CN116751439B - 一种环氧树脂及其生产方法及环氧树脂半固化片 - Google Patents
一种环氧树脂及其生产方法及环氧树脂半固化片 Download PDFInfo
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Abstract
本发明公开一种环氧树脂及其生产方法及环氧树脂半固化片,方法为:S1、贴附层环氧树脂制备:将双酚A型环氧树脂、苯氧基树脂混合后研磨得到第一研磨料,将异氰酸酯改性环氧树脂、第一固化剂和第一促进剂研磨得到第二研磨料;将第一研磨料和第二研磨料投加入反应装置反应后制备得到;S2、表层环氧树脂的制备:将双酚A型环氧树脂、酚醛环氧树脂、第二固化剂和第二促进剂混合后反应后制备得到。本发明特定玻璃纤维布结构并分别配制不同性能环氧树脂配合,采用粘性大、粘结强度高的环氧树脂定型基材,在贴附层之上设置流动性好、固化速度快、硬度高的环氧树脂,使所制半固化片强度高且不易翘曲,固化时间短且具有较低固化温度,产品品质提升同时生产成本降低。
Description
技术领域
本发明涉及环氧树脂半固化片技术领域,尤其涉及一种环氧树脂及其生产方法及环氧树脂半固化片。
背景技术
基于环氧树脂预浸料形成的复合材料正在成为交通、航空航天、电子等领域应用越来越广泛的新型材料,基于这类新型材料的研究也有很多,尤其基于环氧树脂改性进行的研究,目前这类材料在在材料、工艺上均存在一些需要解决的问题,例如这类复合材料通过高温固化和中温固化工艺中普避存在生产效率低,次品率高的问题,导致这类固化片生产成本居高不下,包括环氧树脂流动性和粘性无法均衡导致所生产的板材已出现空泡、翘曲等问题,以及为提升所加工板材整体强度需要添加更多玻璃纤维导致的成本上升等问题。
发明内容
本发明的目的是为了解决现有技术中存在的缺点,而提出的一种环氧树脂及其生产方法及环氧树脂半固化片。
为了实现上述目的,本发明采用了如下技术方案:
一种环氧树脂的生产方法,其中,所生产环氧树脂用于基于的基材的复合材料上,其生产方法如下:
S1、贴附层环氧树脂的制备:首先将双酚A型环氧树脂、苯氧基树脂混合后研磨得到第一研磨料,将异氰酸酯改性环氧树脂、第一固化剂和第一促进剂进行研磨得到第二研磨料;将第一研磨料和第二研磨料投加入反应装置反应后制备得到;
S2、表层环氧树脂的制备:将双酚A型环氧树脂、酚醛环氧树脂、第二固化剂和第二促进剂混合后反应后制备得到。
所述的环氧树脂的生产方法,其中,所述双酚A型环氧树脂和苯氧基树脂的添加质量比为20:3-5。
所述的环氧树脂的生产方法,其中,所述步骤S1中双酚A型环氧树脂的环氧值为0.7-0.9,所述步骤S2中双酚A型环氧树脂的环氧值为0.3-0.5。
所述的环氧树脂的生产方法,其中,第一固化剂和第二固化剂均为双氰胺类固化剂,其中,第一固化剂中含有4,4-二氨基二苯砜,4,4-二氨基二苯砜与双氰胺的质量比为1-2:20,第二固化剂中含有4,4-二氨基二苯砜,4,4-二氨基二苯砜与双氰胺的质量比为0.2-1:20。
所述的环氧树脂的生产方法,其中,第一促进剂为改性脲促进剂,第二促进剂为甲基咪唑促进剂。
所述的环氧树脂的生产方法,其中,所述双酚A型环氧树脂和酚醛环氧树脂的添加质量比为1:1。
一种环氧树脂,其中,包括贴附层环氧树脂和表层环氧树脂,其采用如上所述方法制备得到。
一种环氧树脂半固化片,其中,包括基材和设置于基材上下表面的环氧树脂,所述基材一向内凹陷形成凹坑,对应该表面的反面上对应凹坑位置凸出形成鼓包,所述凹坑鼓包呈阵列分布于基材表面,所述凹坑内设置有如上所述的贴附层环氧树脂,位于贴附层环氧树脂之上设置有如上所述的表层环氧树脂。
所述环氧树脂半固化片,其中,所述基材为玻璃纤维布,该玻璃纤维布由玻璃纤维和树脂纤维作为经纬线经纬编织而成。
所述环氧树脂半固化片,其中,所述基材的一表面上同时具有凹坑和鼓包, 凹坑和鼓包间隔设置,其中位于凹坑中的贴附层环氧树脂的厚度小于鼓包的高度。
有益效果:
基于原有多层板强度不高,易万弯曲的问题,本发明通过改变并定型玻璃纤维布层结构,玻璃纤维布层结构强度的提升使得以其作为基层的多层板的强度得到提升,本发明的凹坑鼓包结构的玻璃纤维布层能够最大限度的提升多层板横向和纵向承载力,避免多层板变形或扭曲,另外分别配制不同性质的环氧树脂配合玻璃纤维布层的结构,贴合玻璃纤维布采用粘性大、粘结固化强度高的环氧树脂配方来定型基材结构,并由于基材新型结构又进一步提升其与贴附层环氧树层的连接强度,同时在贴附层环氧树脂之上设置流动性好、固化速度快、硬度高的表面环氧树脂,该层环氧树脂中可通过添加填料提供特定性能满足需求,且由于两层树脂层的设置,表层与贴附层的粘结更牢,使得基材上环氧树脂不必使用胶膜,简化了工艺,并消除了表层出现脱层鼓包等问题,提升了产品品质,贴附层高稳定性能够确保基材和整个多层板性能稳定,同时高硬度的表层的包裹效果又能赋予多层板整体高硬度性特性。
附图说明
图1为本发明具体实施例中环氧树脂的生产方法流程图;
图2为本发明具体实施例中环氧树脂半固化片的结构示意图;
图3为本发明另一具体实施例中环氧树脂半固化片的结构示意图;
图4为本发明另一具体实施例中环氧树脂半固化片中基材的编织示意图;
图5为本发明具体实施例中复合纤维的断面示意图。
附图标记:100:基材,110:凹坑,120:鼓包,101:经线,102:纬线,200:贴附层环氧树脂,300:表层环氧树脂,400:中心纤维,500:玻璃纤维,600:树脂纤维。
具体实施方式
下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
如图1所示的一种环氧树脂的生产方法,其中,所生产环氧树脂用于基于的基材的复合材料上,其生产方法如下:
S1、贴附层环氧树脂的制备:首先将双酚A型环氧树脂、苯氧基树脂混合后研磨得到第一研磨料,将异氰酸酯改性环氧树脂、第一固化剂和第一促进剂进行研磨得到第二研磨料;将第一研磨料和第二研磨料投加入反应装置反应后制备得到。
本发明的环氧树脂基于复合材料多层板开发,现有玻璃纤维布上浸润环氧树脂的产品普遍存在硬度低,层间连接强度不高,多层板易变形翘曲鼓包等问题,本发明环氧树脂以及新型的基材结构能够解决这些问题,首先在基材表面浸润贴附层环氧树脂,该环氧树脂通过步骤S1制备得到,具体的,首先将双酚A型环氧树脂、苯氧基树脂混合后研磨得到第一研磨料。贴附层环氧树脂层上再设置表层环氧树脂层,所述表层环氧树脂层通过步骤S2制备,
步骤S2、表层环氧树脂的制备:将双酚A型环氧树脂、酚醛环氧树脂、第二固化剂和第二促进剂混合后反应后制备得到。
贴附层和表层环氧树脂均采用双酚A型环氧树脂作为基料,但基于各自的性能需求,分别匹配不同组分使其具备不同性能,贴附层中,双酚A型环氧树脂、苯氧基树脂混合研磨后为第一研磨料,而表层中,双酚A型环氧树脂、酚醛环氧树脂混合,苯氧基树脂配合双酚A型环氧树脂使得贴附层环氧树脂具备更高粘性和强韧性,对基材的连接将更牢固,贴附层作为连接层为基材和表层的连接提供更强的连接,同时其作为中间层能够为多层板提供足够的韧性。优选的,苯氧基树脂采用平均分子量为60000的苯氧基树脂。
具体的,所述双酚A型环氧树脂和苯氧基树脂的添加质量比为20:4。在此添加比例下,能够确保贴附层环氧树脂具备最佳的粘度和合理的流动性能,能够有效填充基材上的凹坑,并充分浸润后,能够与基材形成高强度的粘结。优选实施例中,所述双酚A型环氧树脂和苯氧基树脂的添加质量比为5:1。
进一步的,将异氰酸酯改性环氧树脂、第一固化剂和第一促进剂进行研磨得到第二研磨料。优选实例中,所述第一固化剂为双氰胺类固化剂,第一促进为改性脲促进剂,异氰酸酯改性环氧树脂能够提升树脂耐热性能之外,能进一步提升贴附层树脂的结合力性能,双氰胺和改性脲使用有利于提高固化剂与环氧树脂的相容性,加强固化剂和树脂之间的反应连接,增强环氧树脂与基材之间连接。优选实施例中,异氰酸酯改性环氧树脂、第一固化剂和第一促进剂的添加比例为16:5:1。优选实施例中,异氰酸酯改性环氧树脂和苯氧基树脂的添加总量等于双酚A型环氧树脂的添加量。
贴附层生产过程中通过第一研磨料和第二研磨料的设置能够减小固化时间,同时通过检测还反映出这种制备步骤提升了贴附层环氧树脂的性能,粘结强度等性能有相对明显的提升。发明人分析该研磨过程实现了物料的充分混匀,改善了原有各物料分布不均影响固化效果以及树脂性能的问题,能够加快固化过程,为此,第一研磨料和第二研磨料的研磨粒径需达到D98≤10μm ,由于研磨过程中涉及多种形态物料混合,常规研磨设备无法实现不同物料同一研磨粒径的要求,则采用在混合原料中添加研磨物料的形式,为实现最终各原料研磨粒径能够达标,则需对研磨过程中各物料配比进行设定,第一研磨料准备过程中,双酚A型环氧树脂、苯氧基树脂和研磨物料的添加质量比为20:4:24。在此比例下能够达到最终各物料粒径研磨要求,研磨物料过多和多少都会造成物料研磨不到位或粒径大小不一的问题。
同理,第二研磨料准备中,异氰酸酯改性环氧树脂、第一固化剂、第一促进剂和研磨物料的添加质量比为16:5:1:22。在此比例下能够达到最终各物料粒径研磨要求。
进一步的,步骤S2中,双酚A型环氧树脂和酚醛环氧树脂组合,优选的,所述双酚A型环氧树脂和酚醛环氧树脂的添加质量比为1:1。酚醛环氧树脂能够提升表层环氧树脂层的硬度,使得表层环氧树脂的硬度高于贴附层,能够维持表层性能稳定,上述优选比例下,能够使得表层环氧树脂浸润料具有高流动性和高硬度的特点。高流动性能够加快表层加工时间,并且表层对于内部的浸润更充分,结合更充分,封闭效果更好。
进一步的,所述第二固化剂均为双氰胺类固化剂,第二促进剂为甲基咪唑促进剂,为提升表层流动性和缩短固化时间,优选采用双氰胺作为固化剂以及采用甲基咪唑促进剂,其有利于使环氧分子更容易与贴附层表面的游离键发生化学反应而交联,提高两者间连接强度。
优选实施例中,所述步骤S1中双酚A型环氧树脂的环氧值为0.8,所述步骤S2中双酚A型环氧树脂的环氧值为0.4。两种不同环氧值的双酚A型环氧树脂是由于贴附层和表层不同的性能需求,表层环氧树脂需要形成更强的反应活性以实现对基材和表层的结合,提供足够的韧性,因此,双酚A型环氧树脂的环氧值为0.8,这样其能够与苯氧基树脂、异氰酸酯改性环氧树脂一起固化剂和促进剂作用下充分反应,而表层环氧树脂则反应活性相对低,配合酚醛树脂形成硬度较高的表层环氧树脂,其也能使得表层具有更稳定的理化性能。
优选的,第一固化剂中含有4,4-二氨基二苯砜,4,4-二氨基二苯砜与双氰胺的质量比为1:20,第二固化剂中含有4,4-二氨基二苯砜,4,4-二氨基二苯砜与双氰胺的质量比为0.5:20。在固化剂中加入二氨基二苯砜有利于提高固化剂与环氧树脂的相容性,增强树脂基体与固化剂之间的结合作用,从而进一步降低固化温度,缩短固化时间。贴附层和表层不同固化剂的设置是基于其不同的需求设置, 4,4-二氨基二苯砜与双氰胺为1:20的比例能够确保贴附层具备更强的结合力,有利于其与基材和表层加强结合,4,4-二氨基二苯砜与双氰胺的质量比为0.5:20的设置已经能够满足表层结合需求,同时还能平衡表层高硬度要求。
进一步的,第一促进剂为改性脲促进剂,第二促进剂为甲基咪唑促进剂。促进剂能够促进固化剂所引起的固化反应,其中,贴附层采用改性促进剂是除促进固化反应外,还有进一步提升贴附层环氧树脂韧性的作用。而表层采用甲基咪唑促进剂能够提升固化后环氧树脂层耐久性。
进一步的,在步骤S1和S2中在制备环氧树脂过程中还需要投加水洗料,用以去除氯离子,优选的是,在步骤S1和S2中投加的水洗料均为户内聚酯树脂,在步骤S1水洗次为4次,每次投加0.3公斤,总共投加1.2公斤,产出1.5吨成品料,在步骤S2水洗次为4次,每次投加0.5公斤,总共投加2公斤,产出1.5吨成品料。该水洗料为针对本方案中环氧树脂制备专门研制,该水洗料能够明显减少水洗次数,同时又能不产生副产物,避免环氧树脂掺杂。
本发明提供一种环氧树脂,其中,包括贴附层环氧树脂和表层环氧树脂,其采用如上所述方法制备得到。
本发明还提供一种环氧树脂半固化片,如图2所示,其包括基材100和设置于基材上下表面的环氧树脂,所述基材一向内凹陷形成凹坑110,对应该表面的反面上对应凹坑位置凸出形成鼓包,所述凹坑鼓包呈阵列分布于基材表面,所述凹坑内设置有如上所述的贴附层环氧树脂200,位于贴附层环氧树脂之上设置有如上所述的表层环氧树脂300。具体实施例中,所述基材结构如图2所示,贴附层环氧树脂不仅完全覆盖凹坑,同时也“没过”鼓包,贴附层环氧树脂与表层环氧树脂为平面接触,基材上凹坑和鼓包设计增大了基材与贴附层的接触面,从而提升两者的结合强度,从而避免多层板变形和翘曲问题,优选的,所述基材两表面分别具有凹坑和鼓包,即所述基材的一表面上同时具有凹坑和鼓包, 凹坑和鼓包间隔设置。基材这一特定形状可通过模压形式形成。分布凹坑和鼓包的基材其整体结构强度和抗扭曲能力得到提升。优选的是,所述凹坑和鼓包密度及其大小与基材厚度有关,基材越厚,凹坑和鼓包密度越小,且凹坑和鼓包本身越大,基材越薄,凹坑和鼓包密度越大,且凹坑和鼓包本身越小,这一相适应原则能够确保基材通过凹坑和鼓包提供最佳的结构强度和抗扭曲力。另一优选实施例中,如图3所示,所述贴附层环氧树脂填充凹坑但未没过鼓包,则表层环氧树脂与鼓包顶部接触,此种加工时候加工难度相对大,但各层间结合力度更大,更稳定,且能通过基材将多层板热量传导至各层,通过各层实现热量传导,避免环氧树脂层间热量传导对环氧树脂层的热损伤和老化,从而使得多层板耐热性能提升。
进一步的,所述基材为玻璃纤维布,采用目前市面上常见产品即可,优选的,所述玻璃纤维布由玻璃纤维和树脂纤维作为经纬线经纬编织而成。玻璃纤维提供支撑强度,而树脂纤维能够与贴附层具有更好的结合力,进一步的提升玻璃纤维层和贴附层环氧树脂间的结合力。
优选实施例中,如图4所示,构成基材的玻璃纤维布中,对应鼓包120位置的基材部分由经线101、纬线102以及斜穿插线103编织而成,非凹坑和鼓包部分则不含有斜穿插线,凹坑和鼓包位置经过模压后,该部分纤维之间间隙变大,为提供更好的结构强度,设置斜穿插线能够提升鼓包和凹坑成型后的结构强度,避免变形,优选的,所述斜穿插线可以设置为多根,该多根斜穿插线呈交叉辐射状态交汇于凹坑或鼓包中心,斜穿插线避免了基材模压变形后由于出现疏密不同导致的结构强度分布不均,从而影响后续整体板材强度,斜穿插线的设置也能够进一步提升凹坑和鼓包部分与环氧树脂层的连接强度,优选的,所述斜穿插线为树脂材质线,且其由与贴附层树脂相同或相近的原料制得,在贴附层浸润过程中,其与贴附层同质充分结合,大大提升该部分与贴附层环氧树脂的结合强度,同时由于斜穿插线为单独设置,其并不影响也不破坏玻璃纤维布原有的结构。
优选实施例中,所述基材由复合纤维布构成,所述复合纤维布由树脂纤维与玻璃纤维构成的混纺丝织造而成,具体的,所述混纺丝单位长度中的树脂纤维与玻璃纤维重量用量比为1:1,按照1:1配比的混纺丝能够使得纤维具备较好的结构强度和韧性,同时加入的树脂纤维能够使得最终形成的基材与贴附层具有优异的连接强度,进一步的减小翘曲的可能性,优选实施例中,所述混纺丝采用如图5所示结构,混纺丝由中心纤维400和环绕中心纤维400绞股形成复合纤维的外围纤维,优选的,所述外围纤维包括玻璃纤维500和树脂纤维600,所述玻璃纤维和树脂纤维分别设置为3根,并相间隔设置环绕中心纤维绞股而成,所述中心纤维优选为玻璃纤维,图5所示的复合纤维能够通过玻璃纤维和树脂纤维的复合使得复合纤维本身具备较好的结构强度,同时利用复合纤维编织的基材能够与贴附层中环氧树脂有良好的融合粘结,提升连接强度。由于混纺丝中有3条树脂纤维,并呈绞股形成,这样能够确保基材与贴附层对应面上,必然有树脂纤维能够与贴附层接触,这样就能够确保融合连接,提升层间连接强度。
本发明基于原有多层板强度不高,易万弯曲的问题,通过改变并定型玻璃纤维布层结构,玻璃纤维布层结构强度的提升使得以其作为基层的多层板的强度得到提升,本发明的凹坑鼓包结构的玻璃纤维布层能够最大限度的提升多层板横向和纵向承载力,避免多层板变形或扭曲,另外分别配制不同性质的环氧树脂配合玻璃纤维布层的结构,贴合玻璃纤维布采用粘性大、粘结固化强度高的环氧树脂配方来定型基材结构,并由于基材新型结构又进一步提升其与贴附层环氧树层的连接强度,同时在贴附层环氧树脂之上设置流动性好、固化速度快、硬度高的表面环氧树脂,该层环氧树脂中可通过添加填料提供特定性能满足需求,且由于两层树脂层的设置,表层与贴附层的粘结更牢,使得基材上环氧树脂不必使用胶膜,简化了工艺,并消除了表层出现脱层鼓包等问题,提升了产品品质,贴附层高稳定性能够确保基材和整个多层板性能稳定,同时高硬度的表层的包裹效果又能赋予多层板整体高硬度性特性。
最后应说明的是:以上所述仅为本发明的优选实施例而已,并不用于限制本发明,尽管参照前述实施例对本发明进行了详细的说明,对于本领域的技术人员来说,其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (1)
1.一种环氧树脂半固化片,其特征在于,包括基材和设置于基材上下表面的环氧树脂,所述基材一向内凹陷形成凹坑,对应该表面的反面上对应凹坑位置凸出形成鼓包,所述凹坑鼓包呈阵列分布于基材表面,所述凹坑内设置有如下所述的贴附层环氧树脂,位于贴附层环氧树脂之上设置有如下所述的表层环氧树脂;
所述基材为玻璃纤维布,该玻璃纤维布由玻璃纤维和树脂纤维作为经纬线经纬编织而成;
所述基材的一表面上同时具有凹坑和鼓包, 凹坑和鼓包间隔设置,其中位于凹坑中的贴附层环氧树脂的厚度小于鼓包的高度;
一种环氧树脂的生产方法,所生产环氧树脂用于基于的基材的复合材料上,其生产方法如下:
S1、贴附层环氧树脂的制备:首先将双酚A型环氧树脂、苯氧基树脂混合后研磨得到第一研磨料,将异氰酸酯改性环氧树脂、第一固化剂和第一促进剂进行研磨得到第二研磨料;将第一研磨料和第二研磨料投加入反应装置反应后制备得到;
S2、表层环氧树脂的制备:将双酚A型环氧树脂、酚醛环氧树脂、第二固化剂和第二促进剂混合后反应后制备得到;
所述步骤S1中双酚A型环氧树脂的环氧值为0.7-0.9,所述步骤S2中双酚A型环氧树脂的环氧值为0.3-0.5;
第一固化剂和第二固化剂均为双氰胺类固化剂,其中,第一固化剂中含有4,4-二氨基二苯砜,4,4-二氨基二苯砜与双氰胺的质量比为1-2:20,第二固化剂中含有4,4-二氨基二苯砜,4,4-二氨基二苯砜与双氰胺的质量比为0.2-1:20;
所述双酚A型环氧树脂和苯氧基树脂的添加质量比为20:3-5;
第一促进剂为改性脲促进剂,第二促进剂为甲基咪唑促进剂;
所述双酚A型环氧树脂和酚醛环氧树脂的添加质量比为1:1。
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