CN114456540B - Melamine formaldehyde resin composite material and preparation method thereof - Google Patents
Melamine formaldehyde resin composite material and preparation method thereof Download PDFInfo
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- CN114456540B CN114456540B CN202210044344.7A CN202210044344A CN114456540B CN 114456540 B CN114456540 B CN 114456540B CN 202210044344 A CN202210044344 A CN 202210044344A CN 114456540 B CN114456540 B CN 114456540B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
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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
- C08G12/34—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds and acyclic or carbocyclic compounds
- C08G12/36—Ureas; Thioureas
- C08G12/38—Ureas; Thioureas and melamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/01—Magnetic additives
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Abstract
The invention discloses a melamine formaldehyde resin composite material and a preparation method thereof, wherein the melamine formaldehyde resin composite material is prepared from the following components in parts by weight: 30-33 parts of melamine, 38-42 parts of formaldehyde, 70-200 parts of NdFeB magnetic powder, 0.3-2 parts of diisopropyl di (acetylacetonate) titanate and 0.2-0.25 part of sodium hydroxide. The melamine and formaldehyde are mixed according to a specific proportion, so that a product with excellent performance is prepared. In addition, the invention adopts diisopropyl di (acetylacetonate) titanate to modify NdFeB magnetic powder to obtain modified magnetic powder, and the modified magnetic powder can obviously improve the magnetic performance of the melamine formaldehyde resin composite material.
Description
Technical Field
The invention belongs to the technical field of modification of high polymer materials, and particularly relates to a melamine formaldehyde resin composite material and a preparation method thereof.
Background
Melamine-formaldehyde resin, also known as melamine formaldehyde resin, is a polymer obtained by reacting melamine with formaldehyde, a resin in which the melamine ring is terminated with a plurality of hydroxyl groups derived from formaldehyde, in butylated form, dissolved in n-butanol and xylene.
The melamine formaldehyde resin is crosslinked during processing and forming, and the product is infusible thermosetting resin. It is conventionally commonly referred to as an amino resin with urea-formaldehyde resins. The cured melamine formaldehyde resin is colorless and transparent, stable in boiling water, even can be used at 150 ℃, and has self-extinguishing property, arc resistance and good mechanical property; the water resistance is high, the thermal stability is high, the low-temperature curing capability is strong, the wear resistance is good, the curing is fast, and the strengthening agent is not needed. Melamine formaldehyde resins have been widely used in the fields of construction, machinery, automobiles, agriculture, and the like.
Melamine formaldehyde resins need to have improved magnetic properties in order to be able to be used further in the field of magnetic plastics.
Disclosure of Invention
The invention aims to provide a melamine formaldehyde resin composite material and a preparation method thereof, wherein the melamine formaldehyde resin composite material has good magnetism so as to solve the problems in the prior art.
The aim of the invention is realized by the following technical scheme:
the melamine formaldehyde resin composite material is prepared from the following components in parts by weight:
further, the NdFeB magnetic powder is quick quenched NdFeB magnetic powder, and the average particle size is 1-2 microns.
Further, the alkaline substance is sodium hydroxide or potassium hydroxide, and the alkaline substance is used for adjusting the pH value of a reaction system to be slightly alkaline, so that melamine and formaldehyde are polymerized to generate stable melamine formaldehyde resin.
The invention also discloses a preparation method of the melamine formaldehyde resin composite material, which comprises the following steps:
(1) Uniformly spraying 0.3-2 parts of diisopropyl di (acetylacetonate) titanate on the surface of 70-200 parts of NdFeB magnetic powder to obtain modified magnetic powder;
(2) Dissolving 0.2-0.25 part of sodium hydroxide in 38-42 parts of formaldehyde, then adding 30-33 parts of melamine, and carrying out prepolymerization reaction under the stirring condition to obtain a reaction solution; and (3) adding the modified magnetic powder obtained in the step (1) into the reaction liquid, and continuing to react for 10-60 minutes in a protective atmosphere to obtain a target product. Preferably, the reaction temperature of the prepolymerization reaction is 80-90 ℃ and the reaction time is 30-60 min; the protective atmosphere is nitrogen.
Compared with the prior art, the invention has the beneficial effects that:
the proportion of melamine to formaldehyde used in the present invention directly affects the properties of the final product. The reason for this is probably as follows: when the consumption of melamine is low, the generated methylol is less, the number of unreacted active hydrogen atoms is more, water is lost in condensation between the methylol and the unreacted active hydrogen atoms, and methylene bonds are generated, so that the molecular weight of the melamine formaldehyde resin is low, and the performance is poor; when the melamine content is high, the free aldehyde content is also increased. Therefore, the mixture ratio of the melamine and formaldehyde is not proper, and the melamine and formaldehyde are mixed according to a specific mixture ratio to prepare the product with excellent performance. In addition, the invention adopts diisopropyl di (acetylacetonate) titanate as a coupling agent to modify NdFeB magnetic powder to obtain modified magnetic powder, and the modified magnetic powder can obviously improve the magnetic performance of the melamine formaldehyde resin composite material.
Detailed Description
The present invention will be further described with reference to examples, which are not intended to be limiting, so that those skilled in the art will better understand the present invention and practice it.
The types and suppliers of the reagents used in the following examples and comparative examples are as follows:
the NdFeB magnetic powder is quick-quenched NdFeB magnetic powder, and the average particle size is 1-2 microns, and is manufactured by GM company in the United states.
Diisopropyl di (acetylacetonate) titanate, available from jessaka chemical, hangzhou.
Dicyandiamide, white monoclinic crystal, shandong aojin technology;
formaldehyde is analytically pure, alas Ding Shiji;
sodium hydroxide is analytically pure, tin-free, and available from the chemical industry Co.
The above reagents are merely illustrative of the sources and ingredients of the reagents used in the experiments of the invention and are well disclosed and do not represent the inability to practice the invention using other reagents of the same type or provided by other suppliers.
Example 1
The preparation method of the melamine formaldehyde resin composite material comprises the following steps:
(1) Uniformly spraying 0.5 part of diisopropyl di (acetylacetonate) titanate on the surface of 80 parts of NdFeB magnetic powder to obtain modified magnetic powder;
(2) Fully dissolving 0.21 part of sodium hydroxide in 40 parts of formaldehyde, adding 31.5 parts of melamine, reacting for 60min at 80 ℃ under stirring, adding the modified magnetic powder in the step (1), and continuing reacting for 20 min under the protection of nitrogen to obtain the target product.
Example 2
The preparation method of the melamine formaldehyde resin composite material comprises the following steps:
(1) Uniformly spraying 2 parts of diisopropyl di (acetylacetonate) titanate on the surface of 200 parts of NdFeB magnetic powder to obtain modified magnetic powder;
(2) Fully dissolving 0.25 part of sodium hydroxide in 42 parts of formaldehyde, adding 33 parts of melamine, reacting for 40min at 85 ℃ under stirring, adding the modified magnetic powder in the step (1), and continuing to react for 30 min under the protection of nitrogen to obtain a target product.
Example 3
The preparation method of the melamine formaldehyde resin composite material comprises the following steps:
(1) Uniformly spraying 1 part of diisopropyl di (acetylacetonate) titanate on the surface of 100 parts of NdFeB magnetic powder to obtain modified magnetic powder;
(2) Fully dissolving 0.2 part of sodium hydroxide in 39 parts of formaldehyde, adding 32 parts of melamine, reacting for 35min at 85 ℃ under stirring, adding the modified magnetic powder in the step (1), and continuing to react for 60min under the protection of nitrogen to obtain a target product.
Example 4
The preparation method of the melamine formaldehyde resin composite material comprises the following steps:
(1) Uniformly spraying 1 part of diisopropyl di (acetylacetonate) titanate on the surface of 150 parts of NdFeB magnetic powder to obtain modified magnetic powder;
(2) Fully dissolving 0.2 part of sodium hydroxide in 40 parts of formaldehyde, adding 31 parts of melamine, reacting for 45min at 50 ℃ under stirring, adding the modified magnetic powder in the step (1), and continuing to react for 40min under the protection of nitrogen to obtain a target product.
Comparative example 1
In contrast to example 4. Wherein, the dosage of melamine is 35 parts, and other technical parameters are the same.
Comparative example 2
In contrast to example 4. Wherein, the dosage of melamine is 25 parts, and other technical parameters are the same.
Comparative example 3
In contrast to example 4. Wherein, the dosage of formaldehyde is 50 parts, and other technical parameters are the same.
Comparative example 4
In contrast to example 4. Wherein, the dosage of formaldehyde is 30 parts, and other technical parameters are the same.
Comparative example 5
In contrast to example 4. Wherein the diisopropyl di (acetylacetonate) titanate in example 4 was replaced with gamma-aminoethylaminopropyl trimethoxysilane in equal amounts, and the other technical parameters were the same.
Comparative example 6
In contrast to example 4. Wherein the diisopropyl di (acetylacetonate) titanate in example 4 was replaced with an equivalent amount of vinylbenzyl aminoethylaminopropyl trimethoxysilane, and the other technical parameters were the same.
Comparative example 7
In contrast to example 4. Wherein the diisopropyl di (acetylacetonate) titanate in example 4 was replaced with the coupling agent KH550 in equal amounts, the other technical parameters were the same.
Comparative example 8
In contrast to example 4. Wherein the diisopropyl di (acetylacetonate) titanate in example 4 was replaced with the coupling agent KH570 in equal amounts, the other technical parameters were the same.
Comparative example 9
In contrast to example 4. Wherein the diisopropyl di (acetylacetonate) titanate in example 4 was replaced by 3-isocyanatopropyl dimethoxy silane in equal amounts, and the other technical parameters were the same.
Comparative example 10
In contrast to example 4. Wherein the diisopropyl di (acetylacetonate) titanate in example 4 was replaced by 3-isocyanatopropyltriethoxysilane in equal amounts, the other technical parameters were the same.
The products prepared in each of the above examples and comparative examples were subjected to performance testing as follows:
bending properties were measured according to ASTM D790 (bending speed of 1.25 mm/min), bending spline dimensions of 127 mm. Times.13 mm. Times.3.2 mm;
the maximum magnetic energy product test is carried out by adopting a neodymium iron boron permanent magnet material measuring instrument of the Hunan Union science and technology limited company.
The results of the performance test are shown in Table 1:
table 1 results of performance tests of the products prepared in examples and comparative examples
| Test item | Flexural Strength (MPa) | Maximum magnetic energy product (BH) max/MGOe |
| Example 1 | 54.8 | 9.82 |
| Example 2 | 51.3 | 10.96 |
| Example 3 | 56.7 | 10.05 |
| Example 4 | 55.2 | 10.91 |
| Comparative example 1 | 43.3 | 6.66 |
| Comparative example 2 | 44.8 | 6.72 |
| Comparative example 3 | 40.6 | 5.98 |
| Comparative example 4 | 42.0 | 6.17 |
| Comparative example 5 | 48.5 | 7.39 |
| Comparative example 6 | 45.9 | 7.12 |
| Comparative example 7 | 43.6 | 6.83 |
| Comparative example 8 | 42.4 | 7.02 |
| Comparative example 9 | 47.2 | 7.31 |
| Comparative example 10 | 46.1 | 7.15 |
It can be seen from the above table that the amount of melamine and formaldehyde used in the present invention directly affects the properties of the final product. The reason is that, when the amount of melamine used is low, the amount of generated methylol groups is small, the number of unreacted active hydrogen atoms is large, and water is lost by condensation between the methylol groups and the unreacted active hydrogen atoms to generate methylene bonds. At high melamine levels, the free aldehyde content is also increased. Therefore, too high and too low proportions are not suitable. The coupling agent used in the invention has more excellent effect and the maximum magnetic energy product value is the highest by comparing with the common coupling agents such as KH550 and KH 570.
It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Claims (5)
1. A melamine formaldehyde resin composite, characterized by: the composition is prepared from the following components in parts by weight:
30-33 parts of melamine, and the like,
38-42 parts of formaldehyde and the like,
70-200 parts of NdFeB magnetic powder,
0.3-2 parts of diisopropyl di (acetylacetonate) titanate,
0.2-0.25 part of alkaline substance;
the alkaline substance is sodium hydroxide;
the preparation method of the melamine formaldehyde resin composite material comprises the following steps:
(1) Uniformly spraying 0.3-2 parts of diisopropyl di (acetylacetonate) titanate on the surface of 70-200 parts of NdFeB magnetic powder to obtain modified magnetic powder;
(2) Dissolving 0.2-0.25 part of sodium hydroxide in 38-42 parts of formaldehyde, then adding 30-33 parts of melamine, and carrying out prepolymerization reaction under the stirring condition to obtain a reaction solution; and (3) adding the modified magnetic powder obtained in the step (1) into the reaction liquid, and continuing to react for 10-60 minutes in a protective atmosphere to obtain a target product.
2. The melamine formaldehyde resin composite according to claim 1, characterized in that: the NdFeB magnetic powder is quick-quenched NdFeB magnetic powder, and the average particle size is 1-2 microns.
3. The method for producing a melamine formaldehyde resin composite material according to claim 1 or 2, characterized in that: the method comprises the following steps:
(1) Uniformly spraying 0.3-2 parts of diisopropyl di (acetylacetonate) titanate on the surface of 70-200 parts of NdFeB magnetic powder to obtain modified magnetic powder;
(2) Dissolving 0.2-0.25 part of sodium hydroxide in 38-42 parts of formaldehyde, then adding 30-33 parts of melamine, and carrying out prepolymerization reaction under the stirring condition to obtain a reaction solution; and (3) adding the modified magnetic powder obtained in the step (1) into the reaction liquid, and continuing to react for 10-60 minutes in a protective atmosphere to obtain a target product.
4. A method of preparing a melamine formaldehyde resin composite according to claim 3, characterized in that: in the step (2), the reaction temperature of the prepolymerization reaction is 80-90 ℃ and the reaction time is 30-60 min.
5. A method of preparing a melamine formaldehyde resin composite according to claim 3, characterized in that: the protective atmosphere is nitrogen.
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| CN202210044344.7A CN114456540B (en) | 2022-01-14 | 2022-01-14 | Melamine formaldehyde resin composite material and preparation method thereof |
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| CN202210044344.7A CN114456540B (en) | 2022-01-14 | 2022-01-14 | Melamine formaldehyde resin composite material and preparation method thereof |
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| CN114456540B true CN114456540B (en) | 2023-08-04 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2006100783A (en) * | 2004-09-01 | 2006-04-13 | Kaneka Corp | Resin magnet material |
| CN100593828C (en) * | 2007-04-06 | 2010-03-10 | 浙江工业大学 | Method for preparing NdFeB/PPS injection moulding particle material |
| CN101740193B (en) * | 2009-12-31 | 2011-11-30 | 中国船舶重工集团公司第七二五研究所 | Rare-earth permanent magnet with high magnetic performance and high electric resistance and preparation method thereof |
| CN103554404A (en) * | 2013-11-08 | 2014-02-05 | 东莞市华立实业股份有限公司 | Low-melamine formaldehyde resin and preparation method thereof |
| CN104530340B (en) * | 2014-12-22 | 2016-06-29 | 沙县宏盛塑料有限公司 | A kind of preparation method of boron modification melamine resin |
| CN105206370B (en) * | 2015-10-12 | 2017-11-03 | 北京工业大学 | A kind of high temperature resistant isotropism NdFeB Bonded Magnets and preparation method thereof |
| CN105713161A (en) * | 2016-03-18 | 2016-06-29 | 重庆市森宝木胶有限公司 | Modified reinforced melamine-formaldehyde resin and preparation method thereof |
| CN106916269A (en) * | 2017-04-13 | 2017-07-04 | 河南骏化发展股份有限公司 | A kind of preparation method of high stability melamine resin |
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