CN116162440A - 一种聚磷腈橡胶与金属粘接用底涂胶、制备方法及应用 - Google Patents
一种聚磷腈橡胶与金属粘接用底涂胶、制备方法及应用 Download PDFInfo
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- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
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- C09J185/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Adhesives based on derivatives of such polymers
- C09J185/02—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Adhesives based on derivatives of such polymers containing phosphorus
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- C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
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Abstract
本发明公开了一种聚磷腈橡胶与金属粘接用底涂胶、制备方法及应用，底涂胶的质量百分组成为：基体橡胶5.11％～6.50％、氯化橡胶5.16％～6.39％、增粘树脂3.30％～5.80％、补强填料3.80％～5.00％、交联剂0.09％～0.11％、金属氧化物0.50％～0.54％、偶联剂0.63％～0.67％、余量为溶剂75.75％～80.56％，以本发明所制备的底涂胶与市售开姆洛克面涂胶Chemlok@220组成双涂型胶粘剂，所粘接的金属与聚磷腈橡胶的粘接强度为2.3～2.6MPa。
Description
技术领域
本发明涉及热硫化胶粘剂底涂胶，具体涉及一种聚磷腈橡胶与金属粘接用底涂胶、制备方法及应用。
背景技术
聚磷腈橡胶具有高氧指数、低热导率、低发烟量、耐烧蚀、抗燃气冲刷等优异性能，其与金属的粘接复合制件广泛应用于固体火箭发动机装药领域。采用热硫化粘接工艺使金属与聚磷腈橡胶在橡胶硫化过程中形成硫化制件，能够有效提升两者之间的粘接强度，尤其是对于复杂及难成型制件。然而，聚磷腈属于无机/有机杂化橡胶，其分子结构中极性化学基团含量低、表面活性差，与金属的粘接性能较差。目前，市场上国外品牌的胶粘剂，如开姆洛克、汉高、西邦等，以及国内众多品牌尚无适用于聚磷腈橡胶与金属粘接的专用胶粘剂，现有的适用于天然橡胶/金属、三元乙丙橡胶/金属、丁腈橡胶/金属等粘接体系的胶粘剂产品难以实现聚磷腈橡胶与金属的高强度粘接，不能满足应用需求。因此，研制适用于聚磷腈橡胶与金属粘接的胶粘剂势在必行。
从橡胶与金属粘接工艺角度分析，现有的粘接工艺主要包括为冷粘接与热硫化粘接两种，主要区别在于所粘接的橡胶是硫化橡胶还是混炼橡胶。热硫化粘接工艺，即将未硫化的混炼胶与金属通过单涂型或双涂型胶粘剂贴合在硫化条件(温度、压力、时间)下进行，使橡胶在硫化的过程中与金属产生一定的键合作用形成粘接件。冷粘接对于一些性状简单的制件可以操作简单，节约资源，但对于形状复杂及粘接性能要求较高的制品使用冷粘接工艺并不适合，会造成制品粘接强度低及使用寿命短等问题。因此，目前固体火箭发动机绝热层制造领域主要采用热硫化粘接工艺。然而，现阶段针对聚磷腈与金属的粘接，尤其是聚磷腈与金属的热硫化粘接尚缺乏性能可靠的胶粘剂。
发明内容
本发明的目的是提供一种聚磷腈橡胶与金属粘接用底涂胶、制备方法及应用，以本发明所制备的底涂胶与市售开姆洛克面涂胶Chemlok@220组成双涂型胶粘剂，所粘接的金属与聚磷腈绝热层的粘接强度明显高于开姆洛克底涂胶Chemlok@205和面涂胶Chemlok@220组成的双涂型胶粘剂，能够满足固体火箭发动机对壳体/绝热层界面粘接可靠性的技术需求。
本发明的技术解决方案是：
一种聚磷腈橡胶与金属粘接用底涂胶，质量百分组成为：基体橡胶5.11％～6.50％、氯化橡胶5.16％～6.39％、增粘树脂3.30％～5.80％、补强填料3.80％～5.00％、交联剂0.09％～0.11％、金属氧化物0.50％～0.54％、偶联剂0.63％～0.67％、余量为溶剂75.75％～80.56％。
可选的，质量百分组成为：聚磷腈橡胶6.32％、氯丁橡胶3.16％、氯磺化聚乙烯3.16％、甲阶酚醛树脂5.05％、E51环氧树脂0.63％、气相法白炭1.58％、N330炭黑3.13％、过氧化二异丙苯0.03％、硫磺0.06％、氧化镁0.3％、氧化锌0.2％、γ-氨丙基三乙氧基硅烷0.63％、二甲苯60.6％、甲基异丁基酮15.15％。
可选的，质量百分组成为：聚磷腈橡胶5.12％、氯磺化聚乙烯6.39％、甲阶酚醛树脂5.12％、E51环氧树脂0.65％、气相法白炭黑1.59％、N330炭黑3.17％、过氧化二异丙苯0.03％、硫磺0.06％、氧化镁0.51％、γ-氨丙基三乙氧基硅烷0.64％、二甲苯61.37％和甲基异丁基酮15.35％。
可选的，质量百分组成为：聚磷腈橡胶5.32％、氯丙橡胶2.25％、氯丁橡胶3.27％、甲阶酚醛树脂2.66％、E51环氧树脂0.66％、气相法白炭黑1.66％、N330炭黑3.29％、过氧化二异丙苯0.03％、硫磺0.06％、氧化镁0.25％、氧化锌0.25％、γ-3-缩水甘油醚氧基丙基三甲氧基硅烷0.66％、二甲苯63.72％和乙醇15.92％。
可选的，质量百分组成为：聚磷腈橡胶5.38％、氯丙橡胶2.68％、氯磺化聚乙烯2.69％、甲阶酚醛树脂2.68％、E51环氧树脂0.67％、气相法白炭黑2.68％、N330炭黑1.35％、过氧化二异丙苯0.03％、硫磺0.06％、氧化锌0.54％、γ-3-缩水甘油醚氧基丙基三甲氧基硅烷0.67％、二甲苯64.45％和乙醇16.12％。
可选的，质量百分组成为：聚磷腈橡胶6.47％、氯化天然橡胶5.16％、甲阶酚醛树脂5.16％、E51环氧树脂0.65％、气相法白炭黑1.29％、N330炭黑2.58％、过氧化二异丙苯0.03％、硫磺0.06％、氧化锌0.52％、γ-氨丙基三乙氧基硅烷0.64％、二甲苯61.95％和乙醇15.49％。
可选的，质量百分组成为：聚磷腈橡胶6.37％、氯化天然橡胶2.12％、氯磺化聚乙烯4.24％、甲阶酚醛树脂5.09％、E51环氧树脂0.65％、气相法白炭黑1.27％、N330炭黑2.55％、过氧化二异丙苯0.03％、硫磺0.06％、氧化镁0.51％、γ-甲基丙烯酰氧基丙基三甲氧基硅烷0.64％、二甲苯61.18％和乙醇15.29％。
本发明所述的聚磷腈橡胶与金属粘接用底涂胶的制备方法，该方法的步骤包括：
(1)首先将基体橡胶与氯化橡胶按比例混合，在50～60℃密炼60～80min；
(2)将密炼好的橡胶混合物取出，按照质量百分数配比依次加入补强填料、交联剂和金属氧化物，制备得到混炼胶；
(3)在制备好的混炼胶中按比例加入增粘树脂、偶联剂和溶剂，搅拌后得到混合胶液；
(4)将制备好的混合胶液研磨2～3h，得到底涂胶液。
一种双涂型胶粘剂，包括面涂胶和底涂胶，所述的底涂胶为本发明任一所述的聚磷腈橡胶与金属粘接用底涂胶。
可选的，所述的双涂型胶粘剂用于粘接聚磷腈橡胶与金属的应用，聚磷腈橡胶与金属粘接的制备包括以下步骤：
(1)将金属片表面进行喷砂处理，洗净晾干；
(2)在晾干的金属表面涂覆所述的底涂胶，并在40℃下烘置40～50min；
(3)在(2)中的已涂覆底涂胶的金属表面再涂覆面涂胶，并在40℃下烘置40～50min；
(4)将(3)中的金属片与聚磷腈混炼胶贴合，然后放入硫化模具中，硫化成型温度为150～165℃，硫化压力为10～12MPa，硫化时间为40～60min，进行粘接件的热硫化成型。
本发明与现有技术相比具有如下有益效果：
以本发明所制备的底涂胶与市售开姆洛克面涂胶Chemlok@220组成双涂型胶粘剂，所粘接的金属与聚磷腈橡胶的粘接强度为2.3～2.6MPa，而由开姆洛克底涂胶Chemlok@205和面涂胶Chemlok@220组成的双涂型胶粘剂所粘接的金属与聚磷腈橡胶的粘接强度为1.2～1.4MPa。本发明所制备的底涂胶能够满足固体火箭发动机对壳体/绝热层界面粘接可靠性的技术需求。
具体实施方式
下面结合实施例进一步对本发明作详细说明。
本发明的聚磷腈橡胶与金属热硫化粘接用双涂型胶粘剂底涂胶，由以下质量百分数的原料制备而成：基体橡胶5.11％～6.50％、氯化橡胶5.16％～6.39％、增粘树脂3.30％～5.80％、补强填料3.80％～5.00％、交联剂0.09％～0.11％、金属氧化物0.50％～0.54％、偶联剂0.63％～0.67％、余量为溶剂75.75％～80.56％，底涂胶的固含量控制在20％～25％之间。
基体橡胶为苯氧基、对乙基苯氧基和2-烯丙基苯氧基混合取代的聚磷腈，数均分子量为50000～100000，其结构式如下：
氯化橡胶为氯化天然橡胶、氯丁橡胶、氯磺化聚乙烯、氯丙橡胶，优选氯磺化聚乙烯、氯丁橡胶、氯丙橡胶中的一种或几种的混合物；
增粘树脂为环氧树脂和酚醛树脂的混合物，优选双酚A型环氧树脂E51与甲阶酚醛树脂的混合物；
补强填料为白炭黑、炭黑，优选气相法白炭黑、高补强炭黑N330中的一种或两种的混合物；
交联剂为过氧化物、硫磺，优选过氧化二异丙苯或过氧化苯甲酰与硫磺的混合物；
金属氧化物为氧化锌、氧化镁、二氧化钛，优选氧化锌与氧化镁中的一种或几种的混合物；
偶联剂为γ-氨丙基三乙氧基硅烷、γ-3-缩水甘油醚氧基丙基三甲氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、3-巯丙基三乙氧基硅烷和乙烯基三乙氧基硅烷中的一种或几种的混合物；
溶剂为二甲苯、乙醇和甲基异丁基酮至少两种的混合溶液。
本发明还提供上述的聚磷腈橡胶与金属热硫化粘接用双涂型胶粘剂底涂胶的制备方法，包括以下步骤：
(1)首先将基体橡胶与氯化橡胶按比例混合，在50～60℃密炼60～80min，以使二者混合均匀；
(2)将密炼好的橡胶混合物取出，在开炼机上按照质量百分数配比依次加入补强填料、交联剂和金属氧化物，制备得到混炼胶；
(3)将制备好的混炼胶剪成小块，按比例加入增粘树脂、偶联剂和溶剂，搅拌30min后得到混合胶液；
(4)将制备好的混合胶液通过球磨机研磨2～3h，得到底涂胶液，即为聚磷腈橡胶与金属热硫化粘接用双涂型胶粘剂底涂胶。
一种双涂型胶粘剂，包括面涂胶和底涂胶，底涂胶为本发明的聚磷腈橡胶与金属粘接用底涂胶；面涂胶为现有技术中任意的面涂胶，比如开姆洛克面涂胶Chemlok@220。
聚磷腈橡胶与金属粘接件的制备包括以下步骤：
(1)将金属片表面进行喷砂处理，并用丙酮清洗干净，室温晾干；
(2)在晾干的金属表面涂覆制备好的底涂胶，并在40℃下烘箱中晾置40～50min；
(3)在(2)中的已涂覆底涂胶的金属表面再涂覆开姆洛克面涂胶Chemlok@220，并在40℃下烘箱中晾置40～50min；
(4)将(3)中的金属片与聚磷腈混炼胶贴合，然后放入硫化模具中，硫化成型温度为150～165℃，硫化压力为10～12MPa，硫化时间为40～60min，进行粘接件的热硫化成型。
进一步的，步骤(1)中所用的金属片为铝片、45#钢片、高锰钢或冷轧钢；步骤(4)硫化前预热硫化模具20min以上。
制备好的粘接件按照《GB/T 13936-2014硫化橡胶与金属粘接拉伸剪切强度测定方法》进行聚磷腈橡胶与金属的拉伸剪切粘接强度测试。
以下是给出的实施例，需要说明的是，这些实施例是较优的例子，主要用于理解本发明，但本发明不限于这些实施例。
对比例1：
本对比例采用开姆洛克底涂胶Chemlok@205和面涂胶Chemlok@220组成的双涂型胶粘剂，粘接的聚磷腈橡胶与金属(45#钢)的粘接强度为1.2～1.4MPa。
实施例1：
本实施例参照如下底涂胶配方组成(质量百分数％)实施：
聚磷腈橡胶与金属(45#钢)的粘接强度为2.6MPa。
实施例2：
本实施例参照如下底涂胶配方组成(质量百分数％)实施：
| 组分 | 含量/wt.％ |
| 聚磷腈橡胶 | 5.12 |
| 氯磺化聚乙烯 | 6.39 |
| 甲阶酚醛树脂 | 5.12 |
| E51环氧树脂 | 0.65 |
| 气相法白炭黑 | 1.59 |
| N330炭黑 | 3.17 |
| 过氧化二异丙苯 | 0.03 |
| 硫磺 | 0.06 |
| 氧化镁 | 0.51 |
| γ-氨丙基三乙氧基硅烷 | 0.64 |
| 二甲苯 | 61.37 |
| 甲基异丁基酮 | 15.35 |
聚磷腈橡胶与金属(45#钢)的粘接强度为2.3MPa。
实施例3：
本实施例参照如下底涂胶配方组成(质量百分数％)实施：
| 组分 | 含量/wt.％ |
| 聚磷腈橡胶 | 5.32 |
| 氯丙橡胶 | 2.25 |
| 氯丁橡胶 | 3.27 |
| 甲阶酚醛树脂 | 2.66 |
| E51环氧树脂 | 0.66 |
| 气相法白炭黑 | 1.66 |
| N330炭黑 | 3.29 |
| 过氧化二异丙苯 | 0.03 |
| 硫磺 | 0.06 |
| 氧化镁 | 0.25 |
| 氧化锌 | 0.25 |
| γ-3-缩水甘油醚氧基丙基三甲氧基硅烷 | 0.66 |
| 二甲苯 | 63.72 |
| 乙醇 | 15.92 |
聚磷腈橡胶与金属(45#钢)的粘接强度为2.4MPa。
实施例4：
本实施例参照如下底涂胶配方组成(质量百分数％)实施：
聚磷腈橡胶与金属(45#钢)的粘接强度为2.5MPa。
实施例5：
本实施例参照如下底涂胶配方组成(质量百分数％)实施：
| 组分 | 含量/wt.％ |
| 聚磷腈橡胶 | 6.47 |
| 氯化天然橡胶 | 5.16 |
| 甲阶酚醛树脂 | 5.16 |
| E51环氧树脂 | 0.65 |
| 气相法白炭黑 | 1.29 |
| N330炭黑 | 2.58 |
| 过氧化二异丙苯 | 0.03 |
| 硫磺 | 0.06 |
| 氧化锌 | 0.52 |
| γ-氨丙基三乙氧基硅烷 | 0.64 |
| 二甲苯 | 61.95 |
| 乙醇 | 15.49 |
聚磷腈橡胶与金属(45#钢)的粘接强度为2.4MPa。
实施例6：
本实施例参照如下底涂胶配方组成(质量百分数％)实施：
聚磷腈橡胶与金属(45#钢)的粘接强度为2.3MPa。
以上详细描述了本公开的优选实施方式，但是，本公开并不限于上述实施方式中的具体细节，在本公开的技术构思范围内，可以对本公开的技术方案进行多种简单变型，这些简单变型均属于本公开的保护范围。
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本公开对各种可能的组合方式不再另行说明。
此外，本公开的各种不同的实施方式之间也可以进行任意组合，只要其不违背本公开的思想，其同样应当视为本公开所公开的内容。
Claims (10)
1.一种聚磷腈橡胶与金属粘接用底涂胶，其特征在于，质量百分组成为：基体橡胶5.11％～6.50％、氯化橡胶5.16％～6.39％、增粘树脂3.30％～5.80％、补强填料3.80％～5.00％、交联剂0.09％～0.11％、金属氧化物0.50％～0.54％、偶联剂0.63％～0.67％、余量为溶剂75.75％～80.56％。
2.根据权利要求1所述的聚磷腈橡胶与金属粘接用底涂胶，其特征在于，质量百分组成为：聚磷腈橡胶6.32％、氯丁橡胶3.16％、氯磺化聚乙烯3.16％、甲阶酚醛树脂5.05％、E51环氧树脂0.63％、气相法白炭1.58％、N330炭黑3.13％、过氧化二异丙苯0.03％、硫磺0.06％、氧化镁0.3％、氧化锌0.2％、γ-氨丙基三乙氧基硅烷0.63％、二甲苯60.6％、甲基异丁基酮15.15％。
3.根据权利要求1所述的聚磷腈橡胶与金属粘接用底涂胶，其特征在于，质量百分组成为：聚磷腈橡胶5.12％、氯磺化聚乙烯6.39％、甲阶酚醛树脂5.12％、E51环氧树脂0.65％、气相法白炭黑1.59％、N330炭黑3.17％、过氧化二异丙苯0.03％、硫磺0.06％、氧化镁0.51％、γ-氨丙基三乙氧基硅烷0.64％、二甲苯61.37％和甲基异丁基酮15.35％。
4.根据权利要求1所述的聚磷腈橡胶与金属粘接用底涂胶，其特征在于，质量百分组成为：聚磷腈橡胶5.32％、氯丙橡胶2.25％、氯丁橡胶3.27％、甲阶酚醛树脂2.66％、E51环氧树脂0.66％、气相法白炭黑1.66％、N330炭黑3.29％、过氧化二异丙苯0.03％、硫磺0.06％、氧化镁0.25％、氧化锌0.25％、γ-3-缩水甘油醚氧基丙基三甲氧基硅烷0.66％、二甲苯63.72％和乙醇15.92％。
5.根据权利要求1所述的聚磷腈橡胶与金属粘接用底涂胶，其特征在于，质量百分组成为：聚磷腈橡胶5.38％、氯丙橡胶2.68％、氯磺化聚乙烯2.69％、甲阶酚醛树脂2.68％、E51环氧树脂0.67％、气相法白炭黑2.68％、N330炭黑1.35％、过氧化二异丙苯0.03％、硫磺0.06％、氧化锌0.54％、γ-3-缩水甘油醚氧基丙基三甲氧基硅烷0.67％、二甲苯64.45％和乙醇16.12％。
6.根据权利要求1所述的聚磷腈橡胶与金属粘接用底涂胶，其特征在于，质量百分组成为：聚磷腈橡胶6.47％、氯化天然橡胶5.16％、甲阶酚醛树脂5.16％、E51环氧树脂0.65％、气相法白炭黑1.29％、N330炭黑2.58％、过氧化二异丙苯0.03％、硫磺0.06％、氧化锌0.52％、γ-氨丙基三乙氧基硅烷0.64％、二甲苯61.95％和乙醇15.49％。
7.根据权利要求1所述的聚磷腈橡胶与金属粘接用底涂胶，其特征在于，质量百分组成为：聚磷腈橡胶6.37％、氯化天然橡胶2.12％、氯磺化聚乙烯4.24％、甲阶酚醛树脂5.09％、E51环氧树脂0.65％、气相法白炭黑1.27％、N330炭黑2.55％、过氧化二异丙苯0.03％、硫磺0.06％、氧化镁0.51％、γ-甲基丙烯酰氧基丙基三甲氧基硅烷0.64％、二甲苯61.18％和乙醇15.29％。
8.权利要求1-7任一所述的聚磷腈橡胶与金属粘接用底涂胶的制备方法，其特征在于，该方法的步骤包括：
(1)首先将基体橡胶与氯化橡胶按比例混合，在50～60℃密炼60～80min；
(2)将密炼好的橡胶混合物取出，按照质量百分数配比依次加入补强填料、交联剂和金属氧化物，制备得到混炼胶；
(3)在制备好的混炼胶中按比例加入增粘树脂、偶联剂和溶剂，搅拌后得到混合胶液；
(4)将制备好的混合胶液研磨2～3h，得到底涂胶液。
9.一种双涂型胶粘剂，包括面涂胶和底涂胶，其特征在于，所述的底涂胶为权利要求1-7任一所述的聚磷腈橡胶与金属粘接用底涂胶。
10.权利要求9所述的双涂型胶粘剂用于粘接聚磷腈橡胶与金属的应用，聚磷腈橡胶与金属粘接的制备包括以下步骤：
(1)将金属片表面进行喷砂处理，洗净晾干；
(2)在晾干的金属表面涂覆所述的底涂胶，并在40℃下烘置40～50min；
(3)在(2)中的已涂覆底涂胶的金属表面再涂覆面涂胶，并在40℃下烘置40～50min；
(4)将(3)中的金属片与聚磷腈混炼胶贴合，然后放入硫化模具中，硫化成型温度为150～165℃，硫化压力为10～12MPa，硫化时间为40～60min，进行粘接件的热硫化成型。
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