~90 DEG C;Drying time is 1~5h.
9. the polymer powder that processing method according to claim 1-8 obtains.
10. polymer powder according to claim 9 be applied to including powdery paints, 3D printing, cosmetics, additive, Field of medicaments.
CN201910762541.0A 2019-08-19 2019-08-19 Polymer powder surface treatment method Active CN110437473B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910762541.0A CN110437473B (en) 2019-08-19 2019-08-19 Polymer powder surface treatment method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910762541.0A CN110437473B (en) 2019-08-19 2019-08-19 Polymer powder surface treatment method

Publications (2)

Publication Number Publication Date
CN110437473A true CN110437473A (en) 2019-11-12
CN110437473B CN110437473B (en) 2022-07-12

Family

ID=68436225

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910762541.0A Active CN110437473B (en) 2019-08-19 2019-08-19 Polymer powder surface treatment method

Country Status (1)

Country Link
CN (1) CN110437473B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111334132A (en) * 2020-03-02 2020-06-26 成都新柯力化工科技有限公司 High-sphericity superfine thermoplastic powder coating and preparation method thereof
CN112126086A (en) * 2020-08-06 2020-12-25 湖南华曙高科技有限责任公司 Drying method of nylon powder suspension for selective laser sintering

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1624025A (en) * 2004-11-05 2005-06-08 清华大学 Method for preparing high tap density polyamide powder of controll able average partical size
KR20070098633A (en) * 2006-04-01 2007-10-05 데구사 게엠베하 Polymer powder, process for production of and use of this powder, and resultant shaped articles
CN101301476A (en) * 2008-06-20 2008-11-12 广东药学院 Hydrophobic cyclodextrin clathrate and preparation and use thereof
CN103289026A (en) * 2013-05-07 2013-09-11 江南大学 Preparation method and application of hydrophobization beta-cyclodextrin cation polyelectrolyte
CN105440663A (en) * 2014-08-07 2016-03-30 中国科学院理化技术研究所 Preparation method of nylon micro powder for selective laser sintering
WO2016205504A2 (en) * 2015-06-16 2016-12-22 Water Mark Technologies, Inc. Dry water soluble polymer particles
CN107057090A (en) * 2017-04-27 2017-08-18 万华化学集团股份有限公司 A kind of preparation method of nylon powder
CN107603454A (en) * 2017-10-09 2018-01-19 常州凯途纺织品有限公司 A kind of antibiont sticks the preparation method of surfacing
CN107955191A (en) * 2017-12-25 2018-04-24 万华化学集团股份有限公司 A kind of processing method of powders of thermoplastic polymers mobility
CN108407299A (en) * 2018-03-12 2018-08-17 四川大学 A kind of method of irregular polymer powder sphering

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1624025A (en) * 2004-11-05 2005-06-08 清华大学 Method for preparing high tap density polyamide powder of controll able average partical size
KR20070098633A (en) * 2006-04-01 2007-10-05 데구사 게엠베하 Polymer powder, process for production of and use of this powder, and resultant shaped articles
CN101050282A (en) * 2006-04-01 2007-10-10 德古萨有限责任公司 Polymer powder, its preparation method, its application and finished products therefrom
CN101301476A (en) * 2008-06-20 2008-11-12 广东药学院 Hydrophobic cyclodextrin clathrate and preparation and use thereof
CN103289026A (en) * 2013-05-07 2013-09-11 江南大学 Preparation method and application of hydrophobization beta-cyclodextrin cation polyelectrolyte
CN105440663A (en) * 2014-08-07 2016-03-30 中国科学院理化技术研究所 Preparation method of nylon micro powder for selective laser sintering
WO2016205504A2 (en) * 2015-06-16 2016-12-22 Water Mark Technologies, Inc. Dry water soluble polymer particles
CN107057090A (en) * 2017-04-27 2017-08-18 万华化学集团股份有限公司 A kind of preparation method of nylon powder
CN107603454A (en) * 2017-10-09 2018-01-19 常州凯途纺织品有限公司 A kind of antibiont sticks the preparation method of surfacing
CN107955191A (en) * 2017-12-25 2018-04-24 万华化学集团股份有限公司 A kind of processing method of powders of thermoplastic polymers mobility
CN108407299A (en) * 2018-03-12 2018-08-17 四川大学 A kind of method of irregular polymer powder sphering

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111334132A (en) * 2020-03-02 2020-06-26 成都新柯力化工科技有限公司 High-sphericity superfine thermoplastic powder coating and preparation method thereof
CN112126086A (en) * 2020-08-06 2020-12-25 湖南华曙高科技有限责任公司 Drying method of nylon powder suspension for selective laser sintering
CN112126086B (en) * 2020-08-06 2022-08-16 湖南华曙高科技股份有限公司 Drying method of nylon powder suspension for selective laser sintering

Also Published As

Publication number Publication date
CN110437473B (en) 2022-07-12

Similar Documents

Publication Publication Date Title
CN101249410B (en) Preparation of organic-inorganic composite microballoons
CN110437473A (en) A kind of polymer powder surface treatment method
CN103962074B (en) A kind of hollow sub-micron, its preparation method and application
KR20200041279A (en) Method for surface modification of submicron silicon micropowder
EP0199364A2 (en) Polyimide molding resins and molded articles
WO2014106369A1 (en) Method for preparing transparent liquid-phase magnesium hydroxide dispersion and use thereof
CN112898545B (en) Solvent-free green method for preparing polylactic acid nano material
TW201231397A (en) Surface-treated heavy calcium carbonate, its manufacturing method and resin composition mixed with the same
CN108998894B (en) super-hydrophobic MOFs nanocrystals, composite film material, preparation method and application
CN115057719A (en) Preparation method of silicon carbide ceramic filter membrane material
Chen et al. Homogeneous dispersion of nanostructured aluminum nitride in a polyimide matrix
JP5821213B2 (en) Method for producing polyphenylene sulfide resin fine particle dispersion
Li et al. A novel silica‐based nucleating agent for polypropylene: Preparation, characterization, and application
CN113680314A (en) Fly ash loaded nano spherical magnesium hydroxide composite material and preparation method and application thereof
WO1999020680A1 (en) Fine particle size low bulk density thermoplastic polymers
CN112645366A (en) Preparation method of nano magnesium oxide
CN110386608B (en) Preparation method of light spherical silicon dioxide
US3925323A (en) Poly(meta-phenylene isophthalamide)powder
CN211575816U (en) Expandable microsphere drying system
CN108782606B (en) Rosin-based terpene-titanium dioxide hybrid nano material, preparation method and antibacterial application thereof
CN110478496B (en) Preparation method of high-molecular nano-drug carrier oleylamine grafted polysuccinimide with uniform particle size and controllable size
CN110240902B (en) Preparation method of tungsten oxide quantum dot material
CN111117228A (en) Preparation method of polymer powder material for optical fiber laser sintering
CN106825554B (en) 3D printing nano metal alloy powder and preparation method thereof
Ganjali et al. A novel nanocomposite containing zinc ferrite nanoparticles embedded in carboxymethylcellulose hydrogel plus carbon nitride nanosheets with multifunctional bioactivity

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right
TA01 Transfer of patent application right

Effective date of registration: 20201015

Address after: 264006 No. 17 Tianshan Road, Yantai economic and Technological Development Zone, Shandong

Applicant after: Wanhua Chemical Group Co.,Ltd.

Address before: 201315 118, room 6, 2500 lane, Xiu Pu Road, Pudong New Area, Shanghai.

Applicant before: SHANGHAI WANHUA KEJU CHEMICAL TECHNOLOGY DEVELOPMENT Co.,Ltd.

Applicant before: Wanhua Chemical Group Co.,Ltd.

GR01 Patent grant
GR01 Patent grant