TW201602208A - 以經二烯官能化之（甲基）丙烯酸酯及（雜）狄耳士－阿德爾親二烯物爲基底並具有可逆交聯的模製零件 - Google Patents
以經二烯官能化之（甲基）丙烯酸酯及（雜）狄耳士－阿德爾親二烯物爲基底並具有可逆交聯的模製零件 Download PDFInfo
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Abstract
本發明係關於一種貯存穩定之預浸體的製造方法及由該預浸體所製造之模製物體(複合組件)。依照本發明之製造該預浸體所用的組成物在此含有A)單體，尤其是(甲基)丙烯酸酯及/或苯乙烯，B)至少一種具有含共軛二烯之殘基的(甲基)丙烯酸酯，C)具有至少二個親二烯基團的交聯劑，及D)至少一種合適的起始劑。
另一選擇地，該組成物可含有該二成分B)和C)之狄耳士-阿德爾反應的產物C'代替成分B)和C)或作為成分B)和C)之額外成分。
Description
本發明係關於一種貯存穩定之預浸體的製造方法及由該預浸體所製造之模製物體(複合組件)。
由於預浸體形之纖維強化的處置容易性以及與該替代之濕式疊層技術相比在加工期間之增加的效率，已將預浸體形之纖維強化材料已用在很多應用中。
此種系統之工業使用者除了要求更快之循環時間及更高的貯存穩定性(即使在室溫下)之外，也要求在裁切工具於個別預浸體層之自動裁切和疊層期間不受該常為黏性的基質材料所汙染下，將該預浸體裁切成合適尺寸的選項。不同的模製方法，例如反應轉移模製(RTM)方法，包含將該強化纖維導入模中，關閉該模、將該可交聯之樹脂調合物導入該模，及隨後典型藉由施加熱將該樹脂交聯。
此一方法的限制之一是相對困難將該強化纖維放置在該模中。該紡織織物或非織織物之個別層必須裁切成合適尺寸且符合不同之模形狀。這可以是時間密集且複雜的，
特別是當該經模製之物體也要含有泡體或其他核心時。在此會想要具有簡單處置及現有模製可能性之可模製的纖維強化物。
除了聚酯、乙烯酯和環氧樹脂系統之外，在該交聯樹脂基質系統領域中還有很多專業的樹脂。這些也包括聚胺甲酸酯樹脂，其由於其韌性、耐破壞性及強度而特別用在複合型材之製造中，例如經由拉擠成型方法者。所用之異氰酸酯之毒性是常被提及的缺點。然而，也認為其中所用之環氧系統及固化用成分的毒性是嚴重的。這尤其適用於已知的敏化及過敏症。
以環氧系統為基底之預浸體和由該預浸體所製造之複合材料是例如描述於WO 98/50211、EP 309 221、EP 297 674、WO 89/04335和US 4,377,657中。在WO 2006/043019中，描述一種以環氧化物樹脂-聚胺甲酸酯粉末為基底之預浸體的製造方法。另外，以粉末狀熱塑性塑膠作為基底的預浸體是已知。
在WO 99/64216中，描述預浸體及複合物及彼等之製造方法，其中使用具有小聚合物粒子以致能進行單一纖維塗覆的乳濁液。該等粒子之聚合物具有至少5000厘泊之黏度且是熱塑性塑膠或交聯用聚胺甲酸酯聚合物之任一者。
在EP 0590702中，描述用於製造預浸體之粉末浸透
作用，其中該粉末係由熱塑性塑膠和反應性單體或預聚物之混合物構成。WO 2005/091715也描述使用熱塑性塑膠以製造預浸體。
具有以2-成分聚胺甲酸酯(2-C PUR)為基底之基質的預浸體同樣是已知的。該2-C PUR範疇基本上包含該傳統的反應性聚胺甲酸酯樹脂系統。原則上，這是由二種不同的成分構成的系統。雖然一成分之重要成分總是一種聚異氰酸酯，例如聚合型二異氰酸亞甲基二苯酯(MDI)，第二成分係由多元醇構成，或在最近之發展中也含胺基或胺-多元醇混合物。該二部分僅是在即將加工之前混在一起。在此之後，藉由聚加成並形成聚胺甲基酸酯或聚脲網絡以進行化學固化。在該二成分混合後，2-成分系統具有有限的加工時間(模製時間、適用期)，因為初反應導至黏度逐漸增加且最後導致該系統膠化。然而，很多變數決定其有效的可加工時間：反應伴同物(partner)之反應性、催化作用、濃度、溶解度、水含量、NCO/OH比率及周圍溫度是最重要的[參見：Coating Resins,Stoye/Freitag,Hauser-Verlag 1996,210/212頁]。以此種2-C PUR系統為基底之預浸體的缺點是僅能有短的時間以將該預浸體加工成複合物。因此，此種預浸體在超過數小時即是貯存不穩定的，更別說是數日。
除了不同之黏合劑基底之外，水分固化之塗料大抵在其組成及其性質上對應於類似的2C系統。原則上，使用相同之溶劑、顏料、填料及添加劑。與2C塗料不同的，
由於穩定性理由，這些系統在其應用之前，一點也不能耐受水分。
在DE 102009001793.3及DE 102009001806.9中，描述一種製造貯存穩定之預浸體的方法，該預浸體基本上由A)至少一種纖維載體及B)作為基質材料之至少一種粉末狀之反應性聚胺甲酸酯組成物所製成。
該系統在此也可含有聚(甲基)丙烯酸酯作為輔黏合劑(co-binder)或多元醇成分。在DE 102010029355.5中，藉由直接熔化浸漬方法，將此種組成物導入該纖維材料。在DE 102010030234.1中，藉由以溶劑預處理，這些系統之缺點是高熔體黏度或必須同時被移除之溶劑的使用，或也可能承受毒性方面的缺點。
與該先前技藝相對的，本發明之目的是要提供一種新穎之預浸體技術，其使可無問題地被處置之預浸體系統之更簡單的製造方法可行。
特別地，本發明之目的是要提供一種經加速之製造預浸體的方法，該方法與該先前技藝相比，使能得明顯延長之貯存穩定性及/或加工時間(模製時間、適用期)。另外，重量損失(尤其是以蒸發該反應性稀釋劑的方式)以該基質計應維持在少於20%下。
同時，該纖維之浸漬作用應被簡化。另外，在該方法
中所用之組成物應不僅適合用於預浸體之製造的熔體或粉末浸漬方法，也適合RTM方法。
利用新穎組成物和用於固化此組成物之新穎方法達成該等目的。依照本發明，此組成物較佳作為製造預浸體之樹脂。這些預浸體則適合進一步加工成模製零件。依照本發明之組成物含有至少成分A至D。在此，成分A是具有1至10個碳原子之烷基殘基的(甲基)丙烯酸酯、苯乙烯或此種(甲基)丙烯酸酯及/或苯乙烯之混合物。在成分A之混合物中此種單體之較佳實例是甲基丙烯酸甲酯、(甲基)丙烯酸丁酯及苯乙烯。在此，(甲基)丙烯酸一詞代表對應之甲基丙烯酸酯及/或丙烯酸酯。除了成分A之外，該組成物可含有另外之可與成分A之單體共聚合之不可交聯的單體，例如α-烯烴、環烯烴、(甲基)丙烯酸、順丁烯二酸或依康酸。特別地，該調合物可隨意地且同時較佳地含有官能化之(甲基)丙烯酸酯作為成分A'。較佳地，這些官能化之(甲基)丙烯酸酯是對所用之纖維材料有黏合促進性質的單體。因此，對於碳纖維而言，可極佳地添加(甲基)丙烯酸縮水甘油酯作為成分A'。特別地，鑒於含量及組成，單體組成係參考所要之技術功能和待交聯之載體材料有利地被選擇。
成分B是具有一個含共軛二烯之殘基的(甲基)丙烯酸酯。成分B也可以是不同之此類單體的混合物。成分B
較佳是一或多種下式之化合物：
及/或
在此，R1較佳是氫或甲基且R2是較佳具有1至4個碳原子之二價烷基。
成分C是含有至少二個親二烯基團的交聯劑。成分C較佳是具有至少二個碳-硫雙鍵之親二烯物。特佳地，成分C具有以下結構：
在此，Z是拉電子基團，例如氰基或在α位置上之吡啶，Rm是多價有機基團或聚合物且n是2與20之間的數目。
此種具有至少二個親二烯基團的交聯劑的二實例是以下化合物：
可以在例如WO 2011/101176中發現適合之具有親二烯基團的交聯劑及適合於此之二烯官能度的描述。
本發明之另一選擇但同樣較佳之具體例特徵在於：將此二成分B和C之狄耳士-阿德爾反應的產物C'添加至該組成物以替代該成分B和C或作為成分B和C之額外成分。
關於此另一選擇的具體例，有二個特佳之改良型。在這些改良型之第一者中，化合物C'是具有以下結構之化合物：
其中R1是氫或甲基，R2是具有1至4碳原子之二價烷基，Z是拉電子基團，Rm是多價有機基團或聚合物，n是2與20之間的數目，R5是烷基或芳基且R4是氫或殘基
R4及R5是共享橋接之氧原子或共享橋接之亞甲基。
在與成分C'相關之另一選擇的較佳具體例中，成分C'是一種利用具有以下結構之親二烯物
與上述二烯的狄耳士-阿德爾反應所得之化合物。在此，Rm是多價有機基團或聚合物，n是2與20之間的數目。
在此第二改良型之特佳具體例中，化合物C'是具有以下結構之化合物：
其中R1是氫或甲基，R2是具有1至4碳原子之二價烷基，Z是拉電子基團，Rm是多價有機基團或聚合物，n是2與20之間的數目。
該等單體及隨意之該預聚物具有官能基團對本發明是具有決定性的。此種官能基團是該等二烯，其與該交聯劑
成分之親二烯物反應並加成且因此可逆地交聯。
成分D是可熱活化之起始劑、分解觸媒、起始劑及加速劑及/或光起始劑之組合物。
尤其，過氧化物或氮雜起始劑長久以來對精於此技藝者已知是作為熱活性起始劑。可隨意地被添加以降低起始溫度的加速劑通常是三級胺，大部分是芳香族胺。
可能的分解觸媒是金屬錯合物，其分解所導入之過氧化物且因此釋出自由基。為此，特別使用鈷錯合物諸如由Akzo公司以Accelerator NL-49P之名上市的辛酸鈷、或萘酸鈷。另外，已知例如以銅錯合物為基底之不含鈷的改良型。
光起始劑及其製造是例如在"Radiation Curing in polymer Science & Technology,Vol II：Photoinitiating Systems" by J.P.Fouassier and J.F.Rabek,Elsevier Applied Science,London and New York,1993中所描述的。這些常是α-羥基酮或其衍生物或膦類。該光起始劑若存在，則含量可以是0.2至10重量%。例如在市面上可得之下列產物是可能作為光起始劑：Basf-CGI-725(BASF)、Chivacure 300(Chitec)、Irgacure PAG 121(BASF)、Irgacure PAG 103(BASF)、Chivacure 534(Chitec)、H-Nu 470(Spectra group limited)、TPO(BASF)、Irgacure 651(BASF)、Irgacure 819(BASF)、Irgacure 500(BASF)、Irgacure 127(BASF)、Irgacure 184(BASF)、Duracure(BASF)。
此外，該組成物可含有至高50重量%、較佳15至40重量%之聚合物、較佳是聚(甲基)丙烯酸酯或聚酯。為更好地區分，此隨意之聚合物成分也在以下被描述為預聚物。藉由添加此種聚合物，該組成物之黏度可在該纖維材料之浸漬及該預浸體之加工時，諸如在模製期間被調節。另外，使用該預聚物以改良聚合性、機械性、與該載體材料之黏合性、黏度調節及用於對樹脂之光學需求。這些聚合物較佳可與由該成分A、B和A'所形成之聚合物相容。隨意地，這些聚合物也可能另外以二烯及/或親二烯之基團官能化。
該聚(甲基)丙烯酸酯通常是由相同於該樹脂系統中之單體相關列述者之單體製成。彼可藉由溶液、乳濁液、懸浮液、整體、或沉澱聚合反應獲得且以純物質形被添加至該組成物。
關於在依照本發明之組成物中的重量含量，在95對5至50對50之間的成分A及D對成分B及C或對成分C'之重量比率是較佳的。此種在90對10至10對25之比率是特佳的。特別地，在成分B中之官能基團對在成分C中之官能基團的莫耳比率可在2對1至1對2之間。相當特別地，此比率是約1對1。
特佳地，該組成物含有30至80重量%之成分A、B及隨意之A'、1至30重量%之成分C、0至40重量%之聚合物及0.5至8重量%之成分D。相當特佳地，該組成物含有40至50重量%之成分A及隨意之A'、2至10重量%
之成分B、2至10重量%之成分C、0至30重量%之聚合物及3至6重量%之成分D。
此外，還有之成分可隨意地包含在該組成物中。可另外使用鏈轉移劑、塑化劑、穩定劑及/或抑制劑作為輔助劑和添加劑。另外，可以添加染料、填料、潤濕、分散及勻染添加劑、黏合促進劑、UV穩定劑、消泡劑及流變添加劑。
可以使用所有由自由基聚合已知的化合物作為鏈轉移劑。較佳地，使用硫醇諸如正十二烷基硫醇。
因此，可以使用慣用之UV穩定劑。該UV穩定劑較佳由下列所組成之組群所選：二苯甲酮衍生物、苯並三唑衍生物、9-氧硫衍生物、哌啶醇羧酸酯衍生物或桂皮酸酯衍生物。
由該穩定劑或抑制劑之組群，較佳使用經取代之酚、氫醌衍生物、膦類及亞磷酸鹽。
較佳使用聚羥基羧醯胺、脲衍生物、不飽和接酸之鹽、酸性磷酸衍生物之烷基銨鹽、酮肟類、對甲苯磺酸之胺鹽、磺酸衍生物之胺鹽及該等化合物之水性或有機溶液或混合物作為流變添加劑。據發現：以具有10-700奈米平方/克之BET表面積之熱解或沉澱而也隨意地矽烷化之矽酸為底質之流變添加劑是特別適合的。
消泡劑較佳是選自由醇、烴、以石蠟為基底之礦物油、二醇衍生物、羥乙酸酯衍生物、乙酸酯及聚矽氧烷。
依照本發明之組成物的優點在於製造可模製之假-熱
塑性塑膠半成品/預浸體，其在製造該複合組件或同義之模製零件時，在另一步驟中可逆地被熔化，且因此"被去除交聯"，但再次自主地交聯。令人驚訝地，利用最後二步驟，已真實固化成熱固性塑膠之模製零件的隨後模製是可能的。
起始之調合物是液態且因此適合在不添加溶劑下浸漬纖維材料。該半成品在室溫貯存時是穩定的。
因此獲得具有與現有技藝相比至少相同性質但也具有改良加工性質的複合半成品，其可用於製造供最多樣應用之有效的複合材料。依照本發明可用之反應性組成物是對環境友善的、不昂貴的、具有良好機械性、簡單加工且特徵在於良好耐風化性以及在硬度及可撓性之間的平衡比率。在本發明之背景中，複合半成品一詞與預浸體和有機片二詞同義地被使用。預浸體通常是一種用於熱固化複合組件之先質。有機片一般是一種用於熱塑性複合組件之對應先質。
除了依照本發明之組成物之外，由此組成物製造模製零件的方法同樣是本發明之一部分。此一方法包含以下處理步驟：a)藉由混合製造上述之依照本發明之含有至少成分A、B、C及D或A、C'及D的組成物，b)以得自處理步驟a)之組成物浸漬纖維材料，c)利用熱、電磁輻射、電子束及/或電漿固化該組成物，及
d)隨意模製及隨後冷卻。
在此，在處理步驟c)中於熱之影響下的固化係在溫度T1進行，此對精於此技藝者係特別遵循所用之起始劑之性質。通常，此一分解溫度(在此溫度下在1小時內可獲得一半之該起始劑以作為起始劑)係在70至150℃之間，較佳在80至120℃之間。特佳地，在處理步驟c)中之起始溫度T1高於處理步驟e)之逆狄耳士-阿德爾溫度T2或步驟g)之狄耳士-阿德爾溫度T3。
在依照本發明中所較佳使用之複合半成品中的纖維材料或同義的載體材料特徵在於：該纖維載體大部分係由玻璃、碳、塑膠諸如聚醯胺(聚芳醯胺)或聚酯、天然纖維、或礦物纖維材料諸如玄武岩纖維或陶瓷纖維構成。
該纖維載體以非織物、針織材料、針織或鉤編織物、非針織材料諸如紡織物、非織物或編織物形式、以長纖維或短纖維材料形式存在。
詳細地呈現以下具體例。在本發明中之纖維載體係由纖維材料(也常稱為強化纖維)構成。通常，構成該纖維之任何材料是適合，然而，較佳地使用玻璃、碳、塑膠諸如聚醯胺(聚芳醯胺)或聚酯、天然纖維或礦物纖維材料諸如玄武岩纖維或陶瓷纖維(以氧化鋁及/或氧化矽為基底之氧化物纖維)。也可以使用纖維類型之混合物例如聚芳醯胺及玻璃纖維、或碳及玻璃纖維之紡織織物組合物。同樣地，也可以製造具有由不同的纖維載體所製成之預浸體的混雜型複合組件。
主要由於玻璃纖維之相對低價格，玻璃纖維是最普遍被使用的纖維類型。在此原則上，所有類型之以玻璃為基底之強化纖維是適合的(E-玻璃、S-玻璃、R-玻璃、M-玻璃、C-玻璃、ECR-玻璃、D-玻璃、AR-玻璃、或中空玻璃纖維)。
通常，在高效能複合材料中使用碳纖維，其中在高強度之同時，與玻璃纖維相比更低之密度也是重要因素。碳纖維是由含碳原料所製造之工業製造的纖維，其藉由熱解轉化成類似石墨構形之碳。在等向性與異向性類型間作區別：等向性纖維是具有僅低的強度及低工業重要性，異向性纖維顯現出高強度及剛性，同時顯現出低的破裂點延長性。在此，由植物性和動物性材料所得之所有的紡織纖維和纖維材料(例如木質、纖維素、棉、大麻、黃麻、亞麻、西波爾麻及竹纖維)係描述為天然纖維。聚芳醯胺纖維也與碳纖維類似的，顯現出負的熱膨脹係數，亦即在加熱時變短。其比強度及其彈性模數明顯低於碳纖維者。與該基質樹脂之正膨脹係數組合，可以製造高尺寸穩定的組件。與經碳纖維強化之塑膠相比，聚芳醯胺纖維複合材料之壓縮強度明顯更低。聚芳醯胺纖維之習知商標名是得自DuPont之Nomex®及Kevlar®、或得自Teijin之Teijinconex®、Twaron®及Technora®。由玻璃纖維、碳纖維、聚芳醯胺纖維或陶瓷纖維製成之載體是特別適合的且是較佳的。該纖維材料是紡織織物。非紡織材料之紡織織物也稱為針織材料諸如針織及鉤編、以及非針織織物諸
如紡織物、非織物或編織物是適合的。此外，作為載體之長纖維與短纖維之間有區別。依照本發明，粗紗和細紗也是適合的。在本發明之背景中，所有該材料是適合作為纖維載體。強化纖為之概要被包含在"Composites Technologies",Paolo Ermanni(第4版)，Script for lecture at ETH Zürich,2007年8月，第7章。
在同樣屬於本發明之隨後步驟中，利用該處理步驟a)至d)所製造之模製零件可進一步被處理。為此所需要之這些處理步驟e)至g)可為此重複多次：e)將處理步驟a)至d)得到的模製零件加熱至溫度T2，其在該經固化之組成物的逆狄耳士-阿德爾溫度以上，f)模製及g)再次冷卻至低於該狄耳士-阿德爾溫度T3。在此期間，再次進行該交聯，且該模製零件再次具有彈性或較佳具有熱固性質。
對於精於此技藝者，經由為此所選之特別官能基團可獲知溫度T2(其必須是高的以使該逆狄耳士-阿德爾反應能進行)及溫度T3(其必須是低的以使交聯能利用狄耳士-阿德爾反應再次開始)。理想上，此二溫度幾乎是相同的。
在經二烯官能化之(甲基)丙烯酸酯成分-當T1低於T2或T3時-已在該聚合中交聯或-在T1低於T2或T3的較佳情況中，在冷卻之後與已存在於該組成物中之二或多官能親二烯物成分交聯，且在所定義之配對情況中該反應可藉
由升高之溫度加速。此溫度低於該逆狄耳士-阿德爾溫度T2，在T2下，再次進行狄耳士-阿德爾加合至該二烯官能度和親二烯物質官能性的逆反應。以此方式，低於該逆狄耳士-阿德爾溫度，可以產生尺寸穩定之熱固物或可逆交聯之複合組件。
特別地，以如下方式為此選擇該二烯和親二烯物質官能性：在室溫下這些可彼此進行狄耳士-阿德爾反應，且該逆狄耳士-阿德爾反應之溫度T2係在技術容易取得的範圍中。理想上，T3在50至300℃之間、較佳在80至200℃之間且特佳在100至150℃之間。
在上述之依照本發明之組成物、及該由此組成物製造模製零件之方法或另外之處理之外，這些模製零件及特別地彼之用途也是本發明的部分。此種依照本發明之模製零件的用途特別可以在下列中進行：在營造業中、用於運動用品、在汽車製造、航太工業、電子裝置或設備、風力系統、醫藥技術(尤其是作為骨科材料)或於船和艦之建造中。
Claims (15)
- 一種可作為樹脂以供製造用於進一步加工成模製零件之預浸體的組成物，其特徵在於此組成物含有成分A至D，其中成分A是具有一個具有1至10個碳原子之烷基殘基的(甲基)丙烯酸酯、苯乙烯、或此種(甲基)丙烯酸酯及/或苯乙烯之混合物，成分B是具有一個含有共軛二烯之殘基的(甲基)丙烯酸酯，成分C是具有至少二個親二烯基團的交聯劑，及成分D是可熱活化之起始劑、起始劑及加速劑之組合及/或光起始劑，且該兩成分B和C之狄耳士-阿德爾反應的產物C'可替代成分B和C或額外地加入該組成物。
- 如申請專利範圍第1項之組成物，其中成分B是一或多種下式之化合物：及/或
- 如申請專利範圍第1或2項之組成物，其中成分C是具有至少二個碳-硫雙鍵的親二烯物。
- 如申請專利範圍第3項之組成物，其中成分C是具有以下結構之化合物：
- 如申請專利範圍第1項之組成物，其中化合物C'是具有以下結構之化合物：
- 如申請專利範圍第1或2項之組成物，其中該組 成物另含有15至40重量%之聚合物，較佳是聚(甲基)丙烯酸酯或聚酯。
- 如申請專利範圍第1項之組成物，其中成分C'是申請專利範圍第2項之化合物與具有以下結構之化合物的狄耳士-阿德爾產物
- 如申請專利範圍第7項之組成物，其中化合物C'是具有以下結構之化合物：
- 如申請專利範圍第1或2項之組成物，其中成分 A和D對成分B和C或對成分C'的重量比在95對5與50對50之間。
- 如申請專利範圍第1項之組成物，其中該組成物另含有成分A'，其為官能化之(甲基)丙烯酸酯，較佳是(甲基)丙烯酸環氧丙酯。
- 如申請專利範圍第1或10項之組成物，其中該組成物含有30至80重量%之成分A、B及任意之A'，1至30重量%之成分C，0至40重量%之聚合物和0.5至8重量%之成分D。
- 如申請專利範圍第11項之組成物，其中該組成物含有40至50重量%之成分A及任意之A'，2至10重量%之成分B，2至10重量%之成分C，0至30重量%之聚合物和3至6重量%之成分D。
- 一種模製零件之製造方法，其包含下列步驟：a)藉由混合製造如申請專利範圍第1至12項中至少一項的組成物，b)以得自處理步驟a)之組成物浸漬纖維材料，c)利用熱、電磁輻射、電子束及/或電漿固化該組成物，及d)隨意模製及隨後冷卻。
- 如申請專利範圍第13項之方法，其中將利用該等步驟a)至d)所製造之模製零件e)加熱至溫度T2，其係高於該經固化之組成物的逆狄耳士-阿德爾溫度， f)模製，及g)再次冷卻至低於該狄耳士-阿德爾溫度T3。
- 一種由如申請專利範圍第1至12項中至少一項之組成物所製造或藉由如申請專利範圍第13或14項之方法所製造之模製零件的用途，其係用於營造業、汽車製造、航太工業、電氣裝置或設備、風力系統、用於製造運動用品、用於醫學技術(尤其是作為骨科材料)或於船和艦之建造。
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| EP3199575A1 (de) * | 2016-01-29 | 2017-08-02 | Evonik Degussa GmbH | Neuartiger hetero-diels-alder-vernetzer und deren verwendung in reversibel vernetzenden polymersystemen |
| CN106832091A (zh) * | 2017-01-18 | 2017-06-13 | 福建省支点三维科技有限公司 | 一种热固性聚丙烯酸酯树脂3d打印材料及其制备方法 |
| CN106883341A (zh) * | 2017-01-18 | 2017-06-23 | 福建师范大学泉港石化研究院 | 一种新型结构的聚丙烯酸酯树脂3d打印材料及其制备方法 |
| CN106883328A (zh) * | 2017-01-18 | 2017-06-23 | 福建省支点三维科技有限公司 | 一种户外用的聚丙烯酸酯树脂3d打印材料及其制备方法 |
| CN106832105A (zh) * | 2017-01-18 | 2017-06-13 | 福建师范大学泉港石化研究院 | 一种有机硅改性聚丙烯酸酯树脂3d打印材料及其制备方法 |
| WO2019236247A1 (en) * | 2018-06-08 | 2019-12-12 | Cummins Filtration Ip, Inc. | Cross-linked non-wovens produced by melt blowing reversible polymer networks |
| CN111040247B (zh) * | 2019-12-31 | 2021-03-05 | 大连理工大学 | 一类硫化剂及其应用 |
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| IT1256080B (it) | 1992-07-31 | 1995-11-27 | Enichem | Materiale composito a matrice mista, termoplastica e termoindurente, rinforzato con fibre continue. |
| TW338044B (en) * | 1994-11-15 | 1998-08-11 | Shell Internattonale Res Mij B V | A cross linked resin |
| GB9709166D0 (en) | 1997-05-06 | 1997-06-25 | Cytec Ind Inc | Preforms for moulding process and resins therefor |
| DE69907907T2 (de) | 1998-06-08 | 2004-03-11 | Complastik Corp., Lowell | Verbundgegenstände insbesondere prepregs, vorformlinge, laminate und sandwich formteile, und verfahren zu deren herstellung |
| GB0020630D0 (en) * | 2000-08-22 | 2000-10-11 | Cytec Tech Corp | Support structure or carrier for a curable composition |
| WO2005091715A2 (en) | 2004-03-25 | 2005-10-06 | Pc Composites Ltd. | Improved pre-impregnated materials and apparatus and methods for manufacture thereof |
| GB0423349D0 (en) | 2004-10-21 | 2004-11-24 | Hexcel Composites Ltd | Fibre reinforced assembly |
| JP2006193628A (ja) * | 2005-01-14 | 2006-07-27 | Yokohama Rubber Co Ltd:The | 共役ジエン化合物、硬化性組成物およびその硬化物 |
| DE102009001806A1 (de) | 2009-03-24 | 2010-09-30 | Evonik Degussa Gmbh | Prepregs und daraus bei niedriger Temperatur hergestellte Formkörper |
| DE102009001793A1 (de) | 2009-03-24 | 2010-10-07 | Evonik Degussa Gmbh | Prepregs und daraus hergestellte Formkörper |
| DE102010001987A1 (de) * | 2010-02-16 | 2011-08-18 | Evonik Röhm GmbH, 64293 | Funktionsmaterialien mit reversibler Vernetzung |
| DE102010029355A1 (de) | 2010-05-27 | 2011-12-01 | Evonik Degussa Gmbh | Verfahren zur Herstellung von lagerstabilen Polyurethan-Prepregs und daraus hergestellte Formkörper |
| DE102011087226A1 (de) * | 2011-11-28 | 2013-05-29 | Evonik Degussa Gmbh | Pseudo-thermoplastische, selbstvernetzende Composites |
-
2014
- 2014-11-06 EP EP14795819.3A patent/EP3071632A1/de not_active Withdrawn
- 2014-11-06 US US15/037,833 patent/US20160304683A1/en not_active Abandoned
- 2014-11-06 JP JP2016532567A patent/JP2016540073A/ja active Pending
- 2014-11-06 CA CA2930476A patent/CA2930476A1/en not_active Abandoned
- 2014-11-06 WO PCT/EP2014/073918 patent/WO2015074887A1/de active Application Filing
- 2014-11-06 KR KR1020167016117A patent/KR20160087863A/ko not_active Application Discontinuation
- 2014-11-06 CN CN201480063298.9A patent/CN105916916A/zh active Pending
- 2014-11-17 TW TW103139769A patent/TWI646138B/zh not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| EP3071632A1 (de) | 2016-09-28 |
| JP2016540073A (ja) | 2016-12-22 |
| US20160304683A1 (en) | 2016-10-20 |
| TWI646138B (zh) | 2019-01-01 |
| CA2930476A1 (en) | 2015-05-28 |
| KR20160087863A (ko) | 2016-07-22 |
| CN105916916A (zh) | 2016-08-31 |
| WO2015074887A1 (de) | 2015-05-28 |
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