CN110527051B - 一种高强度gap共混物 - Google Patents

一种高强度gap共混物 Download PDF

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CN110527051B
CN110527051B CN201910801653.2A CN201910801653A CN110527051B CN 110527051 B CN110527051 B CN 110527051B CN 201910801653 A CN201910801653 A CN 201910801653A CN 110527051 B CN110527051 B CN 110527051B
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gap
blend
hydroxyl
curing
htpe
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陈春燕
余然
倪冰
牛余雷
席鹏
王浩
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Xian Modern Chemistry Research Institute
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/482—Mixtures of polyethers containing at least one polyether containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen

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Abstract

本发明公开了一种高强度GAP共混物，是为了解决现有GAP力学性能差，现有共混物与炸药常用增塑剂物理不相容的问题。本发明由GAP与端羟基聚醚共混，N‑100做固化剂，三苯基铋做催化剂。本发明的拉伸强度比纯GAP拉伸强度提高30％，延伸率提高61％。

Description

一种高强度GAP共混物
技术领域
本发明涉及一种高强度GAP/HTPE共混物，主要用于浇注PBX的粘结剂。
背景技术
端羟基叠氮聚醚(GAP)具有能量密度高、安全性好、环境友好、低特征信号等优点，但由于其力学性能差，在浇注PBX中应用时，形成的药柱手捏可碎，无法经受运输、储存及勤务过程外载的作用。共混是聚合物改性中非常常用和有效的方法之一，为了改善GAP粘合剂的力学性能，李平等人采用PET与GAP共混，研究表明此共混物具有纯GAP与纯PET无法比拟的优越性能,拉伸强度显著提高,延伸率较高；尤其在二者重量比率相近(摩尔数相同)时,强度和延伸率均达到最大：倪冰等人采用HTPB和GAP的共混，以异佛尔酮二异氰酸酯(IPDI)为固化剂，三羟甲基丙烷(TMP)为交联剂，1，4-丁二醇(BDO)为扩链剂，二月桂酸二丁基锡(DBTDL)为催化剂，实现了GAP力学性能的提高。但是GAP/PET、GAP/HTPB共混物在炸药中使用时粘度较大，而GAP/PET、GAP/HTPB共混物与炸药常用增塑剂DOA、DOS和三醋精物理不相容，所以上述共混物目前无法在浇注PBX中得到应用。
GAP在浇注PBX中应用的关键是改善GAP的力学性能，且形成的共混物与市面上的增塑剂物理相容性良好，GAP共混物和增塑剂需与含能晶体、AL粉的化学相容性良好。
发明内容
本发明所要解决的技术问题是要满足背景技术中的需求，本发明采用端羟基聚醚(HTPE)与GAP共混，改善了GAP的力学性能，达到了GAP在炸药中的应用要求。
本发明提供的GAP共混物，质量百分组成如下：50-57％GAP、40-46％HTPE、3-4％N-100，0.02％TPB。其中HTPE分子量是4231g/mol，羟值是26.45mgKOH/g，GAP分子量是2770g/mol，羟值是71.8mgKOH/g。其固化工艺是：40℃固化3天，60℃固化4天成型。
本发明配方中以端羟基聚醚(HTPE)与GAP共混，HTPE是一种分子结构中含有醚键的端羟基聚合物，具有良好的力学性能，HTPE与GAP都可以与氰酸酯类固化剂反应，且GAP与HTPE都与三醋精物理相容性良好。固化工艺采用低温固化与高温固化相结合的形式，实现了固化物固化应力小，力学强度大的特性。
本发明的有益效果：
1.采用端羟基聚醚与GAP共混，拉伸强度比纯GAP提高30％，延伸率比纯GAP提高61％
2.端羟基聚醚与GAP共混物与增塑剂三醋精物理相容性良好；
3.此共混物与AL粉、RDX、HMX的化学相容性良好
4.此共混物组分都可以与氰酸酯类固化剂反应，固化剂选择简单。
具体实施方式
下面结合具体实施例对本发明做进一步说明。
实施例中，GAP的分子量是2770g/mol，羟值是71.8mgKOH/g。HTPE的分子量是4231g/mol，羟值是26.45mgKOH/g。
实施例1
本发明参照如下质量百分组成实施：55.51％GAP、41.00％HTPE、3.49％固化剂N-100，0.02％催化剂TPB。
制备方法：
(1)原材料预处理
称取55.51gGAP和41.00gHTPE加入捏合锅内，60℃抽真空混合2h。
(2)胶液混合
称取3.49g固化剂N-100加入胶液中真空混合30min。称取0.02gTPB加入捏合锅中，抽真空混合搅拌15min。
(3)测试样制备
将胶液倒入聚四氟乙烯模具，40℃固化3天，60℃固化4天成型。
实施例2
本发明参照如下质量百分组成实施：57.00％GAP、40.00％HTPE、3.00％固化剂N-100，0.02％催化剂TPB。
制备方法：
(1)原材料预处理
称取57.00gGAP和40.00gHTPE加入捏合锅内，60℃抽真空混合2h。
(2)胶液混合
称取3.00g固化剂N-100加入胶液中真空混合30min。称取0.02gTPB加入捏合锅中，抽真空混合搅拌15min。
(3)测试样制备
将胶液倒入聚四氟乙烯模具，40℃固化3天，60℃固化4天成型。
实施例3
本发明参照如下质量百分组成实施：50.00％GAP、46.00％HTPE、4.00％固化剂N-100，0.02％催化剂TPB。
制备方法：
(1)原材料预处理
称取50.00gGAP和46.00gHTPE加入捏合锅内，60℃抽真空混合2h。
(2)胶液混合
称取4.00g固化剂N-100加入胶液中真空混合30min。称取0.02gTPB加入捏合锅中，抽真空混合搅拌15min。
(3)测试样制备
将胶液倒入聚四氟乙烯模具，40℃固化3天，60℃固化4天成型。
将固化完后的弹性体胶片制成标准哑铃型，采用Instron-4505型材料试验机测试试样的拉伸强度和延伸率，方法依据GJB770B-2005，拉伸速率500mm/min，测试温度为233.0K，293.0K，323.K；
摩擦感度测试依据GJB772A-1997方法602.1；
撞击感度测试依据GJB772A-1997方法601.1；
相容性测试依据GJB772A-97方法501.2；
表1性能测试数据
Figure BDA0002182483450000041
表2与常用材料的相容性
样品名称 样品量 试验温度 试验时间 净放气量 评价
实施例1/AL粉 0.5g/0.5g 100℃ 40h 0.1ml 相容
实施例1/RDX 0.5g/0.5g 100℃ 40h 0.1ml 相容
实施例1/HMX 0.5g/0.5g 100℃ 40h 0.08ml 相容
实施例1/铜 0.5g/0.5g 100℃ 40h 0.05ml 相容
实施例1/钢 0.5g/0.5g 100℃ 40h 0.04ml 相容
实施例2/AL粉 0.5g/0.5g 100℃ 40h 0.08ml 相容
实施例2/RDX 0.5g/0.5g 100℃ 40h 0.06ml 相容
实施例2/HMX 0.5g/0.5g 100℃ 40h 0.1ml 相容
实施例2/铜 0.5g/0.5g 100℃ 40h 0.04ml 相容
实施例2/钢 0.5g/0.5g 100℃ 40h 0.05ml 相容
表3材料的溶度参数
实施例 HTPE GAP 三醋精
溶度参数 20.48 20.95 19.54

Claims (1)

1.一种高强度GAP共混物，其特征在于，各组分按质量份组成为：50-57份端羟基叠氮聚醚GAP、40-46份端羟基聚醚HTPE、3-4份多异氰酸酯N-100，0.02份三苯基铋TPB；所述的端羟基聚醚HTPE分子量为4231g/mol，羟值为26.45mgKOH/g，GAP分子量为2770g/mol，羟值为71.8mgKOH/g，所述高强度GAP共混物固化工艺是：40℃固化3天，60℃固化4天成型。
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