CN116669961A - 混合跑道制品及其制备方法 - Google Patents
混合跑道制品及其制备方法 Download PDFInfo
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- CN116669961A CN116669961A CN202080107371.3A CN202080107371A CN116669961A CN 116669961 A CN116669961 A CN 116669961A CN 202080107371 A CN202080107371 A CN 202080107371A CN 116669961 A CN116669961 A CN 116669961A
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- isocyanate
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Classifications
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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Abstract
本申请提供了一种混合跑道制品，该混合跑道制品从顶到底包括：(I)由包含外部乳化的聚氨酯分散体和橡胶颗粒的第一组合物制成的顶涂层，其中该外部乳化的聚氨酯分散体衍生自：(Ai)包含具有至少两个异氰酸酯基团的一种或多种化合物的异氰酸酯组分，(Bi)包含具有至少两个异氰酸酯反应性基团的一种或多种化合物的异氰酸酯反应性组分，(Ci)任选的催化剂，(Di)外部乳化剂，(Ei)扩链剂和(Fi)水，以及(II)由包含1K无溶剂聚氨酯粘结剂和橡胶颗粒的第二组合物制成的底层。
Description
技术领域
本公开涉及混合跑道制品及其制备方法，特别是包括由包含外部乳化的聚氨酯分散体和橡胶颗粒的第一组合物制成的顶涂层和由1K无溶剂聚氨酯粘结剂和橡胶颗粒制成的底层的混合跑道制品及其制备方法。
背景技术
通常，如图1所示，跑道是包括水泥地基、底漆层、底层和顶涂层的多层结构。底漆层通常是聚氨酯(PU)/环氧树脂基粘合剂。底层由1K非溶剂PU粘结剂和EPDM颗粒组成。顶层由无溶剂2K PU和EPDM颗粒组成。目前，为了制备顶涂层，将EPDM橡胶颗粒和无溶剂2K PU在搅拌下在滚筒中共混以获得均匀混合物，然后将该混合物喷涂在底层的表面上。通常，为了获得高质量的顶涂层，需要双涂层喷涂工艺。两次涂覆之间的时间间隔为约24小时以在施加后的一天内完全实现目标机械强度。
对于当前的无溶剂2K PU体系，在喷涂过程期间存在许多问题。首先，适用期短。无溶剂2K PU体系通常包含两种组分，包括异氰酸酯/预聚物组分和多元醇。在喷涂之前，需要在机械搅拌条件下将两种组分混合，然后将所得混合物装入喷涂机中以用于喷涂。通常，无溶剂2K PU体系将在两种组分混合后0.5小时内开始胶凝。胶凝(残余物)将容易阻塞喷枪，因此每2小时至3小时需要有机溶剂来清洁喷涂机，这将产生VOC问题。此外，大多数施工方没有获得使用、运输和储存有机溶剂的认证。其次，无溶剂2K PU体系的固化时间通常需要一夜，因此工作效率低下。
因此，仍然存在对表现出优异的机械特性诸如拉伸强度和断裂伸长率、短固化时间和无VOC问题的跑道制品的持续需求。
在持续的探索之后，我们已经令人惊讶地发现了一种可以实现上述目标中的一个或多个目标的混合跑道。本发明人用外部乳化的聚氨酯分散体代替当前的无溶剂2K PU体系作为跑道的顶涂层粘结剂。与无溶剂2K PU体系相比，这种替代至少带来了以下优点：没有适用期限制；没有胶凝问题；以及不需要溶剂来清洁喷涂机。对于跑道施工方来说，他们不需要担心由有机溶剂引起的麻烦。本公开具有以下优点：较少的VOC问题；在加工期间较小的健康安全风险；喷涂后短的干燥(固化)时间(在2小时-3小时内)，以及较高的施加效率；比无溶剂2K PU更好的机械特性，以及比无溶剂2KPU更少的PU树脂用量，同时保持PUD对EPDM的良好覆盖。
发明内容
本公开提供了一种具有短干燥时间、良好机械特性且无VOC问题的混合跑道。
在本公开的第一方面，本公开提供了一种混合跑道制品，该混合跑道制品从顶到底包括：
(I)由包含外部乳化的聚氨酯分散体和橡胶颗粒的第一组合物制成的顶涂层，其中外部乳化的聚氨酯分散体衍生自：(Ai)包含具有至少两个异氰酸酯基团的一种或多种化合物的异氰酸酯组分，(Bi)包含具有至少两个异氰酸酯反应性基团的一种或多种化合物的异氰酸酯反应性组分，(Ci)任选的催化剂，(Di)外部乳化剂，(Ei)扩链剂和(Fi)水，以及
(II)由包含1K无溶剂聚氨酯粘结剂和橡胶颗粒的第二组合物制成的底层。
在本公开的第二方面，本公开提供了一种用于生产第一方面的混合跑道制品的方法，该方法包括：
i)将包含1K无溶剂聚氨酯粘结剂和橡胶颗粒的第二组合物施加在地面上；
ii)固化第二组合物以获得底层；
iii)施加包含外部乳化的聚氨酯分散体和橡胶颗粒的第一组合物，其中外部乳化的聚氨酯分散体衍生自：(Ai)包含具有至少两个异氰酸酯基团的一种或多种化合物的异氰酸酯组分，(Bi)包含具有至少两个异氰酸酯反应性基团的一种或多种化合物的异氰酸酯反应性组分，(Ci)任选的催化剂，(Di)外部乳化剂，(Ei)扩链剂和(Fi)水；
iv)干燥第一组合物以在底层上形成顶涂层。
在本公开的第三方面，本公开提供了外部乳化的聚氨酯分散体在跑道制品的顶涂层中的用途，其中外部乳化的聚氨酯分散体衍生自：(Ai)包含具有至少两个异氰酸酯基团的一种或多种化合物的异氰酸酯组分，(Bi)包含具有至少两个异氰酸酯反应性基团的一种或多种化合物的异氰酸酯反应性组分，(Ci)任选的催化剂，(Di)外部乳化剂，(Ei)扩链剂和(Fi)水。
根据第一至第三方面的优选实施方案，外部乳化的聚氨酯分散体不包含任何阳离子或阴离子亲水性侧基或可转化为共价附接至聚氨酯主链的阳离子或阴离子亲水性侧基的基团。
应当理解，前面的一般性描述和以下的详细描述均仅为示例性和解释性的，而非对如所要求保护的本发明的限制。
附图说明
图1是现有技术的跑道的示意图。
具体实施方式
除非另外定义，否则本文所用的所有技术和科学术语具有与本发明所属领域中的普通技术人员通常所理解相同的含义。此外，本文所提及的所有公开案、专利申请、专利以及其他参考文献均以引用的方式并入。
如本文所公开，术语“组合物”、“调配物”或“混合物”是指不同组分的物理共混物，其是通过用物理方式简单地混合不同组分来获得。
如本文所公开，“和/或”意指“和、或作为替代方案”。除非另外指明，否则所有范围均包括端值。
如本文所公开，“溶剂”意指有机溶剂，除非另外指明。
外部乳化的聚氨酯分散体
通过在底层上施加包含外部乳化的聚氨酯分散体和橡胶颗粒的第一组合物来形成顶涂层。
顶涂层由包含外部乳化的聚氨酯分散体和橡胶颗粒的第一组合物制成，其中外部乳化的聚氨酯分散体衍生自：(Ai)包含具有至少两个异氰酸酯基团的一种或多种化合物的异氰酸酯组分，(Bi)包含具有至少两个异氰酸酯反应性基团的一种或多种化合物的异氰酸酯反应性组分，(Ci)任选的催化剂，(Di)外部乳化剂，(Ei)扩链剂和(Fi)水。
外部乳化剂或外部乳化剂的残余部分没有共价附接至聚氨酯的主链。
根据一个优选的实施方案，外部乳化的聚氨酯分散体是水性的并且基本上不含有意添加到其中的任何有机溶剂。通常，基于分散体的总重量计，水性分散体具有至多约1重量％的有机溶剂。优选地，水分散体具有至多约2000重量百万分率(ppm)，更优选地至多约1000ppm，甚至更优选地至多约500ppm并且最优选地至多痕量的有机溶剂。
如本文所述，表述“外部乳化的聚氨酯分散体”是指包含有限量的，优选地不包含内部乳化组分并且因此主要依赖于“外部乳化剂”(即，离子或非离子乳化剂，其不共价键合到分散在液体介质中的聚氨酯颗粒内的主链，特别是经由源自异氰酸酯基团和异氰酸酯反应性基团(诸如羟基基团)之间的反应的氨基甲酸酯键)的乳化功能以稳定聚氨酯分散体的聚氨酯分散体。
根据本公开的一个实施方案，外部乳化的聚氨酯分散体可通过以下步骤制备：(i)使(Ai)包含具有至少两个异氰酸酯基团的一种或多种化合物的异氰酸酯组分与(Bi)包含具有至少两个异氰酸酯反应性基团的一种或多种化合物的异氰酸酯反应性组分在(Ci)任选的催化剂的存在下反应以形成预聚物；(ii)在(Di)外部乳化剂的存在下将步骤(i)中获得的预聚物分散在(Fi)水中以形成乳液；以及(iii)进一步将(Ei)扩链剂添加到乳液中以与步骤(ii)中获得的预聚物反应并形成外部乳化的聚氨酯分散体。
根据本公开的一个实施方案，步骤(i)中制备的预聚物不包含任何离子内部乳化剂或共价键合到氨基甲酸酯预聚物链的离子内部乳化剂的残余部分。根据本公开的另一个实施方案，步骤(i)中制备的预聚物中的聚氨酯链不包含任何阳离子或阴离子侧基。
在本公开的优选实施方案中，外部乳化的聚氨酯分散体不含任何内部乳化剂，并且在分散于外部乳化的PUD中的聚氨酯颗粒的主链中不存在阴离子或阳离子盐基团。
分散在外部乳化的PUD中的PU颗粒的粒度为20nm至5,000nm，优选地为50nm至2,000nm，并且更优选地为50nm至1,000nm。
外部乳化的聚氨酯分散体可具有任何合适的聚氨酯颗粒固体负载，但通常固体负载为分散体总重量的约1重量％至约70重量％固体，优选地至少约2重量％，更优选地至少约4重量％，更优选地至少约6重量％，更优选地至少约15重量％，更优选地至少约25重量％，更优选地至少约30重量％，最优选地至少约40重量％，至至多约70重量％，优选地至多68重量％，更优选地至多约65重量％，更优选地至多约63重量％，最优选地至多约60重量％。
通常，外部乳化的PUD具有至少约10mPa.s至至多约5,000mPa.s，优选地至少约20mPa.s至至多约2,000mPa.s，更优选地至少约30mPa.s至至多约1000mPa.s的粘度。
异氰酸酯组分(Ai)
在各种实施方案中，异氰酸酯组分(Ai)的平均官能度为至少约2.0，优选地约2至10，更优选地约2至约8，并且最优选地约2至约6。在一些实施方案中，异氰酸酯组分包括包含至少两个异氰酸酯基团的一种或多种聚异氰酸酯化合物。合适的聚异氰酸酯化合物包括具有两个或更多个异氰酸酯基团的芳族、脂族、脂环族和芳脂族聚异氰酸酯。在优选的实施方案中，聚异氰酸酯组分包含选自由以下项组成的组的聚异氰酸酯化合物：包含至少两个异氰酸酯基团的C4-C12脂族聚异氰酸酯、包含至少两个异氰酸酯基团的C6-C15脂环族或芳族聚异氰酸酯、包含至少两个异氰酸酯基团的C7-C15芳脂族聚异氰酸酯，以及它们的组合。在另一个优选的实施方案中，合适的聚异氰酸酯化合物包括间亚苯基二异氰酸酯、2,4-甲苯二异氰酸酯和/或2,6-甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)的各种异构体、碳二亚胺改性的MDI产物、六亚甲基-1,6-二异氰酸酯、四亚甲基-1,4-二异氰酸酯、环己烷-1,4-二异氰酸酯、六氢甲苯二异氰酸酯、氢化MDI、亚萘基-1,5-二异氰酸酯、异佛尔酮二异氰酸酯(IPDI)或它们的混合物。在另一个优选实施方案中，合适的聚异氰酸酯化合物包括异佛尔酮二异氰酸酯(IPDI)。
另选地或附加地，聚异氰酸酯组分还可包含具有在2至10、优选地2至8、更优选地2至6范围内的异氰酸酯官能度的异氰酸酯预聚物。异氰酸酯预聚物可通过使上述单体异氰酸酯组分与选自由以下项组成的组的一种或多种异氰酸酯反应性化合物反应而获得：乙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、1,4-丁炔二醇、1,5-戊二醇、新戊二醇、双(羟甲基)环己烷诸如1,4-双(羟甲基)环己烷、2-甲基丙烷-1,3-二醇、甲基戊二醇、二乙二醇、三乙二醇、四乙二醇、聚乙二醇、二丙二醇、聚丙二醇、二丁二醇和聚丁二醇。适合用作聚异氰酸酯组分的预聚物是NCO基团含量为2重量％至40重量％，更优选地4重量％至30重量％的预聚物。这些预聚物优选地通过二异氰酸酯和/或聚异氰酸酯与包含较低分子量的二醇和三醇的材料的反应来制备。单独的示例是含有氨基甲酸酯基团的芳族聚异氰酸酯，其NCO含量优选地为5重量％至40重量％，更优选地20重量％至35重量％，其通过二异氰酸酯和/或聚异氰酸酯与例如较低分子量的二醇、三醇、氧化烯二醇、二氧化烯二醇或分子量高达约800的聚氧化烯二醇的反应来获得。这些多元醇可以单独使用或呈以二氧化烯二醇和/或聚氧化烯二醇的混合物形式使用。例如，可使用二乙二醇、二丙二醇、聚氧乙烯二醇、乙二醇、丙二醇、丁二醇、聚氧丙烯二醇和聚氧丙烯-聚氧乙烯二醇。也可以使用聚酯多元醇，以及烷烃二醇，诸如丁二醇。其他也有用的二醇包含双羟乙基-或双羟丙基-双酚A、环己烷二甲醇和双羟乙基氢醌。
还有利地用于异氰酸酯组分的是所谓的改性多官能异氰酸酯，即通过上述异氰酸酯化合物的化学反应获得的产物。示例性的是含有酯、脲、缩二脲、脲基甲酸酯以及优选地碳二亚胺和/或脲酮亚胺的聚异氰酸酯。也可以使用含有碳二亚胺基团、脲酮亚胺基团和/或异氰脲酸酯环的液体聚异氰酸酯，其异氰酸酯基团(NCO)含量为12重量％至40重量％、更优选地20重量％至35重量％。这些包括例如基于以下的聚异氰酸酯：4,4'-2,4'-和/或2,2'-二苯基甲烷二异氰酸酯和对应的异构体混合物、2,4-和/或2,6-甲苯二异氰酸酯和对应的异构体混合物；二苯基甲烷二异氰酸酯和PMDI的混合物；以及甲苯二异氰酸酯和PMDI和/或二苯基甲烷二异氰酸酯的混合物。
通常，异氰酸酯组分(Ai)的量可基于跑道制品的实际要求而变化。例如，作为一个示例性实施方案，基于异氰酸酯反应性组分(Bi)中的异氰酸酯反应性基团的总摩尔含量计，异氰酸酯组分(Ai)可以以确保异氰酸酯组分(Ai)中的异氰酸酯基团的含量为约101摩尔％至约300摩尔％，优选地约110摩尔％至约280摩尔％，更优选地约150摩尔％至约250摩尔％，更优选地约170摩尔％至240摩尔％，更优选地约180摩尔％至230摩尔％，更优选地190摩尔％至230摩尔％的量使用。
异氰酸酯反应性组分(Bi)
在本公开的另一个实施方案中，异氰酸酯反应性组分包含选自由以下项组成的组的一种或多种多元醇：包含至少两个羟基基团的脂族多元醇、包含至少两个羟基基团的脂环族或芳族多元醇、包含至少两个羟基基团的芳脂族多元醇、聚醚多元醇、聚酯多元醇以及它们的混合物。优选地，多元醇选自由以下项组成的组：包括至少两个羟基基团的C2-C16脂族多元醇、包括至少两个羟基基团的C6-C15脂环族或芳族多元醇、包括至少两个羟基基团的C7-C15芳脂族多元醇、分子量为100至5,000的聚酯多元醇、分子量为800至12,000的聚醚多元醇，以及它们的组合。
在本公开的一个实施方案中，异氰酸酯反应性组分包含两种或更多种不同多元醇的混合物，诸如两种或更多种聚醚多元醇的混合物、两种或更多种聚酯多元醇的混合物、至少一种聚醚多元醇与至少一种聚酯多元醇的混合物、或聚酯多元醇和单体多元醇的混合物。
在一个实施方案中，异氰酸酯反应性组分是官能度(多元醇分子中异氰酸酯反应性基团，特别是羟基基团的平均数)为2.0至3.0并且重均分子量(Mw)为800至12,000g/mol，优选地1,000至10,000g/mol，优选地1,000至8,000g/mol，更优选地1,000至4,000g/mol的聚醚多元醇。通常通过在存在催化剂的情况下选自环氧丙烷(PO)、环氧乙烷(EO)、环氧丁烷、四氢呋喃以及它们的混合物的一种或多种环氧烷与适当的起始剂分子的聚合来制备聚醚多元醇。典型的起始剂分子包括在分子中具有至少2个、优选地4至8个羟基基团或者具有两个或更多个伯胺基团的化合物。合适的起始剂分子例如选自苯胺、EDA、TDA、MDA和PMDA，更优选地选自TDA和PMDA，最优选地为TDA。当使用TDA时，所有异构体可以单独使用或以任何期望的混合物使用。例如，可以使用2,4-TDA、2,6-TDA、2,4-TDA和2,6-TDA的混合物、2,3-TDA、3,4-TDA、3,4-TDA和2,3-TDA的混合物以及所有上述异构体的混合物。借助于在分子中具有至少2个并且优选地2至8个羟基基团的起始剂分子，优选的是使用三羟甲基丙烷、甘油、季戊四醇、蓖麻油、糖化合物诸如例如葡萄糖、山梨糖醇、甘露醇和蔗糖、多元酚、甲阶酚醛树脂诸如酚和甲醛的低聚缩合产物以及苯酚、甲醛和二烷醇胺的曼尼希缩合物，以及三聚氰胺。用于制备聚醚多元醇的催化剂可包括用于阴离子聚合的碱性催化剂，诸如氢氧化钾，或用于阳离子聚合的路易斯酸催化剂，诸如三氟化硼。合适的聚合催化剂可包括氢氧化钾、氢氧化铯、三氟化硼或双氰化物络合物(DMC)催化剂，诸如六氰基钴酸锌或季磷腈鎓化合物。在本公开的一个优选的实施方案中，聚醚多元醇包括(甲氧基)聚乙二醇(MPEG)、聚乙二醇(PEG)、聚(丙二醇)或具有伯羟基封端基团和仲羟基封端基团的环氧乙烷和环氧丙烷的共聚物。可商购获得的聚醚多元醇的示例包括但不限于以商品名VORANOLTM出售的多元醇，诸如VORANOLTM2000LM和VORANOLTM4000LM、VORANOLTM3010以及VORANOLTM222-056等。
在优选的实施方案中，异氰酸酯反应性组分是分子量为500g/mol至5,000g/mol、优选地1000g/mol至3,000g/mol的聚酯多元醇，以便实现PUD顶膜的良好成膜性和弹性。聚酯多元醇通常通过使具有2至12个碳原子、优选地2至6个碳原子的多官能醇与具有2至12个碳原子、优选地2至6个碳原子的多官能羧酸或其酸酐/酯反应而获得。用于制备聚酯多元醇的典型多官能醇优选地为二醇或三醇，并且包括乙二醇、丙二醇、丁二醇、戊二醇或己二醇。典型的多官能羧酸可以是脂族、脂环族、芳脂族、芳族或杂环的，并且可以例如被卤素原子取代，并且/或者可以是饱和或不饱和的。优选地，多官能羧酸选自由以下项组成的组：辛二酸、壬二酸、邻苯二甲酸、间苯二甲酸、邻苯二甲酸酐、四氢邻苯二甲酸酐、六氢邻苯二甲酸酐、四氯邻苯二甲酸酐、内亚甲基四氢邻苯二甲酸酐、戊二酸酐、烯基琥珀酸、马来酸、马来酸酐、富马酸、二聚脂肪酸。优先考虑通式HOOC-(CH2)y-COOH表示的二羧酸，其中y是1至20的整数，优选地2至20的偶数。聚酯多元醇优选地用至少两个羟基基团封端。在优选的实施方案中，聚酯多元醇的羟基官能度为2至10，优选地2至6。在另一个实施方案中，聚酯多元醇的OH值为80mgKOH/g至2,000mgKOH/g，优选地150mgKOH/g至1,000mgKOH/g，并且更优选地200mgKOH/g至500mgKOH/g。聚酯多元醇考虑了各种分子量。例如，聚酯多元醇的数均分子量可为约500g/mol至约5,000g/mol，优选地约600g/mol至约4,000g/mol，优选地约500g/mol至约3,000g/mol，优选地约1000g/mol至约2,500g/mol，优选地约1200g/mol至约2,000g/mol，并且更优选地约1,500g/mol至约1,800g/mol。
另选地，聚酯多元醇包括基于内酯的聚酯二醇，其为内酯的均聚物或共聚物，优选地为内酯与合适的双官能引发剂分子的末端羟基官能加成产物。优选的内酯衍生自由通式HO-(CH2)z-COOH表示的化合物，其中z是1至20的整数，并且亚甲基单元的一个氢原子也可以被C1至C4烷基基团取代。示例性的基于内酯的聚酯二醇包括ε-己内酯、β-丙内酯、γ-丁内酯、甲基-ε-己内酯或它们的混合物。
一般来讲，基于异氰酸酯组分(Ai)中的异氰酸酯基团的总摩尔含量计，本文所用的异氰酸酯反应性组分(Bi)的量可以以确保异氰酸酯反应性组分(Bi)中的异氰酸酯反应性基团为约50摩尔％至约98摩尔％，优选地约60摩尔％至约97摩尔％，更优选地约70摩尔％至约96摩尔％，更优选地约80摩尔％至约96摩尔％，更优选地约85摩尔％至约95摩尔％的量使用。
在本公开的上下文中，包含可与异氰酸酯基团反应的官能团的其他化合物，诸如扩链剂和水，不在所谓的“异氰酸酯反应性组分”的定义内。扩链剂和水可以通过分子结构或它们被添加的时间点与异氰酸酯反应性组分清楚地区分开。
催化剂(Ci)
催化剂(Ci)可包括可以促进异氰酸酯基团与异氰酸酯反应性基团之间的反应的任何物质。不受理论的限制，催化剂可包括例如甘氨酸盐；叔胺；叔膦，诸如三烷基膦和二烷基苯甲基膦；吗啉衍生物；哌嗪衍生物；各种金属的螯合物，诸如可从乙酰丙酮、苯甲酰丙酮、三氟乙酰丙酮、乙酰乙酸乙酯等与金属诸如Be、Mg、Zn、Cd、Pd、Ti、Zr、Sn、As、Bi、Cr、Mo、Mn、Fe、Co和Ni获得的那些；强酸的酸性金属盐，诸如氯化铁和氯化锡；有机酸与多种金属的盐，诸如碱金属、碱土金属、Al、Sn、Pb、Mn、Co、Ni和Cu；有机锡化合物，诸如有机羧酸的锡(II)盐，例如二乙酸锡(II)、二辛酸锡(II)、二乙基己酸锡(II)和二月桂酸锡(II)，以及有机羧酸的二烷基锡(IV)盐，例如二乙酸二丁基锡、二月桂酸二丁基锡、马来酸二丁基锡和二乙酸二辛基锡；有机羧酸的铋盐，例如辛酸铋；三价和五价As、Sb和Bi的有机金属衍生物以及铁和钴的羰基金属；或者它们的混合物。
叔胺催化剂包括包含至少一个叔氮原子并且能够催化羟基/异氰酸酯反应的有机化合物。通过示例而非限制，叔胺、吗啉衍生物和哌嗪衍生物催化剂可包括三亚乙基二胺、四甲基乙二胺、五甲基二亚乙基三胺、双(2-二甲基氨基乙基)醚、三乙胺、三丙胺、三丁胺、三戊胺、吡啶、喹啉、二甲基哌嗪、哌嗪、N-乙基吗啉、2-甲基丙烷二胺、甲基三亚乙基二胺、2,4,6-(三二甲基氨基-甲基)苯酚、N,N’,N”-三(二甲基氨基-丙基)均-六氢三嗪，或它们的混合物。
一般来讲，基于异氰酸酯组分(Ai)和异氰酸酯反应性组分(Bi)的总重量计，本文所用的催化剂的含量大于或等于0重量％并且为至多1.0重量％，优选地至多0.5重量％，更优选地至多0.05重量％，更优选地至多0.02重量％。可以看出，当将异氰酸酯组分(Ai)和异氰酸酯反应性组分(Bi)的总量取为100重量％时，将催化剂的含量计算为附加量。
外部乳化剂(Di)
外部乳化剂可以是阳离子、阴离子或非离子的，并且优选地是阴离子的。合适类别的乳化剂包括但不限于乙氧基化酚的硫酸盐，诸如聚(氧基-1,2-乙烷二基)α-磺基-ω(壬基苯氧基)盐；碱金属脂肪酸盐，诸如碱金属油酸盐和硬脂酸盐；碱金属C12-C16烷基硫酸盐，诸如碱金属月桂基硫酸盐；碱金属C12-C16烷基苯磺酸盐，诸如支链和直链十二烷基苯磺酸钠；阴离子和非离子氟碳乳化剂，诸如氟化C4-C16烷基酯和碱金属C4-C16全氟烷基磺酸盐。示例性外部乳化剂包括十八烷基磺基琥珀酸二钠、十二烷基苯磺酸钠(SDBS)、硬脂酸钠和硬脂酸铵。聚氨酯分散体可通过任何合适的方法制备，诸如本领域熟知的那些方法。
根据本公开的实施方案，基于外部乳化的PUD的总重量计，外部乳化剂的量为0.01重量％至10重量％，或0.05重量％至8重量％，0.1重量％至7重量％，或0.2重量％至6重量％，或0.5重量％至5重量％，或1重量％至5重量％，或1重量％至3重量％。
扩链剂(Ei)
根据本公开的一个实施方案，扩链剂(Ei)可以是聚胺，优选地选自由以下项组成的组：在脂族环内包含至少两个胺基团的C4-C15脂环族聚胺，例如哌嗪；包含至少两个胺基团的C2-C16脂族聚胺，例如乙二胺；在脂族环外包含至少两个胺基团的C4-C15脂环族聚胺，诸如环己二胺，或者包含至少两个胺基团的C5-C15芳族聚胺，诸如对二甲苯二胺；以及包含至少两个胺基团的C7-C15芳脂族聚胺。根据优选的实施方案，扩链剂是在脂族环内包含至少两个胺基团的C4-C15脂环族聚胺或在脂族环外包含至少两个胺基团的C4-C15脂环族聚胺，更优选地在脂族环内包含两个仲胺基团的C4-C15脂环族聚胺或在脂族环外包含两个伯胺基团或仲胺基团的C4-C15脂环族聚胺。优选地，胺扩链剂是哌嗪。
根据本公开的实施方案，扩链剂以确保预聚物的NCO封闭率为约70.0％至约98.5％，或约70.0％、75.0％或80.0％的下限至约98.0％、97.0％、95.0％或85.0％的上限的量使用，其中预聚物通过(i)使(Ai)包含具有至少两个异氰酸酯基团的一种或多种化合物的异氰酸酯组分与(Bi)包含具有至少两个异氰酸酯反应性基团的一种或多种化合物的异氰酸酯反应性组分在(Ci)任选的催化剂的存在下反应来制备。“NCO封闭率”定义为预聚物中被扩链剂诸如哌嗪封闭的NCO基团的摩尔百分比。
1K无溶剂聚氨酯粘结剂
1K无溶剂聚氨酯粘结剂也可称为单组分无溶剂聚氨酯预聚物，其包含通过使(Aii)包含具有至少两个异氰酸酯基团的一种或多种化合物的异氰酸酯组分、(Bii)包含具有至少两个异氰酸酯反应性基团的一种或多种化合物的异氰酸酯反应性组分反应而形成的反应产物，其中(Aii)包含具有至少两个异氰酸酯基团的一种或多种化合物的异氰酸酯组分的详细描述可以是指(Ai)包含具有至少两个异氰酸酯基团的一种或多种化合物的异氰酸酯组分，并且(Bii)包含具有至少两个异氰酸酯反应性基团的一种或多种化合物的异氰酸酯反应性组分的详细描述可以是指(Bi)包含具有至少两个异氰酸酯反应性基团的一种或多种化合物的异氰酸酯反应性组分。1K无溶剂聚氨酯粘结剂是可湿固化的。
通常，基于分散体的总重量计，1K无溶剂聚氨酯粘结剂具有至多约1重量％的有机溶剂。优选地，水分散体具有至多约2000重量百万分率(ppm)，更优选地至多约1000ppm，甚至更优选地至多约500ppm并且最优选地至多痕量的有机溶剂。
优选地，1K无溶剂聚氨酯粘结剂包含通过使二苯基甲烷二异氰酸酯(MDI)组分和多元醇反应而形成的反应产物。二苯基甲烷二异氰酸酯(MDI)组分也可以用TDI组分、IPDI组分、HDI组分、H12MDI组分或它们的混合物代替。
在本公开的实施方案中，基于二苯基甲烷二异氰酸酯组分和多元醇的总重量计，1K无溶剂聚氨酯粘结剂包括通过使15重量％至50重量％的二苯基甲烷二异氰酸酯组分和50重量％至85重量％的多元醇反应而形成的反应产物。二苯基甲烷二异氰酸酯(MDI)组分也可以用TDI组分、IPDI组分、HDI组分、H12MDI组分或它们的混合物代替。
基于二苯基甲烷二异氰酸酯组分的总重量计，二苯基甲烷二异氰酸酯组分可包括90重量％至100重量％的4,4’-二苯基甲烷二异氰酸酯。包括90重量％至100重量％的所有单个值和子范围；例如，基于二苯基甲烷二异氰酸酯组分的总重量计，二苯基甲烷二异氰酸酯组分可包括90重量％、93重量％或95重量％的下限至100重量％、99重量％或97重量％的上限的4,4’-二苯基甲烷二异氰酸酯。二苯基甲烷二异氰酸酯组分还可包括2,2’-二苯基甲烷二异氰酸酯、2,4’-二苯基甲烷二异氰酸酯和/或本领域已知的杂质。
多元醇可具有300g/mol至12,000g/mol的重均分子量。包括300g/mol至12,000g/mol的所有单个值和子范围；例如，多元醇可具有300g/mol、500g/mol、750g/mol、1,000g/mol、1,250g/mol、1,500g/mol、1,750g/mol、2,000g/mol或2,250g/mol的下限至12,000g/mol、11,000g/mol、10,000g/mol、9,000g/mol、8,000g/mol、7,000g/mol、6,000g/mol、5,000g/mol或4,500g/mol的上限的重均分子量。
多元醇可具有1.5至3.5的平均官能度。包括1.5至3.5的所有单个值和子范围；例如，多元醇可具有1.5、1.6、1.7或1.8的下限至3.5、3.4、3.3或3.2的上限的平均官能度。
多元醇可以是聚醚多元醇、聚酯多元醇、以及它们的组合。可商购获得的多元醇的示例包括但不限于以商品名VORANOLTM出售的多元醇，诸如VORANOLTMWD 2130和VORANOLTM4000LM、TERCAROLTM以及VORATECTM等。
多元醇可包括聚醚多元醇。聚醚多元醇可通过已知方法制备。例如，聚醚多元醇可通过至少一种环氧烷烃(例如，环氧乙烷或1,2-环氧丙烷或1,2-氧化丙烯和环氧乙烷的阴离子聚加成来制备。可被称为引发剂的起始化合物是在聚合反应中将被烷氧基化的任何有机化合物。引发剂可包含2个或更多个羟基和/或胺基团。可以使用起始化合物/引发剂的混合物。引发剂化合物的示例包括但不限于乙二醇、二乙二醇、三乙二醇、丙二醇、二丙二醇、三丙二醇、1,4-丁二醇、1,6-己二醇、1,8-辛二醇、环己烷二甲醇、甘油、三羟甲基丙烷、三羟甲基乙烷、季戊四醇、山梨糖醇、蔗糖，以及这些中的任一者的烷氧基化物(特别是乙氧基化物和/或丙氧基化物)、聚胺、二烷醇胺。
多元醇可包括聚酯多元醇。聚酯多元醇可由例如具有2至12个碳原子的有机二羧酸(包括具有8至12个碳原子的芳族二羧酸)和多元醇(包括具有2至12个碳原子的二醇)制备。合适的二羧酸的示例是琥珀酸、戊二酸、己二酸、辛二酸、壬二酸、癸二酸、癸烷二羧酸、马来酸、富马酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸和同分异构的萘二甲酸。二羧酸可以单独使用或彼此混合使用。游离二羧酸可以被对应的二羧酸衍生物代替，例如具有1至4个碳原子的醇的二羧酸酯或二羧酸酐。一些特定示例可使用二羧酸混合物，包括比率为例如20比35:35重量份至50:20比32重量份的琥珀酸、戊二酸和己二酸，以及己二酸，以及邻苯二甲酸和/或邻苯二甲酸酐和己二酸的混合物，邻苯二甲酸或邻苯二甲酸酐、间苯二甲酸和己二酸的混合物或琥珀酸、戊二酸和己二酸的二羧酸混合物，以及对苯二甲酸和己二酸的混合物或琥珀酸、戊二酸和己二酸的二羧酸混合物。二元醇和多元醇的示例是乙二醇、二乙二醇、1,2-和1,3-丙二醇、二丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,10-癸二醇、甘油、三羟甲基丙烷等。一些特定示例提供乙二醇、二乙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇或所述二醇中的至少两者的混合物，特别是1,4-丁二醇、1,5-戊二醇和1,6-己二醇的混合物。此外，也可以采用由内酯(例如，e-己内酯)或羟基羧酸(例如，w-羟基己酸和羟基苯甲酸)制成的聚酯多元醇。
例如，聚酯多元醇可通过使有机多元羧酸和/或其衍生物与多元醇以1:1至1:1.8，例如1:1.05至1:1.2的摩尔比缩聚而制备。
基于二苯基甲烷二异氰酸酯组分和多元醇的总重量计，反应产物可通过使15重量％至50重量％的二苯基甲烷二异氰酸酯组分和50重量％至85重量％的多元醇反应而形成。包括15重量％至50重量％的二苯基甲烷二异氰酸酯组分的所有单个值和子范围；例如，基于二苯基甲烷二异氰酸酯组分和多元醇的总重量计，反应产物可通过使15重量％、20重量％或25重量％的下限至50重量％、45重量％或40重量％的上限的二苯基甲烷二异氰酸酯组分反应而形成。
包括50重量％至85重量％的多元醇的所有单个值和子范围；例如，基于二苯基甲烷二异氰酸酯和多元醇的总重量计，反应产物可通过使50重量％、55重量％或60重量％的下限至85重量％、80重量％或75重量％的上限的多元醇反应而形成。
反应产物可使用已知的设备和反应条件而形成。例如，可以将反应物(即，二苯基甲烷二异氰酸酯组分和多元醇)加热至任何期望的温度，持续足以实现期望的化学/物理转化的指定时间。作为示例，反应产物可以在20℃至100℃的温度下形成；反应可以发生，例如维持约5分钟至约8小时；并且反应可在惰性环境诸如氮气环境中进行。
本文公开的1K聚氨酯粘结剂还可使用脂族异氰酸酯。
脂族异氰酸酯可具有1.5至3.5的平均官能度。包括1.5至3.5的所有单个值和子范围；例如，多元醇可具有1.5、1.6、1.7、1.8或2.0的下限至3.5、3.4、3.3、3.2或3.0的上限的平均官能度。
脂族异氰酸酯的示例包括但不限于异佛尔酮二异氰酸酯、异佛尔酮二异氰酸酯三聚体、六亚甲基二异氰酸酯三聚体、亚甲基二环己基二异氰酸酯和氢化亚甲基二环己基二异氰酸酯。优选地，脂族异氰酸酯选自异佛尔酮二异氰酸酯、异佛尔酮二异氰酸酯三聚体、六亚甲基二异氰酸酯三聚体、以及它们的组合。
基于二苯基甲烷二异氰酸酯组分、多元醇和脂族异氰酸酯的总重量计，本文公开的1K聚氨酯粘结剂包括0.5重量％至20重量％的脂族异氰酸酯。包括0.5重量％至20重量％的所有单个值和子范围；例如，基于二苯基甲烷二异氰酸酯组分、多元醇和脂族异氰酸酯的总重量计，1K聚氨酯粘结剂可包括0.5重量％、0.7重量％、1.0重量％或2.0重量％的下限至20重量％、18重量％、15重量％、10重量％、8重量％或6重量％的上限的脂族异氰酸酯。
脂族异氰酸酯可与二苯基甲烷二异氰酸酯组分以1:20至1:5的重量比使用。包括1:5至1:20的所有单个值和子范围；例如，脂族异氰酸酯可与二苯基甲烷二异氰酸酯组分以1:20、1:18或1:16的下限至1:5、1:5.5或1:6的上限的重量比使用。
本文公开的1K聚氨酯粘结剂可任选地包括季铵化剂。季铵化剂的示例包括但不限于烷基卤化物、芳烷基卤化物、碳酸二烷基酯、硫酸二烷基酯、环氧化物以及它们的组合。特定季铵化剂的示例包括但不限于甲基氯、乙基氯、苄基氯、甲基溴、乙基溴、苄基溴、硫酸二甲酯、硫酸二乙酯、环氧乙烷、环氧丙烷、环氧丁烷、氧化苯乙烯、表氯醇以及它们的组合。在本公开的一个或多个实施方案中，季铵化剂为苄基氯。
基于二苯基甲烷二异氰酸酯组分和多元醇的总重量计，本文公开的1K聚氨酯粘结剂可包括20百万分率至200百万分率的季铵化剂。包括20百万分率至200百万分率的所有单个值和子范围；例如，基于二苯基甲烷二异氰酸酯组分和多元醇的总重量计，1K聚氨酯粘结剂可包括20百万分率、30百万分率或50百万分率的下限至200百万分率、175百万分率或150百万分率的上限的季铵化剂。
本文公开的1K聚氨酯可包括添加剂。添加剂的示例包括但不限于有机酸、磷酸、填料、触变剂、抗氧化剂、颜料、UV吸收剂、粘合促进剂、干燥剂以及它们的组合等。不同量的添加剂可用于各种应用。
1K聚氨酯粘结剂可在单组分可湿固化组合物已知的条件下制备，例如混合、合并。
基于1K聚氨酯粘结剂的总重量计，本文所公开的1K聚氨酯粘结剂可具有3.0重量％至12.0重量％的NCO含量。包括3.0重量％至12.0重量％的所有单个值和子范围；例如，基于1K聚氨酯粘结剂的总重量计，1K聚氨酯粘结剂可具有3.0重量％、5.0重量％或7.0重量％的下限至12.0重量％、11.0重量％或10.0重量％的上限的NCO含量。
本文所公开的1K聚氨酯粘结剂可具有在25℃下1,000mPa·s至6,000mPa·s的粘度，如根据ASTM D4889确定的。包括1,000mPa·s至6,000mPa·s的所有单个值和子范围；例如，1K聚氨酯粘结剂可具有在25℃下1,000mPa·s、1,250mPa·s或1,500mPa·s的下限至6,000mPa·s、5,000mPa·s或4,500mPa·s的上限的粘度，如根据ASTM D4889确定的。
如上所述，本文所公开的1K聚氨酯粘结剂是可湿固化的。换句话讲，1K聚氨酯粘结剂可通过暴露于水(例如，水蒸气)而固化以形成固化产物。环境湿度通常足以促进固化1K聚氨酯粘结剂。如本领域已知的，可以调节固化的湿度以影响用于许多应用的固化。另外，可以使用本领域已知的固化温度。例如，在增加的固化温度可以加速固化的情况下，对于一些应用，可以调节固化温度。
1K无溶剂聚氨酯粘结剂可以是可商购获得的，诸如商标为Voramer MR 1045L。
第一组合物和第二组合物
用于制备顶涂层的第一组合物中的橡胶颗粒是EPDM颗粒。用于制备顶涂层的第一组合物中的橡胶颗粒(优选地EPDM颗粒)具有在0.1mm-4.5mm，优选地0.5mm-2.5mm范围内的平均粒度。顶涂层的厚度可以是0.5mm-10mm，优选地1mm-5mm，更优选地2mm-3mm。
在用于制备顶涂层的第一组合物中，外部乳化的聚氨酯分散体与橡胶颗粒(优选地EPDM颗粒)的重量比为1:0.5-3，优选地1:0.8-2，更优选地1:1-1.5。
根据本公开的一个实施方案，用于制备底层的第二组合物中的橡胶颗粒为EPDM颗粒。用于制备底层的第二组合物中的橡胶颗粒(优选地EPDM颗粒)具有在2mm-10mm，优选地3mm-5mm范围内的平均粒度。底层的厚度可以是2mm-25mm，优选地5mm-20mm，更优选地8mm-12mm，甚至更优选地8mm-10mm。
在用于制备底层的第二组合物中，1K无溶剂聚氨酯粘结剂与橡胶颗粒(优选地EPDM颗粒)的重量比为1:3-12，优选地1:6-10，更优选地1:7。
助剂和添加剂
第一组合物和第二组合物可独立地和任选地包含用于特定目的的任何附加助剂和/或添加剂。
在本公开的一个实施方案中，助剂和/或添加剂中的一者或多者可选自由以下项组成的组：填料、染料/颜料、表面活性化合物、手感剂、消光剂、流变改性剂、消泡剂、交联剂和稳定剂。
可使用任何合适的流变改性剂，诸如本领域已知的那些。优选地，流变改性剂是不会导致分散体变得不稳定的流变改性剂。更优选地，流变改性剂是未离子化的水溶性增稠剂。可用的流变改性剂的示例包括甲基纤维素醚、碱溶胀性增稠剂(例如，钠或铵中和的丙烯酸聚合物)、疏水改性的碱溶胀性增稠剂(例如，疏水改性的丙烯酸共聚物)和缔合增稠剂(例如，疏水改性的基于环氧乙烷的氨基甲酸酯嵌段共聚物)。优选地，流变改性剂是甲基纤维素醚。增稠剂的量为第一组合物或第二组合物总重量的至少约0.2重量％至约5重量％，优选地约0.5重量％至约2重量％。
染料/颜料在本公开中通常也可称为“色母料”。例如，可以添加色母料以赋予层期望的颜色。染料/颜料的示例可包括氧化铁、氧化钛、炭黑以及它们的混合物。基于第一组合物或第二组合物的总重量，染料/颜料的量可以为0.01重量％至15重量％，优选地0.5重量％至10重量％，更优选地1重量％至5重量％。
合适填料的示例包括玻璃纤维、矿物纤维、天然纤维诸如亚麻、黄麻或剑麻、玻璃薄片、硅酸盐诸如云母或闪光物、盐诸如碳酸钙、白垩或石膏。基于顶涂层或底层的总干重计，填料的用量通常以0.5重量％至60重量％，优选地3重量％至30重量％的量使用。
制造技术
本申请的混合跑道制品可以通过包括以下步骤的方法制备：
i)将包含1K无溶剂聚氨酯粘结剂和橡胶颗粒的第二组合物施加在地面上；
ii)固化第二组合物以获得底层；
iii)施加包含外部乳化的聚氨酯分散体和橡胶颗粒的第一组合物，其中外部乳化的聚氨酯分散体衍生自：(Ai)包含具有至少两个异氰酸酯基团的一种或多种化合物的异氰酸酯组分，(Bi)包含具有至少两个异氰酸酯反应性基团的一种或多种化合物的异氰酸酯反应性组分，(Ci)任选的催化剂，(Di)外部乳化剂，(Ei)扩链剂和(Fi)水；
iv)干燥第一组合物以在底层上形成顶涂层。
第一组合物和第二组合物可通过常规涂覆技术诸如喷涂、刮涂、模涂、铸涂等来施加。
第二组合物可在RT(-20℃至40℃)下固化一天。
第一组合物可在0℃至40℃下在阳光(较少的雾和湿气)下干燥1小时-5小时。
本公开的跑道制品还可包括在底层和地面之间的一个或多个粘合剂层。底层和地面之间的一个或多个粘合剂层可通过常规涂覆技术诸如喷涂、刮涂、模涂、铸涂等来施加。
实施例
现在将在以下实施例中描述本发明的一些实施方案，其中所有的份数和百分比都是以重量计，除非另有说明。
下表1中列出了实施例中使用的原材料的信息：
表1.原材料
预聚物制备
将多元醇装入三颈烧瓶中，在110℃下、在76mmHg压力下脱水一小时，然后将脱水的多元醇混合物自然冷却至70℃-75℃。将IPDI在70℃-75℃下、在氮气(N2)流保护和机械搅拌下倒入脱水多醇混合物中，然后将催化剂T12添加到反应物中。该反应在70℃-75℃下持续一小时，然后将反应物加热至80℃-85℃以连续反应2小时-3小时。将产物(预聚物)用塑料瓶包装并在氮气保护下密封储存。
PUD制备
将上述预聚物倒入1000ml塑料杯中，并用分散机搅拌。在高速混合(3,800RPM至4,000RPM)下将SDBS水性溶液缓慢添加到预聚物中。混合几分钟后，在高速混合(3,800RPM至4,000RPM)下将去离子水逐滴添加到预聚物中。一旦发生相反转，就将混合速度减慢至不超过1,500RPM。此时，形成乳液。之后，将扩链剂-哌嗪水性溶液逐滴添加到乳液中。在添加所有扩链剂溶液后，再继续机械搅拌10分钟至15分钟。最后，获得固体含量为约50％的聚氨酯分散体并将其储存在带有盖的塑料容器中。由3种预聚物制备12种PUD。
配制品和PUD性能的细节列于表1中。
跑道制备
300G PUD和H18 PUD(在表1中标记为PUD名称)用于制备跑道制品。
将包含1K PU Dow Voramer MR 1045L粘结剂和EPDM颗粒的组合物(PU粘结剂与EPDM颗粒的重量比为1比7)施加到脱模层(农用膜)上以形成底层(0.5*0.5m2)，并在RT下固化24小时。在固化后，底层的厚度为10mm。
将PUD(50重量％固体含量)、EPDM颗粒和色糊(颗粒和色糊均由浙江跑步运动有限公司提供)的配制品以PUD:EPDM颗粒:色糊为1:1:0.05的重量比通过喷涂机喷涂到底层上。喷涂进行两次。第二次喷涂在冬季第一次喷涂层干燥2小时后进行，这比2K无溶剂体系顶涂层(其需要一夜来固化)快得多。顶涂层的厚度为2mm-3mm。然后剥离脱模层。最终跑道性能列于表3中。
表3.在现场试验中制备的PUD基样品的性能
根据表3中列出的机械特性，与要求拉伸强度≥0.4MPa和伸长率≥40％的中国标准(GB/T14833-2011)相比，两种样品均具有更强的拉伸强度和更长的伸长率，这意味着两者均比中国标准好得多。
此外，喷涂法和PUD合成法都不使用任何有机溶剂，这比以前的2K PU喷涂法更环境友好。其次，PU树脂负载也低于2K PU，这意味着较低的价格。最后，PUD基顶涂层的干燥时间非常快，在冬季约2小时，这比传统的2K PU顶涂层体系快得多(这可以节省建造时间)。
拉伸强度和断裂伸长率(％)的确定
根据GB/T 14833-2011测试拉伸强度和断裂伸长率(％)。
中值粒度的确定
聚氨酯颗粒的中值粒度通过粒度分析仪(型号：LS230，可得自贝克曼库尔特公司(Beckman Coulter,INC))测试。
粘度的确定
使用TA仪器AR2000ex在25℃或明确指定的温度下，利用铝板、连续流和1-100S-l的剪切速率确定粘度。
NCO含量的确定
如下通过滴定确定NCO含量(重量％)。将甲苯以及二丁胺(DBA)(155ml)与N,N-二甲基甲酰胺(DMF)(350ml)的混合物各自经由筛干燥约12小时。
对于样品测试，将待测试的样品添加到容器中并称重；然后将干燥的甲苯(6ml)以及DBA和DMF的干燥混合物(2ml)添加到容器中，随后添加异丙醇(10ml)。使用盐酸(0.5)滴定容器的内容物。
通过下式计算NCO含量(％)：
其中B是空白试验中消耗的盐酸的体积；S是样品测试中消耗的盐酸的体积；N是盐酸的浓度(0.5M)，并且W是样品的重量。
Claims (10)
1.一种混合跑道制品，所述混合跑道制品从顶到底包括：
(I)由包含外部乳化的聚氨酯分散体和橡胶颗粒的第一组合物制成的顶涂层，其中所述外部乳化的聚氨酯分散体衍生自：(Ai)包含具有至少两个异氰酸酯基团的一种或多种化合物的异氰酸酯组分，
(Bi)包含具有至少两个异氰酸酯反应性基团的一种或多种化合物的异氰酸酯反应性组分，(Ci)任选的催化剂，(Di)外部乳化剂，(Ei)扩链剂和(Fi)水，以及
(II)由包含1K无溶剂聚氨酯粘结剂和橡胶颗粒的第二组合物制成的底层。
2.根据权利要求1所述的混合跑道制品，其中所述(Bi)包含具有至少两个异氰酸酯反应性基团的一种或多种化合物的异氰酸酯反应性组分是聚醚多元醇。
3.根据权利要求1所述的混合跑道制品，其中所述(Di)外部乳化剂选自由以下项组成的组：乙氧基化酚；碱金属脂肪酸盐；碱金属C12-C16烷基硫酸盐；碱金属C12-C16烷基苯磺酸盐；阴离子和非离子氟碳乳化剂。
4.根据权利要求1所述的混合跑道制品，其中所述(Ei)扩链剂是在脂族环内包含至少两个胺基团的C4-C15脂环族聚胺、在脂族环外包含至少两个胺基团的C4-C15脂环族聚胺或它们的混合物。
5.根据权利要求4所述的混合跑道制品，其中所述(Ei)扩链剂以确保预聚物的NCO封闭率为约70.0％至约98.5％的量使用，其中所述预聚物通过(i)使(Ai)包含具有至少两个异氰酸酯基团的一种或多种化合物的异氰酸酯组分与(Bi)包含具有至少两个异氰酸酯反应性基团的一种或多种化合物的异氰酸酯反应性组分在(Ci)任选的催化剂的存在下反应来制备。
6.根据权利要求1所述的混合跑道制品，其中所述1K无溶剂聚氨酯粘结剂是可湿固化的。
7.根据权利要求1所述的混合跑道制品，其中所述外部乳化的聚氨酯分散体与所述橡胶颗粒的重量比为1:0.5-1.5。
8.根据权利要求1或7所述的混合跑道制品，其中所述橡胶颗粒是EPDM颗粒。
9.一种用于制备根据权利要求1至8中任一项所述的混合跑道制品的方法，所述方法包括：
i)将包含1K无溶剂聚氨酯粘结剂和橡胶颗粒的第二组合物施加在地面上；
ii)固化所述第二组合物以获得底层；
iii)施加包含外部乳化的聚氨酯分散体和橡胶颗粒的第一组合物，其中所述外部乳化的聚氨酯分散体衍生自：(Ai)包含具有至少两个异氰酸酯基团的一种或多种化合物的异氰酸酯组分，(Bi)包含具有至少两个异氰酸酯反应性基团的一种或多种化合物的异氰酸酯反应性组分，(Ci)任选的催化剂，(Di)外部乳化剂，(Ei)扩链剂和(Fi)水；
iv)干燥所述第一组合物以在所述底层上形成顶涂层。
10.外部乳化的聚氨酯分散体作为跑道制品的顶涂层的用途，其中所述外部乳化的聚氨酯分散体衍生自：(Ai)包含具有至少两个异氰酸酯基团的一种或多种化合物的异氰酸酯组分，(Bi)包含具有至少两个异氰酸酯反应性基团的一种或多种化合物的异氰酸酯反应性组分，(Ci)任选的催化剂，(Di)外部乳化剂，(Ei)扩链剂和(Fi)水。
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