CN101921242A - Fluorenyl benzoxazine and preparation method thereof - Google Patents

Fluorenyl benzoxazine and preparation method thereof Download PDF

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Publication number
CN101921242A
CN101921242A CN2010102596660A CN201010259666A CN101921242A CN 101921242 A CN101921242 A CN 101921242A CN 2010102596660 A CN2010102596660 A CN 2010102596660A CN 201010259666 A CN201010259666 A CN 201010259666A CN 101921242 A CN101921242 A CN 101921242A
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fluorenyl
structural formula
primary amine
benzoxazine
raw materials
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许凯
付子恩
刘新
刘欢
蔡华轮
苏江勋
陈鸣才
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Foshan Function High Polymer Materials & Fine Chemicals Professional Center
Guangzhou Chemical Co Ltd of CAS
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Foshan Function High Polymer Materials & Fine Chemicals Professional Center
Guangzhou Chemical Co Ltd of CAS
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Abstract

The invention discloses a structural formula of fluorenyl benzoxazine and a preparation method thereof. In the invention, reaction raw materials comprise fluorenyl phenol, non-fluorenyl unitary primary amine or non-fluorenyl binary primary amine or fluorenyl unitary primary amine or fluorenyl binary primary amine and methanal; or the reaction raw materials comprise non-fluorenyl phenol, fluorenyl unitary primary amine or fluorenyl binary primary amine and methanal; the fluorenyl benzoxazine is prepared and synthesized by adopting a solvent method, and the reaction temperature is 60-150 DEG C; then the reaction system is washed by adopting distilled water or absolute ethyl alcohol; and water or alcohol is removed in vacuum. The fluorenyl benzoxazine has good heat resistance and dielectrical property and can be applied to the fields of reinforcing materials, fillers, composite materials, and the like of adhesives, coatings, laminated sheets, printed circuit boards and semiconductor packaging materials.

Description

A kind of fluorenyl benzoxazine and preparation method thereof
Technical field
The present invention relates to chemical field, particularly a kind of fluorenyl benzoxazine and preparation method thereof.
Background technology
Benzoxazine is a fast-developing in recent years class novel hot setting resin, and its cured article structure and resol are similar, just with the carbon bridge (CH between phenyl ring in traditional resol 2-) changed carbon nitrogen carbon bridge (CH into 2-N (R)-CH 2-).Benzoxazine has good heat-resistant, electric property, resistance to water soak, low surface active energy, excellent abrasive energy, also have good processing properties, structural stability and Molecular Structure Design handiness, so benzoxazine has obtained widespread use in polymer materials industry.
The modification of benzoxazine can be divided into blending and modifying and Molecular Structure Design modification.Blending and modifying is that benzoxazine and other thermosetting resin blend prepare the matrix material that more high performance " alloy " resin or benzoxazine and inorganic materials blend preparation have nanoscale.The Molecular Structure Design modification is by the feedstock production benzoxazine of selecting different structure or different elements for use its performance to be improved.Handiness characteristic according to the benzoxazine Molecular Structure Design, investigators design the benzoxazine polymer materials of multiple structure, improve its resistance toheat and mechanical property (CN1472205A, US Pat 5 such as in the benzoxazine monomer, introduce two keys by Molecular Structure Design, 973,144); By in benzoxazine, introducing boron to improve the resistance toheat and the flame retardant properties (CN101538283A) of polyphenyl and oxazines resin; By drilling with fluoridize the benzoxazine resin to reduce the specific inductivity (Polymer 44 (2003) 7989-7996, Polymer 46 (2005) 3758-3766) of material.But the resin modified function of existing benzoxazine is all more single, can not improve the thermotolerance and the dielectric properties of benzoxazine resin simultaneously, can not satisfy the application demand in some fields.
Summary of the invention
The objective of the invention is to overcome the shortcoming that exists in the prior art, a kind of fluorenyl benzoxazine with excellent heat resistance energy and dielectric properties is provided.
Another object of the present invention is to provide a kind of preparation method of above-mentioned fluorenyl benzoxazine.
Purpose of the present invention is achieved through the following technical solutions:
A kind of fluorenyl benzoxazine, its structural formula are a kind of among following structural formula A～F:
A: when reaction raw materials was fluorenyl phenol, non-fluorenyl primary amine and formaldehyde, the structural formula of synthetic fluorenyl benzoxazine was:
Figure BDA0000024839600000021
Structural formula A
Wherein, 1≤n1≤10; R nBe hydrogen atom, or contain C substituting group, hetero atom substituents, substituent number n is 10-n 1M can link to each other with 2,3,4,5,6,7,9,10, No. 11 positions of fluorenes ring; The structure of M is the aliphatic chain of 1～36 C atom, or the cycloaliphatic ring of 3～20 C atoms or aromatic ring, or contains the heteroatom group of O, N, P, S, Si or B; R is that the C atomicity is that 1～36 aliphatic chain or C atomicity are 1～20 cycloaliphatic ring, or the C atomicity is the substituting group of 6～20 aromatic nucleus or derivatives thereof, heterochain or the coexistence of above structure; In addition, the phenyl ring of benzoxazine can also directly link to each other with the fluorenes ring, does not promptly have the M group between the two;
B: when reaction raw materials was fluorenyl phenol, non-fluorenyl binary primary amine and formaldehyde, the structural formula of synthetic fluorenyl benzoxazine was:
Figure BDA0000024839600000022
Structural formula B
Wherein, Rn, M, n and n 1Described identical with structural formula A; Described non-fluorenyl binary primary amine comprises following formula 1～formula 5:
Formula 1:NH 2(CH 2) xNH 2, 1≤x≤20 wherein;
Figure BDA0000024839600000023
Formula 2 formulas 3
Figure BDA0000024839600000024
Formula 4 formulas 5
In formula 2～formula 5, R N2And R N3Be OH or the straight or branched aliphatics substituting group that contains 1～10 C atom or contain the aromatic substituents of 6～12 C atoms or contain the aliphatics of 7～12 C atoms and substituting group or other heteroatomic substituting group of aromatic series coexistence; 1≤n2≤4; 1≤n3≤4;
In the formula 5, Y comprises following structure:
Figure BDA0000024839600000031
C: when reaction raw materials was fluorenyl phenol, fluorenyl unary primary amine and formaldehyde, the structural formula of synthetic fluorenyl benzoxazine was:
Figure BDA0000024839600000032
Structural formula C
Wherein, Rn, M, n and n 1Described identical with structural formula A;
D: when reaction raw materials was fluorenyl phenol, fluorenyl binary primary amine and formaldehyde, the structural formula of synthetic fluorenyl benzoxazine was:
Figure BDA0000024839600000033
Structural formula D
Wherein, Rn, M, n and n 1Described identical with structural formula A;
E: when reaction raw materials was non-fluorenyl phenol, fluorenyl unary primary amine and formaldehyde, the structural formula of synthetic fluorenyl benzoxazine was:
Figure BDA0000024839600000034
Structural formula E
Wherein, Rn, n, M and n 1Described identical with structural formula A; Ar is the structural substituting group of non-fluorenyl phenol; The preferred following structure of non-fluorenyl phenol described in the reaction raw materials:
Figure BDA0000024839600000041
F: when reaction raw materials was non-fluorenyl phenol, fluorenyl binary primary amine and formaldehyde, the structural formula of synthetic fluorenyl benzimidazole dihydrochloride was:
Figure BDA0000024839600000042
Structural formula F
Wherein, Ar, M, Rn, n and n 1Described identical with structural formula E.
The preparation method of above-mentioned fluorenyl benzoxazine comprises the steps: that reaction raw materials is fluorenyl phenol, non-fluorenyl unary primary amine or non-fluorenyl binary uncle peace level amine or fluorenyl unary primary amine or fluorenyl binary primary amine, formaldehyde; Reaction raw materials also can be non-fluorenyl phenol, fluorenyl unary primary amine or fluorenyl binary primary amine, formaldehyde; Adopt the solvent method preparation synthetic, temperature of reaction is 60～150 ℃; Adopt distilled water or dehydrated alcohol that reaction system is washed then, and under vacuum, remove and anhydrate or ethanol.Phenolic hydroxyl group in the reaction raw materials: amido: the ratio of the amount of substance of formaldehyde is 1: 1: 2.
Described solvent is nonacid solvent, can avoid fluorenyl benzoxazine open loop in preparation process; Solvent preference chain alkane, alkene, alcohol, aldehyde, amine, ester, ether, ketone, aromatic hydrocarbon, hydrogenate hydrocarbon, terpene hydrocarbon, halohydrocarbon, heterocyclization thing, nitrogenous compound or sulfocompound; More preferably dimethylbenzene, dimethyl sulfoxide (DMSO) or chloroform.
The principle of selective solvent of the present invention is: (1) selects high boiling solvent for use, because in the building-up process of fluorenyl benzoxazine, and synthesis temperature high more (being lower than the open loop temperature), speed of reaction is fast more; (2) select the low-k solvent for use, because the electrocharge effect of solvent is to the influence of oxazines ring stability, under high dielectric system, the oxazines ring is easier to be opened, cause its oligomer content very high, so the oligomer content than the product that obtains in the high-k system lacks in the low-k solvent system.
Principle of the present invention is: introduction is fluorene structured in benzoxazine can reach following three purposes: the one, utilize huge fluorene structured free volume of occupying, and can reduce the dielectric properties of benzoxazine; The 2nd, utilize fluorene structured steric hindrance in polyphenyl and oxazines, can improve the resistance toheat of benzoxazine; The 3rd, the hydrocarbon ratio of whole material is enhanced behind the introduction fluorene group, can improve the flame retardant properties of benzoxazine.
The present invention compared with prior art has following advantage and effect: fluorenyl benzoxazine of the present invention has good heat-resistant and dielectric properties, can be applied to strongthener and filler and prepare composite in binding agent, coating, veneer sheet, circuit printing plate, the semiconductor sealing material.
Description of drawings
Fig. 1 is the hydrogen spectrogram of synthetic BF-a in dimethyl sulfoxide (DMSO) and the dimethylbenzene.
Fig. 2 is the hydrogen spectrogram of synthetic BF-mda in the trichloromethane.
Fig. 3 is the hydrogen spectrogram of synthetic BF-ala in the middle dimethylbenzene.
Embodiment
Below in conjunction with embodiment the present invention is done further detailed description, but embodiments of the present invention are not limited thereto.
Embodiment 1
In the three-necked bottle that thermometer, prolong and agitator are housed, add formaldehyde solution and the 150ml dimethyl sulfoxide (DMSO) of 35g bisphenol fluorene, 9.3g aniline, 8.5g37%.Behind stirring at room 10min, be warming up to 120 ℃ of isothermal reaction 2h, reaction system is washed with 5% (massfraction) NaOH after being cooled to room temperature, remove by filter yellow-green liquid and obtain white solid matter, with distilled water it is washed till neutrality then after, use an amount of washing with alcohol.Last 80 ℃ of vacuum-drying 5h promptly obtain the fluorenyl benzoxazine monomer of white powder, productive rate 93%.
Product abbreviates BF-a as, and structure and hydrogen are composed as shown in Figure 1, and the chemical shift of two methylene radical is respectively 4.46 and 5.28 on the oxazines ring.
Embodiment 2
Employing dimethylbenzene is solvent, and the reaction times is 4h.Aftertreatment is directly with the ethanolic soln washing that is dissolved with NaOH, is washed till that vacuum-drying 5h gets final product under the room temperature of neutral back, and productive rate is 86%.Other reaction raw materials, reaction conditions and product structure are with embodiment 1.
Embodiment 3
In the three-necked bottle that thermometer, prolong and agitator are housed, add 35g bisphenol fluorene, 5.92g Tri N-Propyl Amine, 8.5g 37% formaldehyde solution and 150ml dimethylbenzene and behind stirring at room 10min, be warming up to 120 ℃ of isothermal reaction 4h, reaction system naturally cools to after the room temperature to wash to the benzoxazine monomer with massfraction 3%NaOH ethanolic soln and almost all separates out, filtration obtains white powder, be washed till neutral back normal temperature vacuum-drying 5h, productive rate 94% with ethanol then.
Embodiment 4
In the three-necked bottle that thermometer, prolong and agitator are housed, add 11.4g allylamine, 32.5g37% formaldehyde solution and 50ml dimethyl sulfoxide (DMSO) and in ice-water bath, stir 20min, add dimethylbenzene (100ml) solution that progressively adds dissolving 35g bisphenol fluorene then, continue to stir 10min (whole process is being lower than 5 ℃) after reinforced the finishing, be warming up to 120 ℃ of isothermal reaction 2h then.Reaction soln is cooled to after the room temperature to wash to the benzoxazine monomer with massfraction 3%NaOH ethanolic soln almost all separates out, filter and obtain white powder, be washed till neutral back normal temperature vacuum-drying 5h, productive rate 88% with ethanol then.
Product abbreviates BF-ala as, and structure and hydrogen are composed as shown in Figure 3, and the chemical shift of two methylene radical is respectively 3.81 and 4.77 on the oxazines ring.
Embodiment 5
In the three-necked bottle that thermometer, prolong and agitator are housed, add 20g4,4 '-diaminodiphenylmethane, 35g37% formaldehyde solution and 200ml chloroform stirring at room 1.5h, progressively add 35g bisphenol fluorene and 100ml chloroform back flow reaction 8h then again, remove by filter insoluble solids, obtain the white powder solid with cold washing with alcohol filtrate, use NaHCO then 3The solution washing white powder is washed till neutrality with distilled water again, and moisture and other organic solvent are gone out in last vacuum-drying, productive rate 95%.
Product abbreviates BF-mda as, and structure and hydrogen are composed as shown in Figure 2, and the methylenation displacement study is respectively 4.31,5.17 on the oxazines ring.Mn＝3400，Mw/Mn＝1.12。
Embodiment 6
In the three-necked bottle that thermometer, prolong and agitator are housed, add 34.9g diamine fluorenes, 12.5g Paraformaldehyde 96,18.8g phenol and 150ml dimethylbenzene and be warming up to 140 ℃ of continuation reactions 3 hours after half an hour in reaction under the abundant stirring and refluxing in 80 ℃, system is washed with ice-cold ethanolic soln after naturally cooling to room temperature then, filtration obtains white powder and with its acetone, back NaOH with 5% dissolves into the row washing and filters and obtains white powder, be washed till neutral final vacuum drying with distilled water then and remove moisture and other solvent, productive rate 95%.
Embodiment 7
In the three-necked bottle that thermometer, prolong and agitator are housed, add 35g bisphenol fluorene, 12.5g Paraformaldehyde 96,44.2g γ-amido triethoxy base silane, 20g CaH 2And the 200ml trichloromethane in 85 ℃ under abundant stirring and refluxing reaction remove not tolerant and solvent after 5 hours, obtain the light green powder.
The performance test example
With bisphenol fluorene, aniline and formaldehyde is that the monomeric cured article of raw material synthetic benzoxazine (being called for short PBF-a) is an example, and its thermal characteristics and specific inductivity are as shown in table 1: can see the T of PBF-a from table gBe higher than 200 ℃, initial decomposition temperature has demonstrated good thermal stability up to 330 ℃, and its specific inductivity also approaches 3 in addition, is that the ideal of electronic package material is selected materials.T g(Diamond/Pyris) records for the dsc analysis instrument, and test condition is N 2Protection, heat-up rate is 20 ℃/min; T 5%, T 10%, T MaxWith the carbon residue rate be that TGA thermogravimetric analyzer (Perkin-Elmer TGA-6) records, condition is N 2Protection, heat-up rate is 10 ℃/min, the scanning temperature range is 50～850 ℃; Specific inductivity is that dielectric tester (DEA2970) records, and sample size is 50 * 50 * 3 (mm).
The performance of table 1.PBF-a cured article

Claims (5)

1. fluorenyl benzoxazine, its structural formula are a kind of among following structural formula A～F:
A: when reaction raw materials was fluorenyl phenol, non-fluorenyl primary amine and formaldehyde, the structural formula of synthetic fluorenyl benzoxazine was:
Figure FDA0000024839590000011
Structural formula A
Wherein, 1≤n 1≤ 10; R nBe hydrogen atom, or contain C substituting group, hetero atom substituents, substituent number n is 10-n 1M can link to each other with 2,3,4,5,6,7,9,10, No. 11 positions of fluorenes ring; The structure of M is the aliphatic chain of 1～36 C atom, or the cycloaliphatic ring of 3～20 C atoms or aromatic ring, or contains the heteroatom group of O, N, P, S, Si or B; R is that the C atomicity is that 1～36 aliphatic chain or C atomicity are 1～20 cycloaliphatic ring, or the C atomicity is the substituting group of 6～20 aromatic nucleus or derivatives thereof, heterochain or the coexistence of above structure; In addition, the phenyl ring of benzoxazine can also directly link to each other with the fluorenes ring, does not promptly have the M group between the two;
B: when reaction raw materials was fluorenyl phenol, non-fluorenyl binary primary amine and formaldehyde, the structural formula of synthetic fluorenyl benzoxazine was:
Figure FDA0000024839590000012
Structural formula B
Wherein, Rn, M, n and n 1Described identical with structural formula A; Described non-fluorenyl binary primary amine comprises following formula 1～formula 5:
Formula 1:NH 2(CH 2) xNH 2, 1≤x≤20 wherein;
Figure FDA0000024839590000013
Formula 2 formulas 3
Figure FDA0000024839590000021
Formula 4 formulas 5
In formula 2～formula 5, R N2And R N3Be OH or the straight or branched aliphatics substituting group that contains 1～10 C atom or contain the aromatic substituents of 6～12 C atoms or contain the aliphatics of 7～12 C atoms and substituting group or other heteroatomic substituting group of aromatic series coexistence; 1≤n2≤4; 1≤n3≤4;
In the formula 5, Y comprises following structure:
Figure FDA0000024839590000022
C: when reaction raw materials was fluorenyl phenol, fluorenyl unary primary amine and formaldehyde, the structural formula of synthetic fluorenyl benzoxazine was:
Structural formula C
Wherein, Rn, M, n and n 1Described identical with structural formula A;
D: when reaction raw materials was fluorenyl phenol, fluorenyl binary primary amine and formaldehyde, the structural formula of synthetic fluorenyl benzoxazine was:
Figure FDA0000024839590000024
Structural formula D
Wherein, Rn, M, n and n 1Described identical with structural formula A;
E: when reaction raw materials was non-fluorenyl phenol, fluorenyl unary primary amine and formaldehyde, the structural formula of synthetic fluorenyl benzoxazine was:
Figure FDA0000024839590000031
Structural formula E
Wherein, Rn, n, M and n 1Described identical with structural formula A; Ar is the structural substituting group of non-fluorenyl phenol; The preferred following structure of non-fluorenyl phenol described in the reaction raw materials:
Figure FDA0000024839590000032
F: when reaction raw materials was non-fluorenyl phenol, fluorenyl binary primary amine and formaldehyde, the structural formula of synthetic fluorenyl benzimidazole dihydrochloride was:
Figure FDA0000024839590000041
Structural formula F
Wherein, Ar, M, Rn, n and n 1Described identical with structural formula E.
2. the preparation method of the described fluorenyl benzoxazine of claim 1 is characterized in that comprising the steps: that reaction raw materials is fluorenyl phenol, non-fluorenyl unary primary amine or non-fluorenyl binary uncle peace level amine or fluorenyl unary primary amine or fluorenyl binary primary amine, formaldehyde; Perhaps reaction raw materials is non-fluorenyl phenol, fluorenyl unary primary amine or fluorenyl binary primary amine, formaldehyde; Adopt the solvent method preparation synthetic, temperature of reaction is 60～150 ℃; Adopt distilled water or dehydrated alcohol that reaction system is washed then, and under vacuum, remove and anhydrate or ethanol.
3. the preparation method of fluorenyl benzoxazine according to claim 2, it is characterized in that: the ratio of the amount of substance of phenolic hydroxyl group, amido and formaldehyde is 1: 1: 2 in the reaction raw materials.
4. the preparation method of fluorenyl benzoxazine according to claim 2, it is characterized in that: described solvent is paraffinic hydrocarbons, alkene, alcohol, aldehyde, amine, ester, ether, ketone, aromatic hydrocarbon, hydrogenate hydrocarbon, terpene hydrocarbon, halohydrocarbon, heterocyclization thing, nitrogenous compound or sulfocompound.
5. the preparation method of fluorenyl benzoxazine according to claim 4, it is characterized in that: described solvent is dimethylbenzene, dimethyl sulfoxide (DMSO) or chloroform.
CN2010102596660A 2010-08-23 2010-08-23 Fluorenyl benzoxazine and preparation method thereof Pending CN101921242A (en)

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CN103304578A (en) * 2013-05-31 2013-09-18 哈尔滨工程大学 Spirofluorene xanthenes bisphenol type benzoxazine
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CN108192281A (en) * 2017-12-27 2018-06-22 广东生益科技股份有限公司 A kind of halogen-free thermosetting resin composite and use its prepreg, laminate, metal-clad laminate and printed circuit board
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CN102584884A (en) * 2011-12-19 2012-07-18 中科院广州化学有限公司 Benzoxazine monomer, benzoxazine precursor and low-dielectric benzoxazine resin
CN102702225A (en) * 2012-06-15 2012-10-03 哈尔滨工程大学 Four-phenolic fluorene based benzoxazine and preparation method of four-phenolic fluorine based benzoxazine
CN103288849A (en) * 2013-05-14 2013-09-11 哈尔滨工程大学 Mixed amine-based multi-functionality fluorenyl benzoxazine and synthesis method thereof
CN103304578A (en) * 2013-05-31 2013-09-18 哈尔滨工程大学 Spirofluorene xanthenes bisphenol type benzoxazine
CN103304578B (en) * 2013-05-31 2015-09-30 哈尔滨工程大学 Spiral shell fluorenes xanthene bisphenol type benzoxazine
CN103936686A (en) * 2014-03-21 2014-07-23 哈尔滨工程大学 N-semi aromatic hydrocarbyl diamine-bisphenol tetrafunctional fluorene-based benzoxazine and preparation method thereof
CN103936686B (en) * 2014-03-21 2016-05-04 哈尔滨工程大学 N-semiaromatic alkyl diamine-bisphenol type four degree of functionality fluorenyl benzoxazine and preparation methods
CN108192281A (en) * 2017-12-27 2018-06-22 广东生益科技股份有限公司 A kind of halogen-free thermosetting resin composite and use its prepreg, laminate, metal-clad laminate and printed circuit board
TWI669340B (en) * 2017-12-27 2019-08-21 大陸商廣東生益科技股份有限公司 Halogen-free thermosetting resin composition and prepreg, laminate, metal foil-clad laminate, and printed circuit board using the same
CN108192281B (en) * 2017-12-27 2020-12-15 江西生益科技有限公司 Halogen-free thermosetting resin composition, and prepreg, laminated board, metal foil-clad laminated board and printed circuit board using same
CN113321778A (en) * 2021-06-07 2021-08-31 安徽强邦印刷材料有限公司 Thermosensitive film-forming resin for treatment-free CTP (computer to plate) plate and preparation method thereof

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Application publication date: 20101222