TWI596180B - 胺甲酸乙酯黏著劑 - Google Patents
胺甲酸乙酯黏著劑 Download PDFInfo
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Description
一種有用之黏著劑組成物類別係無溶劑之胺甲酸乙酯黏著劑,其係含有可能與其他成分一起的聚異氰酸酯以及多元醇之液體組成物,。當此組成物係與二個基板接觸以及接著暴露至其中使聚異氰酸酯以及多元醇彼此反應以形成經固化之組成物之條件(諸如昇高之溫度)時,所欲係經固化之組成物於二個基板間形成鍵結。所欲係該黏著劑組成物係具有下述性質之液體組成物:當其第一次混合時係具有相對低的黏度;維持低黏度足夠長的一段時間以徹底混合該成分,以及施用該組成物至基板;於該組成物施用至基板後,相對快速地建立黏著劑強度(「新(green)黏性」(green tack));以及當完全固化時之最終黏合強度可承受熱循環以及暴露於化學品。
美國專利第US 2010/0010110號描述一種撓性聚胺酯發泡物,其係藉由將聚異氰酸酯與高當量多元醇反應而製備,該多元醇係包含至少一種含有至少一種三級胺基團之聚醚或聚酯多元醇。所欲係提供具有部分或全部上述所欲性質之黏著劑組成物。
下述內容係本發明之敘述。
本發明之第一態樣係一種黏著劑組成物,包括:(A)一種或多種聚異氰酸酯以及(B)一種或多種聚合多元醇,其中該聚合多元醇係下述者之反應產物:(I)多元醇引發劑,其中該多元醇引發劑係下述者之反應產物:(a)一種或多種具有結構I之二羥基三級胺化合物:
其中R1係氫或C1至C6直鏈或分支鏈烷基,以及R2以及R3獨立為C1至C6直鏈或分支鏈烷基,以及(b)多羥基醇;(II)一種或多種具有結構X之環氧化合物:
或一種或多種具有結構XI之環氧丙基醚化合物:
或其混合物;其中R4係氫、苯基、環己基、或C1-C18直鏈或分支鏈烷基,以及R5係氫、苯基、C1-C6直鏈或分支鏈之經烷基取代之苯基、或C1-C18直鏈或分支鏈烷基;其中該黏著劑組成物以該黏著劑組成物之重量為基準計,含有含量為0至5重量%之溶劑。
本發明之第二態樣係一種黏合第一基板至第二基板之方法,包括:(i)將如申請專利範圍第1項所述之黏著劑組成物之層施用至該第一基板之表面;(ii)接著將該第二基板之表面與如申請專利範圍第1項所述之黏著劑組成物之層接觸;以及(iii)接著固化如申請專利範圍第1項所述之黏著劑組成物之層。
下述內容係本發明之詳細敘述。
如本文中所使用,下述術語具有所指定之定義,除非文中另有明確指示。
「多元醇」係具有二個或更多個種側接羥基
之化合物。「酯多元醇」係含有一個或多個酯鍵聯之多元醇。「聚酯多元醇」係含有二個或更多個酯鍵聯之多元醇。酯鍵聯係具有結構-C(O)-O-者。「醚多元醇」係具有一種或多種醚鍵聯之多元醇。「聚醚多元醇」係具有二種或更多個種醚鍵聯之多元醇。醚鍵聯係-C-O-C-。「混成多元醇」係含有至少一種酯鍵聯以及至少一種醚鍵聯之多元醇。胺甲酸乙酯鍵聯係-NH-C(O)-O-。
多元醇之特徵在於其羥基數目,其係依據ASTM D4274-11(American Society for Testing and Materials,Conshohocken,PA,USA)測量,並以每公克之KOH微克為單位(mgKOH/g)。此處慮及之羥基數目係未經任何酸度校正者。多元醇之另一特徵在於其酸數,其係使用ASTM D974-12測量,並以mgKOH/g為單位。
「聚異氰酸酯」係具有二個或更多個異氰酸酯基團之化合物。異氰酸酯基團係-NCO。聚異氰酸酯係具有分子量為300或更少,以及不具有脲二酮(uretdione)結構、不具有異氰酸脲酯(isocyanurate)結構、不具有縮二脲(biuret)結構、以及不具有胺甲酸乙酯鍵聯之聚異氰酸酯。聚異氰酸酯二聚體係於脲二酮結構中具有二個聚異氰酸酯單體黏合在一起之分子結構之聚異氰酸酯。聚異氰酸酯三聚體係於異氰酸脲酯結構中具有三個聚異氰酸酯單體黏合在一起之分子結構之聚異氰酸酯。
芳香族化合物係含有一種或多種芳香環之化合物。脂族化合物係不含有芳香環之化合物。
當文中之比率係指稱為X:1或更大時,表示比率係Y:1,其中Y係大於或等於X。舉例而言,若比率係指稱為3:1或更大,則表示比率可係3:1或5:1或100:1,但不會是2:1。相同地,當本文中之比率係指稱為W:1或更少時,表示比率係Z:1,其中Z係小於或等於W。舉例而言,若比率係指稱為15:1或更少,則表示比率可係15:1或10:1或0.1:1,但不會是20:1。
如本文中所使用,「溶劑」係於一定溫度範圍內係液體(該溫度範圍包含20℃至50℃),且不與本發明所使用之任何聚異氰酸酯或多元醇反應之化合物。
如本文中所使用,「膜」係任何組成物之材料,相較於其他二個維度,該材料於一個維度中(稱為「厚度」)相對較小。膜係具有厚度為2微米至1毫米。除了厚度以外,膜之各維度大小係至少為其厚度之100倍。膜係可撓;於25℃,膜可以曲率半徑為1cm彎曲至90°角而不斷裂。膜之「表面」係垂直於厚度維度之膜的平面。
本發明揭露一種用於製造聚醚多元醇之引發劑組成物,以及由此製成之聚胺酯聚合物。引發劑組成物係二羥基三級胺以及多羥基醇(1)之反應產物。較佳係具有下述結構I之二羥基三級胺:
R1係氫或C1-C6直鏈或分支鏈烷基,較佳係C1-C4直鏈或分支鏈烷基,更佳係甲基。R2以及R3係獨立之C1-C6直鏈或分支鏈烷基,較佳係C1-C4直鏈或分支鏈烷基,更佳係乙基。較佳地,該二羥基三級胺係N-甲基二乙醇胺(MDEA)。
合適之多羥基醇(1)係具有2至8個羥基之醇類,該多羥基醇可係C2至C18烷基、芳基、或烷芳基,以及可係直鏈、分支鏈、或環狀。較佳之多羥基醇(1)係亞甲二醇(MEG)、二乙二醇(DEG)、甲基丙二醇(MPG)、二丙二醇(DPG)、甘油、三羥甲基丙烷(TMP)、新戊四醇、以及糖類,諸如蔗糖以及山梨糖醇。最較佳之多羥基醇(1)係甘油、二醇(glycol)、以及糖類。
示於反應圖1之較佳引發劑組成物係MDEA以及甘油之反應產物:
其中x較佳係1至10之整數以及y獨立較佳係1至10之整數。
二羥基三級胺以及多羥基醇(1)之反應產物可包括產物以及部分及/或完全未反應之三級胺及/或多羥基醇(1)之混合物。舉例而言,N-甲基二乙醇胺以及甘油再加上未反應N-甲基二乙醇胺及/或甘油之反應,可產出包括,但不限制於,下列一種或多種等產物之混合物:
較佳地,二羥基三級胺與多羥基醇(1)之莫耳比率係10:1或更少;更佳係5:1或更少;更佳係3:1或更少。較佳地,二羥基三級胺與多羥基醇之莫耳比率係0.1:1或更多;更佳係0.2:1或更多;更佳係0.3:1或更多。
特別較佳之引發劑組成物係於二羥基三級胺以及多羥基醇(1)產物間之反應產物之骨架中,具有大於一種三級胺基團(較佳係N-甲基胺)者。舉例而言,對於結構II,x較佳係大於1,更佳係2,更佳係3,更佳係4,更佳係5。可藉由基質輔助雷射脫附/游離(MALDI)以及核磁共振(NMR)光譜法測定並量化N-甲基胺之存在。
上述引發劑組成物較佳係具有重量平均分子量(Mw)等於或少於5,000,更佳係等於或少於3,000,更佳係等於或少於1,700,更佳係等於或少於1,000。上述引發劑組成物較佳具有Mw等於或大於180,更佳係等於或大於250,以及更佳係等於或大於600。本發明之Mw數據可藉由凝膠滲透層析法測定。
上述引發劑組成物較佳具有平均羥基數目(以mg KOH/g為單位)等於或大於34,更佳係等於或大於56,更佳係等於或大於99,更佳係等於或大於169。上述引發劑組成物較佳具有平均羥基數目等於或少於935,更佳係等於或少於674,更佳係等於或少於280。羥基數目係
以ASTM D4274 D測量。
如上述包括二羥基三級胺I以及多羥基醇(1)之反應產物之引發劑組成物,係有用於製造包括聚合多元醇(B)化合物之聚合多元醇(B)組成物。第一聚合聚合物(B)組成物係如上述引發劑組成物與至少一種具有結構X之環氧化合物之反應產物:
或至少一種具有結構XI之環氧丙基醚化合物:
或其組合;其中R4係氫、苯基、環己基、或C1-C18直鏈或分支鏈烷基;以及R5係氫、苯基、經C1-C6直鏈或分支鏈之烷基取代之苯基、或C1-C18直鏈或分支鏈烷基。
式X中,R4可係氫、苯基、環己基、或C1-C18直鏈或分支鏈烷基。於本發明之一個態樣中,R4係甲基、乙基、丙基、丁基、戊基、己基、庚基、2-乙基己基、辛基、癸基、十二基、十四基、十六基、或十八基。於另一態樣中,R4可係氫、苯基、或環己基。於又另一態樣中,R4係氫、甲基、或苯基。於此態樣中,其中R4係氫、甲基、丁基、或苯基,式X之環氧化合物分別係環氧乙烷、環氧丙烷、環氧丁烷、或環氧苯乙烯。
式XI中之R5可係氫、苯基、經C1-C6直鏈或
分支鏈之烷基取代之苯基、或C1-C18直鏈或分支鏈烷基。例如,於本發明之一個態樣中,R5可係氫、苯基、或經C1-C6直鏈或分支鏈之烷基取代之苯基。於本發明之另一態樣中,R5係甲基、乙基、丙基、丁基、戊基、己基、庚基、2-乙基己基、辛基、癸基、十二基、十四基、十六基、或十八基。於本發明之又另一態樣中,R5可係苯基或經丁基取代之苯基。
上述所得到之聚合多元醇(B)組成物較佳具有Mw等於或少於8,000,更佳係等於或少於7,000,以及又更佳係等於或少於6,000。上述所得到之聚合多元醇(B)組成物較佳具有Mw等於或大於2,000,更佳係等於或大於3,000,以及更佳係等於或大於4,000。
本文如上揭露之聚合多元醇(B)組成物較佳具有羥基數目等於或少於800mg KOH/g,更佳係等於或少於300,更佳係等於或少於170,更佳係等於或少於100,以及又更佳係等於或少於75mg KOH/g。如上揭露之所得到之聚合多元醇組成物(B)較佳係具有羥基數目等於或大於15mg KOH/g,更佳係等於或大於20,更佳係等於或大於25,更佳係等於或大於35,以及又更佳係等於或大於50mg KOH/g。羥基數目係依據ASTM D 4274測定。
於本發明之另一態樣中,本文上述聚合多元醇(B)組成物較佳係具有平均官能度(F)等於或少於8,較佳係等於或少於7,更佳係等於或少於6,更佳係等於或少於5,以及又更佳係等於或少於4。較佳地,上述聚合多元醇
(B)組成物具有平均官能度等於或大於2,以及更佳係等於或大於3。
本發明之聚合多元醇組成物之特徵亦可係其氮含量。例如,本文如上揭露之聚合多元醇組成物之胺值係等於或少於5mg/g,較佳係等於或少於4,更佳係等於或少於3,更佳係等於或少於2mg/g。氮含量係以ASTM D 6979測定,並以mg/g為單位。
製作聚合多元醇組成物係發明所屬技術領域中所周知;任何合適於自上述引發劑I製作聚合多元醇組成物(B)之製程係可接受的。例如,引發劑I可與催化劑混合,且此混合物可係接著與環氧乙烷或環氧丙烷於約100℃至160℃之溫度範圍進行反應。用於此反應中之傳統催化劑以及發明所屬技術領域中具備通常知識者所知者係KOH。其他Ba(鋇)系或Sr(鍶)系之鹼性氫氧化物或氫氧化物水合物催化劑可用作烷氧化催化劑;製造具有較該等使用傳統KOH催化劑製造者較低飽合度之產物。用於使用Ba或Sr催化劑製造多元醇之製程係描述於美國專利第5,070,125號;美國專利第5,010,187號;以及美國專利第5,114,619號。
除了聚合多元醇(B)以外,本發明之黏著劑組成物視需要地含有一種或多種附加之多元醇。較佳之附加之多元醇係聚酯多元醇。較佳之附加之多元醇係具有官能度為2至2.5。較佳之附加之多元醇具有羥基數目為50至150。為聚酯多元醇之較佳之附加之多元醇係一種或多種二
酸以及一種或多種多元醇之反應產物。用於製作此聚酯多元醇之較佳之二酸係己二酸、間苯二甲酸、對苯二甲酸、以及其混合物。用於製作此聚酯多元醇之較佳之多元醇係乙二醇、二乙二醇、三羥甲基丙烷、以及其混合物。
較佳地,全部附加之多元醇與全部聚合多元醇(B)之重量比係0:1至1:1;更佳係0:1至0.45:1;更佳係0:1至0.3:1;更佳係0:1至0.15:1;更佳係0:1。
本發明之黏著劑組成物包括一種或多種聚異氰酸酯。聚異氰酸酯可係芳香族或脂族;較佳係脂族。較佳之聚異氰酸酯係一種或多種聚異氰酸酯單體、一種或多種聚異氰酸酯二聚體、一種或多種聚異氰酸酯三聚體、一種或多種聚異氰酸酯預聚物、以及其混合物。較佳之聚異氰酸酯單體係氫化之二異氰酸二苯基甲酯(MDI)(任何異構物)、二異氰酸異佛酮酯、己-1,6-二異氰酸酯(HDI)、二異氰酸伸己酯、2,2,4-三甲基-二異氰酸伸己酯、2,4,4-三甲基-二異氰酸伸己酯、以及其混合物。
較佳之聚異氰酸酯二聚體以及聚異氰酸酯三聚體係較佳之聚異氰酸酯單體之二聚體以及三聚體。較佳之聚異氰酸酯二聚體以及聚異氰酸酯三聚體係其個別單體組分彼此相同之二聚體以及三聚體。舉例而言,較佳之聚異氰酸酯三聚體係「HDI三聚體」,其於異氰酸脲酯結構中具有三個HDI分子黏合在一起之結構。
聚異氰酸酯預聚物係聚異氰酸酯單體與一種或多種多元醇之反應產物。各聚異氰酸酯預聚物具有二種
或更多個種側接之異氰酸酯基團。較佳之聚異氰酸酯預聚物含有一種或多種脂族聚異氰酸酯單體與一種或多種脂族聚醚多元醇、一種或多種脂族聚酯多元醇、一種或多種脂族混成多元醇、或其混合物之反應產物。較佳之聚異氰酸酯預聚物含有HDI與一種或多種脂族聚醚多元醇、一種或多種脂族聚酯多元醇、一種或多種脂族混成多元醇、或其混合物之反應產物。較佳之聚異氰酸酯預聚物含有一種或多種脂族聚異氰酸酯單體與一種或多種脂族聚醚多元醇以及,視需要地,一種或多種附加之脂族多元醇之反應產物。較佳地,於聚異氰酸酯預聚物之形成中,異氰酸酯基團係與羥基反應而形成胺甲酸乙酯鍵聯。
本發明之黏著劑組成物中多元醇以及聚異氰酸酯之相對量可藉由當量比而特徵化,其係全部異氰酸酯基與全部羥基之莫耳數比。較佳地,當量比係1:1或更高;更佳係1.01或更高;更佳係1.3:1或更高;更佳係1.3:1或更高;更佳係1.6:1或更高;更佳係2:1或更高;更佳係2.3:1或更高。較佳地,當量比係5:1或更低;更佳係4.7:1或更低;更佳係4.3:1或更低;更佳係4:1或更低;更佳係3.7:1或更低。
本發明之黏著劑組成物以黏著劑組成物之重量為基準計,含有含量為0至5重量%;較佳係0至3重量%;更佳係0至1重量%;更佳係0至0.5重量%;更佳係0至0.1重量%之溶劑。
本發明之黏著劑組成物視需要地含有一種或
多種佐劑。佐劑係係非聚異氰酸酯、非多元醇、以及非溶劑之化合物。較佳之佐劑係塑化劑;非反應性之熱塑性聚合物;催化劑;增稠劑;安定劑,以避免由熱、可見光、或紫外光造成之降解;阻燃劑物質;生物滅除劑;界面活性劑;以及其混合物。較佳地,全部佐劑之總重量以黏著劑組成物之重量為基準計,係0至5%;更佳係0至3%;更佳係0至1%;更佳係0至0.5%;更佳係0至0.1%。
本發明之黏著劑組成物可用於任何目的。較佳之用途係將二個基板黏合在一起。此黏合較佳係藉由下述步驟完成:施用黏著劑組成物之層至第一基板之表面,接著將第二基板之表面與黏著劑組成物之層接觸,而形成經組裝之物件。該經組裝之物件接著較佳係暴露於促進該黏著劑組成物中之異氰酸酯基與羥基間之固化反應之條件。
經組裝之物件較佳種類係層壓板,其係其中二種或更多個種膜彼此黏合之物件。為了形成層壓板,本發明之黏著劑組成物之層係施用至第一膜的一個表面,接著第二膜之表面係與黏著劑組成物之層接觸。因而形成之經組裝之物件係視需要地暴露於機械壓力,而於黏著劑組成物中之異氰酸酯基團與羥基間之固化反應之前或期間,使膜更緊密接觸。視需要地,機械壓力係藉由將經組裝之物件穿過二個緊密間隔輥輪之輥隙(nip)而施用。視需要地,附加之膜可使用本發明之黏著劑組成物之附加之層或另外使用其他黏著劑組成物之層,而黏合至該經組裝之物
件。
較佳地,該經組裝之物件之形成係於低於35℃之溫度進行,更佳係20℃至30℃。為了促進黏著劑組成物中異氰酸酯基與羥基之固化反應,經組裝之物件較佳係加熱至高於35℃之溫度,更佳係40℃至60℃之溫度。視需要地,經組裝之物件可於35℃或更高之溫度維持8週或更少;更佳係6週或更少。若經組裝之物件係於施用黏著劑組成物之後暴露於機械壓力,經組裝之物件可視需要地於壓力施用時維持於高於35℃之溫度,以及於該溫度係經組裝之物件不同位置上視需要地不同。視需要地,可於一種溫度施用黏著劑組成物,該溫度係高於35℃,以及經組裝之物件暴露於機械壓力之部分之溫度可係高於35℃,以及其係不同於黏著劑組成物施用之溫度。
黏著劑組成物較佳係於25℃係液體。為了促進施用黏著劑組成物之層至基板表面之製程,該黏著劑組成物更佳係於25℃具有相對較低之黏度。
當經組裝之物件係暴露於昇高之溫度以促進固化反應時,所欲者係將黏著劑組成物於低黏度維持一段時間(「開放時間」(open time)),以允許所須要之重新定位(re-positioning)。然而,所欲者係開放時間係相對地短。更所欲者係於開放時間之後,黏著劑組成物之黏度快速增加。慮及黏度迅速增加將於基板間創造黏合(稱作「新黏性」),其將允許經組裝之物件被和緩地處理及/或移動,即使黏著劑組成物可能尚未完全固化,也不會有基板間之
相對滑動。亦所欲者,係當黏著劑組成物完全固化時,即使在暴露於昇高之溫度及/或暴露於水、油、食物、或其他化學品之後,基板間之黏合應也係相對地強。
下述係本發明之實施例。
於下述實施例中,係使用下述術語:F=官能度。至於多元醇,此係指每分子之羥基數目。至於聚異氰酸酯,此係指每分子之異氰酸酯基數目。至於混合物或分配(distribution),F係係數目平均官能度。
OHN=羥基數目
Visc50=藉由錐板流變儀以10sec-1測量於50℃之黏度。流變儀係Anton Paar之型號MCR 301。
HDI=1,6-二異氰酸十六酯
EG=乙二醇
DEG=二乙二醇
TMP=三羥甲基丙烷
Mw=重量-平均分子量
於下述實施例中,係使用下述多元醇。只有多元醇B1係上述聚合多元醇(B)之實施例。
係使用下述聚異氰酸酯:NCO1=HDI三聚體
NCO2=TDI以及聚乙二醇之預聚物
製作下述黏著劑組成物。比較性黏著劑係以-C字尾標示。所示之量係重量份。
某些黏著劑組成物之固化係如下所測量。混合示於上表之成分,並接著將混合物加熱至50℃。當維持於50℃時,混合物之黏度(Visc50)係如上述所測量。結果係如下:
前述數據之檢驗顯示黏著劑組成物1-C之黏度於0至60分鐘係以恆定速率增加。由於該黏度之增加速率係恆定且非常小,因此得到結論係組成物1-C於任何合理時間內不會達到所欲之高黏度,以及目前為止並未於60分鐘後進一步測量組成物1-C。
組成物3顯示較組成物2-C更所欲之行為或黏度相對時間。組成物2-C之增加黏度速率係相對地恆定,且慮及組成物2-C會須要非常多的時間以達成高達10,000mPa.s之黏度。相反地,組成物3之黏度顯示增加速率係恆定增加的。因此,組成物2-C於超過60分鐘具有相對較低的黏度(低於500mPa.s),且組成物2-C亦在僅120分鐘內達到非常高的黏度(高於10,000mPa.s)。
Claims (5)
- 一種黏著劑組成物,包括:(A)一種或多種聚異氰酸酯,以及(B)一種或多種聚合多元醇,其中該聚合多元醇係下述者之反應產物:(I)多元醇引發劑,其中該多元醇引發劑係下述者之反應產物:(a)一種或多種具有結構I之二羥基三級胺化合物:
- 如申請專利範圍第1項所述之黏著劑組成物,其中,該聚異氰酸酯包括一種或多種脂族聚異氰酸酯。
- 如申請專利範圍第1項所述之黏著劑組成物,其中,R1係甲基;R2以及R3皆係乙基;以及該多羥基醇係甘油。
- 一種黏合第一基板至第二基板之方法,包括:(i)將如申請專利範圍第1項所述之黏著劑組成物之層施用至該第一基板之表面;(ii)接著將該第二基板之表面與如申請專利範圍第1項所述之黏著劑組成物之層接觸;以及(iii)接著固化如申請專利範圍第1項所述之黏著劑組成物之層。
- 如申請專利範圍第4項所述之方法,其中,該第一基板係膜,以及該第二基板係膜。
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TWI756219B (zh) * | 2016-05-10 | 2022-03-01 | 美商陶氏全球科技有限責任公司 | 包括胺引發之多元醇之雙組分無溶劑黏著劑組合物 |
CN106903969B (zh) * | 2016-05-10 | 2022-01-25 | 陶氏环球技术有限责任公司 | 用于形成包含包括胺引发的多元醇的双组分无溶剂胶粘剂组合物的层压体的方法 |
TWI791434B (zh) * | 2016-05-10 | 2023-02-11 | 美商陶氏全球科技有限責任公司 | 包括胺起始多元醇的雙組分無溶劑黏著劑組合物 |
TWI793073B (zh) * | 2016-05-10 | 2023-02-21 | 美商陶氏全球科技有限責任公司 | 包括胺引發的多元醇的雙組分無溶劑黏著劑組合物 |
CN108138022A (zh) | 2016-09-29 | 2018-06-08 | Dic株式会社 | 粘接剂、使用其的层叠膜、以及粘接剂用多元醇组合物 |
TWI621680B (zh) * | 2016-11-21 | 2018-04-21 | 日勝化工股份有限公司 | 基材適應性廣的雙塗佈快速固化無溶劑聚氨酯接著劑、複合膜材及其製備方法 |
WO2019060026A1 (en) * | 2017-09-22 | 2019-03-28 | Dow Global Technologies Llc | LAMINATED FILM STRUCTURES COMPRISING A BARRIER ADHESIVE LAYER |
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US5010187A (en) | 1988-11-18 | 1991-04-23 | Dow Chemical Company | Production of polyether polyols with reduced unsaturation |
US5070125A (en) | 1988-11-18 | 1991-12-03 | The Dow Chemical Company | Production of polyether polyols with reduced unsaturation |
US5114619A (en) | 1989-07-14 | 1992-05-19 | The Dow Chemical Company | Production of polyether polyols with reduced unsaturation |
DE69913167T2 (de) * | 1998-09-10 | 2004-08-26 | Shell Internationale Research Maatschappij B.V. | Co-initiierte polyetherpolyolen und verfahren zu ihrer herstellung |
AU2003209082A1 (en) * | 2002-02-07 | 2003-09-02 | Huntsman International Llc | Cold curable isocyanate adhesives with reduced foaming |
PT2069417E (pt) * | 2006-09-25 | 2013-03-25 | Dow Global Technologies Llc | Espumas de poliuretano feitas a partir de hidroximetilo - contendo polióis poliéster e amina terciária ¿ contendo polióis |
MY163478A (en) * | 2007-05-23 | 2017-09-15 | Huntsman Int Llc | Adhesives, reaction systems, and processes for production of lignocellulosic composites |
US8367870B2 (en) * | 2007-09-19 | 2013-02-05 | Air Products And Chemicals, Inc. | Autocatalytic polyols |
US9458354B2 (en) * | 2010-10-06 | 2016-10-04 | Resinate Technologies, Inc. | Polyurethane dispersions and methods of making and using same |
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CN106661188A (zh) | 2017-05-10 |
EP3180374A1 (en) | 2017-06-21 |
US9738820B1 (en) | 2017-08-22 |
TW201610060A (zh) | 2016-03-16 |
RU2745216C1 (ru) | 2021-03-22 |
WO2016025234A1 (en) | 2016-02-18 |
BR112017002191A2 (pt) | 2018-01-16 |
US20170218238A1 (en) | 2017-08-03 |
EP3180374B1 (en) | 2018-06-06 |
JP2017527658A (ja) | 2017-09-21 |
AR102808A1 (es) | 2017-03-29 |
MX2017001256A (es) | 2017-08-04 |
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