CN103012484A - Phosphorous benzoxazine resin, preparation method and application - Google Patents
Phosphorous benzoxazine resin, preparation method and application Download PDFInfo
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- CN103012484A CN103012484A CN2012105658051A CN201210565805A CN103012484A CN 103012484 A CN103012484 A CN 103012484A CN 2012105658051 A CN2012105658051 A CN 2012105658051A CN 201210565805 A CN201210565805 A CN 201210565805A CN 103012484 A CN103012484 A CN 103012484A
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Abstract
The invention relates to phosphorous benzoxazine resin and a preparation method thereof. The method comprises the steps that aromatic diamine and salicylic aldehyde conduct condensation reaction, conduct addition reaction with DOPO (9,10-dihydro-9-ova-10-phosphaphenanthrene-10-oxide), and then react with methanal to form the phosphorous benzoxazine resin. The obtained phosphorous benzoxazine resin has good heat resistance, mechanical property, dielectric property and flame resistance, and can be applied to the fields of binders, coatings, packaging materials, electrical insulating materials, mold pressing materials, laminated boards, circuit printed boards, composites and the like. A synthetic method is simple and easy to control, the reaction condition and the aftertreatment process are simple, the yield is higher, raw material sources are abundant, and the phosphorous benzoxazine resin is suitable for large-scale production.
Description
Technical field
The present invention relates to a kind of phosphorous benzoxazine resin and preparation method thereof, belong to the flame retardant thermoset resins field.This benzoxazine resin can autohemagglutination or is obtained cured resin with the common polymerization of other thermosetting resins, can improve the flame retardant properties of cured resin.
Background technology
The benzoxazine resin is the hexa-member heterocycle system that is made of Sauerstoffatom and nitrogen-atoms.This compound can ring-opening polymerization form the polymkeric substance of similar resol structure under heating or catalyst action, be called polyphenyl and oxazines.Polyphenyl and oxazines possess outside the advantage of virgin resol also, and curing reaction need not catalyzer, emit without low molecule, and the preparation porosity is low, shrink little or without contraction.Simultaneously polyphenyl and oxazines have thermotolerance and the flame retardant resistance suitable with resol, and might carry out molecular designing and have than the better physical and mechanical properties of Resins, epoxy by the mode of Resins, epoxy.Benzoxazine not only can carry out the open loop auto-polymerization by heating and form macromolecular compound, also can add thermal copolymerization with epoxy, phenolic aldehyde and form macromolecular compound.This family macromolecule compound can be as the glue in the friction materials on the automobile brake sheet, metal-foam materials, the copper-clad plate, fiber reinforced material etc.
The synthetic general of benzoxazine resin adopts common phenols, aminated compounds and formaldehyde reaction to make at present, and similarly patent has CN1451679A, CN111572A, CN137977A, CN149637A8 etc.; Also can adopt plant oil modified phenol-formaldehyde resin to prepare the benzoxazine resin, such as CN1259530A; Can also adopt N-allylic cpd or aryne compound to prepare the benzoxazine resin, such as CN1472205A.The benzoxazine polymer matrix composites of above-mentioned synthetic dixie cup have good preparation and forming process, and good physical and mechanical properties is suitable as high-temperature-resistant structure material and insulating material.
Fire-retardant is the important development direction of benzoxazine resin high performance, phosphorous benzoxazine resin is a kind of novel performance resins of having introduced phosphoric in the molecule of oxazines resin, it has good physical and mechanical properties, thermotolerance, the good advantages such as processing characteristics except having general benzoxazine resin, also possesses good flame retardant properties.Phosphorous benzoxazine resin can aggregate into polyphenyl and the oxazines resin of good flame retardant effect; Can also carry out the flame retardant properties that polymerization improves its system with Resins, epoxy, resol; Phosphorous benzoxazine resin is added into the flame retardant properties that can improve other resins in other resins, provides a kind of approach for other fluoropolymer resins improve flame retardant properties.
Summary of the invention
The purpose of this invention is to provide a kind of phosphorous benzoxazine resin, preparation method and application, it synthesizes phosphorous benzoxazine resin by phosphoric is incorporated in benzoxazine structure, this resin has kept outside all premium propertiess of original oxazines resin, also has good flame retardant properties, can autohemagglutination or jointly solidify to form cured resin with other thermosetting resins, improve flame retardant properties and the comprehensive mechanical property of material.
The preparation method of phosphorous oxazines resin provided by the invention may further comprise the steps:
Aromatic diamines and salicylaldhyde (o-hydroxybenzaldehyde) are joined in the reactor with temperature regulating device and whipping appts according to the ratio of mol ratio 1:2, and add solvent, stir and 0 ℃ of-80 ℃ of temperature condition under react 2-10 h; Then with the DOPO(9 of certain molar weight, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound) join in the described reactor, the mol ratio of this DOPO and described aromatic diamines is 2:1, reacts 1-24 h under stirring and 0 ℃ of-80 ℃ of temperature condition;
Further, the formaldehyde of certain molar weight is added in the described reactor, stir and 30-80 ℃ temperature of reaction under reaction 1-24 h, after reaction was finished, cooling was filtered, and dries, and obtains phosphorous benzoxazine resin; Wherein, the mol ratio of this formaldehyde and described aromatic diamines is 2-8: 1;
Said process is expressed as with reaction equation:
Wherein, R is 4,4 '-penylene; Or R is 4,4 '-biphenylene.
Described aromatic diamines is Isosorbide-5-Nitrae-phenylenediamine or 4,4 '-benzidine.
Described solvent is DMF(N, N '-dimethyl formamide), toluene, dimethylbenzene, ethanol, ethylene glycol, DMSO(dimethyl sulfoxide (DMSO)), one or more combinations in dioxane, tetrahydrofuran (THF), methylene dichloride, orthodichlorobenzene and the water.
The adding quality of described solvent can be described aromatic diamines and salicylaldhyde total mass 2-20 times.
The phosphorous benzoxazine resin that the inventive method obtains comprises: with 4,4 '-penylene base is as the nitrogen-atoms covalent bonding of replacement with two benzoxazine derivatives, wherein covalent bonding 10-oxygen-10-hydrogen-9 oxa--10 λ on 4 methylene radical of benzoxazine
5-phospho hetero phenanthrene-10 base (being called for short the DOPO yl); Perhaps with 4,4 '-biphenylene base is as the nitrogen-atoms covalent bonding that replaces with two benzoxazine derivatives, the wherein formed molecule of covalent bonding DOPO base on 4 methylene radical of benzoxazine;
Its molecular structural formula is as follows:
Wherein, R is 4,4 '-penylene, the phosphorous benzoxazine resin of product called after (
1);
Or R is 4,4 '-biphenylene, the phosphorous benzoxazine resin of product called after (
2).
One of purposes of the above-mentioned phosphorous benzoxazine resin that the inventive method obtains, benzoxazine resin and common curing of Resins, epoxy are obtained cured article, when the phosphorus content of cured article is 1.0 wt%, flame retardant rating reaches UL 94 V-0 levels, limiting oxygen index(LOI) (LOI) reaches 39.8-40.4, the heat decomposition temperature of cured article 5% reaches 330-340 ℃, and under nitrogen test atmosphere, 800 ℃ carbon residue rate is 21.4%-22.7%.
The inventive method is carried out condensation reaction by aromatic diamine and salicylaldhyde, then carries out addition reaction with DOPO, gets phosphorous benzoxazine resin with formaldehyde reaction again.It is incorporated into the DOPO structure in the benzoxazine molecular structure, the synthetic benzoxazine resin that contains ignition-proof element phosphorus, and synthetic method is simple, and raw material sources are abundant, are easy to control, good reproducibility, the post-reaction treatment process is simple, and productive rate is high, is fit to amplify produce.
Its phosphorous benzoxazine resin not only has the premium properties of oxazines resin but also have good flame retardant properties, can autohemagglutination or obtain cured resin with common curing of other thermosetting resins, improve flame retardant properties and the comprehensive mechanical property of material; Can be applied to binding agent, coating, packaged material, electrically insulating material, moulding material, veneer sheet, circuit printing plate, prepare composite.
Specific implementation method
The invention will be described further below in conjunction with specific embodiment, but following embodiment does not limit protection scope of the present invention.
Embodiment 1
Add Isosorbide-5-Nitrae-diamino-benzene 10.8 g, salicylaldhyde 24.4 g, ethanol 352 g in the there-necked flask that agitator and reflux condensing tube are housed, stir, the control temperature of reaction is reacted 10 h at 0 ℃; Then DOPO 43.2 g are joined in this there-necked flask and stir, the control temperature of reaction is reacted 1 h at 80 ℃; At last 26.27 g formalins (containing formaldehyde 9.72g) are joined in this there-necked flask, the control temperature of reaction is cooled off after reacting 24 h at 30 ℃, reaction product is filtered, washing, 60 ℃ of oven dry 8 h in baking oven, obtain phosphorous benzoxazine resin (
1).
The phosphorous benzoxazine resin of gained (
1) infrared, nuclear-magnetism, mass spectral:mass spectrographic test result be as follows:
Infrared: N-C-O stretching vibration peak 962 cm
-1, Ph-O-C symmetrical stretching vibration peak 1037 cm
-1, asymmetric stretching vibration peak 1236 cm of Ph-O-C
-1, C-N stretching vibration peak 1364 cm
-1, P-Ph characteristic peak 1594 cm
-1, P=O characteristic peak 1205 cm
-1
Mass spectrum: m/z=795(M+Na
+).
Nuclear-magnetism:
1H?HMR?(ppm,?DMSO-d
6),?δ=4.90-5.50?(6H),?6.38-6.42?(4H),?6.77-6.84?(3H),?6.94-7.00?(2H),?7.12-7.24?(4H),?7.31-7.45?(4H),?7.47-7.60?(3H),?7.80-7.95?(4H),?8.15-8.34?(4H)；
13C?NMR?(ppm,?DMSO-d
6),?δ=154.55,?149.30,?143.97,?136.25,?134.48,?131.88,?131.56,?131.29,?129.90,?128.83-128.93,?126.15,?125.22,?124.38,?123.09?(C
15),?121.94,?121.63,?121.73,?119.96-120.51,?117.31,?171.13,?115.43,?115.60,?77.18,?57.83,?58.86；
31P?NMR?(ppm,?DMSO-d
6),?δ=31.3,?34.5。
Phosphorous benzoxazine resin and the Resins, epoxy of embodiment 1 preparation are solidified jointly, and when the phosphorus content of cured article was 1.0 wt%, flame retardant rating reached UL 94 V-0 levels, and LOI reaches 40.4, and the heat decomposition temperature of cured article 5 wt% reaches 333 ℃; Under nitrogen test atmosphere, 800 ℃ carbon yield is 21.4%.
Embodiment 2
Add 4 in the there-necked flask that agitator and reflux condensing tube are housed, 4 '-benzidine 18.4g, salicylaldhyde 24.4g, ethanol 856g stir, and the control temperature of reaction is at 80 ℃, react 2 h after; Then DOPO 43.2 g are joined in this there-necked flask, 0 ℃ of stirring and control temperature of reaction are reacted 24 h; Then 26.27 g formalins (containing formaldehyde 9.72g) are joined in this there-necked flask, stir and the control temperature of reaction is 80 ℃, cool off after reacting 1 h, reaction product is filtered, washing, 60 ℃ of oven dry 8 h in baking oven, obtain phosphorous benzoxazine resin (
2).
The phosphorous benzoxazine resin of gained (
2) infrared, nuclear-magnetism, mass spectral:mass spectrographic test result be as follows:
Infrared: N-C-O stretching vibration peak 965 cm
-1, Ph-O-C symmetrical stretching vibration peak 1035 cm
-1, asymmetric stretching vibration peak 1238 cm of Ph-O-C
-1, C-N stretching vibration peak 1368 cm
-1, P-Ph characteristic peak 1599 cm
-1, P=O characteristic peak 1204 cm
-1
Mass spectrum: m/z=871(M+Na
+).
Nuclear-magnetism:
1H?HMR?(ppm,?DMSO-d
6),?δ=5.21-5.61?(6H),?6.67-6.78?(4H),?6.83-6.88?(3H),?6.98-7.03?(2H),?7.08?(1H),?7.18-7.40?(10H),?7.48-7.62?(4H),?7.81-8.03?(4H),?8.22-8.34?(4H)；
13C?NMR?(ppm,?DMSO-d
6),?δ=58.02,?59.12,?76.62,?76.95,?115.74,?115.96,?117.34,?117.49,?119.40,?119.50,?120.29,?120.35,?120.77,?121.35,?121.69,?121.90,?122.03,?123.75,?124.56,?124.72,?125.45,?126.35,?127.06,?127.18,?129.02-129.37,?130.09,?131.69,?131.49,?132.58,?132.08,?134.72,?133.83,?136.08,?136.45,?147.46,?147.64,?149.51,?149.60,?154.90,?154.78；
31P?NMR?(ppm,?DMSO-d
6),?δ=26.48,?29.98。
Phosphorous benzoxazine resin and the Resins, epoxy of embodiment 2 preparations are solidified jointly, and when the phosphorus content of cured article was 1.0 wt%, flame retardant rating reached UL 94 V-0 levels, and LOI reaches 39.8, and the heat decomposition temperature of cured article 5 wt% reaches 335 ℃; Under nitrogen test atmosphere, 800 ℃ carbon yield is 22.7%.
Above for each embodiment and describe purpose in detail and be to illustrate the present invention, can not be used for limiting the present invention, the various improvement of generally doing according to listed claim, be equal to replacement scheme, all should be included in the claim of the present invention.
Claims (7)
1.
OnePlant phosphorous benzoxazine resin, have the following formula molecular structure:
Wherein, R is 4,4 '-penylene; Or R is 4,4 '-biphenylene.
2. the preparation method of a phosphorous benzoxazine resin is characterized in that may further comprise the steps:
Aromatic diamines and salicylaldhyde are joined in the reactor with temperature regulating device and whipping appts according to the ratio of mol ratio 1:2, and add solvent, stir and 0 ℃ of-80 ℃ of temperature condition under react 2-10 h; Then with the DOPO(9 of certain molar weight, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound) join in the described reactor, the mol ratio of this DOPO and described aromatic diamines is 2:1, reacts 1-24 h under stirring and 0 ℃ of-80 ℃ of temperature condition;
Further, the formaldehyde of certain molar weight is added in the described reactor, stir and 30-80 ℃ temperature of reaction under reaction 1-24 h, after reaction was finished, cooling was filtered, and dries, and obtains phosphorous benzoxazine resin; Wherein, the mol ratio of this formaldehyde and described aromatic diamines is 2-8: 1;
Said process is expressed as with reaction equation:
Wherein, R is 4,4 '-penylene; Or R is 4,4 '-biphenylene.
3. method as claimed in claim 2, it is characterized in that: described aromatic diamines is Isosorbide-5-Nitrae-phenylenediamine or 4,4 '-benzidine.
4. method as claimed in claim 2, it is characterized in that: described solvent is one or more combinations in DMF, toluene, dimethylbenzene, ethanol, ethylene glycol, DMSO, dioxane, tetrahydrofuran (THF), methylene dichloride, orthodichlorobenzene and the water.
5. method as claimed in claim 2 is characterized in that: the adding quality of described solvent be described aromatic diamines and described salicylaldhyde total mass 2-20 doubly.
6. method as claimed in claim 2 is characterized in that: the formaldehyde of described certain molar weight is to join in the described reactor take the formalin of concentration as 37%.
7. the purposes of the described phosphorous benzoxazine resin of claim 1, this benzoxazine resin is added in the Resins, epoxy and jointly solidify to form epoxy resin cured product realization ethoxyline resin antiflaming with Resins, epoxy, when the phosphorus content of this epoxy resin cured product is 1.0 wt%, flame retardant rating reaches UL 94 V-0 levels, limiting oxygen index(LOI) reaches 39.8-40.4, and the heat decomposition temperature of cured article 5% reaches 330-340 ℃; Under nitrogen test atmosphere, 800 ℃ carbon residue rate is 21.4%-22.7%.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103755741A (en) * | 2014-01-17 | 2014-04-30 | 合肥工业大学 | DOPO (9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide) contained bisphenol-A-mono-benzoxazine and preparation method thereof |
| CN104774343A (en) * | 2015-03-10 | 2015-07-15 | 三峡大学 | Phenyl phosphate flame retardant containing DOPO, and preparation method and application thereof |
| CN108586803A (en) * | 2018-04-04 | 2018-09-28 | 三峡大学 | A kind of spiro-phosphate fire retardant preparation method and applications containing DOPO and benzoxazine |
| CN109485916A (en) * | 2018-11-20 | 2019-03-19 | 武汉工程大学 | A kind of synthesis and application of Aminopyrazine based flame retardant |
| CN110105567A (en) * | 2019-06-12 | 2019-08-09 | 黄淮学院 | Poly-o-phenylenediamine derivative and its application |
| CN114479362A (en) * | 2022-02-09 | 2022-05-13 | 建滔电子材料（江阴）有限公司 | Preparation method of FR-4 copper-clad plate with high CAF (copper-clad plate) reliability for automobile |
Citations (1)
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| CN102391545A (en) * | 2011-08-05 | 2012-03-28 | 清华大学深圳研究生院 | Nitrogen and phosphorus containing flame retardant agent and preparation method thereof as well as application thereof |
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2012
- 2012-12-24 CN CN2012105658051A patent/CN103012484A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391545A (en) * | 2011-08-05 | 2012-03-28 | 清华大学深圳研究生院 | Nitrogen and phosphorus containing flame retardant agent and preparation method thereof as well as application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 《Journal of polymer science. Part A. Polymer chemistry》 20100902 CHING HSUAN LIN 等 "Facile,One-Pot Synthesis of Aromatic Diamine -Based Phosphinated Benzoxazines and Flame-Retardant Thermosets" 4555-4566 1-7 第48卷, 第20期 * |
| CHING HSUAN LIN 等: ""Facile,One-Pot Synthesis of Aromatic Diamine –Based Phosphinated Benzoxazines and Flame-Retardant Thermosets"", 《JOURNAL OF POLYMER SCIENCE. PART A. POLYMER CHEMISTRY》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103755741A (en) * | 2014-01-17 | 2014-04-30 | 合肥工业大学 | DOPO (9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide) contained bisphenol-A-mono-benzoxazine and preparation method thereof |
| CN103755741B (en) * | 2014-01-17 | 2016-06-01 | 合肥工业大学 | A kind of dihydroxyphenyl propane-mono-benzimidazole dihydrochloride containing DOPO and its preparation method |
| CN104774343A (en) * | 2015-03-10 | 2015-07-15 | 三峡大学 | Phenyl phosphate flame retardant containing DOPO, and preparation method and application thereof |
| CN104774343B (en) * | 2015-03-10 | 2017-08-01 | 三峡大学 | A kind of phenyl phosphate fire retardant containing DOPO, preparation method and applications |
| CN108586803A (en) * | 2018-04-04 | 2018-09-28 | 三峡大学 | A kind of spiro-phosphate fire retardant preparation method and applications containing DOPO and benzoxazine |
| CN109485916A (en) * | 2018-11-20 | 2019-03-19 | 武汉工程大学 | A kind of synthesis and application of Aminopyrazine based flame retardant |
| CN110105567A (en) * | 2019-06-12 | 2019-08-09 | 黄淮学院 | Poly-o-phenylenediamine derivative and its application |
| CN110105567B (en) * | 2019-06-12 | 2021-09-03 | 黄淮学院 | Poly-o-phenylenediamine derivative and application thereof |
| CN114479362A (en) * | 2022-02-09 | 2022-05-13 | 建滔电子材料（江阴）有限公司 | Preparation method of FR-4 copper-clad plate with high CAF (copper-clad plate) reliability for automobile |
| CN114479362B (en) * | 2022-02-09 | 2023-09-15 | 建滔电子材料（江阴）有限公司 | Preparation method of FR-4 copper-clad plate with high CAF reliability for automobile |
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Application publication date: 20130403 |