CN1311267A - 用于塑料本体染色方法 - Google Patents
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
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- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/14—Styryl dyes
- C09B23/143—Styryl dyes the ethylene chain carrying a COOH or a functionally modified derivative, e.g.-CN, -COR, -COOR, -CON=, C6H5-CH=C-CN
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0041—Optical brightening agents, organic pigments
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
一种用于塑料本体染色的方法,其特征在于使用式(Ⅰ)染料,其中Y是选自取代的和未取代的亚芳基和亚烷基的二价基团,如果需要,其中的亚烷基可被诸如O或S的杂原子间断,R1和R1’彼此独立地是吸电子基团,优选氰基或烷氧基羰基,特别是C1-C4-烷氧基羰基,R2、R2’、R3和R3’彼此独立地是氢、烷基,特别是C1-C4-烷基、CF3或卤素,优选F或C1,R4和R4’彼此独立地是未取代的或取代的烷基,优选C1-C6-烷基,或C7-C12芳烷基,特别是苄基。
Description
本发明涉及用于塑料本体染色的方法,其特征在于使用式(Ⅰ)染料
其中
Y是选自取代的和未取代的亚芳基和亚烷基的二价基团,如果需要,其中的亚烷基可被诸如O或S的杂原子间断,
R1和R1’彼此独立地是吸电子基团,优选氰基或烷氧基羰基,特别是C1-C4-烷氧基羰基,
R2、R2’、R3和R3’彼此独立地是氢、烷基,特别是C1-C4-烷基、CF3或卤素,优选F或Cl,
R4和R4’彼此独立地是未取代的或取代的烷基,优选C1-C6-烷基,或C7-C12芳烷基,优选苄基。
在一个优选的实施方案中,
Y表示未取代的或取代的亚苯基,或未取代的或取代的C1-C6-亚烷基,特别优选的Y基团的例子是1,3-亚苯基、1,4-亚苯基或甲基取代的1,3-或1,4-亚苯基,-CH2-CH2-、-CH2CH2CH2-、-(CH2)4-、-CH2CH(CH3)-、-CH2CH2-O-CH2CH2-和-CH2CH2-S-CH2CH2-。
尤其特别优选亚烷基,特别是-CH2-CH2-、-(CH2)3-、-(CH2)4-、和-CH2CH2-O-CH2CH2-。
特别优选的基团R1和R1’是:-CN、-CO2CH3、-CO2CH2CH3、-CO2(CH2)2CH3和-CO2(CH2)3CH3。
特别优选的基团R2、R2’、R3和R3’的实例是:氢、甲基、乙基、Cl、F、CF3、甲氧基和乙氧基。
特别优选的基团R4和R4’的实例是:CH3、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基和叔丁基。
在一个优选的实施方案中,在根据本发明的应用中,式(Ⅰ)中R1=R1’,R2=R2’,R3=R3’和R4=R4’。
其中
Y是选自未取代的和取代的亚苯基,特别是1,3-或1,4-亚苯基,或未取代的或取代的C2-C6亚烷基,特别是亚乙基(ethylene)、亚丙基(propylene)或亚丁基(butylene),
R1是-CN、CO2CH3、CO2CH2CH3或CO2(CH2)3CH3,
R2是氢、CH3或CH2CH3,和
R4是CH3、CH2CH3、正丙基或正丁基。
用样优选使用其中取代基对R1/R1’、R2/R2’、R3/R3’和R4/R4’中至少一个是不相同(例如R1≠R1’)的式(Ⅰ)染料。本发明还提供这些式(Ⅰ)的不对称染料。
基于本申请的目的,本体染色以特定的方式进行,其中将式(Ⅰ)染料与熔融的塑料混合,例如在挤出机的帮助下;或其中在聚合前将染料直接加入到制备塑料的起始原料其加入到单体中。
大概的工艺温度为100-380℃。
根据本发明使用的一些染料是已知的(例如CH-516628、JP-A02292371),其它的可以用从文献可知的方法类似地制备。一个制备的例子是Vilsmeier甲酰化反应,随后与反应性亚甲基化合物、优选丙二腈缩合。
其中
n是2-6,
X表示卤素,特别是Cl或Br,其它的取代基定义如上,
或者取代的苯胺与N-(卤代烷基)苯胺缩合(Eq.2),例如在溶剂中或在本体中,在碱存在下,随后进行Vilsmeier甲酰化反应(优选通过与POCl3和二甲基甲酰胺反应,然后水解),之后与反应性亚甲基化合物、优选丙二腈缩合。
可述及的适合的热塑性塑料的例子是:纤维素酯类,例如硝酸纤维素、乙酸纤维素、三乙酸纤维素、乙酰丁酸纤维素和丙酸纤维素;纤维素醚类,诸如甲基纤维素、乙基纤维素和苄基纤维素;线性饱和的聚酯树脂;苯胺树脂;聚碳酸酯;聚苯乙烯;聚乙烯基咔唑;聚氯乙烯,特别是未增塑的PVC;聚甲基丙烯酸酯;聚偏二氯乙烯;聚丙烯腈;聚甲醛类;线性聚氨基甲酸酯;以及还有共聚物,诸如氯乙烯-乙酸乙烯酯共聚物,和特别是苯乙烯共聚物,诸如苯乙烯-丙烯腈共聚物(SAN)、苯乙烯-丁二烯共聚物(SB)和苯乙烯-α-甲基苯乙烯共聚物(SMS)和丙烯腈-丁二烯-苯乙烯共聚物(ABS)。
所述的高分子量化合物可单独存在或以混合物形式作为塑料或熔融体存在,如果需要,可纺成纤维。
该新方法特别适用于聚苯乙烯的本体染色,尤其是用于聚(甲基)丙烯酸酯的本体染色,并优选用于聚甲基丙烯酸甲酯、SAN、SMS、ABS或聚对苯二酸乙二酯或聚对苯二酸丁二酯。
对于被染色的塑料,方便的是呈粉末状、碎薄片状或粒状形式并且是与染料紧密混合的。实现这一点的一个方法是用细分散的干粉状染料涂敷塑料颗粒,或用染料在有机溶剂中的溶液或分散体处理颗粒并随后除去溶剂。
本发明的方法还可使用不同的式(Ⅰ)染料的混合物和/或式(Ⅰ)染料与其它染料和/或与无机或有机颜料的混合物。
当根据本发明使用式(Ⅰ)染料时,优选以其固体形式使用,特别是粉末状或颗粒状。
这些固体染料制品含有至少95%重量、优选至少98%重量、特别是大于99%重量的式(Ⅰ)染料和如果需要至多5%重量的有机粘合剂,每种情况均以染料制剂为基准计。
本发明还提供这些染料制剂。
可能的粘合剂的例子是环氧乙烷-环氧丙烷嵌段共聚物,优选那些摩尔质量为4000-16000g/mol的。
当用于染色时,染料制剂特别优选为粉末形式,尤其是以已经研磨并过筛的干燥粉末形式,或者以小颗粒的形式,诸如那些可根据例如EP-A-488933制备的。
染料与塑料的比率可在宽范围内变化,取决于所需的颜色强度。基于被染色的塑料的量,通常建议使用0.005-5%重量、优选0.01-2%重量的染料。
通过加入不溶于聚合物的颜料,例如二氧化钛,可得到相应的优质不透明的着色。
基于聚合物的量,可使用的二氧化钛的量的例子是0.01-10%重量,优选0.1-5%重量。
处理后的聚合物颗粒在挤出机中用已知方法熔化并挤塑成制品诸如薄膜或纤维,或铸塑成薄片。
用式(Ⅰ)染料给塑料染色的一种方法是将这种类型的染料与这些基体用辊式捏合机、混合设备或研磨设备混合,如果需要,染料以母炼胶的形式使用。然后,染色了的材料用本身已知的方法诸如通过压延、压塑、挤塑、涂铺、铸塑或注塑加工成所需要的最终形式。
在成型前将已知的增塑剂掺混入所述高分子量化合物中以生产非刚性模制品或降低其脆性经常是可取的。可使用的增塑剂的例子是磷酸、邻苯二甲酸或癸二酸的酯。在本发明的方法中,增塑剂可在染料掺混入聚合物之前或之后掺入。此外,可以将任何所需量的填料和/或其它诸如白色颜料、彩色颜料或黑色颜料之类的着色剂与式(Ⅰ)化合物一起加入到高分子量有机物质中以达到不同的色调。
产生的呈绿色到呈微红-黄的颜色具有好的耐光性和好的耐候性。本发明的染料在热塑性塑料中还非常耐热。
实施例1
和2g二氧化钛(BayertitanR-FK-2)和100g粒化的聚苯乙烯在密封容器中在滚子床上混合2小时。将得到的混合物在约230℃挤压成宽2cm的挤塑制品并再次粒化。在230-240℃将颗粒注塑。得到着微红-黄色的模制品,有高耐光性和高亮度。
实施例2
0.02g式(A)染料和100g粒化的聚苯乙烯在密封容器中在滚子床上混合2小时。然后,将得到的混合物在230-240℃注塑,使用有螺杆的注塑机,得到模制品。着黄色透明的模制品具有高耐光性。
工艺如实施例1所述,得到着黄色的高耐光性的模制品。
实施例4
如果0.035g式(B)染料和100g粒化的聚苯乙烯混合,工艺如实施例2所述,得到高耐光性着黄色的透明模制品。
实施例5
0.03g式(A)染料溶于99.97g甲基丙烯酸甲酯。加入0.01g过氧化二苯甲酰后,溶液加热到120℃,引发聚合。30分钟后,开始聚合的甲基丙烯酸甲酯置于两个玻璃盘中,在80℃10小时完成聚合。得到着黄色的透明聚甲基丙烯酸甲酯薄片。
实施例6
0.02g式(B)染料和100g聚甲基丙烯酸甲酯在双螺杆挤压机中在240℃干混并匀化。将作为挤出物排出的物质粒化。然后通过压塑成型。得到透明的着黄色的塑料,具有非常好的耐光性和耐候性。
实施例7
将100g可从市场购买的粒状聚碳酸酯与0.01g式(A)的固体干混。得到的颗粒在双螺杆挤出机中在350℃匀化。得到透明的黄色着色,具有好的耐光性。被染色的聚碳酸酯作为挤塑制品排出并粒化。可将该颗粒用常规的热塑加工方法加工。
实施例8
将0.04g式(B)的固体和100g苯乙烯-丙烯腈共聚物干混并在双螺杆挤出机中在190℃匀化和粒化,然后通过压塑以常规方法成型。得到透明的着色塑料,具有好的耐光性。如果在操作期间加入1%的二氧化钛,则得到不透明的着色。
实施例9
工艺如实施例1所述,则得到着黄色的高耐光性的模制品。
实施例10-15
Claims (14)
1.用于塑料本体染色的方法,其特征在于使用式(Ⅰ)染料
其中
Y是选自取代的和未取代的亚芳基和亚烷基的二价基团,如果需要,其中的亚烷基可被诸如O或S的杂原子间断,
R1和R1’彼此独立地是吸电子基团,优选氰基或烷氧基羰基,特别是C1-C4-烷氧基羰基,
R2、R2’、R3和R3’彼此独立地是氢、烷基,特别是C1-C4-烷基、CF3或卤素,优选F或Cl,
R4和R4’彼此独立地是未取代的或取代的烷基,优选C1-C6-烷基,或C7-C12芳烷基,优选苄基。
2.根据权利要求1的方法,其特征在于
Y表示未取代的或取代的亚苯基,特别是1,3-亚苯基、1,4-亚苯基或甲基取代的1,3-或1,4-亚苯基;或未取代的或取代的C1-C6-亚烷基,特别是-CH2-CH2-、-CH2CH2CH2-、-(CH2)4-、-CH2CH(CH3)-、-CH2CH2-O-CH2CH2-或-CH2CH2-S-CH2CH2-。
3.根据权利要求1的方法,其特征在于R1和R1’彼此独立地是-CN、-CO2CH3、-CO2CH2CH3、-CO2(CH2)2CH3或-CO2(CH2)3CH3。
4.根据权利要求1的方法,其特征在于基团R2、R2’、R3和R3’分别独立地是氢、甲基、乙基、Cl、F或CF3。
5.根据权利要求1的方法,其特征在于基团R4和R4’是:CH3、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基。
6.根据权利要求1的方法,其特征在于R1=R1’,R2=R2’,R3=R3’和R4=R4’。
8.根据权利要求1的方法,其特征在于使用其中取代基对R1/R1’、R2/R2’、R3/R3’和/或R4/R4’中至少一个是不相同的式(Ⅰ)染料。
11.固体染料制剂,含有至少95%重量的根据权利要求1的式(Ⅰ)染料。
12.制备权利要求10的染料的方法,其特征在于使取代的苯胺与二卤代烷反应,
其中
n是2-6,X表示卤素,特别是Cl或Br,其它的取代基定义如上,
或者使取代的苯胺与N-(卤代烷基)苯胺反应(Eq.2),例如在溶剂中或在本体中、在碱存在下进行,随后进行Vilsmeier甲酰化反应(优选通过与POCl3和二甲基甲酰胺反应,然后水解),之后与反应性亚甲基化合物、优选丙二腈缩合。
13.用权利要求10的至少一种染料染色了的塑料。
14.被至少一种权利要求1的式(Ⅰ)染料染色了的、选自苯乙烯-丙烯腈共聚物(SAN)和丙烯腈-丁二烯-苯乙烯共聚物(ABS)的共聚物。
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US3553245A (en) * | 1964-10-19 | 1971-01-05 | Eastman Kodak Co | Cyanomethylidene aniline compounds |
CH516628A (de) * | 1967-08-08 | 1971-12-15 | Ciba Geigy Ag | Farbstoffpräparate, welche wasserunlösliche Styrylfarbstoffe enthalten |
DE2446759C2 (de) * | 1974-10-01 | 1982-12-02 | Bayer Ag, 5090 Leverkusen | Styrylfarbstoffe |
DE2447229A1 (de) * | 1974-10-03 | 1976-04-15 | Bayer Ag | Styrylfarbstoffe |
US4331584A (en) * | 1979-06-04 | 1982-05-25 | Sumitomo Chemical Company, Limited | Styryl compounds and coloring synthetic resins therewith |
JPS6018700B2 (ja) * | 1980-04-28 | 1985-05-11 | 住友化学工業株式会社 | スチリル系化合物、その製法およびそれを用いる高分子有機材料の着色方法 |
US5218136A (en) * | 1987-12-28 | 1993-06-08 | Sumitomo Chemical Company, Limited | Styryl compounds, process for preparing the same and photoresist compositions comprising the same |
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US5223476A (en) * | 1989-05-02 | 1993-06-29 | Dai Nippon Insatsu Kabushiki Kaisha | Heat transfer sheet |
US5106942A (en) * | 1990-01-08 | 1992-04-21 | Eastman Kodak Company | Copolymerized methine colorant-polyester color concentrates |
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CN108623825B (zh) * | 2018-05-18 | 2021-07-09 | 海南热带海洋学院 | 海洋污染微塑料染色方法 |
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