TWI468427B - 三聚氰胺-多元醇分散液及其於製造聚胺基甲酸酯的用途 - Google Patents
三聚氰胺-多元醇分散液及其於製造聚胺基甲酸酯的用途 Download PDFInfo
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- TWI468427B TWI468427B TW102100059A TW102100059A TWI468427B TW I468427 B TWI468427 B TW I468427B TW 102100059 A TW102100059 A TW 102100059A TW 102100059 A TW102100059 A TW 102100059A TW I468427 B TWI468427 B TW I468427B
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- Prior art keywords
- melamine
- polyol
- pphp
- ethoxylated alcohol
- dispersion
- Prior art date
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 5
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Classifications
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/009—Use of pretreated compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/14—Manufacture of cellular products
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/24—Catalysts containing metal compounds of tin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Description
此揭示內容關於安定的三聚氰胺-多元醇分散液、此分散液的製造方法、其於製造聚胺基甲酸酯發泡物的用途及由彼製造的物件。
在多種產品例如床墊和座面中廣泛使用撓性聚胺基甲酸酯發泡物,其中安全的考量要求其顯現有效的耐燃性質。撓性聚胺基甲酸酯發泡物可藉由添加一或更多耐燃物質來製造以擁有令人滿意的抗點燃性及/或耐火焰蔓延性。
三聚氰胺是製備聚胺基甲酸酯發泡物時常運用的耐燃劑。三聚氰胺一般在發泡之前分散於懸浮液中以便易於處理。適合的懸浮液對於三聚氰胺顯現低溶解力而且呈化學惰性。常見的懸浮液是高分子量液態有機多元醇。
美國專利第4,293,657號教導於多元醇中的三聚氰胺分散液的用途,其中該三聚氰胺具有小於10 μm的粒徑而且係於該多元醇中的原位置以高局部能量密度粉碎。分散
液安定劑也是必須的成分。此外,其揭示該等多元醇可部分以具有200至16,000的分子量之單官能基一級及/或二級羥基化合物來替代。
美國專利第5,125,952號揭示三聚氰胺的儲存安定性濃縮液態分散液,其含有與化學惰性懸浮液及化學惰性增稠劑混合的三聚氰胺細粒。有效的增稠劑包括黃原膠、角叉菜膠、聚丙烯醯胺、經化學處理的纖維素及黏土。
美國專利第4,892,893號揭示耐燃的撓性聚胺基甲酸酯發泡物的製備方法,其添加量介於發泡物重量的約5重量百分比至約25重量百分比之實質未粉碎的三聚氰胺。在此以引用的方式將先前確認的專利之揭示內容併入本文。
耐燃性聚胺基甲酸酯發泡物的製造經常運用三聚氰胺-多元醇分散液,該等分散液係透過將三聚氰胺粒子混入多元醇液體來製備。製造數量的三聚氰胺-多元醇分散液可能得花8至10小時之間的混合形成而且一旦攪動停止,這樣的分散液中的層分離可能於短於24小時內發生,有時候在6小時內。長時間混合消耗能量而且小的安定性範圍均造成加工的挑戰。不均勻的三聚氰胺-多元醇分散液也可能造成不均勻分佈的三聚氰胺粒子之聚胺基甲酸酯發泡物及不均勻的耐燃性質。
本發明藉由提供能保持安定至少24小時的三聚氰胺-多元醇分散液組合物來解決上述問題,有時候在許多其
他目的和益處之中還能多於48小時。
本發明的另一目的在於提供三聚氰胺-多元醇分散液組合物,該等組合物可在短於8小時的時期內在製造條件之下均勻混合,經常短於2小時。
本發明的又另一目的在於提供三聚氰胺-多元醇分散液組合物,該等組合物實質上不含含鹽類的增稠劑及/或安定劑。
另一目的在於提供本發明的三聚氰胺-多元醇分散液的製備方法。
本發明的另一目的在於提供用於製造具有均勻分佈的三聚氰胺粒子及均勻耐燃性質之耐燃性聚胺基甲酸酯發泡物的調合物及方法。
一方面,本揭示內容提供一種三聚氰胺-多元醇分散液,其包含:a)至少一多元醇,b)三聚氰胺,c)至少一下式的乙氧基化醇:RO(CH2
CH2
O)n
H,其中R係C1-C31線性烷基,n係等於或大於18的整數;及其中該至少一乙氧基化醇具有等於或大於約15.7的親水性-親脂性平衡(HLB)值。
另一方面,本發明揭示一種三聚氰胺-多元醇分散液,其包含:
a)至少一多元醇,b)約30 pphp的三聚氰胺,c)至少一下式的乙氧基化醇:RO(CH2
CH2
O)n
H,其中R係C13線性烷基,而且n係40。
又另一方面,本發明提供一種製造上述三聚氰胺-多元醇分散液之方法,此方法包括下述步驟:a)合併至少一多元醇、約大於0至約80 pphp的三聚氰胺及至少一下式的乙氧基化醇:RO(CH2
CH2
O)n
H,其中R係C1-C31線性烷基,n係等於或大於18的整數,而且該至少一乙氧基化醇係於水溶液中並且包含能有效使該分散液維持安定至少24小時的量,其中該至少一乙氧基化醇具有等於或大於約15.7的親水性-親脂性平衡(HLB)值;及b)混合a)的混合物直到形成一安定性分散液。
本發明的另一方面關於一種聚胺基甲酸酯發泡物調合物,其包含以上揭示的三聚氰胺-多元醇分散液,連同至少一異氰酸酯指數約80至約150的聚異氰酸酯、至少一發泡劑、至少一胺觸媒、至少一金屬觸媒及至少一聚矽氧表面活性劑。
另一方面,本發明揭示一種聚胺基甲酸酯發泡物,其係以先前揭示的發泡物調合物製造。
又另一方面,本發明提供一種用於製備聚胺基
甲酸酯發泡物之方法,其包含下列步驟:a)形成一預混物,其包含以上揭示的三聚氰胺-多元醇分散液、至少一發泡劑、至少一胺觸媒、至少一金屬觸媒和至少一聚矽氧表面活性劑;及b)使該預混物與至少一異氰酸酯指數約80至約150的聚異氰酸酯接觸。
圖1比較樣品8和樣品9的發泡外形。
本發明關於一種三聚氰胺-多元醇分散液,其包含多元醇、三聚氰胺及至少一下述式A所示的乙氧基化醇。該分散液可維持安定而不需攪動經過至少24小時,在一些案例中多於48小時。以這樣的分散液製成的聚胺基甲酸酯發泡物中的三聚氰胺粒子分佈更均勻,造成更均勻的耐燃性質。
本發明的至少一乙氧基化醇具有下式A:RO(CH2
CH2
O)n
H,A其中R係C1-C31線性烷基,頭尾包括在內;n係等於或大於18的整數;而且該化合物具有等於或大於約15.7的親水性-親脂性平衡(HLB)值。
文中所用的措辭"烷基"表示僅含有飽和碳-碳鍵
的脂肪族烴基。不含分支和不飽和碳-碳鍵的烷基適合用於本發明。
式A的乙氧基單元的數目"n"可為任何等於或大於18。非限定代表例包括n=18、n=20、n=40、n=50、n=60或n=70。
文中所用的措辭"親水性-親脂性平衡(HLB)值"係一化合物是親水性或親脂性的程度之量度。HLB係使用不同分子區的分子量算出來,如Griffin所述:HLB=20 x Mh/M
其中Mh是該分子的親水部位的分子量,而且M是整個分子的分子量,得到0至20的任意標度的結果。
HLB值為0相當於完全疏水性分子,值為20相當於完全親水性分子。
如一實例,依照下式計算C13
H27
(CH2
CH2
O)40
H的HLB值:HLB=20 X Mh/M=20 x 1761/1944=18.1
其中Mh是該親水性部分(CH2
CH2
O)40
H的分子量而且M是整個分子量分子量。
本發明適合的HLB值的實例包括,但不限於等於或大於15.7、17、18及19的HLB值。
適用於本發明的工業用乙氧基化醇產物包括,但不限於EMULMIN CC200(Sanyo Chemical Industries,Ltd)、YDY-234-103//X300(Air Products and Chemicals)及Newcol 1860(Nippon Nyukazai Co.,Ltd)。這些產物可包含乙氧基化醇與多變的R基團及n值的混合狀態,但是上述產物中的乙氧基化醇中之至少其一落於式A的範疇以內。
工業用乙氧基化醇產物一般供入溶劑例如水中。為了達成本發明的目的,在製備該三聚氰胺-多元醇分散液時運用乙氧基化醇水溶液。然而如請求的三聚氰胺-多元醇分散液中的乙氧基化醇量表示純而未溶解的乙氧基化醇量。舉例來說,若使2克70重量%的含水乙氧基化醇與100克的多元醇合併,該混合物中的乙氧基化醇是:(2 x 0.7/100) x 100=1.4pphp(相對於每一百重量份多元醇的重量份)
本發明中可使用市面上可購得的多種不同粒徑和粒徑分佈的三聚氰胺產物。在製備文中的三聚氰胺-多元醇分散液之前不需要進行三聚氰胺粒子的粉碎或其他特殊處理。
本發明中可使用約大於0至約80pphp,任意地約5至約80pphp,或約30至約80pphp的三聚氰胺。
本發明的多元醇可與聚胺基甲酸酯發泡物調合物中的多元醇不同或相同。其可包含聚醚多元醇、聚酯多元醇或聚合物多元醇而且將在隨後更詳細地加以描述。
在實驗室測試期間,把約100g的多元醇、約大於0至約80g的三聚氰胺及有效量的乙氧基化醇溶液合併在一起並且混合到形成一均勻分散液為止。任何習用的混合方法,例如機械攪拌或搖動均可運用。三聚氰胺和乙氧基化醇加入多元醇的順序影響該分散液的形成。
將該三聚氰胺-多元醇分散液靜止置於室溫(20至25℃)而且緊密地觀察其外觀。安定性分散液意指沒有察覺到固體從分散液沉降下來而且沒有裸眼可察覺的層分離。
"有效"量的乙氧基化醇是使該三聚氰胺-多元醇分散液維持安定至少24小時的量,在一些案例中多於48小時。三聚氰胺-多元醇分散液可包含純度至少約0.5 pphp、至少約0.7 pphp或至少約1.0 pphp的未溶解乙氧基化醇。
典型的製造條件涉及使多元醇、三聚氰胺及式A的乙氧基化醇溶液於容量20 m3
的混合槽中接觸並且利用30瓦機械攪拌器於約每分鐘1800轉(rpm)下混合。
本發明的三聚氰胺-多元醇分散液可另外包含至高400 pphp的包括CaCO3
、BaSO4
及其任何組合在內的填料而且仍舊能保持安定至少24小時。
其他液態耐燃劑,其包括但不限於鹵化耐燃劑、非鹵化耐燃劑及其任何組合,也可加入該三聚氰胺-多元醇分散液而不會影響其安定性。
據記載增稠劑使三聚氰胺-多元醇分散液安定化。有記載的增稠劑包括黃原膠、角叉菜膠、聚丙烯醯胺、經化學處理的纖維素及黏土等。本揭示內容的三聚氰胺-多元醇分散液不需要上述增稠劑來維持安定。或換句話說,本揭示內容的三聚氰胺-多元醇分散液可能實質上不含上述增稠劑。關於"實質上不含",其意指該三聚氰胺-多元醇分散液具有約0至約少於0.5 pphp的上述增稠劑。
美國專利第4,293,657號記載其安定性三聚氰胺
-聚氧化烯聚醚多元醇分散液中必定包括安定劑。那些安定劑由矽酸類和矽酸鹽類;全氟烷基羧酸類、烷基磺酸及全氟烷基磺酸的鹽類;聚全氟醚多元醇類脂肪醇硫酸酯的鹽類組成。本揭示內容的三聚氰胺-多元醇分散液不需要上述安定劑來維持安定。或換句話說,本揭示內容的三聚氰胺-多元醇分散液可實質上不含上述安定劑。關於"實質上不含",其意指該三聚氰胺-多元醇分散液具有約0至約少於0.5 pphp的上述安定劑。
該聚胺基甲酸酯技藝中已知的多種不同類型的任何發泡物可利用本發明的方法製造,該方法使用已經添加根據本發明的三聚氰胺-多元醇分散液之典型聚胺基甲酸酯調合物。典型的聚胺基甲酸酯調合物組分包括至少一多元醇、至少一發泡劑例如水、至少一聚異氰酸酯、至少一胺觸媒、至少一金屬觸媒及至少一聚矽氧表面活性劑。其他添加物可依據該聚胺基甲酸酯的類型及應用而包括在內。舉例來說,撓性聚胺基甲酸酯發泡物典型依照所示的量包含表1所示的組分。表1所示的組分將在後文中詳細討論。
用於根據本發明的聚胺基甲酸酯調合物中的聚異氰酸酯量沒有限制,但是其經常在熟悉此技藝者已知的那些範圍以內。將例示性範圍提供於上表中,引用"NCO指數"(異氟酸酯指數)來表示。如此技藝中已知的,該NCO指數係定義為異氰酸酯的當量數,除以活性氫的總當量數,乘以100。該NCO指數係表示為下式:NCO指數=[NCO/(OH+NH)]X 100
撓性發泡物經常使用聚合物多元醇作為該發泡物組合物中的總多元醇含量,連同重量平均分子量為約2000至5000而且羥基數目為約14至100的基底多元醇,之一部分。本文將於後詳細描述基底多元醇及聚合物多元醇。
在本發明的一些具體實施例中,該觸媒、該發泡劑、該交聯劑、該表面活性劑及任意地一或更多其他常用
於聚胺基甲酸酯調合物中的添加物可併入該三聚氰胺-多元醇分散液。這樣的混合物隨後可與有機異氰酸酯接觸以形成一聚胺基甲酸酯發泡物,此外可任意在此技藝中已知的其他添加物存在的情況之下。
除了製造撓性發泡物之外,本發明也可用以製備半撓性發泡物(semi-flexible foam),例如通常用於汽車產業中的許多應用(例如,儀器面板、車頂內襯及內裝品)。
儘管上文及本文的其他地方討論到特定示範類型的聚胺基甲酸酯發泡物,但是咸了解任何類型的聚胺基甲酸酯發泡物均可根據本發明製備。
文中揭示的聚胺基甲酸酯調合物可含有任何關於聚胺基甲酸酯發泡物製造已知或使用的觸媒及觸媒的組合。有用的觸媒的實例包括氫氧化鈉、醋酸鈉、三級胺類或能產生三級胺類例如三甲胺、三乙撐二胺、雙(二甲胺基乙基)醚、雙(二甲基(胺基-N-丙基)甲胺、N-甲基嗎啉、N,N-二甲基環己胺及N,N-二甲基胺基乙醇的材料。金屬化合物例如羧酸烷酯類、二醋酸二丁錫、二辛酸二丁錫、二月桂酸二丁錫及辛酸亞錫也適用。例示性觸媒是DABCOB 33LV(Air Products and Chemicals)及DABCOB T-9(Air Products and Chemicals)。
必要的話,許多其他種類的觸媒均可取代以上列示者。用於製造根據本發明的發泡物之觸媒裝填量經常在大於0至約2 pphp的範圍中,更常地大於0至約1 pphp,最
常地大於0至約0.5 pphp。然而,任何有效量均可使用。該措辭"pphp"意指相對於每一百重量份的多元醇的重量份。
聚胺基甲酸酯發泡物製造可藉助於內含發泡劑以於聚合期間在該聚胺基甲酸酯基質中產生空隙。此技藝中已知的任何發泡劑均可使用。適合的發泡劑包括在放熱性聚合反應期間汽化的低沸點化合物。這樣的發泡劑一般具有惰性而且因此在該聚合反應期間不會分解或反應。惰性發泡劑包括,但不限於,二氯甲烷、二氧化碳、氟氯碳化物、氫化氟碳化物、氫化氟氯碳化物、丙酮及低沸點烴類例如環戊烷、異戊烷、正戊烷及其混合物。其他適合的發泡劑包括能與異氰酸酯化合物反應產生氣體的化合物,舉例來說水。
適合的有機異氰酸酯化合物包括,但不限於,二異氰酸己二酯(HDI)、二異氰酸苯二酯(PDI)、二異氰酸甲苯二酯(TDI)及4,4'-二苯基甲烷二異氰酸酯(MDI)。在本發明之一方面中,2,4-TDI、2,6-TDI或其任何混合物係用以製造聚胺基甲酸酯發泡物。其他適合的異氰酸酯化合物是商業上稱作"粗製MDI"的二異氰酸酯混合物。有一實例係由Dow Chemical Company以商品名PAPI販售,並且含有約60%的4,4'-二苯基甲烷二異氰酸酯連同其他異構物及類似的高級聚異氰酸酯。
也適合的是這些異氰酸酯化合物的"預聚物",
其包含聚異氰酸酯和聚醚或聚酯多元醇的經部分預反應的混合物以將該聚酯多元醇上的一或更多羥基轉化為經取代的胺基甲酸酯(carbamate)基團。衍生自聚醚和聚酯多元醇的適合預聚物在此技藝中眾所周知。
聚胺基甲酸酯係藉由有機異氰酸酯類與多元醇,經常為多元醇的混合物,中的羥基之反應製造。該反應混合物的多元醇組分包括至少一主要或"基底"多元醇。適用於本發明中的基底多元醇包括,視為非限定例,聚醚和聚酯多元醇。該聚烯醚多元醇包括聚(環氧烷)聚合物例如聚(環氧乙烷)及聚(環氧丙烷)聚合物及與衍生自包括二元醇類和三元醇類在內的多羥基化合物的末端羥基的共聚物。這些包括,但不限於,乙二醇、丙二醇、1,3-丁二醇、1,4-丁二醇、1,6-己二醇、新戊二醇、二乙二醇、二丙二醇、季戊四醇、甘油、二甘油、三羥甲基丙烷、環己二醇及糖類例如蔗糖及諸如此類的低分子量多元醇。
胺聚醚多元醇類均可用於本發明。這些可於胺例如,舉例來說,乙二胺、二乙三胺、伸甲苯基二胺、二苯基甲烷二胺或三乙醇胺與環氧乙烷或環氧丙烷反應時製備而成。
在本發明另一方面中,單一高分子量聚醚多元醇或高分子量聚醚多元醇的混合物,例如不同多官能基材料及/或不同分子量或不同化學組成材料的混合物均能使用。
在本發明又另一方面中,聚酯多元醇類均能使用,包括當二羧酸與過量的二元醇反應時所製造者。非限定例包括與乙二醇或丁二醇反應的己二酸或苯二甲酸或苯二甲酸酐。可用於本發明的多元醇類可藉由使內酯與過量的二元醇反應製造而成,舉例來說,使己內酯與丙二醇反應。在另一方面中,含活性氫的化合物例如聚酯多元醇和聚醚多元醇及其組合均可用於本發明。
除了上述基底多元醇以外,或將彼等取而代之地,根據本發明使用的多元醇組分中可包括通常稱作"聚合物多元醇"的材料。聚合物多元醇可用於聚胺基甲酸酯發泡物中以提高該發泡物對於變形的抗性,舉例來說改善該發泡物的承重性質。依據該聚胺基甲酸酯發泡物的承重要求,聚合物多元醇類可包含總多元醇含量的0至約80重量百分比。聚合物多元醇類的實例包括,但不限於,接枝多元醇類及經聚脲改質的多元醇類,該二者在此技藝中係已知而且可自商業上購得。
為了製造根據本發明的發泡物該等調合物中可包括各式各樣的其他成分。任意組分的實例包括,但不限於,室安定劑(cell stabilizer)、交聯劑、鏈伸長劑、顏料、填料及這些的任何組合。
本發明的實行使聚胺基甲酸酯製造廠商能實現一或更多優點。這些可包括a)縮減形成聚胺基甲酸酯製造時
可輕易使用的三聚氰胺-多元醇分散液所需的時間和能量;b)安定的三聚氰胺-多元醇分散液,其允許用於加工其他供製造聚胺基甲酸酯用的組分之時間更多;c)僅需要微幅調節聚胺基甲酸酯調合物;在使用乙氧基化醇水溶液的案例中,原始聚胺基甲酸酯調合物中的水含量可能必須據此縮減;d)由本發明製造的聚胺基甲酸酯發泡物證實整個發泡物的三聚氰胺粒子分佈越均勻使耐燃性質越均勻;e)運用本發明並不會不利地影響製成的發泡物的其他物性。
下述實施例的上下文中將進一步描述本發明,
其係藉由例示的方式呈現,而非限制。
三聚氰胺-多元醇分散液係利用下述程序於室溫(20至25℃)製備。把100 g聚醚多元醇、約0至約80 g的三聚氰胺和各個不同量的70重量%當下測試的乙氧基化醇類之水溶液加於1000 mL燒杯。接著使用直徑為90 mm的機械攪拌器於1150 rpm下攪拌該混合物300秒或直到形成均勻分散液為止。該分散液接著轉移至20 mL的玻璃安瓿並且靜置該安瓿至多48小時。以目視周期性地檢查該安瓿是否有任何固體自該混合物沉降或任何澄清層形成於該分散液頂部或該分散液中的任何層分離。若觀察到任何上述現象,則將該分散液記錄為不安定;否則,將該分散液記錄為安定。
使用具有不同烷基、乙氧基單元及因此不同HLB值的乙氧基化醇類製備根據實施例1的程序之三聚氰胺-多元醇分散液。依循實施例1的目視檢查方法比較該等乙氧基化醇對於所形成的分散液之安定性並且將結果列於表2中。所有測試的乙氧基化醇類均符合下式:RO(CH2
CH2
O)n
H,其中R是線性烷基而且n係大於0的整數。
樣品1至7均含有80 pphp的三聚氰胺。該"量"
係定義為70重量%乙氧基化醇水溶液的用量。各樣品中使用的純且未溶解的乙氧基化醇的量因此是1.4 pphp。
Tomadol® 91-8、Tomadol® 25-12及Tomadol® 45-13係來自Air Products and Chemicals,Inc.而且NewcolB 1545係來自Nippon Nyukazai Co.Ltd。化合物1至3係指定結構的實驗室樣品。
樣品1至7可含有具有落於指定"R"和"平均數量"範圍內的結構之化合物的混合物。"R"表示該線性烷基的碳數範圍而且"平均數量"是各樣品中的乙氧基單元之範圍或平均數量。
不含任何乙氧基化醇的三聚氰胺-多元醇分散液於少於6小時內變得不安定。當併入其中時,其他化合物,例如來自Sanyo chemical industry industries,Ltd.的PEG2000(其具有式HO-(CH2
CH2
O)4
H)及來自Sanyo chemical industries,Ltd.的Sannix GEP 2800(其係EO/PO比為1:1且分子量為2800並以甘油引起的聚醚多元醇),無法使三聚氰胺-多元醇分散液安定化。
此實施例舉例說明只有滿足一定結構要求的乙氧基化醇類可使三聚氰胺-多元醇分散液安定化至少24小時。
本實施例舉例說明此量的乙氧基化醇類如何影響該三聚氰胺-多元醇分散液的安定性。聚醚多元醇中含有80
pphp的三聚氰胺之三聚氰胺-多元醇分散液係以變化量的化合物2根據實施例1的程序製備。化合物2係依照表2所述的特定結構的乙氧基化醇之70重量%水溶液的形式使用。將結果列於下述表3中。
聚胺基甲酸酯發泡物係使用實驗室級盒模法(box mold method)及發泡機法(foaming machine method)以表4列示的調合物製造。
在上述調合物中,在TDI之外,其餘的組分係以相對於每一百重量份多元醇的重量份(pphp)的方式列示。
上述組分當中,VORANOL® 3022J(Dow chemicals,Inc)係羥基數為56的聚醚多元醇。三聚氰胺係購自Sichuan Hongjie chemicals。Antiblaze® BK69(Albemarle chemicals,Inc)係為液態耐燃劑。所有Dabco®產品係來自Air Products and chemicals,Inc,當中Dabco® DC 5950及Dabco® DC5990二者均為聚矽氧表面活性劑,Dabco® AS45係為抗氧化劑,Dabco® CS90係為胺觸媒而且Dabco® T-9係為錫觸媒。DEOA(二乙醇胺)係來自Dow Chemicals的交聯劑。二氯
甲烷(Zibo Fengchang Chemicals)係為物理性發泡劑。TDI(BASF Chemicals)係為甲苯二異氰酸酯的80/20 2,4/2,6異構物混合物。化合物2係按照表2所述的特定結構的乙氧基化醇類之70重量%水溶液的形式使用。
樣品8及9係利用實驗室級盒發泡物方法來製備。在10 L的槽中加入2500 g的多元醇、625 g的三聚氰胺、在樣品9案例中的50 g化合物2及樣品8案例中的不含化合物2,而且該混合物係利用於1600 rpm旋轉的機械攪拌器混合5分鐘;接下來的步驟將375 g的液態耐燃劑、5 g的胺觸媒、30 g的聚矽氧表面活性劑、87.5 g的水及12.5 g的抗氧化劑加入該槽並且另外混合1分鐘。接著添加並且混合該錫觸媒(11.25 g)經過另外10秒,接著同時添加發泡劑(87.5 g)和TDI(1168 g)並且混合該混合物6秒。接著配合周遭條件(沒加熱)將該混合物倒入開啟的盒模(60 cm X 60 cm X 60 cm)。在該盒模中經過60分鐘的反應時間之後,將該發泡物脫模,而且在23小時之後測量該耐燃性質及其他物性。
樣品10及11係利用熟悉此技藝者眾所周知的習用發泡機方法來製備。利用Maxfoam生產線(Hennecke)的Hanneke高壓發泡機。在20 m3
槽中於1800 rpm的攪拌速度下預混合多元醇、三聚氰胺、在樣品11案例中的指定重量百分比的化合物2及樣品10案例中的不含化合物2。有關樣品10,混合時間為10小時而且有關樣品11,混合時間為2小時。有關樣品10和11二者,等到預混合完成之後,在將該等分散液轉移至該Henneke高壓發泡機以與用於其他製造聚胺基
甲酸酯發泡物的組分合併之前將該等多元醇-三聚氰胺分散液靜置1小時。
因為上述樣品8至11中的乙氧基化醇類係以水溶液的形式使用,運用那些的聚胺基甲酸酯調合物需要較少水。需要的水量可藉由從不含乙氧基化醇水溶液的聚胺基甲酸酯調合物所需的水量扣除該乙氧基化醇水溶液中的水算出來。
樣品8至11的耐燃性質係利用Great Britain Standard Method BS5852第5部測量。結果顯示於下列表5中。
表5舉例說明含有乙氧基化醇類的樣品(樣品9和11)橫過該發泡物具有更均勻的耐燃性。
測量實施例4的樣品8和9的物性並且表示於
表6中。
RT是發泡完成的時間。根據ASTM3 547測定凹陷、密度、空氣流量、於該等發包物樣品壓凹25%和65%時的ILD硬度。
測量樣品8和9的發泡外形並且顯示於圖1中。
表6中的數據和圖1指示包含本發明的乙氧基化醇不會影響發泡動力學。其也不會不利地影響所得的聚胺基甲酸酯發泡物的物性。
儘管本發明已經引用上述實施例描述,但是咸了解熟悉此技藝者可以完成多種不同變化而且可以同等物取代其元件而不會悖離本發明的範疇。此外,可完成許多修飾使特定情況或材料適合本發明的教旨而不會悖離其基本範疇。因此,吾人預期本發明不限於被視為用於進行本發明的最佳模式而揭示的特定具體實施例,但是本發明將包括所有落於後附申請專利範圍的範疇以內之具體實施例。
Claims (25)
- 一種三聚氰胺-多元醇分散液,其包含:d)至少一多元醇,e)三聚氰胺,其中該三聚氰胺相對於每一百重量份的多元醇為大於0至80重量份(pphp),f)至少一下式的乙氧基化醇:RO(CH2 CH2 O)n H,其中R係C1-C31線性烷基,n係等於或大於18的整數,及其中該至少一乙氧基化醇具有等於或大於15.7的親水性-親脂性平衡(HLB)值,及該至少一乙氧基化醇等於或大於0.5pphp的量。
- 如申請專利範圍第1項之三聚氰胺-多元醇分散液,其中該至少一乙氧基化醇包含能有效使該分散液維持安定至少24小時的量。
- 如申請專利範圍第1項之三聚氰胺-多元醇分散液,其中該至少一多元醇包含聚醚多元醇或聚酯多元醇。
- 如申請專利範圍第1項之三聚氰胺-多元醇分散液,其中該至少一多元醇包含聚合物多元醇。
- 如申請專利範圍第1項之三聚氰胺-多元醇分散液,其中該 至少一乙氧基化醇具有等於或大於17.0的親水性-親脂性平衡(HLB)值。
- 如申請專利範圍第1項之三聚氰胺-多元醇分散液,其中該至少一乙氧基化醇係於水溶液中。
- 如申請專利範圍第1項之三聚氰胺-多元醇分散液,其中該至少一乙氧基化醇包含等於或大於0.7pphp的量。
- 如申請專利範圍第1項之三聚氰胺-多元醇分散液,其中該至少一乙氧基化醇包含等於或大於1.0pphp的量。
- 如申請專利範圍第1項之三聚氰胺-多元醇分散液,其包含5至80pphp的三聚氰胺。
- 如申請專利範圍第1項之三聚氰胺-多元醇分散液,其包含30至80pphp的三聚氰胺。
- 如申請專利範圍第1項之三聚氰胺-多元醇分散液,其另外包括含CaCO3 、BaSO4 或其任何組合的填料。
- 如申請專利範圍第11項之三聚氰胺-多元醇分散液,其中該填料包含0至400pphp的CaCO3 、BaSO4 或其任何組合。
- 如申請專利範圍第1項之三聚氰胺-多元醇分散液,其另外包含選自由鹵化耐燃劑、非鹵化耐燃劑及其任何組合所組成的群組之液態耐燃劑。
- 如申請專利範圍第1項之三聚氰胺-多元醇分散液,其中該分散液不含增稠劑。
- 如申請專利範圍第14項之三聚氰胺-多元醇分散液,其中該增稠劑係選自由黃原膠、角叉菜膠、聚丙烯醯胺、經化學處理的纖維素、黏土及其任何組合所組成的群組。
- 一種三聚氰胺-多元醇分散液,其包含:g)至少一多元醇,h)30pphp的三聚氰胺,i)至少一下式的乙氧基化醇:RO(CH2 CH2 O)n H,其中R係C13線性烷基,而且n係40,及其中該至少一乙氧基化醇等於或大於1.4pphp的量。
- 如申請專利範圍第16項之三聚氰胺-多元醇分散液,其中該至少一乙氧基化醇包含能有效使該分散液維持安定至少24小時的量。
- 如申請專利範圍第16項之三聚氰胺-多元醇分散液,其中 該至少一乙氧基化醇係於水溶液中。
- 一種製造如申請專利範圍第1項之三聚氰胺-多元醇分散液之方法,其包含:a)合併至少一多元醇、大於0至80pphp的三聚氰胺及至少一下式的乙氧基化醇:RO(CH2 CH2 O)n H,其中R係C1-C31線性烷基,n係等於或大於18的整數,其中該至少一乙氧基化醇係於水溶液中並且包含能有效使該分散液維持安定至少24小時的量,其中該至少一乙氧基化醇具有等於或大於15.7的親水性-親脂性平衡(HLB)值;及b)混合a)的混合物直到形成一安定性分散液。
- 如申請專利範圍第19項之方法,其中該至少一乙氧基化醇具有等於或大於17.0的親水性-親脂性平衡(HLB)值。
- 如申請專利範圍第19項之方法,其中該至少一乙氧基化醇等於或大於0.7pphp的量。
- 一種聚胺基甲酸酯發泡物調合物,其包含:a)申請專利範圍第1項之三聚氰胺-多元醇分散液,b)至少一異氰酸酯指數80至150的聚異氰酸酯,其中該至 少一聚異氰酸酯的量提供NCO指數=80至150,c)0-40pphp的至少一發泡劑,d)0-1.0pphp的至少一胺觸媒,e)0-1.0pphp的至少一金屬觸媒,及f)0-10pphp的至少一聚矽氧表面活性劑。
- 如申請專利範圍第22項之聚胺基甲酸酯發泡物調合物,其另外包含交聯劑、液態耐燃劑、抗氧化劑其任何組合。
- 一種用於製備聚胺基甲酸酯發泡物之方法,其包含:a)形成一預混物,其包含:i)申請專利範圍第1項之三聚氰胺-多元醇分散液,ii)至少一發泡劑,iii)至少一胺觸媒,iv)至少一金屬觸媒,v)至少一聚矽氧表面活性劑;及b)使該預混物與至少一異氰酸酯指數80至150的聚異氰酸酯接觸。
- 一種聚胺基甲酸酯發泡物,其係以申請專利範圍第22項之聚胺基甲酸酯發泡物調合物所製造者。
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| PCT/CN2012/070015 WO2013102295A1 (en) | 2012-01-06 | 2012-01-06 | Melamine-polyol dispersions and uses thereof in manufacturing polyurethane |
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- 2012-01-06 CN CN201280066079.7A patent/CN104039854B/zh not_active Expired - Fee Related
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| PT2800767T (pt) | 2019-06-07 |
| PL2800767T3 (pl) | 2019-08-30 |
| CN104039854B (zh) | 2016-03-30 |
| DK2800767T3 (da) | 2019-05-27 |
| US9884945B2 (en) | 2018-02-06 |
| EP2800767A4 (en) | 2015-08-19 |
| CN104039854A (zh) | 2014-09-10 |
| EP2800767A1 (en) | 2014-11-12 |
| HUE043486T2 (hu) | 2019-08-28 |
| WO2013102295A1 (en) | 2013-07-11 |
| TW201329125A (zh) | 2013-07-16 |
| MX2014007797A (es) | 2014-07-30 |
| US20140364525A1 (en) | 2014-12-11 |
| EP2800767B1 (en) | 2019-03-06 |
| ES2726533T3 (es) | 2019-10-07 |
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