TWI730916B - 稠環芳香類色素和高分子材料的混合物、其製備方法、色母粒粗品、色母粒產品及高分子顏料 - Google Patents
稠環芳香類色素和高分子材料的混合物、其製備方法、色母粒粗品、色母粒產品及高分子顏料 Download PDFInfo
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- TWI730916B TWI730916B TW109136408A TW109136408A TWI730916B TW I730916 B TWI730916 B TW I730916B TW 109136408 A TW109136408 A TW 109136408A TW 109136408 A TW109136408 A TW 109136408A TW I730916 B TWI730916 B TW I730916B
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Abstract
本申請涉及稠環芳香類色素和高分子材料的混合物、其製備方法、色母粒粗品、色母粒產品及高分子顏料。該方法可選用不同的熱塑性高分子材料與用於生成稠環芳香類色素的反應物混合,通過調節各原料之間的反應莫耳比以及在整個反應體系中的用量,使反應物和高分子材料的混合物能夠通過擠出或捏合,一步得到稠環芳香類色素和高分子材料的混合物,相較於色素,色素的原料反應物在高分子材料中有更好的分散性,因此經擠出或捏合,色素能夠直接生成並均勻分散在高分子材料中,並且擠出或捏合過程中無需加入任何溶劑,鄰二胺化合物也幾乎完全被消耗,得到的混合物無需提純,避免了傳統色素合成過程中三廢的產生,極大地簡化了製程流程,降低了能耗。
Description
本發明涉及稠環芳香類色素和高分子材料的混合物、其製備方法、色母粒粗品、色母粒產品及高分子顏料。
稠環芳香類還原染料(Vat Dyes)色澤鮮豔,各項堅牢度優良,尤其在耐曬、耐溶劑等方面性能優異。但由於稠環芳香類化合物在生產過程中分散性差,需使用高沸點、難去除的溶劑,以致產生大量廢液,且由於染料分子的提純也非常困難,以致該類染料反應收率低、價格高,加工的製程也相對更複雜,大大限制了該類染料的應用和發展。
US20080139813使用鉬酸銨、氧化鉬、羰基鉬、羰基鈦、羰基鐵等金屬催化劑,在溶劑氮甲基吡咯烷酮(NMP)的存在下使苝-3,4,9,10-四羧酸、1,4,5,8-萘-四羧酸及其酸酐、醯亞胺與胺反應,得到苝二酐和苯二胺的反應產物,實施例中反應產率最高達96.7%,整個反應需在200℃左右進行,反應時間超過20小時,並且在反應過後產物需要用NMP和硫酸洗滌純化才能得到最終產品,這過程勢必會產生大量的含有NMP、硫酸和鹼的廢液。
US20070151478為苝二酐或萘二酐和芳香二胺的反應合成黑色顏料的方法,該發明使用高沸點溶劑如硝基苯、三氯苯、N,N-二甲基甲醯胺(DMF)等在150℃~250℃反應,並且用氯化鋅、醋酸鋅、乙酸、鹽酸、呱嗪等作為催化劑。可見,該條件設計的反應溶劑大多毒性很大,反應後的廢液也會對環境造成破壞。
WO2009074504 使用四羧酸及衍生物、胺類化合物、添加劑、以及潤濕劑作用下使用混合裝置合成苝類染料或顏料,同樣合成時間長,溫度高,合成中需使用醇類溶劑,並且反應後粗產品需使用各類溶劑、酸和鹼純化,並沒有降低合成該類色素時產生的廢液量。
CN108329466 使用原位聚合,將苝四酸二酐連接到尼龍6的高分子鏈中,得到含有苝染料的尼龍6材料,但該反應溫度高,時間長,並且不排除使用如氯仿等有毒的有機溶劑。
EP0892018報導了將普通有機顏料分子和可聚合的物質混合並加熱處理,冷卻後得到顏料和高分子的複合材料。該方法採用的顏料分子有很大的局限性,顏料分子需要有可以進行反應的功能取代基。而且可聚合的物質大多在常溫下是液體,造成該類材料的加工需使用加工性能更高的可液體進樣的擠出機。而EP654711、EP542669以及EP456610則採用類似方法製備螢光顏料。由於這些顏料的製備方法不是真正合成顏料分子本身,並沒有避免合成顏料分子時所產生的廢液、廢固以及廢氣等。同樣J. APPL. POLYM. SCI. 2015, DOI: 10.1002/APP.42172 也報導了可聚合的萘醯亞胺類螢光染料合成製備聚乙烯類的螢光高分子,但其中可聚合的萘醯亞胺也需要用傳統方法合成,同樣不能避免產生廢液。
基於此,有必要提供一種無需純化、無三廢產生的稠環芳香類色素和高分子材料的混合物的製備方法,具體方案如下:
一種稠環芳香類色素和高分子材料的混合物的製備方法,包括以下步驟:
將熱塑性高分子材料和用於形成稠環芳香類色素的反應物混合,經捏合或擠出,得到稠環芳香類色素和高分子材料的混合物;所述用於形成稠環芳香類色素的反應物包括酸酐功能化的稠環芳香化合物衍生物、鄰二胺化合物和催化劑,所述稠環芳香類色素和高分子材料的混合物中稠環芳香類色素的品質含量為0.1%~50%,所述鄰二胺化合物與所述酸酐功能化的稠環芳香化合物衍生物中酸酐官能團的莫耳比為1:(1~1.1),所述催化劑與所述酸酐功能化的稠環芳香化合物衍生物的莫耳比為(0.01~10):1。
在其中一個實施例中,所述酸酐功能化的稠環芳香化合物衍生物選自以下化合物中的至少一種:
其中,R
1-R
12分別獨立地選自H、鹵素、胺基、帶有取代基的胺基、C1-C30烷基、C1-C20烷氧基、酚羥基、帶有取代基的酚羥基、苯基、帶有取代基的苯基、萘基、帶有取代基的萘基、巰基、帶有取代基的巰基、氰基、矽烷基、羧酸酯基、磺酸基、磺酸酯基、磷酸基及磷酸酯基中的一種;
R'選自H、C1-C30烷基、C1-C20烷氧基、苯基、帶有取代基的苯基、萘基、帶有取代基的萘基、矽烷基中的一種;
X
1和X
2分別獨立地選自CH
2、CHR''、CR''R'''、NR''、O、S、S=O及SO
2中的一種,R''和R'''分別獨立地選自H、C1-C30烷基、C1-C20烷氧基、帶有取代基的芳香基中的一種。
在其中一個實施例中,所述鄰二胺化合物選自以下化合物中的至少一種:
、
、
、
、
其中,R
1、R
2、R
3、R
4分別獨立地選自H、鹵素、氰基、硝基、醛基、羧基、酸酐、醯胺、醯亞胺、酯基、烷基、烷氧基或巰基中的至少一種;
R'分別獨立地選自H、C1-C30烷基、C1-C20烷氧基、帶有取代基的芳香基中的一種;
X為含有S、N、O、CO、SO、SO2或C=C基團的五元或六元環結構。
在其中一個實施例中,所述催化劑選自去水劑、路易士酸、路易士鹼及金屬氧化物中的至少一種。
在其中一個實施例中,所述擠出的溫度沿物料前進的方向分別為進料段120℃~330℃、擠出段150℃~360℃、出樣段180℃~380℃。
本申請還提供一種由上述任一項所述的製備方法製得的稠環芳香類色素和高分子材料的混合物。
此外,本申請還提供上述稠環芳香類色素和高分子材料的混合物的下游產品,如色母粒粗品、色母粒產品及高分子顏料,具體方案如下:
一種色母粒粗品,由上述稠環芳香類色素和高分子材料的混合物經冷卻、乾燥、切粒而得。
一種色母粒產品,由上述稠環芳香類色素和高分子材料的混合物的原料與添加劑混合,經擠出、冷卻、乾燥、切粒而得;或由上述色母粒粗品與添加劑混合,經擠出、冷卻、乾燥、切粒而得。
在其中一個實施例中,所述色母粒產品的粒徑為200 μm ~ 0.5 cm。
一種高分子顏料,由上述色母粒粗品或上述色母粒產品研磨而得。
在其中一個實施例中,所述高分子顏料的粒徑為0.01 μm~100 μm。
上述稠環芳香類色素和高分子材料的混合物的製備方法,根據相容性、加工溫度和極性,可選用不同的熱塑性高分子材料與用於形成稠環芳香類色素的反應物(酸酐功能化的稠環芳香化合物衍生物、鄰二胺化合物和催化劑)混合,通過調節各原料之間的反應莫耳比以及在整個反應體系中的用量,使它們的混合物能夠經擠出或捏合,一步得到稠環芳香類色素和高分子材料的混合物,相較於色素,色素的原料反應物在高分子材料中有更好的分散性,因此經擠出或捏合,色素能夠直接生成並均勻分散在高分子材料中,並且擠出或捏合過程中無需加入任何溶劑,鄰二胺化合物也幾乎完全被消耗,得到的混合物無需分離純化,避免了傳統色素合成過程中三廢的產生,極大地簡化了製程流程,不僅可以降低能耗,減少所需人工,也可以降低生產成本。
此外,上述稠環芳香類色素和高分子材料的混合物的製備方法,可以根據需要選擇用於生成不同色素的反應物,結合產物可能的顏色,可以得到更多的顏色,並且相較於傳統的將不同色素混合的方法,本申請得到的混合物顏色更均勻。
另外,由於色素的原料反應物在高分子材料中有更好的分散性,本申請的色素經擠出或捏合可直接生成並均勻分散於熱塑性高分子材料中,相較於先生成色素,再將色素和熱塑性高分子材料混合,本申請得到的混合物相容性更好。
為了便於理解本發明,下面將對本發明進行更全面的描述,並給出了本發明的較佳實施例。但是,本發明可以以許多不同的形式來實現,並不限於本文所描述的實施例。相反地,提供這些實施例的目的是使對本發明的公開內容的理解更加透徹全面。
除非另有定義,本文所使用的所有的技術和科學術語與屬於本發明的技術領域的技術人員通常理解的含義相同。本文中在本發明的說明書中所使用的術語只是為了描述具體的實施例的目的,不是旨在於限制本發明。本文所使用的術語「和/或」包括一個或多個相關的所列項目的任意的和所有的組合。
一實施方式的稠環芳香類色素和高分子材料的混合物的製備方法,包括以下步驟:
將熱塑性高分子材料和用於形成稠環芳香類色素的反應物混合,經捏合或擠出,得到稠環芳香類色素和高分子材料的混合物。
其中,用於形成稠環芳香類色素的反應物包括酸酐功能化的稠環芳香化合物衍生物、鄰二胺化合物和催化劑。
需要說明的是,捏合或擠出過程中,酸酐功能化的稠環芳香化合物衍生物和鄰二胺化合物能在催化劑作用下反應得到稠環芳香類色素。
進一步的,酸酐功能化的稠環芳香化合物衍生物選自以下化合物中的至少一種:
其中,R
1-R
12分別獨立地選自H、鹵素、胺基、帶有取代基的胺基、C1-C30烷基、C1-C20烷氧基、酚羥基、帶有取代基的酚羥基、苯基、帶有取代基的苯基、萘基、帶有取代基的萘基、巰基、帶有取代基的巰基、氰基、矽烷基、羧酸酯基、磺酸基、磺酸酯基、磷酸基及磷酸酯基中的一種;
R'選自H、C1-C30烷基、C1-C20烷氧基、苯基、帶有取代基的苯基、萘基、帶有取代基的萘基、矽烷基中的一種;
X
1和X
2分別獨立地選自CH
2、CHR''、CR''R'''、NR''、O、S、S=O及SO
2中的一種,R''和R'''分別獨立地選自H、C1-C30烷基、C1-C20烷氧基、帶有取代基的芳香基中的一種。
進一步的,鄰二胺化合物選自以下化合物中的至少一種:
、
、
、
、
其中,R
1、R
2、R
3、R
4分別獨立地選自H、鹵素、氰基、硝基、醛基、羧基、酸酐、醯胺、醯亞胺、酯基、烷基、烷氧基或巰基中的至少一種;
R'分別獨立地選自H、C1-C30烷基、C1-C20烷氧基、帶有取代基的芳香基中的一種;
X為含有S、N、O、CO、SO、SO
2或C=C基團的五元或六元環結構。
可以理解,本申請可生成的稠環芳香類色素不限於以上描述的幾種,任何酸酐功能化的稠環芳香化合物衍生物與鄰二胺化合物反應可得到的稠環芳香類色素均在本申請保護範圍內,這裡不再一一例舉。
進一步的,稠環芳香類色素和高分子材料的混合物中稠環芳香類色素的品質含量為0.1%~50%。
可以理解,通過控制鄰二胺化合物與酸酐功能化的稠環芳香化合物衍生物中酸酐功能團的莫耳比為1:(1~1.1),催化劑與酸酐功能化的稠環芳香化合物衍生物的莫耳比為(0.1~10):1,使鄰二胺化合物與酸酐功能化的稠環芳香化合物衍生物在催化劑的作用下基本完全反應,得到的混合物中鄰二胺化合物的含量低於10ppm,降低了產品的毒性和致癌性。
進一步的,催化劑選自去水劑(如生石灰、活性氧化鋁、氯化鈣、硫酸鈣、氯化鋰、氯化鈉、硫酸鈉等)、路易士酸、路易士鹼(如氯化鋅、醋酸鋅、氯化鈦、烷基胺等)及金屬氧化物(如氧化鈦、氧化鋅、氧化鋁等)中的至少一種。
進一步的,熱塑性高分子材料選自聚烯烴、聚芳香取代烯烴、聚丙烯酸酯、聚鹵代烯烴、聚醯亞胺、聚酯、聚甲醛、聚乳酸、丙烯腈-丁二烯-苯乙烯共聚物(ABS樹脂),聚苯並咪唑(PBI),聚醚醚酮(PEEK),聚醚醯亞胺(PEI),聚醚碸(PES),聚苯醚(PPO),聚苯硫醚(PPS),聚偏二氟乙烯(PVDF),聚碳酸酯(PC),及聚醯胺(PA)中的至少一種。
進一步的,擠出在擠出機中進行。擠出機可以是單螺杆擠出機或雙螺杆擠出機。
進一步的,擠出的溫度沿物料前進的方向分別為:進料段120℃~330℃,擠出段150℃~360℃,出樣段180℃~380℃。
可以理解,擠出反應的溫度曲線與擠出機的總長度相適配,例如對於具有10節的雙螺杆擠出機,擠出反應的溫度曲線施加區域如下表所示:
進樣 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 出樣 |
溫度/℃ | 160-330 | 170-360 | 180-370 | 190-380 | 190-380 | 190-380 | 190-380 | 190-380 | 190-380 | 200-380 | 200-380 |
對於具有10節的單螺杆擠出機,擠出反應的溫度曲線施加區域如下表所示:
進樣 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 出樣 |
溫度/℃ | 160-330 | 170-360 | 180-360 | 190-380 | 190-380 | 190-380 | 190-380 | 190-380 | 190-380 | 200-380 | 200-380 |
當然,上述溫度曲線還可以施加於更多或更少節數的擠出機,通常取決於所選擇的用於生成稠環芳香類色素的反應物及熱塑性高分子材料。
上述稠環芳香類色素和高分子材料的混合物的製備方法,根據相容性、加工溫度和極性,可選用不同的熱塑性高分子材料與用於形成稠環芳香類色素的反應物(酸酐衍生物、鄰二胺化合物和催化劑)混合,通過調節各原料之間的反應莫耳比以及在整個反應體系中的用量,使它們的混合物能夠經擠出或捏合,一步得到稠環芳香類色素和高分子材料的混合物,相較於色素,色素的原料反應物在高分子材料中有更好的分散性,因此經擠出或捏合,色素能夠直接生成並均勻分散在高分子材料中,並且擠出或捏合過程無需加入任何溶劑,鄰二胺化合物也幾乎完全被消耗,得到的混合物無需分離純化,避免了傳統色素合成過程中三廢的產生,極大地簡化了製程流程,不僅可以降低能耗,減少所需人工,也可以降低生產成本。
可以理解,通過選擇用於形成不同色素的反應物,結合產物可能的顏色,可在擠出或捏合過程中配製非三原色的色彩,如黑色,即可以通過使用可產生紅色、黃色和藍色色素的反應物加工得到;綠色,則可以通過使用可產生黃色和藍色色素的反應物加工得到。相較於傳統的將不同色素混合的方法,本申請得到的混合物顏色更均勻。
此外,由於色素的原料反應物在高分子材料中有更好的分散性,因此經擠出或捏合,本申請的色素可直接生成並均勻分散在熱塑性高分子材料中,相較於先生成色素,再將色素和熱塑性高分子材料混合的方法,本申請的混合物具有更好的相容性。
進一步的,將上述稠環芳香類色素和高分子材料的混合物經冷卻、乾燥、切粒,即可得到色母粒粗品。
進一步的,為了得到優質的色母粒產品,可以選擇性地將傳統色母粒所需的添加劑(如阻燃劑、螢光增白劑、紫外吸收劑、抗氧化劑、潤滑劑、增塑劑、抗菌劑以及其他高分子所需填料)和上述色母粒粗品混合,經擠出、冷卻、乾燥、切粒,即可得到色母粒產品。或選擇性地將上述添加劑和稠環芳香類色素和高分子材料的混合物的原料混合,經擠出、冷卻、乾燥、切粒,即可得到色母粒產品。
其中,色母粒產品的粒徑為200 μm~0.5 cm。
將上述色母粒粗品或色母粒產品進一步研磨即可得到高品質的高分子顏料。
進一步的,高分子顏料的粒徑為0.01 μm~100 μm。
以下為具體實施例。
為了更好的測試色母粒粗品的性能,取色母粒粗品,以1%的濃度和ABS混合後注塑得到不透明的薄片,測試其反射光譜圖。
實施例1-6
實施例1~6均按以下方法製備:
將0.5 kg的PMMA、(32 g,119 mmol)化合物(1-1)、(25 g, 231 mmol)化合物(1-2)和催化劑混合,在單螺杆擠出機中擠出反應,冷卻乾燥切粒後得到含有化合物(1-3)的色母粒粗品。
實施例1~6基本相同,不同的是催化劑的種類和用量,具體如表1所示:
表1
實施例 | 催化劑 | 產物顏色 |
1 | - | Orange(橙色) |
2 | CaO(氧化鈣) 4eq | Yellow-organe(黃橙色) |
3 | Zinc acetate(醋酸鋅) 0.08 eq | Orange(橙色) |
4 | Oxalic acid (草酸)6 eq, CaO(氧化鈣) 4eq | Orange-red(橙色-紅色) |
5 | Oxalic acid (草酸)6 eq | Yellow-orange(黃橙色) |
6 | CaO (氧化鈣)4eq, Zinc acetate (醋酸鋅)0.08eq | Yellow-orange(黃橙色) |
圖1為實施例4製備的色母粒粗品以1%的濃度混合ABS注塑得到1mm厚的塑膠薄片的反射光譜圖,由圖1可知,其吸收主要在藍到橙色光區域,與顏料橙43和顏料紅194的混合物類似。
實施例7
將0.5 kg的PMMA、(30 g,152 mmol)化合物(7-1)、(23.5 g,148 mmol)化合物(7-2)和(3.5 g,19mmol)催化劑醋酸鋅混合,在雙螺杆擠出機中擠出反應,冷卻乾燥切粒後得到含有化合物(7-3)的色母粒粗品,該色母粒粗品呈黃紅色。
請參閱圖2,為實施例7製備的色母粒粗品以1%濃度混合ABS後的反射光譜圖,由圖2可知,該材料主要吸收在綠光區域。
實施例8
將0.5 kg的PC、(28 g,104 mmol)化合物(8-1)、(32 g,203mmol)化合物(8-2)和(4.7 g,26mmol)催化劑醋酸鋅混合,在單螺杆擠出機中擠出反應,冷卻乾燥切粒得到含有化合物(8-3)的色母粒粗品,該色母粒粗品呈深藍色。
實施例9
將0.5 kg的PET、(40 g,75 mmol)化合物(9-1)、(16 g,148mmol)化合物(9-2)和(3.4 g,19mmol)催化劑醋酸鋅混合,在單螺杆擠出機中擠出反應,冷卻乾燥切粒得到含有化合物(9-3)的色母粒粗品,該色母粒粗品呈紫黑色。
請參閱圖3,為實施例9製備的色母粒粗品以1%的濃度混合ABS後的反射光譜圖,由圖3可知,該材料主要吸收藍色到紅光。
實施例10
將0.5 kg的PA、(36 g,68 mmol)化合物(10-1)、(21 g,133 mmol)化合物(10-2)和(3 g,16mmol)催化劑醋酸鋅混合,在雙螺杆擠出機中擠出反應,冷卻乾燥切粒得到含有化合物(10-3)的色母粒粗品,該色母粒粗品呈藍黑色。
請參閱圖4,為實施例10製備的色母粒粗品以1%濃度混合ABS後的反射光譜圖,由圖4可知,該材料吸收可見光很強,但對紅外光吸收很弱,可見該材料為非常好的「冷」黑色材料,即不吸收紅外光的黑色材料。
實施例11
將1 kg的PMMA、(10 g,50 mmol)化合物(11-1)、(5.4 g, 50 mmol)化合物(11-2)和(3 g,16mmol)催化劑醋酸鋅混合,在單螺杆擠出機中擠出反應,冷卻乾燥切粒得到含有化合物(11-3)的色母粒粗品,該色母粒粗品呈粉色。
實施例12
將1 kg的PMMA、(10 g, 50 mmol)化合物(12-1)、(9.4 g,50 mmol)化合物(12-2)和(3.5 g,19mmol)催化劑醋酸鋅混合,在單螺杆擠出機中擠出反應,得到含有化合物(12-3)的色母粒粗品,該色母粒粗品呈灰紅色。
實施例13
將0.5 kg的PMMA、(12 g, 60 mmol)化合物(13-1)、(16 g,60 mmol)化合物(13-2)、(28 g,177 mmol)化合物(13-3)和(3.3 g,18mmol)催化劑醋酸鋅混合,在雙螺杆擠出機中擠出反應,得到含有化合物(13-4)和化合物(13-5)的色母粒粗品,該色母粒粗品呈藍黑色。
請參閱圖5,為實施例13製備的色母粒粗品以1%濃度混合ABS後的反射光譜圖,由圖5可知,該材料比實例10中的「冷」色效果更好,在紅外區域吸收更弱,是非常好的減少太陽光產生熱的藍黑顏色產品。
實施例14
將0.5 kg的PMMA、(20 g,75 mmol)化合物(14-1)、(11 g,70 mmol)化合物(14-2)、(8 g,74mmol)化合物(14-3)和(1.7 g,9mmol)催化劑醋酸鋅混合,在雙螺杆擠出機中擠出反應,得到含有化合物(14-4)、化合物(14-5)和化合物(14-6)的色母粒粗品,該色母粒粗品呈黑綠色。
請參閱圖6,為實施例14製備的色母粒粗品以1%濃度混合ABS後的反射光譜圖,由圖6可知,該材料和實例10和13類似,但性能更好,吸收可見光非常強,但對紅外光的吸收很弱。
實施例15
將0.5 kg的PMMA、(38 g,133 mmol)化合物(15-1)、(20 g,127 mmol)化合物(15-2)、(6 g,31 mmol)化合物(15-3)作為阻止鹵素和胺反應的抑制劑和(2.9 g,16mmol)催化劑醋酸鋅混合,在單螺杆擠出機中擠出反應,冷卻乾燥切粒得到含有化合物(15-4)的色母粒粗品,該色母粒粗品呈紅色。
請參閱圖7,為實施例15製備的色母粒粗品以1%濃度混合ABS後的反射光譜圖,由圖7可知,該材料只在藍到橙光區域有吸收,是非常好的紅色著色劑。
實施例16
將0.5 kg的PMMA、(15 g,52 mmol)化合物(16-1)、(14 g,52 mmol)化合物(16-2)、(24 g,152 mmol)化合物(16-3)、(2.52 g,13 mmol)化合物(16-4)作為阻止鹵素和胺反應的抑制劑和(2.8 g,15mmol)催化劑醋酸鋅混合,在雙螺杆擠出機中擠出反應,冷卻乾燥切粒得到含有化合物(16-5)和化合物(16-6)的色母粒粗品,該色母粒粗品呈黑色。
圖8為實施例16製備的色母粒粗品以1%濃度混合ABS樹脂後的反射光譜圖,由圖8可知為很好的「冷」黑色產品。
為了測試擠出反應的效果,以鄰苯二胺及1,8-二胺萘的0.01mg/mL溶液(溶劑由體積比為3:7的水和乙腈組成)為標樣,取10 mg左右的實例8,9,10的5 mL溶液(溶劑由體積比為3:7的水和乙腈組成),在測試範圍內,實例8和10中未發現1,8-二胺萘,實例9中未發現鄰苯二胺。說明該類方法可以得到轉換率100%的安全色母粒粗品。
以上所述實施例僅表達了本發明的幾種實施方式,其描述較為具體和詳細,但並不能因此而理解為對本發明專利範圍的限制。應當指出的是,對於本領域的普通技術人員來說,在不脫離本發明構思的前提下,還可以做出若干變形和改進,這些都屬於本發明的保護範圍。因此,本發明專利的保護範圍應以所附發明申請專利範圍為准。
無。
圖1為實施例4製備的色母粒粗品與ABS混合的反射光譜圖;
圖2為實施例7製備的色母粒粗品與ABS混合的反射光譜圖;
圖3為實施例9製備的色母粒粗品與ABS混合的反射光譜圖;
圖4為實施例10製備的色母粒粗品與ABS混合的反射光譜圖;
圖5為實施例13製備的色母粒粗品與ABS混合的反射光譜圖;
圖6為實施例14製備的色母粒粗品與ABS混合的反射光譜圖;
圖7為實施例15製備的色母粒粗品與ABS混合的反射光譜圖;
圖8為實施例16製備的色母粒粗品與ABS混合的反射光譜圖。
Claims (10)
- 一種稠環芳香類色素和高分子材料的混合物的製備方法,其特徵在於,包括以下步驟:將熱塑性高分子材料和用於形成稠環芳香類色素的反應物混合,經捏合或擠出,得到稠環芳香類色素和高分子材料的混合物;所述用於形成稠環芳香類色素的反應物包括酸酐功能化的稠環芳香化合物衍生物、鄰二胺化合物和催化劑,所述稠環芳香類色素和高分子材料的混合物中稠環芳香類色素的品質含量為0.1%~50%,所述鄰二胺化合物與所述酸酐功能化的稠環芳香化合物衍生物中酸酐官能團的莫耳比為1:(1~1.1),所述催化劑與所述酸酐功能化的稠環芳香化合物衍生物的莫耳比為(0.01~10):1;所述酸酐功能化的稠環芳香化合物衍生物選自以下化合物中的至少一種:
- 如請求項1所述的稠環芳香類色素和高分子材料的混合物的製備方法,其特徵在於,所述催化劑選自去水劑、路易士酸、路易士鹼及金屬氧化物中的至少一種。
- 如請求項1至3中任一項所述的稠環芳香類色素和高分子材料的混合物的製備方法,其特徵在於,所述擠出的溫度沿物料前進的方向分別為進料段120℃~330℃、擠出段150℃~360℃、出樣段180℃~380℃。
- 一種如請求項1至4中任一項所述的稠環芳香類色素和高分子材料的混合物的製備方法製得的稠環芳香類色素和高分子材料的混合物。
- 一種色母粒粗品,其特徵在於,由如請求項5所述的稠環芳香類色素和高分子材料的混合物經冷卻、乾燥、切粒而得。
- 一種色母粒產品,其特徵在於,由如請求項5所述的稠環芳香類色素和高分子材料的混合物的原料與添加劑混合,經擠出、冷卻、乾燥、切粒而得;或由如請求項6所述的色母粒粗品與添加劑混合,經擠出、冷卻、乾燥、切粒而得。
- 如請求項7所述的色母粒產品,其特徵在於,所述色母粒產品的粒徑為200μm~0.5cm。
- 一種高分子顏料,其特徵在於,由如請求項6所述的色母粒粗品或如請求項8所述的色母粒產品研磨而得。
- 如請求項9所述的高分子顏料,其特徵在於,所述高分子顏料的粒徑為0.01μm~100μm。
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US7169922B2 (en) * | 2000-08-04 | 2007-01-30 | Invitrogen Corporation | Derivatives of 1,2-dihydro-7-hydroxyquinolines containing fused rings |
CN101896555A (zh) * | 2007-12-10 | 2010-11-24 | 巴斯夫欧洲公司 | 着色剂在混合装置中的合成 |
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