CN107936675A - A kind of solidification composition filling and its application - Google Patents
A kind of solidification composition filling and its application Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 33
- 230000008023 solidification Effects 0.000 title abstract 5
- 238000007711 solidification Methods 0.000 title abstract 5
- 238000000576 coating method Methods 0.000 claims abstract description 37
- 229920002379 silicone rubber Polymers 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 239000004945 silicone rubber Substances 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 6
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 4
- 238000005292 vacuum distillation Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 abstract description 35
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- ZRWNRAJCPNLYAK-UHFFFAOYSA-N 4-bromobenzamide Chemical compound NC(=O)C1=CC=C(Br)C=C1 ZRWNRAJCPNLYAK-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- SDTDHTCWRNVNAJ-UHFFFAOYSA-L dimethyltin(2+);diacetate Chemical compound CC(=O)O[Sn](C)(C)OC(C)=O SDTDHTCWRNVNAJ-UHFFFAOYSA-L 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
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Abstract
Description
技术领域technical field
本发明涉及一种硅橡胶基热控涂层用高效固化体系及其制备方法，属于固化剂技术领域。The invention relates to a high-efficiency curing system for a silicone rubber-based thermal control coating and a preparation method thereof, belonging to the technical field of curing agents.
背景技术Background technique
空间热控涂层是空间飞行器热控系统所采用的一种重要材料，它能保证仪器及舱内温度的有效调控，涂料型热控涂层不用改变原有卫星产品结构，具有适应性强、易实现和可修补等优点，是目前国内外航天器实现热控设计的重要选择方案。随着空间技术的不断进步，我国未来低轨道侦察、遥感卫星和空间站等型号向着大容量、长寿命、高分辨率、高精度的方向发展，如遥感卫星设计寿命为8年、空间站设计寿命为15年等，对热控涂层材料提出了长寿命、高可靠和轻量化的新需求。此外，航天器在轨期间，面临严酷的高低温交变环境，因此热控涂层必须具有较高的柔性，以确保涂层与基材的力热匹配性。Space thermal control coating is an important material used in the thermal control system of space vehicles. It can ensure the effective regulation of the temperature in the instrument and cabin. The coating type thermal control coating does not need to change the structure of the original satellite product, and has strong adaptability, The advantages of easy realization and repairability are the important options for the thermal control design of spacecraft at home and abroad. With the continuous advancement of space technology, my country's future low-orbit reconnaissance, remote sensing satellites, and space stations will develop in the direction of large capacity, long life, high resolution, and high precision. For example, the design life of remote sensing satellites is 8 years, and the design life of space stations is 8 years In 15 years, etc., new requirements for long life, high reliability and light weight have been put forward for thermal control coating materials. In addition, during the spacecraft's orbit, it faces a harsh high and low temperature alternating environment, so the thermal control coating must have high flexibility to ensure the mechanical and thermal matching between the coating and the substrate.
硅橡胶热控涂层具有优异的耐原子氧性能、柔性、耐高低温交变性能及耐空间环境性能，常被作为树脂基体用于空间长寿命柔性热控涂层。缩合型硅橡胶是当前应用最为广泛的一类硅橡胶之一。由于缩合型硅橡胶的硅羟基含量低，使用现有的硅烷偶联剂(如正硅酸乙酯)做固化剂涂层经72h仍会出现不固化现象、涂层原子氧剥蚀速率超过10-25cm3/atom，且容易出现发黏现象。因此，有必要研制高效固化体系，解决当前硅橡胶热控涂层固化时间长及涂层发黏等问题，并提高涂层耐原子氧性能。Silicone rubber thermal control coating has excellent atomic oxygen resistance, flexibility, high and low temperature resistance and space environment resistance, and is often used as a resin matrix for space long-life flexible thermal control coating. Condensed silicone rubber is one of the most widely used silicone rubbers. Due to the low silanol content of condensation silicone rubber, if the existing silane coupling agent (such as tetraethyl silicate) is used as the curing agent, the coating will still not be cured after 72 hours, and the atomic oxygen erosion rate of the coating will exceed 10 - 25 cm 3 /atom, and prone to stickiness. Therefore, it is necessary to develop an efficient curing system to solve the problems of long curing time and stickiness of the current silicone rubber thermal control coating, and to improve the atomic oxygen resistance of the coating.
发明内容Contents of the invention
本发明的目的在于提供一种固化组合物及其应用，该固化组合物在加快硅橡胶基热控涂层固化速率的同时，提高硅橡胶基热控涂层的耐原子氧性能。The object of the present invention is to provide a curing composition and its application. The curing composition can improve the atomic oxygen resistance performance of the silicone rubber-based thermal control coating while accelerating the curing rate of the silicone rubber-based thermal control coating.
本发明的上述目的主要是通过如下技术方案予以实现的：Above-mentioned purpose of the present invention is mainly achieved through the following technical solutions:
一种固化组合物，包括以下质量份组分：A curing composition, comprising the following components in parts by mass:
低聚硅氧烷5份、催化剂0.8-1.2份及溶剂5-7份。5 parts of oligosiloxane, 0.8-1.2 parts of catalyst and 5-7 parts of solvent.
在一可选实施例中，所述的低聚硅氧烷为甲基三乙氧基硅烷与正硅酸四乙酯的低聚物。In an optional embodiment, the oligosiloxane is an oligomer of methyltriethoxysilane and tetraethylorthosilicate.
在一可选实施例中，所述低聚物的化学结构式为：In an optional embodiment, the chemical structural formula of the oligomer is:
其中，x+y＝5-10。Among them, x+y=5-10.
在一可选实施例中，所述低聚硅氧烷，其制备方法包括以下步骤：In an optional embodiment, the preparation method of the oligosiloxane comprises the following steps:
步骤1、将10质量份甲基三乙氧基硅烷、9-11质量份正硅酸乙酯、0.18-0.22质量份硝酸、8-9质量份乙醇、1-2质量份水搅拌混合，得到反应体系；Step 1. Stir and mix 10 parts by mass of methyltriethoxysilane, 9-11 parts by mass of ethyl orthosilicate, 0.18-0.22 parts by mass of nitric acid, 8-9 parts by mass of ethanol, and 1-2 parts by mass of water to obtain reaction system;
步骤2、将所述反应体系在60-80℃下反应4h-5h，得到澄清溶液；Step 2, reacting the reaction system at 60-80°C for 4h-5h to obtain a clear solution;
步骤3、对所述澄清溶液进行减压蒸馏除去多余溶剂，得到低聚硅氧烷。Step 3, performing vacuum distillation on the clear solution to remove excess solvent to obtain oligosiloxane.
在一可选实施例中，步骤1所述硝酸的浓度为65％。In an optional embodiment, the concentration of nitric acid in step 1 is 65%.
在一可选实施例中，步骤2所述反应，包括：In an optional embodiment, the reaction described in step 2 includes:
反应时，搅拌速率至少为200rad/min，且保持冷凝水不断循环。During the reaction, the stirring rate should be at least 200rad/min, and the condensed water should be continuously circulated.
在一可选实施例中，步骤3所述的对所述澄清溶液进行减压蒸馏除，包括：In an optional embodiment, the decompression distillation of the clarified solution described in step 3 includes:
将所述澄清溶液置于两口反应釜中，所述反应釜的第一开口与抽真空装置连接，第二开口与密闭容器连接，通过所述第一开口抽真空至釜内压强小于100Pa，加热至35-45℃，保温至少30min，收集所述反应釜中剩余物。Place the clarified solution in two reaction kettles, the first opening of the reaction kettle is connected to the vacuum device, the second opening is connected to the airtight container, the vacuum is pumped through the first opening until the pressure in the kettle is less than 100Pa, and the heating to 35-45° C., keep the temperature for at least 30 minutes, and collect the residue in the reaction kettle.
在一可选实施例中，所述催化剂为纯度为95％以上的二丁基二月桂酸锡或二丁基二乙酸锡的一种或两种组合。In an optional embodiment, the catalyst is one or a combination of dibutyltin dilaurate or dibutyltin diacetate with a purity of more than 95%.
在一可选实施例中，所述溶剂纯度95％以上二甲苯。In an optional embodiment, the purity of the solvent is above 95% xylene.
上述固化组合物作为固化剂在硅橡胶基热控涂层中的应用。The application of the above curing composition as a curing agent in silicone rubber-based thermal control coatings.
本发明与现有技术相比具有如下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
(1)本发明采用低聚硅氧烷/催化剂固化体系，可确保硅橡胶基热控涂层在48h完全固化，且不发生发黏现象。(1) The present invention uses an oligosiloxane/catalyst curing system, which can ensure that the silicone rubber-based thermal control coating is completely cured within 48 hours without stickiness.
(2)本发明可将硅橡胶基热控涂层原子氧剥蚀率从10-25cm3/atom降低至2.025×10-26cm3/atom。(2) The present invention can reduce the atomic oxygen erosion rate of the silicone rubber-based thermal control coating from 10-25 cm 3 /atom to 2.025×10-26 cm 3 /atom.
附图说明Description of drawings
图1实施例1提供的低聚硅氧烷核磁共振氢谱图The oligosiloxane proton nuclear magnetic resonance spectrum that Fig. 1 embodiment 1 provides
图2实施例1提供的低聚硅氧烷红外光谱图。The infrared spectrogram of the oligosiloxane provided in Fig. 2 Example 1.
具体实施方式Detailed ways
下面结合附图和具体实施方式对本发明进行详细说明。The present invention will be described in detail below in conjunction with the accompanying drawings and specific embodiments.
本发明实施例提供了一种固化组合物，包括以下质量份组分：The embodiment of the present invention provides a curing composition, comprising the following components in parts by mass:
低聚硅氧烷5份、催化剂0.8-1.2份及溶剂5-7份。5 parts of oligosiloxane, 0.8-1.2 parts of catalyst and 5-7 parts of solvent.
其中，所述低聚硅氧烷优选三乙氧基硅烷和/或四乙氧基硅烷的低聚物，所述催化剂可以为二甲基二乙酸锡、二甲基二月桂酸锡等，优选纯度为95％以上的二丁基二月桂酸锡或二丁基二乙酸锡的一种或两种组合，以提高催化效率、降低生产成本。所述溶剂为汽油、乙酸乙酯、甲苯等，优选纯度95％以上二甲苯，以提高固化组合物的稳定性，降低固化组合物的挥发性，保证固化组合物粘度均一；Wherein, the oligomeric siloxane is preferably an oligomer of triethoxysilane and/or tetraethoxysilane, and the catalyst can be dimethyl tin diacetate, dimethyl tin dilaurate, etc., preferably One or a combination of dibutyltin dilaurate or dibutyltin diacetate with a purity of more than 95% to improve catalytic efficiency and reduce production costs. The solvent is gasoline, ethyl acetate, toluene, etc., preferably xylene with a purity of more than 95%, to improve the stability of the cured composition, reduce the volatility of the cured composition, and ensure uniform viscosity of the cured composition;
本发明提供的固化组合物，通过使用低聚硅氧烷作为有效固化成分，当固化组合物作为固化剂作用于硅橡胶热控涂层体系时，提高了涂层体系的固化速率及交联度，降低了固化时间，使固化时间由原来的72小时缩短为24小时左右；同时通过增加涂层交联度，还提高了涂层耐原子性能。The curing composition provided by the present invention uses oligosiloxane as an effective curing component, and when the curing composition acts as a curing agent on the silicone rubber thermal control coating system, the curing rate and crosslinking degree of the coating system are improved , reducing the curing time, shortening the curing time from the original 72 hours to about 24 hours; at the same time, by increasing the cross-linking degree of the coating, the atomic resistance of the coating is also improved.
在一可选实施例中，所述的低聚硅氧烷为甲基三乙氧基硅烷与正硅酸四乙酯的低聚物。通过采用甲基三乙氧基硅烷与正硅酸四乙酯的低聚物，与其它低聚物相比，在兼顾固化效率的前提下，储存时间可以延长六个月左右，极大地提高了固化组分储存时间和稳定性。In an optional embodiment, the oligosiloxane is an oligomer of methyltriethoxysilane and tetraethylorthosilicate. By using the oligomer of methyltriethoxysilane and tetraethylorthosilicate, compared with other oligomers, the storage time can be extended by about six months under the premise of taking into account the curing efficiency, which greatly improves the Curing component shelf life and stability.
在一优选实施例中，所述低聚物的化学结构式为：In a preferred embodiment, the chemical structural formula of the oligomer is:
其中，x+y＝5-10。Among them, x+y=5-10.
通过控制聚合度，以保证聚合物的溶解性，避免聚合物聚集沉淀，确保固化剂澄清透明，进一步提高了组合物的稳定性。By controlling the degree of polymerization, the solubility of the polymer is ensured, the aggregation and precipitation of the polymer are avoided, and the curing agent is ensured to be clear and transparent, thereby further improving the stability of the composition.
进一步地，所述低聚硅氧烷的制备方法包括以下步骤：Further, the preparation method of the oligosiloxane comprises the following steps:
步骤1、将10质量份甲基三乙氧基硅烷、9-11质量份正硅酸乙酯、0.18-0.22质量份硝酸、8-9质量份乙醇、1-2质量份水搅拌混合，得到反应体系；Step 1. Stir and mix 10 parts by mass of methyltriethoxysilane, 9-11 parts by mass of ethyl orthosilicate, 0.18-0.22 parts by mass of nitric acid, 8-9 parts by mass of ethanol, and 1-2 parts by mass of water to obtain reaction system;
步骤2、将所述反应体系在60-80℃下反应4h-5h，得到澄清溶液；Step 2, reacting the reaction system at 60-80°C for 4h-5h to obtain a clear solution;
步骤3、对所述澄清溶液进行减压蒸馏除去多余溶剂，得到低聚硅氧烷。Step 3, performing vacuum distillation on the clear solution to remove excess solvent to obtain oligosiloxane.
该制备方法与碱催化及硅酸盐水解法等相比，所得的低聚硅氧烷分子量较小、分子量分布较窄，在溶液中具有更好的溶解性，进一步提高了组合物稳定性。Compared with alkali catalysis, silicate hydrolysis and the like, the preparation method has smaller molecular weight and narrower molecular weight distribution of the obtained oligosiloxane, has better solubility in solution, and further improves the stability of the composition.
步骤1所述硝酸的浓度优选65％，以避免改变反应体系，确保反应速率均匀；The concentration of nitric acid described in step 1 is preferably 65%, to avoid changing the reaction system and ensure uniform reaction rate;
步骤2所述反应，优选在反应时，搅拌速率至少为200rad/min，且保持冷凝水不断循环，以保证低聚硅氧烷分散均匀，反应充分。For the reaction described in step 2, it is preferred that during the reaction, the stirring rate is at least 200 rad/min, and the condensed water is continuously circulated to ensure that the oligosiloxane is dispersed evenly and the reaction is sufficient.
步骤3所述的对所述澄清溶液进行减压蒸馏除，包括：The described clarified solution described in step 3 is carried out underpressure distillation, comprises:
将所述澄清溶液置于两口反应釜中，所述反应釜的第一开口与抽真空装置连接，第二开口与密闭容器连接，通过所述第一开口抽真空至釜内压强小于100Pa，加热至35-45℃，保温至少30min，收集所述反应釜中剩余物。Place the clarified solution in two reaction kettles, the first opening of the reaction kettle is connected to the vacuum device, the second opening is connected to the airtight container, the vacuum is pumped through the first opening until the pressure in the kettle is less than 100Pa, and the heating to 35-45° C., keep the temperature for at least 30 minutes, and collect the residue in the reaction kettle.
本发明实施例还提供了一种上述固化组合物作为固化剂在硅橡胶基热控涂层中的应用。The embodiment of the present invention also provides an application of the above curing composition as a curing agent in a silicone rubber-based thermal control coating.
以下为本发明的几个具体实施例：Below are several specific embodiments of the present invention:
实施例1Example 1
将100g甲基三乙氧基硅烷、100g正硅酸四乙酯、2g硝酸、85g乙醇和15g水加入反应釜中，在200rad/min转速下搅拌均匀，升温至70℃，通过冷凝水不断循环使蒸出物冷凝回流，在该温度下反应5h。反应结束后，将釜内气压降低至100Pa，降温至40℃，保温30min，蒸馏除去溶剂，即制得低聚硅氧烷。Add 100g of methyltriethoxysilane, 100g of tetraethyl orthosilicate, 2g of nitric acid, 85g of ethanol and 15g of water into the reaction kettle, stir evenly at a speed of 200rad/min, raise the temperature to 70°C, and continuously circulate through condensed water The distillate was condensed to reflux and reacted at this temperature for 5h. After the reaction, reduce the pressure in the kettle to 100 Pa, lower the temperature to 40° C., keep the temperature for 30 minutes, and distill off the solvent to obtain the oligosiloxane.
图1中0.2ppm处吸收峰为与硅原子相连的甲基上H的吸收峰，1.4ppm处为乙氧基上甲基H吸收峰，3.7ppm及3.8ppm处为乙氧基上亚甲基H吸收峰。图2中2965cm-1处吸收峰为甲基和亚甲基C-H吸收峰，1261cm-1处吸收峰为Si-C吸收峰，1067cm-1处宽峰和800cm-1处吸收峰为Si-O吸收峰。In Figure 1, the absorption peak at 0.2ppm is the absorption peak of H on the methyl group connected to the silicon atom, the absorption peak at 1.4ppm is the methyl H absorption peak on the ethoxy group, and the absorption peak at 3.7ppm and 3.8ppm is the methylene group on the ethoxy group H absorption peak. In Figure 2, the absorption peak at 2965cm -1 is the absorption peak of methyl and methylene CH, the absorption peak at 1261cm -1 is the absorption peak of Si-C, the broad peak at 1067cm -1 and the absorption peak at 800cm- 1 are Si-O absorption peak.
将10g制得低聚硅氧烷、2g二丁基二月桂酸锡和12g二甲苯混合均匀，得到热控涂层固化体系。10 g of the prepared oligosiloxane, 2 g of dibutyltin dilaurate and 12 g of xylene were uniformly mixed to obtain a thermal control coating curing system.
将硅橡胶9g，白炭黑1g，二氧化钛40g混合均匀，加入10g上述固化体系，搅拌均匀后在0.25MPa压力下喷涂，制成硅橡胶热控涂层。Mix 9g of silicone rubber, 1g of white carbon black, and 40g of titanium dioxide evenly, add 10g of the above-mentioned curing system, stir evenly, and spray under a pressure of 0.25MPa to make a silicone rubber thermal control coating.
对制得的硅橡胶热控涂层进行固化时间测试及耐原子氧性能测试，测试结果如表1所示：The obtained silicone rubber thermal control coating was tested for curing time and atomic oxygen resistance performance, and the test results are shown in Table 1:
表1硅橡胶热控涂层性能Table 1 Properties of silicone rubber thermal control coating
实施例2Example 2
将100g甲基三乙氧基硅烷、100g正硅酸四乙酯、1.8g硝酸、80g乙醇和20g水加入反应釜中，在200rad/min转速下搅拌均匀，升温至70℃，通过冷凝水不断循环使蒸出物冷凝回流，在该温度下反应5h。反应结束后，将釜内气压降低至100Pa，降温至40℃，保温30min，蒸馏除去溶剂，即制得低聚硅氧烷。Add 100g of methyltriethoxysilane, 100g of tetraethylorthosilicate, 1.8g of nitric acid, 80g of ethanol and 20g of water into the reaction kettle, stir evenly at a speed of 200rad/min, raise the temperature to 70°C, and pass through the condensed water continuously The distillate was condensed and refluxed in circulation, and the reaction was carried out at this temperature for 5h. After the reaction, reduce the pressure in the kettle to 100 Pa, lower the temperature to 40° C., keep the temperature for 30 minutes, and distill off the solvent to obtain the oligosiloxane.
将10g低聚硅氧烷、1.6g二丁基二乙酸锡和10g二甲苯合均匀，制备成热控涂层固化体系。10g of oligosiloxane, 1.6g of dibutyltin diacetate and 10g of xylene were uniformly combined to prepare a thermal control coating curing system.
将硅橡胶9g，白炭黑1g，二氧化钛40g混合均匀，加入10g上述固化体系，搅拌均匀后在0.25MPa压力下喷涂，制成硅橡胶热控涂层，性能如表2所示。Mix 9g of silicone rubber, 1g of white carbon black, and 40g of titanium dioxide evenly, add 10g of the above-mentioned curing system, stir evenly, and spray at a pressure of 0.25MPa to make a silicone rubber thermal control coating. The properties are shown in Table 2.
表2硅橡胶热控涂层性能Table 2 Properties of silicone rubber thermal control coating
实施例3Example 3
将100g甲基三乙氧基硅烷、100g正硅酸四乙酯、2.2g硝酸、90g乙醇和10g水加入反应釜中，在200rad/min转速下搅拌均匀，升温至70℃，通过冷凝水不断循环使蒸出物冷凝回流，在该温度下反应5h。反应结束后，将釜内气压降低至100Pa，降温至40℃，保温30min，蒸馏除去溶剂，即制得低聚硅氧烷。Add 100g of methyltriethoxysilane, 100g of tetraethylorthosilicate, 2.2g of nitric acid, 90g of ethanol and 10g of water into the reaction kettle, stir evenly at a speed of 200rad/min, raise the temperature to 70°C, and continuously The distillate was condensed and refluxed in circulation, and the reaction was carried out at this temperature for 5h. After the reaction, reduce the pressure in the kettle to 100 Pa, lower the temperature to 40° C., keep the temperature for 30 minutes, and distill off the solvent to obtain the oligosiloxane.
将10g低聚硅氧烷、2.4g二丁基二乙酸锡和14g二甲苯混合均匀，制备成热控涂层固化体系。10g of oligosiloxane, 2.4g of dibutyltin diacetate and 14g of xylene were uniformly mixed to prepare a thermal control coating curing system.
将硅橡胶9g，白炭黑1g，二氧化钛40g混合均匀，加入10g上述固化体系，搅拌均匀后在0.25MPa压力下喷涂，制成硅橡胶热控涂层。Mix 9g of silicone rubber, 1g of white carbon black, and 40g of titanium dioxide evenly, add 10g of the above-mentioned curing system, stir evenly, and spray under a pressure of 0.25MPa to make a silicone rubber thermal control coating.
表3硅橡胶热控涂层性能Table 3 Properties of silicone rubber thermal control coating
本发明未详细说明部分属于本领域技术人员公知常识。所述的具体实施例仅是对本发明精神作举例说明。本发明所属技术领域的人员可以对所述的具体实施例做不同的修改或补充或采用类似的方式代替，但不偏离本发明的精神或者超越所附权利要求书所定义的范围。Parts not described in detail in the present invention belong to the common knowledge of those skilled in the art. The specific embodiments described are only to illustrate the spirit of the present invention. Those skilled in the art of the present invention may make various modifications or supplements to the specific embodiments or replace them in similar ways without departing from the spirit of the present invention or exceeding the scope defined in the appended claims.
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