CN105837772A - Preparation method for poly(melamine-formaldehyde) polymeric microsphere three-dimensional template material - Google Patents
Preparation method for poly(melamine-formaldehyde) polymeric microsphere three-dimensional template material Download PDFInfo
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- CN105837772A CN105837772A CN201610202903.7A CN201610202903A CN105837772A CN 105837772 A CN105837772 A CN 105837772A CN 201610202903 A CN201610202903 A CN 201610202903A CN 105837772 A CN105837772 A CN 105837772A
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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
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention discloses a preparation method for a poly(melamine-formaldehyde) polymeric microsphere three-dimensional template material. The preparation method comprises the following steps: uniformly mixing melamine and formaldehyde, in a mol ratio of 1: 10-50, in 100 mL of deionized water, then slowing heating the obtained mixture to 30 to 85 DEG C for prepolymerization for 20 to 60 min; then adding a proper amount of formic acid or acetic acid drop by drop for a precipitation reaction for 40 to 80 min and subjecting a reaction product to centrifugation and washing so as to obtain poly(melamine-formaldehyde) polymeric microspheres; dispersing the microspheres in water so as to obtain an emulsion with a solid-liquid ratio of 0.5-1 g: 100 ml, subjecting the emulsion to natural sedimentation for 5 to 10 d and then carrying out vacuum drying at 35 to 45 DEG C. The polymeric microsphere template material prepared by using the method has the characteristics of uniform particle size, small particle size, large specific surface area, neat and ordered structure, strong adsorptivity, great coacervation effect, strong surface reaction capability, etc.
Description
Technical field
The invention belongs to polymer microballoon science and applied technical field, be specifically related to a kind of poly-carbamide polymer micro-
The preparation method of ball three-dimensional template material.
Background technology
Poly-carbamide (MF) microsphere is a widely used material of class, and MF microsphere and inorganic oxide are at physical chemistry
Difference in matter makes it be very easy to remove as template, and good mechanical property can be come as excellent three-dimensional template material
Prepare other three-dimensional large pore material.It is regular, good that single dispersing poly-carbamide type polymer microballoon has uniform particle diameter, pattern
Good surface respond and be prone to the advantages such as functionalization, also has the highest grinding in fields such as immunological technique and disease early diagnosiss
Study carefully and using value.
Although poly-carbamide type polymer microballoon has advantage described above and application prospect, but prior art exists all
The most not enough, including 1 micron order and the control of following poly-carbamide type polymer microballoon polymeric reaction condition difficulty, preparation method
The problems such as complexity, particle diameter is uncontrollable, microspherulite diameter is uneven, space matrix arrangement is irregular.
Summary of the invention
It is an object of the invention to solve existing poly-carbamide type polymer microballoon difficult control of reaction conditions, microspherulite diameter not
Uniformly, space matrix arranges the deficiencies such as irregular, it is provided that the system of a kind of poly-carbamide polymer microballoon three-dimensional template material
Preparation Method, grain size is the most homogeneous, particle diameter is little, specific surface area to use the polymer microballoon mould material prepared of the method to have
The characteristics such as greatly, compound with regular structure is orderly, adsorptivity is strong, cohesion is big and surface respond is strong.Technical scheme is such as
Under:
The preparation method of a kind of poly-carbamide polymer microballoon three-dimensional template material, comprises the following steps: (1) is by trimerization
Cyanamide and formaldehyde join in deionized water and are uniformly mixed, and slowly raise insulation reaction after mixed solution temperature；(2) to mixed
Reaction is continued after conjunction solution drips a certain amount of acid solution regulation pH, after having reacted, warp is centrifuged, washing obtains poly-tripolycyanamide-
Formaldehyde microsphere；(3) poly-carbamide microsphere is dispersed in water to obtain single dispersing carbamide microsphere emulsion, by breast
After liquid room temperature natural subsidence a couple of days is vacuum dried again and get final product.
In step (1), the mol ratio of tripolycyanamide and formaldehyde is 1:10-50, and mixed solution is warming up to 30-85 DEG C, insulation reaction
20-60min。
Step (2) regulation mass ratio that acid is formic acid or acetic acid, formic acid or acetic acid and melamine monomer used by pH is 1:5-15,
Reaction 40-80min is continued after regulation pH.
The solid-to-liquid ratio of step (3) described single dispersing carbamide microsphere emulsion is 0.5-1g/100ml, room temperature natural subsidence
5-10 days, vacuum drying temperature was 35-45 DEG C.
The preparation method of the poly-carbamide polymer microballoon that the present invention provides has the advantages that (1) is with melamine
Amine, formaldehyde are raw material, prepare poly-carbamide polymer microballoon through precipitation polymerization reaction and two steps of natural subsidence, former
Expect that the simple low cost in source, preparation technology are simple, products therefrom purity is higher；(2) compared with traditional polymer microsphere, this
Polymer microballoon prepared by bright method has that grain size is the most homogeneous, particle diameter is little, specific surface area is big, compound with regular structure is orderly, inhales
The characteristics such as attached property is strong, cohesion is big and surface respond is strong；(3) application potential is big, polymer prepared by the inventive method
Microsphere has bigger application potential at biochemistry, analytical chemistry, immunity medical science and some high-technology field.
Accompanying drawing explanation
Fig. 1 is the poly-carbamide polymer microballoon three-dimensional template SEM figure of the embodiment of the present invention 1 preparation, wherein Fig. 1-a
Enlargement ratio is 2000, and the enlargement ratio of Fig. 1-b is 10000；
Fig. 2 is the poly-carbamide polymer microballoon three-dimensional template SEM figure of the embodiment of the present invention 2 preparation, wherein Fig. 2-a
Enlargement ratio is 5000, and the enlargement ratio of Fig. 2-b is 5000；
Fig. 3 is the poly-carbamide polymer microballoon three-dimensional template SEM figure of the embodiment of the present invention 3 preparation, wherein Fig. 3-a
Enlargement ratio is 5000, and the enlargement ratio of Fig. 3-b is 10000；
Fig. 4 is the poly-carbamide polymer microballoon three-dimensional template SEM figure of the embodiment of the present invention 4 preparation, wherein Fig. 4-a
Enlargement ratio is 8000, and the enlargement ratio of Fig. 4-b is 30000.
Detailed description of the invention
For making those of ordinary skill in the art fully understand technical scheme and beneficial effect, below in conjunction with specific embodiment
And accompanying drawing is further described.
In the present invention and embodiment, agents useful for same is commercially available chemical reagent if no special instructions.
Embodiment 1
The preparation method of a kind of poly-carbamide polymer microballoon three-dimensional template material, comprises the following steps: first by three
Poly cyanamid and formaldehyde join in the deionized water of 100ml according to the mol ratio of 1:10, are sufficiently stirred for making its mix homogeneously under room temperature.
Subsequently from room temperature, solution temperature being slowly raised 85 DEG C, insulation carries out prepolymerization reaction 60min, then drips 1 part of first in solution
Acid (quality of 1 part of formic acid and the mass ratio of melamine monomer are 1:12.5) regulation pH, proceeds precipitation 80min.
Product is centrifuged washing after terminating by reaction, obtains white solid powder shape poly-carbamide microsphere.By above-mentioned poly-trimerization
Cyanogen amine-for-aldehyde microsphere is dispersed in water, and obtains the single dispersing poly-carbamide microsphere emulsion that solid-to-liquid ratio is 0.5g/100ml,
Be placed on smooth place room temperature natural subsidence 5d, then at 35 DEG C, be vacuum dried to obtain white flaky solid, be poly-tripolycyanamide-
Yuban microsphere three-dimensional template material.
Embodiment 2
The preparation method of a kind of poly-carbamide polymer microballoon three-dimensional template material, comprises the following steps: first by three
Poly cyanamid and formaldehyde join in the deionized water of 100ml according to the mol ratio of 1:50, are sufficiently stirred for making its mix homogeneously under room temperature.
Subsequently from room temperature, solution temperature being slowly raised 30 DEG C, insulation carries out prepolymerization reaction 30min, drips 1 part of formic acid in solution
(quality of 1 part of formic acid and the mass ratio of melamine monomer are 1:5) regulation pH, proceeds precipitation 50min.Reaction
After end, product is centrifuged washing, obtains white solid powder shape poly-carbamide microsphere.By above-mentioned poly-tripolycyanamide
-formaldehyde microsphere is dispersed in water, and obtains the single dispersing poly-carbamide microsphere emulsion that solid-to-liquid ratio is 1g/100ml, is put
In smooth place room temperature natural subsidence 10d, then at 45 DEG C, it is vacuum dried to obtain white flaky solid, is poly-carbamide and gathers
Compound microsphere three-dimensional template material.
Embodiment 3
The preparation method of a kind of poly-carbamide polymer microballoon three-dimensional template material, comprises the following steps: first by three
Poly cyanamid and formaldehyde join in the deionized water of 100ml according to the mol ratio of 1:16, are sufficiently stirred for making its mix homogeneously under room temperature.
Subsequently from room temperature, solution temperature being slowly raised 80 DEG C, insulation carries out prepolymerization reaction 20min, drips 1 part of formic acid in solution
(quality of 1 part of formic acid and the mass ratio of melamine monomer are 1:15.) regulation pH, proceed precipitation 40min.
Product is centrifuged washing after terminating by reaction, obtains white solid powder shape poly-carbamide microsphere.By above-mentioned poly-trimerization
Cyanogen amine-for-aldehyde microsphere is dispersed in water, and obtains the single dispersing poly-carbamide microsphere emulsion that solid-to-liquid ratio is 1g/100ml, will
It is placed in smooth place room temperature natural subsidence 5d, then is vacuum dried to obtain white flaky solid at 40 DEG C, is poly-tripolycyanamide-first
Aldehyde polymer microsphere three-dimensional template material.
Embodiment 4
The preparation method of a kind of poly-carbamide polymer microballoon three-dimensional template material, comprises the following steps: first by three
Poly cyanamid and formaldehyde join in the deionized water of 100ml according to the mol ratio of 1:20, are sufficiently stirred for making its mix homogeneously under room temperature.
Subsequently from room temperature, solution temperature being slowly raised 80 DEG C, insulation carries out prepolymerization reaction 20min, drips 1 part of acetic acid in solution
(quality of 1 part of acetic acid and the mass ratio of melamine monomer are 1:5) regulation pH, proceeds precipitation 20min.Reaction
After end, product is centrifuged washing, obtains white solid powder shape poly-carbamide microsphere.By above-mentioned poly-tripolycyanamide
-formaldehyde microsphere is dispersed in water, and obtains the single dispersing poly-carbamide microsphere emulsion that solid-to-liquid ratio is 1g/100ml, is put
In smooth place room temperature natural subsidence 7d, then at 40 DEG C, it is vacuum dried to obtain white flaky solid, is poly-carbamide and gathers
Compound microsphere three-dimensional template material.
For understanding the microstructure of this poly-carbamide polymer microballoon three-dimensional template material, it is carried out scanning electron microscope survey
Examination, result is as Figure 1-4.Can be seen that microsphere is spherical in shape and sphericity is preferable from Fig. 1-a, 2-a, 3-a and 4-a；Choosing
Take partial enlargement it has been observed that the particle diameter distribution of poly-carbamide microsphere is more uniform, size about 1 μm, and
Single dispersing poly-carbamide arrangement of microspheres possesses certain ordered degree (as shown in Fig. 1-b, 2-b, 3-b and 4-b).Thus,
Poly-carbamide type polymer microballoon three-dimensional template material (final goal thing) prepared by various embodiments of the present invention and design
Object is consistent, has that grain size is homogeneous, particle diameter is little, specific surface area is big, compound with regular structure is orderly, adsorptivity is strong, cohesion work
By characteristics such as big and surface respond are strong, have at biochemistry, analytical chemistry, immunity medical science and some high-technology field
Bigger application potential.
Claims (4)
1. the preparation method of a poly-carbamide polymer microballoon three-dimensional template material, it is characterised in that comprise the following steps:
(1) tripolycyanamide and formaldehyde being joined in deionized water and be uniformly mixed, after slowly raising mixed solution temperature, insulation is anti-
Should；(2) after a certain amount of acid for adjusting pH of mixed solution and dripping, continue reaction, gathered through centrifugal, washing after having reacted
Carbamide microsphere；(3) poly-carbamide microsphere is dispersed in water to obtain single dispersing carbamide microsphere
Emulsion, after being vacuum dried emulsion room temperature natural subsidence a couple of days and get final product again.
The preparation method of a kind of poly-carbamide polymer microballoon three-dimensional template material the most as claimed in claim 1, its feature
Being: in step (1), the mol ratio of tripolycyanamide and formaldehyde is 1:10-50, mixed solution is warming up to 30-85 DEG C, and insulation is anti-
Answer 20-60min.
The preparation method of a kind of poly-carbamide polymer microballoon three-dimensional template material the most as claimed in claim 1, its feature
It is: step (2) regulation acid used by pH is formic acid or acetic acid, formic acid or acetic acid and the mass ratio of melamine monomer is
1:5-15, continues reaction 40-80min after regulation pH.
The preparation method of a kind of poly-carbamide polymer microballoon three-dimensional template material the most as claimed in claim 1, its feature
Being: the solid-to-liquid ratio of step (3) described single dispersing carbamide microsphere emulsion is 0.5-1g/100ml, room temperature is naturally heavy
Dropping 5-10 days, vacuum drying temperature is 35-45 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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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| CN105837772A true CN105837772A (en) | 2016-08-10 |
| CN105837772B CN105837772B (en) | 2018-08-24 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110358033A (en) * | 2019-06-28 | 2019-10-22 | 南京工程学院 | A kind of monodisperse amphoteric ion exchange thermosetting resin microballoon 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 |
| CN111892039A (en) * | 2020-07-06 | 2020-11-06 | 武汉工程大学 | MXene and carbon nanotube composite hollow nanosphere and autocatalytic preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105080444A (en) * | 2015-08-27 | 2015-11-25 | 齐鲁工业大学 | Method for preparing monodisperse magnetic melamine resin microspheres |
-
2016
- 2016-04-01 CN CN201610202903.7A patent/CN105837772B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
|---|
| 刘亚军等: "单分散三聚氰胺甲醛微球的制备", 《功能高分子学报》 * |
| 李晨健等: "粒径可控单分散三聚氰胺-甲醛(MF)树脂微球的制备研究", 《胶体与聚合物》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110358033A (en) * | 2019-06-28 | 2019-10-22 | 南京工程学院 | A kind of monodisperse amphoteric ion exchange thermosetting resin microballoon 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 |
| CN111892039A (en) * | 2020-07-06 | 2020-11-06 | 武汉工程大学 | MXene and carbon nanotube composite hollow nanosphere and autocatalytic preparation method and application thereof |
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