TWI648340B - 熱塑性聚胺基甲酸酯、其製造及用途 - Google Patents
熱塑性聚胺基甲酸酯、其製造及用途 Download PDFInfo
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- TWI648340B TWI648340B TW104110613A TW104110613A TWI648340B TW I648340 B TWI648340 B TW I648340B TW 104110613 A TW104110613 A TW 104110613A TW 104110613 A TW104110613 A TW 104110613A TW I648340 B TWI648340 B TW I648340B
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- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
本發明關於熱塑性聚胺基甲酸酯類,關於製造該等之方法,及關於該等之用途。
Description
本發明關於熱塑性聚胺基甲酸酯類,關於製造該等之方法,及關於該等之用途。
由於熱塑性聚胺基甲酸酯類(TPUs)具有良好彈性體性質及熱塑性可加工性,它們有很大產業重要性。綜觀TPUs的製造、性質及應用藉由實施例方式被記載於Kunststoff Handbuch[Plastics Handbook][G.Becker,D.Braun],volume 7 "Polyurethane"[Polyurethanes],Carl Hanser Verlag,Munich,Vienna,1983。其它的TPUs的總覽見於Kunststoffe[Plastics]68(1978),第819至825頁及Kautschuk,Gummi,Kunststoffe[Natural rubber,rubber,plastics]35(1982),第568至584頁。
TPUs多數由線性多醇類(聚二醇類)所構成,e.g.聚酯二醇類、聚醚二醇類或聚碳酸酯二醇類、有機二異氰酸酯類及短鏈、主要二元醇類(鏈伸長劑)。它們可被連續地或批次式製得。最有名製造方法為傳送帶式方法(belt process)(GB-A 1 057 018)及擠壓機方法(DE-A
19 64 834)。
該熱塑性可加工的聚胺基甲酸酯彈性體可依步驟(預聚物方法)或經由在一個階段中全部成分之同時反應(一階(one-shot)方法)所建構。
有許多不同加工TPUs之技術,e.g.注射模塑(injection moulding)、擠壓、壓延、粉末濺潑方法(powder slush process)。因而可以製造對於很廣的各種應用之模塑件(mouldings)、型體(profiles)、薄膜、箔片、表層(skins)等,及各個該等用途在聚合物材料上置有特定要求。市場因此持續需求對於各種應用之具新穎或改進性質之TPUs。
因此本發明之一目的係提供一種具改進性質之熱塑性聚胺基甲酸酯類。
令人驚訝地,所述目的係經由以聚氧亞甲基嵌段共聚物(polyoxymethylene block copolymers)為基底的,特別是以多聚甲醛(paraformaldehyde)-系多醇類為基底的熱塑性聚胺基甲酸酯類來達成。
本發明提供一種熱塑性聚胺基甲酸酯類,其可獲自下述成分之反應:
a)至少一種有機二異氰酸酯,b)對異氰酸酯類有反應性之化合物及其在各情形中具有數目-平均莫耳質量為500至10 000g/mol,此處在b)裡的成分整體的數目-平均官能度為1.8至2.5,及c)鏈伸長劑在各情形中具有數目-平均莫耳質量為60至490g/mol,此處在c)裡的鏈伸長劑整體的數目-平均官能度為1.8至2.5,存在有d)選擇性催化劑,e)選擇性單官能性鏈終止劑,f)選擇性助劑及/或其他材料,此處成分b)包含至少一種以多聚甲醛(b1)為基底的多醇。
本發明進一步提供一種製造本發明熱塑性聚胺基甲酸酯類之方法,係經由下述反應
a)至少一種有機二異氰酸酯與b)對異氰酸酯類有反應性之化合物及其在各情形中具有數目-平均莫耳質量為500至10 000g/mol,此處在b)裡的成分整體的數目-平均官能度為1.8至2.5,及c)鏈伸長劑,其具有對異氰酸酯類有反應性之基團及其在各情形中具有數目-平均莫耳質量為60至490g/mol,此處在c)裡的鏈伸長劑整體的數目-平均官能度為1.8至2.5,較佳地1.8至2.2,
存在有d)選擇性催化劑,及e)選擇性單官能性鏈終止劑,及f)選擇性助劑及/或其他材料,此處成分b)包含至少一種以多聚甲醛(b1)為基底的多醇。
本發明TPUs之硬度可經由相當廣的構造成分a)至c)之莫耳比變化來調整。
在成分b)及c)中對異氰酸酯類有反應性之基團與在成分a)中異氰酸酯基團之莫耳比較佳為0.8:1.0至1.2:1.0,特佳地0.9:1.0至1.1:1.0。
本發明之熱塑性聚胺基甲酸酯類係藉已知方法,通常在一傳送帶式系統中或在一反應性擠壓機中一階或預聚物方法,製得的。涵蓋於該反應中的成分a)至c),於此在選擇性d)、e)及f)之存在下,共同或依所指定順序被組合,及經反應。在該反應性擠壓機方法之例中,該構造成分a)至c),在d)及選擇性e)與f)之存在下,個別地連續或共同以一混合物的形式被引入該擠壓機內,e.g.於溫度為100°至250℃,較佳地150°至230℃,及經反應。該最終的TPU從該擠壓機被排出,經冷卻,及經粒化。
可使用已知方法,諸如注射模塑、擠壓、壓延、或燒結,例如,用於本發明TPUs之加工,其通常以粒化材料或粉末之形式使用,以
得到塑膠部件諸如薄膜、表層、塗層及箔片。
TPUs之注射模塑及擠壓為熟知的且廣被敘述。在本申請案中經注射模塑的或經擠壓的塑膠部件為任何形式的組件、物件及形體(shapes),其可藉由注射模塑或擠壓之方式製得。藉注射模塑或藉擠壓之加工可在此項技術領域熟習者已知的常用系統中進行。對於塑膠部件製造之加工溫度通常為140°至240℃,及於此經由在該TPU之製造期間藉在成分b)及c)中對異氰酸酯基團有反應性之基團與在成分a)中異氰酸酯基團之比例方式的目標莫耳質量調整,及/或經由使用單官能性鏈終止劑e),可達成至一特定範圍的可用加工溫度之調整作用。
可製自本發明TPUs之表示塑膠部件例舉意指為箔片、門把(door grips)與門密封件(door seals)、旋轉鈕(rotary buttons)與控制鈕(control buttons)、輥件(rollers)、門儲存室(door storage compartments)、扶手(armrests)、工具把手(tool grips)、衝擊性吸收插件(impact-absorbing inserts)、軟件(hoses)、纜線護件(cable sheathing)、氣囊蓋件(airbag covers)、儀錶板(instrument panels)、保險桿條(bumper strips)、汽車天線(automobile antennas)、窗簾(blinds)及飲料支架(drinks holders)。
通常用於本發明TPUs製造之成分a)至f)藉例舉敘述如下:所用的有機二異氰酸酯類a)為常用芳香族、脂族及/或環脂族二異氰酸酯類。可述及的各個實例為:芳香族二異氰酸酯類,例如伸甲苯基2,4-二異氰酸酯,伸甲苯基2,4-二異氰酸酯與伸甲苯基2,6-二異氰酸酯之混合物,二苯基甲烷4,4'-二異氰酸酯,二苯基甲烷2,4'-二異氰酸酯及二苯基甲烷2,2'-二異氰酸酯,二苯基甲烷2,4'-二異氰酸酯與二苯基甲烷4,4'-二異氰酸酯之混合物,4,4'-二異氰酸酯基-1,2-二苯基乙烷,伸萘基1,5-二異氰酸酯,及胺基甲酸酯-改質的液體二苯基甲烷4,4'-二異氰酸酯類及二苯基甲烷2,4'-二異氰酸酯類。作為芳香族有機二異氰酸酯類,較佳使用二苯基甲烷二異氰酸酯異構物混合物,其含>96重量%二苯基甲烷4,4'-二異氰酸酯含量及特別是二苯基甲烷4,4'-二異氰酸酯與伸萘基1,5-二異氰酸酯。所述及的二異氰酸酯類可單獨地或以彼此的混合物形式使用。它們還可與至多15重量%(以二異氰酸酯的總量為基準)的多異氰酸酯,例如三苯基甲烷4,4',4"-三異氰酸酯或聚苯基聚亞甲基聚異氰酸酯類,一起使用。
可使用的其它二異氰酸酯類a)為脂族及環脂族二異氰酸酯類。可提及例舉為六亞甲基二異氰酸酯,異佛爾酮二異氰酸酯,環己烷1,4-二異氰酸酯,1-甲基環己烷2,4-二異氰酸酯與1-甲基環己烷2,6-二異氰酸酯,還有對應異構物混合物及二環己基甲烷4,4'-、2,4'-與2,2'-二異氰酸酯,還有對應異構物混合物。其較佳是所用的脂族有
機二異氰酸酯由至少50重量%,較佳地75重量%及特佳地100重量%的六亞甲基1,6-二異氰酸酯所構成。
對異氰酸酯類有反應性之可使用的化合物b)為,按照根據本發明欲使用的多聚甲醛-系多醇類,熟知的多羥基化合物,其具數目-平均莫耳質量Mn為500至10 000g/mol,較佳地600至7500g/mol及特佳地800至5000g/mol與適宜的數目-平均官能度為1.8至2.5,特別地1.8至2.2及非常特別地1.9至2.1,此處在b)中成分整體的數目-平均官能度為1.8至2.5,實例為聚酯多醇類、聚醚酯多醇類、聚醚多醇類、聚醚碳酸酯多醇類、己內酯多醇類,及聚碳酸酯多醇類。
適合的聚酯多醇類可例舉為製自具有2至12個碳原子(較佳地4至6個碳原子)的二羧酸,及製自多元醇。可用作為二羧酸例舉如下述:脂族二羧酸,例如丁二酸、順丁烯二酸、戊二酸、己二酸、辛二酸、壬二酸及癸二酸,及芳香族二羧酸,例如鄰苯二甲酸、間苯二甲酸及對苯二甲酸,及所述及的二羧酸之可用的環系酸酐。該二羧酸可單獨地或以混合物形式使用,e.g.以丁二酸、戊二酸與己二酸混合物之形式。對於該聚酯二醇類之製造,替代該二羧酸,有時可有效使用對應二羧酸衍生物,例如在醇部分具有1至4個碳原子之羧酸二酯類,羧酸酐或醯基氯化物。多元醇的實例為具有2至10(較佳地2至6)個碳原子之二醇類,例如乙二醇、二乙二醇、1,2-與1,3-丙烷二醇、1,4-丁烷二醇、1,5-戊烷二醇、1,6-己烷二醇、1,10-癸烷二醇、2,2-二甲基-1,3-丙烷二醇、3-甲基-1,5-戊烷二醇及二丙二醇。該聚酯多醇類之製造還可選擇地使同時使用0至30mol%比例的具有多於2個OH基團之醇類,以所用的二醇類之莫耳數為基準。這些多
元醇的實例為三羥甲基丙烷或丙三醇。該多元醇可單獨地或選擇地以彼此的混合物形式使用,按所希望的性質來要求。其它適合的材料為碳酸與所述及的二醇類之酯類,特別是彼等具有4至6個碳原子,例如1,4-丁烷二醇或1,6-己烷二醇,羥基羧酸的縮合物(condensates),例如羥基己酸,及內酯類的聚合產物,選擇地例舉為經取代的己內酯類。所用的聚酯二醇類較佳為乙烷二醇聚己二酸酯、1,4-丁烷二醇聚己二酸酯、乙烷二醇1,4-丁烷二醇聚己二酸酯、1,6-己烷二醇新戊二醇聚己二酸酯、1,6-己烷二醇1,4-丁烷二醇聚己二酸酯及聚己內酯類。該聚酯二醇類的平均莫耳質量為500至5000,較佳地700至4200g/mol,及它們可獨立地或以彼此的混合物形式使用。
適合的聚醚多醇類可藉使一或多種在伸烷基部分具有2至4個碳原子的環氧烷類(alkylene oxides)與較佳聚有二個結合的活性氫原子的起動劑分子(starter molecule)之反應而製得。作為環氧烷類的實例可如下所述:環氧乙烷,1,2-環氧丙烷,環氧氯丙烷,1,2-環氧丁烷及2,3-環氧丁烷。其較佳是使用環氧乙烷、1,2-環氧丙烷及1,2-環氧丙烷與環氧乙烷的混合物。該環氧烷類可單獨地、以交替接續或以混合物形式使用。可使用的起動劑分子實例為:水,胺醇類,例如N-烷基二乙醇胺類,例如N-甲基二乙醇胺,及二醇類,例如乙二醇、丙-1,2-二醇、丙-1,3-二醇、1,4-丁烷二醇及1,6-己烷二醇。還可以選擇地使用起動劑分子之混合物。其它適合的聚醚二醇類為四氫呋喃之羥化的聚合產物。還可以使用0至30重量%比例的三官能性聚醚類,以二官能性聚醚為基準,但這些量為最多是得到一可熱塑性加工的產物之量。該實質上線性聚醚二醇類之數目-平均莫耳質量Mn
為500至10 000g/mol,較佳地700至4200g/mol。它們既可單獨地或者以彼此的混合物形式或以與另一所述多醇類的混合物使用。
適合的聚碳酸酯多醇類可藉使低分子量碳酸酯(例如二甲基碳酸酯、二乙基碳酸酯或二苯基碳酸酯)與適合的多醇類(較佳地二醇類)之轉酯化而製得,與藉適當的轉酯化催化劑(例如四異丙酸鈦(titanium tetraisopropylate))催化,與消除對應單醇(e.g.甲醇、乙醇或酚)。用於低分子量碳酸酯類之轉酯化的適合二醇類實例為上述提及的用於聚酯多醇類製造之二醇類或者是短鏈聚醚二醇類,e.g.具莫耳質量Mn約250g/mol之聚四氫呋喃。具有特好的適用性之聚碳酸酯多醇類為以1,6-己烷二醇、1,4-丁烷二醇、3-甲基-1,5-戊烷二醇、或這些二醇類的混合物為基底。該實質上線性聚碳酸酯多醇類之數目-平均莫耳質量Mn為500至6000g/mol,較佳地800至4000g/mol。
適合的聚醚碳酸酯多醇類較佳可由特定催化劑(e.g.雙金屬氰化物)催化劑催化經由環氧烷類與二氧化碳之共聚合而製得,或經由低分子量碳酸酯類與聚醚二醇類之轉酯化(如上述)而製得。該實質上線性聚碳酸酯多醇類之數目-平均莫耳質量Mn為500至6000g/mol,較佳地800至4000g/mol。
本發明主要的聚氧亞甲基嵌段共聚物,特別是多聚甲醛-系多醇類b1),較佳為,在下述雙金屬氰化物(DMC)催化劑之存在下,經由使環氧烷類,還有選擇地其它共單體(e.g.CO2),催化性加成到至少一種具有至少一種終端羥基之聚合性甲醛起動劑化合物上,此處
(i)在第一步驟中,該DMC催化劑,在該聚合性甲醛起動劑化合物存在下,藉添加一部分量(以用於活化及聚合方法的環氧烷類量的總量為基準)的一或多種欲活化該DMC催化劑之環氧烷類來達成("活化"),(ii)在第二步驟中,一或多種環氧烷類,還有選擇地其它共單體,被加至該產生自步驟(i)之混合物中;在步驟(ii)中所用的環氧烷類於此可為相同或不同於在步驟(i)中所用的環氧烷類("聚合"),此處在第一步驟(i)中的DMC催化劑之活化係於活化溫度Tact為20°至120℃下進行的。
DMC催化劑理論上為此項用於環氧化物均聚合之先前技術已知的(見例如US 3 404 109 A,US 3 829 505 A,US 3 941 849 A及US 5 158 922 A)。敘述例如於US 5 470 813 A,EP 700 949 A,EP 743 093 A,EP 761 708 A,WO 97/40086 A,WO 98/16310 A及WO 00/47649 A之DMC催化劑在環氧化物之均聚合中具有很高的活性及允許在很低的催化劑濃度(25ppm或更少)下製造聚醚多醇類。敘述於EP-A 700 949之高活性DMC催化劑為一典型實例,包含不只一雙金屬氰化物化合物(e.g.鋅-六氰基鈷酸鹽(III))及一有機配位基(e.g.tert-丁醇)還有一具數目-平均莫耳質量Mn大於500g/mol之聚醚。
該DMC催化劑之用量主要小於1重量%,較佳地小於0.5重量%,特佳地小於500ppm及特別是小於300ppm,以在各例中該聚醚碳酸酯多醇的重量為基準。
適合的聚合性甲醛起動劑化合物理論上為彼等甲醛之寡聚性及聚合性形式,其具有至少一種用於與環氧烷類及與選用的其它共單體反應之終端羥基基團。該表示"終端羥基基團"特別是意指一終端半縮醛官能度,此為一經由該甲醛之聚合製得的構造特點。例舉,該起動劑化合物可為具有通式HO-(CH2O)n-H之甲醛的線性寡聚物及聚合物,式中n為2的整數及式中聚合性甲醛典型地具有重複單元的數目n為8及100。
已知小痕量水的存在係足以聚合甲醛。在水溶液中形成的材料因此,取決於該溶液的濃度與溫度,為一與分子的甲醛及甲醛水合物平衡之不同鏈長度的寡聚物及聚合物之混合物。該材料已知為多聚甲醛沉澱物於此為一白色、來自溶液之不良溶解性的固體及一般為線性甲醛聚合物之混合物,此處重複氧亞甲基單元的數目n為8至100。其較佳是使用後者混合物。
適用於本發明TPUs之聚氧亞甲基嵌段共聚物為聚合性化合物,其包含至少一種聚氧亞甲基嵌段,還有至少一種由環氧烷類或環氧烷類與其它共單體製成的其它寡聚性嵌段(e.g.聚氧烷烯嵌段或聚氧烷烯碳酸酯嵌段),及其較佳不超過四位數範圍內的分子量。
該聚氧亞甲基嵌段共聚物提供許多優於現存聚合物之優點。藉由聚氧亞甲基嵌段相較於其它寡聚性嵌段之長度之方式,其可以達到一定物理性質之目標控制,例如玻璃轉移溫度、熔融範圍、黏度及溶解度。最終聚氧亞甲基嵌段共聚物之合成性可變的區段結構更
且允許提供於一分子程度之經裁製的"硬-軟"區段。
本發明聚氧亞甲基嵌段共聚物之半晶質度典型地為比相同分子量的聚氧亞甲基均聚物較低;該玻璃轉移溫度、熔點及黏度也是較低。化學的及熱的穩定度明顯較高。所用的聚氧亞甲基嵌段共聚物在各種溶劑中一般更是具有良好溶解度,及主要地可容易被熔解及沒有質量損失或於低溫下為液體。相比於聚氧亞甲基均聚物,該聚氧亞甲基嵌段共聚物展現明顯較好的可加工性。
相比於相同分子量的聚醚多醇類,製自對應環氧烷類的聚氧烷烯單元之比例以相對於聚氧亞甲基含量之量減少,與最終對有利的產物成本效率有貢獻。
可使用的對異氰酸酯類有反應性之其它化合物c)(已知為鏈伸長劑)為熟知的多羥基化合物及/或多胺化合物,其具數目-平均莫耳質量為60至490g/mol,較佳地60至400g/mol及特佳地62至300g/mol,較佳此處該鏈伸長劑c)整體的數目-平均官能度為1.8至2.5,較佳地1.8至2.2及特佳地1.9至2.1。適合的多胺化合物實例為二胺類,例如(環)脂族二胺類,例如,異佛爾酮二胺、乙二胺、1,2-丙二胺、1,3-丙二胺、N-甲基丙-1,3-二胺、N,N'-二甲基乙二胺及芳香族二胺類,例如2,4-甲苯基二胺、2,6-甲苯基二胺、3,5-二乙基-2,4-甲苯基二胺或3,5-二乙基-2,6-甲苯基二胺或一級單-、二-、三-或四烷基-取代的4,4'二胺基二苯基甲烷類。還可以使用胺醇類,e.g.N-2-(甲基胺基)乙醇或3-(甲基胺基)-1-丙醇作為鏈伸長劑c)。作為鏈伸長劑c),較佳是使用選自下述組群之一或多種化合物,具有2至14個碳原
子之脂族二醇類,例如乙烷二醇、1,2-丙烷二醇、1,3-丙烷二醇、1,4-丁烷二醇、2,3-丁烷二醇、1,5-戊烷二醇、3-甲基-1,5-戊烷二醇、1,6-己烷二醇、1,8-辛烷二醇、1,10-癸烷二醇、1,12-十二烷二醇、二乙二醇、二丙二醇、1,4-環己烷二醇、1,4-二甲醇環己烷及新戊二醇。
然而,其它適合的化合物為對苯二甲酸與具有2至4個碳原子的二醇類之二酯類,e.g.雙(乙二醇)對苯二甲酸酯或雙(1,4-丁烷二醇)對苯二甲酸酯、氫醌的羥基伸烷基醚類,例如1,4-雙(β-羥乙基)氫醌,及乙氧化的雙酚化合物,例如1,4-二(β-羥乙基)雙酚A。於開環反應中所述及的二醇類還可與各種莫耳量的ε-己內酯反應,得到具數目-平均莫耳質量至多490g/mol的對應鏈伸長劑。特佳使用的鏈伸長劑為乙烷二醇、1,4-丁烷二醇、1,6-己烷二醇、1,4-二甲醇環己烷、1,4-二(β-羥乙基)氫醌及1,4-二(β-羥乙基)雙酚A及這些與ε-己內酯之反應產物。還可以添加(伴隨這些)相當少量(至多10重量%,以成分c)的總量為基準)的三醇類,e.g.三羥甲基丙烷或丙三醇。
適合的催化劑d)可選擇地被用於本發明方法之第一及/或第二步驟中。適用於TPUs製造之催化劑為三級胺類,其為先前技術中常用且已知的,e.g.三乙基胺、二甲基環己基胺、N-甲基嗎啉、N,N'-二甲基哌嗪、2-(二甲基胺基乙氧基)乙醇、二氮雜二環[2.2.2]辛烷,還有有機金屬性化合物,例如鈦化合物,例如四異丙酸鈦、四丁酸鈦、鈦-鉗合複合化合物,鐵化合物,例如乙醯丙酮酸鐵(III),鋯化合物,例如鋯-鉗合複合化合物,或錫化合物,例如二乙酸錫、二辛酸錫、二月桂酸錫或脂族羧酸的二烷基錫鹽,例如二乙酸二丁基錫或二月桂酸二丁基錫。較佳的催化劑為有機金屬性化合物,特別是鈦化合物、鐵化合物、鋯化合物及錫化合物。
在該TPU中催化劑的總量一般為約0至5重量%,較佳地0.0001至1重量%及特佳地0.0002至0.5重量%。
所用的鏈終止劑e)可為具有只有一個對異氰酸酯類a)有反應的基團之化合物,例如單醇類,例如乙醇、1-丙醇、2-丙醇、1-丁醇、1-己醇、1-辛醇或硬脂醇。這些鏈終止劑可用於該TPUs之分子量、熔融黏度及因此還有流變性之控制調整。
可使用的其它助劑及/或其它材料f)為常用添加劑,例如表面-活性物質,滯焰劑,成核劑,潤滑劑與脫模劑,染料,顏料與填充劑,抑制劑,相關於水解、光、熱、氧化或脫色之穩定劑,意欲防止微生物降解之材料,還有強化材料及塑化劑。
本發明之TPUs係適用於本身已知的塑膠加工技術,例如注射模塑,擠壓,壓延,粉末濺潑方法等,及按照要求,在最後產品上提供改進的品質範圍:例舉為模塑件之例中,發現相比於醚-系TPUs有改進的極限拉伸強度及韌性(模量),及較高硬度。
以下實施例意欲提供進一步說明本發明。
多醇1:Acclaim® 2200N,以環氧丙烷為基底的聚醚多醇,具OH數56mg KOH/g,由Bayer MaterialScience AG可商業上取得的產品。
多醇2:聚氧亞甲基嵌段共聚物,以多聚甲醛(20重量%)、環氧丙烷(66重量%)及二氧化碳(14重量%)為基底,具OH數53mg KOH/g。
BDO:1,4-丁烷二醇
MDI:二苯基甲烷4,4'-二異氰酸酯
Tyzor® AA105:鈦催化劑,得自Dorf Ketal
Irganox® 1010:抗氧化劑,得自BASF AG
Licowax® C:脫模劑,得自Clariant International Ltd.
根據表1,各個多醇,1% Licowax® C(以全部混合物為基準)與0.3%的Irganox® 1010(以多醇為基準)在反應容器中用作為初始進料及加熱至200℃,同時攪拌。之後添加20ppm的Tyzor® AA105(以多醇為基準)作為催化劑。加熱至60℃,之後添加該MDI之總量,同時攪拌,及在該反應容器中的溫度於此被降至165℃。在約20秒之後添加總量的1,4-丁烷二醇。在該反應混合物已到達一最大為約215℃
溫度時,以一劇烈程度持續攪拌(持續約7至8秒)。之後將該反應混合物倒入一塗覆金屬片及於80℃下後-調節30分鐘。冷卻得到一鑄造TPU片。
表1敘述用於TPUs製造之各個成分及這些成分之比例。
*非根據本發明
該最終的鑄造TPU片經切碎及粒化。在一Arburg Allrounder 470S注射-模塑機中,於180°至230℃之溫度範圍及於650至750巴之壓力範圍下,以10至35cm3/s之注射速率,加工該粒化材料,以得到棒體(模塑溫度:25℃;棒尺寸:80 x 10 x 4mm)及片體(模塑溫度:25℃;尺寸:125 x 50 x 2mm)。
下述為由該最終的TPUs測定:熔體體積-流速(MVR)及機械值(100%模量,300%模量,極限拉伸強度,斷裂時伸長率及Shore A硬度)。
用於MVR測量之條件,使用得自GöttfertMP-D MVR設備,為190℃以一施重為10kg(98N),以5min.的預熱時間按照ISO 1133。
該拉伸測試,在S1棒上進行(對應於類型5測試樣品按照EN ISO 527,由注射模塑片沖壓出來)按照DIN 53455以200mm/min之拉伸速度。
硬度,按照DIN 53505測得。
以下表2列示所測得數值。
*-非根據本發明
在所製得的三種TPUs之機械性質上發現明顯差異性。對於本發明之TPUs 1及2之100%模量、300%模量及極限拉伸強度在各例中比非根據本發明之TPU 3較高。雖然對於全部三種TPUs而言鏈伸長劑的量是相同的,但二種本發明TPU之Shore A硬度還比該對照的TPU較高。該三種TPUs之斷裂時伸長率值為於非常高程度及足以用於全部應用。
Claims (3)
- 一種熱塑性聚胺基甲酸酯,可獲自下述成分之反應:a)至少一種有機二異氰酸酯,b)對異氰酸酯類有反應性之化合物,及其在各情形中具有數目-平均莫耳質量為500至10 000g/mol,其中在b)裡的成分整體的數目-平均官能度為1.8至2.5,及c)鏈伸長劑,在各情形中具有數目-平均莫耳質量為60至490g/mol,其中在c)裡的鏈伸長劑整體的數目-平均官能度為1.8至2.5,存在有d)視需要之催化劑,e)視需要之單官能性鏈終止劑,f)視需要之助劑及/或其它材料,其中成分b)包含至少一種以多聚甲醛為基底的多醇(b1),其中該以多聚甲醛為基底的多醇(b1)係在雙金屬氰化物(DMC)催化劑之存在下,經由使環氧烷類,還有選擇地其它共單體,催化性加成到至少一種具有至少一種終端羥基之聚合性甲醛起動劑化合物上。
- 一種製造根據申請專利範圍第1項之熱塑性聚胺基甲酸酯之方法,係經由下述成分之反應a)至少一種有機二異氰酸酯,與b)對異氰酸酯類有反應性之化合物,及其在各情形中具有數目-平均莫耳質量為500至10 000g/mol,其中在b) 裡的成分整體的數目-平均官能度為1.8至2.5,及c)鏈伸長劑,其具有對異氰酸酯類有反應性之基團及其在各情形中具有數目-平均莫耳質量為60至490g/mol,其中在c)裡的鏈伸長劑整體的數目-平均官能度為1.8至2.5,存在有d)視需要之催化劑,e)視需要之單官能性鏈終止劑,及f)視需要之助劑及/或其它材料,其中成分b)包含至少一種以多聚甲醛為基底的多醇(b1),其中該以多聚甲醛為基底的多醇(b1)係在雙金屬氰化物(DMC)催化劑之存在下,經由使環氧烷類,還有選擇地其它共單體,催化性加成到至少一種具有至少一種終端羥基之聚合性甲醛起動劑化合物上。
- 一種根據申請專利範圍第1項之熱塑性聚胺基甲酸酯於塑膠部件製造之用途。
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