CN107400359B - Phthalonitrile, benzoxazine and tetra-amino phthalocyanine lead-based anti-radiation composite material and preparation method thereof - Google Patents
Phthalonitrile, benzoxazine and tetra-amino phthalocyanine lead-based anti-radiation composite material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a phthalonitrile, benzoxazine and tetra-amino phthalocyanine lead-based anti-radiation composite material and a preparation method thereof. The method comprises the steps of carrying out melt blending on phthalonitrile, benzoxazine and tetraamino metal phthalocyanine lead at 70-120 ℃, uniformly mixing, placing in a pre-preheated mold, carrying out vacuum defoaming at 100 ℃, and then carrying out segmented curing at 160-350 ℃ for 6-20 hours to obtain the phthalonitrile/benzoxazine/tetraamino metal phthalocyanine lead-based composite material, wherein the mass ratio of phthalonitrile to benzoxazine is 1: 0.1-1, and the mass ratio of the blend of phthalonitrile and benzoxazine to tetraamino metal phthalocyanine lead is 1: 0.03-0.3. The composite material has excellent gamma ray irradiation resistance, and the dynamic mechanical property, the thermal property and the structure of the polymer are not obviously changed before and after irradiation. The material can meet the requirements on material performance under extreme environments, and can also be used for manufacturing high-performance structural materials, electronic packaging materials, high-temperature-resistant adhesives, ablation-resistant materials and the like.
Description
Technical Field
The invention relates to a radiation protection material for resisting high-energy ray irradiation, and also relates to a preparation method of the radiation protection material for resisting high-energy ray irradiation, in particular to a phthalonitrile/benzoxazine/tetraaminophthalocyanine lead-based radiation-resistant composite material for resisting gamma ray irradiation and a preparation method thereof.
Background
At present, a large amount of high polymer materials and resin-based composite materials are used in the environments of nuclear power plants, aerospace vehicles, hospitals and the like, the high polymer materials and the composite materials are easily radiated by high-energy rays such as gamma rays, x rays and the like under the environments, and free radicals generated by radiation can cause high radiationThe molecular material is subjected to cross-linking and degradation, so that the mechanical property, the thermal property and the like of the high polymer material are changed, the service life of the high polymer material is shortened, and particularly, the failure of aircraft components and even aircraft accidents can be caused by the complex radiation environment of outer space. Although adding functional elements, e.g. PbO, WO3、BaSO4、CeO2、La2O3The inorganic functional powder can improve the gamma and X radiation resistance of the material (how to build flood, grand courage, forever, Fangdong rise. research progress of ray and neutron radiation shielding material. material guide, 2011, 25: 347-351; Zhangpencheng, Li, Xulijun. a neutron and gamma ray protection latex composite material. Chinese invention patent, 201210307365.X, 2012-08-27), but also reduces the mechanical property of the composite material, and the metal inorganic powder has high density and poor dispersibility in matrix resin, and the powder needs to be subjected to surface modification before use so as to improve the uniform distribution of the powder in the matrix resin. Under the continuous ray irradiation, the mechanical property and the thermal stability of the high polymer material can be greatly changed, and the durability is reduced. For example, polyolefin radiation-proof materials are easy to age under the action of ultraviolet or electromagnetic waves and have poor durability; epoxy resin has poor fatigue resistance and wet heat resistance, and the mechanical property after ray irradiation is greatly reduced; the polyurethane has good radiation resistance, but generates harmful gases such as hydrocyanic acid and the like after combustion. Therefore, the structural stability of the resin matrix itself becomes particularly important.
The phthalonitrile resin is a high-temperature resistant resin which is comparable to polyimide, and the structure of the polymer mainly comprises an isoindoline ring, a phthalocyanine ring and a triazine ring, so that the phthalonitrile resin has better structural stability, high temperature resistance, flame retardance and less smoke and toxic gas, and is the only organic polymer material which can meet the fireproof performance of American navy submarines at present. However, pure phthalonitrile resin is difficult to generate crosslinking reaction, the curing temperature is high, and compounds containing active hydrogen are needed to initiate the resin to be cured, such as organic amines, phenols, carboxylic acids and the like, and although the introduction of these small molecular compounds can initiate the phthalonitrile resin to be crosslinked, the volatilization of small molecules occurs at high curing temperature (generally higher than 300 ℃), which leads to the reduction of the mechanical properties of the material.
The benzoxazine resin is obtained by reacting phenols, primary amine compounds and formaldehyde, the monomer can realize crosslinking and curing under heating without adding a catalyst, and the polybenzoxazine resin has certain unique advantages, such as small volume change in the curing process; the water absorption rate is very low; no by-product is generated in the curing process; the flexibility of molecular design is high. After the benzoxazine resin is cured and ring-opened, a large amount of phenolic hydroxyl groups can be generated, and the crosslinking reaction of the phthalonitrile resin can be promoted at low temperature, so that the curing temperature of the phthalonitrile resin is reduced. But the benzoxazine resin has high curing temperature and the cured product has low crosslinking density and thermal property far lower than that of phthalonitrile resin.
Disclosure of Invention
The invention aims to provide a phthalonitrile and benzoxazine and tetra-amino lead phthalocyanine based radiation-resistant composite material with excellent radiation resistance, mechanical property and thermal property. The invention also aims to provide a preparation method of the phthalonitrile, benzoxazine and tetraaminophthalocyanine lead-based anti-radiation composite material.
The phthalonitrile, benzoxazine and tetraamino metal phthalocyanine lead-based anti-radiation composite material is prepared by melting and blending phthalonitrile, benzoxazine and tetraamino metal phthalocyanine lead at 70-120 ℃, uniformly mixing, placing in a preheated mold, defoaming in vacuum at 100 ℃, and then curing in sections at 160-350 ℃ for 6-20 hours to obtain the phthalonitrile/benzoxazine/tetraamino phthalocyanine lead-based composite material, wherein the mass ratio of phthalonitrile to benzoxazine is 1: 0.1-1, and the mass ratio of the blend of phthalonitrile and benzoxazine to tetraamino metal phthalocyanine lead is 1: 0.03-0.3.
The phthalonitrile is one of 4-aminophenoxy phthalonitrile, 3-aminophenoxy phthalonitrile, 2-methoxyphenoxy phthalonitrile, 2-methoxy-4-allylphenoxy phthalonitrile, bisphenol A phthalonitrile and bisphenol AF phthalonitrile.
The benzoxazine is one of phenol-anilino benzoxazine, phenol-furfuryl amino benzoxazine, bisphenol A-anilino benzoxazine, bisphenol AF benzoxazine or 4, 4' -diaminodiphenylmethane-phenol benzoxazine.
The preparation method of the phthalonitrile, benzoxazine and tetra-amino phthalocyanine lead-based anti-radiation composite material comprises the following steps:
carrying out melt blending on phthalonitrile, benzoxazine and tetraamino metal phthalocyanine lead at 70-120 ℃, wherein the mass ratio of phthalonitrile to benzoxazine is 1: 0.1-1, and the mass ratio of the blend of phthalonitrile and benzoxazine to tetraamino metal phthalocyanine lead is 1: 0.03-0.3;
uniformly mixing, placing in a pre-preheated mold, performing vacuum defoaming at 100 ℃, and then performing segmented curing at 160-350 ℃ for 6-20 hours to obtain the phthalonitrile, benzoxazine and tetraaminophthalocyanine lead-based composite material.
The segmented curing and heating process comprises the following steps: 180 ℃/2h +220 ℃/4h +260 ℃/4h +300 ℃/2 h.
The invention provides a phthalonitrile/benzoxazine/tetra-amino lead phthalocyanine based composite material with gamma ray irradiation resistance and a preparation method thereof, wherein phthalonitrile and benzoxazine are used as matrix resin, tetra-amino lead phthalocyanine is a curing accelerator and a ray absorbent of the phthalonitrile and benzoxazine resin, amino on the lead phthalocyanine can reduce the curing temperature of the phthalonitrile and benzoxazine resin, and lead can absorb gamma rays so as to endow the blended resin with excellent irradiation resistance, and the composite material prepared by the material has excellent mechanical property and thermal property.
The structural characterization of the phthalonitrile/benzoxazine/tetra-amino phthalocyanine lead-based composite material is tested by using infrared spectroscopy (Spotlight 100, PE company in America), a potassium bromide tabletting method is adopted, a sample is scanned for 4 times, and the resolution is 4cm-1The scanning range is 4000-500 cm-1(ii) a Thermal and dynamic mechanical properties were measured using a thermogravimetric analyzer (TGA, TA USA) and a dynamic thermomechanical analyzer (DMA, TA USA). Wherein, the TGA uses nitrogen atmosphere, and the heating rate is 20 ℃/min; DMA uses airAtmosphere, single cantilever mode, heating rate of 3 deg.C/min. The gamma ray irradiation experiment is to put the solidified phthalonitrile/benzoxazine/tetra-amino phthalocyanine lead-based composite material into60In the Co irradiation device, the irradiation dose rate is 5kGy/h, the irradiation dose is 100KGy, and the infrared spectrum, TGA and DMA of the sample are tested after the irradiation is finished.
By means of the excellent heat resistance, mechanical property and radiation resistance of the phthalonitrile and the benzoxazine and the special structure of the tetra-amino lead phthalocyanine, the curing temperature of the phthalonitrile and the benzoxazine resin is effectively reduced, the processing manufacturability is improved, and meanwhile, the prepared composite material has excellent heat resistance and radiation resistance and is suitable for being used in the environments of space, nuclear power stations and the like.
Drawings
FIGS. 1a to 1f are structural formulas of phthalonitrile, wherein FIG. 1a is 3-aminophenoxy phthalonitrile, FIG. 1b is 4-aminophenoxy phthalonitrile, FIG. 1c is 2-methoxyphenoxy phthalonitrile, FIG. 1d is 2-methoxy-4-allylphenoxy phthalonitrile, FIG. 1e is bisphenol A-based phthalonitrile, and FIG. 1f is bisphenol AF-based phthalonitrile.
Fig. 2 a-2 e are structural formulas of benzoxazines, wherein fig. 2a is phenol-anilino benzoxazine, fig. 2b is phenol-furfuryl amino benzoxazine, fig. 2c is bisphenol a-anilino benzoxazine, fig. 2d is bisphenol AF benzoxazine, and fig. 2e is 4, 4' -diaminodiphenylmethane-phenol benzoxazine.
FIG. 3 is the infrared spectrum before and after irradiation of phthalonitrile/benzoxazine/tetra-amino phthalocyanine lead-based composite material (A-before irradiation; B-after irradiation).
FIG. 4 shows the storage modulus curve before and after irradiation of phthalonitrile/benzoxazine/tetra-amino phthalocyanine lead-based composite material (A-before irradiation; B-after irradiation).
FIG. 5 shows the loss factor curves before and after irradiation of phthalonitrile/benzoxazine/tetra-amino phthalocyanine lead-based composite material (A-before irradiation; B-after irradiation).
FIG. 6 TGA curves before and after irradiation of phthalonitrile/benzoxazine/tetraaminophthalocyanine lead-based composite material (A-before irradiation; B-after irradiation).
Detailed Description
The present invention will be described in further detail with reference to examples. It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
Example 1
Putting 2-methoxy-4-allylphenoxy phthalonitrile (10g), phenol-anilino benzoxazine (1g) and tetraaminophthalocyanine lead (0.7g) into a beaker, slowly heating to 100 ℃ under stirring, continuing to stir for 20-30 min when the solid is completely melted, adding the mixture into a preheated (about 100 ℃) mould while the mixture is hot, carrying out vacuum defoamation for 3h at 100 ℃, then putting the mixture into a forced air drying oven for segmented curing, wherein the segmented curing and heating process comprises the following steps: 180 ℃/2h +220 ℃/4h +260 ℃/4h +300 ℃/2h, and finally the phthalonitrile/benzoxazine/tetraaminophthalocyanine lead-based composite material is obtained. Placing the composite sample in60And in the Co irradiation device, taking out a sample after 20 hours, and testing the composite material before and after irradiation. The infrared spectrum (figure 3) of the 2-methoxy-4-allylphenoxy phthalonitrile/phenol-anilino benzoxazine/tetra-amino phthalocyanine lead-based composite material before and after irradiation can be seen, and the characteristic peak of the sample is not obviously changed after the sample is irradiated for 20 hours by gamma rays; the DMA (FIGS. 4 and 5) test results showed that the storage modulus before and after irradiation (E', 50 ℃ C.) was 1036 and 1001MPa, respectively, and the glass transition temperature (Tan. delta. peak temperature, T, C)g) 394 and 390 ℃ respectively; the TGA (FIG. 6) test results show that the thermal decomposition temperature (abbreviated as T) corresponds to 5% weight loss5) The carbon residue rates at 465 and 462 ℃ and 800 ℃ (abbreviated as Y)c) 77.5 percent and 76.5 percent respectively, which shows that the composite material prepared by the invention has good thermal property and radiation resistance.
Example 2
Example 1 was repeated, except that 2-methoxy-4-allylphenoxyphthalonitrile was replaced by bisphenol A phthalonitrile and the amount of phenol-anilinobenzoxazine was changed from 1g to 2 g. Composite material before and after irradiationE' of the material is 2265 MPa and 2249MPa, TgAt 376 and 373 ℃ respectively, T5463 and 461 ℃ respectively, Yc66.7% and 66.5%, respectively.
Example 3
The process is the same as example 2 except that the dosage of the phenol-anilino benzoxazine is changed from 2g to 4g, the dosage of the tetraamino phthalocyanine lead is changed from 0.7g to 1.5g, the melt blending temperature is changed from 100 ℃ to 80 ℃, and the segmented curing temperature rise process is changed from 180 ℃/2h +220 ℃/4h +260 ℃/4h +300 ℃/2h to 170 ℃/2h +210 ℃/3h +250 ℃/3h +280 ℃/2 h. E' of the composite material before and after irradiation is 2527 and 2531MPa respectively, and TgAt 348 and 351 ℃ respectively, T5443 and 447 ℃ respectively, Yc70.2% and 70.5%, respectively.
Example 4
The same as example 1 except that 2-methoxy-4-allylphenoxy phthalonitrile was changed to 2-methoxyphenoxy phthalonitrile, the amount of tetraaminophthalocyanine lead was changed from 0.7g to 2g, and the temperature rise during the stepwise curing was changed from 180 ℃/2h +220 ℃/4h +260 ℃/4h +300 ℃/2h to 180 ℃/2h +230 ℃/3h +280 ℃/3h +320 ℃/2 h. E' of the composite material before and after irradiation is 2354 MPa, 2345MPa and TgAt 375 and 372 ℃ respectively, T5432 and 427 ℃ respectively, Yc68.7% and 68.1%, respectively.
Example 5
The method is the same as example 1 except that 2-methoxy-4-allylphenoxy phthalonitrile is changed into bisphenol AF phthalonitrile, phenol-anilino benzoxazine is changed into bisphenol A-anilino benzoxazine, and the segmented curing and temperature rising process is changed from 180 ℃/2h +220 ℃/4h +260 ℃/4h +300 ℃/2h into 180 ℃/3h +220 ℃/5h +260 ℃/5h +300 ℃/3 h. E' of the composite material before and after irradiation is 2558 MPa and 2648MPa respectively, and Tg291 and 288 ℃ respectively, T5470 and 472 ℃ respectively, Yc64.1% and 65.6%, respectively.
Example 6
Example 1 was repeated except that 2-methoxy-4-allylphenoxyphthalonitrile was changed to 4-aminophenoxyphthalonitrile and phenol-anilinobenzoxazine was changed to 4, 4' -diaminodiphenylmethane-phenolobenzoxazine. Before and after irradiationE' of the composite material is 2202 and 2318MPa respectively, and T isg315 and 309 ℃ respectively, T5438 and 450 ℃ respectively, Yc62.8% and 64.2%, respectively.
Example 7
Except that 2-methoxy-4-allylphenoxy phthalonitrile was changed to bisphenol AF phthalonitrile, phenol-anilino benzoxazine was changed to phenol-furfuryl amino benzoxazine, the amount was changed from 1g to 8g, the amount of tetraamino lead phthalocyanine was changed from 0.7g to 4g, and the melt blending temperature was changed from 100 ℃ to 80 ℃, the same as in example 1. E' of the composite material before and after irradiation is 2415 MPa and 2411MPa respectively, and Tg299 and 301 ℃ respectively, T5At 452 and 455 ℃ and Yc60.2% and 61.3%, respectively.
Comparative example 1
Slowly heating bisphenol A-based phthalonitrile (9g) and 4, 4' -diaminodiphenylmethane (1g) to 160 ℃ under stirring, continuously stirring for 20-30 min until the solid is completely melted, adding the mixture into a preheated (about 160 ℃) mould while the mixture is hot, carrying out vacuum defoamation for 3h at 150 ℃, and then placing the mixture into a forced air drying oven for segmented curing, wherein the segmented curing and temperature rising process comprises the following steps: 180 ℃/2h +200 ℃/3h +240 ℃/3h +280 ℃/3h +320 ℃/2h, and finally obtaining the bisphenol A-based poly phthalonitrile resin. E' of the poly-phthalonitrile resin before and after irradiation is 2241 and 2235MPa respectively, and TgAt 372 and 370 ℃ respectively, T5419 and 414 ℃ respectively, Yc72.3% and 71.5%, respectively.
Comparative example 2
Placing phenol-anilino benzoxazine in a mold, defoaming for 2h at 80 ℃, and then placing in a forced air drying oven for segmented curing, wherein the segmented curing and temperature rise process is as follows: 160 ℃/2h +180 ℃/2h +20 ℃/2h to obtain the phenol-anilino polybenzoxazine. E' of polybenzoxazine before and after irradiation is 3474 and 3465MPa respectively, and T g157 and 150 ℃ respectively, T5286 and 324 ℃ respectively, Yc36.7% and 34.5%, respectively.
In the invention, the dynamic mechanical property, the thermal property and the structure of the composite material are not obviously changed before and after irradiation, and the radiation-resistant composite material with high glass transition temperature and high thermal stability can be obtained by adjusting the structures and the using amounts of phthalonitrile, benzoxazine and tetra-amino lead phthalocyanine. Meanwhile, benzoxazine and tetraaminophthalocyanine lead can promote the phthalonitrile resin to generate cross-linking polymerization at low temperature, thereby reducing the curing temperature and curing time of the resin, the material can meet the requirements on the material performance under extreme environments, and can also be used for manufacturing high-performance structural materials, electronic packaging materials, high-temperature-resistant adhesives, ablation-resistant materials and the like.
Claims (6)
1. A phthalonitrile, benzoxazine and tetra-amino phthalocyanine lead-based radiation-resistant composite material is characterized in that: carrying out melt blending on phthalonitrile, benzoxazine and tetraamino metal lead phthalocyanine at 70-120 ℃, uniformly mixing, placing in a pre-preheated mold, carrying out vacuum defoaming at 100 ℃, and then carrying out segmented curing to obtain a phthalonitrile/benzoxazine/tetraamino metal lead phthalocyanine-based composite material, wherein the mass ratio of phthalonitrile to benzoxazine is 1: 0.1-1, and the mass ratio of the blend of phthalonitrile and benzoxazine to tetraamino metal lead phthalocyanine is 1: 0.03-0.3; the segmented curing and heating process comprises the following steps: 180 ℃/2h +220 ℃/4h +260 ℃/4h +300 ℃/2 h.
2. The phthalonitrile-benzoxazine and tetraaminophthalocyanine lead-based radiation resistant composite material according to claim 1, characterized in that: the phthalonitrile is one of 4-aminophenoxy phthalonitrile, 3-aminophenoxy phthalonitrile, 2-methoxyphenoxy phthalonitrile, 2-methoxy-4-allylphenoxy phthalonitrile, bisphenol A phthalonitrile and bisphenol AF phthalonitrile.
3. The phthalonitrile-benzoxazine and tetraaminophthalocyanine lead-based radiation-resistant composite material according to claim 1 or 2, characterized in that: the benzoxazine is one of phenol-anilino benzoxazine, phenol-furfuryl amino benzoxazine, bisphenol A-anilino benzoxazine, bisphenol AF benzoxazine or 4, 4' -diaminodiphenylmethane-phenol benzoxazine.
4. A method for preparing a phthalonitrile-benzoxazine and tetraaminophthalocyanine lead-based radiation-resistant composite material according to claim 1, characterized in that:
carrying out melt blending on phthalonitrile, benzoxazine and tetraamino metal phthalocyanine lead at 70-120 ℃, wherein the mass ratio of phthalonitrile to benzoxazine is 1: 0.1-1, and the mass ratio of the blend of phthalonitrile and benzoxazine to tetraamino metal phthalocyanine lead is 1: 0.03-0.3;
uniformly mixing, placing in a pre-preheated mold, performing vacuum defoaming at 100 ℃, and then performing segmented curing to obtain the phthalonitrile, benzoxazine and tetraaminophthalocyanine lead-based composite material; the segmented curing and heating process comprises the following steps: 180 ℃/2h +220 ℃/4h +260 ℃/4h +300 ℃/2 h.
5. The method for preparing the phthalonitrile-benzoxazine and tetraaminophthalocyanine lead-based radiation-resistant composite material according to claim 4, characterized in that: the phthalonitrile is one of 4-aminophenoxy phthalonitrile, 3-aminophenoxy phthalonitrile, 2-methoxyphenoxy phthalonitrile, 2-methoxy-4-allylphenoxy phthalonitrile, bisphenol A phthalonitrile and bisphenol AF phthalonitrile.
6. The method for preparing a phthalonitrile-benzoxazine and tetraaminophthalocyanine lead-based radiation-resistant composite material according to claim 4 or 5, characterized in that: the benzoxazine is one of phenol-anilino benzoxazine, phenol-furfuryl amino benzoxazine, bisphenol A-anilino benzoxazine, bisphenol AF benzoxazine or 4, 4' -diaminodiphenylmethane-phenol benzoxazine.
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| CN105255109A (en) * | 2015-10-16 | 2016-01-20 | 中科院广州化学有限公司南雄材料生产基地 | Phthalonitrile modified benzoxazine and epoxy resin composite material, preparation and application |
| WO2017105890A1 (en) * | 2015-12-15 | 2017-06-22 | 3M Innovative Properties Company | Benzoxazine and phthalonitrile resin blends |
| CN106967001A (en) * | 2017-04-07 | 2017-07-21 | 常州焱晶科技有限公司 | A kind of ternary benzoxazine phthalonitrile intermediate, preparation method and its polymer |
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| CN105255109A (en) * | 2015-10-16 | 2016-01-20 | 中科院广州化学有限公司南雄材料生产基地 | Phthalonitrile modified benzoxazine and epoxy resin composite material, preparation and application |
| WO2017105890A1 (en) * | 2015-12-15 | 2017-06-22 | 3M Innovative Properties Company | Benzoxazine and phthalonitrile resin blends |
| CN106967001A (en) * | 2017-04-07 | 2017-07-21 | 常州焱晶科技有限公司 | A kind of ternary benzoxazine phthalonitrile intermediate, preparation method and its polymer |
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| 芴基苯并恶嗪单体的合成及热性能研究;王军等;《湖南大学学报（自然科学版）》;20100630;第37卷(第6期);67-80 * |
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