CN105837772B - The preparation method of poly- melamine-formaldehyde polymer microballoon three-dimensional template material - Google Patents
The preparation method of poly- melamine-formaldehyde polymer microballoon three-dimensional template material Download PDFInfo
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- CN105837772B CN105837772B CN201610202903.7A CN201610202903A CN105837772B CN 105837772 B CN105837772 B CN 105837772B CN 201610202903 A CN201610202903 A CN 201610202903A CN 105837772 B CN105837772 B CN 105837772B
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- melamine
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
- C08G12/32—Melamines
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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
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
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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
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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
- 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
Abstract
The invention discloses a kind of preparation methods of poly- melamine formaldehyde polymer microballoon three-dimensional template material, include the following steps：By melamine and formaldehyde according to 1:10 50 molar ratio is uniformly mixed in 100ml deionized waters, is then to slowly warm up to 30 85 DEG C and is carried out 20 60min of prepolymerization reaction；Then appropriate formic acid is added dropwise or acetic acid carries out 40 80min of precipitation reaction, reaction product washes to obtain poly- melamino-formaldehyde microballoon through centrifugation；By microballoon be dispersed in water solid-to-liquid ratio be 0.5g 1g/100ml lotion, lotion natural subsidence is dried in vacuo after 5 10 days at 35 45 DEG C to obtain the final product.There are the characteristics such as grain size is extremely uniform, grain size is small, large specific surface area, compound with regular structure are orderly, strong adsorption, cohesion are big and surface respond is strong using polymer microballoon mould material prepared by this method.
Description
Technical field
The invention belongs to polymer microballoon science and applied technical fields, and in particular to a kind of poly- melamine-formaldehyde is poly-
Close the preparation method of object microballoon three-dimensional template material.
Background technology
Poly- melamine-formaldehyde (MF) microballoon is a kind of widely used material, and MF microballoons are with inorganic oxide in physics
Difference in chemical property makes it be very easy to removal as template, and good mechanical property can be as excellent three-dimensional mould
Plate material prepares other three-dimensional large pore materials.The poly- melamine-formaldehyde type polymer microballoon of monodisperse has uniform particle diameter, shape
Looks rule, good surface respond and the advantages that be easy to functionalization the fields such as early diagnose in immunological technique and disease
With very high research and application value.
Although poly- melamine-formaldehyde type polymer microballoon has advantage and application prospect as described above, the prior art
There are many deficiencies, including 1 micron order and following poly- melamine-formaldehyde type polymer microballoon polymeric reaction condition it is difficult to control,
The problems such as preparation method is complicated, grain size is uncontrollable, microspherulite diameter is uneven, space matrix arrangement is irregular.
Invention content
It is an object of the invention to solve existing poly- melamine-formaldehyde type polymer microballoon difficult control of reaction conditions, micro-
The deficiencies of spherolite diameter is uneven, space matrix arrangement is irregular, provides a kind of poly- melamine-formaldehyde polymer microballoon three-dimensional mould
The preparation method of plate material, the polymer microballoon mould material prepared using this method extremely uniform, grain size with grain size
The characteristics such as small, large specific surface area, compound with regular structure are orderly, strong adsorption, cohesion are big and surface respond is strong.The present invention's
Technical solution is as follows：
A kind of preparation method of poly- melamine-formaldehyde polymer microballoon three-dimensional template material, includes the following steps：(1)
Melamine and formaldehyde are add to deionized water and are uniformly mixed, insulation reaction after mixed solution temperature is slowly increased；
(2) the reaction was continued after adjusting pH to a certain amount of acid solution of mixed solution and dripping, through centrifuging, washing to obtain poly- three after reaction completion
Paracyanogen amine-for-aldehyde microballoon；(3) poly- melamine-formaldehyde microballoon is dispersed in water to obtain monodisperse melamine-formaldehyde microballoon breast
Liquid, after lotion room temperature natural subsidence a couple of days is dried in vacuo again to obtain the final product.
The molar ratio of melamine and formaldehyde is 1 in step (1):10-50, mixed solution are warming up to 30-85 DEG C, and heat preservation is anti-
Answer 20-60min.
It is formic acid or acetic acid that step (2), which adjusts the acid used in pH, and formic acid or the mass ratio of acetic acid and melamine monomer are
1:5-15 adjusts the reaction was continued 40-80min after pH.
The solid-to-liquid ratio of step (3) the monodisperse melamine-formaldehyde microballoon lotion is 0.5-1g/100ml, and room temperature is natural
Sedimentation 5-10 days, vacuum drying temperature are 35-45 DEG C.
The preparation method of poly- melamine-formaldehyde polymer microballoon provided by the invention has the advantages that：(1) with
Melamine, formaldehyde are raw material, and poly- melamine-formaldehyde polymer is made through precipitation polymerization reaction and two steps of natural subsidence
Microballoon, raw material sources are simply at low cost, preparation process is simple, products therefrom purity is higher；(2) with traditional polymer microballoon phase
Than polymer microballoon prepared by the method for the present invention is with grain size is extremely uniform, grain size is small, large specific surface area, compound with regular structure
The characteristics such as orderly, strong adsorption, cohesion are big and surface respond is strong；(3) application potential is big, prepared by the method for the present invention
Polymer microballoon has larger application potential in biochemistry, analytical chemistry, immune medicine and certain high-technology fields.
Description of the drawings
Fig. 1 is poly- melamine-formaldehyde polymer microballoon three-dimensional template SEM figures prepared by the embodiment of the present invention 1, wherein scheming
The enlargement ratio that the enlargement ratio of 1-a is 2000, Fig. 1-b is 10000；
Fig. 2 is poly- melamine-formaldehyde polymer microballoon three-dimensional template SEM figures prepared by the embodiment of the present invention 2, wherein scheming
The enlargement ratio that the enlargement ratio of 2-a is 5000, Fig. 2-b is 5000；
Fig. 3 is poly- melamine-formaldehyde polymer microballoon three-dimensional template SEM figures prepared by the embodiment of the present invention 3, wherein scheming
The enlargement ratio that the enlargement ratio of 3-a is 5000, Fig. 3-b is 10000；
Fig. 4 is poly- melamine-formaldehyde polymer microballoon three-dimensional template SEM figures prepared by the embodiment of the present invention 4, wherein scheming
The enlargement ratio that the enlargement ratio of 4-a is 8000, Fig. 4-b is 30000.
Specific implementation mode
To make those of ordinary skill in the art fully understand technical scheme of the present invention and advantageous effect, with reference to specific
Embodiment and attached drawing are further described.
Agents useful for same is commercially available chemical reagent unless otherwise specified in of the invention and embodiment.
Embodiment 1
A kind of preparation method of poly- melamine-formaldehyde polymer microballoon three-dimensional template material, includes the following steps：First
By melamine and formaldehyde according to 1:10 molar ratio is added in the deionized water of 100ml, and be sufficiently stirred keeps it mixed at room temperature
It closes uniform.Solution temperature is then slowly raised 85 DEG C from room temperature, heat preservation carries out prepolymerization reaction 60min, then is dripped into solution
Adding 1 part of formic acid, (quality of 1 part of formic acid and the mass ratio of melamine monomer are 1:12.5) pH is adjusted, precipitation reaction is continued
80min.Product is subjected to centrifugation washing after reaction, obtains the poly- melamine-formaldehyde microballoon of white solid powder shape.It will be upper
It states poly- melamine-formaldehyde microballoon to be dispersed in water, obtains the poly- melamine-formaldehyde of monodisperse that solid-to-liquid ratio is 0.5g/100ml
Microballoon lotion places it in smooth place's room temperature natural subsidence 5d, then is dried in vacuo to obtain white flaky solid at 35 DEG C, as poly-
Melamine-formaldehyde polymer microballoon three-dimensional template material.
Embodiment 2
A kind of preparation method of poly- melamine-formaldehyde polymer microballoon three-dimensional template material, includes the following steps：First
By melamine and formaldehyde according to 1:50 molar ratio is added in the deionized water of 100ml, and be sufficiently stirred keeps it mixed at room temperature
It closes uniform.Solution temperature is then slowly raised 30 DEG C from room temperature, heat preservation carries out prepolymerization reaction 30min, and 1 is added dropwise into solution
(quality of 1 part of formic acid and the mass ratio of melamine monomer are 1 for part formic acid:5) pH is adjusted, precipitation reaction 50min is continued.
Product is subjected to centrifugation washing after reaction, obtains the poly- melamine-formaldehyde microballoon of white solid powder shape.By above-mentioned poly- three
Paracyanogen amine-for-aldehyde microballoon is dispersed in water, and obtains the poly- melamine-formaldehyde microballoon breast of monodisperse that solid-to-liquid ratio is 1g/100ml
Liquid places it in smooth place's room temperature natural subsidence 10d, then is dried in vacuo to obtain white flaky solid at 45 DEG C, as poly- trimerization
Cyanamide-yuban microballoon three-dimensional template material.
Embodiment 3
A kind of preparation method of poly- melamine-formaldehyde polymer microballoon three-dimensional template material, includes the following steps：First
By melamine and formaldehyde according to 1:16 molar ratio is added in the deionized water of 100ml, and be sufficiently stirred keeps it mixed at room temperature
It closes uniform.Solution temperature is then slowly raised 80 DEG C from room temperature, heat preservation carries out prepolymerization reaction 20min, and 1 is added dropwise into solution
(quality of 1 part of formic acid and the mass ratio of melamine monomer are 1 for part formic acid:15.) pH is adjusted, continue precipitation reaction
40min.Product is subjected to centrifugation washing after reaction, obtains the poly- melamine-formaldehyde microballoon of white solid powder shape.It will be upper
It states poly- melamine-formaldehyde microballoon to be dispersed in water, it is micro- to obtain the poly- melamine-formaldehyde of monodisperse that solid-to-liquid ratio is 1g/100ml
Ball lotion places it in smooth place's room temperature natural subsidence 5d, then is dried in vacuo to obtain white flaky solid at 40 DEG C, and as poly- three
Poly cyanamid-yuban microballoon three-dimensional template material.
Embodiment 4
A kind of preparation method of poly- melamine-formaldehyde polymer microballoon three-dimensional template material, includes the following steps：First
By melamine and formaldehyde according to 1:20 molar ratio is added in the deionized water of 100ml, and be sufficiently stirred keeps it mixed at room temperature
It closes uniform.Solution temperature is then slowly raised 80 DEG C from room temperature, heat preservation carries out prepolymerization reaction 20min, and 1 is added dropwise into solution
(quality of 1 part of acetic acid and the mass ratio of melamine monomer are 1 for part acetic acid:5) pH is adjusted, precipitation reaction 20min is continued.
Product is subjected to centrifugation washing after reaction, obtains the poly- melamine-formaldehyde microballoon of white solid powder shape.By above-mentioned poly- three
Paracyanogen amine-for-aldehyde microballoon is dispersed in water, and obtains the poly- melamine-formaldehyde microballoon breast of monodisperse that solid-to-liquid ratio is 1g/100ml
Liquid places it in smooth place's room temperature natural subsidence 7d, then is dried in vacuo to obtain white flaky solid at 40 DEG C, as poly- melamine
Amine-for-aldehyde polymer microballoon three-dimensional template material.
To understand the microstructure of the poly- melamine-formaldehyde polymer microballoon three-dimensional template material, it is swept
Electronic Speculum test is retouched, as a result as shown in Figs 1-4.Can be seen that microballoon is spherical in shape from Fig. 1-a, 2-a, 3-a and 4-a and sphericity compared with
It is good；Partial enlargement is chosen it has been observed that the particle diameter distribution of poly- melamine-formaldehyde microballoon is more uniform, particle size is on 1 μm of left side
The right side, and the poly- melamine-formaldehyde arrangement of microspheres of monodisperse has certain ordered degree (as shown in Fig. 1-b, 2-b, 3-b and 4-b).By
This, various embodiments of the present invention prepare poly- melamine-formaldehyde type polymer microballoon three-dimensional template material (final goal object) with
The object of design is consistent, with grain size is uniform, grain size is small, large specific surface area, compound with regular structure are orderly, strong adsorption, coagulates
The characteristics such as poly- effect is big and surface respond is strong, in biochemistry, analytical chemistry, immune medicine and certain new and high technologies neck
There is larger application potential in domain.
Claims (1)
1. a kind of preparation method of poly- melamine-formaldehyde polymer microballoon three-dimensional template material, it is characterised in that including following
Step：
(1) melamine and formaldehyde are add to deionized water and are uniformly mixed, protected after slowly increasing mixed solution temperature
Temperature reaction；
(2) to the reaction was continued after a certain amount of acid for adjusting pH of mixed solution and dripping, reaction complete after through centrifuging, washing to obtain poly- three
Paracyanogen amine-for-aldehyde microballoon；
(3) poly- melamine-formaldehyde microballoon is dispersed in water to obtain monodisperse melamine-formaldehyde microballoon lotion, lotion is normal
Warm natural subsidence a couple of days be dried in vacuo again after to obtain the final product；
Wherein, the molar ratio of melamine and formaldehyde is 1 in step (1):10-50, mixed solution are warming up to 30-85 DEG C, heat preservation
React 20-60min；
It is formic acid or acetic acid that step (2), which adjusts the acid used in pH, and formic acid or the mass ratio of acetic acid and melamine monomer are 1:5-
15, adjust the reaction was continued 40-80min after pH；
The solid-to-liquid ratio of step (3) the monodisperse melamine-formaldehyde microballoon lotion is 0.5-1g/100ml, room temperature natural subsidence
5-10 days, vacuum drying temperature was 35-45 DEG C.
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| CN201610202903.7A CN105837772B (en) | 2016-04-01 | 2016-04-01 | The preparation method of poly- melamine-formaldehyde polymer microballoon three-dimensional template material |
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| CN110358033B (en) * | 2019-06-28 | 2022-05-10 | 南京工程学院 | Monodisperse amphoteric ion exchange thermosetting resin microsphere and preparation method thereof |
| CN111303363A (en) * | 2020-04-08 | 2020-06-19 | 安徽壹石通材料科技股份有限公司 | Preparation method of large-particle-size melamine formaldehyde resin microspheres |
| CN111892039B (en) * | 2020-07-06 | 2022-04-19 | 武汉工程大学 | MXene and carbon nanotube composite hollow nanosphere and autocatalytic preparation method and application thereof |
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| CN105080444A (en) * | 2015-08-27 | 2015-11-25 | 齐鲁工业大学 | Method for preparing monodisperse magnetic melamine resin microspheres |
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| CN105080444A (en) * | 2015-08-27 | 2015-11-25 | 齐鲁工业大学 | Method for preparing monodisperse magnetic melamine resin microspheres |
Non-Patent Citations (2)
| Title |
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| 单分散三聚氰胺甲醛微球的制备;刘亚军等;《功能高分子学报》;20040331;第17卷(第1期);第113-118页 * |
| 粒径可控单分散三聚氰胺-甲醛(MF)树脂微球的制备研究;李晨健等;《胶体与聚合物》;20150930;第33卷(第3期);第116-118页 * |
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