用於可逆交聯聚合物系統之新穎交聯劑單元Novel crosslinker unit for reversible crosslinked polymer systems[0001] 本發明係關於用於可逆交聯聚合物系統之狄耳士-阿德爾交聯系統中的新穎交聯劑單元，其中本發明中之該系統係首度可只由一種組分組成。 [0002] 該交聯劑單元及其衍生物之應用可在用於射出成型及擠出成型化合物、用於製造發泡體、用於加法製造部門(例如藉由SLS或FDM法)之應用的可逆交聯聚合物系統之製造中發現。此外，該交聯劑單元及其衍生物應用於複合組件之製造、已可逆交聯或鏈增長之聚合物纖維的製造或簡化加工、具儲存安定性之預浸體及由彼製造之模製物(複合組件)的製造、以及用於黏著劑及塗料。此等單元同樣可用於與彈性體或熱塑性彈性體鍵聯以使該彈性體系統可逆交聯。 [0003] 可逆交聯方法使得即使在室溫亦能非常迅速交聯或轉化成較高分子量，且在較高溫度下使至少適當比例之結合位點分開，以回復熱塑性加工性，以及例如原本黏著劑結合之基板可容易地再次彼此分離。具體態樣係採用本系統而可能交聯及交聯分開數次。The present invention relates to a novel crosslinker unit for use in a Dixter-Adel cross-linking system for a reversibly crosslinked polymer system, wherein the system of the present invention may be composed of only one component for the first time. . [0002] The use of the crosslinker unit and its derivatives can be used in injection molding and extrusion molding compounds, in the manufacture of foams, in applications in the additive manufacturing sector (for example by SLS or FDM processes). Found in the manufacture of reversible crosslinked polymer systems. In addition, the cross-linking unit and its derivatives are used in the manufacture of composite components, in the manufacture or simplification of reversible cross-linking or chain-growth polymer fibers, in prepreg with storage stability, and molded by the same. Manufacture of materials (composite components), as well as for adhesives and coatings. These units are also useful for bonding with elastomers or thermoplastic elastomers to reversibly crosslink the elastomer system. [0003] Reversible cross-linking methods allow very rapid cross-linking or conversion to higher molecular weights even at room temperature, and at least a suitable ratio of binding sites at higher temperatures to restore thermoplastic processability, and for example, The substrates to which the adhesive is bonded can be easily separated from each other again easily. The specific aspect is that the system is used and it is possible to crosslink and crosslink several times.
[0004] 聚合物之可逆交聯方法在廣泛應用領域中相當重要。在黏著劑結合應用中，描述例如汽車工業或半導體工業之非常廣泛的可能性。然而，此等黏著劑亦對於機械之建造、高精密度機械裝置、或在建築工業中相當重要。除了黏著劑結合應用之外，可逆可交聯聚合物在密封劑、塗覆材料，諸如清漆或油漆、射出成型應用、或模製物件之製造中亦相當重要。 [0005] DE 198 32 629及DE 199 61 940描述將基於環氧基、脲、(甲基)丙烯酸酯或異氰酸酯之黏著劑熱分解的方法。為此目的，來自DE 199 61 940之黏著劑調配物含有於加熱時被活化之熱不安定物質。DE 198 32 629中之黏著層係藉由供應特別大量的能而被破壞。黏著劑層之去活化在二者情況下均為不可逆的。 [0006] US 2005/0159521/US 2009/0090461描述藉由光化輻射照射而自由基交聯並藉由超音波破壞的黏著劑系統。此方法在一個黏著劑結合回合之後亦不可逆地無法再進行。 [0007] 在EP 2 062 926中，用於黏著劑結合應用之聚胺甲酸酯的鏈中併入熱不穩定、位阻脲基，該熱不穩定、位阻脲基經由供應熱能而被破壞，因此黏著作用充分降低以使結合分開。 [0008] US 2009/0280330描述可能使用超過一次且具有雙層構造的黏著劑系統。一層為可具熱撓性或經固化之形狀記憶層。另一層為視結構而具有不同黏著強度的乾燥黏著劑。然而，具有此種系統之問題係雙層結構，其建造複雜且成本高昂，以及在加熱形狀記憶層之後預期有殘餘膠黏性。 [0009] 用於建構嵌段共聚物之方法已成為研究主題多年，尤其是在學術界，在概括性術語「 鏈接化學(click chemistry)」之下。此處，將具有可鍵聯端基之兩種不同同元聚合物混合，並利用例如狄耳士-阿德爾反應、類狄耳士-阿德爾反應或其他環加成使之接合。該反應之目的係建構熱安定、直鏈且隨意的高分子量之聚合物鏈。例如，Inglis等人之著作(Macromolecules 2010, 43，第33-36頁)描述該具有環戊二烯端基之目標聚合物，其可從藉由ATRP製備之聚合物獲得。該等環戊二烯基在雜狄耳士-阿德爾反應中可非常迅速地與具有缺電子之二硫酯作為端基的聚合物反應(Inglis等人之著作，Angew. Chem. Int. Ed. 2009, 48，第2411-2414頁)。 [0010] 經由雜狄耳士-阿德爾反應使單官能RAFT聚合物用於與具有二氫噻喃基之單官能聚合物鍵聯的用途可見Sinnwell等人之著作(Chem. Comm. 2008, 2052-2054)。該方法使得能實現AB雙嵌段共聚物。該雜狄耳士-阿德爾鍵聯用於合成具有於RAFT聚合之後存在的二硫酯基及具有二烯基端基之AB嵌段共聚物的迅速變體係描述於Inglis等人之著作(Angew. Chem. Int. Ed. 2009, 48，第2411-14頁)及Inglis等人之著作(Macromol. Rapd Commun. 2009, 30，第1792-98頁)。多臂星型共聚物之類似製造方法詳見Sinnwell等人之著作(J. Pol. Sci.: Part A: Pol. Chem. 2009, 47，第2207-13頁)。 [0011] US 6,933,361描述用於製造容易修補之透明模製品的系統。該系統係由兩種多官能單體所組成，該等多官能單體係利用狄耳士-阿德爾反應來聚合以形成高度緻密網狀結構。官能基之一為順丁烯二醯亞胺，另一官能基為呋喃。此種高密度網狀結構之熱轉換係用於其修補。交聯發生在高於100℃之溫度。在更高溫度下發生部分逆反應。 [0012] Syrett等人之著作(Polym. Chem. 2010, DOI: 10.1039/b9py00316a)描述星型共聚物用作油中之流動改良劑。該等聚合物具有利用可逆狄耳士-阿德爾反應而可控制的自癒性質。為此，單官能聚甲基丙烯酸酯臂係與在該鏈中間的聚甲基丙烯酸酯結合，成為所使用之引發劑的片段，包含可用於可逆狄耳士-阿德爾反應中之基團。 [0013] EP 2 536 797揭示由兩種組分A及B構成的可逆可交聯系統。組分A為具有至少兩個親二烯基團之化合物，而組分B為具有至少兩個二烯官能基之化合物。在可能轉換回合之最多次數及組成物之貯存安定性方面，EP 2 536 797中所揭示之組分A及B的組合一定可進一步最佳化。 [0014] 此外，另一先前技術係特別與複合物技術領域中之可逆交聯系統應用相關。由於呈預浸體形式之纖維強化材料相較於替代性濕式積層技術更容易處理及在加工期間之效率提高，其已用於許多工業應用。 [0015] 除了較快速循環時間及甚至在室溫下之高貯存安定性之外，此等系統之工業使用者亦需要可將預浸體切成適當大小且在自動化裁切成適當大小及積層個別預浸體層期間該等裁切工具不會被通常具膠黏性之基質材料污染。各種模製法(諸如例如反應轉移模製(RTM)法)包含將該強化纖維導入模中，封閉該模，將該可交聯樹脂調配物導入該模中，然後交聯該樹脂，通常藉由施加熱交聯。 [0016] 此種方法的限制之一係將強化纖維鋪設於該模中相對困難。編織或不縐縮織物之個別層必須切成適當大小，並順應模之特別部分的不同幾何形狀。此可能費時且亦複雜，特別是當該模亦含有發泡體核心或其他核心時。此處會希望有容易處理且展現形成選項的可預模製之纖維強化系統。 [0017] 除了聚酯、乙烯基酯及環氧樹脂系統之外，交聯基質系統領域中還有一系列特殊樹脂。其等亦包括聚胺甲酸酯樹脂，由於其韌性、容損度及強度之故，該等聚胺甲酸酯樹脂特別用於經由拉擠法製造複合型材。經常提及的缺點係所使用之異氰酸酯具有毒性。然而，所使用之環氧樹脂系統及硬化劑組分的毒性亦應視為緊要的。對於已知之致敏化及過敏尤其如此。 [0018] 此外，大部分用以製造複合物之預浸體的基質材料具有在施加至纖維材料時係呈固體形式，例如呈粉末形式，或呈高度黏性液體或熔體形式的缺點。在任一情況下，基質材料只能最小程度地滲透纖維材料，且此又導導致預浸體及/或複合部件之非最佳安定性。 [0019] 由彼製造之基於環氧樹脂系統的預浸體及複合物係描述於例如WO 98/50211、EP 0 309 221、EP 0 297 674、WO 89/04335及US 4,377,657。WO 2006/043019描述製造基於環氧樹脂-聚胺甲酸酯粉末之預浸體的方法。此外，已知基於呈粉末形式之熱塑性塑膠作為基質的預浸體。 [0020] WO 99/64216描述預浸體及複合物以及其製造方法，其中使用包含具有充分小尺寸的聚合物粒子之乳液以容許包裹個別纖維。該等粒子之聚合物的黏度為至少5000厘泊，且為熱塑性塑膠或交聯聚胺甲酸酯聚合物。 [0021] EP 0 590 702描述製造預浸體之粉末浸漬法，其中該粉末係由熱塑性及反應性單體/預聚合物之混合物組成。WO 2005/091715同樣描述使用熱塑性塑膠製造預浸體。 [0022] 使用狄耳士-阿德爾反應及可能可活化之逆狄耳士-阿德爾反應所製造的預浸體同樣已知。A. M. Peterson等人之著作(ACS Applied Materials & Interfaces (2009), 1(5), 992-5)描述環氧樹脂系統中之對應基團。此修改在組件部件上賦予自癒性質。類似但不依賴環氧樹脂基質之系統亦尤其可見J. S. Park等人之著作(Composite Science and Technology(2010), 70(15), 2154-9)或A. M. Peterson等人之著作(ACS Applied Materials & Interfaces(2010), 2(4), 1141-9)。然而，所引用之系統無一可後修改複合物至超出自癒範圍。典型的狄耳士-阿德爾反應在可能的條件下只有不充分的可逆性，因此在此處可能只有最小效果，對於受損組件部件之自癒可能足夠。 [0023] EP 2 174 975及EP 2 346 935各描述併入雙順丁烯二醯亞胺及呋喃基之可用作積層物的可熱回收複合材料。對於熟習本領域之人士而言很顯而易見的，此種系統可再活化，即，僅在相對高溫下至少大程度地解交聯(decrosslinked)。然而，此等溫度往往迅速引發進一步次級反應，因此如所述機制只適於回收但不適於改質複合物。 [0024] WO 2013/079286描述複合材料及製造彼之包括用於可逆雜狄耳士-阿德爾反應的基團之預浸體。此等系統係可逆可交聯，因此模製物甚至可回收。然而，該等系統僅能作為100%液態系統或自有機溶液施加。此對於該技術的可用性設下明顯限制。 [0025] 所述系統均基於有機溶劑或呈熔體形式或100%液態系統形式施加。然而，所述系統中無一能呈水性分散液形式施加。然而，具體而言，此等水性系統在關於工業安全性以及製造預浸體及/或複合材料之另外可用加工技術方面會具有龐大優點。 [0026] 關於㗁唑啉化學之其他先前技術係列於下文： [0027] 經由已轉化成㗁唑啉之脂肪酸羧酸基團而將脂肪酸附接在帶有羧基之丙烯酸酯聚合物上且隨後進行雙鍵環氧化以及不可逆交聯以作為塗料係描述於D. L. Trumbo, J. T. Otto; J. Coat. Technol. Res., 5(1), 107-111, 2008。 [0028] DE 42 09 283描述具有㗁唑啉基團之聚合物可經由㗁唑啉的接枝反應而具備反應性雙鍵的方式。因而帶有㗁唑啉基團之聚合物則會與例如二羧酸不可逆交聯。 [0029] DE 34 02 280描述可經由使用雙㗁唑啉於加熱時固化或交聯的密封劑及黏著劑。 [0030] US 8,258,254揭示狄耳士-阿德爾組分之長清單，其中環己二烯亦列為二烯組分。此等組分係供聚合物之生物降解性。沒有兩相之間多次轉換的揭示。 [0031] US 2007/148465揭示用於形狀記憶系統之組分的相似長清單。此意指此處之轉換只在兩種具有不同交聯度的狀態之間才可能。 [0032] JP 2007 284643揭示環己二烯作為二烯用於順丁烯二醯亞胺之狄耳士-阿德爾反應。形狀記憶材料亦為本文之主題。 [0033] 關於複合物應用之先前技術，應注意下列： [0034] 由於呈預浸體形式之纖維強化材料相較於替代性濕式積層技術更容易處理及在加工期間之效率提高，其已用於許多工業應用。 [0035] 所述系統均基於有機溶劑或呈熔體形式或100%液態系統形式施加。然而，所述系統中無一能呈水性分散液形式施加。然而，具體而言，此等水性系統在關於工業安全性以及製造預浸體及/或複合材料之另外可用加工技術方面會具有龐大優點。The reversible crosslinking method of polymers is quite important in a wide range of applications. In adhesive bonding applications, a very wide range of possibilities such as the automotive industry or the semiconductor industry are described. However, such adhesives are also of great importance for the construction of machinery, high precision mechanical devices, or in the construction industry. In addition to adhesive bonding applications, reversibly crosslinkable polymers are also important in the manufacture of sealants, coating materials such as varnishes or paints, injection molding applications, or molded articles. [0005] DE 198 32 629 and DE 199 61 940 describe a method of thermally decomposing an adhesive based on an epoxy group, a urea, a (meth) acrylate or an isocyanate. For this purpose, the adhesive formulation from DE 199 61 940 contains a thermally unstable substance which is activated upon heating. The adhesive layer of DE 198 32 629 is destroyed by the supply of a particularly large amount of energy. Deactivation of the adhesive layer is irreversible in both cases. [0006] US 2005/0159521/US 2009/0090461 describes an adhesive system that is free radically crosslinked by actinic radiation and destroyed by ultrasonic waves. This method is irreversibly impossible to perform after an adhesive bond. [0007] In EP 2 062 926, a chain of thermally unstable, hindered urea groups is incorporated into the chain of polyurethanes for adhesive bonding applications, which are thermally unstable and hindered urea groups are supplied by supplying heat energy. Destruction, so the stickiness is sufficiently reduced to separate the bonds. [0008] US 2009/0280330 describes an adhesive system that may be used more than once and has a two-layer construction. One layer is a shape memory layer that can be thermally flexible or cured. The other layer is a dry adhesive with different adhesion strength depending on the structure. However, the problem with such a system is a two-layer structure that is complicated to construct and costly, and that residual adhesiveness is expected after heating the shape memory layer. [0009] Methods for constructing block copolymers have been the subject of research for many years, especially in academia, under the general term "click chemistry." Here, two different homopolymers having a bondable end group are mixed and joined by, for example, a Dimes-Adel reaction, a Dimes-Adel reaction or other cycloaddition. The purpose of this reaction is to construct a thermally stable, linear and random high molecular weight polymer chain. For example, the work of Inglis et al. (Macromolecules 2010, 43, pages 33-36) describes the target polymer having a cyclopentadiene end group available from a polymer prepared by ATRP. These cyclopentadienyl groups react very rapidly with polymers having electron-deficient dithioesters as end groups in the hetero-Diels-Alder reaction (Inglis et al., Angew. Chem. Int. Ed 2009, 48, pp. 2411-2414). [0010] The use of a monofunctional RAFT polymer for bonding to a monofunctional polymer having a dihydrothiopyranyl group via a heterodyne-Adel reaction can be found in the work of Sinnwell et al. (Chem. Comm. 2008, 2052). -2054). This method enables the realization of AB diblock copolymers. The hybrid system for the synthesis of disulfide groups present after RAFT polymerization and AB block copolymers having dienyl end groups is described in Inglis et al. (Angew) Chem. Int. Ed. 2009, 48, pp. 2411-14) and the work of Inglis et al. (Macromol. Rapd Commun. 2009, 30, pp. 1792-98). A similar manufacturing process for multi-arm star copolymers is found in the work of Sinnwell et al. (J. Pol. Sci.: Part A: Pol. Chem. 2009, 47, pp. 2207-13). [0011] US 6,933,361 describes a system for making a transparent molded article that is easy to repair. The system consists of two polyfunctional monomers that are polymerized using a Dimes-Alder reaction to form a highly dense network structure. One of the functional groups is maleimide and the other functional group is furan. The thermal conversion of such a high density network is used for its repair. Crosslinking occurs at temperatures above 100 °C. Partial retrogression occurs at higher temperatures. [0012] The work of Syrett et al. (Polym. Chem. 2010, DOI: 10.1039/b9py00316a) describes the use of star copolymers as flow improvers in oils. These polymers have self-healing properties that are controllable using a reversible Dickens-Alder reaction. To this end, the monofunctional polymethacrylate arm is combined with a polymethacrylate in the middle of the chain to form a fragment of the initiator used, comprising groups which can be used in the reversible Dickens-Alder reaction. [0013] EP 2 536 797 discloses a reversibly crosslinkable system consisting of two components A and B. Component A is a compound having at least two dienophile groups, and component B is a compound having at least two diene functional groups. The combination of components A and B disclosed in EP 2 536 797 must be further optimized in terms of the maximum number of possible conversions and the storage stability of the composition. [0014] Furthermore, another prior art is particularly relevant to reversible cross-linking system applications in the field of composite technology. Fiber-reinforced materials in the form of prepregs have been used in many industrial applications because of their ease of handling and increased efficiency during processing compared to alternative wet laminate techniques. [0015] In addition to faster cycle times and even high storage stability at room temperature, industrial users of such systems also need to be able to cut prepregs into appropriate sizes and automatically cut to size and laminate. These cutting tools are not contaminated by the generally adhesive matrix material during individual prepreg layers. Various molding methods, such as, for example, a reaction transfer molding (RTM) process, involve introducing the reinforcing fibers into a mold, sealing the mold, introducing the crosslinkable resin formulation into the mold, and then crosslinking the resin, usually by Apply heat to crosslink. [0016] One of the limitations of this method is that it is relatively difficult to lay the reinforcing fibers in the mold. Individual layers of woven or non-retracted fabric must be cut to size and conform to the different geometries of the particular portion of the mold. This can be time consuming and complicated, especially when the mold also contains a foam core or other core. Here, it would be desirable to have a pre-mouldable fiber reinforced system that is easy to handle and exhibits forming options. [0017] In addition to polyester, vinyl ester and epoxy resin systems, there is a range of specialty resins in the field of crosslinked matrix systems. These also include polyurethane resins which are particularly useful for the manufacture of composite profiles via pultrusion due to their toughness, tolerance and strength. A disadvantage often mentioned is that the isocyanate used is toxic. However, the toxicity of the epoxy resin system and hardener components used should also be considered critical. This is especially true for known allergens and allergies. Furthermore, most of the matrix material used to make the prepreg of the composite has the disadvantage of being applied to the fibrous material in solid form, for example in powder form, or in the form of a highly viscous liquid or melt. In either case, the matrix material can only minimally penetrate the fibrous material, and this in turn leads to non-optimal stability of the prepreg and/or composite component. [0019] Epoxy resin system-based prepregs and composites made by the same are described in, for example, WO 98/50211, EP 0 309 221, EP 0 297 674, WO 89/04335, and US 4,377,657. WO 2006/043019 describes a process for producing a prepreg based on an epoxy resin-polyurethane powder. Furthermore, prepregs based on thermoplastics in powder form as a matrix are known. [0020] WO 99/64216 describes prepregs and composites and methods for their manufacture in which an emulsion comprising polymer particles of sufficiently small size is used to allow for the incorporation of individual fibers. The particles of the particles have a viscosity of at least 5000 centipoise and are thermoplastic or crosslinked polyurethane polymers. [0021] EP 0 590 702 describes a powder impregnation process for the manufacture of prepregs, wherein the powder consists of a mixture of thermoplastic and reactive monomers/prepolymers. WO 2005/091715 likewise describes the use of thermoplastic plastics for the manufacture of prepregs. [0022] Prepregs produced using the Diles-Alder reaction and the potentially activatable inverse Diles-Adel reaction are also known. The work of A. M. Peterson et al. (ACS Applied Materials & Interfaces (2009), 1(5), 992-5) describes the corresponding groups in the epoxy resin system. This modification gives self-healing properties on the component parts. Systems similar to but not dependent on epoxy matrices are also particularly well documented by JS Park et al. (Composite Science and Technology (2010), 70(15), 2154-9) or by AM Peterson et al. (ACS Applied Materials & Interfaces). (2010), 2(4), 1141-9). However, none of the cited systems can modify the complex beyond the self-healing range. The typical Dimes-Adel reaction has only insufficient reversibility under the possible conditions, so there may be only minimal effects here, which may be sufficient for self-healing of damaged component parts. [0023] EP 2 174 975 and EP 2 346 935 each describe a heat-recoverable composite material which can be used as a laminate in which a dim-butyleneimine and a furan group are incorporated. It will be apparent to those skilled in the art that such systems can be reactivated, i.e., decrosslinked at least to a large extent at relatively high temperatures. However, such temperatures tend to rapidly initiate further secondary reactions, so the mechanism is only suitable for recovery but not suitable for upgrading complexes. [0024] WO 2013/079286 describes composite materials and the manufacture of prepregs comprising groups for the reversible hetero-Diels-Alder reaction. These systems are reversibly crosslinkable, so the moldings are even recyclable. However, such systems can only be applied as a 100% liquid system or from an organic solution. This places significant limitations on the availability of this technology. [0025] The systems are all based on an organic solvent or in the form of a melt or a 100% liquid system. However, none of the systems can be applied as an aqueous dispersion. In particular, however, such aqueous systems can have significant advantages in terms of industrial safety and additional processing techniques for making prepregs and/or composites. [0026] Other prior art series on oxazoline chemistry are described below: [0027] The fatty acid is attached to a carboxyl group-containing acrylate polymer via a fatty acid carboxylic acid group that has been converted to an oxazoline and subsequently Double bond epoxidation and irreversible crosslinking are described as coating systems in DL Trumbo, JT Otto; J. Coat. Technol. Res., 5(1), 107-111, 2008. [0028] DE 42 09 283 describes a way in which a polymer having an oxazoline group can have a reactive double bond via a graft reaction of an oxazoline. Thus a polymer bearing an oxazoline group will be irreversibly crosslinked with, for example, a dicarboxylic acid. [0029] DE 34 02 280 describes encapsulants and adhesives which can be cured or crosslinked by heating using bisoxazolines. [0030] US 8,258,254 discloses a long list of Diles-Adel components, wherein cyclohexadiene is also listed as a diene component. These components are biodegradable for the polymer. There is no revealing of multiple conversions between two phases. [0031] US 2007/148465 discloses a similarly long list of components for a shape memory system. This means that the conversion here is only possible between two states with different degrees of cross-linking. [0032] JP 2007 284643 discloses cyclodene as a diene for the Dier-Adel reaction of maleimide. Shape memory materials are also the subject of this article. [0033] With regard to the prior art of composite application, the following should be noted: [0034] Since the fiber reinforcement in the form of a prepreg is easier to handle and more efficient during processing than the alternative wet laminate technique, it has Used in many industrial applications. [0035] The systems are all based on an organic solvent or in the form of a melt or a 100% liquid system. However, none of the systems can be applied as an aqueous dispersion. In particular, however, such aqueous systems can have significant advantages in terms of industrial safety and additional processing techniques for making prepregs and/or composites.
課題 [0036] 本發明所針對的課題係提供用於聚合物之新穎可逆鏈增長或交聯方法的單元，例如可用於不同應用及廣泛調配物範圍者。 [0037] 所針對的另一課題係發現具有充分熱安定性且無保護基之交聯劑結構，以使得不必要使用環戊二烯或相似結構作為阻斷劑(blocking agent)。 [0038] 此外，為了經濟上可行地製造交聯系統，合成步驟以及所獲致之產率應獲得改善以提供簡單且穩健的製造方法。 [0039] 同時，聚合物之鏈增長或交聯應最佳不使用二烯以及對應的親二烯物，而是使用本身進入狄耳士-阿德爾反應之分子進行。 [0040] 從以下說明、申請專利範圍及實例將明瞭未明確提出之其他課題。 解決方案 [0041] 該等課題係藉由發展適於進行可用於各種聚合物而不管調配物成分(諸如黏合劑)為何的可逆交聯機制之新穎調配物而獲得解決。令人意外的，已發現所述課題可藉由可利用狄耳士-阿德爾反應轉化之新穎調配物而解決，其中僅例如呈聚合或寡聚形式之單一組分必須用於該狄耳士-阿德爾反應。 [0042] 已意外地發現，利用在一個分子中同時為二烯及親二烯物之狄耳士-阿德爾反應性結構的組合，交聯及鏈增長反應不只是簡單地發揮作用，而是尤其亦容許合成面的明顯簡化。 [0043] 為此目的，本發明之特徵係利用狄耳士-阿德爾反應而交聯或具鏈增長反應性的可逆反應性調配物。為此目的，該調配物包含組分P，較佳作為超過80重量%之主要成分，其具有下示結構單元Z中之至少一例[0044] 在該式中，R1為氫、具有1至20個(較佳為1至10個及更佳為1至5個)碳原子之伸烷基、具有介於1與50之間(較佳介於1與10之間)的聚合度之聚醚基、羥基、胺基、環氧基、異氰酸酯基、羧基或㗁唑啉基，其中後者定義群可只代表R1或是可結合至所述之烷基或聚醚基中之一者。在後者化合物中，亦可能存在超過一個官能基或在此等官能基當中之各種基團的組合。 [0045] R2為氫，具有1至5個碳原子及隨意地具有一或多個羥基之烷基，或是羥基或具有1至12個碳原子之烷氧基。較佳之烷氧基可為甲氧基或乙氧基。 [0046] R3、R4、R5及R6獨立地或至少其中一些係相同地為氫，具有1至20個碳原子且可隨意地具有一或多個羥基、胺基、鹵基、環氧基、異氰酸酯基、羧基或㗁唑啉基之直鏈或支鏈烷基或伸烷基，或為直接結合之羥基、胺基、鹵基、環氧基、異氰酸酯基、羧基或㗁唑啉基。 [0047] 可逆狄耳士-阿德爾反應係以下示反應式進行：[0048] 根據本發明之調配物可用於兩個不同實施態樣中。在第一實施態樣中，組分P具有一或最多兩個結構單元Z。該調配物可利用狄耳士-阿德爾反應可逆地反應而有鏈增長及分子量增加，且無交聯。 [0049] 第二實施態樣之特徵係組分P具有超過兩個結構單元Z，以及調配物係利用狄耳士-阿德爾反應而可逆地交聯。 [0050] 不論實施態樣為何，特佳係當R3、R4、R5及R6基中之至少一者，較佳為一者，係利用官能基與其他化合物A結合時，聚合物或寡聚物隨意地具有其他結構單元Z，一起形成組分A。 [0051] 該聚合物或寡聚物較佳為聚丙烯酸酯，聚甲基丙烯酸酯，聚苯乙烯，由丙烯酸酯、甲基丙烯酸酯及/或苯乙烯所製成之混合聚合物，聚丙烯腈，聚醚，聚酯，聚乳酸，聚醯胺，聚酯醯胺，聚胺甲酸酯，聚碳酸酯，非晶形或半結晶聚-α-烯烴，EPDM，EPM，氫化或非氫化之聚丁二烯，ABS，SBR，聚矽氧烷及/或此等聚合物之嵌段、梳型及/或星型共聚物。附接至待交聯或接合之聚合物或寡聚物通常係經由結構單元Z之羥基、胺基、鹵基、環氧基、㗁唑啉基、異氰酸酯基或羧基官能基進行。 [0052] 更佳的是，該聚合物或寡聚物為具有至少一個結構單元Z之聚醚、聚醯胺、聚酯或聚碳酸酯作為組分A。通常的情況係結構單元在末端位置，因此有單及雙官能鏈之混合物或純單或雙官能組分。 [0053] 在已發現特別適用之本發明的一實施態樣中，官能基R1至R6中之一者，較佳為官能基R3，係原酸或具有1至20個碳原子且具有酸或酯基作為官能基之烷基，該作為官能基之酸或酯基已例如與式H2N-CR7R8-CH2OH之α-羥胺反應以產生㗁唑啉。隨後，該㗁唑啉基係與其他之化合物A(例如聚合物)的羧基官能基反應，以將結構單元Z附接至化合物A。此種反應係根據下示反應式進行：[0054] 該酸或酯基不需要直接鍵結至環：[0055] 其中，在此等結構式中，存在作為根據本發明之命名法的R1或R3基之成分的酸基係分別顯示。 [0056] 在替代方案中，第二反應步驟係根據例如下示反應式進行：[0057] 此係與雙㗁唑啉，例如1,3-伸苯基雙㗁唑啉，反應以產生對應之㗁唑啉。 [0058] 在最佳情況下，調配物在室溫下可交聯且所形成之交聯在更高溫度下可再次回復至至少50%之程度。 [0059] 在另一可能與其他實施態樣組合的實施態樣中，具有多個羧基官能基之聚合物，例如具有(甲基)丙烯酸單元或分支(共)聚酯、-聚醚、-聚醯胺或-聚丙烯酸酯之(甲基)丙烯酸酯(共)聚合物，或者具有例如具有羧基官能基之經共聚單體的彈性體係具備有結構單元Z。此等起始聚合物之出現係例如下示：[0060] 此處可能經由與在室溫下為二聚物的本發明之經環氧基或㗁唑啉官能化但尚未附接的組分Z反應來進行可逆交聯。此亦適用於具有羧基官能基之接枝單元，例如藉由接枝(甲基)丙烯酸、順丁烯二酸或反丁烯二酸。 [0061] 類似的，另一實施態樣中具有多個羥基或胺官能基之聚合物，例如具有(甲基)丙烯酸羥基烷酯單元或分支(共)聚酯、-聚醚、-聚醯胺或-聚丙烯酸酯之(甲基)丙烯酸酯(共)聚合物，或者具有羥基或胺官能基之隨意地經共聚單體的彈性體可經由與本發明之經羧基-或異氰酸酯基官能化狄耳士-阿德爾單元反應而經歷可逆交聯。此亦適用於具有羥基官能基之接枝單元，例如藉由接枝(甲基)丙烯酸羥基烷酯或其他可接枝單元，例如順丁烯二酸或反丁烯二酸之乙二醇二酯。[0062] 可能與根據本發明之調配物的可逆交聯使得即使在低第一溫度下亦能非常迅速轉化並在遠較高之溫度下分開，而使得理想地回復熱塑性加工性或改變至少一種相關材料性質，諸如黏著劑之內聚力，使得可有不同加工選項，諸如結合位點之分開。 [0063] 此外，例如用於壓製作為複合物中之積層物的單層區域中的情況下之原已交聯層可容易地再次彼此分離，或例如形成呈例如預浸體形式之已交聯個別層並壓製成積層物。具體態樣係採用本系統而可能交聯及交聯分開數次。所述之呈純形式的交聯劑/鏈增長劑分子對於溫度升高具有充分安定性，不需要用保護基阻斷。 [0064] 特別是，根據本發明之調配物具有下列特別優點： ∙ 在合成中反應性親二烯物不需要保護基/阻斷基。 ∙ 採用具有成本效益之反應物且具有高產率的非常簡單且穩健的合成作用 ∙ 即使在無保護的情況下，調配物耐高於200℃之溫度 ∙ 在容許整體系統之熔點/玻璃轉化溫度大於100℃之溫度下進行逆狄耳士-阿德爾反應。 [0065] 在其他可能實施態樣中，組分A為利用原子轉移自由基聚合(ATRP)所製造的雙官能聚合物。在該情況下，利用結構單元Z的官能化係經由末端鹵素原子之聚合物類似取代或在封端期間所施行者來進行。該取代可藉由添加例如二烯官能化硫醇來進行。 [0066] 本發明之其他態樣為可逆交聯根據本發明之調配物的方法。在該方法之進行中，包含組分A之調配物係在室溫下利用狄耳士-阿德爾反應交聯，此步驟通常已在組分A之合成中進行。在第二方法步驟中，在高於100℃之更高溫度下，使至少10%，較佳至少15%，及更佳至少50%之交聯係利用逆狄耳士-阿德爾反應再次分開。 除了交聯之外，如同前文關於調配物已進一步詳細說明，該方法同樣亦用以提高分子量。 [0067] 其他調配物成分可添加至該調配物中，例如，呈塗覆組成物或黏著劑組成物形式。根據本發明，該組成物除了組分A之外還隨意地包含額外添加的組分。該等額外組分可為針對個別應用而特別選擇的添加劑物質，諸如例如填料、顏料、添加劑、相容劑、共黏合劑、塑化劑、衝擊性改質劑、增稠劑、消泡劑、分散添加劑、流變性改良劑、黏著促進劑、耐刮添加劑、觸媒或安定劑，以及隨意的其他添加劑物質。 [0068] 在其他替代實施態樣中，調配物包含降低逆狄耳士-阿德爾反應之活化溫度的觸媒。該等觸媒可為例如鐵或鐵化合物。 [0069] 圖1舉例顯示用於交聯及解偶之反應式。此涉及㗁唑啉封端之狄耳士-阿德爾結構附接至聚合物之末端羧基，然後熱引發逆狄耳士-阿德爾反應，以及在冷卻過程中再接合該等聚合物。 [0070] 根據本發明之結構、調配物及方法可用於非常廣泛的應用領域中。下示清單提供一些較佳應用領域之實例，但在這方面不以任何形式限制本發明。 此等較佳使用領域為黏著劑、密封劑、可射出成型或可擠出成型之化合物、清漆、漆料、塗料、(纖維強化)複合材料、聚合物纖維、用於加法製造(3D列印、SLS、FDM)之材料、油墨或油添加劑，諸如流動改良劑。 該等油墨為例如可藉由熱方法施加並在基材上固化的組成物。使用傳導性寡聚物或用於產生傳導性之添加劑通常提供導電性油墨，該油墨可藉由例如泡沫式噴墨法來處理。 可射出成型或可擠出成型之化合物之實例為聚酯、聚碳酸酯或聚醯胺，其中在高溫下發生之聚合物鏈鍵聯(交聯或鏈增長)(其在相對低溫下存在並在冷卻過程再次形成)的逆狄耳士-阿德爾解偶實際上使得能降低黏度或實際上造成流動性，此等為聚合物射出成型的優點。在較低溫及在冷卻期間形成之聚合物鍵聯提高例如機械性質。 來自施加清漆、塗料及漆料之領域的實例為可浸漬或濕潤例如特別容易處於低黏度狀態的多孔材料，且偶合的結果提供高黏著性材料。 [0071] 相似特徵對於應具有高內聚力但希望容易濕潤待黏著劑結合之材料表面的黏著劑而言非常重要。 在黏著劑結合領域中之其他應用係例如只是暫時需要且在稍後再次分開的接合，如同例如在汽車工程或在機械工程中之各種製程中會發生者。 其他可想像的應用為組件之黏著劑結合，從產品整體壽命來看，其極可能被置換，因此應儘可能容易地可再次移除且無殘留物。此種應用的一實例為汽車擋風玻璃的黏著劑結合。其他實例為電子業、資訊技術領域、或建築或家具產業領域中之製程。本發明之低溫解偶操作的其他關切的應用可見醫療技術、或骨科技術領域。 黏著劑或密封劑之一特別實例係用於食品包裝，該食品包裝可在加熱期間，例如在微波爐中，自動開啟或分開。 [0072] 本文所述之交聯及解交聯材料的迅速原型化領域中之應用實例之一可見FDM(熔融沉積塑模)或藉由採用低黏度熔體之噴墨法的3D列印領域。 [0073] 本發明尤其亦適於製造可逆交聯聚合物結構及特別是當所使用聚合物具有高分子量或當涉及高反應性系統時呈貯存安定性供應形式的新穎系統。利用根據本發明之結構交聯的聚合物，例如呈分散液形式，可用於例如藉由已知方法浸漬纖維材料，例如碳纖維、玻璃纖維或聚合物纖維，以製造預浸體。 本發明因而尤其亦關於利用狄耳士-阿德爾機制採用本發明之交聯劑分子進行粒子內交聯(intraparticulately crosslinked)的乳化聚合物。已交聯聚合物然後可經由逆狄耳士-阿德爾或逆雜狄耳士-阿德爾反應藉由熱處理而完全或部分解交聯，例如呈複合基質形式，以及在冷卻時粒子間再交聯(interparticulately recrosslinked)。此使得可能製備用於複合物之長擱置壽命預浸體。但亦可能因而實現在使用溫度下具有熱固性質但在更高溫度下具有熱塑性加工性質的其他材料。Problem [0036] The subject addressed by the present invention is to provide a unit for a novel reversible chain growth or crosslinking process for polymers, for example, for a variety of applications and a wide range of formulations. Another subject addressed is the discovery of a crosslinker structure with sufficient thermal stability and no protecting groups to make it unnecessary to use cyclopentadiene or a similar structure as a blocking agent. Furthermore, in order to economically manufacture a cross-linking system, the synthesis steps and the yields obtained should be improved to provide a simple and robust manufacturing process. At the same time, the chain growth or crosslinking of the polymer should preferably be carried out without the use of diene and the corresponding dienophile, but with molecules which themselves enter the Dimes-Alder reaction. [0040] Other issues not explicitly mentioned will be apparent from the following description, the scope of the patent application, and examples. Solution [0041] These problems are solved by developing novel formulations suitable for performing reversible crosslinking mechanisms that can be used for various polymers regardless of formulation ingredients such as binders. Surprisingly, it has been found that the subject matter can be solved by a novel formulation that can be converted using the Diles-Adel reaction, wherein only a single component, for example in a polymeric or oligomeric form, must be used for the Dix - Adel reaction. [0042] It has been surprisingly discovered that by using a combination of dimes-Alder reactive structures which are both diene and dienophile in one molecule, cross-linking and chain-growth reactions do not simply work, but rather In particular, a significant simplification of the synthetic surface is also permitted. [0043] To this end, the invention features a reversible reactive formulation that crosslinks or has chain-growth reactivity using a Dimes-Alder reaction. For this purpose, the formulation comprises component P, preferably as more than 80% by weight of the main component, having at least one of the structural units Z shown below In the formula, R1 is hydrogen, an alkylene group having 1 to 20 (preferably 1 to 10 and more preferably 1 to 5) carbon atoms, having a relationship between 1 and 50 a polyether group, a hydroxyl group, an amine group, an epoxy group, an isocyanate group, a carboxyl group or an oxazoline group having a degree of polymerization (preferably between 1 and 10), wherein the latter definition group may represent only R1 or may be bonded. To one of the alkyl or polyether groups described. In the latter compounds, it is also possible to have more than one functional group or a combination of various groups among the functional groups. R2 is hydrogen, an alkyl group having 1 to 5 carbon atoms and optionally having one or more hydroxyl groups, or a hydroxyl group or an alkoxy group having 1 to 12 carbon atoms. Preferred alkoxy groups can be methoxy or ethoxy. And R3 , R4 , R5 and R6 are independently or at least some of them are hydrogen identically, have 1 to 20 carbon atoms and optionally have one or more hydroxyl groups, amine groups, halogen groups, A linear or branched alkyl or alkylene group of an epoxy group, an isocyanate group, a carboxyl group or an oxazoline group, or a directly bonded hydroxyl group, an amine group, a halogen group, an epoxy group, an isocyanate group, a carboxyl group or a carbazole. Alkyl group. [0047] The reversible Dickens-Alder reaction is carried out as follows: [0048] Formulations according to the invention can be used in two different embodiments. In a first embodiment, component P has one or at most two structural units Z. The formulation can reversibly react with the Diles-Alder reaction with chain growth and molecular weight increase without cross-linking. [0049] The feature of the second embodiment is that the component P has more than two structural units Z, and the formulation is reversibly crosslinked by the Dimes-Alder reaction. [0050] Regardless of the embodiment, it is preferred that at least one of R3 , R4 , R5 and R6 groups, preferably one, is a polymer when a functional group is bonded to another compound A. Or the oligomer optionally has other structural units Z which together form component A. [0051] The polymer or oligomer is preferably a polyacrylate, a polymethacrylate, a polystyrene, a mixed polymer made of acrylate, methacrylate and/or styrene, polypropylene. Nitrile, polyether, polyester, polylactic acid, polyamide, polyester decylamine, polyurethane, polycarbonate, amorphous or semi-crystalline poly-α-olefin, EPDM, EPM, hydrogenated or non-hydrogenated Polybutadiene, ABS, SBR, polyoxyalkylene and/or block, comb and/or star copolymers of such polymers. The polymer or oligomer attached to the crosslinking or bonding is typically carried out via the hydroxyl, amine, halo, epoxy, oxazolinyl, isocyanate or carboxyl functional groups of structural unit Z. More preferably, the polymer or oligomer is a component A of a polyether, polyamine, polyester or polycarbonate having at least one structural unit Z. It is usually the case that the structural unit is at the end position and therefore has a mixture of mono- and difunctional chains or a pure mono- or difunctional component. In one embodiment of the invention which has been found to be particularly useful, one of the functional groups R1 to R6 is preferably a functional group R3 , an ortho acid or having from 1 to 20 carbon atoms. An alkyl group having an acid or ester group as a functional group, the acid or ester group as a functional group has been reacted, for example, with an α-hydroxylamine of the formula H2 N-CR7 R8 -CH2 OH to give an oxazoline. Subsequently, the oxazoline group is reacted with a carboxyl functional group of another compound A (for example, a polymer) to attach the structural unit Z to the compound A. This reaction is carried out according to the following reaction formula: [0054] The acid or ester group need not be directly bonded to the ring: Among these structural formulas, there are acid groups which are components of the R1 or R3 group as a nomenclature according to the present invention, respectively. [0056] In the alternative, the second reaction step is carried out according to, for example, the following reaction formula: This is reacted with a bisoxazoline such as 1,3-phenylenebisoxazoline to give the corresponding oxazoline. [0058] In the best case, the formulation is crosslinkable at room temperature and the resulting crosslinks can again return to at least 50% at higher temperatures. [0059] In another embodiment which may be combined with other embodiments, a polymer having a plurality of carboxyl functional groups, for example having a (meth)acrylic unit or a branched (co)polyester, a polyether, The (meth) acrylate (co)polymer of polyamine or polyacrylate, or an elastic system having, for example, a comonomer having a carboxyl functional group, is provided with a structural unit Z. The appearance of such starting polymers is as follows: Reversible crosslinking may be carried out here by reaction with component O which is functionalized with an epoxy or oxazoline of the invention which is a dimer at room temperature but which has not yet been attached. This also applies to graft units having carboxyl functional groups, for example by grafting (meth)acrylic acid, maleic acid or fumaric acid. Similarly, a polymer having a plurality of hydroxyl or amine functional groups in another embodiment, for example, having a hydroxyalkyl (meth)acrylate unit or a branched (co)polyester, a polyether, a polyfluorene An amine or polyacrylate (meth) acrylate (co)polymer, or an optionally conjugated elastomer having a hydroxyl or amine functional group, may be functionalized via a carboxy- or isocyanate-based group of the invention. The Dix-Adel unit undergoes a reversible cross-linking reaction. This also applies to graft units having a hydroxyl functional group, for example by grafting a hydroxyalkyl (meth)acrylate or other graftable unit, such as ethylene glycol of maleic acid or fumaric acid. ester. [0062] Reversible cross-linking, possibly in combination with the formulation according to the invention, enables very rapid conversion and separation at much higher temperatures even at low first temperatures, so that it is desirable to restore thermoplastic processability or to change at least one Relevant material properties, such as the cohesion of the adhesive, allow for different processing options, such as separation of binding sites. Furthermore, the original crosslinked layers, for example in the case of pressing in a single layer region as a laminate in the composite, can be easily separated from one another again, or for example formed into a crosslinked form, for example in the form of a prepreg. The individual layers are pressed into a laminate. The specific aspect is that the system is used and it is possible to crosslink and crosslink several times. The crosslinker/chain extender molecule in pure form has sufficient stability for elevated temperatures and does not require blocking with a protecting group. [0064] In particular, the formulations according to the invention have the following particular advantages: ∙ The reactive dienophile does not require a protecting group/blocking group in the synthesis.进行 Very simple and robust synthesis with cost-effective reactants and high yields ∙ Even in the absence of protection, the formulation is resistant to temperatures above 200 ° C. Allows the melting point/glass transition temperature of the overall system to be greater than The inverse Diles-Alder reaction was carried out at a temperature of 100 °C. [0065] In other possible embodiments, component A is a bifunctional polymer produced by atom transfer radical polymerization (ATRP). In this case, the functionalization using the structural unit Z is carried out by similar substitution of the polymer of the terminal halogen atom or by the person performing the capping. This substitution can be carried out by adding, for example, a diene-functional thiol. [0066] A further aspect of the invention is a method of reversibly crosslinking a formulation according to the invention. In the course of this process, the formulation comprising component A is crosslinked at room temperature using a Dimes-Alder reaction, which step has typically been carried out in the synthesis of component A. In a second method step, at least 10%, preferably at least 15%, and more preferably at least 50% of the cross-linking is again separated by the inverse Diles-Adel reaction at a higher temperature above 100 °C. In addition to cross-linking, as described in the foregoing with respect to formulations, the method is also used to increase molecular weight. Other formulation ingredients may be added to the formulation, for example, in the form of a coating composition or an adhesive composition. According to the invention, the composition optionally contains, in addition to component A, additional added components. These additional components may be additive materials specifically selected for individual applications such as, for example, fillers, pigments, additives, compatibilizers, co-binders, plasticizers, impact modifiers, thickeners, defoamers , dispersing additives, rheology modifiers, adhesion promoters, scratch-resistant additives, catalysts or stabilizers, and optional other additive substances. [0068] In other alternative embodiments, the formulation comprises a catalyst that reduces the activation temperature of the Dedicel-Adel reaction. These catalysts can be, for example, iron or iron compounds. [0069] FIG. 1 exemplifies a reaction formula for crosslinking and decoupling. This involves the attachment of an oxazoline-terminated Diershi-Adel structure to the terminal carboxyl group of the polymer, which then thermally initiates the inverse Dickens-Alder reaction and rejoins the polymer during cooling. [0070] The structures, formulations and methods according to the present invention can be used in a very wide range of applications. The following list provides examples of some preferred fields of application, but does not limit the invention in any way. These preferred areas of use are adhesives, sealants, injection-molded or extrudable compounds, varnishes, lacquers, coatings, (fiber-reinforced) composites, polymer fibers, for additive manufacturing (3D printing) , SLS, FDM) materials, inks or oil additives, such as flow improvers. The inks are, for example, compositions that can be applied by thermal methods and cured on a substrate. The use of conductive oligomers or additives for the production of conductivity generally provides a conductive ink which can be treated by, for example, a foam ink jet process. Examples of compounds which can be injection molded or extrudable are polyesters, polycarbonates or polyamines, wherein polymer chain linkages (crosslinking or chain extension) occur at elevated temperatures (which are present at relatively low temperatures and The inverse Diles-Adel solution that is formed again during the cooling process actually enables the viscosity to be reduced or actually causes fluidity, which is an advantage of polymer injection molding. Polymer linkages formed at lower temperatures and during cooling increase, for example, mechanical properties. Examples from the field of application of varnishes, coatings and lacquers are those which can be impregnated or wetted, for example, which are particularly susceptible to low viscosity, and the result of the coupling provides a highly adherent material. [0071] Similar features are very important for adhesives that should have high cohesion but which are desirable to wet the surface of the material to be bonded by the adhesive. Other applications in the field of adhesive bonding are, for example, only joints that are temporarily needed and then separated again later, as would occur, for example, in various processes in automotive engineering or in mechanical engineering. Other conceivable applications are adhesive bonding of components, which are highly likely to be displaced from the overall life of the product and should therefore be removed as easily as possible without residue. An example of such an application is an adhesive bond for an automotive windshield. Other examples are processes in the electronics, information technology, or construction or furniture industries. Other concerns of the low temperature decoupling operation of the present invention can be found in the medical technology, or in the field of orthopedics. A particular example of an adhesive or sealant is used in food packaging that can be automatically opened or separated during heating, such as in a microwave oven. [0072] One of the application examples in the field of rapid prototyping of crosslinked and decrosslinked materials described herein can be seen in FDM (melt deposition molding) or in the 3D printing field by inkjet method using a low viscosity melt. . The invention is also particularly suitable for the manufacture of reversible crosslinked polymer structures and, in particular, novel systems in which the polymers used have a high molecular weight or in the form of a storage stability supply when involving highly reactive systems. The polymer crosslinked by the structure according to the invention, for example in the form of a dispersion, can be used, for example, to impregnate a fibrous material, such as carbon fiber, glass fiber or polymer fiber, by known methods to produce a prepreg. The invention thus relates in particular to an intraparticulately crosslinked emulsion polymer using the Dimes-Adel mechanism using the crosslinker molecules of the invention. The crosslinked polymer can then be completely or partially decrosslinked by heat treatment via a Detroit-Adel or Reversed Dier-Adel reaction, for example in the form of a composite matrix, and re-crossing between particles upon cooling Interparticulately recrosslinked. This makes it possible to prepare a long shelf life prepreg for the composite. However, it is also possible to achieve other materials which have thermosetting properties at the use temperature but have thermoplastic processing properties at higher temperatures.
實施例 [0075] 以下為新穎狄耳士-阿德爾交聯系統之具體實例的合成方法之選擇，以及製造用於附接至聚合物之官能基的方法的說明。 實施例1：6-(羥基)-2,6-二甲基環己-2,4-二烯-1-酮(CHD-OH)之合成 [0076] 將2,6-二甲苯酚(1.00 g，8.18 mmol，1.0當量)懸浮於150 ml水及50 ml THF之混合物中。隨後，添加3.50 g之NaIO4(16.37 mmol，2.0當量)於50 ml水中的溶液，且該溶液轉變成黃色。在攪拌1小時之後，該溶液變澄清，並藉由添加二氯甲烷使反應停止。然後水相係每次用200 ml二氯甲烷萃取三次。組合有機相係在MgSO4上乾燥，並在減壓下移除溶劑。粗製產物為橘色油，於其中添加5 ml環己烷，並沉澱出白色晶體。將此等濾出並用甲苯清洗。產率為53%(0.59 g，4.30 mmol)。 實施例2：乙酸6-(羥基)-2,6-二甲基環己-2,4-二烯-1-酮酯(CHD-Ac)之合成 [0077] 在攪拌下製備10 ml之乙酸乙酯(EtOAc)、0.1 ml之H2SO4及0.4 ml之乙醯丙酮鹽(acetylacetonate)(AcOAc)的溶液。在10分鐘後，將另外2 ml之AcOAc添加至該溶液。隨後，將3 ml之該溶液添加至495.6 mg來自實施例1之產物(1.79 mmol，1.0當量)並攪動該混合物4分鐘。然後，該反應混合物係每次用20 ml之一莫耳HCl清洗五次，然後用20 ml之飽和NaHCO3清洗及最後用20 ml之飽和氯化鈉溶液清洗。在減壓下去除揮發性成分並真空乾燥之後，獲得白色晶體作為產物，其產率為49.16%(316.8 mg，0.88 mmol)。 實施例3：6-(伸乙基氧基)環己-2,4-二烯-1-酮(CHD-環氧樹脂)之合成 [0078] 在圓底燒瓶中，採用非常劇烈攪拌將1.00 g之2-羥基苯甲醇(8.06 mmol，1.0當量)懸浮於60 ml水中。隨後，將2.00 g之NaIO4(9.35 mmol，1.16當量，溶解於40 ml水中)逐漸添加至該溶液。反應溶液轉變成黃色。在又攪拌5分鐘之後，沉澱出黃棕色固體。該反應係在又30分鐘之後停止，藉由過濾最終獲得淺粉紅色固體作為產物。產率為65%(0.64 mg，5.24 mmol)。 實施例4：6-(羥基)-6-(疊氮基甲基)環己-2,4-二烯-1-酮(CHD-疊氮化物)之合成 [0079] 將1.00 g來自實施例3之反應產物(4.09 mmol，1.0當量)、1.35 g之NaN3(20.75 mmol，5.07當量)及1.13 g之NH4Cl(21.12 mmol，5.16當量)收集在25 ml甲醇及5 ml水的混合物中。該溶液在80℃加熱以及攪拌2小時期間變澄清。冷卻之後，水相係每次用10 ml乙酸乙酯萃取三次。組合有機相係在MgSO4上乾燥，並在減壓下移除溶劑。獲得呈橘棕色固體的產物，產率為85%(1.17 g，3.54 mmol)。 實施例5：6-(羥基)-6-(羥甲基)環己-2,4-二烯-1-酮(CHD-DiOH)之合成 [0080] 將200 mg來自實施例3之反應產物(0.82 mmol，1.0當量)及232.5 mg之NH4Cl(4.23 mmol，5.16當量)懸浮於25 ml甲醇及5 ml水的混合物中。在80℃攪拌2小時並隨後冷卻之後，水相係每次用50 ml乙酸乙酯萃取三次。組合有機相係在MgSO4上乾燥，並在減壓下移除溶劑。獲得的產物呈淺棕色固體，產率為62%(144 mg，0.51 mmol)。 本質上來說，來自前述實例之所有產物在處理之後均呈二聚物形式。此亦適用於實施例2、3及5中之個別對應反應物。 [0081] 下示實施例8之特徵係將鍵聯子(linker)併入聚合物。實施例6及7描述實施例8之鍵聯子的合成。 實施例6：6-(伸乙基氧基)環己-2,4-二烯-1-酮之合成(CHD-環氧樹脂；替代合成作用)[0082] 在圓底燒瓶中，採用非常劇烈攪拌將12.4 g之2-羥基苯甲醇(100 mmol，1.0當量)懸浮於750 ml水中。隨後，在10分鐘內將25.7 g之NaIO4(120 mmol，1.2當量)添加至該溶液。此使該反應溶液轉變成黃色。在進一步攪拌之後，沉澱出黃棕色固體。在添加所有反應之後在總共攪拌30分鐘之後停止反應，過濾出固體，並用總計400 ml的水清洗。在減壓下於60℃乾燥之後，最後獲得淺粉紅色固體。產率為65.4%(7.99 g)。該粗製產物最終係在甲醇中再結晶。 實施例7：6-(羥基)-6-(羥甲基)環己-2,4-二烯-1-酮之合成(CHD-CL-OH；替代合成作用)[0083] 將1.22 g來自實施例6之反應產物(5 mmol，1.0當量)溶解於ACN中，然後將1.34 g之NH4Cl(25.0 mmol，5.00當量)添加至該溶液。在90℃攪拌17小時然後冷卻之後，移除水相，並將有機相濃縮成5 ml且每次用50 ml乙酸乙酯萃取三次。組合之有機相隨後係用100 ml之濃縮氯化鈉溶液清洗，且最終係在MgSO4上乾燥。之後在第三丁基甲基醚中再結晶。最後，在減壓下於50℃去除溶劑。獲得的產物呈淺棕色固體，產率為71.3%(1.3 g)。 本質上來說，來自前述實例之所有產物在處理之後均呈二聚物形式。 實施例8：CHD-官能基聚胺甲酸酯之合成 [0084] 在套手工作箱中，根據表1設置三個並行合成作用。基於此目的，在各例中將來自實施例7之產物溶解於600 μl之DMF中，並添加336.4 mg(1.0當量)之1,6-二異氰酸六亞甲酯(HMDI)及0.1當量之DABCO。該反應混合物各在90℃下攪拌60分鐘，然後冷卻至室溫，並根據表1添加己-1,6-二醇。該反應產物係在80℃下再攪拌20分鐘，在90℃下攪拌20分鐘以及最終在100℃下攪拌10分鐘。利用在DMSO-d6中之1H NMR光譜術偵測到CHD-CI-OH成功併入聚胺甲酸酯。用於偵測解偶鍵結之高溫NMR測量 [0085] 為了檢查與逆狄耳士-阿德爾反應相關之可逆性，首先進行溫度相依性NMR光譜術測量，其次藉由加熱經由逆狄耳士-阿德爾反應將狄耳士-阿德爾加成物轉化成單體/「開放式」物質並利用順丁烯二醯亞胺阻斷以防止在冷卻過程中再二聚化。 製程： [0086] 為了準備高溫NMR測量，將個別組分溶解於d6-DMSO(c=40 mg/l)中，轉移至耐壓NMR管並預熱至稍後之測量溫度。在加熱期間，取得在不同溫度之1H NMR光譜。為此目的，該測量係在室溫(20℃)下開始，並以20℃之梯級加熱至最高溫度為140℃為止。在再次冷卻至室溫之後，測量其他光譜。為了評估，測定在5.5與6.5 ppm之間的乙烯基質子的共振位移。此等信號係二聚二烯結構的打開的適當指示。該等信號之整合另外提供關於鍵結打開的百分比之資訊。例如，實施例1之該比例係在140℃下的打開程度為約18%。 截留實驗 [0087] 在圓底燒瓶中，將56.0 mg來自實施例2之產物(「Ac二聚物」，0.16 mmol，1.0當量)及56.46 mg之苯基順丁烯二醯亞胺(0.33 mmol，2.1當量)溶解於3.5 ml之DMSO-d6中。該溶液係在預熱至190℃(±2℃)之油浴中加熱。以5分鐘間隔取得樣本，並利用1H-NMR及ESI-MS分析。在5.5與6.5 ppm之間的乙烯基質子的共振位移係封閉(即，二聚物)結構之比例的強烈跡象。在190℃下35分鐘之後，因而可能顯示具有順丁烯二醯亞胺之環己二烯酮結構的開放結構完全清除。EXAMPLES [0075] The following is a selection of synthetic methods for the specific examples of the novel Dimes-Alder cross-linking system, and an explanation of a method for producing a functional group for attachment to a polymer. Example 1: Synthesis of 6-(hydroxy)-2,6-dimethylcyclohexan-2,4-dien-1-one (CHD-OH) [0076] 2,6-xylenol (1.00) g, 8.18 mmol, 1.0 eq.) was suspended in a mixture of 150 ml of water and 50 ml of THF. Subsequently, a solution of 3.50 g of NaIO4 (16.37 mmol, 2.0 eq.) in 50 ml of water was added and the solution turned to yellow. After stirring for 1 hour, the solution became clear and the reaction was stopped by the addition of dichloromethane. The aqueous phase was then extracted three times with 200 ml of dichloromethane each time. The combined organic phase based on dry MgSO4, and the solvent removed under reduced pressure. The crude product was an orange oil to which 5 ml of cyclohexane was added, and white crystals precipitated. These were filtered off and washed with toluene. The yield was 53% (0.59 g, 4.30 mmol). Example 2: Synthesis of 6-(hydroxy)-2,6-dimethylcyclohexan-2,4-dien-1-one acetate (CHD-Ac) [0077] 10 ml of acetic acid was prepared under stirring A solution of ethyl ester (EtOAc), 0.1 ml of H2 SO4 and 0.4 ml of acetylacetonate (AcOAc). After 10 minutes, an additional 2 ml of AcOAc was added to the solution. Subsequently, 3 ml of this solution was added to 495.6 mg of the product from Example 1 (1.79 mmol, 1.0 eq.) and the mixture was stirred for 4 min. The reaction mixture was then washed five times with 20 ml of one mole of HCl each time, then with 20 ml of saturated NaHCO3 and finally with 20 ml of saturated sodium chloride solution. After removing the volatile component under reduced pressure and drying in vacuo, white crystals were obtained as a product, yield: 49.1% (316.8 mg, 0.88 mmol). Example 3: Synthesis of 6-(ethylideneoxy)cyclohexan-2,4-dien-1-one (CHD-epoxy resin) [0078] In a round bottom flask, 1.00 was used with very vigorous stirring. G-hydroxybenzyl alcohol (8.06 mmol, 1.0 eq.) was suspended in 60 ml of water. Subsequently, 2.00 g of NaIO4 (9.35 mmol, 1.16 equivalents, dissolved in 40 ml of water) was gradually added to the solution. The reaction solution turned yellow. After stirring for a further 5 minutes, a yellow-brown solid precipitated. The reaction was stopped after another 30 minutes and a light pink solid was finally obtained as a product by filtration. The yield was 65% (0.64 mg, 5.24 mmol). Example 4: Synthesis of 6-(hydroxy)-6-(azidomethyl)cyclohexan-2,4-dien-1-one (CHD-azide) [0079] 1.00 g from the examples The reaction product of 3 (4.09 mmol, 1.0 eq.), 1.35 g of NaN3 (20.75 mmol, 5.07 eq.) and 1.13 g of NH4 Cl (21.12 mmol, 5.16 eq.) were collected in a mixture of 25 ml of methanol and 5 ml of water. . The solution became clear during heating and stirring for 2 hours at 80 °C. After cooling, the aqueous phase was extracted three times with 10 ml of ethyl acetate each time. The combined organic phase based on dry MgSO4, and the solvent removed under reduced pressure. The product was obtained as an orange brown solid with a yield of 85% (1.17 g, 3.54 mmol). Example 5: Synthesis of 6-(hydroxy)-6-(hydroxymethyl)cyclohexan-2,4-dien-1-one (CHD-DiOH) [0080] 200 mg of the reaction product from Example 3 (0.82 mmol, 1.0 eq) and 232.5 mg of NH4 Cl (4.23 mmol, 5.16 equiv) was suspended in a mixture of 25 ml of methanol and 5 ml water. After stirring at 80 ° C for 2 hours and then cooling, the aqueous phase was extracted three times with 50 ml of ethyl acetate each time. The combined organic phase based on dry MgSO4, and the solvent removed under reduced pressure. The product obtained was a light brown solid with a yield of 62% (144 mg, 0.51 mmol). Essentially, all products from the foregoing examples were in the form of a dimer after treatment. This also applies to the individual corresponding reactants of Examples 2, 3 and 5. The feature of Example 8 shown below is the incorporation of a linker into the polymer. Examples 6 and 7 describe the synthesis of the bond of Example 8. Example 6: Synthesis of 6-(ethylideneoxy)cyclohexan-2,4-dien-1-one (CHD-epoxy resin; alternative synthesis) In a round bottom flask, 12.4 g of 2-hydroxybenzyl alcohol (100 mmol, 1.0 eq.) was suspended in 750 ml of water with very vigorous stirring. Subsequently, 25.7 g of NaIO4 (120 mmol, 1.2 eq.) was added to the solution over 10 minutes. This turns the reaction solution to yellow. After further stirring, a yellow-brown solid precipitated. The reaction was stopped after a total of 30 minutes of stirring after all the reactions were added, the solid was filtered off and washed with a total of 400 ml of water. After drying at 60 ° C under reduced pressure, a light pink solid was finally obtained. The yield was 65.4% (7.99 g). The crude product was finally recrystallized from methanol. Example 7: Synthesis of 6-(hydroxy)-6-(hydroxymethyl)cyclohexan-2,4-dien-1-one (CHD-CL-OH; alternative synthesis) 1.22 g of the reaction product from Example 6 (5 mmol, 1.0 eq.) was dissolved in ACN, then 1.34 g of NH4 Cl (25.0 mmol, 5.00 eq.) was added to the solution. After stirring at 90 ° C for 17 hours and then cooling, the aqueous phase was removed and the organic phase was concentrated to 5 ml and extracted three times with 50 ml of ethyl acetate each time. The combined organic phases were then washed with 100 ml of lines concentrated sodium chloride solution, dried and eventually based on MgSO4. It is then recrystallized from the third butyl methyl ether. Finally, the solvent was removed at 50 ° C under reduced pressure. The product obtained was a light brown solid with a yield of 71.3% (1.3 g). Essentially, all products from the foregoing examples were in the form of a dimer after treatment. Example 8: Synthesis of CHD-Functional Polyurethane [0084] In a hand-held work box, three parallel syntheses were set according to Table 1. For this purpose, the product from Example 7 was dissolved in 600 μl of DMF in each case, and 336.4 mg (1.0 equivalent) of hexamethylene 1,6-diisocyanate (HMDI) and 0.1 equivalents were added. DABCO. The reaction mixture was each stirred at 90 ° C for 60 minutes, then cooled to room temperature, and hex-1,6-diol was added according to Table 1. The reaction product was further stirred at 80 ° C for 20 minutes, at 90 ° C for 20 minutes and finally at 100 ° C for 10 minutes. Successful incorporation of CHD-CI-OH into the polyurethane was detected by1 H NMR spectroscopy in DMSO-d6. High-temperature NMR measurement for detecting decoupling bonds [0085] In order to examine the reversibility associated with the inverse Diles-Adel reaction, temperature-dependent NMR spectroscopy is first performed, followed by heating via Trans-Diles-A The Del reaction converts the Diles-Adel-addition into a monomer/"open" material and blocks with maleimide to prevent re-dimerization during cooling. Procedure: [0086] To prepare for high temperature NMR measurements, individual components were dissolved in d6-DMSO (c=40 mg/l), transferred to a pressure resistant NMR tube and preheated to a later measured temperature. During heating,1 H NMR spectra were taken at different temperatures. For this purpose, the measurement was started at room temperature (20 ° C) and heated in steps of 20 ° C until the maximum temperature was 140 ° C. After cooling again to room temperature, other spectra were measured. For evaluation, the resonance shift of the vinyl proton between 5.5 and 6.5 ppm was determined. These signals are a suitable indication of the opening of the dimeric diene structure. The integration of these signals additionally provides information on the percentage of key opening. For example, the ratio of the ratio of Example 1 is about 18% at 140 °C. Interception Experiment [0087] In a round bottom flask, 56.0 mg of the product from Example 2 ("Ac dimer", 0.16 mmol, 1.0 eq.) and 56.46 mg of phenylsynyleneimide (0.33 mmol) , 2.1 equivalents) was dissolved in 3.5 ml of DMSO-d6. The solution was heated in an oil bath preheated to 190 ° C (± 2 ° C). Samples were taken at 5 minute intervals and analyzed by1 H-NMR and ESI-MS. The resonance shift of the vinyl proton between 5.5 and 6.5 ppm is a strong sign of the ratio of closed (ie, dimeric) structures. After 35 minutes at 190 ° C, it is thus possible to show complete elimination of the open structure of the cyclohexadienone structure with maleimide.
[0074] 圖1舉例顯示用於交聯及解偶之反應式。[0074] FIG. 1 exemplifies a reaction formula for crosslinking and decoupling.