CN102134254B - Silicon-containing benzoxazine resin as well as preparation method and application thereof - Google Patents
Silicon-containing benzoxazine resin as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN102134254B CN102134254B CN201110001172.7A CN201110001172A CN102134254B CN 102134254 B CN102134254 B CN 102134254B CN 201110001172 A CN201110001172 A CN 201110001172A CN 102134254 B CN102134254 B CN 102134254B
- Authority
- CN
- China
- Prior art keywords
- silicon
- benzoxazine
- dihydro
- propyl
- polybenzoxazine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 0 C*N1COc2ccccc2C1 Chemical compound C*N1COc2ccccc2C1 0.000 description 1
Images
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention discloses a silicon-containing benzoxazine resin. A monomer of the silicon-containing benzoxazine resin is synthesized through Mannich reaction according to theoretical mole ratio by taking phenols compounds, formaldehyde and amine compounds as reactive raw materials; and a polymer of the silicon-containing benzoxazine resin is obtained by carrying out hydrolytic condensation and heating ring-opening polymerization reaction on the monomer. Silicon-containing benzoxazine has higher carbon residual rate, glass transition temperature and silicon content and lower surface energy, thereby having potential application prospect in preparing ablation resisting materials, heat resisting material, flame-retardant materials and waterproof materials; and in addition, the invention has the advantages of simplicity, convenience and easy operation of a synthesis method of a benzoxazine monomer and a solidification process of poly-benzoxazine without specific equipment requirements and can carry out industrial production in a general plant.
Description
Technical field
The present invention relates to a kind of novel benzoxazine colophony---containing silicon benzoxazine monomer and polymkeric substance, with and preparation method thereof with application, belong to the technical field of introducing silicon modified polyphenyl oxazine on molecular level.
Background technology
Benzoxazine colophony is a kind of novel phenolic resins newly developed, it is to take phenolic compound, aldehydes and aminated compounds as the intermediate of the synthetic class of raw material containing heterocycle structure, under heating and/or catalyst action, there is ring-opening polymerization, generate the reticulation of nitrogenous similar resol.Compare with traditional resol; when the advantage of benzoxazine colophony is the thermotolerance with common heat-reactive phenolic resin or novolac resin, flame retardant resistance, resin does not have small molecules to discharge in forming and hardening process, goods porosity is low, approaching zero shrinks, stress is little, there is no tiny crack, adding benzoxazine colophony ring-opening polymerization front is low relative molecular mass, low viscous cyclic monomer, solvability is good, there is good processing performance, can be used as the body material of preparing matrix material.
In prior art, people often utilize active group and other resin reactions on benzoxazine molecule, it is carried out to various modifications, and the benzoxazine colophony after modification has more good over-all properties, in fields such as electronics, aviations, has been widely used.
Organosilicon macromolecule has the performance of many uniquenesses, such as weather-proof, high-low temperature resistant, hydrophobic, difficult combustion etc., therefore, can adopt organosilicon to come modified polyphenyl oxazine resin, the performance of Polybenzoxazine is further improved, such as thermotolerance, toughness, flame retardant resistance, low surface property etc.
With the report of organic-silicon-modified Polybenzoxazine, mainly contain:
(1) with polyhedral oligomeric silsesquioxane (POSS) modified polyphenyl Bing oxazine.Chang etc. " Syntheses; thermal properties; and phase morphologies of novel benzoxazines functionalized with polyhedral oligomeric silsesquioxane (POSS) nanocomposites[doi:10.1016/j.polymer.2004.04.055] reported that adopting the synthetic monocycle benzoxazine monomer that contains POSS of two kinds of methods, a kind of method is that to contain amino POSS, phenol and a formaldehyde be that raw material is reacted and synthesized by Mannich in article; Another kind method is to synthesize by addition reaction of silicon with hydrogen containing the POSS of a si-h bond and the benzoxazine monomer of ethenyl blocking.Subsequently, again at " Synthesis and characterization of polybenzoxazine networks nanocomposites containing multifunctional polyhedral oligomeric silsesquioxane (POSS) " [Polymer, 2006,47,4378-4386] reported with eight (dimethylsilyl bis) silicious sesquioxane (Q in article
8m
8 h) by addition reaction of silicon with hydrogen, synthesized with the benzoxazine of ethenyl blocking the eight ring benzoxazine monomers that contain POSS, after ring-opening polymerization, obtained crosslinked nano composite material.Yu etc. are at " A novel poly-benzoxazinyl functionalized polyhedral oligomeric silsesquioxane and its nanocomposite with polybenzoxazine " [European Polymer Journal, 2007,43,743-752] reported that take the POSS, p-cresol and the formaldehyde that contain eight p-aminophenyls has synthesized similarly, contained the eight ring benzoxazine monomers of POSS as raw material in article.Kuo etc. are at " Synthesis and characterization of polyhedral oligomeric silsesquioxane (POSS) with multifunctional benzoxazine groups through click chemistry " [Polymer, 2010,51,3948-3955] in article report by eight-nitrine POSS and the benzoxazine monomer that contains propargyl by click chemistry react synthesized similar, contain eight of POSS and encircle benzoxazine monomers, reduced the solidification value of benzoxazine, and cured product surface can be very low.Huang etc. are at " Preparation of VB-a/POSS Hybrid Monomer and Its Polymerization of Polybenzoxazine/POSS Hybrid Nanocomposites " [J.Appl.Polym.Sci., 2009,111,628-634] reported in article and used Q
8m
8 hcarry out addition reaction of silicon with hydrogen with the bisphenol A-type benzoxazine of ethenyl blocking, obtained containing 16 of POSS and encircled benzoxazine monomers, after its ring-opening polymerization, resulting product second-order transition temperature is up to 310.7 ℃.Yu etc. are at " Polyhedral Oligomeric Silsesquioxane (POSS) Nanoscale Reinforcement of Thermosetting Resin from Benzoxazine and Bisoxazoline " [Macromol.Rapid Commun.2005,26,1878-1882] reported and will contain amino POSS, bisphenol A-type benzoxazine, bisoxazoline three copolymerization in article, wherein bisoxazoline can also, as expanding material, strengthen the consistency of POSS and benzoxazine monomer.Subsequently, again at " Preparation and characterization of polybenzoxazine/trisilanol polyhedral oligomeric silsesquioxanes composites " [J.Mater.Design, 2009,31,1720-1725] reported in article the POSS that contains silicon hydroxyl has been mixed with bisphenol A-type benzoxazine, then in solidification process, carry out copolymerization.
(2) with silicon rubber modified polyphenyl Bing oxazine.Kiskan etc. are at " Synthesis, Characterization, and Thermally Activated Curing of Oligosiloxanes Containing Benzoxazine Moieties in the Main Chain " [Journal of Polymer Science:Part A:Polymer Chemistry, 2009, 47, 804-811] reported with the bisphenol A-type benzoxazine monomer of tetramethyl-dihydro sily oxide and ethenyl blocking in article and passed through addition reaction of silicon with hydrogen, synthesized the silicon rubber containing benzoxazine, after benzoxazine ring-opening polymerization, obtained the Polybenzoxazine of silicon rubber modification, its toughness is greatly improved.Takeichi etc. are at " Performance enhancement of polybenzoxazine by hybridization with polysiloxane " [Polymer, 2008,49,4585-4591] reported in article after dimethyldiethoxysilane is mixed with bisphenol A-type Polybenzoxazine monomer and carried out sol gel reaction, the low-molecular-weight silicon rubber of in-situ generation, its cured product toughness is better and separated without macroface.Subsequently again at " Effect of pendant group of polysiloxanes on the thermal and mechanical properties of polybenzoxazine hybrids " [Polymer, 2009,50,5959-5969] in article with the diethoxy silane containing methyl, phenyl with same method modified bisphenol A type benzoxazine, studied methyl, the impact of phenyl on modification post polymerization physical performance.Wang etc. are at " Morphology and thermomechanical properties of main-chainpolybenzoxazine-block-polydimethylsiloxane multiblock copolymers " [Polymer, 2010,51,1124-1132] reported in article with the benzoxazine monomer of two ends phenolic hydroxy group and reacted by Mannich with end amido silicon oil, formaldehyde, benzoxazine-polydimethylsiloxane the segmented copolymer that has synthesized silicon rubber block, its cured product has lower surface energy.
(3) with silicone resin modified polyphenyl Bing oxazine.Liu etc. are at " Polybenzoxazine Containing Polysilsesquioxane:Preparation and Thermal Properties " [J.Appl.Polym.Sci., 2006,99,927-936] reported that take amino silicone couplet γ-aminopropyltrimethoxysilane (KH-560), paraformaldehyde and phenol synthesizes the silicone couplet of Han oxazine ring as raw material in article, then by having obtained the Polybenzoxazine of silicone resin modification after hydrolytic condensation, ring-opening polymerization.Xin etc. in patent CN2010:101750896 " Low-surface-energy fluorine-or silicon-containingpolybenzoxazine material used for nanoimprint lithography ", reported take to methyl trifluoro phenol and γ-aminopropyl triethoxysilane (KH550) as raw material has synthesized fluorine-containing and benzoxazine monomer silicon, after solidifying, obtain silicone resin modification, low surface energy Polybenzoxazine.
Yet, above-mentionedly with silicone resin modified polyphenyl Bing oxazine synthetic, mainly concentrate on the synthetic of monocycle benzoxazine monomer based on monohydric phenol, the synthetic report that there is not yet of the many rings benzoxazine based on polyphenol.
Summary of the invention
For above-mentioned prior art, the present invention mainly synthesized based on polyphenol, Novel siliceous encircles benzoxazine monomer more, as systematic study, also comprise some and had no the siliceous monocycle benzoxazine monomer of report, then by hydrolytic condensation, add thermal-ring-opening polymerization, obtained silicone resin modification, high-performance poly benzoxazine.
The present invention is achieved by the following technical solutions:
The present invention be take phenolic compound, formaldehyde and aminated compounds as reaction raw materials, according to theoretical molar than (unit phenol, x: y: z=1: 2: 1; Dihydric phenol, x: y: z=2: 4: 1; Trihydric phenol, x: y: z=3: 6: 1), by Mannich, react, synthesized series of new benzoxazine monomer, step is as follows:
Under condition of ice bath, to the phenol that adds the aldehyde of 10-30 weight part, the amine of 20-50 weight part and 20-40 weight part in the solvent of 60-80 weight part, then mixed solution reacts 2-4h at 70-100 ℃; Then by gained reaction solution separatory, remove the water on upper strata, obtain water white solution, pressure reducing and steaming solvent, vacuum-drying, obtains containing silicon benzoxazine colophony monomer; Wherein, described amine is selected from a kind of in γ-aminopropyl triethoxysilane (KH-550), γ-aminopropyl methyl dimethoxysilane (KH-660), γ-aminopropyltrimethoxysilane or γ-aminopropyl methyldiethoxysilane;
Described phenol is selected from phenol, dihydroxyphenyl propane, 4,4-dihydroxy diphenylsulphone, 4, a kind of in 4-dihydroxy benaophenonel, phenolphthalein, naphthols or 1,1,1-tri-(4-hydroxy phenyl) ethane; Described aldehyde is selected from a kind of in formalin, trioxymethylene or paraformaldehyde; Described solvent is selected from least one in dioxane, normal hexane, hexanaphthene, tetrahydrofuran (THF), chloroform, toluene or dimethylbenzene.
Its reaction equation is shown in Scheme 1:
x∶y∶z＝1∶2∶1?or?2∶4∶1?or?3∶6∶1
The synthetic route of Scheme 1 benzoxazine monomer
Of the present invention containing silicon benzoxazine colophony monomer, include, but is not limited to following compound:
(1) two (3-triethoxyl silane-n-propyl-3,4-dihydro-2H-1,3-benzoxazinyl) isopropyl alkane, its structural formula is as follows:
(2) 3-(methyl-dimethoxy silane)-n-propyl-3,4-dihydro-2H-1,3-benzoxazine, its structural formula is as follows:
(3) two (3-methyl-dimethoxy silane-n-propyl-3,4-dihydro-2H-1,3-benzoxazinyl) isopropyl alkane, its structural formula is as follows:
(4) two (3-triethoxyl silane-n-propyl-3,4-dihydro-2H-1,3-benzoxazinyl) two sulfones, its structural formula is as follows:
(5) two (3-triethoxyl silane-n-propyl-3,4-dihydro-2H-1,3-benzoxazinyl) Ketene dimethyl, its structural formula is as follows:
(6) two (3-methyl-dimethoxy silane-n-propyl-3,4-dihydro-2H-1,3-benzoxazinyl) two sulfones, its structural formula is as follows:
(7) two (3-methyl-dimethoxy silane-n-propyl-3,4-dihydro-2H-1,3-benzoxazinyl) diketone, its structural formula is as follows:
Two (3-triethoxyl silane-n-propyl-3,4-dihydro-2H-1,3-benzoxazinyl)-1 (the 3H)-isobenzofuranones of (8) 3,3-, its structural formula is as follows:
Two (3-methyl-dimethoxy silane-n-propyl-3,4-dihydro-2H-1,3-benzoxazinyl)-1 (the 3H)-isobenzofuranones of (9) 3,3-, its structural formula is as follows:
(10) 1,1,1-tri-(3-triethoxyl silane-n-propyl-3,4-dihydro-2H-1,3-benzoxazinyl) ethane, its structural formula is as follows:
(11) 1,1,1-tri-(3-methyl-dimethoxy silane-n-propyl-3,4-dihydro-2H-1,3-benzoxazinyl) ethane, its structural formula is as follows:
The present invention also provides siliceous Polybenzoxazine, and it is by forming containing silicon benzoxazine colophony monomer polymerization.Its preparation method is as follows: will be dissolved in tetrahydrofuran (THF) containing silicon benzoxazine colophony monomer, add and the water that contains contained silicon alkoxyl group equimolar ratio in silicon benzoxazine colophony monomer, add the acid of 0.1% (accounting for the massfraction of benzoxazine monomer), at room temperature stir 12-72h; Revolve to steam and remove most of solvent, pour in culture dish, in Constant Temp. Oven, segmentation is solidified and is obtained siliceous Polybenzoxazine, curing temperature-rise period is: within the scope of 100-220 ℃, time variable control gradient increased temperature, the every rising 20-30 ℃ of temperature, isothermal curing 2-3h;
Described solvent is selected from a kind of in tetrahydrofuran (THF), acetone, ethanol or methyl alcohol; Described acid is a kind of in hydrochloric acid, sulfuric acid, oxalic acid, boric acid, acetic acid or tosic acid.
Polymerization process containing silicon benzoxazine monomer is divided into two stages, with the example that is polymerized to of two (3-triethoxyl silane-n-propyl-3,4-dihydro-2H-1,3-benzoxazinyl) isopropyl alkane (BZB-550), sees Scheme2.First stage is mainly organosilyl hydrolysis-condensation reaction, but due to sour existence, can be accompanied by the part ring-opening polymerization of benzoxazine.Second stage is mainly the thermal-ring-opening polymerization that adds of benzoxazine, and further crosslinked (as shown in Figure 8) of silicone resin.In addition, we have studied hydrolysis time to the impact containing silicon benzoxazine monomer hydrolysis-condensation reaction with gel permeation chromatography GPC, find that hydrolysis time is that 24h is optimum reacting time.
Synthetic route is as follows:
The synthetic route of Scheme 2 PBZB-550
Siliceous Polybenzoxazine of the present invention has higher carbon yield, therefore in preparing ablation resistant material, has potential application prospect.
Siliceous Polybenzoxazine of the present invention has higher second-order transition temperature, therefore in preparing heat-stable material, has good application prospect.
In siliceous Polybenzoxazine of the present invention, silicone content is higher, therefore in preparing fire retardant material, has potential application prospect.
Siliceous Polybenzoxazine of the present invention have lower surface can, therefore there is good application prospect preparing aspect waterproof paint.
The present invention has the following advantages:
(1) the present invention is incorporated into silicone resin in Polybenzoxazine resin from molecular level, has suppressed macroface separation common in silicone resin blending and modifying, has obtained dispersed good matrix material.
(2) the novel polyphenyl Bing oxazine resin obtaining has excellent resistance toheat, and second-order transition temperature is all higher than 250 ℃, and wherein the second-order transition temperature of PBZB-660 is up to 330 ℃.
(3) the novel polyphenyl Bing oxazine resin obtaining has lower surface energy, preferably hydrophobic nature.
(4) the novel polyphenyl Bing oxazine resin obtaining has higher carbon yield, and the carbon yield of PBZS-660 is up to 70% (N
2atmosphere, 800 ℃), preparing the potential development prospect of tool aspect ablation resistant material.
(5) the novel benzoxazine obtaining and the cured product after dimethyldiethoxysilane copolymerization, have excellent toughness.
(6) raw material used in the present invention: phenol, p-cresol, dihydroxyphenyl propane, paraformaldehyde, formalin, silane coupling agent etc. are commerical prod, and cost is lower.
(7) synthetic method of benzoxazine monomer used herein and the curing process of Polybenzoxazine are simple and easy to do, without especial equipment requirements, can carry out industrial production in general factory.
Accompanying drawing explanation
Fig. 1 is BZB-550's
1h NMR spectrogram.
Fig. 2 is the FTIR spectrogram of BZB-550.
Fig. 3 is the FTIR spectrogram after BZB-550 hydrolytic condensation.
Fig. 4 is the FTIR spectrogram of BZS-660.
Fig. 5 is the FTIR spectrogram of BZB-660.
Fig. 6 is the GPC spectrogram of the different hydrolysis time products of BZB-550 monomer.
Fig. 7 is the curing DSC of BZB-550 medial section and FTIR spectrogram, wherein, and A:DSC figure; B:FTIR spectrogram.
Fig. 8 is the point and line chart of the curing DSC of BZB-550 medial section and FTIR, wherein, and A: the variation of heat enthalpy value; The variation of B silica silicon absorption peak.
Fig. 9 is the TGA spectrogram of PBZB-550.
Figure 10 is the TGA spectrogram of PBZS-660, PBZB-660.
Figure 11 is the DMA spectrogram of PBZB-550.
Figure 12 is the DMA spectrogram of PBZS-660.
Figure 13 is the DMA spectrogram of PBZB-660.
Figure 14 is the surface contact angle of PBZS-550 and water.
Figure 15 is the surface contact angle of PBZS-660 and water.
Figure 16 is the surface contact angle of PBZB-660 and water.
Embodiment
Below by specific examples, the present invention is specifically described, it is important to point out: this example is only applicable to further illustrate of the present invention, but do not limit to its scope.Those skilled in the art, after reading this patent, are apparent in the various improvement of having done without prejudice to essence of the present invention, all belong to the claimed scope of the present invention.
1 pair of (3-triethoxyl silane-n-propyl-3,4-dihydro-2H-1,3-benzoxazinyl) isopropyl alkane (BZB-550) of embodiment
In the there-necked flask of 100mL, add successively 15mL trichloromethane and 3.2g (0.1mol) paraformaldehyde, and stir.11.0g γ-aminopropyl triethoxysilane (KH-550) (0.05mol) is dissolved in 12mL trichloromethane, stir and join in paraformaldehyde solution, be warming up to 85 ℃ of reaction 10min, add 5.7g (0.025mol) dihydroxyphenyl propane, backflow 3h.Separatory is removed generated water, revolves and steams except desolventizing, obtains water white liquid, productive rate 84%.
Ultimate analysis: C
37h
62n
2o
8si
2, theoretical value %:C, 61.8%; H, 8.69%; N, 3.9%.Analytical value: C, 62.1%; H, 8.44%; N, 3.84%.
Its
1as shown in Figure 1, FTIR spectrogram as shown in Figure 2 for H NMR spectrogram.
1H?NMR(CDCl
3，300MHz，δ)：3.93ppm(s，Ar-CH
2-N)，4.82ppm(s，O-CH
2-N)，1.59ppm(-C(CH
3)
2-)，2.71-2.76ppm(t，N-CH
2-C)，1.67-1.72(m，C-CH
2-C)，0.62-0.68(t，C-CH
2-Si)，3.67-3.86(m，O-CH
2-C)，119-1.24(t，O-C-CH
3)。FTIR (KBr) v:1022cm
-1(C-O-C is symmetrical flexible), 1232cm
-1(C-O-C asymmetric stretch), 1498cm
-1(trisubstituted benzene ring), 935cm
-1the phenyl ring that (is connected Yu oxazine ring), 1079cm
-1(silicon alkoxyl group), 1105cm
-1(silicon alkoxyl group).
Embodiment 23-(methyl-dimethoxy silane)-n-propyl-3,4-dihydro-2H-1,3-benzoxazine (BZS-660)
In the there-necked flask of 100mL, add successively 15mL dioxane and 3.2g (0.1mol) paraformaldehyde, and stir.8.16g γ-aminopropyl methyl dimethoxysilane (KH-660) (0.05mol) is dissolved in 12mL dioxane, stir and join in paraformaldehyde solution, be warming up to 90 ℃ of reaction 10min, add 4.7g (0.05mol) phenol, backflow 3h.Separatory is removed generated water, revolves and steams except desolventizing, obtains water white liquid, productive rate 86%.
Ultimate analysis: C
14h
23nO
3si, theoretical value %:C, 59.75%; H, 8.24%; N, 4.98%; Analytical value: C, 61.1%; H, 8.06%, N, 4.87%.
Its FTIR spectrogram as shown in Figure 4.
1H NMR (CDCl3,300MHz, δ): 3.95ppm (s, Ar-CH2-N), 4.86ppm (s, O-CH2-N), 2.64-2.769ppm (t, N-CH2-C), 1.60-1.62 (m, C-CH2-C), 0.68-0.74 (t, C-CH
2-Si), 3.4 (t, Si-O-CH
3), 0.14 (t, Si-CH
3); FTIR (KBr) v:1022cm
-1(C-O-C is symmetrical flexible), 1230cm
-1(C-O-C asymmetric stretch), 1492cm
-1(trisubstituted benzene ring), 927cm
-1the phenyl ring that (is connected Yu oxazine ring), 1083cm
-1(silicon alkoxyl group).
3 pairs of (3-methyl-dimethoxy silane-n-propyl-3,4-dihydro-2H-1,3-benzoxazinyl) isopropyl alkane (BZB-660) of embodiment
In the there-necked flask of 100mL, add successively 15mL trichloromethane and 7.8ml (0.1mol) formalin, and stir.8.16g KH-660 (0.05mol) is dissolved in 12mL trichloromethane, stirs and join in paraformaldehyde solution, be warming up to 85 ℃ of reaction 10min, add 5.7g (0.025mol) dihydroxyphenyl propane, backflow 3h.Separatory is removed generated water, revolves and steams except desolventizing, obtains water white liquid, productive rate 82%.
Ultimate analysis: C
31h
50n
2o
6si
2, theoretical value %:C, 61.76%; H, 8.36%; N, 4.65%; Analytical value: C, 61.62%; H, 8.246%; N, 4.78%.
Its FTIR spectrogram as shown in Figure 5.
1h NMR (CDCl
3, 300MHz, δ): 3.95ppm (s, Ar-CH
2-N), 4.86ppm (s, O-CH
2-N), 1.59ppm (C (CH
3)
2-), 2.64-2.769ppm (t, N-CH
2-C), 1.60-1.62 (m, C-CH
2-C), 0.68-0.74 (t, C-CH
2-Si), 3.4 (t, Si-O-CH
3), 0.14 (t, Si-CH
3); FTIR (KBr) v:1022cm
-1(C-O-C is symmetrical flexible), 1230cm
-1(C-O-C asymmetric stretch), 1492cm
-1(trisubstituted benzene ring), 932cm
-1the phenyl ring that (is connected Yu oxazine ring), 1082cm
-1(silicon alkoxyl group).
4 pairs of (3-triethoxyl silane-n-propyl-3,4-dihydro-2H-1,3-benzoxazinyl) two sulfones (BSB-550) of embodiment
In the there-necked flask of 100mL, add successively 15mL methyl alcohol and 7.8ml (0.1mol) formalin, and stir.11.0g KH-550 (0.05mol) is dissolved in 12mL methyl alcohol, stirs and join in paraformaldehyde solution, be warming up to 70 ℃ of reaction 10min, add 6.25g (0.025mol) 4,4-dihydroxy diphenylsulphone, backflow 3h.Separatory is removed generated water, revolves and steams except desolventizing, obtains water white liquid, productive rate 84%.
Ultimate analysis: C
34h
56n
2o
10sSi
2, theoretical value %:C, 55.11%; H, 7.62%; N, 3.78%; Analytical value: C, 55.2%; H, 8.04%; N, 3.64%;
1h NMR (CDCl
3, 300MHz, δ): 3.93ppm (s, Ar-CH
2-N), 4.82ppm (s, O-CH
2-N), 2.71-2.76ppm (t, N-CH
2-C), 1.67-1.72 (m, C-CH
2-C), 0.62-0.68 (t, C-CH
2-Si), 3.67-3.86 (m, O-CH
2-C), 1.19-1.24 (t, O-C-CH
3); FTIR (KBr) v:1022cm
-1(C-O-C is symmetrical flexible), 1232cm
-1(C-O-C asymmetric stretch), 1498cm
-1(trisubstituted benzene ring), 935cm
-1the phenyl ring that (is connected Yu oxazine ring), 1079cm
-1(silicon alkoxyl group), 1105cm
-1(silicon alkoxyl group), 1356cm
-1(O=S=O).
5 pairs of (3-triethoxyl silane-n-propyl-3,4-dihydro-2H-1,3-benzoxazinyl) Ketene dimethyls (BNB-550) of embodiment
In the there-necked flask of 100mL, add successively 15mL trichloromethane and 3.2g (0.1mol) paraformaldehyde, and stir.11.0g KH-550 (0.05mol) is dissolved in 12mL trichloromethane, stirs and join in paraformaldehyde solution, be warming up to 85 ℃ of reaction 10min, add 5.35g (0.025mol) 4,4-dihydroxy benaophenonel, backflow 3h.Separatory is removed generated water, revolves and steams except desolventizing, obtains water white liquid, productive rate 84%.
Ultimate analysis: C
35h
56n
2o
9si
2, theoretical value %:C, 59.63%; H, 8.01%; N, 3.97%; Analytical value: C, 62.8%; H, 8.87%; N, 4.16%;
1h NMR (CDCl
3, 300MHz, δ): 3.92ppm (s, Ar-CH
2-N), 4.86ppm (s, O-CH
2-N), 2.71-2.76ppm (t, N-CH
2-C), 1.67-1.72 (m, C-CH
2-C), 0.62-0.68 (t, C-CH
2-Si) 3.67-3.86 (m, O-CH
2-C), 119-1.24 (t, O-C-CH
3); FTIR (KBr) v:1022cm
-1(C-O-C is symmetrical flexible), 1232cm
-1(C-O-C asymmetric stretch), 1498cm
-1(trisubstituted benzene ring), 935cm
-1the phenyl ring that (is connected Yu oxazine ring), 1079cm
-1(silicon alkoxyl group), 1105cm
-1(silicon alkoxyl group), 1641cm
-1(C=O).
6 pairs of (3-methyl-dimethoxy silane-n-propyl-3,4-dihydro-2H-1,3-benzoxazinyl) two sulfones (BSB-660) of embodiment
In the there-necked flask of 100mL, add successively 15mL toluene and 3.2g (0.1mol) paraformaldehyde, and stir.8.16g KH-660 (0.05mol) is dissolved in 12mL toluene, stirs and join in paraformaldehyde solution, be warming up to 95 ℃ of reaction 10min, add 6.25g (0.025mol) 4,4-dihydroxy diphenylsulphone, backflow 3h.Separatory is removed generated water, revolves and steams except desolventizing, obtains water white liquid, productive rate 82%.
Ultimate analysis: C
28h
44n
2o
8sSi
2, theoretical value %:C, 54.28%; H, 7.45%; N, 4.28%; Analytical value: C, 55.3%; H, 7.36%; N, 4.47%;
1h NMR (CDCl
3, 300MHz, δ): 3.95ppm (s, Ar-CH
2-N), 4.86ppm (s, O-CH
2-N), 2.64-2.769ppm (t, N-CH
2-C), 1.60-1.62 (m, C-CH
2-C), 0.68-0.74 (t, C-CH
2-Si), 3.4 (t, Si-O-CH
3), 0.14 (t, Si-CH
3); FTIR (KBr) v:1022cm
-1(C-O-C is symmetrical flexible), 1230cm
-1(C-O-C asymmetric stretch), 1492cm
-1(trisubstituted benzene ring), 927cm
-1the phenyl ring that (is connected Yu oxazine ring), 1083cm
-1(silicon alkoxyl group), 1356cm
-1(O=S=O).
7 pairs of (3-methyl-dimethoxy silane-n-propyl-3,4-dihydro-2H-1,3-benzoxazinyl) diketone (BNB-660) of embodiment
In the there-necked flask of 100mL, add successively 15mL trichloromethane and 3.2g (0.1mol) paraformaldehyde, and stir.8.16g KH-660 (0.05mol) is dissolved in 12mL trichloromethane, stirs and join in paraformaldehyde solution, be warming up to 85 ℃ of reaction 10min, add 5.35g (0.025mol) 4,4-dihydroxy benaophenonel, backflow 3h.Separatory is removed generated water, revolves and steams except desolventizing, obtains water white liquid, productive rate 82%.
Ultimate analysis: C
29h
44n
2o
7si
2, theoretical value %:C, 59.15%; H, 7.53%; N, 4.76%; Analytical value: C, 57.6%; H, 7.47%; N, 4.88%;
1h NMR (CDCl
3, 300MHz, δ): 3.95ppm (s, Ar-CH
2-N), 4.86ppm (s, O-CH
2-N), 2.64-2.769ppm (t, N-CH
2-C), 1.60-1.62 (m, C-CH
2-C), 0.68-0.74 (t, C-CH
2-Si), 3.4 (t, Si-O-CH
3), 0.14 (t, Si-CH
3); FTIR (KBr) v:1022cm
-1(C-O-C is symmetrical flexible), 1230cm
-1(C-O-C asymmetric stretch), 1492cm
-1(trisubstituted benzene ring), 927cm
-1the phenyl ring that (is connected Yu oxazine ring), 1083cm
-1(silicon alkoxyl group), 1641cm
-1(C=O).
Embodiment 83, two (3-triethoxyl silane-n-propyl-3,4-dihydro-2H-1,3-benzoxazinyl)-1 (the 3H)-isobenzofuranones (BFB-550) of 3-
In the there-necked flask of 100mL, add successively 15mL trichloromethane and 7.8ml (0.1mol) formalin, and stir.11.0g KH-550 (0.05mol) is dissolved in 12mL trichloromethane, stirs and join in paraformaldehyde solution, be warming up to 75 ℃ of reaction 10min, add 7.95g (0.025mol) phenolphthalein, backflow 3h.Separatory is removed generated water, revolves and steams except desolventizing, obtains water white liquid, productive rate 84%.
Ultimate analysis: C
42h
60n
2o
10si
2, theoretical value %:C, 62.35%; H, 7.47%; N, 3.46%; Analytical value: C, 65.2%; H, 7.84%; N, 3.55%;
1h NMR (CDCl
3, 300MHz, δ): 3.93ppm (s, Ar-CH
2-N), 4.82ppm (s, O-CH
2-N), 2.71-2.76ppm (t, N-CH
2-C), 1.67-1.72 (m, C-CH
2-C), 0.62-0.68 (t, C-CH
2-Si), 3.67-3.86 (m, O-CH
2-C), 119-1.24 (t, O-C-CH
3); FTIR (KBr) v:1022cm
-1(C-O-C is symmetrical flexible), 1232cm
-1(C-O-C asymmetric stretch), 1498cm
-1(trisubstituted benzene ring), 935cm
-1the phenyl ring that (is connected Yu oxazine ring), 1079cm
-1(silicon alkoxyl group), 1105cm
-1(silicon alkoxyl group).
Embodiment 93, two (3-methyl-dimethoxy silane-n-propyl-3,4--dihydro-2H-1,3-benzoxazinyl)-1 (the 3H)-isobenzofuranones (BFB-660) of 3-
In the there-necked flask of 100mL, add successively 15mL normal hexane and 3.2g (0.1mol) paraformaldehyde, and stir.8.16g KH-660 (0.05mol) is dissolved in 12mL normal hexane, stirs and join in paraformaldehyde solution, be warming up to 75 ℃ of reaction 10min, add 7.95g (0.025mol) phenolphthalein, backflow 3h.Separatory is removed generated water, revolves and steams except desolventizing, obtains water white liquid, productive rate 82%.
Ultimate analysis: C
36h
48n
2o
8si
2, theoretical value %:C, 62.4%; H, 6.98%; N, 4.04%; Analytical value: C, 62.5%; H, 7.15%; N, 4.36%;
1h NMR (CDCl
3, 300MHz, δ): 3.95ppm (s, Ar-CH
2-N), 4.86ppm (s, O-CH
2-N), 2.64-2.769ppm (t, N-CH
2-C), 1.60-1.62 (m, C-CH
2-C), 0.68-0.74 (t, C-CH
2-Si), 3.4 (t, Si-O-CH
3), 0.14 (t, Si-CH
3); FTIR (KBr) v:1022cm
-1(C-O-C is symmetrical flexible), 1230cm
-1(C-O-C asymmetric stretch), 1494cm
-1(trisubstituted benzene ring), 931cm
-1the phenyl ring that (is connected Yu oxazine ring), 1083cm
-1(silicon alkoxyl group), 1641cm
-1.
In the there-necked flask of 100mL, add successively 15mL tetracol phenixin and 7.8ml (0.1mol) formalin, and stir.11.0g KH-550 (0.05mol) is dissolved in 12mL tetracol phenixin, stirs and join in paraformaldehyde solution, be warming up to 80 ℃ of reaction 10min, add 5.1g (0.0167mol) 1,1,1-tri-(4-hydroxy phenyl) ethane, backflow 3h.Separatory is removed generated water, revolves and steams except desolventizing, obtains water white liquid, productive rate 84%.
Ultimate analysis: C
53h
37n
3o
12si
3, theoretical value %:C, 61.06%; H, 8.41%; N, 4.03%; Analytical value: C, 59.8%; H, 8.14%; N, 4.35%;
1h NMR (CDCl
3, 300MHz, δ): 3.93ppm (s, Ar-CH
2-N), 4.82ppm (s, O-CH
2-N), 2.71-2.76ppm (t, N-CH
2-C), 1.67-1.72 (m, C-CH
2-C), 0.62-0.68 (t, C-CH
2-Si), 3.67-3.86 (m, O-CH
2-C), 119-1.24 (t, O-C-CH
3); FTIR (KBr) v:1022cm
-1(C-O-C is symmetrical flexible), 1232cm
-1(C-O-C asymmetric stretch), 1498cm
-1(trisubstituted benzene ring), 935cm
-1the phenyl ring that (is connected Yu oxazine ring), 1079cm
-1(silicon alkoxyl group), 1105cm
-1(silicon alkoxyl group).
In the there-necked flask of 100mL, add successively 15mL hexanaphthene and 3.2g (0.1mol) paraformaldehyde, and stir.8.16g KH-660 (0.05mol) is dissolved in 12mL hexanaphthene, stirs and join in paraformaldehyde solution, be warming up to 85 ℃ of reaction 10min, add 5.1g (0.0167mol) 1,1,1-tri-(4-hydroxy phenyl) ethane, backflow 3h.Separatory is removed generated water, revolves and steams except desolventizing, obtains water white liquid, productive rate 82%.
Ultimate analysis: C
44h
69n
3o
9si
3, theoretical value %:C, 60.86%; H, 8.01%; N, 4.84%; Analytical value: C, 61.6%; H, 7.96%; N, 4.49%;
1h NMR (CDCl
3, 300MHz, δ): 3.95ppm (s, Ar-CH
2-N), 4.86ppm (s, O-CH
2-N), 2.64-2.769ppm (t, N-CH
2-C), 1.60-1.62 (m, C-CH
2-C), 0.68-0.74 (t, C-CH
2-Si), 3.4 (t, Si-O-CH
3), 0.14 (t, Si-CH
3); FTIR (KBr) v:1022cm
-1(C-O-C is symmetrical flexible), 1230cm
-1(C-O-C asymmetric stretch), 1494cm
-1(trisubstituted benzene ring), 931cm
-1the phenyl ring that (is connected Yu oxazine ring), 1083cm
-1(silicon alkoxyl group), 1641cm
-1.
The hydrolytic condensation of 12 pairs of (3-triethoxyl silane-n-propyl-3,4-dihydro-2H-1,3-benzoxazinyl) isopropyl alkane of embodiment
6.92g BZB-550 is dissolved in the THF of 40ml, adds successively 1.08g water, 0.11g hydrochloric acid (37%), stirs under room temperature, and respectively at 1d, 2d, samples after 3d, after it is dried, carries out GPC test, as shown in Figure 6.Poly-two (3-triethoxyl silane-n-propyl-3,4-dihydro-2H-1,3-benzoxazinyl) the isopropyl alkane (PBZB-550) of embodiment 13
6.92g BZB-550 is dissolved in the THF of 40ml, adds successively 1.08g water, 0.11g hydrochloric acid (concentration 37%), stirs 24h under room temperature, obtains yellow transparent solution.Solution is poured in culture dish, under room temperature, placed 24h, make the most of volatilization of solvent.Then in Constant Temp. Oven, segmentation is solidified.Concrete intensification solidification process is: 120 ℃/3h; 140 ℃/2h; 160 ℃/2h; 180 ℃/3h; Finally obtain yellow lump shape Polybenzoxazine PBZB-550.
The FTIR spectrogram of hydrolytie polycondensation product as shown in Figure 3.Add the DSC, FTIR spectrogram of thermal-ring-opening polymerization process as shown in Figure 7.
Embodiment 14 poly-3-(methyl-dimethoxy silane)-n-propyl-3,4-dihydro-2H-1,3-benzoxazine (PBZS-660)
5.62g BZB is dissolved in the acetone of 40ml, adds successively 0.72g water, 0.11g hydrochloric acid (concentration 37%), stirs 24h under room temperature, obtains yellow transparent solution.Solution is poured in culture dish, under room temperature, placed 24h, make the most of volatilization of solvent.Then in Constant Temp. Oven, segmentation is solidified.Concrete intensification solidification process is: 120 ℃/3h; 140 ℃/2h; 160 ℃/2h; 180 ℃/3h; Finally obtain yellow sheet Polybenzoxazine PBZS-660.
Poly-two (3-methyl-dimethoxy silane-n-propyl-3,4-dihydro-2H-1,3-benzoxazinyl) the isopropyl alkane (PBZB-660) of embodiment 15
6.03g BZB is dissolved in the methyl alcohol of 40ml, adds successively 0.72g water, 0.11g tosic acid, stirs 24h under room temperature, obtains yellow transparent solution.Solution is poured in culture dish, under room temperature, placed 24h, make the most of volatilization of solvent.Then in Constant Temp. Oven, segmentation is solidified.Concrete intensification solidification process is: 120 ℃/3h; 140 ℃/2h; 160G/2h; 180 ℃/2h; 200 ℃/1h; Finally obtain yellow sheet Polybenzoxazine PBZB-660.
Embodiment 16 dimethyldiethoxysilanes (content 20%) and BZB-660 multipolymer (PBZB-660-PDMS-20%)
2.4g BZB-660 is dissolved in the THF of 27ml, adds successively 0.6g dimethyldiethoxysilane, 0.49g water, 0.15g hydrochloric acid (concentration 37%), under room temperature, stir 24h, obtain yellow transparent solution.Solution is poured in culture dish, under room temperature, placed 24h, make the most of volatilization of solvent.Then in Constant Temp. Oven, segmentation is solidified.Concrete intensification solidification process is: 120 ℃/3h; 140 ℃/2h; 160 ℃/2h; 180 ℃/3h; Finally obtain yellow sheet Polybenzoxazine PBZB-660-20%.
Embodiment 17 dimethyldiethoxysilanes (content 50%) and BZB-660 multipolymer (PBZB-660-PDMS-50%)
1.5g BZB-660 is dissolved in the THF of 35ml, adds successively 1.5g dimethyldiethoxysilane, 0.64g water, 0.19g hydrochloric acid (concentration 37%), under room temperature, stir 24h, obtain yellow transparent solution.Solution is poured in culture dish, under room temperature, placed 24h, make the most of volatilization of solvent.Then in Constant Temp. Oven, segmentation is solidified.Concrete intensification solidification process is: 120 ℃/3h; 140 ℃/2h; 160 ℃/2h; 180 ℃/2h; 200 ℃/1h; Finally obtain yellow sheet Polybenzoxazine PBZB-660-50%.
Embodiment 18 dimethyldiethoxysilanes (content 70%) and BZB-660 multipolymer (PBZB-660-PDMS-70%)
0.9g BZB-660 is dissolved in the THF of 30ml, adds successively 2.1g dimethyldiethoxysilane, 0.54g water, 0.16g hydrochloric acid (concentration 37%), under room temperature, stir 24h, obtain yellow transparent solution.Solution is poured in culture dish, under room temperature, placed 24h, make the most of volatilization of solvent.Then in Constant Temp. Oven, segmentation is solidified.Concrete intensification solidification process is: 120 ℃/3h; 140 ℃/2h; 160 ℃/2h; 80 ℃/3h; Finally obtain yellow sheet Polybenzoxazine PBZB-660-70%.
The performance study of siliceous Polybenzoxazine of the present invention is as follows:
The thermal characteristics of Polybenzoxazine
The thermal characteristics of Polybenzoxazine is mainly analyzed (product that embodiment 13,14,15 is obtained is measured and analyzed) by differential scan calorimeter DSC, dynamic thermal analysis instrument DMA and thermogravimetric analyzer TGA, test acquired results is in Table 1, and Fig. 9-Figure 13.
The thermal characteristics of table 1 Polybenzoxazine
In table, data can be found out, these several Polybenzoxazines all have higher second-order transition temperature, especially PBZB-660, Tg is up to 353 ℃, with containing organosilyl Polybenzoxazine, do not compare and be significantly improved, silicon is introduced in explanation in Polybenzoxazine, can effectively improve the thermal characteristics of resulting polymers.The carbon yield of these several novel polyphenyl Bing oxazines is very high, and wherein the carbon yield of PBZS-660 is up to 70%, and this is also due to the cause of having introduced element silicon.Although we do not characterize the thermal characteristics of all the other nine kinds of siliceous Polybenzoxazines,, because element silicon can improve the thermal characteristics of polymkeric substance, affiliated technical field personnel, can infer all the other in nine siliceous Polybenzoxazine there is higher thermal characteristics.
The surface property of Polybenzoxazine
The surface of the Polybenzoxazine after organic-silicon-modified can characterize (product that embodiment 13,14,15 is obtained is tested) by the surface contact angle of itself and water, and test acquired results is in Table 2, and Figure 14-Figure 16.
The surface contact angle of table 2 Polybenzoxazine and water
As seen from table, the surface contact angle of these several Polybenzoxazines and water is all very large, illustrates that the introducing of silicon has reduced its surface property effectively, makes it have good hydrophobic nature, PBZS-660 especially, with the surface contact angle of water up to 127 °.
In addition, although we do not characterize the surface property of all the other nine kinds of Polybenzoxazines, but, because organosilicon has lower surface energy, affiliated technical field technician can go out all the other nine kinds of siliceous Polybenzoxazines according to above-mentioned experimental result legitimate inference and have lower surface property.
Claims (1)
1. the preparation method of siliceous Polybenzoxazine, is characterized in that:
The preparation method of poly-two (3-triethoxyl silane-n-propyl-3,4-dihydro-2H-1,3-benzoxazinyl) isopropyl alkane is: 6.92g BZB-550 is dissolved in the THF of 40ml, add successively 1.08g water, 0.11g concentration is 37% hydrochloric acid, under room temperature, stirs 24h, obtains yellow transparent solution; Solution is poured in culture dish, under room temperature, placed 24h, make the most of volatilization of solvent; Then in Constant Temp. Oven, segmentation is solidified, and concrete intensification solidification process is: 120 ℃/3h; 140 ℃/2h; 160 ℃/2h; 180 ℃/3h; Finally obtain yellow lump shape Polybenzoxazine PBZB-550; Described reaction raw materials BZB-550 refers to two (3-triethoxyl silane-n-propyl-3,4-dihydro-2H-1,3-benzoxazinyl) isopropyl alkane;
Poly-3-(methyl-dimethoxy silane)-n-propyl-3,4-dihydro-2H-1, the preparation method of 3-benzoxazine is: by 5.62g3-(methyl-dimethoxy silane)-n-propyl-3,4-dihydro-2H-1,3-benzoxazine is dissolved in the acetone of 40ml, adds successively 0.72g water, the hydrochloric acid that 0.11g concentration is 37%, under room temperature, stir 24h, obtain yellow transparent solution; Solution is poured in culture dish, under room temperature, placed 24h, make the most of volatilization of solvent; Then in Constant Temp. Oven, segmentation is solidified, and concrete intensification solidification process is: 120 ℃/3h; 140 ℃/2h; 160 ℃/2h; 180 ℃/3h; Finally obtain yellow sheet Polybenzoxazine PBZS-660;
Poly-two (3-methyl-dimethoxy silane-n-propyl-3,4-dihydro-2H-1,3-benzoxazinyl) preparation method of isopropyl alkane is: by two (3-methyl-dimethoxy silane-n-propyl-3 of 6.03g, 4-dihydro-2H-1,3-benzoxazinyl) isopropyl alkane is dissolved in the methyl alcohol of 40ml, adds successively 0.72g water, 0.11g tosic acid, under room temperature, stir 24h, obtain yellow transparent solution; Solution is poured in culture dish, under room temperature, placed 24h, make the most of volatilization of solvent; Then in Constant Temp. Oven, segmentation is solidified, and concrete intensification solidification process is: 120 ℃/3h; 140 ℃/2h; 160 ℃/2h; 180 ℃/2h; 200 ℃/1h; Finally obtain yellow sheet Polybenzoxazine PBZB-660.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110001172.7A CN102134254B (en) | 2011-01-05 | 2011-01-05 | Silicon-containing benzoxazine resin as well as preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110001172.7A CN102134254B (en) | 2011-01-05 | 2011-01-05 | Silicon-containing benzoxazine resin as well as preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102134254A CN102134254A (en) | 2011-07-27 |
| CN102134254B true CN102134254B (en) | 2014-04-02 |
Family
ID=44294200
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110001172.7A Active CN102134254B (en) | 2011-01-05 | 2011-01-05 | Silicon-containing benzoxazine resin as well as preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102134254B (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9068050B2 (en) * | 2011-08-31 | 2015-06-30 | Chung-Shan Institute of Science and Technology, Armaments, Bureau, Ministry of National Defense | Bridged bis(alkoxysilane) or silsesquioxane compound having benzoxazine-containing group |
| 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 |
| CN102757644B (en) * | 2012-07-26 | 2014-04-30 | 合肥工业大学 | Fluorenyl siloxane type polybenzoxazine resin composite material and preparation method thereof |
| KR102066167B1 (en) * | 2013-08-07 | 2020-01-14 | 코오롱인더스트리 주식회사 | Benzoxazine Compound and Preparing Method Thereof |
| CN103433186B (en) * | 2013-08-09 | 2015-01-07 | 如皋市日鑫电子有限公司 | Low-temperature curing process for protective glue of diode table face |
| CN103694192B (en) * | 2013-12-26 | 2015-06-17 | 上海交通大学 | Benzoxazine compound with photo-initiation performance, preparation method and application of benzoxazine compound |
| CN105037800A (en) * | 2015-07-13 | 2015-11-11 | 中科院广州化学有限公司南雄材料生产基地 | Silicon-containing polybenzoxazine surface modified ammonium polyphosphate and preparation therefor and application thereof |
| CN108546272B (en) * | 2018-02-12 | 2020-08-04 | 山东大学 | Polybenzoxazine crosslinked by Si-O-Ph organic-inorganic hybrid bond, polybenzoxazine monomer and preparation method thereof |
| CN108744600B (en) * | 2018-07-03 | 2021-05-04 | 福建师范大学 | Preparation method of oil-water separation membrane |
| CN109054734B (en) * | 2018-07-20 | 2020-10-13 | 山东大学 | Adhesive prepared based on amino-containing siloxane and preparation and use methods thereof |
| CN109867895B (en) * | 2019-02-18 | 2021-03-12 | 西安文理学院 | Containing SiO2Benzoxazine/bismaleimide resin composite material and preparation method thereof |
| CN111848959A (en) * | 2019-04-29 | 2020-10-30 | 华东理工大学 | Benzoxazine modified organic silicon resin and preparation method and application thereof |
| CN110862793A (en) * | 2019-12-03 | 2020-03-06 | 山东大学 | Preparation and use method of benzoxazine adhesive for polyethylene |
| CN110804409A (en) * | 2019-12-03 | 2020-02-18 | 山东大学 | Benzoxazine adhesive for polyimide and preparation and use methods thereof |
| WO2021134604A1 (en) * | 2019-12-31 | 2021-07-08 | 广州市白云化工实业有限公司 | Organosilicon-modified phenolic resin composition, composite material, and preparation method thereof |
| CN111040377A (en) * | 2019-12-31 | 2020-04-21 | 广州市白云化工实业有限公司 | Organic silicon modified phenolic resin composition, composite material and preparation method thereof |
| CN113461949A (en) * | 2021-07-26 | 2021-10-01 | 福建师范大学 | Benzoxazine modified organic silicon compound with high substrate binding force and preparation method and application thereof |
| CN114774900B (en) * | 2022-04-13 | 2023-12-29 | 沈阳化工大学 | Method for increasing surface roughness of steel wire for rubber tube by adopting self-roughening process |
| CN117087208A (en) * | 2023-07-21 | 2023-11-21 | 江门建滔积层板有限公司 | Heat-resistant flexible copper-clad plate and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101220153A (en) * | 2007-12-11 | 2008-07-16 | 山东大学 | Production method for dihydric phenol type high fire-retardancy benzoxazine resin containing phosphor |
| CN101235131A (en) * | 2008-02-27 | 2008-08-06 | 山东大学 | Method for preparing benzoxazine intermediate containing propargyl ether and resin thereof |
| CN101585917A (en) * | 2009-06-19 | 2009-11-25 | 南京大学 | Polybenzoxazine precursor and preparing method thereof |
| CN101750896A (en) * | 2008-12-16 | 2010-06-23 | 华东理工大学 | Fluorine-containing silicon low-surface-energy material for nano-imprinting and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2796803A1 (en) * | 2010-05-20 | 2011-11-24 | Dow Corning Corporation | Polymer compositions containing oxazine-based alkoxysilanes |
-
2011
- 2011-01-05 CN CN201110001172.7A patent/CN102134254B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101220153A (en) * | 2007-12-11 | 2008-07-16 | 山东大学 | Production method for dihydric phenol type high fire-retardancy benzoxazine resin containing phosphor |
| CN101235131A (en) * | 2008-02-27 | 2008-08-06 | 山东大学 | Method for preparing benzoxazine intermediate containing propargyl ether and resin thereof |
| CN101750896A (en) * | 2008-12-16 | 2010-06-23 | 华东理工大学 | Fluorine-containing silicon low-surface-energy material for nano-imprinting and preparation method thereof |
| CN101585917A (en) * | 2009-06-19 | 2009-11-25 | 南京大学 | Polybenzoxazine precursor and preparing method thereof |
Non-Patent Citations (3)
| Title |
|---|
| Polybenzoxazine containing polysilsesquioxane: preparation and thermal properties;Yonghong Liu等,;《Journal of Applied Polymer Science》;20051118;第99卷(第3期);第927-936页, 尤其是第927页第2段 * |
| Silica surface modified with benzoxazine-functional silane;Suwabun Chirachanchai等,;《Composite Interfaces》;20011001;第8卷(第5期);第355-366页，尤其是第357页图1 * |
| Yonghong Liu等,.Polybenzoxazine containing polysilsesquioxane: preparation and thermal properties.《Journal of Applied Polymer Science》.2005,第99卷(第3期),第927-936页, 尤其是第927页第2段. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102134254A (en) | 2011-07-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102134254B (en) | Silicon-containing benzoxazine resin as well as preparation method and application thereof | |
| Demir et al. | Thermally curable main-chain benzoxazine prepolymers via polycondensation route | |
| Choi et al. | Synthesis and characterization of UV‐curable ladder‐like polysilsesquioxane | |
| JP6526417B2 (en) | Resin-linear organosiloxane block copolymer curable composition | |
| Wang et al. | Morphology and thermomechanical properties of main-chain polybenzoxazine-block-polydimethylsiloxane multiblock copolymers | |
| Meng et al. | Design and synthesis of non-crystallizable, low-t g polysiloxane elastomers with functional epoxy groups through anionic copolymerization and subsequent epoxidation | |
| Liu et al. | Polybenzoxazine containing polysilsesquioxane: Preparation and thermal properties | |
| Ardhyananta et al. | Preparation and properties of polybenzoxazinepoly (dimethylsiloxane-co-diphenylsiloxane) hybrids as high performance polymers | |
| Li et al. | Synthesis and characterization of a novel arylacetylene oligomer containing POSS units in main chains | |
| CN110540648A (en) | Organic siloxane containing benzocyclobutene group and preparation and application thereof | |
| Jiang et al. | Characterization of a modified silicon-containing arylacetylene resin with POSS functionality | |
| Fu et al. | Preparation and properties of hybrid materials originating from polybenzoxazines and silsesquioxanes | |
| Zhang et al. | Silane‐functional benzoxazine: synthesis, polymerization kinetics and thermal stability | |
| CN108546272A (en) | The crosslinked Polybenzoxazine of Si-O-Ph organic inorganic hybridization keys, Polybenzoxazine monomer and preparation method thereof | |
| Liu et al. | Melt fluidity and thermal property of thermosetting siloxane-containing polyimide resins and their organic/inorganic hybrid characteristics | |
| CN108997582A (en) | A kind of preparation method of the single-ended polysiloxane fluid containing active hydrogen | |
| Ling et al. | Synthesis of a comb-like silicone-epoxy co-polymer with high thermal stability and mechanical properties for ablative materials | |
| Tian et al. | Piers-Rubinsztajn reaction for BCB functionalized silphenylene/silbiphenylene siloxane oligomers to highly crosslinked low-k thermosets | |
| Zhu et al. | Synthesis, characterization, and properties of a novel aromatic ester-based polybenzoxazine | |
| Zhu et al. | Preparation of polysiloxane oligomers bearing benzoxazine side groups and tunable properties of their thermosets | |
| CN108299645B (en) | Preparation and use of directly thermally curable organosiloxanes | |
| CN115536847B (en) | Liquid vinyl functionalized cage-type oligomeric silsesquioxane modified by low molecular weight polysiloxane and preparation method thereof | |
| CN1314731C (en) | Polysiloxane benzoxazine of polysiloxane at aryne end capping and preparation method | |
| CN104411748A (en) | Crosslinkable siloxanes by acid-catalyzed polymerization of oxasilacyclenes | |
| Chruściel et al. | Thermal properties of polymethylvinylborosiloxanes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |