CN108102119A - A kind of preparation method of melamine resin hollow microsphere - Google Patents
A kind of preparation method of melamine resin hollow microsphere Download PDFInfo
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- CN108102119A CN108102119A CN201711389625.1A CN201711389625A CN108102119A CN 108102119 A CN108102119 A CN 108102119A CN 201711389625 A CN201711389625 A CN 201711389625A CN 108102119 A CN108102119 A CN 108102119A
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- melamine resin
- melamine
- hollow microsphere
- performed polymer
- under agitation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/122—Pulverisation by spraying
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
- C08J9/286—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum the liquid phase being a solvent for the monomers but not for the resulting macromolecular composition, i.e. macroporous or macroreticular polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
- C08J2201/0504—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being aqueous
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08J2361/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08J2361/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2429/00—Characterised 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
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
Abstract
The invention discloses a kind of preparation methods of melamine resin hollow microsphere, it is related to Material Field, the present invention adjusts melamine resin performed polymer to a certain concentration, utilize spray drying device, it can rapidly volatilize in aqueous solution and foaming agent is generated under the collective effect of gas, cavity is formed inside melamine resin microballoon.Prepare melamine resin hollow microsphere using this method, method is simple and practicable, the reaction time is short, easy industrialization, at low cost, the hollow microsphere any surface finish prepared, degree of hollowness is good.
Description
Technical field
The present invention relates to Material Fields, are a kind of preparation methods of melamine resin hollow microsphere specifically.
Background technology
Hollow microsphere section bar material physics and chemical property with uniqueness due to its special hollow structure, in recent years just
Cause the concern of people more and more, become the research hotspot of Material Field.Up to now, inorganic material, polymer material,
During metal oxide materials and semi-conducting material (gallium oxide, gallium nitride) etc. are prepared by the trial of domestic and international researcher
Empty microspheric material, these materials show the specific function different from corresponding solid material.These are in special characteristics
Empty microspheric material is expected to be applied to the sides such as microreactor, drug conveying, control release, photocatalysis, enzyme cladding, photonic crystal
Face.Further, since hollow microsphere type density of material is low, effective area is big, there is heat-insulated, sound-absorbing and light to cover performance, therefore can
Using as density palliative, resin additive and space filler etc., be widely used in papermaking, oil exploitation, building coating and
The industries such as biological medicine and field.
Li Yuntao etc. coats ammonium polyphosphate, is obtained the micro- glue of ammonium polyphosphate melamine resin with melamine resin micro-capsule material
Capsule (performance characterization [J] China papermaking .2013 (07) of the ammonium polyphosphate melamine resin microcapsules such as Li Yuntao).Its technical side
The main contents of case divide two parts (1) to be prepared for melamine performed polymer as raw material using melamine and formaldehyde；(2) with melamine performed polymer
For raw material, coated ammonium polyphosphate by adjusting temperature and pH value, cures performed polymer, forms the micro- glue of ammonium polyphosphate melamine resin
Capsule.Above experiment is all realized in flask.This method realizes the scattered of drop and reaction in the solution, shortcoming be low yield,
Time used is long, and product is also needed to filter, dried, and has waste liquid generation.
The content of the invention
To solve above-mentioned technical problem existing in the prior art, the present inventor provides a kind of melamine resin hollow microsphere and prepares
Method.The melamine resin can also be melamine formaldehyde resin, be the main component of Ceramic-imitated tableware, have it is non-toxic and tasteless,
It is resistance to collide with, be corrosion-resistant, high temperature resistant, it is low temperature resistant the advantages that.The present invention passes through spray drying using melamine resin performed polymer for raw material
Equipment is sprayed, and prepares hollow microsphere.It can add in foaming agent in melamine resin performed polymer, foaming agent foam in spray process,
Melamine performed polymer is completed by heat cure, one step of hollow microsphere preparation process.Compared to the prior art, it is spray-dried then in the present invention
It is the process that integrated-type, granulation, reaction are integrated, it is significantly different with the mode of operation and mechanism reacted in the solution.The present invention
Method it is simple and practicable, the reaction time is short, easy industrialization, at low cost, the hollow microsphere any surface finish prepared, degree of hollowness is good.
The application prepares melamine resin hollow microsphere using the method for spraying.The advantages of preparing melamine resin hollow microsphere with this method is just
It is uniform particle sizes, speed is fast, and the product quality than preparing in the solution is high.Melamine resin microballoon compares phenolic resin microspheres toughness
More preferably, equal conditions lower density is low.
To realize above-mentioned technical purpose, the technical solution adopted by the present invention is as follows：
A kind of preparation method of melamine resin hollow microsphere, includes the following steps：
(1) under agitation, polyvinyl alcohol is dissolved in deionized water, it is 1.8-13.0mg/mL's that concentration, which is made,
Polyvinyl alcohol water solution；
(2), weak acid under agitation, is added in into polyvinyl alcohol water solution, adjusting pH value of solution is 2.0-6.0, described
Weak acid is glacial acetic acid；
(3), under agitation, melamine is uniformly mixed with formalin, the substance of melamine and formaldehyde
The ratio between amount is 1:1.0-1:6.0,30min is reacted below 60 DEG C, obtains prepolymer melamine methylol；
(4), under agitation, polyvinyl alcohol glacial acetic acid aqueous solution is mixed with prepolymer melamine methylol
It is even, keep the temperature in 60 DEG C, after white opacity occurs in system to be mixed, start timing, and the reaction was continued 6min, after be put into 0 DEG C of ice bath
In, fast cooling terminates reaction, obtains melamine resin performed polymer；
(5) adjust the solid content of melamine resin performed polymer obtained above as 10-20%wt, add foaming agent and/or
Surfactant is thoroughly mixed to form uniform slurries, and by the slurries through high temperature spray-drying, it is hollow that the melamine resin is made
Microballoon.
It further limits, step specifically comprises the following steps in (5)：
A, it is 10~20%wt to adjust melamine resin performed polymer solid content, and adjusting pH value with acid, adding dosage is to 4~6
The foaming agent and dosage of 0~10%wt of melamine resin performed polymer solid content is 0~0.08%wt of melamine resin performed polymer solid content
Surfactant, be thoroughly mixed to form uniform slurries；
B, through high temperature spray-drying the melamine resin hollow microsphere is made, wherein what is be spray-dried enters in above-mentioned slurries
Mouth temperature is 150~250 DEG C.
It further limits, the rate that dosage pump is adjusted in the step B is 10~100mL/min.
It further limits, foaming agent is at least one of sodium acid carbonate, ammonium hydrogen carbonate, ammonium hydroxide, urea.
The present invention adjusts melamine resin performed polymer to a certain concentration, can be rapid in aqueous solution using spray drying device
Volatilization and foaming agent are generated under the collective effect of gas, and cavity is formed inside melamine resin microballoon.It is prepared using this method close
Polyimide resin hollow microsphere, method is simple and practicable, the reaction time is short, it is easy industrialization, at low cost, the hollow microsphere surface light prepared
Clean, degree of hollowness is good.
Specific embodiment
In order to make those skilled in the art that the present invention may be better understood, with reference to embodiment to the technology of the present invention
Scheme further illustrates.
Test method：
The assay method of melamine resin hollow microsphere grain size：Using laser particle size analyzer (German good fortune Ritz FRITSCH,
Model：ANALYSETTE22MicroTec plus) it measures.
The assay method of melamine resin hollow microsphere density：200mL tap water is taken to place in beaker, adding in wherein
0.4g xanthans improves liquid phase viscosity, hollow microsphere is enable to suspend in the liquid phase as stick is carried；It is added in after being uniformly dissolved
20g melamine resin hollow microspheres match somebody with somebody to obtain low density drilling fluid after stirring evenly, the drilling fluid density is measured as ρ 1, if bead
Density is ρ balls.According to ρ=m/v principles, then ρ 1=(200+0.4+20)/[200+ (20/ ρ balls)] (xanthans can be dissolved into water
In, volume is ignored), you can ρ balls are calculated.The measuring method of drilling fluid density ρ 1 is shown in GB/T16783-1997《Water
Base drilling fluid On-Site Test Procedure》" 1 drilling fluid density ".
Embodiment 1
(1) under agitation, polyvinyl alcohol is dissolved in deionized water, the polyethylene that concentration is 1.8mg/mL is made
Alcohol solution；
(2) under agitation, weak acid is added in into polyvinyl alcohol water solution, it is 6.0 to adjust pH value of solution, and the weak acid is
Glacial acetic acid；
(3) under agitation, melamine is uniformly mixed with formalin, the amount of the substance of melamine and formaldehyde
The ratio between be 1:1.0,30min is reacted below 60 DEG C, obtains prepolymer melamine methylol；
(4), under agitation, polyvinyl alcohol glacial acetic acid aqueous solution is mixed with prepolymer melamine methylol
It is even, keep the temperature in 60 DEG C, after white opacity occurs in system to be mixed, start timing, and the reaction was continued 6min, after be put into 0 DEG C of ice bath
In, fast cooling terminates reaction, obtains melamine resin performed polymer；
(5) A, adjustment melamine resin performed polymer solid content are 20%wt, with acid pH value are adjusted to add dosage to 6 as melamine
The ammonium hydroxide and dosage of resin prepolymer solid content 5%wt is the surfactant of melamine resin performed polymer solid content 0.08%wt,
It is thoroughly mixed to form uniform slurries；
B, through high temperature spray-drying the melamine resin hollow microsphere is made, wherein what is be spray-dried enters in above-mentioned slurries
Mouth temperature is 150 DEG C.
Embodiment 2
(1) under agitation, polyvinyl alcohol is dissolved in deionized water, the poly- second that concentration is 12.0mg/mL is made
Enol aqueous solution；
(2), weak acid under agitation, is added in into polyvinyl alcohol water solution, it is 4.0 to adjust pH value of solution, the weak acid
For glacial acetic acid；
(3), under agitation, melamine is uniformly mixed with formalin, the substance of melamine and formaldehyde
The ratio between amount is 1:5.0,30min is reacted below 60 DEG C, obtains prepolymer melamine methylol；
(4), under agitation, polyvinyl alcohol glacial acetic acid aqueous solution is mixed with prepolymer melamine methylol
It is even, keep the temperature in 60 DEG C, after white opacity occurs in system to be mixed, start timing, and the reaction was continued 6min, after be put into 0 DEG C of ice bath
In, fast cooling terminates reaction, obtains melamine resin performed polymer；
(5) A, adjustment melamine resin performed polymer solid content are 10%wt, with acid pH value are adjusted to add dosage to 6 as melamine
The urea and dosage of resin prepolymer solid content 10%wt is the surfactant of melamine resin performed polymer solid content 0.08%wt,
It is thoroughly mixed to form uniform slurries；
B, through high temperature spray-drying the melamine resin hollow microsphere is made, wherein what is be spray-dried enters in above-mentioned slurries
Mouth temperature is 250 DEG C.
A kind of preparation method of melamine resin hollow microsphere provided by the invention is described in detail above.It is specific real
The explanation for applying example is only intended to help the method and its core concept for understanding the present invention.It should be pointed out that for the art
For those of ordinary skill, without departing from the principle of the present invention, can also to the present invention some improvement and modification can also be carried out,
These improvement and modification are also fallen into the protection domain of the claims in the present invention.
Claims (3)
1. a kind of preparation method of melamine resin hollow microsphere, which is characterized in that include the following steps：
(1) under agitation, polyvinyl alcohol is dissolved in deionized water, the poly- second that concentration is 1.8-13.0mg/mL is made
Enol aqueous solution；
(2), weak acid under agitation, is added in into polyvinyl alcohol water solution, adjusting pH value of solution is 2.0-6.0, the weak acid
For glacial acetic acid；
(3), under agitation, melamine is uniformly mixed with formalin, the amount of the substance of melamine and formaldehyde it
Than for 1:1.0-1:6.0,30min is reacted below 60 DEG C, obtains prepolymer melamine methylol；
(4), under agitation, polyvinyl alcohol glacial acetic acid aqueous solution with prepolymer melamine methylol is uniformly mixed, is protected
Temperature is in 60 DEG C, after white opacity occurs in system to be mixed, starts timing, and the reaction was continued 6min, after be put into 0 DEG C of ice bath, soon
Prompt drop temperature terminates reaction, obtains melamine resin performed polymer；
(5) solid content of melamine resin performed polymer obtained above is adjusted as 10-20%wt, adds foaming agent and/or surface
Activating agent is thoroughly mixed to form uniform slurries, and by the slurries through high temperature spray-drying, it is hollow micro- that the melamine resin is made
Ball.
2. the preparation method of a kind of melamine resin hollow microsphere according to claim 1, which is characterized in that in step (5)
Specifically comprise the following steps：
A, it is 10~20%wt to adjust melamine resin performed polymer solid content, with acid pH value is adjusted to add dosage to 4~6 as melamine
The foaming agent and dosage of 0~10%wt of resin prepolymer solid content is the table of 0~0.08%wt of melamine resin performed polymer solid content
Face activating agent is thoroughly mixed to form uniform slurries；
B, through high temperature spray-drying the melamine resin hollow microsphere is made, wherein the entrance temperature being spray-dried in above-mentioned slurries
It spends for 150~250 DEG C.
3. the preparation method of a kind of melamine resin hollow microsphere according to claim 2, which is characterized in that foaming agent is carbon
At least one of sour hydrogen sodium, ammonium hydrogen carbonate, ammonium hydroxide, urea.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201711389625.1A CN108102119A (en) | 2017-12-21 | 2017-12-21 | A kind of preparation method of melamine resin hollow microsphere |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711389625.1A CN108102119A (en) | 2017-12-21 | 2017-12-21 | A kind of preparation method of melamine resin hollow microsphere |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109824920A (en) * | 2019-01-22 | 2019-05-31 | 齐鲁工业大学 | One-step method prepares polyvinyl alcohol copolymer melamine resin nanosphere |
| CN110841608A (en) * | 2019-11-28 | 2020-02-28 | 朱润栋 | Preparation method of penicillin fermentation liquor refined adsorbent |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104167302A (en) * | 2014-08-26 | 2014-11-26 | 齐鲁工业大学 | Preparation method for grapheme/melamine resin hollow ball composite material |
| CN104356594A (en) * | 2014-11-27 | 2015-02-18 | 长春工业大学 | Preparation method of organosilicon melamine resin composite particles |
| CN106140039A (en) * | 2015-05-12 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of melamine resin hollow microsphere and its preparation method and application |
-
2017
- 2017-12-21 CN CN201711389625.1A patent/CN108102119A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104167302A (en) * | 2014-08-26 | 2014-11-26 | 齐鲁工业大学 | Preparation method for grapheme/melamine resin hollow ball composite material |
| CN104356594A (en) * | 2014-11-27 | 2015-02-18 | 长春工业大学 | Preparation method of organosilicon melamine resin composite particles |
| CN106140039A (en) * | 2015-05-12 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of melamine resin hollow microsphere and its preparation method and application |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109824920A (en) * | 2019-01-22 | 2019-05-31 | 齐鲁工业大学 | One-step method prepares polyvinyl alcohol copolymer melamine resin nanosphere |
| CN110841608A (en) * | 2019-11-28 | 2020-02-28 | 朱润栋 | Preparation method of penicillin fermentation liquor refined adsorbent |
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