CN105906785B - 含有膦酸根和次膦酸根官能团的环氧树脂阻燃剂 - Google Patents
含有膦酸根和次膦酸根官能团的环氧树脂阻燃剂 Download PDFInfo
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- CN105906785B CN105906785B CN201610081515.8A CN201610081515A CN105906785B CN 105906785 B CN105906785 B CN 105906785B CN 201610081515 A CN201610081515 A CN 201610081515A CN 105906785 B CN105906785 B CN 105906785B
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Classifications
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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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/08—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the cooling method
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
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Abstract
本发明提供了一种用于固化热固性树脂例如环氧树脂的固化剂化合物,一种包含热塑性和/或热固性树脂例如环氧树脂和所述固化剂的组合物,一种包含所述固化剂的制品,以及一种制备所述固化剂的方法等。该化合物具有通式(I)的结构;其中每个R独立地选自H;‑OH;含有1至约8个碳原子的烷基等。本发明的不含卤素的固化剂的化合物所固化后的环氧树脂可用于电子应用,同时维持低介电常数和低吸湿性以及高玻璃化转变温度(Tg)。
Description
技术领域
本发明涉及阻燃剂领域,更具体地涉及用于诸如印刷线路板的电子应用的含磷阻燃剂领域。
背景技术
合成树脂由于其突出的耐化学性、机械强度及电学性质而被广泛地用于工业及消费品电子业中。例如,合成树脂可在电子业中用作保护膜、胶粘剂材料和/或绝缘材料,诸如内层绝缘膜。为了可用于这些用途,合成树脂需要提供方便的操作性和某些必要的物理、热学、电绝缘以及抗湿性质。例如,具有低绝缘常数和低吸湿性以及高玻璃化转变温度(Tg)的合成树脂可以是电子应用期望的性质组合。
然而,合成树脂可能是易燃的。由此,已经采取了不同的方法赋予合成树脂(例如,环氧树脂)所需程度的阻燃性,其中此类方法采用不含卤素的阻燃剂化合物或含卤素的阻燃剂化合物。然而,卤化化合物现在正在接受额外的审查,并且可用的各种非卤化化合物不能为合成树脂提供所需程度的阻燃性。期望为诸如环氧树脂的合成树脂提供所需程度的阻燃性,同时仍维持适于电子应用的性质组合。
发明内容
因此,本发明的特征是提供可用作热固性树脂(例如,环氧树脂)的不含卤素的固化剂的化合物,固化后的环氧树脂可用于电子应用,同时维持低介电常数和低吸湿性以及高玻璃化转变温度(Tg)。
在本文将理解的是,在一个非限制性实施方案中,表述“环氧树脂的不含卤素的固化剂”可与“环氧树脂的不含卤素的固化剂”、“环氧化物固化剂”、“用作环氧化物的固化剂”、“环氧树脂固化剂”和“固化剂”等互换使用。
本文在一个实施方案中提供具有通式(I)的化合物:
其中每个R独立地选自H;-OH;含有1至约8个碳原子的烷基;其中R*为含有1至8个碳原子的烷基基团或为取代或未取代的苯基;
式(II)的次膦酸根部分:
其中R1为1至3个碳原子的二价直链或支链亚烷基部分,而虚线表示与以上式(I)的结构结合的键;
通式(III)的膦酸根部分:
以及
通式(IV)的取代的芳基部分:
其中R2为1至4个碳原子的二价直链或支链亚烷基部分,而虚线表示与以上式(I)的结构结合的键,并且R3的定义与R相同,但R3不能是通式(IV)的取代的芳基部分而至少一个R3为式(II)的基团;
并且前提条件是式(I)中具有式(II)的R基团的数量为1或2,式(I)中具有式(III)的R基团的数量为1或2,同时前提条件是式(I)的所有R基团都不具有式(IV)或式(I)的仅一个R基团具有式(IV),
另外前提条件是当式(I)的所有R基团都不具有式(IV)时,则具有式(II)和(III)的R基团的总数最多可以为4,并且如果式(I)的R基团之一具有式(IV),则具有式(II)、(III)和(IV)的R基团的总数最多为4。
在本文将理解的是,如本文所述的式(I)的化合物可用作用于固化如本文所述的热固性树脂(例如,环氧树脂)的固化剂,或在另一个实施方案中用作热塑性树脂组合物和/或配方的(反应性阻燃剂)阻燃添加剂。
附图说明
图1是使用合成实施例1的化合物1在10℃/min下产生的DSC曲线图,所述化合物用在如层压体实施例2中所述的层压体中。
图2是使用层压体实施例2的层压体在连续受控应变和法向力条件下在流变仪中处于5℃/min升温速率(实心圆)的B阶段预浸料坯的动态粘度(空心圆)分布曲线图。
图3是曲线图,展示了在层压体实施例2中制备的层压体的玻璃化转变温度(Tg)的动态力学分析(DMA)测量(3℃/min)。
图4显示了使用分子(V)化合物1的固化环氧化物(DEN438和EPON164)和苯酚酚醛清漆SD1708的TGA曲线图。
具体实施方式
本发明涉及可用作热固性树脂(例如,环氧树脂)的不含卤素的固化剂的化合物,固化的环氧树脂可用于需要阻燃剂的任何商业或工业环氧化物应用,诸如电子应用的非限制性实例,同时维持低介电常数和低吸湿性以及高玻璃化转变温度(Tg)。在本文中有利的是,用作热固性树脂(例如,环氧树脂)的不含卤素的固化剂的化合物在与环氧树脂反应时,产物不存在羟基基团,诸如仲羟基基团,从而避免了常规固化体系的高吸水性和更高的介电常数,而常规的固化体系与环氧化物反应时,其中的产物包含此类仲羟基基团。此外,本文所述的不含卤素的固化剂可用作热塑性组合物和/或配方中的阻燃添加剂同时维持热塑性材料的最佳性质。
可用作用于固化热固性树脂(例如,环氧树脂)的固化剂化合物的化合物的一些更具体的实施方案选自式(V)-(XI)中的任一种或多种:
在一个实施方案中,可用作用于固化热固性树脂(例如,环氧树脂)的固化剂化合物(例如,本文所述的环氧树脂的不含卤素的固化剂)的化合物可以为含磷化合物,诸如每个分子具有至少一个膦酸根基团和至少一个次膦酸根基团并且磷含量为至少4重量%的那些化合物。并且更优选地,含磷化合物为每个分子具有至少一个膦酸根基团和至少一个次膦酸根基团并且磷含量为6%的那些化合物。本文所述的化合物(I)和/或(V)-(XI)满足这些要求并且优选地基本上不含(或完全不含)溴原子,并且更优选地基本上不含(或完全不含)卤素原子。本文所述的化合物(I)和/或(V)-(XI)还可用作非反应性添加剂,诸如当与热塑性或其他热固性体系(例如,环氧化物之外的)一起使用时。例如,上述化合物(I)和/或(V)-(XI)可用作成炭剂以在升高的温度下为热塑性配方和热固性配方提供炭绝缘层,并且它们也可以气相的形式发挥作用。
术语不含卤素的固化剂是指可根据以下方案与环氧化物反应的芳族酯:
其中在这里针对以上方案定义的R可以为1至6个碳原子的直链或支链烷基或包含最多约12个碳原子的非取代的苯基或取代的苯基,其中取代的苯基可被1至6个碳原子的直链或支链烷基取代。
与常规的环氧化物固化方案形成对比:
在本文的一个实施方案中,提供了可通过反应、共混或混合化合物(I)和/或相关化合物(V)-(XI)与其他组分(诸如热固性树脂或热塑性材料或热固性树脂与热塑性材料的混合物)而获得的化合物、组合物和/或配方,以形成可用于诸如预浸料坯、层压体、涂料、模制品和复合材料产品的各种应用的各种抗引燃化合物、组合物或配方。
本文的另一个实施方案涉及含磷环氧树脂可固化配方,所述配方包含:(i)化合物(I)和/或相关化合物(V)-(XI),(ii)环氧树脂或环氧树脂混合物,(iii)任选地共交联剂,(iv)任选地固化催化剂,和(v)任选地路易斯酸。
而在本文的另一个实施方案中,提供了可固化的阻燃环氧树脂组合物,所述组合物包含:(i)以上含磷化合物(例如,化合物(I)和/或(V)-(XI)),(ii)任选地含苯并噁嗪的化合物,(iii)可交联的环氧树脂或两种或更多种每个分子具有多于一个环氧基团的环氧树脂的共混物,(iv)任选地共交联剂,以及(v)任选地固化催化剂以获得可固化的耐燃环氧树脂组合物。此类可固化的耐燃环氧树脂组合物可用于制备预浸料坯,所述预浸料坯可用于制备可用在电子行业中的层压体和电路板。该环氧树脂组合物还可用于涂布诸如铜箔的金属箔,以制备用于所谓的增层技术(build-up)的涂有树脂的铜箔。
含磷化合物(本文所述的化合物(I)和/或(V)-(XI))及其衍生物还可以与至少一种热塑性树脂组合以制备抗引燃热塑性组合物。
含磷化合物(本文所述的化合物(I)和/或(V)-(XI))及其衍生物还可以与至少一种热塑性树脂和热固性体系(环氧化物和固化剂)组合以制备混杂抗引燃的热塑性的(包括热固性的)组合物。
抗引燃环氧树脂组合物(环氧树脂组合物)
在本发明的一个实施方案中,本文所述的含磷化合物(I)和/或(V)-(XI)以及在一个实施方案中它们的组合,可用作可固化的(可交联的)含磷阻燃环氧树脂组合物的一种组分。在该实施方案中,可固化的含磷阻燃环氧树脂组合物包含:(i)本文所述的含磷化合物,即化合物(I)和/或(V)-(XI);(ii)至少一种环氧树脂,诸如选自不含卤素的环氧化物、不含磷的环氧化物和含磷环氧化物及其混合物的那些环氧树脂,包括但不限于DEN 438、DER330、EPON 164(DEN和DER是陶氏化学公司(The Dow Chemical Company)的商标)、含环氧官能化聚噁唑烷酮的化合物、环脂族环氧化物、GMA/苯乙烯共聚物以及DEN 438和DOPO树脂的反应产物;以及任选地(iii)至少一种共交联剂,以及任选地固化催化剂、路易斯酸、阻聚剂和含苯并噁嗪的化合物中的一种或多种。可固化的含磷阻燃环氧树脂组合物任选地可包含至少一种另外的可交联环氧树脂或与以上组分(ii)不同的两种或更多种环氧树脂的共混物。可固化的含磷阻燃环氧树脂组合物还可以任选地包含至少一种固化催化剂和至少一种阻聚剂。所有以上组分可按任何顺序共混或混合在一起以形成可固化的含磷阻燃环氧树脂组合物。
根据本发明制备的可固化的含磷阻燃环氧树脂组合物(无论是通过使本文所述的化合物(I)和/或化合物(V)-(XI)、环氧树脂以及任选地另一种共交联剂(即,另一种固化剂)的混合物反应而制成的)可用于制备预浸料坯,预浸料坯又可用于制备电子工业中有用的层压体和电路板。含磷阻燃环氧树脂组合物还可以用于涂布诸如铜箔的金属箔以制备用于所谓的增层技术的涂有树脂的铜箔。
可在本文用于所述发明的环氧树脂在一个实施方案中包括具有以下通式(XII)的聚环氧化物:
其中"R7"为具有"q"的价态的取代或未取代的芳族、脂族、环脂族或杂环基团,其中"q"优选地具有从1至低于约8的平均值。可用于本发明的聚环氧化合物的实例包括以下化合物的二缩水甘油醚:间苯二酚、儿茶酚、氢醌、双酚、双酚A、双酚AP(1,1-双(4-羟基苯基)-1-苯基乙烷)、双酚F、双酚K、苯酚-甲醛酚醛清漆树脂、烷基取代的苯酚-甲醛树脂、苯酚-羟基苯甲醛树脂、甲酚-羟基苯甲醛树脂、二环戊二烯-苯酚树脂、二环戊二烯取代的苯酚树脂、四甲基联苯二酚及其任意组合。
可用于本发明的特定的聚环氧化合物的实例包括:由陶氏化学公司以商标D.E.R.330销售的环氧当量(EEW)介于177与189之间的双酚A的二缩水甘油醚;不含卤素的环氧封端的聚噁唑烷酮树脂;含磷元素的化合物;环脂族环氧化物;以及甲基丙烯酸缩水甘油酯和苯乙烯的共聚物。
优选的聚环氧化合物包括环氧酚醛清漆,诸如D.E.N.438或D.E.N.439(陶氏化学的商标);甲酚环氧酚醛清漆,诸如可得自汽巴盖吉(Ciba Geigy)的QUATREX 3310、3410和3710;三环氧化合物,诸如TACTIX 742(瑞士巴塞尔的汽巴盖吉公司的商标);环氧化双酚A酚醛清漆,二环戊二烯苯酚环氧酚醛清漆;四酚基乙烷的缩水甘油醚;双酚A的二缩水甘油醚;双酚F的二缩水甘油醚;和氢醌的二缩水甘油醚。
在一个实施方案中,最优选的环氧化合物为环氧酚醛清漆树脂(有时称为环氧化酚醛清漆树脂,该术语旨在既涵盖环氧苯酚酚醛清漆树脂又涵盖环氧甲酚酚醛清漆树脂)。环氧酚醛清漆树脂(包括环氧甲酚酚醛清漆树脂)可容易地商购获得,例如以商品名D.E.N.(陶氏化学公司的商标)以及QUATREX和TACTIX 742(汽巴盖吉的商标)商购获得。
上述类型的优选化合物具有介于150-400之间且最优选地从160-300的环氧当量和高于500且最优选地介于700-2500之间的分子量。
可用于本发明的聚环氧化物优选地基本上不含(或完全不含)溴原子,并且更优选地基本上不含(或完全不含)卤素原子。
可用于本发明的并且基本上不含卤素原子的聚环氧化物的一个非限制性实例为含磷环氧树脂,诸如为含有至少两个环氧基团的环氧化合物与反应性含磷化合物的反应产物的那些含磷环氧树脂,诸如3,4,5,6-二苯并-1,2-氧杂磷烷-2-氧化物(DOP)或10-(2',5'-二羟基苯基)-9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOP-HQ)。
环氧化物在本文所述的组合物(例如,可固化的含磷阻燃环氧树脂组合物、热固性组合物和混杂组合物)中的量使得环氧化物、任何任选的含磷环氧化物、通式(I)和/或(V)-(XI)的化合物以本文所述的量以及任何其他组分以本文所述的或本领域技术人员已知的量形成的最终配方使得组合物的总磷含量为1重量%至约5重量%,更具体地讲约2重量%至约3.5重量%。因此,本领域的技术人员可将环氧化物的量配制成与此类其他组分的量相称,以便具有如上所述的最终磷含量。
此类含磷环氧化物在最终组合物中的量按100份环氧树脂计可从10-90份、优选地20-80份并且最优选地从30-50份变化。
本文所述的环氧树脂的量在一个非限制性实施方案中可以为本文所述的热塑性组合物中的热塑性树脂的量、本文所述的热固性组合物中的热固性树脂的量以及本文所述的混杂组合物中的树脂的合并量。
可在本文所述的可固化环氧树脂组合物中用作固化本文的环氧树脂的化合物的化合物(I)和/或(V)-(XI)的阻燃有效量将根据以下方面而变化:具体的环氧树脂和所用的具体化合物以及本领域技术人员已知的具体加工参数。在一个非限制性实施方案中,可用于固化环氧树脂的化合物(I)和/或化合物(V)-(XI)的阻燃有效量相对于每100份环氧树脂为从约10至约150重量份,更具体地讲相对于每100份环氧树脂为从约30至约100重量份,最具体地讲相对于每100份环氧树脂为从约50至约70重量份。为了提供足够的阻燃性,本文的组合物在最终组合物中将具有1.0%的P至约5%的P。在一个实施方案中,化合物(I)和/或(V)-(XI)的上述量可以是用在本文所述的环氧树脂组合物、热塑性组合物、热固性组合物和混杂组合物的任一者中的化合物(I)和/或(V)-(XI)的量。
如上所述,含磷阻燃环氧树脂组合物可通过共混以下物质而形成:(i)含磷产物,即本文所述的化合物(I)和/或化合物(V)-(XI),(ii)至少一种可交联的环氧化合物,以及任选地(iii)至少一种共交联剂,以及本文所述的其他任选组分的任一种;或在另一个实施方案中,含磷阻燃环氧树脂组合物可通过共混以下物质而形成:(i)环氧化化合物(I)和/或化合物(V)-(XI),至少一种可交联的含磷环氧化合物,以及(iii)至少一种共交联剂,以及本文所述的其他任选组分的任一种。含磷阻燃环氧树脂组合物可任选地包含除上文(ii)中的可交联含磷环氧化合物之外的至少一种可交联的环氧树脂。在本文的一个实施方案中,将理解的是,在可交联的含磷环氧化合物中的术语“可交联的”应理解成具有多于2个环氧官能团的含磷环氧化合物,这也是本领域的技术人员的理解。
对于其中存在环氧树脂的以上组合物中的任一种,还可以任选地使用多种共交联剂(即,除了磷化合物(I)和/或(V)-(XI)以外)。可任选地与根据本发明的含磷环氧化合物组合存在的合适的共交联剂包括例如本领域技术人员已知的多官能共交联剂。
共交联剂包括例如分子量(Mw)在1,500至50,000的范围内且酸酐含量高于15%的苯乙烯与马来酸酐的共聚物。这些材料的商业实例包括苯乙烯-马来酸酐比率分别为1:1、2:1、3:1和4:1且分子量在6,000至15,000范围内的SMA 1000、SMA 2000和SMA 3000及SMA4000,它们可得自埃尔夫阿托化学(ElfAtochem S.A.)。
可用于本发明的其他优选的共交联剂包括含羟基的化合物,诸如由下式(XIII)表示的那些化合物:
其中"R8"为氢或具有1至20个、优选1至10个、更优选1至5个碳原子的烷基基团,并且"t"为0至20、优选1至10、更优选2至5的整数。
具有上式(XIII)的市售产品包括例如PERSTORP 85.36.28,其为得自苯酚和甲醛的平均梅特勒软化点为103℃、150℃下的熔体粘度为1.2Pas且官能度为6至7的酚树脂。另一个实例包括SD1708(得自迈图公司(Momentive)):150℃下的粘度为2200-3800cps,软化点为110℃;HRJ13399(得自硅群公司(SI Group)):比重为1.20,软化点为90-105;HRJ12952(得自硅群公司):比重为1.25,软化点为97-107;FRJ425(得自硅群公司):比重为1.24,软化点为112-118;BRJ 473液体(得自硅群公司):比重为1.10,布氏粘度为1000-4500cps。
适于本文所述的组合物的共交联剂的一个实例为具有通式(XIV)的酚树脂:
其中R9为氢,1至10个碳原子的脂族部分,或苯基或取代的苯基;R10为1至4个碳原子的脂族部分,或苯基或取代的苯基基团。这种类型的商业固化体系的一个实例为可得自日本的DIC公司的EPICLON HPC-8000-65T。
其他适合作为共交联剂的酚官能化材料包括在加热时形成官能度为至少2的酚交联剂的化合物。这些化合物的一些实例为包含苯并噁嗪基团的化合物。在加热时形成酚交联剂的化合物的实例包括通过加热苯并噁嗪而获得的酚类物质,例如,如下化学方程式所示:
其中"u"大于1且优选地为约100,000以下;并且其中"R11和"R12"可独立且单独地为相同或不同的氢、1至约10个碳原子的烷基(诸如甲基)、6至20个碳原子的芳族基团(诸如苯基)或4至20个碳原子的环脂族基团(诸如环己烷)。
以上化合物的实例还包括酚酞的苯并噁嗪、双酚A的苯并噁嗪、双酚F的苯并噁嗪、苯酚酚醛清漆的苯并噁嗪及其混合物。这些化合物和式(XI)的混合物也可用于本发明。得自猎人公司(Huntsman)的商业苯并噁嗪的非限制性实例包括诸如双酚A苯并噁嗪(MT35600)、双酚F苯并噁嗪(MT35700)、酚酞苯并噁嗪(MT35800)、硫代二苯酚苯并噁嗪(MT35900)和二环戊二烯苯并噁嗪(MT36000)的实例
当将共交联剂用于本发明时,共交联剂的含量低于固化热固性树脂(例如,环氧树脂)所需的化学计算量的50%,更优选地低于固化热固性树脂(例如,环氧树脂)所需的量的约40%,最优选地低于固化热固性树脂(例如,环氧树脂)所需的量的约35%。
本文所述的本发明的任何可固化组合物可包含固化催化剂。可用于本发明的合适的固化催化剂(催化剂)材料的实例包括含胺、膦、铵、鏻、鉮或锍部分的化合物或其混合物。特别优选的催化剂是杂环含氮化合物。
催化剂(区别于共交联剂)优选地平均每个分子含有不超过约1个活性氢部分。活性氢部分包括键合到胺基团、酚羟基基团或羧酸基团的氢原子。例如,催化剂中的胺和膦部分优选地为叔胺或膦部分;并且铵和鏻部分优选地为季铵和鏻部分。
可用作催化剂的优选的叔胺包括具有开链或环状结构的那些单胺或多胺,其所有的胺氢都被合适的取代基置换,所述取代基诸如为烃基,并且优选地为脂族、环脂族或芳族基团。
这些胺的实例例如1,8-二氮杂双环(5.4.0)十一碳-7-烯(DBU)、甲基二乙醇胺、三乙胺、三丁胺、二甲基苄胺、三苯胺、三环己胺、吡啶和喹啉等。优选的胺为三烷基胺、三环烷基胺和三芳基胺,诸如三乙胺、三苯胺、三(2,3-二甲基环己基)胺以及烷基二烷醇胺(诸如甲基二乙醇胺)和三烷醇胺(诸如三乙醇胺)。弱叔胺(例如,在水溶液中以1M浓度的水溶液得到小于10的pH的胺)是特别优选的。尤其优选的叔胺催化剂是苄基二甲胺和三(二甲氨基甲基)苯酚。
可用于本文的合适的杂环含氮催化剂(包括杂环仲胺和叔胺或含氮催化剂)的实例包括例如咪唑类、苯并咪唑类、咪唑烯类(imidazolidine)、咪唑啉类、噁唑类、吡咯类、噻唑类、吡啶类、吡嗪类、吗啉类、哒嗪类、嘧啶类、吡咯烷类、吡唑类、喹喔啉类、喹唑啉类、酞嗪类(phthalozines)、喹啉类、嘌呤类、吲唑类、吲哚类、吲哚嗪类(indolazines)、吩嗪类、吩吡嗪类、吩噻嗪类、吡咯啉类、二氢吲哚类、哌啶类、哌嗪类及其组合。尤其优选的是烷基取代的咪唑类、2,5-氯-4-乙基咪唑和苯基取代的咪唑及其混合物。甚至更优选的是N-甲基咪唑、2-甲基咪唑、2-乙基-4-甲基咪唑、1,2-二甲基咪唑和2-甲基咪唑及其混合物。尤其优选的是2-苯基咪唑。
所用的固化催化剂的量取决于催化剂的分子量、催化剂的活性和旨在进行的聚合反应的速度。一般来讲,固化催化剂以相对于每100份树脂为从0.01份(p.h.r.)至约1.0p.h.r.,更具体地讲从约0.01p.h.r.至约0.5p.h.r.并且最具体地讲从约0.1p.h.r.至约0.5p.h.r.的量使用。在本文的一个实施方案中,将理解的是,树脂的份数与本文所述的可固化的环氧树脂的份数相关,即排除催化剂的可固化组合物的总量(环氧化物+化合物(I)和除固化催化剂之外存在的任何其他组分的总克数=100%,然后取该组合物100g等于100份树脂);催化剂按上述范围添加到100份该总重量中。
优选地,尤其是当催化剂特别是杂环含氮化合物时,还在本文所述的本发明的任何可固化环氧树脂组合物中采用路易斯酸。
可用于本发明的路易斯酸包括例如锌、锡、钛、钴、锰、铁、硅、铝和硼的卤化物、氧化物、氢氧化物和醇盐中的一种,或两种或更多种的混合物,例如硼的路易斯酸,和硼的路易斯酸的酸酐,例如硼酸、偏硼酸、任选取代的环硼氧烷(诸如三甲氧基环硼氧烷)、任选取代的硼氧化物、硼酸烷基酯、卤化硼、卤化锌(诸如氯化锌)和具有相对弱共轭碱的其他路易斯酸。优选地,路易斯酸是硼的路易斯酸,和硼的路易斯酸的酸酐,例如硼酸、偏硼酸、任选取代的环硼氧烷(诸如三甲氧基环硼氧烷、三甲基环硼氧烷或三乙基环硼氧烷)、任选取代的硼氧化物或硼酸烷基酯。最优选的路易斯酸是硼酸。当与上文提及的杂环含氮化合物组合时,这些路易斯酸在固化环氧树脂方面非常有效。
路易斯酸和胺可在混入配方之前加以组合或通过与催化剂原位混合而组合,以制备固化催化剂结合物。
所用的路易斯酸的量优选地相对于每摩尔杂环氮化合物为至少0.1摩尔路易斯酸,更优选地相对于每摩尔杂环氮化合物为至少0.3摩尔路易斯酸。
本发明的可固化组合物可任选地具有作为固化阻聚剂而存在的硼酸和/或马来酸。在此情况下,固化剂优选地为聚胺或聚酰胺。固化阻聚剂的量将是本领域技术人员已知的。
本发明的可固化组合物还可以任选地包含一种或多种另外的阻燃添加剂,包括例如红磷、包覆红磷或液态或固态含磷化合物,例如得自科莱恩GmbH的“EXOLIT OP 930”、EXOLIT OP 910,和聚磷酸铵(诸如得自科莱恩GmbH的“EXOLIT 700”),亚磷酸盐、或膦腈;含氮阻燃剂和/或增效剂,例如三聚氰胺、蜜勒胺、氰尿酸、异氰脲酸及这些含氮化合物的衍生物;卤化阻燃剂和卤化环氧树脂(尤其是溴化环氧树脂);增效的含磷-卤素化学品或含有有机酸盐的化合物;无机金属水合物,诸如Sb2O3、Sb3O5、氢氧化铝和氢氧化镁,诸如得自德国Martinswerke GmbH(公司名称)的“ZEROGEN 30”,更优选氢氧化铝,诸如得自德国Martinswerke GmbH(公司名称)的“MARTINAL TS-610”;含硼化合物;含锑化合物;二氧化硅及其组合。
当在本发明的组合物中存在含有磷的另外的阻燃剂时,含磷阻燃剂的存在量优选地使得环氧树脂组合物的总磷含量为0.2重量%至5重量%。
本发明的可固化组合物还可以任选地包含常见传统类型的其他添加剂,包括例如稳定剂、其他有机或无机添加剂、颜料、湿润剂、流动改性剂、紫外线阻隔剂和荧光添加剂。这些添加剂可以按0至5重量%的量存在,并优选地以小于3重量%的量存在。
阻燃环氧树脂优选地不含溴原子,更优选地不含卤素原子。
上述组合物可用于制备涂料配方、封装剂、复合材料、胶粘剂、模制件、粘结片和层压板。通过行业中熟知的技术,例如通过拉挤、模制、封装或涂布,本发明的组合物可用于制备复合材料。作为例证,涂料配方可包含:(i)化合物(I)和/或化合物(V)-(XI),(ii)固体环氧树脂,和(iii)硬化剂,诸如胺或酚类硬化剂。硬化剂的量将是本领域技术人员已知的。
通过行业中熟知的技术,本发明尤其可用于制备B阶段预浸料坯、层压体、粘结片和涂有树脂的铜箔。
抗引燃热塑性树脂(热塑性树脂组合物)
在本发明的另一个实施方案中,将含磷产物即化合物(I)和/或化合物(V)-(XI)用于制备含磷抗引燃热塑性树脂。
不含卤素的抗引燃热塑性树脂组合物可通过以下方式获得:将(i)根据本发明的含磷化合物即化合物(I)和/或化合物(V)-(XI)与(ii)至少一种热塑性树脂以及任选地针对本文所述的热固性(例如,环氧)树脂组合物所述的任选组分中的任一种或多种进行共混。
典型的热塑性聚合物包括但不限于由乙烯基芳族单体及其氢化形式制成的聚合物,所述氢化形式包括二烯和芳族氢化形式,包括芳族氢化,诸如苯乙烯-丁二烯嵌段共聚物、聚苯乙烯(包括高抗冲聚苯乙烯)、丙烯腈-丁二烯-苯乙烯(ABS)共聚物和苯乙烯-丙烯腈共聚物(SAN);聚碳酸酯(PC)、ABS/PC组合物、聚对苯二甲酸乙二醇酯、环氧树脂、羟基苯氧醚聚合物(PHE)、乙烯-乙烯醇共聚物、乙烯-丙烯酸共聚物、聚烯烃-一氧化碳互聚物、氯化聚乙烯、聚烯烃(例如,乙烯聚合物和丙烯聚合物,诸如聚乙烯、聚丙烯以及乙烯和/或丙烯与彼此或与具有至少4个、更优选至少6个且优选最多12个、更优选最多8个碳原子的α-烯烃的共聚物)、环状烯烃共聚物(COC)、其他烯烃共聚物(尤其是乙烯与另一种烯烃单体诸如1至12个碳原子的烯-1-基基团的共聚物)和均聚物(例如,使用传统非均相催化剂制得的那些均聚物)、聚苯醚聚合物(PPO)及其任何组合或共混物。
热塑性聚合物及其制备方法是本领域技术人员熟知的。在一个实施方案中,热塑性聚合物是通过使乙烯基芳族单体在存在溶解的弹性体或橡胶的情况下聚合而得的橡胶改性的单亚乙烯基芳族聚合物。
以100重量份的本发明的不含卤素的抗引燃聚合物组合物计,在本发明的不含卤素的抗引燃聚合物组合物中使用至少35重量份,优选至少40重量份,更优选至少45重量份,最优选至少50重量份的热塑性聚合物或聚合物共混物。一般来讲,以100重量份的本发明的不含卤素的抗引燃聚合物组合物计,热塑性聚合物组分的用量低于或等于99重量份,优选低于或等于95重量份,更优选低于或等于约90重量份,最优选低于或等于约85重量份。
在一个实施方案中,本发明的不含卤素的抗引燃聚合物组合物包含化合物(I)和/或化合物(V)-(XI)以及两种热塑性聚合物的共混物,其中至少一种热塑性聚合物是例如聚苯醚。聚苯醚通过多种熟知的催化和非催化方法由相应的苯酚或其反应性衍生物而制备。
当与另一种热塑性聚合物结合使用时,以100重量份的本发明的不含卤素的抗引燃聚合物组合物计,聚苯醚树脂在本发明的不含卤素的抗引燃聚合物组合物中的用量优选为至少5重量份,优选10重量份,更优选至少12重量份,更优选至少15重量份,最优选至少18重量份至30重量份,优选至多28重量份,更优选至多25重量份。可以在掺入本发明的组合物中之前将热塑性聚合物和聚苯醚聚合物制成共混物,或将每种聚合物单独掺入本发明的组合物中。
本发明的组合物可以包含其他添加剂,诸如改性剂,其包括含有将增强组合物的机械性能并与热塑性树脂相容的官能团的化合物。对于热塑性树脂,诸如单亚乙烯基芳族化合物和共轭二烯,此类官能团包括但不限于丁二烯、苯乙烯-马来酸酐、聚丁二烯-马来酸酐共聚物、羧酸封端的丁二烯和羧酸官能化的聚苯乙烯。可以使用改性剂的任何组合对含磷元素的环氧化合物进行改性。
以抗引燃聚合物组合物的总重量计,本发明的抗引燃热塑性聚合物组合物中使用的化合物(I)和/或化合物(V)-(XI)的量通常为至少1重量%,通常至少5重量%,优选至少10重量%,更优选至少15重量%,最优选至少20重量%,且低于50重量%,优选低于45重量%,更优选低于40重量%,最优选低于35重量%。
本文的热塑性树脂组合物可包含本文针对热固性组合物、环氧树脂组合物或混杂组合物所述的以及热塑性组合物的任何组分和/或组分的量的范围,反之亦然,也就是说,可将本文所述的热塑性组合物的任何组分和/或组分的量用于本文所述的任何热固性组合物、环氧树脂组合物或混杂组合物。
本发明的抗引燃热塑性聚合物组合物的制备可以通过本领域已知的任何合适的混合方式实现,包括将各种组分干混,随后熔体混合,这直接在用于制备最终制品的挤出机中进行或在单独的挤出机中预混。组合物的干共混物也可以在不预先熔体混合的情况下直接注射成型。
当通过施热而软化或熔融时,本发明的抗引燃热塑性聚合物组合物可以使用传统技术形成或模制,诸如单独或结合使用压缩模制、注射成型、气体辅助注射成型、压延、真空成型、热成型、挤出和/或吹塑。也可以将抗引燃热塑性聚合物组合物成型、纺丝或拉成薄膜、纤维、多层层压体或挤出片材,或可以与一种或多种有机或无机物质在适于此目的的任何机器上配混。
在一个实施方案中,本发明的热塑性组合物可用于制备泡沫。将抗引燃热塑性聚合物组合物如下挤出形成泡沫:将其与发泡剂熔融加工以形成可发泡的混合物,将所述可发泡的混合物通过挤出模头挤出到压力降低的区域,以及使可发泡的混合物膨胀并冷却。可以使用传统的泡沫挤出设备,诸如螺杆挤出机、双螺杆挤出机和累积挤出装置(accumulating extrusion apparatus)。
在本发明的另一个实施方案中,本发明的不含卤素的抗引燃热塑性聚合物组合物可以除化合物(I)和/或化合物(V)-(XI)之外还任选地包含其他含磷化合物。任选地,本发明的热塑性组合物还可以包含其他阻燃添加剂,其可以是如上所述的磷或非磷材料。
本发明的组合物中使用的除化合物(I)和/或化合物(V)-(XI)和/或任选的阻燃添加剂外的任选的含磷化合物的量可以为0至最多30重量%。当存在除化合物(I)和/或化合物(V)-(XI)外的任选的含磷组分时,按热塑性树脂的总重量计,其量优选地为至少1重量%且优选地为最多30重量%。
按热塑性树脂的总重量计,化合物(I)和/或化合物(V)-(XI)组分的量优选地为至少5重量%且优选地为最多20重量%。
抗引燃热塑性树脂优选地基本上不含溴原子,更优选地完全不含卤素原子。
本发明的不含卤素的抗引燃热塑性聚合物组合物可用于制造许多有用的制品和部件。特别适合的一些制品包括通常要求具有优异的可燃性等级的电视柜、电脑显示器、相关打印机外壳。其他应用包括汽车和小型电器。
抗引燃热固性组合物(热固性组合物)
在本发明的另一个实施方案中,将含磷产物即化合物(I)和/或化合物(V)-(XI)用于制备含磷抗引燃热固性组合物,例如,在一个非限制性实施方案中,其中除了环氧化物外还存在热固性聚合物,或存在环氧化物之外的热固性聚合物。
不含卤素的抗引燃热固性组合物通过以下方式获得:将(i)根据本发明的含磷化合物即化合物(I)和/或化合物(V)-(XI)与(ii)至少一种热固性体系共混。热固性体系的实例为环氧化物、聚氨酯、聚异氰酸酯、含苯并噁嗪环的化合物、含双键或三键的不饱和树脂体系、聚氰酸酯、双马来酰亚胺、三嗪、双马来酰亚胺及其混合物。
本文的热固性树脂组合物可包含本文针对可固化的环氧树脂组合物、热塑性组合物或混杂组合物以及热固性组合物的任何组分和/或此类组分的量的范围,反之亦然,也就是说,可将本文所述的热固性组合物的任何组分和/或组分的量用于本文所述的任何环氧化物组合物、热塑性树脂组合物或混杂组合物。
抗引燃热塑性/热固性混杂体系(混杂组合物)
在本发明的另一个实施方案中,将含磷产物即化合物(I)和/或化合物(V)-(XI)用于制备含磷抗引燃混杂树脂体系,其既包含热塑性体系又包含热固性体系。
混杂抗引燃热塑性和热固性组合物可通过以下方式获得:将(i)根据本发明的含磷化合物即化合物(I)和/或化合物(V)-(XI)与(ii)热塑性树脂和(iii)热固性体系共混。热塑性树脂的实例为聚苯醚(PPO)、其混合物以及如上所述的其他树脂。热固性体系的实例为环氧化物、聚氨酯、聚异氰酸酯、含苯并噁嗪环的化合物、含双键或三键的不饱和树脂体系、聚氰酸酯、双马来酰亚胺、三嗪、双马来酰亚胺及其混合物。混杂抗引燃热塑性和热固性组合物可包含在本主体发明中所述的任何任选的组分及其量。
热塑性树脂在混杂组合物中的量可为从约20至约95,优选地从约30至约80,而热固性树脂的量可为从约10至约20,更优选地从约30至约40,其中所述量按所用的热塑性和热固性树脂的总量计。
本文的混杂树脂组合物可包含本文针对环氧树脂组合物、热固性树脂组合物或热塑性树脂组合物的任何组分和/或组分的量的范围,反之亦然,任意一种环氧树脂组合物、热固性树脂组合物和热塑性树脂组合物可包含本文所述的混杂树脂组合物的任何组分和/或组分的量。
在本文的一个实施方案中,提供了包含本文所述的任何组合物的制品。在一个实施方案中,本文的制品可用于无铅焊接应用和电子器件,例如印刷线路板应用,具体地讲,所述制品可以为预浸料坯和/或层压体。在一个具体实施方案中,提供了包含本文所述的组合物中的任一种或多种的层压体和/或预浸料坯。在一个其他实施方案中,本文提供了包括一个或多个预浸料坯和/或层压体(例如,固化的、部分固化的或完全固化的)的印刷线路版,任选地多层印刷线路板,其中所述预浸料坯和/或层压体包含本文所述的组合物中的任一种或多种。在一个实施方案中,提供了包括预浸料坯和/或层压体的印刷线路板,其中所述预浸料坯和/或层压体包含本文所述的组合物中的任一种。
如本文所用的部分固化可包括任何程度的固化、非完全固化,并将根据具体的材料和制造条件以及所需的最终应用而广泛变化。在一个具体实施方案中,本文的制品还可以包括铜箔。在一个实施方案中,制品可包括印刷线路板。在一个实施方案中,提供了包括本发明的预浸料坯和/或层压体的FR-4层压体。在一个更具体的实施方案中,提供了包括FR-4层压体的印刷电路板,其中FR-4层压体包括本发明的预浸料坯或层压体。
在本文的一个实施方案中,提供了制备包含本文所述的任何组合物的层压体的方法,所述方法包括将相应的组合物浸渍到填充材料中,例如玻璃纤维毡中,以形成预浸料坯,然后将预浸料坯在升高的温度和/或压力下加工以促进部分固化到B阶段,然后将两个或更多个所述预浸料坯层压形成所述层压体。在一个实施方案中,所述层压体和/或预浸料坯可用于本文所述的应用,例如,印刷线路板。
本文指出:本文所述的任何组合物可用于制备具有层压体性质与热稳定性的良好平衡的预浸料坯和/或层压体,这些性质诸如为高Tg(即,高于130℃)、330℃及以上的Td、5分钟及以上的t288、V-0的耐燃性等级、良好的韧性以及与铜箔良好的粘附性。近几年来,Td已成为最重要的参数之一,因为行业不断转变成无铅焊料,其在比传统锡-铅焊料更高的温度下熔化。
在本文的一个实施方案中,本文所述的组合物可按根据特定的应用而视为必需的量用于其他应用,例如电子元件的封装剂、保护性涂料、结构性胶粘剂、结构性和/或装饰性复合材料。
在本文的又一个实施方案中,提供了制备用于热固性树脂(例如,用于环氧树脂)的不含卤素的固化剂的方法,所述固化剂在一个非限制性实施方案中通过以下反应机理(A)中所述的方法制备:
在一个非限制性实施方案中,制备式(I)和/或(V)-(XI)的不含卤素的固化剂的方法可包括:使任何磷杂菲-烷基取代的、羟基取代的并且任选地亚烷基取代的芳族化合物与烷氧基化的磷杂菲化合物在存在至少一种烃溶剂和基于氮的催化剂的情况下反应以产生通式(I)和/或(V)-(XI)的化合物。
在本文的一个非限制性实施方案中,制备式(I)和/或(V)-(XI)的不含卤素的固化剂的方法可包括以下一般反应机理:
磷杂菲-烷基取代的、羟基取代的(并且任选地亚烷基取代的)芳族化合物+DOP-O-烷基
其中磷杂菲-烷基取代的、羟基取代的(并且任选地亚烷基取代的)芳族化合物和DOP-O-烷基在以下各种非限制性实施方案中予以定义。
磷杂菲-烷基取代的、羟基取代的(并且任选地亚烷基取代的)芳族化合物
其通式的一个非限制性实例为(A):
其中每个R︿独立地选自H;-OH;如本文所定义的式(II)的次膦酸根部分;如本文所定义的通式(III)的膦酸根部分;以及如本文所定义的通式(IV)的取代芳基部分,其中至少一个R︿为-OH并且至少一个R︿为具有通式(II)的基团。
DOP-O-烷基:
在一个非限制性实施方案中,DOP-O-烷基选自通式(B):
其中R1”’为包含1至8个碳原子,更具体地讲1至约4个碳原子的直链或支链烷基基团;R2”’-R9”’中的每一个独立地为氢原子或可包含一个或多个诸如O、S、N、P或Si的杂原子的烃基团,前提条件是R2”’-R5”’中不超过3个为氢原子,并且R1-R9中的每一个独立地包含少于7个碳原子。
试剂和溶剂
在以上反应机理中指出的试剂CCl4和CH3Cl是本发明的一个实施方案,但溶剂可以为有机溶剂,优选地为非质子溶剂。溶剂可以为极性的或非极性的。示例性极性非质子溶剂为二甲基甲酰胺、二甲基乙酰胺和N-甲基吡咯烷酮。优选的溶剂为非质子和非极性的,便利地为脂族烃,典型地为庚烷、辛烷、环己烷、十氢萘、矿物油馏分(诸如石油醚、石油英、煤油)、芳族烃(诸如苯、甲苯或二甲苯)或所述溶剂的混合物。溶剂的量可设为约5重量%至约90重量%,更具体地讲约20%至约70%。
催化剂
上文指出的催化剂为三乙胺,但任何基于氮的催化剂都是合适的。诸如,非限制性实例为酰胺、酰亚胺、胺、季铵盐和脲。优选的催化剂为N,N-二取代的酰胺,诸如N,N-二甲基甲酰胺、N-甲基吡咯烷酮等;N-单取代的酰胺,诸如N-甲基甲酰胺、N-甲基乙酰胺等;叔胺,诸如吡啶、三乙胺等;仲胺,诸如吡咯烷、二乙胺等;以及取代的脲,诸如四甲基脲。所用的催化剂的量可为约500ppm至约10,000ppm,更具体地讲约1,000ppm至约5,000ppm。
(A)和(B)的用量为等摩尔量,但(A)或(B)中的一种或多种过量最多20%,优选地最多10%也是有用的。以上反应机理的反应温度在从室温(例如,25℃)至最多约200℃,优选地从50℃至约140℃,且最优选地从60℃至约120℃的范围内。
使用以下实施例来阐述本发明。
实施例
合成实施例1
1.经由阿瑟顿托德(Atherton-Todd)反应使DOPO-BPA材料与DOPO-Cl(9,10-二氢-9-氧杂-10-磷杂菲-10-氯化物)反应:
合成实施例1
将DOPO-BPA材料(4.37g,4.23mmol,1当量)溶于5mL无水氯仿,并将溶于5mL氯仿的DOPO(9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物)(2.01g,9.3mmol,2.2当量)转移到反应混合物中。将三乙胺(3mL,21.13mmol,5当量)在室温下加到反应混合物中。将混合物冷却到0℃,将3mL氯仿中的四氯甲烷(0.98mL,10.14mmol,2.4当量)逐滴加入并搅拌2小时,然后升至室温并搅拌过夜。将粗混合物用氯仿稀释,将有机相用去离子水、氯化铵、0.2M盐酸(×2)、去离子水(×2)洗涤,然后用各占一半的碳酸氢钠和盐水溶液洗涤。将有机相经MgSO4干燥、过滤并浓缩得到5.22g产物,收率为84%。
实施例2层压体制备
层压体实施例2
1.材料
将得自合成实施例1的化合物1用作固化剂。用于本研究的环氧化物包括得自陶氏化学的苯酚酚醛清漆环氧化物DEN 438,和得自瀚森化工(Hexion chemicals)的甲酚酚醛清漆环氧化物EPON 164。将苯酚酚醛清漆SD-1708用作该配方中的共固化剂。将得自空气化工产品公司(AirProducts)的2-甲基咪唑用作固化加速剂。将陶氏醇(Dowanol)用作清漆制备期间的溶剂。所有材料信息均在表1中列出。
2.清漆的制备
清漆配方在表2中给出。将称取重量的环氧树脂和固化剂加入配有机械搅拌器的玻璃罐中。添加陶氏醇以使得清漆配方的总固含量接近66.67%。添加陶氏醇有助于降低清漆的粘度,帮助玻璃纤维织物的手工刷涂,并维持清漆的固含量。最终将2mL加速剂加入清漆中。将清漆连续搅拌数小时直到得到均匀的溶液。将以10℃/min运行到最高250℃的DSC加热用于测定配方的固化动力学,最高固化温度出现在接近197℃,其在图1中示出。在171℃的热板上测试清漆凝胶时间。该配方的清漆凝胶时间为255秒。
3.预浸料坯的制造
在室温下将玻璃织物(10.5×11.0英寸)用清漆在两面上手工刷涂。将玻璃织物悬挂在实验室中过夜,以缓慢蒸发陶氏醇。随后,将玻璃织物置于165℃的预热空气循环烘箱中3分40秒,在其中剩余的溶剂将蒸发并且树脂将会固化到B阶段。应用不同的干燥时间,并测试所得的预浸料坯的树脂流动。根据IPC-TM-650测试2.3.16.2测量树脂流动。用该清漆制备了预浸料坯,并在165℃下干燥3分40秒,其得到接近25-30.0%的树脂流动。另外,树脂含量被控制在45-50%以上,其通过玻璃织物与预浸料坯之间的重量差确定。通过以下方式测定预浸料坯凝胶时间:将预浸料坯在自封袋中压碎而收集易熔的热塑性树脂。将收集的树脂置于171℃的热板上并测定凝胶时间。预浸料坯性质在下表中示出:
所选的处理条件导致所有溶剂蒸发,并且预浸料坯具有<2.5重量%的残余溶剂。
4.压制层压体
将4个直径为25mm的预浸料坯的圆形叠堆置于一次性Al板之间以通过在壳体内部在AR2000ex流变仪中以5℃/min电加热到200℃而研究树脂的流变行为。图2显示了预浸料坯的复数粘度分布线,B阶段树脂体系的温度以振荡测试模式升高。基于图1和图2,设计了固化循环以获得良好的玻璃织物润湿。在95℃下施加了10psi的低初始压力(预浸料坯的复数粘度为约12,000pa-s),该压力足以润湿玻璃织物,其基于在制备各种实验用环氧化物层压体期间的研究。随后,压力降低,温度升高,并在110℃下将压力再次升回到10psi。在125℃下施加20psi的压力,其中复数粘度接近11,160Pa-s,并将压力维持在20psi,甚至在155℃下也是如此。最后,在195℃下将压力每10分钟升高一次,直到达到260psi,并将压机等温维持在195℃下保持90分钟。采用B阶段体系的温度和时间,制备了8个预浸料坯。将8个预浸料坯堆叠在一起,在叠堆的顶部和底部放置铜箔。然后,将该组合件置于两块不锈钢板之间,并放入液压机中,其中在钢板上下放置4张牛皮纸。将压机线性加热到195℃,并在如上所述的加热过程中将压力从10psi逐渐增至260psi。将层压体在195℃下固化90min。之后,通过打开冷却水将压机冷却到室温。层压体显示出良好的树脂流动,并且最终层压体的厚度接近1.35mm(不包括铜)。
5.可燃性测试和压力锅测试
按照ASTM D3601-06方法使用阿特拉斯(Atlas)UL-94燃烧室记录层压体的可燃性(UL-94等级)(V-0是可能最高的等级)。根据IPC-TM-650测试2.3.7.1将铜箔从层压体剥离。根据IPC-TM 650测试2.6.16但作出以下修改而进行压力锅测试(PCT):(a)将样本暴露于高压釜中的蒸汽30分钟;(b)将焊浴的温度维持在288℃,(c)将样本浸入焊料中20秒。
6.层压体的玻璃化转变和热分解温度
使用DMA方法测定层压体的玻璃化转变温度。测试以3℃/min进行,其中加热从室温升至180℃。层压体的Td通过TGA测量。测试以10℃/min进行,其中温度最高为500℃。DMA和TGA测量结果分别在图3和图4中示出。
7.结果
作为环氧化物层压体应用的固化剂,探索了得自实施例1的化合物1。将化合物1与苯酚酚醛清漆一起用作固化剂以固化多官能环氧树脂DEN 438和EPON 164。清漆配方具有3.0%的磷含量和大约66.67%的固含量。清漆在171℃下具有255秒的凝胶时间,而预浸料坯在171℃下具有接近180秒的凝胶时间。在165℃下将预浸料坯处理3分40秒以实现大约25.0-30.0%的树脂流动和大约45-50%的树脂含量,而残余溶剂可忽略不计。研究了预浸料坯的动态复数粘度分布线,并设计了固化循环以制备具有1.35mm的最终厚度(不包括铜)的层压体。层压体评级为V-0,最大燃烧时间为8秒。层压体的玻璃化转变温度为约141℃,而层压体的热分解(Td-5重量%损失)出现在383℃,如通过TGA获取。在PCT测试中,30分钟后的吸水分别为0.41%和0.48%。
表1材料
商品名(生产商) | 一般信息 | 功能 |
化合物1 | DOPO衍生物 | 固化剂 |
环氧树脂(DEN438,得自陶氏) | 苯酚酚醛清漆环氧化物 | 树脂 |
环氧树脂(EPON164,得自瀚森) | 甲酚酚醛清漆环氧化物 | 树脂 |
苯酚酚醛清漆(SD-1708,得自迈图) | 苯酚酚醛清漆 | 共固化剂 |
2-mI(得自空气化工产品) | 2-甲基咪唑 | 催化剂 |
陶氏醇(得自福如卡(Fluka)) | 1-甲氧基-2-丙醇 | 溶剂 |
表2具有化合物1的环氧化物层压体配方
DEN438(g) | EPON164(g) | 化合物1(g) | SD-1708(g) | 2-mI(g) | |
22.02 | 26.91 | 29.79 | 21.28 | 0.05 |
表3测试方法
表4具有化合物1的环氧化合物层压体配方的UL-94可燃性
虽然已参照某些实施方案描述了本发明,但是本领域的技术人员将理解的是,在不脱离本发明范围的情况下,可进行多种变化,并且等同形式可代替其要素。此外,在不脱离本发明实质范围的情况下,基于本发明的教导可进行许多修改以适应特定的情况或材料。因此,本发明意在不限于作为设想用于实施本发明方法的最好模式而公开的具体实施方案,而是本发明将包括落在所附权利要求书范围内的所有实施方案。
Claims (19)
1.一种具有通式(I)的化合物:
其中每个R独立地选自H;-OH;含有1至8个碳原子的烷基;其中R*为含有1至8个碳原子的烷基基团或为取代或未取代的苯基;
式(II)的次膦酸根部分:
其中R1为1至3个碳原子的二价直链或支链亚烷基部分,而虚线表示与以上式(I)的结构结合的键;
通式(III)的膦酸根部分:
和
通式(IV)的取代的芳基部分:
其中R2为1至4个碳原子的二价直链或支链亚烷基部分,而虚线表示与以上式(I)的结构结合的键,并且R3的定义与R相同,但R3不能是通式(IV)的取代的芳基部分而至少一个R3为式(II)的基团;
并且前提条件是式(I)中具有式(II)的R基团的数量为1或2,式(I)中具有式(III)的R基团的数量为1或2,同时前提条件是式(I)的所有R基团都不具有式(IV)或式(I)的仅一个R基团具有式(IV),另外前提条件是当式(I)的所有R基团都不具有式(IV)时,则具有式(II)和(III)的R基团的总数最多为4,并且如果式(I)的R基团之一具有式(IV),则具有式(II)、(III)和(IV)的R基团的总数最多为4。
2.根据权利要求1所述的化合物,其中所述化合物选自式(V)-(XI):
3.一种组合物,包含热固性树脂、相对于每100重量份的所述热固性树脂而言10至150重量份的权利要求1的式(I)所述的化合物,以及任选地以下一种或多种:共交联剂、固化催化剂、路易斯酸、含苯并噁嗪的化合物和任选地阻聚剂。
4.根据权利要求3所述的组合物,其中所述热固性树脂为环氧树脂。
5.根据权利要求3所述的组合物,其中所述热固性树脂选自环氧化物、聚氨酯、聚异氰酸酯、含苯并噁嗪环的化合物、含双键或三键的不饱和树脂体系、聚氰酸酯、双马来酰亚胺、三嗪及其混合物。
6.一种组合物,包含热塑性树脂、相对于每100重量份的所述热塑性树脂而言10至150重量份的权利要求1的式(I)所述的化合物,以及任选地共交联剂、任选地路易斯酸、任选地含苯并噁嗪的化合物和任选地阻聚剂。
7.一种组合物,包含热塑性树脂、热固性树脂、相对于每100重量份的所述热塑性树脂和所述热固性树脂的合计重量而言10至150重量份的权利要求1的式(I)所述的化合物,以及任选地共交联剂、任选地固化催化剂、任选地路易斯酸、任选地含苯并噁嗪的化合物和任选地阻聚剂。
8.根据权利要求3所述的组合物,其中所述式(I)的化合物不存在卤素。
9.根据权利要求3所述的组合物,由以下的任一种形成:涂料、封装剂、复合材料、胶粘剂、模制件、粘结片或层压板。
10.一种制品,包含权利要求3所述的组合物。
11.根据权利要求10所述的制品,其中所述制品可用于无铅焊接应用和电子器件。
12.根据权利要求10所述的制品,其中所述制品还包括铜箔。
13.根据权利要求12所述的制品,其中所述制品为印刷线路板。
14.一种预浸料坯,包含权利要求3所述的组合物。
15.一种层压体或粘结片,包含权利要求3所述的组合物。
16.一种印刷线路板,包含权利要求14所述的预浸料坯。
17.一种印刷线路板,包含权利要求15所述的层压体。
18.一种制备包含权利要求3所述的组合物的层压体的方法,包括将所述组合物浸渍到填充材料中,以形成预浸料坯,然后在升高的温度下加工所述预浸料坯以促进部分固化至B阶段,然后将两个或更多个所述预浸料坯在升高的温度和压力下层压以形成层压体。
19.一种包含通过权利要求18所述的方法制备的层压体的印刷线路板。
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ES2964815T3 (es) * | 2015-03-19 | 2024-04-09 | Zephyros Inc | Acidos esterificados para su uso en materiales poliméricos |
CN106432340B (zh) * | 2016-05-10 | 2020-11-20 | 淮安丹文化工科技有限公司 | 一种含多dopo环状磷酸酯的复合结构磷阻燃剂及其制备方法 |
CN106543228B (zh) * | 2016-10-25 | 2018-07-17 | 北京工商大学 | 一种含磷杂菲基团的烷基次膦酸盐衍生物阻燃剂及其制备方法 |
CN106832407B (zh) * | 2017-03-02 | 2018-11-16 | 广州市银塑阻燃材料有限公司 | 一种高含磷量阻燃剂及其制备方法 |
CN108976705B (zh) | 2017-06-05 | 2020-01-24 | 广东生益科技股份有限公司 | 一种无卤环氧树脂组合物以及使用它的预浸料和层压板 |
CN110330689B (zh) * | 2018-03-27 | 2021-06-29 | 台光电子材料股份有限公司 | 含磷阻燃剂、其制备方法、含有该含磷阻燃剂的树脂组合物及其制品 |
WO2019204713A1 (en) * | 2018-04-20 | 2019-10-24 | Frx Polymers, Inc. | High comparative tracking index, halogen-free flame-retardant thermosetting compositions |
CN111116660A (zh) * | 2019-10-10 | 2020-05-08 | 苏州巨峰新材料科技有限公司 | 一种含磷活性酯化合物及其制备方法 |
CN110669074A (zh) * | 2019-10-18 | 2020-01-10 | 广东聚航新材料研究院有限公司 | 一种新型有机磷阻然剂及其制备方法 |
WO2023043930A1 (en) * | 2021-09-15 | 2023-03-23 | Zephyros, Inc. | Fire resistant two-part system |
CN113801318A (zh) * | 2021-09-24 | 2021-12-17 | 兰州瑞朴科技有限公司 | 双羟基低分子量聚苯醚烷基磷酸酯及其热固性树脂组合物和应用 |
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TWI503339B (zh) * | 2009-05-19 | 2015-10-11 | Albemarle Corp | Dopo衍生的阻燃劑及環氧樹脂組合物 |
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US9217053B2 (en) | 2012-03-21 | 2015-12-22 | Dic Corporation | Active ester resin, thermosetting resin composition, cured product of same, semiconductor encapsulation material, prepreg, circuit board, and build-up film |
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