CN114213612A - Polyethylene glycol modified melamine resin and preparation method thereof - Google Patents
Polyethylene glycol modified melamine resin and preparation method thereof Download PDFInfo
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- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
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Abstract
The invention belongs to the technical field of polymer materials, and discloses polyethylene glycol modified melamine resin and a preparation method thereof. The preparation method comprises the following steps: adding polyethylene glycol, polyether-terminated polysiloxane, hydroquinone, melamine, water and an acid catalyst into a reactor, stirring and mixing uniformly, and then heating to 85-95 ℃ for heat preservation reaction to obtain a prepolymer; then adding a pH regulator to regulate the pH to 7-9, cooling to below 80 ℃, adding hydroquinone, melamine, formaldehyde and an alkaline catalyst, heating to 90-100 ℃, and carrying out heat preservation reaction; and after the reaction is finished, adding water and methanol for dilution to obtain the polyethylene glycol modified melamine resin. According to the preparation method, the molecular flexibility is improved and the moisture absorption rate is reduced by introducing the long-chain polyethylene glycol and polysiloxane structures, the heat resistance of a system is improved by introducing the benzene ring structure, and finally the obtained melamine resin has the comprehensive properties of high strength, high heat resistance and low moisture absorption rate.
Description
Technical Field
The invention belongs to the technical field of polymer materials, and particularly relates to polyethylene glycol modified melamine resin and a preparation method thereof.
Background
Melamine resins, also known as melamine formaldehyde resins or melamine formaldehyde resins, are polymers obtained by the reaction of melamine with formaldehyde. It is often used as resin for adhesives, laminates, coatings, molding compounds, and as a treating agent for fabrics, paper, leather, etc.
The traditional preparation method of melamine resin is that under the condition of certain temperature and pH value, melamine and solid paraformaldehyde are subjected to hydroxymethylation reaction under the condition of taking water as a solvent to generate polyhydroxy melamine, and most of the melamine resin at this stage is oligomers and has low viscosity. Then carrying out acid polycondensation reaction: the polyhydroxy melamine slowly generates three-dimensional net polymerization reaction under the acid condition to obtain the melamine resin with certain molecular weight.
The melamine resin is cured by crosslinking with each other through methylene or dimethylene ether bonds. Because two ends of the methylene are connected with triazine rings with large steric hindrance, and a plurality of methylene and triazine rings are mutually staggered, the cured resin has large hardness, is not easy to bend and stretch, and has almost no toughness. The larger the crosslinking density, the lower the impact strength and bending strength after curing the resin. Modification of melamine resins with polyethylene glycol is a viable method to increase strength and reduce brittleness. Polyethylene glycol has a flexible long chain, and can improve the brittleness of melamine resin to a certain extent (Martianxin, modification research on melamine formaldehyde resin by polyethylene glycol, 1999, 02).
Patent CN 106750073 a discloses a synthesis process of polyethylene glycol modified melamine resin, which comprises subjecting melamine and 37% formaldehyde solution to hydroxymethylation reaction at 80-90 ℃ and pH 8.0-9.0 to generate polyhydroxy melamine; and then adding polyethylene glycol into polyhydroxy melamine to perform three-dimensional network polymerization reaction under a weak acid condition to obtain the three-dimensional network polymeric resin. The main effect is that the stability of the melamine resin is improved and the content of free formaldehyde is reduced by modifying the polyethylene glycol, so that the requirement of higher environmental protection grade is met.
Although the brittleness can be improved and the content of free formaldehyde can be reduced to a certain extent by modifying the melamine resin through polyethylene glycol, long-chain polyethylene glycol has strong hydrophilicity and molecular flexibility, and can cause adverse effects on the water absorption rate and the heat resistance of a product. Therefore, the obtained polyethylene glycol modified melamine resin with high strength, good heat resistance and low water absorption rate has obvious commercial value.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention mainly aims to provide a preparation method of polyethylene glycol modified melamine resin. According to the preparation method, the heat resistance of a system is improved by introducing a benzene ring structure into the melamine resin, the moisture absorption rate is reduced and the molecular flexibility is further improved by introducing a long-chain polysiloxane structure, and finally the obtained melamine resin has the comprehensive properties of high strength, high heat resistance and low moisture absorption rate.
Another object of the present invention is to provide a polyethylene glycol-modified melamine resin prepared by the above method.
The purpose of the invention is realized by the following technical scheme:
a preparation method of polyethylene glycol modified melamine resin comprises the following preparation steps:
(1) adding polyethylene glycol, polyether-terminated polysiloxane, hydroquinone, melamine, water and an acid catalyst into a reactor, stirring and mixing uniformly, and then heating to 85-95 ℃ for heat preservation reaction to obtain a prepolymer;
(2) adding a pH regulator into the prepolymer obtained in the step (1) to regulate the pH value to 7-9, then cooling to below 80 ℃, adding hydroquinone, melamine, formaldehyde and an alkaline catalyst, heating to 90-100 ℃, and carrying out heat preservation reaction;
(3) and (3) after the reaction in the step (2) is finished, adding water and methanol for dilution to obtain the polyethylene glycol modified melamine resin.
Further, in the step (1), the polyethylene glycol is preferably 200-2000 polyethylene glycol.
Further, the polyether-terminated polysiloxane in step (1) has a structure shown in formula I below:
wherein n is an integer of 0 to 20, and m is an integer of 0 to 20; the average molecular weight of the polyether-terminated polysiloxane is 350-4000.
The preparation of the polyether-terminated polysiloxane refers to a preparation method of polyether modified silicone oil, and is prepared by the following steps:
stirring and mixing hydrogen-terminated silicone oil and allyl polyether uniformly, adding a chloroplatinic acid catalyst under the protection of nitrogen, heating to 90-115 ℃, keeping the temperature, reacting for 1-6 hours until the system is a uniform transparent phase, and removing unreacted low-boiling-point substances in vacuum to obtain the polyether-terminated polysiloxane.
Further, the acidic catalyst in the step (1) is sulfuric acid or hydrochloric acid.
Further, the adding amount and the weight part ratio of each material in the step (1) are as follows:
further, the reaction time in the step (1) is preferably 1-4 h.
Further, in the step (2), the pH regulator is at least one of sodium hydroxide and potassium hydroxide.
Further, the adding amount and the weight part ratio of each material in the step (2) are as follows:
further, in the step (2), the basic catalyst is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia water and triethanolamine.
Further, the reaction time in the step (2) is preferably 0.5-2 h.
Further, the adding amount of the materials in the step (3) is as follows in parts by weight:
50-200 parts of water;
50-100 parts of methanol.
Polyethylene glycol modified melamine resin is prepared by the method.
The principle of the invention is as follows: under the acidic condition, the flexible long chains of the polyethylene glycol and the polysiloxane and the thermal stability structure of the benzene ring are added into the molecular structure by the reaction of the hydroxyl groups at two ends of the polyethylene glycol, the polyether-terminated polysiloxane and the hydroquinone molecule and the melamine to obtain the prepolymer with the macromolecular chain. A partial reaction scheme of polyethylene glycol, polyether-terminated polysiloxane, and hydroquinone with melamine under acidic conditions is shown in figure 1 (the remaining possible reactions include further micro-crosslinking reactions and etherification reactions between hydroxyl groups). After the reaction is finished, under the alkaline condition, the prepolymer of the macromolecular chain is subjected to dehydration condensation with formaldehyde and is crosslinked with formaldehyde to form a macromolecular network crosslinked structure. Meanwhile, hydroquinone, melamine and formaldehyde are further added for dehydration condensation and mutual crosslinking to form a micromolecule network crosslinking structure. Through the combination of the macromolecular network cross-linked structure and the micromolecular network cross-linked structure, the melamine resin with toughness, heat resistance and low water absorption rate is prepared.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, the polyethylene glycol structure is introduced into the melamine resin, so that the brittleness defect of the melamine resin can be obviously improved.
(2) According to the invention, a polysiloxane structure is introduced into the melamine resin through polyether-terminated polysiloxane, and the polysiloxane structure has better molecular flexibility than polyethylene glycol, so that the brittleness defect of the melamine resin can be further improved. Meanwhile, the polysiloxane structure has strong hydrophobicity, so that the water absorption of the melamine resin can be obviously reduced, and the water resistance of the material is greatly improved.
(3) The invention can obviously improve the heat resistance of the melamine resin by introducing a benzene ring structure into the melamine resin.
(4) According to the preparation method disclosed by the invention, the polyethylene glycol is added in the preparation process of the prepolymer, the water solubility of the prepolymer can be obviously improved after the polyethylene glycol reacts with the melamine, the mixing uniformity of the polyether-terminated polysiloxane, the hydroquinone and the melamine in an aqueous reaction system is improved, the generation of the prepolymer can be obviously promoted, and the comprehensive performance of the obtained product is finally improved.
(5) The invention forms a macromolecular network crosslinking structure by dehydrating, condensing and crosslinking a prepolymer with macromolecular chains and formaldehyde. Meanwhile, hydroquinone, melamine and formaldehyde are further added for dehydration condensation and mutual crosslinking to form a micromolecule network crosslinking structure. Through the combination of the macromolecular network cross-linked structure and the micromolecular network cross-linked structure, the melamine resin with toughness, heat resistance and low water absorption rate is prepared.
Drawings
FIG. 1 is a schematic diagram of a partial reaction of polyethylene glycol, polyether-terminated polysiloxane, and hydroquinone with melamine in accordance with the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
The preparation method of the polyethylene glycol modified melamine resin of the embodiment comprises the following preparation steps:
(1) adding the materials 1-6 into a reactor according to the material names and the feeding amount (parts by weight) shown in the table 1, stirring and mixing uniformly, then stirring and heating to about 90 ℃ within 30min, keeping the temperature and reacting for 1.5h, and monitoring by infrared spectroscopy to remove the hydroxyl absorption peak to obtain the prepolymer.
(2) Adding a material 7 into the prepolymer in the step (1) to adjust the pH value to 7.5, then cooling to 60 ℃, adding materials 8-11, heating to about 95 ℃ again, and carrying out heat preservation reaction for 1 hour to complete the reaction.
(3) Adding the materials 12-13 into the reactor, and uniformly stirring to obtain the polyethylene glycol modified melamine resin.
TABLE 1 materials code and proportion
The polyether-terminated polysiloxane in this example had an average molecular weight of 800, and was prepared by the following method:
stirring and mixing hydrogen-terminated silicone oil with the average molecular weight of 400 and allyl polyether with the average molecular weight of 200 uniformly according to the molar ratio of 1:2, adding a chloroplatinic acid alcohol solution catalyst under the protection of nitrogen, heating to 105 ℃, keeping the temperature, reacting for 3.5 hours until the system is a uniform transparent phase, detecting by infrared spectroscopy that a double bond characteristic peak disappears, and removing unreacted low-boiling-point substances in vacuum to obtain the polyether end-capped polysiloxane.
Example 2
The preparation method of the polyethylene glycol modified melamine resin of the embodiment comprises the following preparation steps:
(1) adding the materials 1-6 into a reactor according to the material names and the feeding amount (parts by weight) shown in Table 2, stirring and mixing uniformly, then stirring and heating to about 90 ℃ within 30min, carrying out heat preservation reaction for 2h, and monitoring by infrared spectroscopy to remove the hydroxyl absorption peak to obtain the prepolymer.
(2) Adding a material 7 into the prepolymer in the step (1) to adjust the pH value to 7.5, then cooling to 70 ℃, adding materials 8-11, heating to about 95 ℃ again, and carrying out heat preservation reaction for 1 hour to complete the reaction.
(3) Adding the materials 12-13 into the reactor, and uniformly stirring to obtain the polyethylene glycol modified melamine resin.
TABLE 2 materials code and proportion
The polyether-terminated polysiloxane in this example had an average molecular weight of 1200, and was prepared by the following method:
stirring and mixing evenly hydrogen-terminated silicone oil with the average molecular weight of 800 and allyl polyether with the average molecular weight of 200 according to the molar ratio of 1:2, adding a chloroplatinic acid alcohol solution catalyst under the protection of nitrogen, heating to 105 ℃, keeping the temperature, reacting for 3 hours until the system is a uniform transparent phase, detecting by infrared spectroscopy that a double bond characteristic peak disappears, and removing unreacted low-boiling-point substances in vacuum to obtain the polyether end-capped polysiloxane.
Example 3
The preparation method of the polyethylene glycol modified melamine resin of the embodiment comprises the following preparation steps:
(1) adding the materials 1-6 into a reactor according to the material names and the feeding amount (parts by weight) shown in Table 3, stirring and mixing uniformly, then stirring and heating to about 90 ℃ within 30min, carrying out heat preservation reaction for 3h, and monitoring by infrared spectroscopy to remove the hydroxyl absorption peak to obtain the prepolymer.
(2) Adding a material 7 into the prepolymer in the step (1) to adjust the pH value to 7.5, then cooling to 65 ℃, adding materials 8-11, heating to about 95 ℃ again, and carrying out heat preservation reaction for 2 hours to complete the reaction.
(3) Adding the materials 12-13 into the reactor, and uniformly stirring to obtain the polyethylene glycol modified melamine resin.
TABLE 3 materials code and proportion
The average molecular weight of the polyether-terminated polysiloxane in this example was 1600, which was prepared by the following method:
stirring and mixing hydrogen-terminated silicone oil with the average molecular weight of 1000 and allyl polyether with the average molecular weight of 300 uniformly according to the molar ratio of 1:2, adding a chloroplatinic acid alcohol solution catalyst under the protection of nitrogen, heating to 105 ℃, keeping the temperature, reacting for 4 hours until the system is a uniform transparent phase, detecting by infrared spectroscopy that a double bond characteristic peak disappears, and removing unreacted low-boiling-point substances in vacuum to obtain the polyether-terminated polysiloxane.
Comparative example 1
Compared with the embodiment 1, the preparation method of the prepolymer has the following specific steps that no polyethylene glycol 400 is added in the preparation process of the prepolymer:
(1) adding the materials 2-6 into a reactor according to the material names and the feeding amount (parts by weight) shown in the table 1, stirring and mixing uniformly, stirring and heating to about 90 ℃ within 30min, carrying out heat preservation reaction, sampling every 1h, carrying out infrared spectrum detection on hydroxyl absorption peaks, and obtaining a prepolymer after the hydroxyl absorption peaks are not completely disappeared after 6h of reaction.
(2) Adding a material 7 into the prepolymer in the step (1) to adjust the pH value to 7.5, then cooling to 60 ℃, adding materials 8-11, heating to about 95 ℃ again, and carrying out heat preservation reaction for 1 hour to complete the reaction.
(3) Adding the materials 12-13 into the reactor, and uniformly stirring to obtain the modified melamine resin.
Comparative example 2
Compared with example 1, the prepolymer preparation process is not added with polyether-terminated polysiloxane, and the rest is the same.
Comparative example 3
Compared with the embodiment 1, the preparation process of the prepolymer and the crosslinking process in the step (2) are the same without adding hydroquinone.
Comparative example 4
Compared with the example 1, in the step (2), hydroquinone and melamine are not added in the crosslinking process, and the preparation process comprises the following specific steps:
(1) adding the materials 1-6 into a reactor according to the material names and the feeding amount (parts by weight) shown in the table 1, stirring and mixing uniformly, then stirring and heating to about 90 ℃ within 30min, keeping the temperature and reacting for 1.5h, and monitoring by infrared spectroscopy to remove the hydroxyl absorption peak to obtain the prepolymer.
(2) Adding a material 7 into the prepolymer in the step (1) to adjust the pH value to 7.5, then cooling to 60 ℃, adding a material 11, heating to about 95 ℃ again, and carrying out heat preservation reaction for 1 hour to complete the reaction.
(3) Adding the materials 12-13 into the reactor, and uniformly stirring to obtain the polyethylene glycol modified melamine resin.
The modified melamine resins obtained in the above examples and comparative examples were subjected to performance tests after curing on test boards, and mainly included shear impact strength (GB/T6328-86), heat resistance (thermal decomposition temperature Td), flame retardancy (UL94), and water absorption (24h soaking water absorption). The test results are shown in table 4 below.
TABLE 4
As can be seen from the results in Table 4, the melamine resin obtained by the invention has the comprehensive properties of good toughness, heat resistance, flame retardance and low water absorption. As can be seen from the comparison result between example 1 and comparative example 1, no polyethylene glycol is added in the preparation process of the prepolymer, the prepolymer is generated slowly, and the hydroxyl absorption peak is not completely disappeared after 6 hours of reaction, because the melamine, the polyether-terminated polysiloxane and the hydroquinone have poor solubility in an aqueous reaction system without adding the polyethylene glycol, the prepolymerization process is slow, the polymerization rate of the long-chain polysiloxane and the heat-resistant benzene ring structure is low, and the improvement effect of the product strength and the heat resistance is not significant. The addition of the polyethylene glycol has good synergistic effect on the modification effect of the polyether-terminated polysiloxane and the hydroquinone. From the results of comparison of example 1 with comparative example 2, it can be seen that the product strength, heat resistance, flame retardant property and water absorption rate were deteriorated to some extent without adding polyether-terminated polysiloxane, and particularly the water absorption rate was significantly increased. The introduction of the polyether end-capped polysiloxane structure can obviously improve the water resistance of the resin, and simultaneously has good improvement effect on the strength, heat resistance and flame retardant property of the product. As can be seen from the results of comparison with comparative example 3, the introduction of the benzene ring structure has a significant effect of improving the heat resistance of the product. The comparison result with the comparative example 4 shows that the strength and heat resistance of the product are obviously reduced by directly crosslinking the prepolymer with formaldehyde, because the crosslinking density of the macromolecular network crosslinking structure formed by crosslinking the prepolymer containing macromolecular chains with formaldehyde is low, and the cured product cannot achieve good strength and heat resistance.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The preparation method of the polyethylene glycol modified melamine resin is characterized by comprising the following preparation steps:
(1) adding polyethylene glycol, polyether-terminated polysiloxane, hydroquinone, melamine, water and an acid catalyst into a reactor, stirring and mixing uniformly, and then heating to 85-95 ℃ for heat preservation reaction to obtain a prepolymer;
(2) adding a pH regulator into the prepolymer obtained in the step (1) to regulate the pH value to 7-9, then cooling to below 80 ℃, adding hydroquinone, melamine, formaldehyde and an alkaline catalyst, heating to 90-100 ℃, and carrying out heat preservation reaction;
(3) and (3) after the reaction in the step (2) is finished, adding water and methanol for dilution to obtain the polyethylene glycol modified melamine resin.
2. The method for preparing polyethylene glycol-modified melamine resin according to claim 1, wherein in step (1), the polyethylene glycol is polyethylene glycol 200-2000.
3. The method for producing a polyethylene glycol-modified melamine resin according to claim 1, wherein said polyether-terminated polysiloxane in step (1) has a structure represented by the following formula I:
wherein n is an integer of 0 to 20, and m is an integer of 0 to 20; the average molecular weight of the polyether-terminated polysiloxane is 350-4000.
4. The method for preparing a polyethylene glycol-modified melamine resin according to claim 3, wherein said polyether-terminated polysiloxane is prepared by the following method:
stirring and mixing hydrogen-terminated silicone oil and allyl polyether uniformly, adding a chloroplatinic acid catalyst under the protection of nitrogen, heating to 90-115 ℃, keeping the temperature, reacting for 1-6 hours until the system is a uniform transparent phase, and removing unreacted low-boiling-point substances in vacuum to obtain the polyether-terminated polysiloxane.
5. The process for producing a polyethylene glycol-modified melamine resin according to claim 1, wherein said acidic catalyst in the step (1) is sulfuric acid or hydrochloric acid; the reaction time is 1-4 h.
6. The method for preparing polyethylene glycol-modified melamine resin according to claim 1, wherein the materials added in step (1) are in the following weight parts:
7. the method for producing a polyethylene glycol-modified melamine resin according to claim 1, wherein said pH adjusting agent in the step (2) is at least one of sodium hydroxide and potassium hydroxide; the alkaline catalyst is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia water and triethanolamine; the reaction time is 0.5-2 h.
8. The method for preparing polyethylene glycol-modified melamine resin according to claim 6, wherein the materials added in step (2) are in the following weight parts:
9. the method for preparing polyethylene glycol-modified melamine resin according to claim 8, wherein the materials added in step (3) are as follows in parts by weight:
50-200 parts of water;
50-100 parts of methanol.
10. A polyethylene glycol-modified melamine resin, which is produced by the method according to any one of claims 1 to 9.
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| CN101735555A (en) * | 2009-12-22 | 2010-06-16 | 四川大学 | High-flexibility melamino-formaldehyde foam material and preparation method thereof |
| JP2011132509A (en) * | 2009-11-26 | 2011-07-07 | Dainichiseika Color & Chem Mfg Co Ltd | Polysiloxane modified polyhydroxy polyurethane resin, composition containing the resin and process for producing resin |
| CN106750073A (en) * | 2016-11-30 | 2017-05-31 | 合力泰科技股份有限公司 | Poly ethyldiol modified melmac synthesis technique |
| CN107602787A (en) * | 2017-08-31 | 2018-01-19 | 浙江亚迪纳新材料科技股份有限公司 | The preparation technology of the high daily melamine foam of resilience |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011132509A (en) * | 2009-11-26 | 2011-07-07 | Dainichiseika Color & Chem Mfg Co Ltd | Polysiloxane modified polyhydroxy polyurethane resin, composition containing the resin and process for producing resin |
| CN101735555A (en) * | 2009-12-22 | 2010-06-16 | 四川大学 | High-flexibility melamino-formaldehyde foam material and preparation method thereof |
| CN106750073A (en) * | 2016-11-30 | 2017-05-31 | 合力泰科技股份有限公司 | Poly ethyldiol modified melmac synthesis technique |
| CN107602787A (en) * | 2017-08-31 | 2018-01-19 | 浙江亚迪纳新材料科技股份有限公司 | The preparation technology of the high daily melamine foam of resilience |
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