CN108586685A - A kind of melamine-type benzoxazine prepolymer, copolymer resins and preparation method thereof - Google Patents
A kind of melamine-type benzoxazine prepolymer, copolymer resins and preparation method thereof Download PDFInfo
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- CN108586685A CN108586685A CN201810330531.5A CN201810330531A CN108586685A CN 108586685 A CN108586685 A CN 108586685A CN 201810330531 A CN201810330531 A CN 201810330531A CN 108586685 A CN108586685 A CN 108586685A
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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
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B35/524—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from polymer precursors, e.g. glass-like carbon material
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
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- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
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Abstract
The present invention relates to a kind of melamine-type benzoxazine prepolymers, copolymer resins and preparation method thereof.It prepares：Aldehyde compound, bisphenol-A and melamine and diamine compounds are added into reaction vessel, organic solvent dissolving is added；Or aldehyde compound and melamine and diamine compounds are added into reaction vessel, organic solvent is added, bisphenol-A is added after being sufficiently stirred, then above-mentioned reaction system is reacted 4~post-processing for 24 hours in 75~115 DEG C to obtain, the molar ratio of phenolic hydroxyl group, melamine wherein in aldehyde compound in aldehyde radical and bisphenol-A and the amido total amount in diamine compounds is 2：1：1.The melamine-type benzoxazine prepolymer of the present invention, thermal stability higher, with outstanding toughness, and there is good processability, the melamine-type benzoxazine copolymer resins that the final temperature programming of the performed polymer cures have excellent heat resistance, mechanical property and electrical property, can be widely used in the composite materials such as electrode material, laminate.
Description
Technical field
The present invention relates to high-molecular organic material technical fields, and in particular to a kind of melamine-type benzoxazine pre-polymerization
Body, copolymer resins and preparation method thereof.
Background technology
Benzoxazine is a kind of novel phenolic resin, be a kind of by phenolic compound, aminated compounds and aldehydes is original
Material is reacted through Mannich and the 6-membered heterocyclic compound of synthesis.It is maintaining the excellent hot property of traditional phenolic resin, fire-retardant
Property and while electrical insulating property, also possess the advantages of many traditional phenolic resin are not had such as in processing solidification process without small
Molecule discharges, and products made thereby porosity is low, and volume is shunk close to zero, and material has more excellent high-temperature thermal stability performance, fire-retardant
Performance, mechanical property and chemical stability etc., and it is not necessarily to strong acid or strong base catalyst during water imbibition is low and preparation process, subtract
The small damage to equipment.Therefore it is with a wide range of applications in fields such as building, electronics, aerospaces, causes people
Research interest.
But Polybenzoxazine resin also has the shortcomings that some are intrinsic, and such as most of benzoxazine monomer is solid, they
It is difficult to easily use as liquid thermosetting resin presoma in process；It is obtained after common benzoxazine polymerization
Polybenzoxazine resin brittleness is big, and molecular weight is small, and the degree of cross linking is low, and mechanical performance and thermal property need to be further increased.
Invention content
It is a kind of with excellent the technical problem to be solved by the present invention is to aiming at the above shortcomings existing in the prior art, provide
Good heat resistance, melamine-type benzoxazine prepolymer easy to process, copolymer resins and preparation method thereof.
In order to solve the above technical problems, technical solution provided by the invention is：
A kind of melamine-type benzoxazine prepolymer is provided, formula is had the following structure：
The present invention also provides the preparation methods of above-mentioned melamine-type benzoxazine prepolymer, and its step are as follows：To reaction
Aldehyde compound, bisphenol-A and melamine and diamine compounds are added in container, organic solvent dissolving are added, in 75~115
DEG C reaction 4~for 24 hours, post-processing obtains melamine-type benzoxazine prepolymer, wherein in aldehyde compound in aldehyde radical and bisphenol-A
Phenolic hydroxyl group, melamine and the amido total amount in diamine compounds molar ratio be 2：1：1；
Or aldehyde compound and melamine and diamine compounds are added into reaction vessel, organic solvent is added, fills
Point stirring after bisphenol-A is added, in 75~115 DEG C react 4~for 24 hours, post-processing obtain melamine-type benzoxazine prepolymer,
Mole of aldehyde radical and phenolic hydroxyl group, melamine and the amido total amount in diamine compounds in bisphenol-A in middle aldehyde compound
Than being 2：1：1；
The aldehyde compound is formaldehyde or paraformaldehyde；
The diamine compounds are 4,4'- diaminodiphenylmethane, and molecular structural formula is as follows：
By said program, the melamine is 1 with the amido molar ratio in diamine compounds:9~4：6, preferably
2:8~4:6.
By said program, the organic solvent is toluene, dimethylbenzene, ethyl alcohol, chloroform, dimethylformamide, Isosorbide-5-Nitrae-
Any one or more in dioxane.
By said program, the post-processing is：Reaction solution is poured into methanol solution and is precipitated, it is suspended to obtain milky
Liquid removes supernatant liquor after standing and obtains white precipitate, after white precipitate is dried grinding obtain melamine-type benzoxazine
Performed polymer.
By said program, the concentration of methanol solution is 50~90wt%.
Melamine-type benzoxazine copolymer resins, melamine-type benzoxazine prepolymer is cured to obtain.
By said program, it is described be cured as dissolving melamine-type benzoxazine prepolymer with solvent after 100~250
DEG C 4~48h of curing reaction.Obtained melamine-type benzoxazine copolymer resins are for copper-clad plate, binder, laminate, print
In printed circuit board, semiconductor sealing material or composite material, and in storing up electricity, pollutant process, drug loading, the side such as gas absorption
Also there is good application prospect in face.
A kind of resin material is provided, with porous structure, is carbonized by melamine-type benzoxazine colophony, institute
The carbonization stated is nitrogen protection, 600~800 DEG C of processing 5-15h.
The beneficial effects of the present invention are：
1, melamine-type benzoxazine prepolymer provided by the invention be highly -branched benzoxazine, and hang chain end
Density is small, thermal stability higher, and the benzoxazine prepolymer of highly -branched is intended to be crosslinked and obtain outstanding toughness, and this
Performed polymer has good processability, can be dissolved in solvent, can also be processed in the molten state, thus which can finally consolidate
Change and obtain the melamine-type benzoxazine colophony with three branched structures, this melamine-type benzoxazine colophony is thermosetting
Property polymer, there is higher molecular weight, crosslink density, higher Residual carbon (31~34%) and superior vitrifying to turn
Temperature (255~285 DEG C, 39 DEG C are improved compared to bisphenol-A/246 DEG C of DDM types benzoxazine) has excellent heat resistance
Energy, mechanical property and electrical property, can be widely used in the composite materials such as copper-clad plate, laminate；
2. the introducing of melamine is so that the resin after solidification has higher nitrogen content so that the resin after carbonization has
Many electroactive functional groups；And triazine ring structure improves crosslink material density；The resin after carbonization is set to be easily formed porous knot
Structure, therefore material is in storing up electricity, pollutant process, drug loading, gas absorption etc. also has good application prospect.
3. preparation process of the present invention is simple, raw material is easy to get, using bisphenol-A as phenol source, with melamine and diamine compounds
For amine source, by regulating and controlling aldehyde radical and the phenolic hydroxyl group in bisphenol-A, the amido molar ratio in diamine compounds in aldehyde compound,
Melamine and the amido molar ratio in diamine compounds are controlled, tool of the present invention can be synthesized using a step solvent method
There are higher molecular weight, crosslink density, higher Residual carbon (31~34%) and superior glass transition temperature (255
~285 DEG C, 39 DEG C are improved compared to bisphenol-A/246 DEG C of DDM types benzoxazine), there is excellent heat resistance, mechanical property
With the melamine-type benzoxazine prepolymer of electrical property, on this basis based on the easy of melamine-type benzoxazine prepolymer
Processing performance is the curable melamine-type benzoxazine colophony for obtaining having three branched structures.
Description of the drawings
Fig. 1 is the infrared spectrogram of melamine/bisphenol-A/paraformaldehyde performed polymer prepared by comparative example 1 of the present invention.
Fig. 2 be by melamine/bisphenol-A/paraformaldehyde prepolymer of comparative example 1 and 4,4'- diaminodiphenylmethane with
And the paraformaldehyde product infrared spectrum that the reaction was continued.
Fig. 3 is the infrared spectrogram of the melamine-type benzoxazine copolymer performed polymer prepared by the embodiment of the present invention 1.
Specific implementation mode
To make those skilled in the art more fully understand technical scheme of the present invention, below in conjunction with the accompanying drawings to the present invention make into
One step is described in detail.
Comparative example 1
The preparation of melamine/bisphenol-A/paraformaldehyde performed polymer：
By 3.86g (0.03mol) melamine, 10.56g (0.046mol) bisphenol-A, 5.56g (0.184mol) poly first
Aldehyde, which is added, to be stirred, equipped with condenser pipe, magneton in the three-necked flask of the 250mL of thermometer, and aldehyde radical, phenolic hydroxyl group and amidine functional group rub
You are than being 2：1：1, add 75mL toluene/ethanols mixed solvent (toluene and ethyl alcohol volume ratio 1:2) it, is heated to after mixing
Reaction solution is poured into 100mL methanol solutions (concentration 50wt%) precipitate after reaction, obtains milky by 80 DEG C of reaction 12h
Suspension is stood for 24 hours, is removed supernatant liquor and is obtained white precipitate, white precipitate is dried in vacuo 12h at 60 DEG C, finally will
The powder that the product of drying grinds to obtain brown color is melamine/bisphenol-A/paraformaldehyde performed polymer.Comparative example 1 of the present invention
The infrared spectrogram of prepared melamine/bisphenol-A/paraformaldehyde performed polymer is shown in Fig. 1.
Melamine structural formula used in the present embodiment is：
Further by melamine/bisphenol-A/paraformaldehyde prepolymer and 4,4'- diaminodiphenylmethane and poly first
Aldehyde continues the product infrared spectrum of reaction, can find benzoxazine ring characteristic absorption peak (as shown in Figure 2).
Embodiment 1
The preparation of melamine-type benzoxazine prepolymer：
By 8.20g (0.041mol) 4,4'- diaminodiphenylmethane, 0.39g (0.003mol) melamine, 10.56g
The 250mL for being furnished with condenser pipe, magneton stirring, thermometer is added in (0.046mol) bisphenol-A, 5.56g (0.184mol) paraformaldehyde
Three-necked flask in, aldehyde radical, phenolic hydroxyl group and amidine functional group molar ratio be 2：1：1, add 75mL toluene/ethanol mixed solvents
(toluene and ethyl alcohol volume ratio 1:2) it, is heated to 80 DEG C of reaction 12h after mixing, reaction solution is poured into 100mL after reaction
(concentration 50wt%) is precipitated in methanol solution, obtains milky suspension, stands 12h, is removed supernatant liquor and is obtained white precipitate,
White precipitate is dried in vacuo 12h at 60 DEG C, the powder for finally grinding the product of drying to obtain brown color is melamine
Amine type benzoxazine copolymer performed polymer.
4,4'- diaminodiphenylmethane structural formula used in the present embodiment is：
It is illustrated in figure 3 the infrared spectrogram of melamine-type benzoxazine copolymer performed polymer manufactured in the present embodiment,
Wherein 944cm-1The C-H out-of-plane bending vibration absorption peaks of the adjacent phenyl ring of Shi oxazine rings, 1234cm-1It is asymmetric corresponding to C-O-C
Stretching vibration peak.In addition 1325cm-1It is-CH2Methylene characteristic absorption peak, 1560cm-1Belong to the characteristic absorption of triazine ring
Peak shows the formation of triazine ring, when only melamine and paraformaldehyde, bisphenol-A rub in aldehyde radical, phenolic hydroxyl group and amidine functional group
You are than being 2：1：1 is mixed in 75mL toluene/ethanols mixed solvent (toluene and ethyl alcohol volume ratio 1:2) react (right when 12h at 80 DEG C
Ratio 1), by infrared spectrum it is observed that melamine characteristic absorption peak, but benzoxazine ring characteristic absorption can not be obtained
Peak (as shown in Figure 1).To sum up, illustrate that the present embodiment synthetic product is melamine-type main chain benzoxazine copolymer performed polymer,
Its molecular structural formula is：
The preparation of melamine-type benzoxazine copolymer resins：
For in copper-clad plate, being placed in vacuum drying chamber after the melamine-type benzoxazine prepolymer of above-mentioned preparation is dissolved
Inherent 80 DEG C of heating 8h, cures 2h at 100 DEG C, 120 DEG C, 140 DEG C, 160 DEG C, 180 DEG C, 200 DEG C, 220 DEG C later and obtains respectively
To melamine-type benzoxazine colophony, glass transition temperature is 255 DEG C, and 800 DEG C of carbon yields are up to 31%.
Embodiment 2
The preparation of melamine-type benzoxazine prepolymer：
By 7.29g (0.037mol) 4,4'- diaminodiphenylmethane, 0.78g (0.006mol) melamine, 10.56g
The 250mL for being furnished with condenser pipe, magneton stirring, thermometer is added in (0.046mol) bisphenol-A, 5.56g (0.184mol) paraformaldehyde
Three-necked flask in, aldehyde radical, phenolic hydroxyl group and amidine functional group molar ratio be 2：1：1, add 75mL toluene/ethanol mixed solvents
(toluene and ethyl alcohol volume ratio 2:1) it, is heated to 75 DEG C of reactions after mixing for 24 hours, reaction solution is poured into 100mL after reaction
(concentration 50wt%) is precipitated in methanol solution, obtains milky suspension, stands 12h, is removed supernatant liquor and is obtained white precipitate,
White precipitate is dried in vacuo 8h at 60 DEG C, the powder for finally grinding the product of drying to obtain brown color is melamine
Type benzoxazine prepolymer.
4,4'- diaminodiphenylmethane structural formula used in the present embodiment is：
For in copper-clad plate, being placed in vacuum drying chamber after the melamine-type benzoxazine prepolymer of above-mentioned preparation is dissolved
Inherent 80 DEG C of heating 8h, it is solid respectively at 100 DEG C, 120 DEG C, 140 DEG C, 160 DEG C, 180 DEG C, 200 DEG C, 220 DEG C, 240 DEG C later
Change 2h and obtain melamine-type benzoxazine copolymer resins, glass transition temperature is 260 DEG C, and 800 DEG C of carbon yields are reachable
31%.
Embodiment 3
The preparation of melamine-type benzoxazine prepolymer：
By 6.38g (0.032mol) 4,4'- diaminodiphenylmethane, 1.17g (0.009mol) melamine, 10.56g
The 250mL for being furnished with condenser pipe, magneton stirring, thermometer is added in (0.046mol) bisphenol-A, 5.56g (0.184mol) paraformaldehyde
Three-necked flask in, aldehyde radical, phenolic hydroxyl group and amidine functional group molar ratio be 2：1：1,75mL toluene is added, is added after mixing
Reaction solution is poured into 100mL methanol solutions (concentration 50wt%) precipitate after reaction, obtain breast by heat to 115 DEG C of reaction 4h
White suspension stands 12h, removes supernatant liquor and obtains white precipitate, white precipitate is dried in vacuo 8h at 60 DEG C, finally
The powder for grinding the product of drying to obtain brown color is melamine-type benzoxazine prepolymer.
4,4'- diaminodiphenylmethane structural formula used in the present embodiment is：
For in copper-clad plate, being placed in vacuum drying chamber after the melamine-type benzoxazine prepolymer of above-mentioned preparation is dissolved
Inherent 80 DEG C of heating 8h, cures 2h at 100 DEG C, 120 DEG C, 140 DEG C, 160 DEG C, 180 DEG C, 200 DEG C, 250 DEG C later and obtains respectively
To melamine-type benzoxazine copolymer resins, glass transition temperature is 281 DEG C, and 800 DEG C of carbon yields are up to 34%.
Embodiment 4
The preparation of melamine-type benzoxazine prepolymer：
By 5.46g (0.028mol) 4,4'- diaminodiphenylmethane, 1.56g (0.012mol) melamine, 10.56g
The 250mL for being furnished with condenser pipe, magneton stirring, thermometer is added in (0.046mol) bisphenol-A, 5.56g (0.184mol) paraformaldehyde
Three-necked flask in, aldehyde radical, phenolic hydroxyl group and amidine functional group molar ratio be 2：1：1, add 75mL toluene/dimethylformamide
Mixed solvent (toluene and dimethylformamide volume ratio 2:1) it, is heated to 90 DEG C of reactions after mixing for 24 hours, after reaction
Reaction solution is poured into 100mL methanol solutions (concentration 50wt%) and is precipitated, milky suspension is obtained, stands 12h, removes upper layer
Clear liquid obtains white precipitate, and white precipitate is dried in vacuo 8h at 60 DEG C, finally grinds the product of drying to obtain brown color
Powder be melamine-type benzoxazine prepolymer.
4,4'- diaminodiphenylmethane structural formula used in the present embodiment is：
The melamine-type benzoxazine prepolymer of above-mentioned preparation is dissolved in after solvent dimethylformamide for covering copper
It in plate, is placed in vacuum drying chamber and heats 8h at 80 DEG C, curing 48h at 100 DEG C later, to obtain melamine-type benzoxazine total
Poly resin, glass transition temperature are 285 DEG C, and 800 DEG C of carbon yields are up to 34%.
In terms of the resin can also be applied to storing up electricity after carbonization treatment, further retouched in detail below in conjunction with embodiment work
It states.
Embodiment 5
Melamine-type benzoxazine colophony prepared by embodiment 4 is placed in tube furnace, with heating rate 2 in nitrogen atmosphere
DEG C/min is warming up to the resin after 600 DEG C of heat preservation 15h be carbonizeds, by resin after carbonization and acetylene black, polytetrafluoroethylene (PTFE) mixes
Uniformly, mixture will be obtained electrode material for super capacitor coated in foam nickel surface, the specific capacitance of the material is 4,4'-
2 times of diaminodiphenylmethane/bisphenol A-type benzoxazine.
In terms of the resin can also be applied to photocatalytic degradation water pollutant after carbonization treatment, below in conjunction with implementation
Example is described in further detail.
Embodiment 6
Melamine-type benzoxazine prepolymer prepared by embodiment 6 is dissolved in dimethyl with a certain amount of titanium dioxide
Formamide solvent, which is placed in vacuum drying chamber, heats 8h at 80 DEG C, later at 100 DEG C, 120 DEG C, 140 DEG C, 160 DEG C, 180 DEG C,
Cure 2h respectively at 200 DEG C, 220 DEG C, 250 DEG C and obtains melamine-type benzoxazine colophony.By above-mentioned melamine-type benzo
Oxazine resin/titanium dioxide mixture is placed in tube furnace, and being warming up to 800 DEG C in nitrogen atmosphere with 2 DEG C/min of heating rate keeps the temperature 5h,
And pulverize, putting into water can pollutant such as formaldehyde effectively in degradation water through ultraviolet light.
Claims (9)
1. a kind of melamine-type benzoxazine prepolymer, it is characterised in that：Have the following structure formula：
2. the preparation method of melamine-type benzoxazine prepolymer described in claim 1, it is characterised in that：Steps are as follows：
Aldehyde compound, bisphenol-A and melamine and diamine compounds are added into reaction vessel, organic solvent dissolving is added, in
75~115 DEG C reaction 4~for 24 hours, post-processing obtain melamine-type benzoxazine prepolymer, wherein in aldehyde compound aldehyde radical with
The molar ratio of the amido total amount in phenolic hydroxyl group, melamine and diamine compounds in bisphenol-A is 2：1：1；
Or aldehyde compound and melamine and diamine compounds are added into reaction vessel, organic solvent is added, fully stirs
Bisphenol-A is added after mixing, in 75~115 DEG C react 4~for 24 hours, post-processing obtain melamine-type benzoxazine prepolymer, wherein aldehyde
Aldehyde radical and the molar ratio of the amido total amount in phenolic hydroxyl group, melamine and the diamine compounds in bisphenol-A are in class compound
2：1：1；
Wherein：The aldehyde compound is formaldehyde or paraformaldehyde；
The diamine compounds are 4,4'- diaminodiphenylmethane, and molecular structural formula is as follows：
3. preparation method according to claim 2, it is characterised in that：The melamine and the amine in diamine compounds
Base molar ratio is 1:9~4：6.
4. preparation method according to claim 2, it is characterised in that：The organic solvent be toluene, dimethylbenzene, ethyl alcohol,
Any one or more in chloroform, dimethylformamide, Isosorbide-5-Nitrae-dioxane.
5. preparation method according to claim 2, it is characterised in that：The post-processing is：Reaction solution is poured into methanol
It is precipitated in solution, obtains milky suspension, removing supernatant liquor after standing obtains white precipitate, is ground after white precipitate is dried
Mill obtains melamine-type benzoxazine prepolymer.
6. preparation method according to claim 5, it is characterised in that：The concentration of methanol solution is 50~90wt%.
7. melamine-type benzoxazine copolymer resins are by melamine-type benzoxazine pre-polymerization described in claim 1
What body cured.
8. preparation method according to claim 2, it is characterised in that：Described is cured as melamine-type benzoxazine
100~250 DEG C of 4~48h of curing reaction after performed polymer is dissolved with solvent.
9. a kind of resin material is carbonized with porous structure by melamine-type benzoxazine colophony described in claim 1
It obtains, the carbonization is nitrogen protection, 600~800 DEG C of processing 5-15h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110818868A (en) * | 2019-11-29 | 2020-02-21 | 淮北绿洲新材料有限责任公司 | Monoamine-terminated ultrahigh-frequency low-dielectric-property main chain benzoxazine copolymer oligomer, copolymer resin and preparation method thereof |
| CN110845682A (en) * | 2019-11-29 | 2020-02-28 | 河南骏化发展股份有限公司 | Modified melamine hard foam material and preparation method thereof |
| CN114561006A (en) * | 2022-03-18 | 2022-05-31 | 四川金象赛瑞化工股份有限公司 | Melamine modified phthalonitrile resin and preparation method of composite material thereof |
| CN115521427A (en) * | 2022-10-14 | 2022-12-27 | 四川金象赛瑞化工股份有限公司 | Preparation method of benzoxazine resin containing Schiff base structure based on melamine |
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| CN110845682A (en) * | 2019-11-29 | 2020-02-28 | 河南骏化发展股份有限公司 | Modified melamine hard foam material and preparation method thereof |
| CN110845682B (en) * | 2019-11-29 | 2022-07-26 | 河南骏化发展股份有限公司 | Modified melamine hard foam material and preparation method thereof |
| CN110818868B (en) * | 2019-11-29 | 2023-12-12 | 淮北绿洲新材料有限责任公司 | Monoamine-terminated ultrahigh-frequency low-dielectric main chain benzoxazine copolymer oligomer, monoamine-terminated ultrahigh-frequency low-dielectric main chain benzoxazine copolymer resin and preparation method of monoamine-terminated ultrahigh-frequency low-dielectric main chain benzoxazine copolymer oligomer |
| CN114561006A (en) * | 2022-03-18 | 2022-05-31 | 四川金象赛瑞化工股份有限公司 | Melamine modified phthalonitrile resin and preparation method of composite material thereof |
| CN115521427A (en) * | 2022-10-14 | 2022-12-27 | 四川金象赛瑞化工股份有限公司 | Preparation method of benzoxazine resin containing Schiff base structure based on melamine |
| CN115521427B (en) * | 2022-10-14 | 2024-02-06 | 四川金象赛瑞化工股份有限公司 | Preparation method of melamine-based benzoxazine resin containing Schiff base structure |
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