CN102585239A - Novel high temperature resistant phenylboronic acid-siloxane-imino linear polymer and preparation method thereof - Google Patents
Novel high temperature resistant phenylboronic acid-siloxane-imino linear polymer and preparation method thereof Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- GTCLFEMMPGBNOI-UHFFFAOYSA-N 2-phenylethynamine Chemical group NC#CC1=CC=CC=C1 GTCLFEMMPGBNOI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910003867 O—B—O Inorganic materials 0.000 claims abstract description 12
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- 239000012467 final product Substances 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- ALQPJHSFIXARGX-UHFFFAOYSA-N 2-ethynylaniline Chemical group NC1=CC=CC=C1C#C ALQPJHSFIXARGX-UHFFFAOYSA-N 0.000 claims 2
- NNKQLUVBPJEUOR-UHFFFAOYSA-N 3-ethynylaniline Chemical group NC1=CC=CC(C#C)=C1 NNKQLUVBPJEUOR-UHFFFAOYSA-N 0.000 claims 2
- JXYITCJMBRETQX-UHFFFAOYSA-N 4-ethynylaniline Chemical group NC1=CC=C(C#C)C=C1 JXYITCJMBRETQX-UHFFFAOYSA-N 0.000 claims 2
- 230000035484 reaction time Effects 0.000 claims 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 abstract description 11
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052796 boron Inorganic materials 0.000 abstract description 10
- 238000007254 oxidation reaction Methods 0.000 abstract description 10
- 239000002861 polymer material Substances 0.000 abstract description 8
- 239000010703 silicon Substances 0.000 abstract description 8
- 229910052710 silicon Inorganic materials 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 7
- 125000001841 imino group Chemical group [H]N=* 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 5
- 230000007123 defense Effects 0.000 abstract description 3
- 230000007062 hydrolysis Effects 0.000 abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001345 alkine derivatives Chemical group 0.000 abstract 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical group [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000007039 two-step reaction Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 8
- 239000002131 composite material Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000012700 ceramic precursor Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 229910010271 silicon carbide Inorganic materials 0.000 description 4
- 238000002679 ablation Methods 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000001979 organolithium group Chemical group 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 229920005573 silicon-containing polymer Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
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- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CBYDUPRWILCUIC-UHFFFAOYSA-N 1,2-diethynylbenzene Chemical compound C#CC1=CC=CC=C1C#C CBYDUPRWILCUIC-UHFFFAOYSA-N 0.000 description 1
- ROGBPNDEFHPGSY-UHFFFAOYSA-N 2-phenylethynylsilicon Chemical class [Si]C#CC1=CC=CC=C1 ROGBPNDEFHPGSY-UHFFFAOYSA-N 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- CFOAUMXQOCBWNJ-UHFFFAOYSA-N [B].[Si] Chemical compound [B].[Si] CFOAUMXQOCBWNJ-UHFFFAOYSA-N 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000002468 ceramisation Methods 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- SDKRUFVRUPVMFT-UHFFFAOYSA-N dimethoxy-phenylmethoxy-propylsilane Chemical compound C(CC)[Si](OCC1=CC=CC=C1)(OC)OC SDKRUFVRUPVMFT-UHFFFAOYSA-N 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 229920003257 polycarbosilane Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- -1 polysiloxane Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
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- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Silicon Polymers (AREA)
Abstract
Description
技术领域 technical field
本发明属于一类新型耐高温苯硼酸-硅氧烷-亚氨基线型聚合物及其制备方法,特别涉及主链含有硅原子、硼原子及氨基苯乙炔的一类有机-无机杂化聚合物材料。The invention belongs to a class of novel high-temperature-resistant phenylboronic acid-siloxane-imino linear polymers and a preparation method thereof, in particular to a class of organic-inorganic hybrid polymers whose main chain contains silicon atoms, boron atoms and aminophenylacetylene Material.
背景技术 Background technique
随着航空航天领域的快速发展,对耐高温聚合物材料的性能提出了更高的要求:更轻质、更高强和耐更高的温度。含硅聚合物(如聚硅烷、聚碳硅烷、聚氮硅烷及聚碳硅氮烷等)作为一类热固性聚合物材料,由于其独特的物理化学性能和突出的耐热性能,已得到广泛的研究与应用。其中,主链中含-Si-C≡C-活性基团的有机硅聚合物,在固化过程中形成三维交联网络结构,使得聚合物材料具有很高的热稳定性、耐溶剂等性能,在高性能复合材料、光刻材料、半导体材料、光学材料和陶瓷前驱体等领域有广阔的应用前景。近年来,在聚硅氧烷聚合物分子主链结构中引入一些其他类型的元素,如B、Al、Ti、Sn等,能够使所得到的聚合物材料具备许多特殊的性能。其中B元素的引入可明显地改善有机硅材料的耐热氧化性能,近年来已成为耐高温聚合物材料的一个研究热点。With the rapid development of the aerospace field, higher requirements are put forward for the performance of high temperature resistant polymer materials: lighter weight, higher strength and higher temperature resistance. As a class of thermosetting polymer materials, silicon-containing polymers (such as polysilane, polycarbosilane, polynitrosilane, and polycarbosilazane, etc.) have been widely used due to their unique physical and chemical properties and outstanding heat resistance. Research and Application. Among them, the silicone polymer containing -Si-C≡C-active group in the main chain forms a three-dimensional cross-linked network structure during the curing process, which makes the polymer material have high thermal stability and solvent resistance. It has broad application prospects in the fields of high-performance composite materials, lithography materials, semiconductor materials, optical materials and ceramic precursors. In recent years, some other types of elements, such as B, Al, Ti, Sn, etc., have been introduced into the main chain structure of polysiloxane polymer molecules, which can make the obtained polymer materials have many special properties. Among them, the introduction of B element can obviously improve the thermal oxidation resistance of organosilicon materials, and has become a research hotspot of high temperature resistant polymer materials in recent years.
日本学者Itoh等以氧化镁为催化剂、苯基硅烷和二乙炔基苯为原料进行脱氢加成聚合反应,制备得到了重复单元中含有[-Si(Ph)H-C≡C-C6H4-C≡C-]的耐高温芳炔聚合物(MSP树脂)并对其耐热氧化性能进行了研究;法国学者Buvat等在MSP树脂的基础上合成了一种既含有Si-H和C≡C活性基团,同时还有乙炔基封端的苯基芳炔类树脂,该树脂高温分解温度较MSP低,但是其固化温度较低且在室温加工性较好;Craig等通过缩聚反应和有机锂试剂制备得到了一种线型(亚芳基-硅氧基-2-乙炔基)聚合物,其含有的-SiC≡C-C≡CH结构在300℃下即可交联固化,具有很高的应用价值;Devapal等以盐酸作为催化剂、二甘醇二甲醚作为反应溶剂,采用硼酸与苯基(丙基)三甲氧基硅烷(PTMOS)为原料,经缩聚反应制备得到陶瓷化率在64~75%范围(惰性气体900℃)的硅氧硼聚合物,研究表明,此类材料在升温至500℃时,基本没有发生失重,耐热稳定性能优异;华东理工大学周权等以甲基二氯硅烷、碳硼烷、苯乙炔和有机锂试剂为原料合成得到了一种新型的碳硼烷-硅烷-苯乙炔基聚合物(简称PACS),研究表明,PACS在热引发作用下反应聚合得到的固化产物具有很高的耐热及耐热氧化性能;陈麒等在国内也开展了有机-无机硅炔杂化材料的研究工作,设计合成了一系列苯乙炔基硅烷树脂,包括甲基二苯乙炔基硅烷(MDPES)(ZL02151140.3;ZL200510110133.5)、甲基三苯乙炔基硅烷(MTPES)和四苯乙炔基硅烷(TPES)。这三种树脂在普通有机溶剂中具有良好的溶解性,通过预聚反应可以有效地控制体系的粘度,适用于各种先进复合材料成型工艺。但是研究得到的聚合物材料中无机元素的含量和烧结物形成的SiC,B2O3等含量一般都较低,如能提高聚合物中的无机元素的含量,则可形成连续的SiC,B2O3等陶瓷结构,从而提高材料的耐热氧化性能。Japanese scholar Itoh et al. used magnesium oxide as a catalyst, phenylsilane and diethynylbenzene as raw materials for dehydrogenation addition polymerization, and prepared a repeating unit containing [-Si(Ph)HC≡CC 6 H 4 -C≡ C-] high-temperature-resistant aryne polymer (MSP resin) and its thermal oxidation resistance were studied; French scholar Buvat et al. synthesized a compound containing both Si-H and C≡C active groups on the basis of MSP resin At the same time, there are phenylarynyl resins terminated by ethynyl groups. The resin has a lower pyrolysis temperature than MSP, but its curing temperature is lower and it has better processability at room temperature; Craig et al. prepared by polycondensation reaction and organolithium reagent A linear (arylene-siloxy-2-ethynyl) polymer, which contains a -SiC≡CC≡CH structure, can be cross-linked and cured at 300°C, and has high application value; Devapal etc. take hydrochloric acid as a catalyst, diglyme as a reaction solvent, and adopt boric acid and phenyl (propyl) trimethoxysilane (PTMOS) as raw materials to obtain a ceramization rate in the range of 64 to 75% through polycondensation reaction ( Inert gas 900°C) silicon boron polymer, the research shows that when the temperature rises to 500°C, this kind of material basically does not lose weight, and has excellent heat resistance and stability; Zhou Quan of East China University of Science and Technology et al. A new type of carborane-silane-phenylethynyl polymer (PACS for short) was synthesized from borane, phenylacetylene and organolithium reagents. Studies have shown that the cured product obtained by reaction polymerization of PACS under the action of thermal initiation has High heat resistance and thermal oxidation resistance; Chen Qi and others have also carried out research work on organic-inorganic silyne hybrid materials in China, and designed and synthesized a series of phenylethynyl silane resins, including methyl tolanyl silane (MDPES) (ZL02151140.3; ZL200510110133.5), methyltriphenylethynylsilane (MTPES) and tetraphenylethynylsilane (TPES). These three resins have good solubility in common organic solvents, and can effectively control the viscosity of the system through prepolymerization, and are suitable for various advanced composite material molding processes. However, the content of inorganic elements in the researched polymer materials and the content of SiC and B 2 O 3 formed by sintering are generally low. If the content of inorganic elements in the polymer can be increased, continuous SiC, B can be formed. 2 O 3 and other ceramic structures, thereby improving the thermal oxidation resistance of the material.
本发明采用一种全新的合成路线,合成了一类新型的主链中含有无机元素硼和硅,并用氨基苯乙炔封端的有机-无机杂化聚合物。本发明以苯硼酸、二氯硅烷和氨基苯乙炔为主要原料合成了一类新型耐高温苯硼酸-硅氧烷-亚氨基线型聚合物。通过调节苯硼酸与二氯硅烷的摩尔比,很容易地控制聚合物中无机元素硅和硼的含量,利用C≡C键与C≡C键的加成反应和C≡C键与C≡C的Diels-Alder反应等,使得这种杂化聚合物在加热条件下可形成三维网络结构,同时聚合物主链中的硼和硅原子在高温下转化为B2O3、SiO2和SiC等陶瓷结构,其中B2O3在高温下具有良好的流动性,可以对涂层和微裂纹进行修复,具有自愈合的能力,有效地提高纤维材料的耐热氧化能力,极大的提高了复合材料在高温下空气中的质量保留率。这类聚合物具有优良的耐高温、耐热氧化及介电性能等,适用于制备陶瓷前躯体、高性能复合材料基体、耐烧蚀材料、耐高温涂层等,在国防、航空、航天等高端领域中有着极其宽广的应用前景。The invention adopts a brand-new synthesis route to synthesize a new type of organic-inorganic hybrid polymer which contains inorganic elements boron and silicon in the main chain and is capped with aminophenylacetylene. The invention synthesizes a novel high temperature resistant phenylboric acid-siloxane-imino linear polymer by using phenylboric acid, dichlorosilane and aminophenylacetylene as main raw materials. By adjusting the molar ratio of phenylboronic acid to dichlorosilane, it is easy to control the content of inorganic elements silicon and boron in the polymer, using the addition reaction of C≡C bond and C≡C bond and the addition reaction of C≡C bond and C≡C The Diels-Alder reaction, etc., make this hybrid polymer form a three-dimensional network structure under heating conditions, and at the same time, the boron and silicon atoms in the main chain of the polymer are converted into B 2 O 3 , SiO 2 and SiC at high temperature. Ceramic structure, in which B 2 O 3 has good fluidity at high temperature, can repair coating and micro cracks, has self-healing ability, effectively improves the thermal oxidation resistance of fiber materials, and greatly improves Mass retention of composite materials in air at elevated temperatures. This kind of polymer has excellent high temperature resistance, thermal oxidation resistance and dielectric properties, etc., and is suitable for the preparation of ceramic precursors, high-performance composite material substrates, ablation-resistant materials, high-temperature resistant coatings, etc., in national defense, aviation, aerospace, etc. There are extremely broad application prospects in the high-end field.
发明内容 Contents of the invention
本发明合成了一类新型耐高温苯硼酸-硅氧烷-亚氨基线型聚合物,所述的聚合物结构式如下:The present invention has synthesized a new type of high temperature resistant phenylboronic acid-siloxane-imino linear polymer, and the structural formula of the polymer is as follows:
其中:(1)R1、R2为氢原子、烷基或芳基;(2)n为≥1的整数;Among them: (1) R 1 and R 2 are hydrogen atoms, alkyl groups or aryl groups; (2) n is an integer ≥ 1;
(3)Ar为或三种的混合物。(3) Ar is or a mixture of all three.
本发明提供了一种结构全新的聚合物,其重复单元至少含有一个Si-O-B-O结构,并且含有两个乙炔基封端。通过调节苯硼酸和二氯硅烷,苯硼酸和氨基苯乙炔的摩尔比,可以很容易地控制聚合物的分子量、交联密度和硅/硼的含量,从而达到聚合物性能可调整性的目标。The invention provides a polymer with a completely new structure, the repeating unit of which contains at least one Si-O-B-O structure and contains two ethynyl end caps. By adjusting the molar ratio of phenylboronic acid and dichlorosilane, phenylboronic acid and aminophenylacetylene, the molecular weight, crosslink density and silicon/boron content of the polymer can be easily controlled, so as to achieve the goal of polymer performance adjustability.
本发明从分子结构设计出发,在Si-O-B-O结构单元中引入亚氨基和端炔基结构,得到了既含硅、硼无机元素,又含有乙炔基的有机-无机杂化材料。通过调节聚合物中Si-O-B-O结构的含量,很容易地控制结构中硅和硼的含量,从而改善这类聚合物的耐热氧化性能。利用亚氨基和Si-O-B-O结构的螯合作用,从而改善这类聚合物材料的水解性能。所述聚合物在光、热或化学引发剂的作用下发生交联固化反应形成三维网状结构。并可以在空气或惰性气体中进一步热解形成陶瓷结构。这类聚合物适合于制备陶瓷前躯体、高性能复合材料基体、耐烧蚀材料、耐高温涂层等,在国防、航空、航天等高端领域中有着极其宽广的应用前景。Starting from molecular structure design, the present invention introduces imino and terminal alkynyl structures into the Si-O-B-O structural unit to obtain an organic-inorganic hybrid material containing both silicon and boron inorganic elements and ethynyl groups. By adjusting the content of the Si-O-B-O structure in the polymer, it is easy to control the content of silicon and boron in the structure, thereby improving the thermal oxidation resistance of this type of polymer. The chelating effect of imino group and Si-O-B-O structure is used to improve the hydrolysis performance of this kind of polymer material. The polymer undergoes a cross-linking and curing reaction under the action of light, heat or a chemical initiator to form a three-dimensional network structure. And can be further pyrolyzed in air or inert gas to form a ceramic structure. This type of polymer is suitable for preparing ceramic precursors, high-performance composite material substrates, ablation-resistant materials, high-temperature-resistant coatings, etc., and has extremely broad application prospects in high-end fields such as national defense, aviation, and aerospace.
本发明所述新型耐高温苯硼酸-硅氧烷-亚氨基线型聚合物为低粘度液体至粘稠状固体,易溶于各类普通有机溶剂中,可用于制备耐高温复合材料、陶瓷前驱体、耐高温涂层等。The novel high-temperature-resistant phenylboronic acid-siloxane-imino linear polymer described in the present invention is a low-viscosity liquid to viscous solid, easily soluble in various common organic solvents, and can be used to prepare high-temperature-resistant composite materials and ceramic precursors. Body, high temperature resistant coating, etc.
本发明的另一目的是提供一种制备所述新型耐高温苯硼酸-硅氧烷-亚氨基线型聚合物的方法。本发明以苯硼酸、二氯硅烷、氨基苯乙炔为原料、无水二乙二醇二甲醚、无水四氢呋喃(THF)作溶剂,在惰性气体保护下分二步反应而得。制备方法如下:Another object of the present invention is to provide a method for preparing the novel high temperature resistant phenylboronic acid-siloxane-imino linear polymer. The invention uses phenylboronic acid, dichlorosilane and aminophenylacetylene as raw materials, anhydrous diethylene glycol dimethyl ether and anhydrous tetrahydrofuran (THF) as solvents, and reacts in two steps under the protection of an inert gas. The preparation method is as follows:
第一步反应:在惰性气体保护下,通过苯硼酸与二氯硅烷反应生成具有Si-O-B-O重复结构单元,两端为氯原子封端的聚合物,反应式如下所示:The first step reaction: under the protection of an inert gas, react phenylboronic acid with dichlorosilane to generate a polymer with Si-O-B-O repeating structural units, both ends of which are terminated by chlorine atoms. The reaction formula is as follows:
其中:(1)R1、R2为氢原子、烷基或芳基;(2)n为≥1的整数;Among them: (1) R 1 and R 2 are hydrogen atoms, alkyl groups or aryl groups; (2) n is an integer ≥ 1;
(3)Ar为或三种的混合物。(3) Ar is or a mixture of all three.
第二步反应:在惰性气体保护下,氨基苯乙炔与第一步生成的聚合物反应,后处理得到最终产物,反应式如下所示:The second step reaction: under the protection of inert gas, aminophenylacetylene reacts with the polymer generated in the first step, and the final product is obtained after post-processing. The reaction formula is as follows:
其中:(1)R1、R2为氢原子、烷基或芳基;(2)n为≥1的整数;Among them: (1) R 1 and R 2 are hydrogen atoms, alkyl groups or aryl groups; (2) n is an integer ≥ 1;
(3)Ar为或三种的混合物。(3) Ar is or a mixture of all three.
本发明从分子结构设计出发,在Si-O-B-O结构单元中引入亚氨基和端炔基结构,得到了既含硅、硼无机元素,又含有乙炔基的有机-无机杂化材料。通过调节聚合物中Si-O-B-O结构的含量,很容易地控制结构中硅和硼的含量,从而改善这类聚合物的耐热氧化性能。利用亚氨基和Si-O-B-O结构的螯合作用,改善这类聚合物材料的水解性能。该合成工艺简单,反应条件易于控制,操作方便;所需的原材料来源丰富,产物在室温下具有良好的稳定性,耐高温及抗氧化性能优异,具有工业实用性,适用于制备陶瓷前驱体、高性能复合材料基体、耐烧蚀材料、耐高温涂层等。Starting from molecular structure design, the present invention introduces imino and terminal alkynyl structures into the Si-O-B-O structural unit to obtain an organic-inorganic hybrid material containing both silicon and boron inorganic elements and ethynyl groups. By adjusting the content of the Si-O-B-O structure in the polymer, it is easy to control the content of silicon and boron in the structure, thereby improving the thermal oxidation resistance of this type of polymer. Utilize the chelation effect of imino group and Si-O-B-O structure to improve the hydrolysis performance of this kind of polymer material. The synthesis process is simple, the reaction conditions are easy to control, and the operation is convenient; the required raw materials are rich in sources, the product has good stability at room temperature, excellent high temperature resistance and oxidation resistance, and has industrial applicability. It is suitable for preparing ceramic precursors, High-performance composite material matrix, ablation-resistant materials, high-temperature-resistant coatings, etc.
具体实施方式: Detailed ways:
结合实施例进一步说明本发明的技术解决方案,但其并不限制本发明的保护范围:Further illustrate the technical solution of the present invention in conjunction with embodiment, but it does not limit protection scope of the present invention:
实施方案1:制备新型耐高温苯硼酸-硅氧烷-亚氨基线型聚合物(其中,M二苯基二 氯硅烷∶M苯硼酸=2∶1;M二苯基二氯硅烷、M苯硼酸分别表示二苯基二氯硅烷、苯硼酸的摩尔数)Embodiment 1: Preparation of novel high temperature resistant phenylboronic acid-siloxane-imino linear polymer (wherein, M diphenyl dichlorosilane: M phenylboronic acid = 2: 1; M diphenyl dichlorosilane , M benzene Boronic acid represents the moles of diphenyldichlorosilane and phenylboronic acid respectively)
在高纯氮气保护条件下,将40mmol苯硼酸和60ml二乙二醇二甲醚加入装有搅拌器、温度计、恒压滴液漏斗和回流装置的250ml四口烧瓶中,然后在20~30℃条件下,通过恒压滴液漏斗缓慢滴加80mmol二苯基二氯硅烷和30ml二乙二醇二甲醚配成的溶液,滴加完毕后,缓慢升温到165℃,保持回流反应48小时。待回流反应结束后,减压蒸馏除去溶剂二乙二醇二甲醚,并将产物冷却到室温,加入10ml THF溶解产物,控制体系温度在0~10℃,通过恒压滴液漏斗缓慢滴加80mmol氨基苯乙炔和50ml二乙二醇二甲醚配成的溶液,滴加完毕后控制温度在20~30℃条件下继续反应3小时。待反应结束后,将产物冷却,加入饱和NH4Cl溶液,充分搅拌,分液,取上层油相,重复洗涤、分液3~5次,直至水相和油相都呈中性。收集上层油状物,减压蒸馏除尽溶剂后即得产物。FT-IR:3288cm-1(C≡C-H),3068cm-1(Ph-H),3374cm-1(-NH),1079cm-1(Si-O),1430cm-1(B-Ph),1122cm-1(Si-Ph);1H-NMR(CDCl3,TMS)δ:6.79-7.67(Ph-H),3.05(≡CH),3.98(-NH);13C-NMR(CDCl3,TMS)δ:77.4(≡CH),115.8-134.8(Ph),83.9(-C≡CH)。Under the condition of high-purity nitrogen protection, add 40mmol phenylboronic acid and 60ml diethylene glycol dimethyl ether into a 250ml four-neck flask equipped with a stirrer, thermometer, constant pressure dropping funnel and reflux device, and then Under certain conditions, a solution prepared by 80mmol diphenyldichlorosilane and 30ml diethylene glycol dimethyl ether was slowly added dropwise through a constant pressure dropping funnel. After the dropwise addition, the temperature was slowly raised to 165° C., and the reaction was kept under reflux for 48 hours. After the reflux reaction is completed, the solvent diethylene glycol dimethyl ether is distilled off under reduced pressure, and the product is cooled to room temperature, and 10ml of THF is added to dissolve the product, and the temperature of the system is controlled at 0-10°C, and slowly added dropwise through a constant pressure dropping funnel A solution formed of 80mmol aminophenylacetylene and 50ml diethylene glycol dimethyl ether was added dropwise and the temperature was controlled at 20-30°C to continue the reaction for 3 hours. After the reaction is finished, cool the product, add saturated NH 4 Cl solution, stir well, separate the liquid, take the upper oil phase, repeat washing and liquid separation for 3 to 5 times, until both the water phase and the oil phase are neutral. The upper layer oil was collected, and the product was obtained after vacuum distillation to remove the solvent. FT-IR: 3288cm -1 (C≡CH), 3068cm -1 (Ph-H), 3374cm -1 (-NH), 1079cm -1 (Si-O), 1430cm -1 (B-Ph), 1122cm - 1 (Si-Ph); 1 H-NMR (CDCl 3 , TMS) δ: 6.79-7.67 (Ph-H), 3.05 (≡CH), 3.98 (-NH); 13 C-NMR (CDCl 3 , TMS) δ: 77.4 (≡CH), 115.8-134.8 (Ph), 83.9 (-C≡CH).
实施方案2:制备新型耐高温苯硼酸-硅氧烷-亚氨基线型聚合物(其中,M二苯基二 氯硅烷∶M苯硼酸=1.5∶1;M二苯基二氯硅烷、M苯硼酸分别表示二苯基二氯硅烷、苯硼酸的摩尔数)Embodiment 2: Preparation of novel high temperature resistant phenylboronic acid-siloxane-imino linear polymer (wherein, M diphenyl dichlorosilane: M phenylboronic acid = 1.5: 1; M diphenyl dichlorosilane , M benzene Boronic acid represents the moles of diphenyldichlorosilane and phenylboronic acid respectively)
在高纯氮气保护条件下,将40mmol苯硼酸和60ml二乙二醇二甲醚加入装有搅拌器、温度计、恒压滴液漏斗和回流装置的250ml四口烧瓶中,然后在20~30℃条件下,通过恒压滴液漏斗缓慢滴加60mmol二苯基二氯硅烷和25ml二乙二醇二甲醚配成的溶液,滴加完毕后,缓慢升温到165℃,保持回流反应48小时。待回流反应结束后,减压蒸馏除去溶剂二乙二醇二甲醚,并将产物冷却到室温,加入10ml THF溶解产物,控制体系温度在0~10℃,通过恒压滴液漏斗缓慢滴加40mmol氨基苯乙炔和30ml二乙二醇二甲醚配成的溶液,滴加完毕后控制温度在20~30℃条件下继续反应3小时。待反应结束后,将产物冷却,加入饱和NH4C1溶液,充分搅拌,分液,取上层油相,重复洗涤,分液3~5次,直至水相和油相都呈中性。收集上层油状物,减压蒸馏除尽溶剂后即得产物。FT-IR:3290cm-1(C≡C-H),3070cm-1(Ph-H),3380、1185cm-1(-NH),1348cm-1(B-O),1080cm-1(Si-O),1437cm-1(B-Ph),1122cm-1(Si-Ph);1H-NMR(CDCl3,TMS)δ:6.80-7.71(Ph-H),3.06(≡CH),4.08(-NH);13C-NMR(CDCl3,TMS)δ:77.8(≡CH),115.3-134.8(Ph),86.4(-C≡CH)。Under the condition of high-purity nitrogen protection, add 40mmol phenylboronic acid and 60ml diethylene glycol dimethyl ether into a 250ml four-neck flask equipped with a stirrer, thermometer, constant pressure dropping funnel and reflux device, and then Under certain conditions, a solution prepared by 60 mmol diphenyldichlorosilane and 25 ml diethylene glycol dimethyl ether was slowly added dropwise through a constant pressure dropping funnel. After the dropwise addition, the temperature was slowly raised to 165° C., and the reaction was kept under reflux for 48 hours. After the reflux reaction is completed, the solvent diethylene glycol dimethyl ether is distilled off under reduced pressure, and the product is cooled to room temperature, and 10ml of THF is added to dissolve the product, and the temperature of the system is controlled at 0-10°C, and slowly added dropwise through a constant pressure dropping funnel A solution made of 40mmol aminophenylacetylene and 30ml diethylene glycol dimethyl ether was added dropwise and the temperature was controlled at 20-30°C to continue the reaction for 3 hours. After the reaction is over, cool the product, add saturated NH 4 C1 solution, fully stir, separate liquid, take the upper oil phase, repeat washing, separate liquid 3 to 5 times, until both the water phase and the oil phase are neutral. The upper layer oil was collected, and the product was obtained after vacuum distillation to remove the solvent. FT-IR: 3290cm -1 (C≡CH), 3070cm -1 (Ph-H), 3380, 1185cm -1 (-NH), 1348cm -1 (BO), 1080cm -1 (Si-O), 1437cm - 1 (B-Ph), 1122 cm -1 (Si-Ph); 1 H-NMR (CDCl 3 , TMS) δ: 6.80-7.71 (Ph-H), 3.06 (≡CH), 4.08 (-NH); 13 C-NMR (CDCl 3 , TMS) δ: 77.8 (≡CH), 115.3-134.8 (Ph), 86.4 (-C≡CH).
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