TW201619227A - Aliphatic thermoplastic polyurethanes made from telechelic N-alkylated polyamides - Google Patents
Aliphatic thermoplastic polyurethanes made from telechelic N-alkylated polyamides Download PDFInfo
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Abstract
Description
本發明係關於一種使用遙爪聚醯胺所製造之脂肪族聚合物，其中該遙爪聚醯胺包括在低於約70℃係液體的那些及其可反應進其它聚合物網絡中以授予想要的性質。 The present invention relates to an aliphatic polymer produced using telechelic polyamine, wherein the telechelic polyamine includes those liquids below about 70 ° C and can be reacted into other polymer networks to give The nature of the desire.
熱塑性聚胺基甲酸酯(TPU)係在技藝中熟知之有用的材料。它們通常藉由讓聚異氰酸酯與多元醇及選擇性鏈伸長劑反應而製備。所產生的材料具有許多有用的性質及係使用在廣泛多種應用中。 Thermoplastic polyurethanes (TPU) are useful materials well known in the art. They are usually prepared by reacting a polyisocyanate with a polyol and a selective chain extender. The materials produced have many useful properties and are used in a wide variety of applications.
TPU包括硬鏈段及軟鏈段，其中該軟鏈段典型係以聚酯為基底或以聚醚為基底。聚酯TPU會遭遇到水解降解，聚醚TPU有氧化及/或熱降解的傾向。對具有預計有用的性質而且亦提供改良的水解、氧化及/或熱穩定性之TPU材料有現行的需求。 The TPU comprises a hard segment and a soft segment, wherein the soft segment is typically based on a polyester or a polyether. Polyester TPU will suffer from hydrolytic degradation, and polyether TPU has a tendency to oxidize and/or thermally degrade. There is a current need for TPU materials that have properties that are expected to be useful and that also provide improved hydrolysis, oxidation, and/or thermal stability.
亦想要改良TPU材料對諸如聚醯胺或聚酯例如耐綸-6,6之極性材料的黏附力。現在，由於現存的TPU 材料與極性材料間之黏附力相當差，組合著使用TPU材料與極性材料的能力受限制，特別是該應用包括結合TPU材料層與極性材料層時。層間之黏附力太弱將無法滿足此層組合其它方面將係非常有用的許多應用之需求。因此，TPU無法使用在TPU與其它材料層間，特別是極性材料層間需要高黏附程度的許多應用中。對其它材料特別是極性材料具有黏附力之TPU材料有持續性需求，此將允許TPU使用在需要對其它材料特別是極性材料有好的/改良的黏附力之應用中。 It is also desirable to improve the adhesion of TPU materials to polar materials such as polyamide or polyester such as nylon-6,6. Now due to the existing TPU The adhesion between the material and the polar material is rather poor, and the ability to combine the use of TPU materials with polar materials is limited, particularly when the application includes a layer of TPU material and a layer of polar material. Too weak adhesion between layers will not meet the needs of many applications where this layer combination will be very useful. Therefore, TPU cannot be used in many applications where TPU and other material layers, particularly polar material layers, require high adhesion. There is a continuing need for TPU materials that have adhesion to other materials, particularly polar materials, which will allow TPUs to be used in applications where good/improved adhesion to other materials, particularly polar materials, is required.
整體來說，對具有預計有用的聚醚及/或聚酯TPU性質而且亦提供改良的水解、氧化及/或熱穩定性、改良對極性材料諸如聚醯胺或聚酯之黏附力及其某些組合之改良的TPU材料有持續性需求。 Overall, it has the expected useful polyether and/or polyester TPU properties and also provides improved hydrolysis, oxidation and/or thermal stability, improved adhesion to polar materials such as polyamide or polyester and some These combined improved TPU materials have a continuing need.
本發明係關於一種從低分子量聚醯胺寡聚物及在骨架結構中包含N-烷基化醯胺基團之遙爪聚醯胺(包括共聚物)所製造之脂肪族聚合物。所描述的遙爪聚醯胺係使用在所描述的TPU中作為軟鏈段。這些遙爪聚醯胺在其於溫度20至50或80℃下為液體被加工的能力上具獨特性。雖然不意欲由理論限制，咸信此可係由於其具有未預期地低的玻璃轉換溫度，使得其合適於進一步反應及聚合，允許用以形成所描述的TPU。所產生的脂肪族聚合物具有獨特的性質組合，使得其合適於某些應用及最終用途。 The present invention relates to an aliphatic polymer produced from a low molecular weight polyamine oligomer and a telechelic polyamine (including a copolymer) comprising an N-alkylated guanamine group in a backbone structure. The described telechelic polyamine is used as a soft segment in the described TPU. These telechelic polyamines are unique in their ability to process liquids at temperatures of 20 to 50 or 80 °C. While not intending to be bound by theory, it is believed that this may be due to its undesirably low glass transition temperature, making it suitable for further reaction and polymerization, allowing for the formation of the described TPU. The resulting aliphatic polymers have a unique combination of properties that make them suitable for certain applications and end uses.
本發明提供一種聚合物組成物，其包括下列之反應產物：(i)一包含遙爪聚醯胺的多元醇組分；及(ii)一脂肪族聚異氰酸酯組分；及選擇性(iii)一鏈伸長劑組分；其中該遙爪聚醯胺：(a)具有衍生自聚合單體的重覆單元，其中該聚合單體係藉由在重覆單元與選自於羧基或一級或二級胺的官能性末端基團之間的鍵聯而連接，其中該遙爪聚醯胺的至少70莫耳百分比精確具有二個相同官能性型式之選自於由胺基或羧酸末端基團所組成之群的官能性末端基團；(b)具有一包含特徵為衍生自胺與羧基反應之至少二個醯胺鍵聯的聚醯胺鏈段，及該聚醯胺鏈段包含衍生自聚合二或更多種選自於內醯胺、胺基羧酸、二羧酸及二胺的單體之重覆單元；(c)其中該連接烴型式鍵聯之含雜原子鍵聯的總數之至少10百分比具有醯胺鍵聯特徵；及(d)其中該醯胺鍵聯的至少25百分比具有三級醯胺鍵聯特徵。 The present invention provides a polymer composition comprising the following reaction products: (i) a polyol component comprising telechelic polyamine; and (ii) an aliphatic polyisocyanate component; and selectivity (iii) a chain extender component; wherein the telechelic polyamine: (a) has a repeating unit derived from a polymerized monomer, wherein the polymerized single system is selected from the group consisting of a carboxyl group or a primary or secondary a linkage between the functional end groups of the amines, wherein at least 70 mole percent of the telechelic polyamine has exactly two identical functionalities selected from amine or carboxylic acid end groups a functional end group of the group; (b) having a polyamine segment comprising at least two guanamine linkages derived from the reaction of an amine with a carboxyl group, and wherein the polyamine segment is derived from a repeating unit that polymerizes two or more monomers selected from the group consisting of an intrinsic amine, an aminocarboxylic acid, a dicarboxylic acid, and a diamine; (c) a total number of hetero atom-containing bonds in which the linked hydrocarbon type is bonded At least 10 percent having a guanamine linkage feature; and (d) wherein at least 25 percent of the guanamine linkage has a tertiary Wherein the amine linkage.
本發明提供所描述的聚合物組成物，其中該特徵(b)之聚醯胺鏈段的特徵為滿足下列條件之至少一種：(i)其中該醯胺鍵聯係衍生自聚合醯胺形成單體，及該等單體的至少90莫耳百分比係選自於由內醯胺及胺基羧酸單體所組成之群，如此該聚醯胺係至少二種不同單體的共聚物；或(ii)其中該醯胺鍵聯係衍生自聚合醯胺形成單體，及該二羧酸與二胺單體之結合量佔該等單體的至少90莫耳百分比，如此該聚醯胺係至少三種不同單體的三元共聚物；或(iii)其中該醯胺鍵聯係衍生自聚合二羧酸、二胺及內醯胺及/或胺基羧酸單體的組合，如此 該二羧酸單體及二胺單體之總存在量係10莫耳百分比或更多，及存在於該單體摻合物中的內醯胺及/或胺基羧酸單體總量係10莫耳百分比或更多。 The present invention provides a polymer composition as described, wherein the polyamidene segment of feature (b) is characterized by at least one of the following conditions: (i) wherein the guanamine linkage is derived from a polymeric guanamine forming monomer And at least 90 mole percent of the monomers are selected from the group consisting of endoamines and aminocarboxylic acid monomers, such that the polyamine is a copolymer of at least two different monomers; or Ii) wherein the indole linkage is derived from a polymeric guanamine forming monomer, and the dicarboxylic acid is combined with the diamine monomer in an amount of at least 90 mole percent of the monomers, such that the polyamine is at least three a terpolymer of a different monomer; or (iii) wherein the guanamine bond is derived from a combination of a polymeric dicarboxylic acid, a diamine, and an indoleamine and/or an aminocarboxylic acid monomer, The total amount of the dicarboxylic acid monomer and the diamine monomer is 10 mole percent or more, and the total amount of the indoleamine and/or aminocarboxylic acid monomer present in the monomer blend is 10 mole percentage or more.
本發明提供所描述的聚合物組成物，其中該遙爪聚醯胺之至少50重量百分比係由衍生自選自於內醯胺單體、胺基羧酸單體、二羧酸單體及二胺單體之群的單體之重覆單元所構成。 The present invention provides a polymer composition as described, wherein at least 50% by weight of the telechelic polyamine is derived from a monomer selected from the group consisting of an indoleamine monomer, an aminocarboxylic acid monomer, a dicarboxylic acid monomer, and a diamine. A monomer repeating unit of a group of monomers.
本發明提供所描述的聚合物組成物，其中該聚合物之至少10重量百分比係由衍生自選自於內醯胺單體、胺基羧酸單體、二羧酸單體及二胺單體之群的單體之重覆單元所構成。 The present invention provides a polymer composition as described, wherein at least 10% by weight of the polymer is derived from a monomer selected from the group consisting of an indoleamine monomer, an aminocarboxylic acid monomer, a dicarboxylic acid monomer, and a diamine monomer. The unit consists of a single unit of repeating units.
本發明提供所描述的聚合物組成物，其中該聚醯胺鏈段之至少50重量百分比包含下列結構的重覆單元：
其中Ra係該二羧酸的伸烷基部分及係2至36個碳原子之環狀、線性或分枝伸烷基，選擇性包括該二酸每3或10個碳原子中的最高1個雜原子；及其中Rb係直接鍵結或2至60個碳原子的線性或分枝伸烷基；及Rc與Rd各別係1至8個碳原子之線性或分枝烷基，或Rc與Rd連接在一起以形成1至8個碳原子之單一線性或分枝伸烷基，或選擇性Rc及Rd之一係在碳原子處連接至Rb，更想要Rc及Rd係1或2至4個碳原子之烷基。 Wherein R a is an alkylene moiety of the dicarboxylic acid and a cyclic, linear or branched alkyl group of 2 to 36 carbon atoms, the selectivity comprising the highest of every 3 or 10 carbon atoms of the diacid a hetero atom; and a linear or branched alkyl group in which R b is directly bonded or 2 to 60 carbon atoms; and R c and R d are linear or branched alkyl groups each having 1 to 8 carbon atoms , or R c and R d are joined together to form a single linear or branched alkyl group of 1 to 8 carbon atoms, or one of the selective R c and R d is attached to R b at a carbon atom, more R c and R d are an alkyl group of 1 or 2 to 4 carbon atoms.
本發明提供一種聚合物組成物，其包括下列之反應產物：(i)一包括遙爪聚醯胺的多元醇組分；及(ii)一脂肪族聚異氰酸酯組分；及選擇性(iii)一鏈伸長劑組分；其中該遙爪聚醯胺包括：(a)二個選自於羥基、羧基或一級或二級胺之官能性末端基團；及(b)一聚醯胺鏈段，其中：(i)該聚醯胺鏈段包含至少二個特徵為衍生自胺與羧基反應的醯胺鍵聯；(ii)該聚醯胺鏈段包含衍生自聚合二或更多種選自於由內醯胺單體、胺基羧酸單體、二羧酸單體及二胺單體所組成之群的單體之重覆單元；及(iii)該醯胺鍵聯的至少25莫耳百分比係衍生自二級胺基團與羧基之反應；其中該遙爪聚醯胺具有在70℃下係具有黏度少於100,000cps之液體的特徵，如藉由Brookfield圓盤型黏度計，使用5rpm旋轉該圓盤來測量；及其中該遙爪聚醯胺之特徵為數量平均分子量約200至10,000克/莫耳，及包含中斷在醯胺組分間之氫鍵的多樣性醯胺形成重覆單元。 The present invention provides a polymer composition comprising the following reaction products: (i) a polyol component comprising telechelic polyamine; and (ii) an aliphatic polyisocyanate component; and selectivity (iii) a chain extender component; wherein the telechelic polyamine comprises: (a) two functional end groups selected from a hydroxyl group, a carboxyl group or a primary or secondary amine; and (b) a polyamidole segment Wherein: (i) the polyamine segment comprises at least two indole linkages characterized by a reaction between an amine and a carboxyl group; (ii) the polyamine segment comprises a derivative derived from two or more selected from the group consisting of a repeating unit of a monomer consisting of a group consisting of a mesaconamine monomer, an aminocarboxylic acid monomer, a dicarboxylic acid monomer, and a diamine monomer; and (iii) at least 25 moles of the guanamine linkage The percentage of the ear is derived from the reaction of a secondary amine group with a carboxyl group; wherein the telechelic polyamine has a characteristic of a liquid having a viscosity of less than 100,000 cps at 70 ° C, such as by a Brookfield disc type viscometer. Rotating the disc at 5 rpm for measurement; and wherein the telechelic polyamine is characterized by a number average molecular weight of about 200 to 10,000 g/mole, and Diversity repeating unit formed Amides Amides of hydrogen bonds between the components.
本發明提供所描述的聚合物組成物，其中該反應產物進一步包含一或多個聚醚鏈段、聚酯鏈段及/或聚碳酸酯鏈段，其中該等鏈段係化學鍵結進該反應產物中或與該反應產物物理摻合。 The present invention provides a polymer composition as described, wherein the reaction product further comprises one or more polyether segments, polyester segments and/or polycarbonate segments, wherein the segments are chemically bonded into the reaction The product is physically blended with or with the reaction product.
本發明提供所描述的聚合物組成物，其中該組分(ii)的脂肪族聚異氰酸酯組分包含二異氰酸異佛爾酮酯(IPDI)、二異氰酸1,4-環己基酯(CHDI)、二異氰酸己二酯(HDI)、二異氰酸4,4’-亞甲基二環己基酯(H12 MDI)、1,6-二異氰酸基-2,2,4,4-四甲基己烷(TMDI)、二 異氰酸1,10-癸烷酯、二異氰酸反-二環己基甲烷酯(HMDI)、二異氰酸伸茬酯(XDI)、二異氰酸間-四甲基伸茬酯(TMXDI)、或其任何組合。 The present invention provides a polymer composition as described, wherein the aliphatic polyisocyanate component of component (ii) comprises isophorone diisocyanate (IPDI), 1,4-cyclohexyl diisocyanate (CHDI), hexamethylene diisocyanate (HDI), 4,4'-methylene dicyclohexyl diisocyanate (H 12 MDI), 1,6-diisocyanato-2,2 , 4,4-tetramethylhexane (TMDI), 1,10-decyl diisocyanate, di-dicyclohexylmethane diisocyanate (HMDI), diisopropyl cyanide (XDI) , diisocyanate-tetramethyl decyl ester (TMXDI), or any combination thereof.
本發明提供所描述的聚合物組成物，其中該組分(iii)的鏈伸長劑組分包含一或多種具有約2至約20個碳原子的短鏈二醇。 The present invention provides a polymer composition as described wherein the chain extender component of component (iii) comprises one or more short chain diols having from about 2 to about 20 carbon atoms.
本發明提供所描述的聚合物組成物，其中該組分(iii)的鏈伸長劑組分包含乙二醇、二甘醇、丙二醇、二丙二醇、三丙二醇、三甘醇、環己基二甲醇之順-反-異構物、新戊二醇、1,4-丁二醇、1,6-己二醇、1,3-丁二醇及1,5-戊二醇、苯二醇(HQEE)、伸茬基二醇類、間苯二酚、兒茶酚、1,3-丙二醇、1,12-十二烷二醇、1,9-壬二醇或其任何組合。 The present invention provides a polymer composition as described, wherein the chain extender component of the component (iii) comprises ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, triethylene glycol, cyclohexyl dimethanol Cis-trans-isomer, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, 1,3-butanediol, 1,5-pentanediol, benzenediol (HQEE And thioglycols, resorcinol, catechol, 1,3-propanediol, 1,12-dodecanediol, 1,9-nonanediol or any combination thereof.
本發明提供一種物件，其包括任何於本文中所描述的聚合物組成物。 The present invention provides an article comprising any of the polymer compositions described herein.
本發明提供所描述的物件，其中該物件係注塑成型物件、汽車外部物件、電子構件或擠壓膜。 The present invention provides the described article wherein the article is an injection molded article, an automotive exterior article, an electronic component, or a squeeze film.
定義為包括二個反應性末端基團之大分子的遙爪聚合物可使用作為交聯劑、鏈伸長劑及用於多種大分子結構的重要建構嵌段，其包括嵌段及接枝共聚物、星形、高分枝或樹狀聚合物。該聚二烯、聚酯、聚醚及聚碳酸酯型式的遙爪聚合物在技藝中熟知。這些具有選 自於一級或二級羥基、一級或二級胺及羧酸的官能性末端基團之先述技藝遙爪聚合物已經與互補反應物反應，而形成具有遙爪前驅物性質的較大聚合物。可容易加工的聚醯胺遙爪物尚無法獲得，及同樣如此的是，從此聚醯胺遙爪物製得的聚合物，諸如從此聚醯胺遙爪物製得的熱塑性聚胺基甲酸酯(TPU)尚無法有效獲得。 Telechelic polymers defined as macromolecules comprising two reactive end groups can be used as crosslinkers, chain extenders, and important building blocks for a variety of macromolecular structures, including block and graft copolymers. , star, high-branched or dendritic polymer. The teledentate polymers of the polydienes, polyesters, polyethers, and polycarbonates are well known in the art. These have the choice The prior art telechelic polymers from primary or secondary hydroxyl, primary or secondary amines, and functional end groups of carboxylic acids have reacted with complementary reactants to form larger polymers with telechelic precursor properties. Polyamides that are easily processable are not yet available, and so are the polymers made from the polyamides, such as the thermoplastic polyurethanes made from the polyamides. Esters (TPU) are not yet available.
從聚酯多元醇製得的聚合物諸如TPU提供好的機械性質及耐UV及耐熱性，但是它們遭遇到差的抗水解性。聚醚多元醇具有比聚酯多元醇好的水解穩定性，但是其耐UV及熱性不足。聚碳酸酯多元醇提供超過聚酯多元醇之改良的耐水解及耐熱性且增加一些硬度程度，但是它們比其它多元醇更貴一個數量級。聚二烯多元醇係有用的，但是其太疏水而無法與極性基材良好地交互作用。某些聚二烯多元醇係經氫化以減低與來自該二烯單體的剩餘不飽和度相依之降解機制。從這些材料之任何製得的TPU通常對極性材料諸如聚醯胺及聚酯具有差的黏附力。因此，新種類的遙爪聚醯胺將幫助克服這些問題及允許製備出具有改良的整體性質之聚合物，諸如TPU。 Polymers made from polyester polyols such as TPU provide good mechanical properties and resistance to UV and heat, but they suffer from poor hydrolysis resistance. Polyether polyols have better hydrolytic stability than polyester polyols, but are insufficient in UV and heat resistance. Polycarbonate polyols provide improved hydrolysis and heat resistance over polyester polyols and increase some degree of hardness, but they are an order of magnitude more expensive than other polyols. Polydiene polyols are useful, but they are too hydrophobic to interact well with polar substrates. Certain polydiene polyols are hydrogenated to reduce the degradation mechanism associated with residual unsaturation from the diene monomer. TPUs made from any of these materials typically have poor adhesion to polar materials such as polyamides and polyesters. Thus, a new class of telechelic polyamines will help overcome these problems and allow the preparation of polymers with improved overall properties, such as TPU.
該胺終端的聚醯胺寡聚物係製成具有低黏度、低玻璃轉換溫度、經抑制的結晶性、低酸數、具有多種氮或醯胺：烴重量比率(或親水性/疏水性平衡)、具有經控制的氫鍵或無氫鍵醯胺基團數目。從所描述的胺終端聚醯胺寡聚物製得聚合物及更特別是TPU。本發明係與這些聚合物相關。 The amine terminated polyamine oligomers are made with low viscosity, low glass transition temperature, inhibited crystallinity, low acid number, and various nitrogen or guanamine: hydrocarbon weight ratios (or hydrophilic/hydrophobic balance) The number of guanamine groups having a controlled hydrogen bond or no hydrogen bond. Polymers and more particularly TPU are prepared from the amine terminated polyamine oligomers described. The invention is related to these polymers.
本發明提供一種聚合物組成物，其包括下列之反應產物：(i)一包含所描述的遙爪聚醯胺之多元醇組分；及(ii)一聚異氰酸酯組分；及選擇性(iii)一鏈伸長劑組分。 The present invention provides a polymer composition comprising the following reaction products: (i) a polyol component comprising the described telechelic polyamine; and (ii) a polyisocyanate component; and selectivity (iii) a chain extender component.
該使用來製備於本文中所描述的聚合物組成物之聚異氰酸酯組分包括脂肪族聚異氰酸酯。有用的脂肪族聚異氰酸酯未過度限制及可包括任何通常使用於TPU之製備的脂肪族聚異氰酸酯。在某些具體實例中，該脂肪族聚異氰酸酯包括脂肪族二異氰酸酯。 The polyisocyanate component used to prepare the polymer composition described herein includes an aliphatic polyisocyanate. Useful aliphatic polyisocyanates are not unduly limited and may include any of the aliphatic polyisocyanates commonly used in the preparation of TPU. In certain embodiments, the aliphatic polyisocyanate comprises an aliphatic diisocyanate.
該聚異氰酸酯組分可包括一或多種脂肪族聚異氰酸酯。在某些具體實例中，該聚異氰酸酯組分亦可包括芳香族聚異氰酸酯，但是在此等具體實例中，多數的聚異氰酸酯組分係由脂肪族聚異氰酸酯所構成。 The polyisocyanate component can include one or more aliphatic polyisocyanates. In certain embodiments, the polyisocyanate component can also include aromatic polyisocyanates, but in these embodiments, most of the polyisocyanate components are comprised of aliphatic polyisocyanates.
在某些具體實例中，該聚異氰酸酯係二異氰酸酯。因此，該聚異氰酸酯組分可包括一或多種脂肪族二異氰酸酯。在某些具體實例中，該聚異氰酸酯組分亦可包括芳香族二異氰酸酯，但是在此等具體實例中，多數的聚異氰酸酯組分係由脂肪族二異氰酸酯所構成。 In certain embodiments, the polyisocyanate is a diisocyanate. Thus, the polyisocyanate component can include one or more aliphatic diisocyanates. In certain embodiments, the polyisocyanate component can also include aromatic diisocyanates, but in these embodiments, most of the polyisocyanate components are comprised of aliphatic diisocyanates.
在某些具體實例中，該聚異氰酸酯組分係無芳香族聚異氰酸酯。在某些具體實例中，該聚異氰酸酯組分係無芳香族二異氰酸酯。 In certain embodiments, the polyisocyanate component is free of aromatic polyisocyanates. In certain embodiments, the polyisocyanate component is free of aromatic diisocyanates.
在某些具體實例中，通常避免使用將造成所產生的聚合物交聯之多官能基異氰酸酯化合物，即，三異氰酸酯等等，因此在此等具體實例中，若有的話，其 使用量通常少於4莫耳百分比或甚至少於2莫耳百分比，以所使用的全部多種異氰酸酯之總莫耳為基準。 In certain embodiments, the use of polyfunctional isocyanate compounds that will crosslink the resulting polymer, i.e., triisocyanates, etc., is generally avoided, and thus, in such specific examples, if any, The amount used is generally less than 4 mole percent or even less than 2 mole percent, based on the total moles of all of the various isocyanates used.
合適的脂肪族二異氰酸酯之實施例包括二異氰酸異佛爾酮酯(IPDI)、二異氰酸1,4-環己基酯(CHDI)、二異氰酸己二酯(HDI)、二異氰酸4,4’-亞甲基二環己基酯(H12 MDI)、1,6-二異氰酸基-2,2,4,4-四甲基己烷(TMDI)、二異氰酸1,10-癸烷酯、二異氰酸反-二環己基甲烷酯(HMDI)、二異氰酸伸茬酯(XDI)、二異氰酸間-四甲基伸茬酯(TMXDI)或其任何組合。普通使用的二異氰酸酯有4,4’-亞甲基雙(異氰酸苯酯)(MDI)、二異氰酸己二酯(HDI)及二異氰酸4,4’-亞甲基二環己基酯(H12 MDI)。亦可使用上述的二異氰酸酯之二聚物及三聚物和二或更多種二異氰酸酯的摻合物。 Examples of suitable aliphatic diisocyanates include isophorone diisocyanate (IPDI), 1,4-cyclohexyl diisocyanate (CHDI), hexamethylene diisocyanate (HDI), two 4,4'-methylene dicyclohexyl isocyanate (H 12 MDI), 1,6-diisocyanato-2,2,4,4-tetramethylhexane (TMDI), diiso 1,10-decyl cyanate, trans-dicyclohexylmethane diisocyanate (HMDI), diisocyanate diisocyanate (XDI), m-tetramethyl decyl diisocyanate (TMXDI) ) or any combination thereof. Commonly used diisocyanates are 4,4'-methylenebis(phenylisocyanate) (MDI), dihexyl diisocyanate (HDI) and 4,4'-methylene diisocyanate. Cyclohexyl ester (H 12 MDI). Mixtures of dimers and trimers of the above diisocyanates and two or more diisocyanates may also be used.
在某些具體實例中，該聚異氰酸酯組分係4,4’-亞甲基雙(異氰酸苯酯)(MDI)。在某些具體實例中，該聚異氰酸酯組分係二異氰酸己二酯(HDI)。在某些具體實例中，該聚異氰酸酯組分係二異氰酸4,4’-亞甲基二環己基酯(H12 MDI)。 In certain embodiments, the polyisocyanate component is 4,4'-methylenebis(phenylisocyanate) (MDI). In certain embodiments, the polyisocyanate component is hexamethylene diisocyanate (HDI). In certain embodiments, the polyisocyanate component is 4,4'-methylene dicyclohexyl diisocyanate (H 12 MDI).
在本發明中所使用的脂肪族聚異氰酸酯亦可呈以異氰酸酯端蓋的低分子量聚合物或寡聚物形式。例如，羥基終端的聚酯中間物可與含異氰酸酯化合物反應以產生以異氰酸酯端蓋的低分子量聚合物。在TPU領域中，此等材料正常指為預聚合物。此等預聚合物正常具有數量平均分子量(Mn)在約500至約10,000道耳吞(Daltons)之範圍內。 The aliphatic polyisocyanate used in the present invention may also be in the form of a low molecular weight polymer or oligomer covered with an isocyanate end. For example, a hydroxyl terminated polyester intermediate can be reacted with an isocyanate containing compound to produce a low molecular weight polymer capped with an isocyanate. In the field of TPU, such materials are normally referred to as prepolymers. These prepolymers normally have a number average molecular weight (Mn) in the range of from about 500 to about 10,000 Daltons.
該選擇性鏈伸長劑組分不過度限制及可包括在TPU之製備時通常使用的任何鏈伸長劑。 The selective chain extender component is not unduly limited and can include any chain extender commonly used in the preparation of TPU.
合適的鏈伸長劑包括具有約2至約10個碳原子之低級脂肪族或短鏈二醇，及包括例如乙二醇、二甘醇、丙二醇、二丙二醇、三丙二醇、三甘醇、環己基二甲醇之順-反-異構物、新戊二醇、1,4-丁二醇、1,6-己二醇、1,3-丁二醇及1,5-戊二醇。亦可使用芳香族二醇作為該鏈伸長劑及其經常係用於高熱應用的選擇。苯二醇(HQEE)及伸茬基二醇係合適於使用來製造本發明的TPU之鏈伸長劑。伸茬基二醇係1,4-二(羥甲基)苯與1,2-二(羥甲基)苯之混合物。苯二醇係一種合適的芳香族鏈伸長劑，及特別包括氫醌，即，雙(β-羥乙基)醚，亦已知為1,4-二(2-羥基乙氧基)苯；間苯二酚，即，雙(β-羥乙基)醚，亦已知為1,3-二(2-羥乙基)苯；兒茶酚，即，雙(β-羥乙基)醚，亦已知為1,2-二(2-羥基乙氧基)苯；及其組合。在某些具體實例中，該鏈伸長劑係1,4-丁二醇。 Suitable chain extenders include lower aliphatic or short chain diols having from about 2 to about 10 carbon atoms, and include, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, triethylene glycol, cyclohexyl Cis-trans-isomer of dimethanol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, 1,3-butanediol, and 1,5-pentanediol. Aromatic diols can also be used as the chain extender and its selection for high heat applications. Benzene glycol (HQEE) and decyl diol are suitable for use in the manufacture of the chain extender of the TPU of the present invention. A mixture of decyl glycol 1,4-bis(hydroxymethyl)benzene and 1,2-bis(hydroxymethyl)benzene. Benzene glycol is a suitable aromatic chain extender, and particularly includes hydroquinone, ie, bis(β-hydroxyethyl)ether, also known as 1,4-bis(2-hydroxyethoxy)benzene; Resorcinol, ie, bis(β-hydroxyethyl)ether, also known as 1,3-bis(2-hydroxyethyl)benzene; catechol, ie, bis(β-hydroxyethyl)ether Also known as 1,2-bis(2-hydroxyethoxy)benzene; and combinations thereof. In certain embodiments, the chain extender is 1,4-butanediol.
合適的鏈伸長劑亦包括二胺鏈伸長劑。合適的二胺鏈伸長劑可在本質上係脂肪族或芳香族，諸如1-30個碳原子之伸烷基二胺(例如，乙二胺、丁烷二胺、己二胺)。 Suitable chain extenders also include diamine chain extenders. Suitable diamine chain extenders may be aliphatic or aromatic in nature, such as alkyl diamines of from 1 to 30 carbon atoms (e.g., ethylenediamine, butanediamine, hexamethylenediamine).
在某些具體實例中，本發明的TPU係使用一或多種鏈伸長劑製得。在其它具體實例中，本發明的TPU係沒有使用任何鏈伸長劑製得。 In certain embodiments, the TPUs of the invention are made using one or more chain extenders. In other embodiments, the TPU of the present invention is made without the use of any chain extender.
在本發明中所使用的多元醇組分包括所描述的N-烷基化遙爪聚醯胺。它們可描述為低分子量聚醯胺寡聚物及在骨架結構中包括N-烷基化醯胺基團之遙爪聚醯胺(包括共聚物)。 The polyol component used in the present invention includes the N-alkylated telechelic polyamine described. They can be described as low molecular weight polyamine oligomers and telechelic polyamines (including copolymers) comprising N-alkylated guanamine groups in the backbone structure.
在本發明中所使用的遙爪聚醯胺具獨特性，它們在低於約70℃下可係液體及可反應進其它聚合物網絡中以授予想要的性質。許多聚醯胺，例如多種耐綸聚合物在溫度約80至260℃下係不溶的固體，因此將難以均勻地反應進其它聚合物網絡中。N-烷基化聚醯胺的氮原子或聚醯胺的承載氮前驅物會中斷某些氫鍵，使得本揭示之聚醯胺具有較低的熔點及更可溶。 The telechelic polyamines used in the present invention are unique in that they can be liquid at less than about 70 ° C and can be reacted into other polymer networks to impart the desired properties. Many polyamines, such as a variety of nylon polymers, are insoluble solids at temperatures of about 80 to 260 ° C and therefore will be difficult to uniformly react into other polymer networks. The nitrogen atom of the N-alkylated polydecylamine or the nitrogen-carrying precursor of the polyamidamine interrupts certain hydrogen bonds, such that the polyamines of the present disclosure have a lower melting point and are more soluble.
下列用語具有如在下列所描述的定義：遙爪聚合物係定義為包括二個反應性末端基團之大分子，及其使用作為交聯劑、鏈伸長劑及用於多種大分子結構的重要建構嵌段，包括嵌段及接枝共聚物、星形、高分枝或樹狀聚合物。該聚二烯、聚酯、聚醚及聚碳酸酯型式的遙爪聚合物在技藝中熟知。這些具有選自於一級或二級羥基、一級或二級胺及羧酸的官能性末端基團之先述技藝遙爪聚合物已經與互補反應物反應，而形成具有遙爪前驅物性質的較大聚合物。容易加工之具有低熔點的聚醯胺遙爪物尚無法獲得。 The following terms have the definitions as described below: Telechelic polymers are defined as macromolecules comprising two reactive end groups and their use as crosslinkers, chain extenders and for the use of various macromolecular structures. Construct blocks, including block and graft copolymers, star, high-branched or dendrimers. The teledentate polymers of the polydienes, polyesters, polyethers, and polycarbonates are well known in the art. These prior art telechelic polymers having functional end groups selected from primary or secondary hydroxyl, primary or secondary amines and carboxylic acids have reacted with complementary reactants to form larger properties with telechelic precursors. polymer. Polyamides with low melting points that are easy to process are not yet available.
我們將使用圓括號來標明出1)某些事情係選擇性存在，如此單體(類)意謂著單體或許多單體，或(甲基)丙烯酸酯意謂著甲基丙烯酸酯或丙烯酸酯；2)限定或 進一步定義先前所提到的用語；或3)列出較窄的具體實例。 We will use parentheses to indicate that 1) certain things are selective, such that monomer (class) means monomer or many monomers, or (meth) acrylate means methacrylate or acrylic acid. Ester; 2) limited or Further define the terms mentioned previously; or 3) list narrower specific examples.
聚酯多元醇及經常從此等多元醇製得的TPU提供好的機械性質及抗UV性，但是它們遭遇到差的抗水解性。聚醚多元醇及所產生的TPU具有比聚酯好的水解穩定性，但是抗UV性不足。聚碳酸酯多元醇及所產生的TPU提供超過聚酯之改良的抗水解性且增加一些硬度程度，但是它們比其它多元醇更貴一個數量級。聚二烯多元醇係有用的，但是其太疏水而無法與極性基材良好地交互作用。某些聚二烯多元醇係經氫化以減低與來自二烯單體的剩餘不飽和度相依之降解機制。因此，新種類的遙爪聚醯胺將幫助克服這些問題。 Polyester polyols and TPUs often made from such polyols provide good mechanical properties and UV resistance, but they suffer from poor hydrolysis resistance. The polyether polyol and the resulting TPU have better hydrolytic stability than polyester, but are insufficient in UV resistance. Polycarbonate polyols and the resulting TPU provide improved hydrolysis resistance over polyesters and increase some degree of hardness, but they are an order of magnitude more expensive than other polyols. Polydiene polyols are useful, but they are too hydrophobic to interact well with polar substrates. Certain polydiene polyols are hydrogenated to reduce the degradation mechanism associated with residual unsaturation from the diene monomer. Therefore, a new class of telechelic polyamines will help overcome these problems.
現在已發現胺終端的聚醯胺寡聚物具有低黏度、低玻璃轉換溫度、經抑制的結晶性、低酸數、具有多種氮或醯胺：烴重量比率(或親水性/疏水性平衡)、及具有經控制的氫鍵或無氫鍵醯胺基團數目。 It has now been found that amine terminated polyamine oligomers have low viscosity, low glass transition temperature, inhibited crystallinity, low acid number, and a variety of nitrogen or guanamine: hydrocarbon weight ratios (or hydrophilic/hydrophobic balance) And the number of guanamine groups having a controlled hydrogen bond or no hydrogen bond.
從習知的二官能基酸及胺製得一系列聚醯胺寡聚物。初始的寡聚物包括胺終端及在與二異氰酸酯的反應中形成之聚醯胺-聚尿素骨架。但是，在這些結構中存在有強的氫鍵使得其甚至在低分子量下亦非常硬(高玻璃轉換)，因此不合適於進一步結構修改或製備成較高分子量聚合物或交聯網絡。我們發現在這些聚合物上的N-烷基取代使得其軟化及容易加工。 A series of polyamine oligomers are prepared from conventional difunctional acids and amines. The initial oligomer includes an amine termination and a polyamine-polyurea backbone formed in the reaction with the diisocyanate. However, the presence of strong hydrogen bonds in these structures makes them very hard even at low molecular weights (high glass transition) and is therefore not suitable for further structural modification or preparation into higher molecular weight polymers or crosslinked networks. We have found that N-alkyl substitutions on these polymers make them soft and easy to process.
本發明係關於從這些聚醯胺寡聚物或遙爪聚醯胺製備的TPU組成物，其對例如藉由水解或UV降解 的斷鏈具抗性，其有用作為大單體、預聚物或聚合物鏈段以製得較高分子量聚合物及/或交聯的聚合物網絡。所產生的TPU組成物由於該醯胺鍵結之較高的熱穩定性而具有比來自聚醚及/或聚酯之類似聚合物或網絡物更好的熱穩定性。從中等分子量聚醯胺寡聚物與共反應物建構聚合物，其中該共反應物可與在該寡聚物的終端處之共反應性基團形成化學鍵。這些聚合物具有許多製得該聚合物之聚醯胺寡聚物的性質，因為該等寡聚物形成該最後聚合物之實質重量百分比。可使用修改該寡聚物的分子量及組成物來達成想要的性質。該組成物可包括小量的其它聚合物及材料如為物理摻合物，或該其它聚合物或材料可共反應進該聚醯胺中。 The present invention relates to TPU compositions prepared from these polyamido oligo or telechelic polyamines, for example by hydrolysis or UV degradation The broken chains are resistant and useful as macromers, prepolymers or polymer segments to produce higher molecular weight polymers and/or crosslinked polymer networks. The resulting TPU composition has better thermal stability than similar polymers or network materials from polyethers and/or polyesters due to the higher thermal stability of the guanamine linkage. The polymer is constructed from a medium molecular weight polyamine oligomer and a co-reactant, wherein the coreactant can form a chemical bond with a co-reactive group at the terminal of the oligomer. These polymers have many properties of the polyamine oligomers from which the polymer is formed because the oligomers form a substantial weight percent of the final polymer. The molecular weight and composition of the oligomer can be modified to achieve the desired properties. The composition can include small amounts of other polymers and materials such as physical blends, or the other polymers or materials can be co-reacted into the polyamine.
用語「聚醯胺寡聚物」將指為具有二或更多個醯胺鍵聯之寡聚物或有時將具體指定該醯胺鍵聯的量。該聚醯胺寡聚物的子集將係遙爪聚醯胺。該遙爪聚醯胺將係具有高百分比或具體指定百分比之二個單一化學型式官能基之聚醯胺寡聚物，例如二個終端胺基團(意謂著一級、二級或混合物)、二個終端羧基、二個終端羥基(再次意謂著一級、二級或混合物)、或二個終端異氰酸酯基團(意謂著脂肪族、芳香族或混合物)。與較高或較低官能性相對比，符合該遙爪定義的較佳二官能基百分比範圍係該寡聚物的至少70或80，更想要為至少90或95莫耳%係二官能基。該反應性胺終端遙爪聚醯胺將係該終端基團二者係一級或二級及其混合物之胺型式遙爪聚醯胺寡聚物，即，排除三級胺基團。 The term "polyamido oligo" will be taken to mean an amount of an oligomer having two or more guanamine linkages or, in some cases, specifically conjugated to the guanamine. A subset of the polyamido oligo will be telechelic polyamine. The telechelic polyimide will be a polyamine oligomer having a high percentage or a specified percentage of two single chemical formula functional groups, such as two terminal amine groups (meaning primary, secondary or mixtures), Two terminal carboxyl groups, two terminal hydroxyl groups (again, meaning primary, secondary or mixtures), or two terminal isocyanate groups (meaning aliphatic, aromatic or mixtures). Preferred difunctional percentage ranges consistent with the definition of the telechelic are at least 70 or 80 of the oligomer, more desirably at least 90 or 95 mole % difunctional, as opposed to higher or lower functionality. . The reactive amine terminal telechelic polyamine will be an amine type telechelic polyamine oligomer which is a primary or secondary of the terminal group and a mixture thereof, i.e., excludes tertiary amine groups.
本發明包括將所描述的聚醯胺寡聚物或遙爪聚醯胺使用於TPU組成物之製備。該聚醯胺寡聚物或遙爪聚醯胺可使用在該TPU形成反應中作為多元醇組分。 The invention includes the use of the described polyamidomethacrylate or telechelic polyamine for the preparation of a TPU composition. The polyamine oligomer or telechelic polyamine can be used as a polyol component in the TPU formation reaction.
本發明包括以聚醯胺鏈段取代在遙爪寡聚物中的聚酯、聚醚或聚碳酸酯軟鏈段。該聚醯胺鏈段對聚酯、聚醚或聚碳酸酯鏈段之置換或取代可係部分或全部。由於聚醚及聚酯較易斷鏈的潛力，完全置換聚酯及聚醚鏈段將產生最理想的環境抗性，包括熱穩定性。在某些具體實例中，因為軟化該彈性體部分或修改所產生的聚合物與其它聚合物表面之相容性的能力，可在該遙爪聚醯胺或聚醯胺寡聚物中保留一些聚酯及或聚醚鏈段。當來自聚酯或聚醚的聚合物係由水解或UV活化的斷鏈降解時，該聚合物之分子量減低，如此該聚合物或鏈段很快失去其抗張強度、斷裂伸長率、抗溶劑性等等。 The invention includes the replacement of a polyester, polyether or polycarbonate soft segment in a telechelic oligomer with a polyamidene segment. The polyamine moiety may be partially or fully substituted or substituted for the polyester, polyether or polycarbonate segment. Due to the potential of polyether and polyester to break chains, complete replacement of polyester and polyether segments will result in optimal environmental resistance, including thermal stability. In some embodiments, some of the telechelic polyamine or polyamine oligomers may remain in the elastomeric moiety or modify the ability of the resulting polymer to be compatible with other polymer surfaces. Polyester and or polyether segments. When the polymer from polyester or polyether is degraded by hydrolysis or UV-activated chain scission, the molecular weight of the polymer is reduced, so that the polymer or segment quickly loses its tensile strength, elongation at break, and solvent resistance. Sex and so on.
本發明之以軟聚醯胺鏈段取代軟聚醚或聚酯鏈段的第二利益為該聚醯胺鏈段趨向於促進對多種極性基材，諸如玻璃、耐綸及金屬有比以聚酯或聚醚為基底的聚合物較好的潤溼及黏附力。可藉由在該聚醯胺中使用不同的烴對醯胺鍵聯或氮原子重量比率來調整該聚醯胺之疏水性/親水性本質。相對於醯胺鍵聯部分，具有大的脂肪烴部分之二酸、二胺、胺基羧酸及內醯胺趨向於具疏水性。當烴對醯胺鍵聯或氮原子的重量比率變小時，該聚醯胺更具親水性。增加在聚合物中的聚醯胺量可增加對具有類似聚醯胺或與其相容的表面之基材的黏附力。 A second benefit of the present invention in replacing a soft polyether or polyester segment with a soft polyamine segment is that the polyamine segment tends to promote a combination of a plurality of polar substrates, such as glass, nylon, and metal. The ester or polyether is a base polymer with better wetting and adhesion. The hydrophobic/hydrophilic nature of the polyamine can be adjusted by using a different hydrocarbon to guanamine linkage or nitrogen atom weight ratio in the polyamine. Diacids, diamines, amine carboxylic acids, and decylamine having large aliphatic hydrocarbon moieties tend to be hydrophobic relative to the guanamine linkage moiety. When the weight ratio of hydrocarbon to guanamine linkage or nitrogen atom becomes small, the polyamide is more hydrophilic. Increasing the amount of polyamidamine in the polymer increases the adhesion to substrates having a similar polyamine or a surface compatible therewith.
從所描述的聚醯胺鏈段製得之TPU可具有好的耐溶劑性。溶劑可造成聚合物變形及膨脹，因此造成聚合物過早損毀。溶劑可造成塗層膨脹及在二層間之界面處從基材剝離。 The TPU made from the polyamine segments described can have good solvent resistance. Solvents can cause deformation and expansion of the polymer, thus causing premature failure of the polymer. The solvent can cause the coating to swell and peel off from the substrate at the interface between the two layers.
應注意的是，先述技藝的許多聚醯胺係高熔點的結晶聚醯胺，諸如6-耐綸、6,6-耐綸、6,10-耐綸，其在過高的溫度例如超過100℃下熔化，若想要嵌段熱塑性聚合物時，其無法提供作為軟鏈段。在某些先述技藝公開中，加入經常為結晶或高Tg聚醯胺型式的聚醯胺全然為了增加其與一與聚醯胺相容的基材之表面交互作用。為了產生較低Tg的聚合物，將軟(低Tg)聚酯、聚醚或聚碳酸酯加入至該聚醯胺鏈段以提供較低的複合物Tg彈性體鏈段。在其它先述技藝公開中，僅將少數聚醯胺鍵聯嵌入聚合物中來修改該聚合物的極性、增加耐溶劑性或提高軟化溫度。 It should be noted that many of the polyamines of the prior art are high melting point crystalline polyamines, such as 6-Nylon, 6,6-Nylon, 6,10-Nylon, which are at too high a temperature, for example, over 100. Melting at ° C, if a block thermoplastic polymer is desired, it cannot be provided as a soft segment. In certain prior art disclosures, polyamines, often in the form of crystalline or high Tg polyamines, are added to increase their surface interaction with a polyamide-compatible substrate. To produce a lower Tg polymer, a soft (low Tg) polyester, polyether or polycarbonate is added to the polyamine segment to provide a lower composite Tg elastomer segment. In other prior art disclosures, only a small amount of polyamine linkage is incorporated into the polymer to modify the polarity of the polymer, increase solvent resistance, or increase softening temperature.
本專利申請案的一個目標為在包含一或多個聚醯胺鏈段之遙爪寡聚物中使用高百分比的醯胺鍵聯，以提供抗因水解及/或UV活化斷鏈之抗斷鏈性。因此，許多具體實例將描述出在軟鏈段中於重覆單元間之總鍵聯具有高百分比之軟鏈段係醯胺鍵聯。某些具體實例可考慮到在重覆單元間除了醯胺鍵聯外尚有某些鍵聯。 One object of the present patent application is to use a high percentage of guanamine linkages in a telechelic oligomer comprising one or more polyamido segments to provide resistance to breakage due to hydrolysis and/or UV activation. Chain. Thus, many specific examples will describe a high percentage of soft segmented guanamine linkages in the soft link in the total linkage between the repeating units. Some specific examples may allow for some linkages between the repeating units in addition to the indole linkage.
從習知聚醯胺獲得低Tg聚醯胺軟鏈段的重要修改為在形成該聚醯胺時使用具有二級胺終端基團之單體。從二級胺與羧酸型式基團所形成的醯胺鍵聯稱為三級醯胺鍵聯。一級胺與羧酸型式基團反應而形成二級 醯胺。二級醯胺的氮原子具有接附的氫原子，其經常與附近醯胺的羰基形成氫鍵。該分子內H鍵引發結晶性與高熔點及可作用為減低鏈移動率之交聯。在三級醯胺基團中，於該醯胺鍵聯的氮上之氫係與氫鍵一起消除。當該聚合物存在於整體聚合物樣品中時，如與具有氫接附之二級醯胺基團比較，具有一個額外烷基接附的三級醯胺鍵聯與附近醯胺基團具有減低的極***互作用。減低的極***互作用意謂著包括該醯胺鍵聯的玻璃或結晶相在比係二級醯胺基團的類似醯胺基團低之溫度下熔化。一種取得二級胺反應物來源的方法為以烷基取代該含胺單體的氮原子，其中該二級胺反應物係三級醯胺鍵聯的前驅物。另一種取得二級胺反應物來源的方法為使用雜環分子，其中該胺的氮係該環結構之部分。哌係一種常見的環狀二胺，其中該二氮原子係二級型式且係該雜環的部分。 An important modification to obtain a low Tg polyamine soft segment from conventional polyamines is to use a monomer having a secondary amine terminal group in forming the polyamine. The guanamine linkage formed from the secondary amine with a carboxylic acid type group is referred to as a tertiary guanamine linkage. The primary amine reacts with the carboxylic acid type group to form a secondary guanamine. The nitrogen atom of the secondary guanamine has an attached hydrogen atom which often forms a hydrogen bond with the carbonyl group of the nearby guanamine. The intramolecular H bond initiates crystallinity and high melting point and acts to reduce crosslinking of chain mobility. In the tertiary guanamine group, the hydrogen on the guanamine-linked nitrogen is eliminated together with the hydrogen bond. When the polymer is present in the monolithic polymer sample, the tertiary guanamine linkage with an additional alkyl attachment has a reduced affinity for the nearby guanamine group as compared to the secondary guanamine group with hydrogen attachment. Polar interactions. The reduced polarity interaction means that the glass or crystalline phase comprising the guanamine linkage is melted at a lower temperature than the similar guanamine group of the secondary guanamine group. One method of obtaining a source of a secondary amine reactant is to replace the nitrogen atom of the amine-containing monomer with an alkyl group, wherein the secondary amine reactant is a precursor of a tertiary guanamine linkage. Another way to obtain a source of secondary amine reactants is to use a heterocyclic molecule wherein the nitrogen of the amine is part of the ring structure. Piper A common cyclic diamine wherein the dinitrogen atom is in a secondary form and is part of the heterocyclic ring.
另一種減低聚醯胺軟鏈段的Tg之修改為除了最小單體數目外，使用至少一種額外的單體來形成該聚醯胺。因此，對從諸如從N-甲基-十二烷基內醯胺進行內醯胺聚合所形成的聚醯胺來說，將在用於聚合的單體中包括額外的內醯胺、胺基羧酸、二胺或二羧酸，以改變在由該單體所形成之醯胺鍵聯間的間隔(在重覆單元當中)，以便對在每個寡聚物中的某些重覆單元來說，在該聚醯胺中於醯胺鍵聯間之間隔係沿著骨架不規則，例如，不相同的實體尺寸。對胺基羧酸之聚合來說，將在用於聚合的單體摻合物中包括額外的內醯胺、胺基羧 酸、二胺或二羧酸(在該單體之一級反應性基團間具有不同實體長度)，以改變在重覆單元當中於醯胺鍵聯間之間隔。切換在單體上的末端基團亦可中斷在極性醯胺鍵聯的間隔中之規律性及降低該共聚物的有效Tg。因此，共聚合C6胺基羧酸與小部分C6二酸及C6二胺可中斷醯胺鍵聯的規律性，因為該二酸及二胺單元會將醯胺鍵聯之取向從頭至尾取向切換成尾至頭取向，此稍微中斷沿著聚醯胺骨架的醯胺鍵聯之間隔的一致性。典型來說，當遵循此程序時，將嘗試加入一中斷單體，其將增加或減少於聚醯胺中在使用作為一級單體之單體的醯胺形成末端基團間之原子數目。亦可使用具有環狀結構的第二中斷單體，諸如哌，一種二個亞甲基原子形成該環的上半部及二個亞甲基原子形成該環的下半部之環狀二胺單體，以便中斷從二酸與在該二胺之氮原子間具有二個亞甲基原子的二胺單體反應所形成之聚醯胺的規律性。 Another modification to reduce the Tg of the polydecyl soft segment is to use at least one additional monomer to form the polyamine in addition to the minimum number of monomers. Thus, for polyamines formed from, for example, the indoleamine polymerization from N-methyl-dodecylnadecan, additional endolenes, amine groups will be included in the monomers used for the polymerization. a carboxylic acid, a diamine or a dicarboxylic acid to change the spacing (in the repeating unit) between the indole linkages formed by the monomer to facilitate some of the repeating units in each oligomer The spacing between the indole linkages in the polyamine is irregular along the backbone, for example, a different physical size. For the polymerization of the aminocarboxylic acid, an additional indoleamine, aminocarboxylic acid, diamine or dicarboxylic acid will be included in the monomer blend used for the polymerization (in the monomer-level reactive group) There are different physical lengths between the groups to change the spacing between the indole linkages in the repeat unit. Switching the terminal groups on the monomer can also interrupt the regularity in the spacing of the polar guanamine linkages and reduce the effective Tg of the copolymer. Therefore, the copolymerization of the C 6 aminocarboxylic acid with a small portion of the C 6 diacid and the C 6 diamine interrupts the regularity of the indole linkage because the diacid and diamine units will shift the indole linkage orientation from the head to the The tail orientation is switched to a tail-to-head orientation which slightly interrupts the consistency of the spacing of the indole linkages along the polyamine backbone. Typically, when following this procedure, an attempt will be made to add an interrupted monomer which will increase or decrease the number of atoms in the polyamine to form a terminal group between the amines using the monomer as the primary monomer. It is also possible to use a second interrupting monomer having a cyclic structure, such as a piperidine. a cyclic diamine monomer in which two methylene atoms form the upper half of the ring and two methylene atoms form the lower half of the ring to interrupt the diazo acid from the diamine and the nitrogen atom in the diamine The regularity of the polyamine formed by the reaction of a diamine monomer having two methylene atoms.
另一種表達出使用共聚合方法來減低Tg及因此減低聚醯胺的硬度之方式為該聚醯胺具有在(a)、(b)或(c)中的特徵：(a)當該醯胺鍵聯係衍生自聚合一或多種單體且該等單體之多於90莫耳百分比係衍生自選自於內醯胺及胺基羧酸單體的聚合單體時，則該聚醯胺係定義為至少二種不同單體的共聚物(意謂著該等單體具有係至少二種不同單體的特徵，因為它們在胺與羧酸基團間具有不同間隔長度之烴基部分，其中該至少二種不同單體每種所呈現的莫耳濃度係在該聚醯胺中的總內醯胺及/或胺基羧酸單體之至少10%，更想要為至少20或 30%)；或(b)當該醯胺鍵聯係衍生自聚合二或更多種單體及該等單體之多於90莫耳百分比係衍生自聚合二羧酸及二胺單體時，則該聚醯胺係定義為至少三種不同單體的三元共聚物(意謂著該醯胺鍵聯係從至少三種選自於二羧酸及二胺單體之群的不同單體形成，其中該至少三種不同單體的特徵為在二羧酸之羧酸基團間的不同間隔長度、或在二胺之胺基團間的不同間隔長度之烴基彼此不同，其中該至少三種不同單體每種所呈現的濃度係在該聚醯胺中的總單體之至少10莫耳%，更想要為至少20或30莫耳百分比)；或(c)其限制為若該醯胺鍵聯係衍生自聚合二羧酸、二胺及內醯胺及/或胺基羧酸單體之組合，如此該總二羧酸單體及二胺單體係以濃度至少10莫耳百分比，更想要為至少20或30莫耳百分比存在於該單體摻合物中，及該總內醯胺及胺基羧酸單體係以濃度至少10莫耳%，更想要為至少20或30莫耳百分比存在於該單體摻合物中時，則並無限制需要額外不同單體。 Another way of expressing the use of a copolymerization process to reduce the Tg and thus the hardness of the polyamine is that the polyamine has the characteristics in (a), (b) or (c): (a) when the guanamine The bond is derived from the polymerization of one or more monomers and the more than 90 mole percent of the monomers are derived from a polymerized monomer selected from the group consisting of an indoleamine and an aminocarboxylic acid monomer, then the polyamine derivative is defined a copolymer of at least two different monomers (meaning that the monomers have the characteristics of being at least two different monomers because they have a hydrocarbyl moiety having a different spacing length between the amine and the carboxylic acid group, wherein the at least Each of the two different monomers exhibits a molar concentration of at least 10% of the total indoleamine and/or aminocarboxylic acid monomer in the polyamine, more preferably at least 20 or 30%); or (b) when the indole linkage is derived from the polymerization of two or more monomers and more than 90 mole percent of the monomers are derived from the polymeric dicarboxylic acid and diamine monomer, The polyamine is defined as a terpolymer of at least three different monomers (meaning that the amide linkage is formed from at least three different monomers selected from the group consisting of dicarboxylic acids and diamine monomers, wherein The at least three different monomers are characterized by different spacing lengths between carboxylic acid groups of the dicarboxylic acid or different spacing lengths of hydrocarbon groups between the amine groups of the diamines, wherein the at least three different monomers each The concentration exhibited is at least 10 mol% of the total monomer in the polyamine, more desirably at least 20 or 30 mole percent); or (c) is limited to if the indole bond is derived Self-polymerizing a combination of a dicarboxylic acid, a diamine and an indoleamine and/or an aminocarboxylic acid monomer, such that the total dicarboxylic acid monomer and the diamine single system are at a concentration of at least 10 mole percent, more preferably At least 20 or 30 mole percent is present in the monomer blend, and the total indoleamine and aminocarboxylic acid monosystem is at a concentration of at least 10 mole percent More desirably, when at least 20 or 30 mole percent is present in the monomer blend, there is no limitation that additional different monomers are required.
通常來說，具有幾乎相等量的二或更多種不同醯胺形成單體係沿著聚醯胺骨架在醯胺鍵聯間產生不同間隔，及給予最理想的結晶熔化及玻璃轉換溫度減低。例如，50：50莫耳之二種不同的二胺將係想要的摻合物。50：50莫耳之二種不同的二酸將係想要的摻合物。33：33；33莫耳之內醯胺與二酸及二胺將係想要的摻合物。 Generally, two or more different guanamine forming monolithic systems having nearly equal amounts produce different spacing between the guanamine linkages along the polyamine backbone, and impart the most desirable crystallization melting and glass transition temperature reduction. For example, two different diamines of 50:50 moles will be the desired blend. The 50:50 molar two different diacids will be the desired blend. 33:33; 33 melamine and diacid and diamine will be the desired blend.
我們使用「低玻璃轉換溫度Tg」之用語，即使我們認知到大部分的聚醯胺鏈段初始具有低分子量及 將無法容易地測量該低分子量寡聚物之Tg，所測量的值將戲劇性地受分子量影響。高Tg例如具有如藉由示差掃描卡計(DSC)測量高於70、80或90℃之Tg值的聚合物將趨向於甚至在低分子量下形成固體或凝膠。因此，在本專利說明書中，經常藉由在特定溫度下的黏度來描述該聚醯胺寡聚物、遙爪聚醯胺及甚至來自該遙爪聚醯胺或聚醯胺寡聚物之寡聚物。低Tg聚醯胺寡聚物將定義為若其具有分子量大於20,000克/莫耳時，將具有Tg係低於50℃，更想要為低於25或0℃的那些組成物。 We use the term "low glass transition temperature Tg" even though we recognize that most of the polyamide segments initially have low molecular weight and The Tg of the low molecular weight oligomer will not be readily measurable and the measured value will be dramatically affected by the molecular weight. A high Tg such as a polymer having a Tg value greater than 70, 80 or 90 ° C as measured by a differential scanning card (DSC) will tend to form a solid or gel even at low molecular weights. Thus, in this patent specification, the polyamine oligomer, telechelic polyamine, and even the oligomer from the telechelic polyamine or polyamine oligomer are often described by viscosity at a specific temperature. Polymer. A low Tg polyamido oligo will be defined as those compositions which, if they have a molecular weight greater than 20,000 grams per mole, will have a Tg system below 50 °C, more desirably below 25 or 0 °C.
在一個具體實例中，該遙爪寡聚物或遙爪聚醯胺將具有黏度在溫度70℃下係少於100,000cps，更想要為在70℃下係少於15,000或10,000cps，仍然更想要為在60或50℃下係少於100,000cps，及更佳為在60℃下係少於15,000或10,000cps，及仍然更佳為在50℃下係少於15,000或10,000cps，此係藉由Brookfield圓盤型黏度計，使用5rpm旋轉該圓盤來測量。想要的是，這些黏度係沒有溶劑或塑化劑的純遙爪預聚物或聚醯胺寡聚物之黏度。這些黏度值將使得在該想要的反應係以合理的速率發生及不想要的反應例如側反應不發生至任何明顯程度之合適的條件下，容易混合該遙爪聚醯胺與共反應物及或微粒狀材料。在某些具體實例中，該遙爪聚醯胺可以溶劑稀釋以達成該黏度係在這些範圍內。 In one embodiment, the telechelic oligomer or telechelic polyamine will have a viscosity of less than 100,000 cps at a temperature of 70 ° C, more preferably less than 15,000 or 10,000 cps at 70 ° C, still more Want to be less than 100,000 cps at 60 or 50 ° C, and more preferably less than 15,000 or 10,000 cps at 60 ° C, and still more preferably less than 15,000 or 10,000 cps at 50 ° C, this system The disc was rotated using a Brookfield disc type viscometer using 5 rpm. It is desirable that these viscosities are the viscosity of pure telechelic prepolymers or polyamido oligos without solvent or plasticizer. These viscosity values will allow for easy mixing of the telechelic polyamide and the co-reactant when the desired reaction occurs at a reasonable rate and an undesired reaction such as a side reaction does not occur to any significant extent. Or particulate material. In some embodiments, the telechelic polyamine can be solvent diluted to achieve the viscosity within these ranges.
本專利說明書的許多寡聚物、遙爪物及聚合物係藉由在想要的單體上之反應性基團的縮合反應製得。藉由鏈聚合方法將內醯胺聚合進聚醯胺中會產生類 似的醯胺鍵聯，此在技藝中熟知。這些在羧酸基團與胺或羥基間之縮合反應係熟知，且藉由移除水及或觸媒驅動。可藉由硼酸、硼酸酯、硼烷、亞磷酸、磷酸鹽、磷酸酯、胺、酸、鹼、矽酸鹽及倍半矽氧烷類來催化羧酸基團與胺基團之反應而形成醯胺。可在教科書諸如由Larock的“Comprehensive Organic Transformations”中獲得額外的觸媒、條件等等。 Many of the oligomers, telechelators and polymers of this patent specification are made by condensation of reactive groups on the desired monomers. Polymerization of indoleamine into polydecylamine by chain polymerization will result in a class Similar guanamine linkages are well known in the art. These condensation reactions between the carboxylic acid group and the amine or hydroxyl group are well known and are driven by the removal of water and or a catalyst. The reaction of a carboxylic acid group with an amine group can be catalyzed by boric acid, a boric acid ester, a borane, a phosphorous acid, a phosphate, a phosphate, an amine, an acid, a base, a citrate, and a sesquioxane. Forming guanamine. Additional catalysts, conditions, etc. can be obtained in textbooks such as "Comprehensive Organic Transformations" by Larock.
該反應性基團的縮合反應將定義為在單體間產生化學鍵聯。併入該寡聚物或聚合物中的單體部分將定義為來自該特別單體之重覆單元。當該單體從單體變成聚合物的重覆單元時，與二胺之一端反應的某些單體諸如胺基羧酸或二酸之一端會失去一分子水。其它單體諸如內醯胺、異氰酸酯、胺與異氰酸酯反應、羥基與異氰酸酯反應等等不會將該分子的一部分釋放至環境，而是將全部單體保留在所產生的聚合物中。 The condensation reaction of the reactive group will be defined as the creation of a chemical linkage between the monomers. The portion of the monomer incorporated into the oligomer or polymer will be defined as the repeating unit from the particular monomer. When the monomer changes from a monomer to a repeating unit of a polymer, some of the monomers reactive with one end of the diamine, such as an aminocarboxylic acid or a diacid, lose one molecule of water. Other monomers such as indoleamine, isocyanate, amine to isocyanate, hydroxyl to isocyanate, and the like do not release a portion of the molecule to the environment, but retain all of the monomer in the polymer produced.
我們將聚醯胺寡聚物定義為分子量低於20,000克/莫耳的物種，例如經常低於10,000、5,000、2,500或2000克/莫耳，其中每個寡聚物具有二或更多個醯胺鍵聯。晚後，我們將定義出較佳的醯胺鍵聯或單體百分比，其在多種寡聚性物種中提供每重覆單元平均一個醯胺鍵聯。該聚醯胺寡聚物的子集將係遙爪寡聚物。該遙爪聚醯胺具有較佳與上述聚醯胺寡聚物相同的分子量。用語「遙爪」較早已經定義。可使用縮合反應連結多種聚醯胺寡聚物或遙爪聚醯胺以形成通常大於100,000克/莫耳之聚合物。 We define polyamine oligomers as species with a molecular weight below 20,000 g/mole, such as often below 10,000, 5,000, 2,500 or 2000 g/mole, where each oligomer has two or more quinones. Amine linkage. Later in the day, we will define a preferred indole linkage or monomer percentage that provides an average of one amine linkage per refraction unit in a variety of oligomeric species. A subset of the polyamido oligo will be a telechelic oligomer. The telechelic polyamine has a molecular weight preferably the same as that of the above polyamine oligomer. The term "distant claws" has been defined earlier. A condensation reaction can be used to link a plurality of polyamido oligo or telechelic polyamines to form a polymer typically greater than 100,000 grams per mole.
通常來說，醯胺鍵聯係從羧酸基團與胺基團之反應或內醯胺的開環聚合所形成，例如在環結構中的醯胺鍵聯係轉換成在聚合物中之醯胺鍵聯。在較佳具體實例中，該單體的大部分胺基團係二級胺基團，或該內醯胺的氮係三級醯胺基團。當該胺基團與羧酸反應而形成醯胺時，二級胺基團形成三級醯胺基團。為了本揭示的目的，該醯胺例如如在內醯胺中之羰基將視為衍生自羧酸基團。內醯胺之醯胺鍵聯係從胺基羧酸的羧酸基團與相同胺基羧酸的胺基團反應而形成。在一個具體實例中，我們想要該使用來製造聚醯胺的單體之少於20、10或5莫耳百分比，在醯胺鍵聯之聚合中具有3或更多之官能性。此將減少在聚醯胺寡聚物或遙爪聚醯胺中的分枝。 In general, a guanamine bond is formed by a reaction of a carboxylic acid group with an amine group or a ring opening polymerization of an indoleamine, for example, a guanamine bond in a ring structure is converted into a guanamine bond in a polymer. Union. In a preferred embodiment, the majority of the amine groups of the monomer are secondary amine groups, or the nitrogen tertiary tertiary amine groups of the internal amine. When the amine group is reacted with a carboxylic acid to form a guanamine, the secondary amine group forms a tertiary guanamine group. For the purposes of this disclosure, the guanamine, such as a carbonyl group such as inlactone, will be considered to be derived from a carboxylic acid group. The indole bond of the indoleamine is formed by reacting a carboxylic acid group of the aminocarboxylic acid with an amine group of the same aminocarboxylic acid. In one embodiment, we want less than 20, 10 or 5 mole percent of the monomers used to make the polyamine, and 3 or more functionalities in the polymerization of the indoleamine linkage. This will reduce branching in the polyamido oligo or telechelic polyamine.
若使用來形成這些鍵聯的額外單體對該聚合物之意欲的用途係有用時，本揭示的聚醯胺寡聚物及遙爪聚醯胺可包括小量的酯鍵聯、醚鍵聯、胺基甲酸酯鍵聯、尿素鍵聯等等。此允許包含在該聚醯胺中的其它單體及寡聚物提供出特定性質，而此性質可係需要且無法以100%聚醯胺鏈段寡聚物達成。有時，所加入的聚醚、聚酯或聚碳酸酯提供較軟例如較低Tg的鏈段。有時，想要將聚醯胺的羧酸末端基團或一級或二級胺末端基團轉換成能縮合聚合之其它官能性末端基團。具有羧酸末端基團的遙爪聚醯胺可藉由讓該遙爪聚醯胺與具有二個羥基末端基團的聚醚或具有一個一級或二級胺基與一個羥基末端基團的聚醚反應，而被轉換成具有羥基末端基團 之寡聚物。具有聚醚鏈段的寡聚物或聚合物對由於UV曝露的鏈斷裂具有敏感性。UV曝露在耐綸6-聚乙二醇嵌段共聚物的嵌段共聚物上之效應係在Gauvin，Pascal；Lemaire，Jacques in Makromolekulare Chemie(1987)，188(5)，971-986中有報導。有時，對內醯胺的寡聚物鏈聚合使用不會產生醯胺鍵聯之起始劑。有時，可使用聚醚作為聚醯胺的鏈段或部分來減低Tg，或提供所產生的聚醯胺寡聚物之軟鏈段。有時，可以二個聚醚末端鏈段(諸如來自JeffamineTM D230)對例如可能具有羧酸或胺終端基團的二官能基之聚醯胺鏈段進行官能化，以進一步降低該聚醯胺寡聚物的Tg或在其中提供軟鏈段，及產生一具有胺或羥基末端基團的遙爪聚醯胺。有時，羧酸終端的遙爪聚醯胺鏈段係藉由與胺基醇例如N-甲基胺基乙醇反應而被官能化，其可產生一具有終端羥基的遙爪聚醯胺。在一個具體實例中，該遙爪聚醯胺的官能性一級或二級胺基團係與2、3或4至10個碳原子的內酯(例如，丁、戊或己內酯)及/或3至30個碳原子的羥基羧酸反應，以在該遙爪聚醯胺上產生一或二個衍生自該內酯或該羥基羧酸之羥基官能性末端基團。最理想的是，僅將一個來自該內酯或羥基羧酸的重覆單元加入至該遙爪聚醯胺之每個末端。 The polyamidomethacrylates and telechelic polyamines of the present disclosure may include small amounts of ester linkages, ether linkages, if the additional monomers used to form these linkages are useful for the intended use of the polymer. , urethane linkage, urea linkage, and the like. This allows other monomers and oligomers contained in the polyamine to provide specific properties that may be desirable and not achieved with 100% polyamine segment oligomers. Sometimes, the added polyether, polyester or polycarbonate provides a softer, e.g., lower Tg segment. Sometimes, it is desirable to convert the carboxylic acid end group or the primary or secondary amine end group of the polyamine to other functional end groups capable of condensation polymerization. Telechelic polyamine having a carboxylic acid end group can be obtained by allowing the telechelic polyamine to be combined with a polyether having two hydroxyl end groups or having a primary or secondary amine group and a hydroxyl end group The ether reacts and is converted into an oligomer having a hydroxyl end group. Oligomers or polymers having polyether segments are sensitive to chain scission due to UV exposure. The effect of UV exposure on block copolymers of nylon 6-polyethylene glycol block copolymers is reported in Gauvin, Pascal; Lemaire, Jacques in Makromolekulare Chemie (1987), 188(5), 971-986. . Occasionally, oligomeric chain polymerization of indoleamine uses an initiator which does not produce a guanamine linkage. Sometimes, a polyether can be used as a segment or moiety of polyamine to reduce the Tg or to provide a soft segment of the polyamine oligomer produced. Sometimes, two may be terminated polyether segments (such as from Jeffamine TM D230) Polyamide segments may, for example, difunctional carboxylic acid or amine having the terminal groups of functionalized, to further reduce the polyamide The Tg of the oligomer either provides a soft segment therein and produces a telechelic polyamine having an amine or hydroxyl end group. Sometimes, the telechelic polyamine moiety of the carboxylic acid terminal is functionalized by reaction with an amine alcohol such as N-methylaminoethanol, which produces a telechelic polyamine having a terminal hydroxyl group. In one embodiment, the functional primary or secondary amine group of the telechelic polyamine is linked to a lactone of 2, 3 or 4 to 10 carbon atoms (eg, butyl, pentane or caprolactone) and/or Or a hydroxycarboxylic acid having from 3 to 30 carbon atoms is reacted to produce one or two hydroxyl functional end groups derived from the lactone or the hydroxycarboxylic acid on the telechelic polyamine. Most desirably, only one repeating unit derived from the lactone or hydroxycarboxylic acid is added to each end of the telechelic polyamine.
如較早指示出，許多醯胺形成單體產生每重覆單元平均一個醯胺鍵聯。這些單體包括當彼此反應時的二酸及二胺、胺基羧酸及內醯胺。這些單體當與在相同群組中的其它單體反應時，亦在所形成的重覆單元之 二末端處產生醯胺鍵聯。因此，我們將使用醯胺鍵聯的百分比及來自醯胺形成單體的重覆單元之莫耳百分比及重量百分比二者。將使用醯胺形成單體來指出在正常醯胺形成縮合連結反應中形成每重覆單元平均一個醯胺鍵聯之單體。 As indicated earlier, many of the guanamine forming monomers produce an average of one guanamine linkage per repeating unit. These monomers include diacids and diamines, aminocarboxylic acids and indoleamines when reacted with each other. These monomers, when reacted with other monomers in the same group, are also in the formed re-unit A guanamine linkage is produced at the two ends. Therefore, we will use both the percentage of guanamine linkages and the molar percentage and weight percentage of the repeating unit from the guanamine-forming monomer. The use of a guanamine forming monomer will indicate the formation of an average of one guanamine linkage per repeating unit in the normal guanamine forming condensation linkage reaction.
在一個具體實例中，想要該連接烴型式鍵聯之含雜原子鍵聯的總數之至少10莫耳百分比，更想要為至少25、45或50，及仍然更想要為至少60、70、80、90或95莫耳%具有醯胺鍵聯特徵。該雜原子鍵聯係諸如醯胺、酯、胺基甲酸酯、尿素、醚鍵聯之鍵聯，其中該雜原子連接通常具有烴特徵(或具有碳碳鍵結，諸如烴鍵聯)的寡聚物或聚合物之二個部分。當在聚醯胺中的醯胺鍵聯量增加時，在該聚醯胺中來自醯胺形成單體的重覆單元量增加。 In one embodiment, it is desirable to have at least 10 mole percent of the total number of hetero atom-containing linkages associated with the bonded hydrocarbon type linkage, more desirably at least 25, 45 or 50, and still more preferably at least 60, 70. , 80, 90 or 95 mole % has a guanamine linkage feature. The heteroatom bond is linked to a linkage such as a guanamine, an ester, a urethane, a urea, an ether linkage, wherein the heteroatom linkage typically has a hydrocarbon character (or has a carbon-carbon bond, such as a hydrocarbon linkage). Two parts of a polymer or polymer. When the amount of the guanamine linkage in the polyamine is increased, the amount of the repeating unit derived from the guanamine forming monomer in the polyamine is increased.
在一個具體實例中，想要該聚醯胺寡聚物或遙爪聚醯胺的至少25重量%，更想要為至少30、40、50，更想要為至少60、70、80、90或95重量%係來自醯胺形成單體之重覆單元，其亦鑑別為在該重覆單元的二末端處形成醯胺鍵聯之單體。此等單體包括內醯胺、胺基羧酸、二羧酸及二胺。 In one embodiment, at least 25% by weight of the polyamido oligo or telechelic polyamine is desired, more preferably at least 30, 40, 50, more desirably at least 60, 70, 80, 90 Or 95% by weight is a repeating unit derived from a guanamine-forming monomer, which is also identified as a monomer which forms a guanamine linkage at the two ends of the repeating unit. These monomers include indoleamines, aminocarboxylic acids, dicarboxylic acids, and diamines.
在一個具體實例中，想要在該聚醯胺寡聚物或遙爪聚胺中的醯胺鍵聯之至少50、65、75、76、80、90或95莫耳百分比係三級醯胺鍵聯。如較早的解釋，該三級醯胺鍵聯產生自內醯胺與三級醯胺之開環聚合，或二級胺與羧酸基團的反應。 In one embodiment, at least 50, 65, 75, 76, 80, 90 or 95 mole percent of the indole linkage to be desired in the polyamine oligomer or telechelic polyamine is a tertiary amine. Bonding. As explained earlier, the tertiary guanamine linkage results from the ring opening polymerization of the indoleamine and the tertiary decylamine, or the reaction of the secondary amine with a carboxylic acid group.
使用下列方程式計算總醯胺鍵聯數目的三級醯胺鍵聯百分比：
其中n係單體數目；索引i指為某一單體；w tertN 係在聚合中形成三級醯胺鍵聯或係其一部分之單體的平均氮原子數目(注意：該末端基團形成胺在聚合期間不會形成醯胺基團及其量係從w tertN 中排除)；w totalN 係在聚合中形成三級醯胺鍵聯或係其一部分之單體的平均氮原子數目(注意：該末端基團形成胺在聚合期間不會形成醯胺基團及其量係從w totalN 中排除)；及n i 係具有索引i的單體之莫耳數。 Wherein n is the number of monomers; index i refers to a certain monomer; w tertN is the average number of nitrogen atoms of the monomer forming a tertiary guanamine bond or a part thereof in the polymerization (Note: the terminal group forms an amine acyl not formed during the polymerization and the amount of amine groups from the excluded line in the w tertN); the average number of nitrogen atoms is part of monomer (w totalN note based Amides formed three or linkage system during polymerization: the The terminal group forming amine does not form a guanamine group during polymerization and its amount is excluded from w totalN ; and n i is the number of moles of the monomer having index i .
藉由下列方程式計算全部含雜原子鍵聯(連接烴鍵聯)總數目之醯胺鍵聯百分比：
其中wtotalS係在單體中的含雜原子鍵聯(連接烴鍵聯)之平均數目與從該單體藉由在聚醯胺聚合期間與承載羧酸單體反應所形成之含雜原子鍵聯(連接烴鍵聯)數目的總和；及全部其它變量係如上述所定義。如於本文中所使用，用語「烴鍵聯」僅係在重覆單元中從連續的碳碳鍵(即，沒有雜原子諸如氮或氧)形成之每個重覆單元的烴部分。此烴部分將係環氧乙烷或環氧丙烷的伸乙基或伸丙基部分；十二烷基內醯胺的十一烷基；乙二胺的伸乙基；及己二酸的(CH2)4(或伸丁基)。 Wherein w totalS is the average number of hetero atom-containing linkages (linked hydrocarbon linkages) in the monomer and the hetero atom-containing bonds formed from the monomer by reaction with the carboxylic acid-carrying monomer during polymerization of the polyamine The sum of the number of linked (hydrocarbon linkages); and all other variables are as defined above. As used herein, the term "hydrocarbon linkage" refers only to the hydrocarbon portion of each repeating unit formed from continuous carbon-carbon bonds (ie, free of heteroatoms such as nitrogen or oxygen) in the repeating unit. The hydrocarbon moiety will be an ethyl or propyl moiety of ethylene oxide or propylene oxide; an undecyl group of lauryl decylamine; an ethylidene group of ethylenediamine; and adipic acid ( CH 2 ) 4 (or butyl).
較佳的醯胺或三級醯胺形成單體包括二羧酸、二胺、胺基羧酸及內醯胺。較佳的二羧酸有該二羧酸之伸烷基部分係2至36個碳原子的環狀、線性或分枝(選擇性包括芳香族基團)伸烷基，選擇性對該二酸的每3或10個碳原子會包括最高1個雜原子，更佳為4至36個碳原子(該二酸將包括比該伸烷基部分更多2個碳原子)。這些包括二聚物脂肪酸、氫化的二聚物酸、癸二酸等等。通常來說，我們寧願選擇具有較大伸烷基的二酸，因為其通常提供具有較低Tg值的聚醯胺重覆單元。 Preferred guanamine or tertiary guanamine forming monomers include dicarboxylic acids, diamines, aminocarboxylic acids, and decylamine. Preferably, the dicarboxylic acid has a cyclic, linear or branched (optionally aromatic group) alkyl group having from 2 to 36 carbon atoms in the alkyl moiety of the dicarboxylic acid, optionally the diacid Each 3 or 10 carbon atoms will comprise up to 1 heteroatom, more preferably 4 to 36 carbon atoms (the diacid will comprise 2 more carbon atoms than the alkyl moiety). These include dimer fatty acids, hydrogenated dimer acids, sebacic acid, and the like. In general, we prefer to choose a diacid with a larger alkylene group because it typically provides a polyamine repeat unit with a lower Tg value.
較佳的二胺包括具有最高60個碳原子，選擇性對該二胺的每3或10個碳原子會包括一個雜原子(除了二個氮原子外)的那些，及選擇性包括多種環狀、芳香族或雜環基團，其限制為該胺基團之一或二者係二級胺，較佳的式為：
其中Rb係直接鍵結，或2至36個碳原子及更佳為2或4至12個碳原子的線性或分枝(選擇性係或包括環狀、雜環或芳香族部分)伸烷基(選擇性對該二胺的每10個碳原子會包括最高1或3個雜原子)；及Rc與Rd各別係1至8個碳原子，更佳為1或2至4個碳原子之線性或分枝烷基，或Rc與Rd連接在一起以形成1至8個碳原子的單一線性或分枝伸烷基，或選擇性Rc及Rd之一係在碳原子處連接至Rb，更想要為Rc及Rd係1或2至4個碳原子。 Wherein R b is a direct bond, or a linear or branched (selective or includes cyclic, heterocyclic or aromatic moiety) alkylene of 2 to 36 carbon atoms and more preferably 2 or 4 to 12 carbon atoms a base (selectively including up to 1 or 3 heteroatoms per 10 carbon atoms of the diamine); and R c and R d each independently 1 to 8 carbon atoms, more preferably 1 or 2 to 4 a linear or branched alkyl group of a carbon atom, or a single linear or branched alkyl group having R c and R d joined to form 1 to 8 carbon atoms, or one of the selective R c and R d is attached to carbon The atom is attached to R b and more desirably R c and R d are 1 or 2 to 4 carbon atoms.
此等二胺包括來自Albermarle的EthacureTM 90(根據推測係N,N’-雙(1,2,2-三甲基丙基)-1,6-己二胺)；來自Dorfketal的ClearlinkTM 1000，或來自Huntsman的JefflinkTM 754；N-甲基胺基乙醇；二羥基終端、羥基與胺終端或二胺終端的聚(環氧伸烷基)，其中該伸烷基具有2至4個碳原子及具有分子量約40或100至2000；N,N’-二異丙基-1,6-己二胺；N,N’-二(二級丁基)苯二胺；哌；高哌；及甲基-哌。JefflinkTM 754具有下列結構：
同時ClearlinkTM 1000具有下列結構：
同時另一種具有芳香基團的二胺為：N,N’-二(二級丁基)苯二胺，參見下列結構：
其中較佳的二胺係該二胺基團係二級胺的二胺。 Among the preferred diamines are the diamines of which the diamine group is a secondary amine.
較佳的內醯胺有在其中包括4至12個碳原子的直鏈或分枝伸烷基鏈段之內醯胺，如此在該內醯胺的氮上沒有取代基之環結構具有總共5至13個碳原子(當一個包括羰基時)，及在該內醯胺的氮上之取代基(若該內醯胺係三級醯胺時)係1至8個碳原子的烷基及更想要為1至4個碳原子的烷基。十二烷基內醯胺、經烷基取代的十二烷基內醯胺、己內醯胺、經烷基取代的己內醯胺及具有較大的伸烷基之其它內醯胺係較佳的內醯胺，因為它們提供具有較低Tg值的重覆單元。該胺基羧酸具有與內醯胺相同的碳原子數目。想要的是，在線性或分枝伸烷基中，於胺基羧酸之胺與羧酸基團間的碳原子數目係4至12，及在胺基團(若其係二級胺基團時)的氮上之取代基係具有1至8個碳原子，更佳為1或2至4個碳原子的烷基。具有二級胺基團的胺基羧酸係較佳。 Preferred indoleamines have a decylamine having a linear or branched alkyl group having 4 to 12 carbon atoms therein, such that the ring structure having no substituent on the nitrogen of the indoleamine has a total of 5 Up to 13 carbon atoms (when one includes a carbonyl group), and a substituent on the nitrogen of the indoleamine (if the indoleamine is a tertiary decylamine) is an alkyl group of 1 to 8 carbon atoms and more It is intended to be an alkyl group of 1 to 4 carbon atoms. Dodecyl decylamine, alkyl-substituted dodecyl decylamine, caprolactam, alkyl-substituted caprolactam, and other endoamines with larger alkylene groups Good indoleamines because they provide repeating units with lower Tg values. The aminocarboxylic acid has the same number of carbon atoms as the indoleamine. It is desirable that in a linear or branched alkyl group, the number of carbon atoms between the amine and the carboxylic acid group of the aminocarboxylic acid is 4 to 12, and in the amine group (if it is a secondary amine group) The substituent on the nitrogen of the group is an alkyl group having 1 to 8 carbon atoms, more preferably 1 or 2 to 4 carbon atoms. Aminocarboxylic acids having a secondary amine group are preferred.
在一個具體實例中，想要該聚醯胺寡聚物或遙爪聚醯胺的至少50重量%，更想要為至少60、70、80或90重量%包含來自二酸及二胺的重覆單元，該重覆單元之結構係：
其中Ra係該二羧酸的伸烷基部分及係2至36個碳原子的環狀、線性或分枝(選擇性包括芳香族基團)伸烷 基，選擇性對該二酸每3或10個碳原子會包括最高1個雜原子，更佳為4至36個碳原子(該二酸將包括比該伸烷基部分更多2個碳原子)；及Rb係直接鍵結，或2至36或60個碳原子及更佳為2或4至12個碳原子之線性或分枝(選擇性係或包括環狀、雜環或芳香族部分)伸烷基(選擇性每10個碳原子包括最高1或3個雜原子)；及Rc與Rd各別係1至8個碳原子，更佳為1或2至4個碳原子的線性或分枝烷基，或Rc與Rd連接在一起以形成1至8個碳原子的單一線性或分枝伸烷基，或選擇性Rc及Rd之一係在碳原子處連接至Rb，更想要為Rc及Rd係1或2至4個碳原子的烷基。 Wherein R a is an alkylene moiety of the dicarboxylic acid and a cyclic, linear or branched (optionally comprising an aromatic group) alkyl group of 2 to 36 carbon atoms, optionally 3 per mole of the diacid Or 10 carbon atoms may comprise up to 1 heteroatom, more preferably 4 to 36 carbon atoms (the diacid will comprise 2 more carbon atoms than the alkyl moiety); and R b is directly bonded, Or a linear or branched (selective or including cyclic, heterocyclic or aromatic moiety) alkyl group of 2 to 36 or 60 carbon atoms and more preferably 2 or 4 to 12 carbon atoms (selective per 10 One carbon atom includes up to 1 or 3 heteroatoms); and R c and R d are each a linear or branched alkyl group of 1 to 8 carbon atoms, more preferably 1 or 2 to 4 carbon atoms, or R c is linked to R d to form a single linear or branched alkyl group of 1 to 8 carbon atoms, or one of the selective R c and R d is attached to R b at a carbon atom, more preferably R c and R d are an alkyl group of 1 or 2 to 4 carbon atoms.
在一個具體實例中，想要該聚醯胺寡聚物或遙爪聚醯胺的至少50重量%，更想要為至少60、70、80或90重量%包含來自內醯胺或來自下列結構的胺基羧酸之重覆單元：
該重覆單元可依起始劑型式而在衍生自內醯胺或胺基羧酸的寡聚物中有多種取向，其中每個Re各自獨立地係4至12個碳原子的線性或分枝伸烷基，及每個Rf各自獨立地係1至8，更想要為1或2至4個碳原子的線性或分枝烷基。 The repeating unit may have a plurality of orientations in the oligomer derived from the indoleamine or the aminocarboxylic acid depending on the starting dosage form, wherein each of the R e is independently linear or sub-divided from 4 to 12 carbon atoms. The alkyl group, and each R f are each independently 1 to 8, more preferably a linear or branched alkyl group of 1 or 2 to 4 carbon atoms.
對藉由讓聚醯胺寡聚物或遙爪聚醯胺與具有二或更多個反應性基團的共反應物反應來製得聚合物來說，上述的聚醯胺寡聚物及遙爪聚醯胺係有用的，其中該反應性基團當與該聚醯胺寡聚物或遙爪聚醯胺之官能基(例如，該聚醯胺的這些官能基包括一級及二級胺、一級或二級羥基、或羧酸基團)反應時可形成化學鍵。在該共反應物上的反應性基團可係異氰酸酯；或使用特別的遙爪聚醯胺時，它們可係羥基、胺或羧酸基團。 For the preparation of a polymer by reacting a polyamido oligo or telechelic polyamine with a co-reactant having two or more reactive groups, the above-mentioned polyamine oligomer and remote Cleavage polyamines useful in that the reactive group is a functional group with the polyamido oligo or telechelic polyamine (for example, these functional groups of the polyamine include primary and secondary amines, A primary or secondary hydroxyl group, or a carboxylic acid group) can form a chemical bond upon reaction. The reactive groups on the co-reactant may be isocyanates; or when particular telechelic polyamines are used, they may be hydroxyl, amine or carboxylic acid groups.
雖然不意欲由理論限制，咸信於本文中所描述的遙爪聚醯胺獨特地適合於使用在包括TPU的聚合物之製備。此主要係由於其黏度性質及其相對低的玻璃轉換溫度。這些性質使得於本文中所描述的遙爪聚醯胺更易於在通常使用來製備聚合物如TPU之條件下使用及處理，因此克服使用聚醯胺材料的明顯阻礙，其中該阻礙使得先前難以有效使用聚醯胺材料來製備TPU。 While not intending to be limited by theory, the telechelic polyamines described herein are uniquely suited for use in the preparation of polymers including TPU. This is mainly due to its viscosity properties and its relatively low glass transition temperature. These properties make the telechelic polyamine described herein easier to use and handle under conditions commonly used to prepare polymers such as TPU, thus overcoming significant impediments to the use of polyamine materials, which hinder previous difficulties Polyurethane materials were used to prepare the TPU.
本發明的聚合物亦可與一或多種習知聚合物摻合。例如，本發明的一或多種聚合物可與聚酯TPU、聚醚TPU、聚碳酸酯TPU或其任何組合物理摻合。 The polymers of the present invention may also be blended with one or more conventional polymers. For example, one or more polymers of the present invention can be physically blended with a polyester TPU, a polyether TPU, a polycarbonate TPU, or any combination thereof.
本發明的聚合物之重量平均分子量(Mw)範圍可係80,000至600,000克/莫耳，或100,000至300,000，或80,000至約250,000克/莫耳。該聚合物的Mw係根據凝膠滲透層析法(GPC)對著標準聚苯乙烯測量。 The weight average molecular weight (Mw) of the polymer of the present invention may range from 80,000 to 600,000 g/mole, or from 100,000 to 300,000, or from 80,000 to about 250,000 g/mole. The Mw of the polymer was measured against gel permeation chromatography (GPC) against standard polystyrene.
本發明的TPU聚合物可與多種習知添加劑或複合劑混合，諸如充填劑、抗氧化劑、抗臭氧劑、抗水 解劑、擠壓助劑、UV安定劑、鏈終止劑、光安定劑、著色劑、增量劑、顏料、潤滑劑、塑化劑、阻燃劑、UV吸收劑及其類似物。可使用的充填劑包括滑石、矽酸鹽、黏土、碳酸鈣及其類似物。該添加劑之程度將依想要的最終用途應用之最後性質及成本而定，如係由熟悉複合TPUs技藝之人士所熟知。該等添加劑可在反應以形成TPU期間或在第二複合步驟中加入。 The TPU polymer of the present invention can be mixed with various conventional additives or complexing agents, such as a filler, an antioxidant, an antiozonant, and a water resistant Decomposers, extrusion aids, UV stabilizers, chain terminators, light stabilizers, colorants, extenders, pigments, lubricants, plasticizers, flame retardants, UV absorbers and the like. Fillers that can be used include talc, citrate, clay, calcium carbonate, and the like. The extent of the additive will depend on the final nature and cost of the desired end use application, as is well known to those skilled in the art of composite TPUs. The additives may be added during the reaction to form the TPU or during the second compounding step.
抗氧化劑典型防止或終止造成聚胺基甲酸酯物件在該物件的壽命內降解之氧化反應。典型的抗氧化劑包括酮類、醛類及芳基胺類、和酚型化合物。特定的化合物實施例包括伸乙基雙(氧基伸乙基)雙(3-三級丁基-4-羥基-5-甲基桂皮酸酯)及肆-[亞甲基(3,5-雙三級丁基-4-羥基氫桂皮酸酯)]甲烷。合適的商業抗氧化劑之實施例包括Irganox 1010、Irganox 1098、Irganox 565及Irganox 1035(Ciba-Geigy Corp.，Ards1ey，N.Y.)。 Antioxidants typically prevent or terminate the oxidation reaction that causes the polyurethane article to degrade over the life of the article. Typical antioxidants include ketones, aldehydes and arylamines, and phenolic compounds. Specific examples of specific compounds include ethyl bis(oxyethyl) bis(3-tert-butyl-4-hydroxy-5-methylcinnamate) and hydrazine-[methylene (3,5-double) Tert-butyl-4-hydroxyhydrocinnamate)]methane. Examples of suitable commercial antioxidants include Irganox 1010, Irganox 1098, Irganox 565, and Irganox 1035 (Ciba-Geigy Corp., Ards Iey, N.Y.).
抗臭氧劑防止或減低由臭氧造成的損傷，及抗水解劑防止或減低由水及其它水解化合物損傷。合適的抗臭氧劑實施例包括對-苯二胺衍生物。該抗水解劑包括例如Stabaxol P及Stabaxol P-200(Rhein Chemie，Trenton，N.Y.)。 Antiozonants prevent or reduce damage caused by ozone, and anti-hydrolysis agents prevent or reduce damage from water and other hydrolyzed compounds. Suitable antiozonant examples include p-phenylenediamine derivatives. Such anti-hydrolysis agents include, for example, Stabaxol P and Stabaxol P-200 (Rhein Chemie, Trenton, N.Y.).
擠壓助劑使得聚胺基甲酸酯容易移動通過擠壓器。蠟諸如Wax E(Hoechst-Celanese Corp.，Chatham，N.J.)、Acrawax(Lonza Inc.，Fair Lawn，N.Y.)及氧化的聚乙烯629A(Allied-Signal Inc.，Morristown，N.J.)係合適的擠壓助劑。這些擠壓助劑亦可作用為脫模劑，或可將額外的脫模劑加入至該組成物。 The extrusion aid allows the polyurethane to move easily through the extruder. Waxes such as Wax E (Hoechst-Celanese Corp., Chatham, NJ), Acrawax (Lonza Inc., Fair Lawn, NY), and oxidized polyethylene 629A (Allied-Signal Inc., Morristown, NJ) are suitable extrusion aids. Agent. These extrusion aids may also function as a release agent, or an additional release agent may be added to the composition.
使用鏈終止劑來控制分子量。該鏈終止劑的實施例包括具有8或更多個碳原子之單醇化合物。 Chain terminators are used to control molecular weight. Examples of the chain terminator include monoalcohol compounds having 8 or more carbon atoms.
光安定劑防止或減低聚合物產物由於可見或紫外光降解。合適的光安定劑之實施例包括苯并***，諸如Tinuvin P；及位阻胺光安定劑，諸如Tinuvin 770。 Light stabilizers prevent or reduce degradation of the polymer product due to visible or ultraviolet light. Examples of suitable light stabilizers include benzotriazoles such as Tinuvin P; and hindered amine light stabilizers such as Tinuvin 770.
通常來說，本發明的組成物聚焦在熱塑性聚胺基甲酸酯上。在某些具體實例中，本發明的組成物實質上無及甚至無熱固性聚胺基甲酸酯，其例如由於明顯的交聯或類似反應係無法再熔化或再加工的材料，此係熱固性材料的特徵。 Generally, the compositions of the present invention are focused on a thermoplastic polyurethane. In certain embodiments, the compositions of the present invention are substantially free of or even thermoset-free polyurethanes, such as materials that are not remeltable or reprocessable due to significant crosslinking or similar reactions, which are thermoset materials. Characteristics.
本發明的聚合物特別適合用於習知聚合物及更特別是習知TPU所不具有而需要耐溶劑性、水解穩定性、氧化穩定性、熱穩定性及/或對極性材料之黏附程度的應用群。這些應用包括注塑成型物件、汽車外部物件、電子構件、擠壓膜或其組合。 The polymers of the present invention are particularly suitable for use in conventional polymers and more particularly in conventional TPUs which require solvent resistance, hydrolytic stability, oxidative stability, thermal stability and/or adhesion to polar materials. Application group. These applications include injection molded articles, automotive exterior articles, electronic components, extruded films, or combinations thereof.
在某些具體實例中，於本文中所描述的聚合物組成物係使用來製造注塑成型物件。在某些具體實例中，於本文中所描述的聚合物組成物係使用來製造汽車外部物件。在某些具體實例中，於本文中所描述的聚合物組成物係使用來製造電子構件。在某些具體實例中，於本文中所描述的聚合物組成物係使用來製造擠壓膜。於本文中所描述的聚合物組成物已顯示出其本身具有異常相當適合於這些最終用途應用及/或加工方法之平衡性質。 In certain embodiments, the polymer compositions described herein are used to make injection molded articles. In certain embodiments, the polymer compositions described herein are used to make automotive exterior articles. In certain embodiments, the polymer compositions described herein are used to make electronic components. In certain embodiments, the polymer compositions described herein are used to make extruded films. The polymer compositions described herein have been shown to have inherently anomalous properties that are quite suitable for these end use applications and/or processing methods.
雖然為了闡明本發明的目的已經顯示出某些典型的具體實例及細節，將由熟悉此技藝之人士明瞭，可在其中製得多種改變及修改而沒有離開本發明的範圍。 While the invention has been shown and described with reference to the embodiments of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made therein without departing from the scope of the invention.
本發明將藉由下列之提出特別優良的具體實例之實施例進一步闡明。雖然提供該等實施例來闡明本發明，但其不想要限制本發明。 The invention will be further elucidated by the following examples of specific examples which are particularly preferred. While the examples are provided to illustrate the invention, it is not intended to limit the invention.
製備一系列的脂肪族熱塑性聚胺基甲酸酯(TPU)，其包括數個使用亦可指為1,6-己烷二異氰酸酯的二異氰酸己二酯(HDI)及包含於本文中所描述的遙爪聚醯胺之多元醇組分所製得的發明實施例。這些TPU係與使用標準商業多元醇製得的類似材料比較，以評估多種性質的差異，包括較高耐熱性。 Preparation of a series of aliphatic thermoplastic polyurethanes (TPU) comprising several dihexyl diisocyanates (HDI), which may also be referred to as 1,6-hexane diisocyanate, and are included herein Inventive examples of the polyol component of the telechelic polyamine described. These TPUs are compared to similar materials made using standard commercial polyols to evaluate differences in various properties, including higher heat resistance.
該等TPU實施例係藉由在反應條件下，讓多元醇組分、聚異氰酸酯、及當存在時，鏈伸長劑組分反應而製備。使用40ppm的錫觸媒。為了更適當地比較，該等TPU組成物的硬鏈段係從18%改變至40%，以製造出不同硬度之TPU。 The TPU examples are prepared by reacting a polyol component, a polyisocyanate, and, when present, a chain extender component, under reaction conditions. A 40 ppm tin catalyst was used. For a more appropriate comparison, the hard segments of the TPU compositions were varied from 18% to 40% to produce TPUs of different hardnesses.
該等實施例使用下列多元醇組分：(i)一包含遙爪聚醯胺之多元醇組分，其係從癸二酸及十二烷二酸、哌及聚氧化四亞甲基(PTMO)製備，其具有重量平均分子量約1600，指為A-POLYOL A；(ii)一包含遙爪聚醯胺的多元醇組分，其係從癸二酸、哌及PTMO製備，其具有重量平均分子量約2600，指為A-POLYOL B；(iii) 一包含遙爪聚醯胺的多元醇組分，其係從癸二酸、哌及PTMO製備，其具有重量平均分子量約2100，指為A-POLYOL C；(iv)一包含遙爪聚醯胺的多元醇組分，其係從癸二酸、哌及PTMO製備，其具有重量平均分子量約3100，其指為A-POLYOL D；(v)一包含遙爪聚醯胺的多元醇組分，其係從癸二酸、哌及PTMO製備，其具有重量平均分子量約4100，其指為AMIDE POLYOL E；然後係用於比較用材料，(vi)一具有重量平均分子量約2000的聚己內酯聚酯多元醇，其指為POLYOL F；(vii)一具有重量平均分子量約1000的聚丁二醇聚醚多元醇，其指為POLYOL G；及(viii)一具有重量平均分子量約2000的線性、羥基終端脂肪族聚碳酸酯，其可從Bayer商業購得如為DesmophenTM C2200，指為POLYOL H。 The examples use the following polyol components: (i) a polyol component comprising telechelic polyamine, which is derived from azelaic acid and dodecanedioic acid, piperazine And polyoxytetramethylene (PTMO) prepared having a weight average molecular weight of about 1600, referred to as A-POLYOL A; (ii) a polyol component comprising telechelic polyamine, which is derived from azelaic acid, Piper And PTMO prepared having a weight average molecular weight of about 2600, referred to as A-POLYOL B; (iii) a polyol component comprising telechelic polyamine, which is derived from azelaic acid, piperidine And PTMO prepared having a weight average molecular weight of about 2100, referred to as A-POLYOL C; (iv) a polyol component comprising telechelic polyamine, which is derived from azelaic acid, piperazine And PTMO prepared having a weight average molecular weight of about 3,100, which is referred to as A-POLYOL D; (v) a polyol component comprising telechelic polyamine, which is derived from azelaic acid, piperazine And PTMO prepared having a weight average molecular weight of about 4,100, which is referred to as AMIDE POLYOL E; then for comparison materials, (vi) a polycaprolactone polyester polyol having a weight average molecular weight of about 2000, which is referred to as POLYOL F; (vii) a polytetramethylene glycol polyether polyol having a weight average molecular weight of about 1000, which is referred to as POLYOL G; and (viii) a linear, hydroxyl terminated aliphatic polycarbonate having a weight average molecular weight of about 2,000 , which is commercially available from Bayer such as Desmophen TM C2200, refers to the POLYOL H.
該等實施例使用下列聚異氰酸酯組分：(i)二異氰酸己二酯(HDI)；及係用於比較用材料，甲烷-4,4’-二異氰酸二苯基酯(MDI)。 These examples use the following polyisocyanate components: (i) hexamethylene diisocyanate (HDI); and the material used for comparison, methane-4,4'-diphenylisocyanate (MDI) ).
全部實施例係使用1,4-丁二醇(BDO)作為鏈伸長劑。 All of the examples used 1,4-butanediol (BDO) as a chain extender.
該等實施例係總整理在下列表中。 These examples are summarized in the following list.
藉由本發明家所發展的方法，使用動態機械分析儀來評估每個實施例的耐熱性及決定在頻率1Hz下tan δ等於1時的溫度。tan δ等於1時所報導的值愈高，樣品耐熱性愈好。樣品特徵亦包括藉由ASTM D 2240決定Shore硬度，藉由ASTM D412決定張力及伸長特徵，及藉由ISO 4649決定磨耗損失。使用數位霧度測量儀(BYK Haze-gard plus)測量在2毫米厚飾板中的霧值，其中較低值指示出較好的結果。在NMP溶液中對著PS標準物測量GPC。下表總整理出關鍵結果及包括比較。 The dynamic mechanical analyzer was used to evaluate the heat resistance of each of the examples by the method developed by the inventors and to determine the temperature at which tan δ is equal to 1 at a frequency of 1 Hz. The higher the value reported when tan δ is equal to 1, the better the heat resistance of the sample. Sample characteristics also include Shore hardness as determined by ASTM D 2240, tension and elongation characteristics as determined by ASTM D412, and abrasion loss by ISO 4649. The haze value in a 2 mm thick plaque was measured using a digital haze meter (BYK Haze-gard plus), with lower values indicating better results. GPC was measured against the PS standard in NMP solution. The table below summarizes key results and includes comparisons.
對某些樣品測試額外的性質。藉由ASTM D-792決定密度。藉由將模塑樣品保持在80℃及95%RH的氣候艙中數週測量耐氣候性，然後藉由ASTM D412決定測量抗張強度保留率，其中較高的物理性質保留率指示出較好的耐氣候性質。藉由本發明人發展的方法，使用氙氣燈測試儀器(xenotest instrument)及UV-A，10小時，80℃，550瓦之條件來評估抗UV性，及測量在曝光前後之黃色指數(YI)，其中較低的值及較小的改變指示出較好的抗UV性。下表總整理出所收集的結果，其中空白欄指示出該實施例的該測試之資料係未收集。 Additional properties were tested on certain samples. Density is determined by ASTM D-792. The weatherability was measured by keeping the molded samples in a climate chamber at 80 ° C and 95% RH for several weeks, and then measuring the tensile strength retention rate by ASTM D412, where a higher retention rate of physical properties indicates better. Weather resistant properties. The anti-UV property was evaluated by the method developed by the present inventors using a xenotest instrument and a UV-A, 10 hours, 80 ° C, and 550 watts, and the yellow index (YI) before and after exposure was measured. Lower values and smaller changes indicate better UV resistance. The table below summarizes the collected results, with a blank column indicating that the data for this test for this example was not collected.
結果顯示出本發明的芳香族聚合物組成物提供獨特的性質組合，此使得其非常良好地適合於需要強的物理性質及好的耐熱性，和選擇性好的耐氣候性及/或抗UV性之應用。如由上述提供的參考實施例闡明，這些性質組合未顯現在其它類似的聚合物組成物中。 The results show that the aromatic polymer composition of the present invention provides a unique combination of properties which makes it very well suited to require strong physical properties and good heat resistance, and good weatherability and/or UV resistance. Application of sex. As exemplified by the reference examples provided above, these combinations of properties are not manifested in other similar polymer compositions.
上述提出的每篇文件係以參考方式併入本文。除了在實施例中或其它方面指示出外，要了解的是，在此說明中具體指定的量、反應條件、分子量、碳原子數目等等之全部數值量係藉由措辭「約」修飾。除非其它方面有指示出，否則全部百分比及配方值係以莫耳為基礎。除非其它方面有指示出，否則全部分子量係數量平均分子量。除非其它方面有指示出，否則於本文中指出的每種化學或組成物應該解釋為商業等級材料，其可包括正常了解存在於商業等級中之異構物、副產物、衍 生物及其它此材料。但是，每種化學組分的量係以不包括可習慣上存在於商業材料中之任何溶劑或稀釋劑呈現，除非其它方面有指示出。要瞭解於本文中提出的上下量、範圍及比率極限可各自獨立地結合。類似地，本發明的每種元件之範圍及量可與任何其它元件的範圍或量一起使用。如於本文中所使用，用詞「實質上由...組成」准許內含不顯著影響在考量下之組成物的基本及新穎特徵之物質。於本文中所描述的本發明之全部具體實例考慮到開放式及內含式觀點(即，使用「包含」的文字)與封閉式及專屬式觀點(即，使用「由...組成」的文字)二者及可以此方式讀取。如於本文中所使用，使用圓括號標明出1)某些事情係選擇性存在，諸如單體(類)意謂著單體或許多單體，或(甲基)丙烯酸酯意謂著甲基丙烯酸酯或丙烯酸酯；2)限定或進一步定義先前提到的用語；或3)列出較窄的具體實例。 Each of the documents set forth above is incorporated herein by reference. Except in the examples or other aspects, it is to be understood that all numerical values specified in the specification, such as amounts, reaction conditions, molecular weight, number of carbon atoms, and the like, are modified by the word "about." All percentages and recipe values are based on Moore unless otherwise indicated. All molecular weight coefficients are average molecular weights unless otherwise indicated. Unless otherwise indicated, each chemistry or composition referred to herein should be interpreted as a commercial grade material, which may include normal understanding of the isomers, by-products, derivatives present in the commercial grade. Biological and other such materials. However, the amount of each chemical component is presented without any solvent or diluent that may be customarily present in the commercial materials, unless otherwise indicated. It is to be understood that the upper and lower amounts, ranges, and ratio limits set forth herein can be independently combined. Similarly, the scope and amount of each element of the invention can be used with the scope or amount of any other element. As used herein, the term "consisting essentially of" permits the inclusion of a substance that does not materially affect the basic and novel characteristics of the composition under consideration. All of the specific examples of the invention described herein take into account open and inclusive views (ie, using "contained" text) and closed and proprietary views (ie, using "consisting of" Text) Both can be read in this way. As used herein, the use of parentheses indicates that 1) certain things are selective, such as monomer (class) means monomer or many monomers, or (meth) acrylate means methyl Acrylate or acrylate; 2) define or further define the previously mentioned terminology; or 3) list narrower specific examples.
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