TW201527421A - 膨脹熱塑性彈性體之製造 - Google Patents
膨脹熱塑性彈性體之製造 Download PDFInfo
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- TW201527421A TW201527421A TW103134155A TW103134155A TW201527421A TW 201527421 A TW201527421 A TW 201527421A TW 103134155 A TW103134155 A TW 103134155A TW 103134155 A TW103134155 A TW 103134155A TW 201527421 A TW201527421 A TW 201527421A
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- Prior art keywords
- polymer
- blowing agent
- stage
- melt
- thermoplastic elastomer
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title abstract description 22
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- HHJJPFYGIRKQOM-UHFFFAOYSA-N sodium;oxido-oxo-phenylphosphanium Chemical compound [Na+].[O-][P+](=O)C1=CC=CC=C1 HHJJPFYGIRKQOM-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B11/00—Making preforms
- B29B11/06—Making preforms by moulding the material
- B29B11/10—Extrusion moulding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/88—Adding charges, i.e. additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/34—Auxiliary operations
- B29C44/3461—Making or treating expandable particles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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Abstract
本發明係關於一種用於製造膨脹熱塑性彈性體之方法,該方法包含以下步驟:(a)在存在或不存在其他起始材料之情況下,將用於製造該熱塑性彈性體之單體及/或寡聚物添加至聚合物加工機之第一階段中,(b)在該聚合物加工機之第一階段中,將該等單體及/或寡聚物以及視情況添加之其他起始材料混合且使該等單體及/或寡聚物反應以產生聚合物熔體,(c)將該聚合物熔體傳送至聚合物加工機之第二階段中且在存在或不存在其他起始材料之情況下添加物理發泡劑以獲得包含發泡劑之聚合物熔體,(d)將該包含發泡劑之聚合物熔體模製成膨脹熱塑性彈性體。
Description
本發明係關於一種用於製造膨脹熱塑性彈性體,尤其呈丸粒形式之膨脹熱塑性彈性體的方法。熱塑性聚胺甲酸酯(thermoplastic polyurethane)為用於該方法中之熱塑性彈性體的一個實例。
膨脹熱塑性彈性體之用途包括例如製造所有類型之固體發泡材料製品,例如用於體操墊、身體保護器、汽車構造中之飾板元件、聲音及振動吸收器、封裝或鞋底。較佳之程序為用膨脹彈性體之丸粒填充模具且施加熱量以使個別丸粒最初在其表面熔融且從而將其熔合在一起。可以此方式製造複雜成形之中間物或具有凹穴之最終模製物以及簡單製品。
發泡材料(包括尤其珠粒發泡體)為人所熟知且已充分描述於例如Ullmann之「Enzyklopadie der technischen Chemie」,第4版,第20卷,416ff頁之文獻中。
WO-A 2007/082838揭示一種用於製造包含發泡劑之膨脹熱塑性聚胺甲酸酯的方法。該方法之第一步驟包含將熱塑性聚胺甲酸酯擠壓成丸粒。在第二步驟中,在壓力下在水性懸浮液中用發泡劑浸漬該等丸粒且在第三步驟中膨脹。在該方法之另一個具體實例中,使熱塑性聚胺甲酸
酯與發泡劑一起在擠壓機中熔融且使熔體在無防止發泡之裝置的情況下粒化。未描述熱塑性聚胺甲酸酯之製造及在相同機器中之成為膨脹熱塑性聚胺甲酸酯之進一步加工。
可熱塑性加工之聚胺甲酸酯彈性體的製造自例如EP-A 1 213 307已知。藉由其中所描述之方法獲得的聚胺甲酸酯為壓實的且不用於膨脹彈性體之製造。
WO-A 2011/005705描述一種用於在擠壓機中製造發泡聚胺甲酸酯之方法。將用於製造聚胺甲酸酯之單體引入至擠壓機之第一部分中且在第二位置摻合發泡劑,之後在真空壓力下進行介入去揮發。聚合物熔體隨後在擠壓機中或其下游端處發泡且發泡材料被擠出。此處在製造方法中即使微小的變化亦可導致發泡體構造中之差異,因此若欲獲得均勻之發泡體,則製程控制必須極其嚴格。所獲得之中間物及最終製品由交聯聚胺甲酸酯構成,該交聯聚胺甲酸酯隨後不可能藉由熱成型或其他熱處理來進一步加工。因此,所需中間物或最終製品必須以最後的最終形狀模製。無法實現具有凹穴的複雜成形之幾何形狀。
製造可膨脹熱塑性聚胺甲酸酯丸粒材料自DE-A 1 300 282已知。然而,進一步加工需要例如在擠壓機中再次熔融,在此情況下發泡一般已在擠壓機中進行。特定言之,不可能以此方式製造膨脹丸粒材料。
WO-A 96/20966描述一種方法,其中將聚胺甲酸酯製造組分在擠壓機中混合、施用至帶上且發泡且在該帶上固化。DE-A 100 56 251描述另一種用於製造聚胺甲酸酯發泡體之方法,其中在自擠壓機出現單體時立即進行固化單體以形成聚胺甲酸酯之步驟。WO-A 96/20966及DE-A 100 56
251均描述由熱固性聚胺甲酸酯組成之發泡體。此等發泡體原則上不可能如同熱塑性彈性體在模具中進一步加工。值得注意的是,在WO-A 96/20966中獲得之聚胺甲酸酯發泡體就形狀而言極其有限,因為帶加工僅僅能夠製造板材狀發泡體,其不具有所定義的輪廓。此等材料無法直接模製成成形製品,而需要例如藉由機械加工或切割進一步加工成中間物或最終製品,在此情況下可能產生大量的廢品。描述於該兩個文獻中之材料亦並非隨後可熱形成的,因為材料交聯且因此不再可被軟化。因此,複雜成形之最終製品的直接模製為不可能的,且自材料後續製造複雜成形之最終製品僅僅在極大費用及不便且產生切割廢品之情況下為可能的。詳言之,在任一情況下均無法實現珠粒。
本發明之目標為提供一種用於製造膨脹熱塑性彈性體,尤其用於製造具有所界定孔隙率之膨脹丸粒材料的方法。
此目標藉由一種用於製造膨脹熱塑性彈性體之方法來達成,該方法包含以下步驟:(a)在存在或不存在其他起始材料之情況下,將用於製造該熱塑性彈性體之單體及/或寡聚物添加至聚合物加工機之第一階段中,(b)在該聚合物加工機之第一階段中,將該等單體及/或寡聚物以及視情況添加之其他起始材料混合且使該等單體及/或寡聚物反應以產生聚合物熔體,(c)將該聚合物熔體傳送至該聚合物加工機之第二階段中且在存在或不存在其他起始材料之情況下添加物理發泡劑以獲得包含發泡劑之聚合物
熔體,(d)將該包含發泡劑之聚合物熔體模製成膨脹熱塑性彈性體。
本發明之方法提供在無其他介入步驟之情況下,自單體及視情況選用之其他反應物或待使用之起始材料直接獲得發泡中間物製品的方法,該發泡中間物製品例如膨脹丸粒材料,包含膨脹熱塑性彈性體。該方法亦為改變發泡體結構提供較大範疇。根據本發明獲得之膨脹熱塑性彈性體珠粒藉由模製,亦即,在無極大成本或不便且不產生切割廢品之情況下可進一步加工成複雜成形之最終製品。
製程條件可在步驟(d)中之模製期間變化以產生發泡體之不同孔隙率及具有不間斷表皮之膨脹熱塑性彈性體。舉例而言,就觸感原因而言可能需要不間斷表皮。不間斷表皮亦可用於減緩或甚至完全防止濕氣進入發泡熱塑性彈性體中。
根據本發明,除術語「彈性體(elastomer)」以外,亦使用術語「聚合物(polymer)」,遵循一般語言用法。關於藉由本發明方法製造的熱塑性彈性體之主要組分,術語「聚合物(polymer)」表示熱塑性彈性體。
適用之聚合物加工機可尤其包括螺桿活塞機或熔體泵。亦可使用能夠製造聚合物及隨後聚合物之珠粒的任何其他機器。然而,螺桿活塞機為尤其較佳的。
擠壓機較佳用作螺桿活塞機以進行本發明之方法。一般而言,當單體及/或寡聚物之轉化率提高時,所使用的無論哪個設備中之黏度亦提高。
在本發明之一個具體實例中,步驟(b)及步驟(c)在一個機器中進行。在此情況下,第一階段為螺桿活塞機之第一區段,在該區段中在存在或不存在其他起始材料下進行單體及/或寡聚物至聚合物之轉化,且第二階段為螺桿活塞機之第二區段,該區段為第一區段之即刻下游且在該區段中饋入物理發泡劑。此設備就丸粒製造而言尤其適合於採用擠壓機。
或者,亦有可能在步驟(b)中採用第一螺桿活塞機以製造聚合物且在步驟(c)中採用第二螺桿活塞機以饋入物理發泡劑,在此情況下第一及第二螺桿活塞機之間存在耦合以將在該第一螺桿活塞機中獲得之聚合物熔體直接轉移至該第二螺桿活塞機中。因此將聚合物熔體供應至第二螺桿活塞機以便進行步驟(c),避免否則必需的熔融聚合物之步驟。在此處使用的適當設備之實例為串列式擠壓機,其中螺桿活塞機之第一階段為串列式擠壓機之第一擠壓機且螺桿活塞機之第二階段為串列式擠壓機之第二擠壓機。
在一個尤其較佳具體實例中,雙螺桿擠壓機用作螺桿活塞機之第一階段。此雙螺桿擠壓機饋入有用於製造熱塑性彈性體之單體及/或寡聚物以及視情況選用之其他起始材料。在雙螺桿擠壓機中使單體及/或寡聚物反應以產生熱塑性彈性體。在此情況下,螺桿活塞機之第一階段之組態使得滯留時間足以將所使用之單體及/或寡聚物轉化成熱塑性彈性體。此可例如藉由改變第一階段之長度、螺桿活塞機中至少一個螺桿之旋轉速度及螺桿之旋溝深度來達成。第一階段之幾何資料及至少一個螺桿之旋轉速度
決定滯留時間。
在螺桿活塞機之第二階段中隨後添加物理發泡劑。為確保物理發泡劑在聚合物熔體中之均勻分佈,螺桿活塞機之第二階段將包括例如螺桿上之適合混合單元。此處亦可另外使用靜態混合器。
亦可使用熔體泵作為擠壓機之替代物。為達成物理發泡劑在聚合物中之均勻分佈,熔體泵較佳後接靜態混合器,該靜態混合器之上游入口進入粒化系統。
丸粒材料典型地藉由將聚合物熔體擠壓成股,隨後切割成丸粒材料來製造。由於其摻合物具有物理發泡劑,自擠壓機出現的聚合物熔體因壓力下降而經受膨脹以製造發泡產物,同時粒化因而製造膨脹丸粒材料。
在一個較佳具體實例中,丸粒材料藉由以下來獲得:在步驟(d)中迫使聚合物熔體通過經溫度調節之粒化沖模(pelletizing die)、使用切割裝置將該被迫通過該經溫度調節之粒化沖模的聚合物熔體切割成個別膨脹中之丸粒及使用液體流自該粒化室輸出該等丸粒。在此具體實例中,經溫度調節之粒化沖模的溫度較佳在150℃與280℃之間。
為防止粒化室中之聚合物熔體的不受控制之發泡且為獲得均勻發泡之丸粒材料,有利地向粒化室施加高於環境之壓力。進一步尤其較佳的是,使粒化室充滿液體,因而將包含發泡劑之熱塑性聚合物熔體直接至液體中。水較佳為在粒化室中使用之液體。
為製造具有不間斷表皮之膨脹丸粒,一個較佳具體實例提供以液流形式流經粒化室的經溫度調節之液體具有介於10℃至60℃範圍內之
溫度及比環境壓力高介於0.7巴至20巴範圍內之壓力,同時選擇粒化室中之液體之壓力及溫度以及粒化沖模之溫度以使得丸粒在加壓液體中藉由其所含有之物理發泡劑膨脹以製造具有不間斷表皮之膨脹丸粒。
在聚合物加工機中之粒化裝置處之所需粒化壓力以及熔體之所需溫度視待加工彈性體以及所使用之輔助材料及所使用之物理發泡劑而定。所需壓力及所需溫度進一步視彈性體中之組分之間的混合比率而定。
在粒化室中,將被迫通過經溫度調節之粒化沖模的聚合物模製成股,切割裝置將該等股粉碎成個別膨脹丸粒。切割裝置可以例如快速旋轉刀片之形式實施。所得丸粒之形狀視粒化沖模中之孔洞的形狀及尺寸以及迫使熔體通過粒化沖模中之孔洞的壓力及切割裝置之速度而定。較佳選擇迫使壓力、切割裝置之速度及粒化沖模中之孔洞之尺寸以使得丸粒之形狀實質上為球形。刀片之數目、孔洞之數目與旋轉刀片速度之間的關係為熟悉此項技術者已知的。
使用例如流經粒化室的經溫度調節之液體將丸粒自粒化室輸出。選擇經溫度調節之液體的壓力及溫度以使得聚合物股/丸粒以受控方式藉由其所含有之物理發泡劑膨脹以在丸粒之表面上形成不間斷表皮。
使丸粒與經溫度調節之液體一起流動至例如乾燥器中,在該乾燥器中丸粒與液體分離。預先已製造之膨脹丸粒可收集在容器中,同時將液體過濾且經由泵送回到粒化室中。
在液體溫度受控制之情況下的加壓液體中之粒化防止包含
發泡劑之聚合物熔體經受不受控制之膨脹,在該不受控制之膨脹中可能無法進行不間斷表皮之形成。此類珠粒起初將具有較低容積密度,但將再次
快速各自崩散。結果將為具有較高容積密度及較低彈性之不均勻珠粒。本發明之方法以受控方法減緩丸粒之膨脹來製造具有不間斷表皮及內部多孔狀結構之均勻結構化顆粒,其中在表面處泡孔尺寸較小且朝向中心增大。在中心處之泡孔尺寸低於250μm,較佳低於100μm。膨脹丸粒之容積密度典型地在30g/l至250g/l範圍內且較佳在80g/l至140g/l範圍內。
藉由控制粒化室中經溫度調節之液體的壓力及溫度以及藉由控制粒化沖模之溫度來管理丸粒膨脹。當丸粒膨脹過快及/或以不受控制之方式膨脹時,意謂未形成不間斷表皮,粒化室中之液體的壓力升高及/或粒化室中經溫度調節之液體的溫度下降。環繞丸粒的經溫度調節之液體的壓力升高抵消物理發泡劑之膨脹效果且抑制丸粒之膨脹。降低粒化室中經溫度調節之液體的溫度在珠粒上產生較厚表皮且因此提供較多膨脹阻力。當經溫度調節之液體相對於所使用之物理發泡劑處於過高壓力或過低溫度下時,丸粒之膨脹可能過度受阻或甚至完全停止,製造容積密度過高之丸粒。在此情況下,粒化室中經溫度調節之液體的壓力下降及/或經溫度調節之液體的溫度升高。
膨脹丸粒較佳在流經粒化室的經溫度調節之液體中的壓力介於0.7巴與20巴之間時自包含發泡劑之聚合物熔體製造。液體中之壓力更佳在5巴與15巴之間且甚至更佳在10巴與15巴之間。
作為調節粒化室中經溫度調節之液體的壓力及/或溫度之附加方案或替代方案,丸粒之膨脹亦可經由經溫度調節之粒化沖模的溫度影響。降低經溫度調節之粒化沖模的溫度具有將熱量自聚合物熔體較快速地釋放至環境中之效果。此有助於形成不間斷表皮,該不間斷表皮為穩定發
泡丸粒之前提條件。若經溫度調節之粒化沖模及/或粒化室中之液體的溫度過低,則聚合物熔體將冷卻過快且在可開始充分膨脹之前固化。丸粒藉由其所含有之物理發泡劑的膨脹受到如此嚴重之阻礙以致於形成具有過高容積密度之丸粒。因此,粒化室中經溫度調節之液體的溫度及/或經溫度調節之粒化沖模的溫度在此情況下升高。
粒化室中液體之溫度較佳在10℃與60℃之間以使丸粒可經受受控制之膨脹,其中形成不間斷之發泡表皮。液體之溫度較佳在25℃與45℃之間。經溫度調節之粒化沖模的溫度較佳在150℃與280℃之間,更佳在220℃與260℃之間且甚至更佳在245℃至255℃範圍內。
就粒化沖模而言過度之溫度產生珠粒表面上之較薄表皮及表面隨後崩塌。就粒化沖模而言過低之溫度降低膨脹程度且在珠粒上產生較厚之未發泡表面。
使用本發明之方法獲得的丸粒材料之珠粒重量較佳在1mg至40mg範圍內。膨脹熱塑性彈性體之密度較佳在30g/l至350g/l範圍內。
根據本發明,術語物理發泡劑描述其化學結構在膨脹製程期間保持不變、其凝聚狀態在膨脹製程期間可改變且其在膨脹製程中為氣態的發泡劑。發泡劑例如描述於Thermoplastic Foam Processing Principles and Development,Richard Gendron編,CRC出版社,2005中。
在一個較佳具體實例中之物理發泡劑包含二氧化碳、氮氣或二氧化碳與氮氣之混合物。此處可使用氮氣與二氧化碳之任何所需混合物。然而,較佳將包含50wt%至100wt%之二氧化碳及0wt%至50wt%之氮氣的二氧化碳與氮氣之混合物用作發泡劑。替代性地或另外地,發泡劑亦
可包含有機發泡劑,例如烷烴、鹵化烴或其混合物。就此而言,適用之烷烴包括例如乙烷、丙烷、丁烷及戊烷。僅僅使用CO2及/或N2以及其組合作為發泡劑而不添加其他發泡劑為尤其有利的,因為其為不可燃之惰性氣體,所以在製造過程中不可能產生潛在爆炸性氛圍。此使得成本密集型安全防護措施變得不必要且極大地降低在製造過程中之潛在的風險。同樣有利的是不必在將產品運送出去之前儲存產品以使可燃性揮發物呈氣體放出。
向包含發泡劑之聚合物熔體中另外添加一或多種成核劑產生其他優點。適用之成核劑尤其包括各自單獨地或呈任何混合物形式之滑石、氟化鈣、苯基亞膦酸鈉、氧化鋁、碳黑、石墨、顏料及細粉狀聚四氟乙烯。滑石用作成核劑尤其較佳。可歸因於成核劑的熱塑性模製組成物或聚合物熔體之總質量的比例較佳在0wt%至4wt%範圍內且尤其在0.1wt%至2wt%範圍內。成核劑可在第一階段中或在第二階段中添加。
可例如使用氣體或液體饋入單元(視物理發泡劑之物理狀態而定)經由噴射閥將物理發泡劑添加至聚合物加工機中。
用於製造膨脹丸粒材料之熱塑性彈性體選自例如熱塑性聚酯彈性體(例如聚醚酯或聚酯酯)、熱塑性共聚醯胺(例如聚醚共聚醯胺)或苯乙烯嵌段共聚物(例如苯乙烯丁二烯嵌段共聚物)。熱塑性彈性體尤其較佳為熱塑性聚胺甲酸酯。
除反應產生熱塑性彈性體之單體及/或寡聚物之外,還可添加其他起始材料。其他起始材料之混合物可用於調節彈性體之物理及/或化學特性。此外,催化劑亦可視情況作為另一種起始材料添加以催化單體及/
或寡聚物之反應以產生聚合物。
其他添加劑可選自例如成核劑、表面活性物質、填充劑、阻燃劑(例如含磷系統)、晶核形成劑、氧化穩定劑、另外的其他穩定劑(例如抗水解、光、熱或變色),增強劑及塑化劑、滑動及脫模助劑、染料及顏料以及其任何所需混合物。當使用填充劑時,此等填充劑可為有機及/或無機粉末或纖維材料以及其混合物。填充劑之平均粒子直徑或(在纖維填充劑之情況下)長度應為大約泡孔尺寸或更小。優先考慮0.1μm至100μm範圍內,較佳1μm至50μm範圍內之平均粒子直徑或平均纖維長度。
當使用熱塑性聚胺甲酸酯時,熱塑性聚胺甲酸酯可為熟習此項技術者已知之任何所需熱塑性聚胺甲酸酯。熱塑性聚胺甲酸酯及其製成方法已廣泛描述於例如Gerhard W.Becker及Dietrich Braun,Kunststoffhandbuch,第7卷,「Polyurethane」,Carl Hanser Verlag,Munich,Vienna,1993中。
在一個較佳具體實例中,藉由使異氰酸酯之混合物與作為單體或寡聚物的分子量較佳為0.5kg/mol至10 kg/mol之異氰酸酯反應性化合物及分子量較佳為0.05kg/mol至0.5kg/mol之視情況選用之擴鏈劑反應來製備熱塑性聚胺甲酸酯。在另一個較佳具體實例中,藉由另外向混合物中添加至少一種鏈轉移劑、催化劑及視情況選用之至少一種填充劑、輔助及/或摻合劑來製備熱塑性聚胺甲酸酯。
熱塑性聚胺甲酸酯之製備需要呈任何比率之異氰酸酯與異氰酸酯反應性化合物之混合物。擴鏈劑、鏈轉移劑、催化劑及填充劑、輔助及/或摻合劑之另外添加為視情況選用的且可單獨或以所有可能的變化形
式進行。
較佳具體實例利用脂族、環脂族及/或芳族異氰酸酯作為有機異氰酸酯。特別優先使用芳族、脂族及/或環脂族二異氰酸酯。較佳二異氰酸酯之實例為二異氰酸三亞甲酯、二異氰酸四亞甲酯、二異氰酸五亞甲酯、二異氰酸六亞甲酯、二異氰酸七亞甲酯、二異氰酸八亞甲酯、二異氰酸2-甲基-1,5-五亞甲酯、二異氰酸2-乙基-1,4-伸丁酯、二異氰酸1,5-五亞甲酯、二異氰酸1,4-伸丁酯、1-異氰酸酯基-3,3,5-三甲基-5-異氰酸酯基甲基環己烷、1,4-雙(異氰酸酯基甲基)環己烷、1,3-雙(異氰酸酯基甲基)環己烷、1,4-環己烷二異氰酸酯、1-甲基-2,4-環己烷二異氰酸酯、1-甲基-2,6-環己烷二異氰酸酯、2,2'-二環己基甲烷二異氰酸酯、2,4'-二環己基甲烷二異氰酸酯、4,4'-二環-己基甲烷二異氰酸酯、2,2'-二苯基甲烷二異氰酸酯、2,4'-二苯基甲烷二異氰酸酯、4,4'-二苯基甲烷二異氰酸酯、二異氰酸1,5-伸萘酯、二異氰酸2,4-甲伸苯酯、二異氰酸2,6-甲伸苯酯、二苯基甲烷二異氰酸酯、二異氰酸3,3'-二甲基聯苯酯、1,2-二苯基乙烷二異氰酸酯及二異氰酸伸苯酯。
除異氰酸酯之外,熱塑性模製組成物還由具有至少兩個異氰酸酯反應性含氫基團之化合物構成。異氰酸酯反應性含氫基團較佳為羥基。具有至少兩個異氰酸酯反應性含氫基團之化合物尤其較佳選自聚醚醇、聚酯醇及聚碳酸酯二醇。在此情形中,聚酯醇、聚醚醇及/或聚碳酸酯二醇通常亦包含在術語「聚醇(polyol)」內。
較佳自聚醚醇製備熱塑性聚胺甲酸酯。在此使用聚醚二醇尤其較佳。聚四氫呋喃為尤其較佳之聚醚二醇。優先考慮使用聚醚醇,例如分子量在0.6kg/mol與2.5kg/mol之間的聚四氫呋喃。單獨地或以多種聚醚
醇之混合物形式使用聚醚醇。
在一個替代性具體實例中,使用聚酯醇來製備熱塑性聚胺甲酸酯。在一個較佳具體實例中,為此使用聚酯二醇。自己二酸及1,4-丁二醇製備較佳之聚酯二醇。聚酯醇之較佳具體實例的分子量在0.6kg/mol與2.5kg/mol之間。
在其他較佳具體實例中,用於製備熱塑性聚胺甲酸酯之聚醇的分子量為0.5kg/mol至8kg/mol,更佳0.6kg/mol至6kg/mol且尤其0.8kg/mol至4kg/mol。在其他較佳具體實例中,聚醇之平均官能度為1.8至2.3,更佳1.9至2.2且尤其為2。在一個尤其較佳具體實例中,聚醇為聚酯醇,較佳合成自聚四氫呋喃且在另一個較佳具體實例中的分子量在0.6kg/mol與2.5kg/mol之間。
當使用擴鏈劑製備熱塑性聚胺甲酸酯時,此等擴鏈劑較佳為脂族、芳族及/或環脂族化合物,其在其他較佳具體實例中之分子量為0.05kg/mol至0.5kg/mol。擴鏈劑為例如具有兩個官能基的化合物,例如在伸烷基部分具有2至10個碳原子之二胺及/或烷二醇,尤其1,4-丁二醇、1,6-己二醇及/或具有3至8個碳原子之二-、三-、四-、五-、六-、七-、八-、九-及/或十烷二醇及相對應的寡-及/或聚丙二醇。製備熱塑性聚胺甲酸酯之其他具體實例利用擴鏈劑之混合物。
當使用鏈轉移劑時,此等鏈轉移劑之分子量典型地為0.03kg/mol至0.5kg/mol。鏈轉移劑為僅僅具有一個與異氰酸酯相關之官能基的化合物。鏈轉移劑之實例為單官能醇、單官能胺,較佳為甲胺及/或單官能聚醇。鏈轉移劑可用於特定地控制個別組分之混合物的流動特徵。在較佳
具體實例中,以具有至少兩個異氰酸酯反應性含氫基團之化合物之100重量份計,鏈轉移劑以0重量份至5重量份且更佳0.1重量份至1重量份範圍內之量使用。除擴鏈劑之外或替代擴鏈劑使用鏈轉移劑。
其他具體實例利用至少一種催化劑來製備熱塑性聚胺甲酸酯以尤其催化二異氰酸酯之異氰酸酯基團與異氰酸酯反應性化合物(較佳具有至少兩個異氰酸酯反應性含氫基團之化合物、鏈轉移劑及擴鏈劑的羥基)之間的反應。在較佳具體實例中,催化劑係選自三級胺之群,例如三乙胺、二甲基環己胺、N-甲基嗎啉、N,N'-二甲基哌嗪、2-(二甲基胺基乙氧基)乙醇、二氮雜雙環(2,2,2)辛烷及類似物質。在其他較佳具體實例中,至少一種催化劑係選自有機金屬化合物之群且舉例而言提及為鈦酯、鐵化合物(例如乙醯基丙酮酸鐵(III))、錫化合物(例如二乙酸錫、二辛酸錫、二月桂酸錫或脂族羧酸之錫二烷基鹽,諸如二乙酸二丁基錫、二月桂酸二丁基錫或其類似物)。
一些具體實例單獨地利用催化劑,而其他具體實例利用催化劑之混合物。在一個較佳具體實例中使用之催化劑為以具有至少兩個異氰酸酯反應性含氫基團之化合物(較佳聚羥基化合物)計,0.0001wt%至0.1wt%之量的催化劑之混合物。
適用之輔助及/或摻合劑包括例如水解控制劑及阻燃劑。其他摻合劑及輔助劑可辯別自標準參考文獻著作,諸如上文所引用之Gerhard W.Becker及Dietrich Braun,Kunststoffhandbuch,第7卷,「Polyurethane」,Carl HanserVerlag,Munich,Vienna,1993。
除催化劑之外,且亦在未使用催化劑之情況下,亦可將水解
控制劑(例如聚合物及低分子量碳化二亞胺)添加至異氰酸酯及具有至少兩個異氰酸酯反應性含氫基團之化合物中來製備熱塑性聚胺甲酸酯。
在另一個具體實例中,熱塑性聚胺甲酸酯可包含磷化合物。
為設定熱塑性聚胺甲酸酯之蕭氏硬度(Shore hardness),具有至少兩個異氰酸酯反應性含氫基團之化合物及擴鏈劑可在相對較廣泛的莫耳比內變化。在較佳具體實例中,具有至少兩個異氰酸酯反應性含氫基團之化合物與所使用之總擴鏈劑的莫耳比在10:1至1:10範圍內,較佳在5:1至1:8範圍內,且更佳在1:1至1:4範圍內,熱塑性聚胺甲酸酯之硬度隨著擴鏈劑含量提高而提高。蕭氏硬度較佳在A44至D30範圍內,更佳在A62至A95範圍內,最佳地在A62至A85範圍內。蕭氏硬度係根據用於壓實(亦即非膨脹)熱塑性聚胺甲酸酯之DIN 53505測定。
在其他較佳具體實例中,在慣用指數下進行形成熱塑性聚胺甲酸酯之反應。指數定義為用於反應中之芳族、脂族及/或環脂族二異氰酸酯之異氰酸酯基團之總數與具有至少兩個異氰酸酯反應性含氫基團之化合物及擴鏈劑中異氰酸酯反應性基團之總數(亦即,活性氫之數目)的比率。指數100意謂芳族、脂族及/或環脂族二異氰酸酯之每個異氰酸酯基團存在一個活性氫原子,亦即,具有至少兩個異氰酸酯反應性含氫基團之化合物及擴鏈劑之異氰酸酯反應性官能基。指數高於100意謂存在的異氰酸酯基團比存在的異氰酸酯反應性基團(例如羥基)多。
在尤其較佳具體實例中,形成熱塑性聚胺甲酸酯之反應在介於60與120之間的指數下,且更佳在介於80與110之間的指數下進行。
此外,熱塑性模製組成物可視情況包含至少一種添加劑。術
語添加劑包含填充劑、輔助及摻合物以及上文所描述之鏈轉移劑、擴鏈劑及催化劑。添加劑可以任何所需混合物形式加以使用。可歸因於添加劑的熱塑性模製組成物之總質量的分數較佳在0wt%至80wt%範圍內。
根據本發明,將用於製造熱塑性聚胺甲酸酯之材料添加至聚合物加工機之第一階段中。可將其經由在入口處之聯合饋入口添加至聚合物加工機中,或經由沿著聚合物加工機(尤其螺桿活塞機)之長度分佈的兩個或兩個以上饋入口添加至聚合物加工機中。較佳首先添加單體及/或寡聚物以及視情況所需之催化劑,且在單體及/或寡聚物的至少一部分已反應產生聚合物之後,在後續口處進一步加入用於設定聚合物之特性的添加劑。
雙螺桿擠壓機為用於製造膨脹丸粒材料之適合聚合物加工機的一個實例。選擇雙螺桿擠壓機之長度以使得單體及/或寡聚物反應以產生聚合物之區域可後接壓力建立區域。出於此目的,尤其有利的是在第二階段之下游端之上游選擇長度以使得壓力可沿至少15L/D之長度建立,其中L/D描述的長度與直徑之比率。至少一個限制性傳輸元件或捏合元件,較佳兩個至三個限制性傳輸元件或捏合元件可用於將反應區域與壓力建立區域彼此隔開。可例如藉由螺桿元件之構造、製程參數(諸如螺桿速度)及/或在擠壓機下游使用齒輪泵來確保在單體與/或寡聚物之間之反應下游建立壓力。此在雙螺桿擠壓機中產生不低於50巴,較佳比環境壓力高60巴至100巴的壓力。在此壓力主導之區域中,例如使用氣計量單元經由噴射閥添加物理發泡劑。在添加之後,混合元件將物理發泡劑與聚合物熔體沿不低於5L/D,較佳不低於10L/D之長度均勻地混合。為傳輸包含發泡劑之熔體,可進一步在雙螺桿擠壓機之至少一個螺桿上提供傳輸元件。
在一個替代性具體實例中,聚合物加工機之第一階段後接具有物理發泡劑之饋入口的熔體通道作為第二階段。在此情況下,第二階段進一步包含熔體泵及靜態混合器。熔體通道為例如可加熱管道,聚合物熔體流經該可加熱管道且可向該可加熱管道中導入物理發泡劑。可同樣為此提供噴射閥及用於添加發泡劑之氣計量單元。熔體泵產生迫使包含所添加物理發泡劑之聚合物熔體通過靜態混合器及粒化工具所需要的必需壓力。熔體泵可位於熔體通道與靜態混合器之間,或替代地在第一階段與熔體通道之間。當熔體泵安置在熔體通道與靜態混合器之間時,有必要組態第一階段以使得在單體及/或寡聚物反應產生聚合物之過程中在第一階段中壓力增大,且此外壓力亦足以將聚合物熔體傳輸通過熔體通道。此外,為此有必要將熔體通道直接或經由管道線連接至第一階段。
靜態混合器用於將物理發泡劑均勻地分佈於聚合物熔體中。靜態混合器較佳經加熱以防止聚合物熔體之固化且由例如具有至少1L/D之製程長度,較佳至少5L/D之長度,且經組態以使得聚合物熔體之滯留時間大於0.5秒,較佳大於3秒的混合元件構成。
雙螺桿擠壓機或靜態混合器隨後後接用於製造丸粒材料之適合系統,尤其後接粒化設備。
實施例
實施例1
在距離用作反應擠壓機以混合及合成熱塑性聚胺甲酸酯之Coperion GmbH ZSK43雙螺桿擠壓機之加工部分之上游端6L/D的部位,添加2mol之4,4'-二苯基甲烷二異氰酸酯、1mol莫耳質量(molar mass)為1000
g/mol之聚丁二醇、1mol之1,4-丁二醇以及0.2重量份之滑石成核劑及30ppm之二辛酸錫(II)催化劑,在180℃與220℃之間的溫度下混合且使其反應。選擇6L/D之距離以防止回流單體進入驅動單元。螺桿再次夾帶回流單體以沿傳輸方向運輸。
將反應混合物自反應擠壓機轉移至用作主擠壓機之Coperion GmbH ZSK92雙螺桿擠壓機中。主擠壓機之饋入鬥位於距離加工部分之上游端6L/D處。在主擠壓機中,在200℃至240℃範圍內之溫度下進一步向前驅動反應。在距離主擠壓機之下游端15L/D的部位,使用氣計量站將用作物理發泡劑之0.2重量份之氮氣及1.5重量份之二氧化碳噴射至聚合物熔體中。熔體泵迫使包含發泡劑之聚合物熔體經在200℃下的經溫度調節之粒化沖模進入粒化室,水流流動通過該粒化室。粒化沖模中之孔洞的直徑為1.8mm。粒化室中之旋轉刀片在粒化沖模之表面將聚合物熔體切碎成珠粒重量20mg之丸粒。具有10巴之壓力及30℃之溫度的水將丸粒自粒化室輸出且將其傳輸至離心乾燥器中。在離心乾燥器中,丸粒與水分離且乾燥。由此獲得的膨脹丸粒材料之容積密度為140g/l。
實施例2
除了所使用之物理發泡劑為0.2重量份之氮氣及2重量份之二氧化碳之外,重複實施例1。粒化沖模中之孔洞的直徑為2.4mm。流經粒化室之水具有5巴之壓力及20℃之溫度。以此方式獲得之丸粒的珠粒重量為32mg且容積密度為120g/l。
實施例3
除了所使用之物理發泡劑為0.3重量份之氮氣及2.5重量份
之二氧化碳之外,重複實施例1。主擠壓機後接熔體通道,向該熔體通道中噴射物理發泡劑。熔體通道後接熔體泵,從而迫使包含物理發泡劑之聚合物熔體進入在240℃下的經溫度調節之靜態混合器,其用作分散組件。靜態混合器後接具有直徑1毫米之孔洞的粒化沖模,且經由該粒化沖模將聚合物熔體按壓至粒化室中。將由此獲得之丸粒材料調節為5mg之珠粒重量。流經粒化室之水具有20巴之壓力及35℃之溫度。由此獲得的丸粒材料之容積密度為100g/l。
Claims (15)
- 一種用於製造膨脹熱塑性彈性體之方法,該方法包含以下步驟:(a)在存在或不存在其他起始材料之情況下,將用於製造該熱塑性彈性體之單體及/或寡聚物添加至聚合物加工機之第一階段中,(b)在該聚合物加工機之第一階段中,將該等單體及/或寡聚物以及視情況添加之其他起始材料混合且使該等單體及/或寡聚物反應以產生聚合物熔體,(c)將該聚合物熔體傳送至該聚合物加工機之第二階段中且在存在或不存在其他起始材料之情況下添加物理發泡劑以獲得包含發泡劑之聚合物熔體,(d)將該包含發泡劑之聚合物熔體模製成膨脹熱塑性彈性體。
- 如申請專利範圍第1項之方法,其中該聚合物加工機為螺桿活塞機。
- 如申請專利範圍第2項之方法,其中該螺桿活塞機之第一階段及該螺桿活塞機之第二階段為擠壓機之區段。
- 如申請專利範圍第2項之方法,其中該螺桿活塞機之第一階段為串列式擠壓機之第一擠壓機且該螺桿活塞機之第二階段為該串列式擠壓機之第二擠壓機。
- 如申請專利範圍第2項之方法,其中該聚合物加工機之第二階段包含熔體泵,加工機且視情況具有熔體篩或靜態混合器。
- 如申請專利範圍第1項中任一項之方法,其中該膨脹熱塑性彈性體為膨脹丸粒材料。
- 如申請專利範圍第6項之方法,其中該丸粒材料藉由以下來獲得:在 步驟(d)中迫使該聚合物熔體通過溫度調節在150℃至280℃範圍內之粒化沖模(pelletizing die)、使用切割裝置將該被迫通過該經溫度調節之粒化沖模的聚合物熔體切割成個別膨脹中之丸粒及使用液體流自該粒化室輸出該等丸粒。
- 如申請專利範圍第7項之方法,其中以液流形式流經該粒化室的經溫度調節之液體具有介於10℃至60℃範圍內之溫度及比環境壓力高介於0.7巴至20巴範圍內之壓力。
- 如申請專利範圍第6項中任一項之方法,其中該膨脹丸粒材料之珠粒重量在1mg至40mg範圍內。
- 如申請專利範圍第1項中任一項之方法,其中該發泡劑包含二氧化碳、氮氣或二氧化碳與氮氣之混合物。
- 如申請專利範圍第10項之方法,其中該發泡劑包含50wt%至100wt%之二氧化碳及0wt%至50wt%之氮氣且無其他發泡劑。
- 如申請專利範圍第1項中任一項之方法,其中該發泡劑包含選自烷烴、鹵化烴或其混合物之有機發泡劑。
- 如申請專利範圍第1項中任一項之方法,其中該熱塑性彈性體為熱塑性聚胺甲酸酯(thermoplastic polyurethane)。
- 如申請專利範圍第1項中任一項之方法,其中該膨脹熱塑性彈性體之密度在30g/l至350g/l範圍內。
- 如申請專利範圍第1項中任一項之方法,其中該膨脹熱塑性彈性體具有不間斷表皮。
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---|---|---|---|---|
DE102012206094B4 (de) | 2012-04-13 | 2019-12-05 | Adidas Ag | Sohlen für Sportschuhe, Schuhe und Verfahren zur Herstellung einer Schuhsohle |
DE102013202306B4 (de) | 2013-02-13 | 2014-12-18 | Adidas Ag | Sohle für einen Schuh |
DE102013002519B4 (de) | 2013-02-13 | 2016-08-18 | Adidas Ag | Herstellungsverfahren für Dämpfungselemente für Sportbekleidung |
US9610746B2 (en) | 2013-02-13 | 2017-04-04 | Adidas Ag | Methods for manufacturing cushioning elements for sports apparel |
DE102013202291B4 (de) | 2013-02-13 | 2020-06-18 | Adidas Ag | Dämpfungselement für Sportbekleidung und Schuh mit einem solchen Dämpfungselement |
US9930928B2 (en) | 2013-02-13 | 2018-04-03 | Adidas Ag | Sole for a shoe |
USD776410S1 (en) | 2013-04-12 | 2017-01-17 | Adidas Ag | Shoe |
DE102014215897B4 (de) | 2014-08-11 | 2016-12-22 | Adidas Ag | adistar boost |
DE102014216115B4 (de) | 2014-08-13 | 2022-03-31 | Adidas Ag | Gemeinsam gegossene 3D Elemente |
DE102015202013B4 (de) | 2015-02-05 | 2019-05-09 | Adidas Ag | Verfahren zur Herstellung eines Kunststoffformteils, Kunststoffformteil und Schuh |
JP6679363B2 (ja) | 2015-03-23 | 2020-04-15 | アディダス アーゲー | ソールおよびシューズ |
DE102015206486B4 (de) | 2015-04-10 | 2023-06-01 | Adidas Ag | Schuh, insbesondere Sportschuh, und Verfahren zur Herstellung desselben |
DE102015206900B4 (de) | 2015-04-16 | 2023-07-27 | Adidas Ag | Sportschuh |
DE102015209795B4 (de) | 2015-05-28 | 2024-03-21 | Adidas Ag | Ball und Verfahren zu dessen Herstellung |
USD783264S1 (en) | 2015-09-15 | 2017-04-11 | Adidas Ag | Shoe |
US11168175B2 (en) * | 2015-09-24 | 2021-11-09 | Basf Se | TPU pneumatic tubes made with mono ethyleneglycol as chain extender for high temperature use |
DE102016209044B4 (de) | 2016-05-24 | 2019-08-29 | Adidas Ag | Sohlenform zum Herstellen einer Sohle und Anordnung einer Vielzahl von Sohlenformen |
DE102016209046B4 (de) | 2016-05-24 | 2019-08-08 | Adidas Ag | Verfahren zur herstellung einer schuhsohle, schuhsohle, schuh und vorgefertigte tpu-gegenstände |
DE102016209045B4 (de) | 2016-05-24 | 2022-05-25 | Adidas Ag | Verfahren und vorrichtung zum automatischen herstellen von schuhsohlen, sohlen und schuhe |
USD840136S1 (en) | 2016-08-03 | 2019-02-12 | Adidas Ag | Shoe midsole |
USD840137S1 (en) | 2016-08-03 | 2019-02-12 | Adidas Ag | Shoe midsole |
WO2018029040A1 (de) | 2016-08-08 | 2018-02-15 | Basf Se | Verfahren zur herstellung von expandiertem granulat |
USD852475S1 (en) | 2016-08-17 | 2019-07-02 | Adidas Ag | Shoe |
JP1582717S (zh) | 2016-09-02 | 2017-07-31 | ||
WO2018082984A1 (de) | 2016-11-04 | 2018-05-11 | Basf Se | Partikelschaumstoffe auf basis von expandierten thermoplastischen elastomeren |
WO2018087362A1 (de) | 2016-11-14 | 2018-05-17 | Basf Se | Expandierte thermoplastische polyurethanpartikel, verfahren zu deren herstellung sowie verfahren zur herstellung eines formteils |
DE102016223980B4 (de) | 2016-12-01 | 2022-09-22 | Adidas Ag | Verfahren zur Herstellung eines Kunststoffformteils |
JP6397949B2 (ja) * | 2017-03-06 | 2018-09-26 | 株式会社ジェイエスピー | 発泡粒子成形体 |
DE102017205830B4 (de) | 2017-04-05 | 2020-09-24 | Adidas Ag | Verfahren für die Nachbehandlung einer Vielzahl einzelner expandierter Partikel für die Herstellung mindestens eines Teils eines gegossenen Sportartikels, Sportartikel und Sportschuh |
CN107298847B (zh) * | 2017-08-04 | 2019-01-18 | 南通德亿新材料有限公司 | 一种热塑性微气囊聚合物弹性体材料及其制备方法 |
CN107383854B (zh) * | 2017-08-04 | 2018-04-13 | 南通德亿新材料有限公司 | 一种热塑性聚氨酯微气囊弹性体材料的制备方法 |
JP1617832S (zh) | 2017-09-21 | 2018-11-12 | ||
USD899061S1 (en) | 2017-10-05 | 2020-10-20 | Adidas Ag | Shoe |
JP2021507030A (ja) | 2017-12-14 | 2021-02-22 | ビーエイエスエフ・ソシエタス・エウロパエアBasf Se | 低いガラス転移温度を有する熱可塑性ポリウレタンの製造方法 |
US11945904B2 (en) | 2017-12-20 | 2024-04-02 | Basf Se | Flexible polyurethane foams |
EP3762437B1 (en) | 2018-03-06 | 2022-04-13 | Basf Se | A preparation comprising thermoplastic polyisocyanate polyaddition product, a process for preparing the same and use thereof |
US11993689B2 (en) * | 2018-06-13 | 2024-05-28 | Sunko Ink Co., Ltd. | Foamed thermoplastic polyurethane and microwave molded body thereof |
US20220259382A1 (en) | 2019-07-31 | 2022-08-18 | Basf Se | New block copolymers |
CN114222792A (zh) | 2019-08-21 | 2022-03-22 | 巴斯夫欧洲公司 | 含热塑性多异氰酸酯加成聚合产物的制剂、其制备方法和用途 |
US11872776B2 (en) | 2019-12-19 | 2024-01-16 | The Boeing Company | Methods for recovering expanded polymer tooling |
CN116981553A (zh) | 2021-03-15 | 2023-10-31 | 巴斯夫欧洲公司 | 制备膨胀热塑性弹性体颗粒的方法 |
Family Cites Families (31)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1300282B (de) | 1962-03-09 | 1969-07-31 | Elastomer Ag | Verfahren zum Herstellen von thermoplastischen, treibmittelhaltigen, verschaeumbaren Polyurethanen |
US3310617A (en) * | 1963-06-19 | 1967-03-21 | Shell Oil Co | Process for preparing uniform melt dispersion of blowing agent and polymer and its use in making foamed products |
US3673126A (en) | 1967-11-13 | 1972-06-27 | Dow Chemical Co | Continuous process for making expandable thermoplastic resin compositions |
BE759829A (fr) | 1969-12-03 | 1971-06-03 | Upjohn Co | Preparation de polyurethanes |
WO1991000304A1 (en) | 1989-06-27 | 1991-01-10 | The Dow Chemical Company | Melt polymerization process for making polyurethanes |
DE69228606T2 (de) | 1991-07-03 | 1999-06-24 | Kanebo Ltd | Verfahren und vorrichtung zur herstellung eines thermoplastischen polyurethan-elastomers |
US5424014A (en) | 1992-09-18 | 1995-06-13 | Apache Products Company | Method for extruding foamable polymer material |
US6783710B1 (en) * | 1994-02-21 | 2004-08-31 | Sulzer Chemtech Ag | Method for the production of expandable plastics granulate |
US5707573A (en) * | 1995-11-09 | 1998-01-13 | Biesenberger; Joseph A. | Method of preparing thermoplastic foams using a gaseous blowing agent |
BR9812576A (pt) | 1997-10-01 | 2000-10-03 | Dow Chemical Co | Polìmeros lìquidos preparados por modelagem (tlp's) e extrusão reativa desses |
JP2000327822A (ja) * | 1999-03-15 | 2000-11-28 | Sekisui Chem Co Ltd | エステル系エラストマー発泡体及びそれを用いた発泡体積層シート |
US6391931B1 (en) * | 1999-04-28 | 2002-05-21 | 3M Innovative Properties Co | Uniform small cell foams and a continuous process for making same |
EP1283767B1 (en) | 2000-05-25 | 2006-12-06 | Trexel, Inc. | Polymer foam processing with low blowing agent levels |
WO2002032986A1 (fr) | 2000-10-18 | 2002-04-25 | Mitsui Chemicals, Inc. | Mousse a base d"une composition d"elastomere d"urethane thermoplastique et son procede de preparation |
DE10056251B4 (de) | 2000-11-14 | 2006-06-08 | Basf Ag | Verfahren zur Herstellung von Polyurethan-Schaumstoffen |
US6979701B2 (en) | 2000-12-08 | 2005-12-27 | Kuraray Co., Ltd. | Thermoplastic polyurethane foam, process for production thereof and polishing pads made of the foam |
DE10061067C1 (de) | 2000-12-08 | 2002-06-06 | Bayer Ag | Kontinuierliches Verfahren zur Herstellung von thermoplastisch verarbeitbaren Polyurethanelastomeren mit definiertem und standardisiertem Schmelze-Fließ-Verhalten und hoher Thermostabilität |
JP4807765B2 (ja) * | 2001-05-25 | 2011-11-02 | 日本発條株式会社 | 熱可塑性ポリウレタン発泡体の製造方法 |
US6995231B2 (en) | 2001-12-21 | 2006-02-07 | Noveon Ip Holdings, Corp. | Extrudable highly crystalline thermoplastic polyurethanes |
DE10241298A1 (de) | 2002-09-04 | 2004-03-18 | Basf Ag | Verfahren zur Herstellung von Polystyrolschaumpartikeln mit niedriger Schüttdichte |
US6783170B1 (en) * | 2003-01-04 | 2004-08-31 | Ford Global Technologies, Llc | Backlite storage and convertible decklid system for automotive vehicle |
US20100222442A1 (en) | 2006-01-18 | 2010-09-02 | Basf Se | Foams based on thermoplastic polyurethanes |
CN101003646A (zh) * | 2006-12-25 | 2007-07-25 | 刘津平 | 可发泡生物材料及生物泡沫制品的生产方法 |
DE102007050681A1 (de) | 2007-10-22 | 2009-04-23 | Coperion Werner & Pfleiderer Gmbh & Co. Kg | Verfahren und Vorrichtung zur Herstellung eines Polymergranulats |
BRPI0817834A2 (pt) | 2007-10-26 | 2015-03-31 | Russell Gottesman | Método e dispositivo para aumentar o lucro de propaganda em sistemas de transmissão pública através de programação de trânsito e sistemas enunciadores |
WO2011005705A2 (en) | 2009-07-06 | 2011-01-13 | Boral Material Technologies Inc. | Vacuum removal of entrained gasses in extruded, foamed polyurethane |
CN102276785B (zh) | 2011-07-12 | 2013-01-30 | 山东奥邦聚氨酯有限公司 | 低密度发泡热塑性聚氨酯弹性体及其制备工艺 |
EP2565223A1 (de) | 2011-08-31 | 2013-03-06 | Basf Se | Expandierbares Granulat |
CN103183805B (zh) | 2011-12-28 | 2015-04-29 | 北京中能江龙科技开发有限公司 | 一种新型发泡热塑性聚氨酯弹性体材料的制备方法 |
EP2836543B1 (de) | 2012-04-13 | 2020-03-04 | Basf Se | Verfahren zur herstellung von expandiertem granulat |
WO2013153153A1 (de) | 2012-04-13 | 2013-10-17 | Basf Se | Thermoplastische formmasse |
-
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- 2014-10-17 EP EP14786180.1A patent/EP3058018B1/de not_active Revoked
- 2014-10-17 US US15/029,686 patent/US11142625B2/en active Active
- 2014-10-17 ES ES14786180.1T patent/ES2651851T3/es active Active
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- 2014-10-17 PT PT147861801T patent/PT3058018T/pt unknown
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JP6496722B2 (ja) | 2019-04-03 |
PT3058018T (pt) | 2017-12-21 |
US11142625B2 (en) | 2021-10-12 |
WO2015055811A1 (de) | 2015-04-23 |
PL3058018T3 (pl) | 2018-02-28 |
TWI667285B (zh) | 2019-08-01 |
EP3058018B1 (de) | 2017-09-13 |
BR112016008207B1 (pt) | 2022-02-22 |
JP2016533418A (ja) | 2016-10-27 |
EP3058018A1 (de) | 2016-08-24 |
BR112016008207A2 (zh) | 2017-08-01 |
KR102374907B1 (ko) | 2022-03-16 |
ES2651851T3 (es) | 2018-01-30 |
US20160244587A1 (en) | 2016-08-25 |
CN105637021B (zh) | 2019-07-19 |
KR20160073996A (ko) | 2016-06-27 |
CN105637021A (zh) | 2016-06-01 |
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