CN113348199A - 支链有机硅化合物、制备支链有机硅化合物的方法以及用其形成的共聚物 - Google Patents
支链有机硅化合物、制备支链有机硅化合物的方法以及用其形成的共聚物 Download PDFInfo
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- CN113348199A CN113348199A CN201980090319.9A CN201980090319A CN113348199A CN 113348199 A CN113348199 A CN 113348199A CN 201980090319 A CN201980090319 A CN 201980090319A CN 113348199 A CN113348199 A CN 113348199A
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- Prior art keywords
- acrylate
- organosilicon compound
- osir
- composition
- compound
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- 150000001875 compounds Chemical class 0.000 claims abstract description 167
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Classifications
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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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
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Abstract
提供了具有以下通式的支链有机硅化合物(“化合物”):(R1)3Si‑X‑NR2R3,其中X为二价连接基团;R2为H或R;R3包含丙烯酰氧基部分;每个R1选自R和‑OSi(R4)3,前提条件是至少一个R1为‑OSi(R4)3;其中每个R4选自R、‑OSi(R5)3和‑[OSiR2]mOSiR3;其中每个R5选自R、‑OSi(R6)3和‑[OSiR2]mOSiR3;并且其中每个R6选自R和‑[OSiR2]mOSiR3,前提条件是R4、R5和R6中的至少一者为‑[OSiR2]mOSiR3;0≤m≤100;并且每个R为取代或未取代的烃基基团。还提供了制备所述化合物的方法、包含所述化合物和与所述化合物反应的第二化合物的反应产物的共聚物、形成所述共聚物的方法以及包含所述化合物和所述共聚物中的至少一者的组合物。
Description
相关申请的交叉引用
本申请要求2018年12月31日提交的美国临时专利申请号62/786,843的优先权和所有优点,该专利申请的内容以引用方式并入本文。
技术领域
本发明整体涉及有机硅化合物,并且更具体地,涉及支链有机硅化合物、用支链有机硅化合物形成的共聚物、制备支链有机硅化合物中的每一种的方法以及包含支链有机硅化合物的组合物。
背景技术
有机硅是用于许多商业应用的聚合物材料,主要是由于它们具有优于它们的碳基类似物的显著优点。更确切地说,被称为聚合硅氧烷或聚硅氧烷的有机硅具有无机硅-氧主链(…-Si-O-Si-O-Si-O-…),其中有机侧基附接到硅原子。
有机侧基可用于将这些主链中的两个或更多个主链连接在一起。通过改变-Si-O-链长、侧基和交联,可合成具有多种性质和组成的有机硅。它们的稠度可从液体到凝胶到橡胶到硬塑料而变化。最常见的硅氧烷为直链聚二甲基硅氧烷(PDMS),一种有机硅油。第二大组有机硅材料基于由支链和笼状低聚硅氧烷形成的有机硅树脂。
另一组有机硅材料为有机硅树枝状体。树枝状体是具有从单个核径向延伸的高度支化结构的聚合物。树枝状体是通常围绕核对称的(或接近对称的)重复支化的分子,并且通常采用球形或椭球体三维形态。树枝状聚合物也可被描述为由独特的支链-接-支链-接-支链结构组织或世代组成的树状大分子。
树枝状有机硅或大分子具有为许多潜在的最终应用提供的分子形状、尺寸和官能度。因此,仍然有机会提供改善的基于硅的支链化合物,以及改善的形成此类化合物的方法。仍然有机会提供改善的共聚物和改善的基于或具有此类化合物的组合物。
发明内容
本发明提供了一种支链有机硅化合物。该支链有机硅化合物具有通式:
其中X为二价连接基团;R2为H或R,其中R为取代或未取代的烃基基团;R3包含丙烯酰氧基部分;并且每个R1选自R和-OSi(R4)3,前提条件是至少一个R1为-OSi(R4)3;其中每个R4选自R、-OSi(R5)3和-[OSiR2]mOSiR3;其中每个R5选自R、-OSi(R6)3和-[OSiR2]mOSiR3;其中每个R6选自R和-[OSiR2]mOSiR3;并且其中0≤m≤100;前提条件是R4、R5和R6中的至少一者为-[OSiR2]mOSiR3。
还提供了一种制备支链有机硅化合物的方法。该方法包括使(A)有机硅化合物和(B)官能化合物任选地在存在(C)催化剂的情况下反应以得到支链有机硅化合物。
还提供了一种共聚物。共聚物包含支链有机硅化合物和与支链有机硅化合物反应的第二化合物的反应产物。
本发明还提供了一种制备所述共聚物的方法,并且所述方法包括使所述支链有机硅化合物和与所述支链有机硅化合物反应的所述第二化合物反应以得到所述共聚物。
还提供了一种组合物。该组合物包含支链有机硅化合物和共聚物中的至少一者。
具体实施方式
一种支链有机硅化合物,所述支链有机硅化合物具有通式:
其中X为二价连接基团;R2为H或R,其中R为取代或未取代的烃基基团;R3包含丙烯酰氧基部分;并且每个R1选自R和-OSi(R4)3,前提条件是至少一个R1为-OSi(R4)3;其中每个R4选自R、-OSi(R5)3和-[OSiR2]mOSiR3;其中每个R5选自R、-OSi(R6)3和-[OSiR2]mOSiR3;其中每个R6选自R和-[OSiR2]mOSiR3;并且其中0≤m≤100;前提条件是R4、R5和R6中的至少一者为-[OSiR2]mOSiR3。
每个R独立地选择并且可为直链、支链、环状或它们的组合。环状烃基基团包括芳基基团以及饱和或非共轭的环状基团。环状烃基基团可为单环的或多环的。直链和支链烃基基团可以独立地为饱和或不饱和的。直链和环状烃基基团的组合的一个示例为芳烷基基团。所谓“取代的”意指一个或多个氢原子可用除氢之外的原子(例如,卤素原子,诸如氯、氟、溴等)替代,或者R的链内的碳原子可用除碳之外的原子替代,即,R可包括链内的一个或多个杂原子,诸如氧、硫、氮等。合适的烷基基团的示例有但不限于甲基、乙基、丙基(例如异丙基和/或正丙基)、丁基(例如异丁基、正丁基、叔丁基和/或仲丁基)、戊基(例如异戊基、新戊基和/或叔戊基)、己基以及具有6个碳原子的支链饱和烃基团。合适的芳基基团的示例有但不限于苯基、甲苯基、二甲苯基、萘基、苄基和二甲基苯基。合适的烯基基团包括乙烯基、烯丙基、丙烯基、异丙烯基、丁烯基、异丁烯基、戊烯基、庚烯基、己烯基和环己烯基基团。合适的单价卤代烃基团包括但不限于1个至6个碳原子的卤代烷基基团、或6个至10个碳原子的卤代芳基基团。合适的卤代烷基基团的示例有但不限于上述烷基基团,其中一个或多个氢原子被卤素原子诸如F或Cl替代。例如,氟甲基、2-氟丙基、3,3,3-三氟丙基、4,4,4-三氟丁基、4,4,4,3,3-五氟丁基、5,5,5,4,4,3,3-七氟戊基、6,6,6,5,5,4,4,3,3-九氟己基、以及8,8,8,7,7-五氟辛基、2,2-二氟环丙基、2,3-二氟环丁基、3,4-二氟环己基、以及3,4-二氟-5-甲基环庚基、氯甲基、氯丙基、2-二氯环丙基和2,3-二氯环戊基为合适的卤代烷基的示例。合适的卤代芳基基团的示例有但不限于上述芳基基团,其中一个或多个氢原子被卤素原子诸如F或Cl替代。例如,氯苄基和氟苄基为合适的卤代芳基。
在具体的实施方案中,每个R独立地为具有1个至10个、另选地1个至8个、另选地1个至6个、另选地1个至4个、另选地1个至3个、另选地1个至2个、另选地1个碳原子的烷基基团。
每个R1选自R和-OSi(R4)3,前提条件是至少一个R1为-OSi(R4)3。在某些实施方案中,至少两个R1为-OSi(R4)3。在具体的实施方案中,所有三个R1为-OSi(R4)3。当更多数量的R1为-OSi(R4)3时,有机硅化合物具有更高的支化水平。例如,当每个R1为-OSi(R4)3并且Si-X键为硅-碳键时,每个R1所键合的硅原子为T甲硅烷氧基单元。另选地,当两个R1为-OSi(R4)3并且Si-X键为硅-碳键时,每个R1所键合的硅原子为D甲硅烷氧基单元。
每个R4选自R、-OSi(R5)3和-[OSiR2]mOSiR3,其中0≤m≤100。根据R4和R5的选择,另外的支链可存在于支链有机硅化合物中。例如,当每个R4为R时,则每个-OSi(R4)3部分为末端M甲硅烷氧基单元。换句话讲,当每个R1为-OSi(R4)3时,并且当每个R4为R时,则每个R1可写为OSiR3,并且每个R1为M甲硅烷氧基单元。在此类实施方案中,支链有机硅化合物包含由三个M甲硅烷氧基单元封端的T甲硅烷氧基单元(X键合至该单元)。当R4为-[OSiR2]mOSiR3时,R4包含任选的D甲硅烷氧基单元(即,由下标m指示的部分中的那些甲硅烷氧基单元)和M甲硅烷氧基单元(由OSiR3表示)。因此,例如,当每个R1为-OSi(R4)3时,并且当每个R4为-[OSiR2]mOSiR3时,则每个R1包含Q甲硅烷氧基单元。在此类实施方案中,每个R1具有式-OSi([OSiR2]mOSiR3)3。当每个m为0时,每个R1为用三个M甲硅烷氧基单元封端的Q甲硅烷氧基单元。当m大于0时,每个R1包含聚合度可归因于m的线性部分。如果存在的话,该线性部分通常为二有机硅氧烷部分。
下标m为(并包括)0至100、另选地0至80、另选地0至60、另选地0至40、另选地0至20、另选地0至19、另选地0至18、另选地0至17、另选地0至16、另选地0至15、另选地0至14、另选地0至13、另选地0至12、另选地0至11、另选地0至10、另选地0至9、另选地0至8、另选地0至7、另选地0至6、另选地0至5、另选地0至4、另选地0至3、另选地0至2,另选地为0至1,另选地为0。通常,每个下标m为0,使得支链有机硅化合物的支链部分不含D甲硅烷氧基单元。
如上文所示出,每个R4也可为-OSi(R5)3。在此类实施方案中,根据R5的选择,另外的支链可存在于支链有机硅化合物中。每个R5选自R、-OSi(R6)3和-[OSiR2]mOSiR3,其中m如上定义;其中每个R6选自R和-[OSiR2]mOSiR3,其中m如上定义。R4、R5和R6中的至少一者为-[OSiR2]mOSiR3,其中m如上定义。当R1具有式-OSi(R4)3时,并且当R4具有式-OSi(R5)3时,另外的硅氧烷键和支链存在于支链有机硅化合物中。当R5为-OSi(R6)3时,也是这种情况。
具体地讲,支链有机硅化合物中的每个后续R部分可赋予另外一代的支链。例如,R1可具有式-OSi(R4)3,R4可具有式-OSi(R5)3,并且R5可为-OSi(R6)3。因此,取决于每个取代基的选择,可归因于T和/或Q甲硅烷氧基单元的另外的支链可存在于支链有机硅化合物中。
重要的是,独立地选择R、R1、R4、R5和R6中的每一者。因而,上文关于这些取代基中的每一个取代基的描述并不意味着意指或暗示每个取代基是相同的。上文关于R1的任何描述可涉及支链有机硅化合物中的仅一个R1或任何数量的R1,等等。
此外,对R、R1、R4、R5和R6的不同选择可导致相同的结构。例如,如果R1为-OSi(R4)3,并且如果每个R4为-OSi(R5)3,并且如果每个R5为R,则R1可写为-OSi(OSiR3)3。类似地,如果R1为-OSi(R4)3,并且如果每个R4为-[OSiR2]mOSiR3(其中m为0),则R1可写为-OSi(OSiR3)3。基于对R4的不同选择,这导致R1的相同结构。为此,R4、R5和R6中的至少一者为-[OSiR2]mOSiR3。然而,当m为0时,该条件可通过另选的选择而内在地得到满足。例如,如上所述,如果每个R4为-OSi(R5)3,并且如果每个R5为R,则R1可写为-OSi(OSiR3)3,其与以下情况中相同:如果R1为-OSi(R4)3,并且如果每个R4为-[OSiR2]mOSiR3,其中m为0。即使另选的选择可导致与条件中所要求相同的结构,也应当认为条件得到满足。
在某些实施方案中,每个R1为-OSi(R4)3。在其中每个R1为-OSi(R4)3的具体实施方案中,至少一个R4为-[OSiR2]mOSiR3,其中m为0。因为m为0,所以至少一个R4为-OSiR3。这是与以下情况中相同的结构:如果至少一个R4为-OSi(R5)3,并且如果每个R5为R。两种选择都导致至少一个R4为-OSiR3。因此,如果至少一个R4为-OSi(R5)3,并且如果每个R5为R,则还应当认为至少一个R4为-[OSiR2]mOSiR3,其中m为0。
对于支链有机硅化合物中另外一代的支链也是如此。例如,正如对与R4和R5相关联的不同选择可导致与上文相同的结构,对R5和R6的不同选择可类似地导致相同的结构。
在某些实施方案中,每个R1为-OSi(R4)3。在其中每个R1为-OSi(R4)3的具体实施方案中,在每个-OSi(R4)3中有一个R4为R,使得每个R1为-OSiR(R4)2。在另外的具体实施方案中,-OSiR(R4)2中的两个R4各自为-OSi(R5)3部分,使得支链有机硅化合物具有以下结构:
其中每个R、R2、R3、R5和X独立地选择并在上文定义。在某些实施方案中,每个R5为R,并且每个R为甲基。
如上文所述,支链有机硅化合物的相同结构可因不同的选择引起。例如,如上文所例示的相同支链有机硅化合物通过以下选择得到:每个R1为-OSi(R4)3,其中一个R4为R,并且另两个R4为-[OSiR2]mOSiR3,其中m为0。因此,在上文所例示的结构中,前提条件是R4、R5和R6中的至少一者为-[OSiR2]mOSiR3,而不管用于获得所得结构的R4和R5的选择。
在其他实施方案中,一个R1为R,并且另两个R1为-OSi(R4)3。在其中两个R1为-OSi(R4)3的具体实施方案中,在每个-OSi(R4)3中有一个R4为R,使得两个R1为-OSiR(R4)2。在另外的具体实施方案中,-OSiR(R4)2中的每个R4为-OSi(R5)3,使得支链有机硅化合物具有以下结构:
其中每个R、R2、R3、R5和X独立地选择并在本文定义。在某些实施方案中,每个R5为R,并且每个R为甲基。
如上文所述,支链有机硅化合物的相同结构可因不同的选择引起。例如,如上文例示的相同支链有机硅化合物通过以下选择得到:一个R1为R;另两个R1为-OSi(R4)3,在每个-OSi(R4)3中,一个R4为R,并且另两个R4为-[OSiR2]mOSiR3,其中m为0。因此,在上文所例示的结构中,前提条件是R4、R5和R6中的至少一者为-[OSiR2]mOSiR3,而不管用于获得所得结构的R4和R5的选择。
在另外的实施方案中,两个R1为R,并且另一个R1为-OSi(R4)3。在其中一个R1为-OSi(R4)3的具体实施方案,在-OSi(R4)3中有一个R4为R,使得该具体R1为-OSiR(R4)2。在另外的具体实施方案中,-OSiR(R4)2中的每个R4为-OSi(R5)3,使得支链有机硅化合物具有以下结构:
其中每个R、R2、R3、R5和X独立地选择并在本文定义。在某些实施方案中,每个R5为R,并且每个R为甲基。
如上文所述,支链有机硅化合物的相同结构可因不同的选择引起。例如,如上文例示的相同支链有机硅化合物通过以下选择得到:两个R1为R;另一个R1为-OSi(R4)3,在-OSi(R4)3中,一个R4为R,并且另两个R4为-[OSiR2]mOSiR3,其中m为0。因此,在上文所例示的结构中,前提条件是R4、R5和R6中的至少一者为-[OSiR2]mOSiR3,而不管用于获得所得结构的R4和R5的选择。
在上文示出的示例性结构中,每个R5为R,并且每个R为甲基。然而,当R5不是R时,即当R5选自OSi(R6)3和-[OSiR2]mOSiR3(其中m如上定义;其中每个R6选自R和-[OSiR2]mOSiR3,其中m如上定义)时,可将另外一代支链引入支链有机硅化合物中。
如上文所示出,X为二价连接基团。X通常随用于制备支链有机硅化合物的机制而变。在某些实施方案中,例如当支链有机硅化合物通过氢化硅烷化制备时,X为二价烃基团。当X为二价烃基团时,X通常具有2个至18个碳原子,并且其中/其上可包括取代和/或杂原子。例如,X可包含一个或多个氧杂原子,使得X包含醚部分。另选地,X可仅包含纯烃。在一些实施方案中,X包含具有通式–(CH2)n–的亚烷基基团,另选地为具有通式–(CH2)n–的亚烷基基团,其中下标n≥1,为诸如1至18、另选地1至16、另选地1至12、另选地1至10、另选地1至8、另选地1至6、另选地2至6。在特定实施方案中,下标n为3。
R2为H或R。因此,在一些实施方案中,R2为H并且支链有机硅化合物具有以下通式:
其中每个R1、R3和X独立地选择并在本文定义。在其它实施方案中,R2为R,即独立选择的取代或未取代的烃基基团。在一些此类实施方案中,R2为烷基基团。在具体的实施方案中,R2为甲基。
R3包含丙烯酰氧基部分,另选地为丙烯酰氧基部分。换句话讲,R3为包含丙烯酰氧基基团的部分。R3的丙烯酰氧基基团通常间接(例如,经由二价连接基团)键合至上文支链有机硅化合物的通式中所示的氮原子。
在一些实施方案中,丙烯酰氧基部分R3具有式-D-O-C(O)C(R7)CH2,使得支链有机硅化合物具有以下通式:
其中D为二价连接基团;R7为H或R;并且其中每个R1、R2、X和R独立地选择并在本文定义。在此类实施方案中,D为独立选择的二价连接基团,其可为直链或支链的以及取代或未取代的。
通常,D选自二价取代或未取代的烃基团。通常,D选自取代和未取代的烃基团。在具体的实施方案中,D包含C1-C18烃基团,另选地为C1-C18烃基团。例如,在一些实施方案中,D包含具有式–(CH2)m–的烃部分,另选地为具有式–(CH2)m–的烃部分,其中下标m≥1,为诸如1至18、另选地1至16、另选地1至12、另选地1至10、另选地1至8、另选地1至6、另选地2至6。在这些或其他实施方案中,D可包含取代的烃,另选地可为取代的烃,即包含具有至少一个杂原子(例如O、N、S等)的主链的烃基团。例如,在一些实施方案中,D为具有包含醚部分的主链的烃。
在某些实施方案中,R7为H,使得丙烯酰氧基部分R3可被定义为丙烯酸酯部分。在其他实施方案中,R7选自取代或未取代的烃基基团,诸如上文关于取代基R所述的那些。例如,在一些此类实施方案中,R7为烷基基团,使得丙烯酰氧基部分R3可被定义为丙烯酸烷基酯部分。在具体的实施方案中,R7为甲基,使得丙烯酰氧基部分R3可被定义为丙烯酸甲酯部分。
制备支链有机硅化合物的方法
还提供了一种制备支链有机硅化合物的方法(“制备方法”)。制备方法包括使(A)有机硅化合物和(B)官能化合物反应以得到支链有机硅化合物。
使有机硅化合物(A)和官能化合物(B)反应通常包括将有机硅化合物(A)和官能化合物(B)组合。换句话讲,除了将有机硅化合物(A)和官能化合物(B)组合之外,反应还原通常不需要主动步骤,尽管本文描述了各种任选的步骤。
有机硅化合物
一般来讲,有机硅化合物(A)为具有一个醇官能部分的支链有机硅化合物(即,为单羟基官能的)。具体地,该支链有机硅化合物(A)具有通式(I):
其中由子式R1 3Si–X–N(R2)–表示的有机硅部分如上文针对支链有机硅化合物所定义,并且Y1包含醇官能部分。
更具体地,参考式(I),X为二价连接基团;R2为H或R;并且每个R1通常选自R和-OSi(R4)3,前提条件是至少一个R1为-OSi(R4)3;每个R4选自R、-OSi(R5)3和-[OSiR2]mOSiR3;每个R5选自R、-OSi(R6)3和-[OSiR2]mOSiR3;并且每个R6选自R和-[OSiR2]mOSiR3;前提条件是R4、R5和R6中的至少一者为-[OSiR2]mOSiR3。在每种情况下,每个R独立地为取代或未取代的烃基基团,并且每个下标m被选择为使得0≤m≤100。尽管有以上描述,但本领域中技术人员根据上述支链有机硅化合物的描述将容易理解对有机硅部分R1 3Si–X–N(R2)–的限制的具体变型。
如以上所介绍,Y1包含醇官能部分。醇官能部分不受特别限制,并且可以是适用于制备根据本文方法的支链有机硅化合物的任何醇官能部分。一般来讲,醇官能部分包含醇基团,即,烃键合的羟基基团。因此,适用于Y1的醇官能部分的一般示例包括上文关于取代基R所述的烃基基团,其中此类烃基基团包含一个羟基取代基(例如,代替其它碳键合的氢原子)。
在某些实施方案中,醇官能部分Y1具有通式–D–OH,使得有机硅化合物(A)具有下式:
其中D为独立选择的二价基团,并且每个R1、R2和X独立地选择并如以上所定义。
通常,D选自取代和未取代的烃基团。在具体的实施方案中,D包含C1-C18烃基团,另选地为C1-C18烃基团。例如,在一些实施方案中,D包含具有式–(CH2)m–的烃部分,另选地为具有式–(CH2)m–的烃部分,其中下标m≥1,为诸如1至18、另选地1至16、另选地1至12、另选地1至10、另选地1至8、另选地1至6、另选地2至6。在这些或其他实施方案中,D可包含取代的烃,另选地可为取代的烃,即包含具有至少一个杂原子(例如O、N、S等)的主链的烃基团。例如,在一些实施方案中,D为具有包含醚部分的主链的烃。仅作为一个示例,在特定实施方案中,下标m为2,使得支链有机硅化合物(A)具有下式:
其中每个R1、R2和X独立地选择并如以上所定义。
如从对支链有机硅化合物的描述将会理解,除非另外指明,否则应当理解这同样适用于制备方法,当存在时,对R、R1、R2、R4、R5、R6、X、D和下标m的选择不受限制,并且包括制备如上文所述的支链有机硅化合物所必需的任何和所有选择以及选择的组合。例如,在某些实施方案中,有机硅化合物(A)具有通式(I),其中每个R1独立于式-OSi(R4)3,其中至少一个R4为-[OSiR2]mOSiR3,并且其中每个R和m独立地选择并如以上所定义。
在一些实施方案中,有机硅化合物(A)具有下式:
其中每个R、R2、R5、X和D独立地选择并在上文定义。在某些实施方案中,每个R5为R,并且每个R为甲基。
在特定实施方案中,有机硅化合物(A)具有以下结构:
其中每个R、R2、R5、X和D独立地选择并在上文定义。在某些实施方案中,每个R5为R,并且每个R为甲基。
在某些实施方案中,有机硅化合物(A)具有以下结构:
其中每个R、R2、R5、X和D独立地选择并在上文定义。在某些实施方案中,每个R5为R,并且每个R为甲基。
有机硅化合物(A)可以任何形式使用,诸如纯形式(即不存在溶剂、载体媒介物、稀释剂等),或设置在载体媒介物(诸如溶剂或分散剂)中。载体媒介物(如果存在的话)可包含或为有机溶剂(例如,芳族烃,诸如苯、甲苯、二甲苯等;脂族烃,诸如庚烷、己烷、辛烷等;卤代烃,诸如二氯甲烷、1,1,1-三氯乙烷、氯仿;等等;醚,诸如乙醚、四氢呋喃等)、有机硅流体、水性溶剂(例如水)或它们的组合。在某些实施方案中,有机硅化合物(A)在不存在载体媒介物的情况下使用。在一些此类实施方案中,在不存在与有机硅化合物(A)和/或官能化合物(B)反应的水和载体媒介物/挥发物的情况下利用有机硅化合物(A)。例如,在某些实施方案中,该方法可包括汽提挥发物和/或溶剂(例如有机溶剂、水等)的有机硅化合物(A)。用于汽提有机硅化合物(A)的技术是本领域已知的,并且可包括蒸馏、加热、施加减压/真空、与溶剂共沸、使用分子筛等,以及它们的组合。
有机硅化合物(A)可以本领域技术人员将例如取决于所选择的特定官能化合物(B)、所采用的反应参数、反应规模(例如要反应的组分(A)和/或(B)和/或要制备的支链有机硅化合物的总量)等选择的任何量使用。
官能化合物
官能化合物(B)不受特别限制,并且可为适于用丙烯酰氧基基团(例如,经由取代反应、置换反应、酯交换反应、烷化反应等)取代醇官能部分Y1的任何化合物,如本领域中技术人员根据本文的描述将理解的。
官能化合物(B)通常为丙烯酸酯,尽管也可利用其他丙烯酸酯(例如,丙烯酸酐)。通常,官能化合物(B)具有下式:
其中R7选自取代或未取代的烃基基团和H;并且Y为取代或未取代的烃基基团。
通常,Y为具有1至4个碳原子的烷基基团(即,使得丙烯酸酯化合物(B)可被定义为丙烯酸烷基酯),并且选自甲基、乙基、丙基基团(正丙基、异丙基)和丁基基团(例如,正丁基、仲丁基、异丁基、叔丁基)。例如,在某些实施方案中,Y为甲基、乙基、正丙基或正丁基。然而,Y可为任何取代或未取代的烃基基团或者包含任何取代或未取代的烃基基团,并且因此可选自本文所述的烃基基团中的任一种。
在某些实施方案中,R7为H,使得官能化合物(B)可被定义为丙烯酸烷基酯。在其他实施方案中,R7选自取代或未取代的烃基基团,诸如上文关于R所述的那些中的任一个烃基基团。在一些此类实施方案中,R7为烷基基团,使得官能化合物(B)可被定义为烷基丙烯酸烷基酯。在具体的实施方案中,R7为甲基,使得丙烯酸酯化合物(B)可被定义为甲基丙烯酸烷基酯。
适于用作官能化合物(B)的化合物的具体示例通常包括(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸异丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸仲丁酯和(甲基)丙烯酸叔丁酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙酯、丙烯酸异丙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸仲丁酯和丙烯酸叔丁酯。在某些实施方案中,官能化合物(B)选自(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯和(甲基)丙烯酸正丁酯。在一些实施方案中,官能化合物(B)选自丙烯酸甲酯、丙烯酸乙酯和丙烯酸正丁酯。
官能化合物(B)可以任何形式利用,诸如纯形式(即不存在溶剂、载体媒介物、稀释剂等),或设置在载体媒介物(诸如溶剂或分散剂)中。载体媒介物(如果存在的话)可包含或为有机溶剂(例如,芳族烃,诸如苯、甲苯、二甲苯等;脂族烃,诸如庚烷、己烷、辛烷等;卤代烃,诸如二氯甲烷、1,1,1-三氯乙烷、氯仿;等等;醚,诸如乙醚、四氢呋喃等)、硅氧烷流体或它们的组合。
在某些实施方案中,官能化合物(B)在不存在载体媒介物的情况下使用。在一些此类实施方案中,在不存在与有机硅化合物(A)和/或官能化合物(B)反应的水和载体媒介物/挥发物的情况下利用官能化合物(B)。例如,在某些实施方案中,该方法可包括汽提挥发物和/或溶剂(例如有机溶剂、水等)的官能化合物(B)。用于汽提官能化合物(B)的技术是本领域已知的,并且可包括蒸馏、加热、施加减压/真空、与溶剂共沸、使用分子筛等,以及它们的组合。
在某些实施方案中,该方法包括利用超过一种官能化合物(B),诸如2种、3种、4种或更多种官能化合物(B)。在此类实施方案中,每种官能化合物(B)独立地选择,并且可与任何其它官能化合物(B)相同或不同。
官能化合物(B)可以本领域技术人员将例如取决于所选择的特定有机硅化合物(A)和/或官能化合物(B)、所采用的反应参数、反应规模(例如要反应的组分(A)和/或(B)和/或要制备的支链有机硅化合物的总量)等选择的任何量使用。
有机硅化合物(A)和官能化合物(B)通常以1.5:1至1:1.5、另选地1.4:1至1:1.4、另选地1.3:1至1:1.3、另选地1.2:1至1:1.2、另选地1.1:1至1:1.1、另选地1.1:1至1:1的摩尔比反应。然而,所利用的有机硅化合物(A)和官能化合物(B)的相对量可例如基于所选择的特定有机硅化合物(A)、所选择的特定官能化合物(B)、所采用的反应参数等而变化。如根据本文的描述本领域中技术人员将理解的,有机硅化合物(A)和官能化合物(B)制备支链有机硅化合物的反应以理论最大摩尔比1:1(A):(B)发生。然而,过量的组分之一通常用于完全消耗化合物(A)或(B)之一,例如以简化所形成的反应产物的纯化等。例如,在某些实施方案中,利用相对过量的化合物(B)以使有机硅化合物(A)向支链有机硅化合物的转化率最大化。
在某些实施方案中,有机硅化合物(A)和官能化合物(B)以0.1至20(A):(B)的摩尔比反应。例如,在某些实施方案中,有机硅化合物(A)和官能化合物(B)以1:1至1:10诸如1:1.1至1:10、另选地1:1.5至1:10、另选地1:2至1:10、另选地1:2.5至1:10、另选地1:3至1:10、另选地1:4至1:10、另选地1:5至1:10、另选地1:6至1:10(A):(B)的摩尔比反应。在一些实施方案中,有机硅化合物(A)和官能化合物(B)以1:1至20:1诸如1.1:1至20:1、另选地1.5:1至20:1、另选地2:1至20:1、另选地2.5:1至20:1、另选地3:1至20:1、另选地4:1至20:1、另选地5:1至20:1、另选地10:1至20:1、另选地15:1至20:1(A):(B)的摩尔比反应。应当理解,也可利用这些范围之外的比率。例如,在某些实施方案中,诸如当官能化合物(B)在反应期间用作载体(即,溶剂、稀释剂等)时,官能化合物(B)以显著过量(例如,以有机硅化合物(A)的摩尔量的≥10倍、另选地≥15倍、另选地≥20倍的量)利用。
催化剂(C)
在某些实施方案中,有机硅化合物(A)和官能化合物(B)在存在(C)催化剂的情况下反应。催化剂不受限制,并且可为适于用官能化合物(B)的丙烯酰氧基基团(例如,经由取代反应、置换反应、酯交换反应、烷化反应等)取代有机硅化合物(A)的醇官能部分Y1的任何催化剂,如本领域中技术人员根据本文的描述将理解的。
在具体的实施方案中,催化剂(C)具有式M[RC(O)CHC(O)R]4,其中M为第IV族过渡金属,并且每个R为独立选择的取代或未取代的烃基基团。
第IV族过渡金属包括钛(Ti)、锆(Zr)、铪(Hf)和鈩(Rf)。通常,M选自锆和铪。例如,在一些实施方案中,催化剂(C)具有式Zr[RC(O)CHC(O)R]4。在其他实施方案中,催化剂(C)具有式Hf[RC(O)CHC(O)R]4。
每个R为独立选择的取代或未取代的烃基基团,诸如上述那些中的任一种。因此,式RC(O)CHC(O)R的每种β-二酮可与催化剂(C)中的任何其它β-二酮相同或不同。然而,通常催化剂(C)中每种β-二酮是相同的。每个R可与催化剂(C)中的任何其它R相同或不同(即,特定β-二酮的基团R可相同或不同,并且特定β-二酮的基团R可与催化剂(C)中另一种特定β-二酮的基团R相同或不同。用于R的此类烃基基团的具体示例包括甲基、乙基、三氟甲基、4-甲氧基苯基、4-氯苯基、叔丁基、2-吡啶基、七氟丙基、异丁基、2-间甲苯基、苯基、苄基、2-噻吩基和2-萘基基团。通常,每个R独立地选自甲基和乙基基团。在某些实施方案中,每个R为甲基,此类催化剂(C)的β-二酮各自为戊烷-2,4-二酮的阴离子,并因此可被定义为酰基丙酮(AcAc)配体。虽然常规地以二酮(即二酮”)形式描述,但是本领域中技术人员将容易理解,由式RC(O)CHC(O)R表示的阴离子配体通常被表征为母体二酮的烯醇化物(例如β-酮烯醇酯)。
在具体的实施方案中,催化剂(C)为Zr(AcAc)4和/或Hf(AcAc)4。
在某些实施方案中,该方法包括利用超过一种催化剂(C),诸如2种不同的催化剂(C)。在此类实施方案中,独立地选择每种催化剂(C),并且可与所利用的任何其它催化剂(C)相同或不同。例如,在一些实施方案中,催化剂(C)为碘化钠和碘化钾的组合(即,为混合盐催化剂)。
制备适于用于催化剂(C)中或用作催化剂(C)的化合物的方法是本领域中熟知的,并且本文所列化合物中的许多可从各种供应商商购获得。因此,催化剂(C)可作为该方法的一部分制备,或以其他方式获得(即,作为所制备的化合物)。
催化剂(C)可以任何形式使用,诸如纯形式(即,不存在溶剂、载体媒介物、稀释剂等),或设置在载体媒介物诸如溶剂或分散剂(例如,诸如上文关于有机硅化合物(A)所列出的那些中的任一者)中。在一些实施方案中,在不存在与有机硅化合物(A)、官能化合物(B)和/或催化剂(C)本身反应的水和载体媒介物/挥发物的情况下(即,在与组分(A)和(B)混合之前)使用催化剂(C)。例如,在某些实施方案中,该方法可包括汽提挥发物和/或溶剂(例如,水、有机溶剂等)的催化剂(C)。用于汽提催化剂(C)的技术是本领域已知的,并且可包括加热、干燥、施加减压/真空、与溶剂共沸、使用分子筛等,以及它们的组合。
催化剂(C)可以本领域技术人员将例如取决于所选择的特定催化剂(C)、所采用的反应参数、反应规模(例如组分(A)和(B)的总量)等选择的任何量使用。用于反应中的催化剂(C)与组分(A)和/或(B)的摩尔比可影响组分(A)与(B)反应以用其制备支链有机硅化合物的速率和/或量。因此,与组分(A)和/或(B)相比,催化剂(C)的量以及它们之间的摩尔比可变化。通常,选择这些相对量和摩尔比以最大程度增加组分(A)和(B)的偶联以制备支链有机硅化合物(例如,以增加反应的经济效率、增加所形成的反应产物的纯化容易度等)。
在某些实施方案中,催化剂(C)以基于所用的组分(A)的总量计0.001摩尔%至10摩尔%的量用于反应中。例如,催化剂(C)可以基于所用的组分(A)的总量计0.01摩尔%至10摩尔%、另选地0.1摩尔%至10摩尔%、另选地0.1摩尔%至5摩尔%的量使用。
在特定实施方案中,催化剂(C)以基于所用的组分(B)的总量计0.001摩尔%至10摩尔%的量用于反应中。例如,催化剂(C)可以基于所用的组分(B)的总量计0.01摩尔%至10摩尔%、另选地0.1摩尔%至10摩尔%、另选地0.1摩尔%至5摩尔%的量使用。
聚合抑制剂(D)
在某些实施方案中,有机硅化合物(A)和官能化合物(B)在存在(D)聚合抑制剂的情况下反应。聚合抑制剂不受限制,并且可包含,另选地可为自由基清除剂、抗氧化剂、光稳定剂、紫外线吸收剂等,或它们的组合。此类化合物是本领域已知的,并且通常为或包括能够与自由基相互作用,例如通过与自由基形成共价键而消除自由基以使自由基失活的化合物或部分。聚合抑制剂(D)还可为,或另选地为聚合阻滞剂,即降低自由基聚合的引发和/或增长速率的化合物。例如,在一些实施方案中,聚合抑制剂(D)包含氧气,另选地为氧气。一般来讲,聚合抑制剂(D)用于防止和/或抑制副产物的形成,所述副产物可经由丙烯酸酯化合物(B)和/或丙烯酸酯官能支链有机硅化合物的自由基聚合形成。
聚合抑制剂(D)不受限制,并且可包含酚类化合物、醌或氢醌化合物、N-氧基化合物、吩噻嗪化合物、受阻胺化合物或它们的组合,另选地可为酚类化合物、醌或氢醌化合物、N-氧基化合物、吩噻嗪化合物、受阻胺化合物或它们的组合。
酚类化合物的示例包括苯酚、烷基酚、氨基酚(例如,对氨基酚)、亚硝基酚和烷氧基酚。此类苯酚化合物的具体示例包括邻甲酚、间甲酚和对甲酚(甲基苯酚)、2-叔丁基-4-甲基苯酚、6-叔丁基-2,4-二甲基苯酚、2,6-二叔丁基-4-甲基苯酚、2-叔丁基苯酚、4-叔丁基苯酚、2,4-二叔丁基苯酚、2-甲基-4-叔丁基苯酚、4-叔丁基-2,6-二甲基苯酚或2,2'-亚甲基双(6-叔丁基-4-甲基苯酚)、4,4'-氧基联苯、3,4-亚甲基二氧基联苯酚(芝麻酚)、3,4-二甲基苯酚、焦儿茶酚(1,2-二羟基苯)、2-(1'-甲基环己-1'-基)-4,6-二甲基苯酚、2-或4-(1'-苯基乙-1'-基)苯酚、2-叔丁基-6-甲基苯酚、2,4,6-三叔丁基苯酚、2,6-二叔丁基苯酚、壬基苯酚、辛基苯酚、2,6-二甲基苯酚、双酚A、双酚B、双酚C、双酚F、双酚S、3,3',5,5'-四溴双酚A、2,6-二叔丁基-对甲酚、3,5-二叔丁基-4-羟基苯甲酸甲酯、4-叔丁基焦儿茶酚、2-羟基苄醇、2-甲氧基-4-甲基苯酚、2,3,6-三甲基苯酚、2,4,5-三甲基苯酚、2,4,6-三甲基苯酚、2-异丙基苯酚、4-异丙基苯酚、6-异丙基间甲酚、β-(3,5-二叔丁基-4-羟基苯基)丙酸正十八烷基酯、1,1,3-三(2-甲基-4-羟基-5-叔丁基苯基)丁烷、1,3,5-三甲基-2,4,6-三-(3,5-二叔丁基-4-羟基苄基)苯、1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰脲酸酯、1,3,5-三(3,5-二叔丁基-4-羟基苯基)丙酰氧基乙基异氰脲酸酯、1,3,5-三(2,6-二甲基-3-羟基-4-叔丁基苄基)异氰脲酸酯或季戊四醇四[对-(3,5-二叔丁基-4-羟基苯基)丙酸酯]、2,6-二叔丁基-4-二甲基氨基甲基苯酚、6-仲丁基-2,4-二硝基苯酚、3-(3',5'-二叔丁基-4'-羟基苯基)丙酸十八烷基酯、3-(3',5'-二叔丁基-4'-羟基苯基)丙酸十六烷基酯、3-(3',5'-二叔丁基-4'-羟基苯基)丙酸辛酯、3-硫代-1,5-戊二醇双[(3',5'-二叔丁基-4'-羟基苯基)丙酸酯]、4,8-二氧杂-1,11-十一烷二醇双[(3',5'-二叔丁基-4'-羟基苯基)丙酸酯]、4,8-二氧杂-1,11-十一烷二醇双[(3'-叔丁基-4'-羟基-5'-甲基苯基)丙酸酯]、1,9-壬二醇双[(3',5'-二叔丁基-4'-羟基苯基)丙酸酯]、1,7-庚二胺双[3-(3',5'-二叔丁基-4'-羟基苯基)丙酰胺]、1,1-甲烷二胺双[3-(3',5'-二叔丁基-4'-羟基苯基)丙酰胺]、3-(3',5'-二叔丁基-4'-羟基苯基)丙酸酰肼、3-(3',5'-二甲基-4'-羟基苯基)丙酸酰肼、双(3-叔丁基-5-乙基-2-羟基苯-1-基)甲烷、双(3,5-二叔丁基-4-羟基苯-1-基)甲烷、双[3-(1'-甲基环己-1'-基)-5-甲基-2-羟基苯-1-基]甲烷、双(3-叔丁基-2-羟基-5-甲基苯-1-基)甲烷、1,1-双(5-叔丁基-4-羟基-2-甲基苯-1-基)乙烷、双(5-叔丁基-4-羟基-2-甲基苯-1-基)硫化物、双(3-叔丁基-2-羟基-5-甲基苯-1-基)硫化物、1,1-双(3,4-二甲基-2-羟基苯-1-基)-2-甲基丙烷、1,1-双(5-叔丁基-3-甲基-2-羟基苯-1-基)丁烷、1,3,5-三-[1'-(3Δ,5”-二叔丁基-4”-羟基苯-1”-基)甲-1'-基]-2,4,6-三甲基苯、1,1,4-三(5'-叔丁基-4'-羟基-2'-甲基苯-1'-基)丁烷和叔丁基表儿茶酚、对亚硝基苯酚、对亚硝基邻甲酚、甲氧基苯酚(愈创木酚、焦儿茶酚单甲醚)、2-乙氧基苯酚、2-异丙氧基苯酚、4-甲氧基苯酚(氢醌单甲醚)、一或二-叔丁基-4-甲氧基苯酚、3,5-二叔丁基-4-羟基苯甲醚、3-羟基-4-甲氧基苄醇、2,5-二甲氧基-4-羟基苄醇(丁香醇)、4-羟基-3-甲氧基苯甲醛(香草醛)、4-羟基-3-乙氧基苯甲醛(乙基香草醛)、3-羟基-4-甲氧基苯甲醛(异香草醛)、1-(4-羟基-3-甲氧基苯基)乙酮(乙酰香草酮)、丁子香酚、二氢丁子香酚、异丁子香酚、生育酚(诸如α-、β-、γ-、δ-和ε-生育酚)、母育酚、α-生育酚氢醌、2,3-二氢-2,2-二甲基-7-羟基苯并呋喃(2,2-二甲基-7-羟基香豆素)等。
合适的醌和氢醌包括氢醌、氢醌单甲醚(4-甲氧基苯酚)、甲基氢醌、2,5-二叔丁基氢醌、2-甲基对氢醌、2,3-二甲基氢醌、三甲基氢醌、4-甲基焦儿茶酚、叔丁基氢醌、3-甲基焦儿茶酚、苯醌、2-甲基对氢醌、2,3-二甲基氢醌、td甲基氢醌、叔丁基氢醌、4-乙氧基苯酚、4-丁氧基苯酚、氢醌单苄基醚、对苯氧基苯酚、2-甲基氢醌、四甲基对苯醌、1,4-环己二酮2,5-二羧酸二乙酯、苯基对苯醌、2,5-二甲基-3-苄基对苯醌、2-异丙基-5-甲基对苯醌(百里香醌)、2,6-二异丙基-对苯醌、2,5-二甲基-3-羟基-对苯醌、2,5-二羟基-对苯醌、恩贝酸、四羟基-对苯醌、2,5-二甲氧基-1,4-苯醌、2-氨基-5-甲基-对苯醌、2,5-双苯基氨基-1,4-苯醌、5,8-二羟基-1,4-萘醌、2-苯胺基-1,4-萘醌、蒽醌、N,N-二甲基靛苯胺(N,N-dimethylindoaniline)、N,N-二苯基-对苯醌二亚胺、1,4-苯醌二肟、木醋醌、3,3'-二叔丁基-5,5'-二甲基联苯醌、对玫红酸(金精)、2,6-二叔丁基-4-亚苄基苯醌、2,5-二叔戊基氢醌等。
合适的N-氧基化合物(即硝酰基或N-氧基自由基)包括具有至少一个N—O●基团的化合物,诸如4-羟基-2,2,6,6-四甲基哌啶-N-氧基化合物、4-氧代-2,2,6,6-四甲基哌啶-N-氧基化合物、4-甲氧基-2,2,6,6-四甲基哌啶-N-氧基化合物、4-乙酰氧基-2,2,6,6-四甲基哌啶-N-氧基化合物、2,2,6,6-四甲基哌啶-N-氧基化合物(TEMPO)、4,4',4”-三(2,2,6,6-四甲基哌啶-N-氧基)亚磷酸酯、3-氧代-2,2,5,5-四甲基吡咯烷-N-氧基化合物、1-氧基-2,2,6,6-四甲基-4-甲氧基哌啶、1-氧基-2,2,6,6-四甲基-4-三甲基甲硅烷氧基哌啶、1-氧基-2,2,6,6-四甲基哌啶-4-基2-乙基己酸酯、1-氧基-2,2,6,6-四甲基哌啶-4-基癸二酸酯、1-氧基-2,2,6,6-四甲基哌啶-4-基硬脂酸酯、1-氧基-2,2,6,6-四甲基哌啶-4-基苯甲酸酯、1-氧基-2,2,6,6-四甲基哌啶-4-基(4-叔丁基)苯甲酸酯、双(1-氧基-2,2,6,6-四甲基哌啶-4-基)琥珀酸酯、双(1-氧基-2,2,6,6-四甲基哌啶-4-基)己二酸酯、双(1-氧基-2,2,6,6-四甲基哌啶-4-基)1,10-癸二酸酯、双(1-氧基-2,2,6,6-四甲基哌啶-4-基)正丁基丙二酸酯、双(1-氧基-2,2,6,6-四甲基哌啶-4-基)邻苯二甲酸酯、双(1-氧基-2,2,6,6-四甲基哌啶-4-基)间苯二甲酸酯、双(1-氧基-2,2,6,6-四甲基哌啶-4-基)对苯二甲酸酯、双(1-氧基-2,2,6,6-四甲基哌啶-4-基)六氢对苯二甲酸酯、N,N'-双(1-氧基-2,2,6,6-四甲基哌啶-4-基)己二酰二胺、N-(1-氧基-2,2,6,6-四甲基哌啶-4-基)己内酰胺、N-(1-氧基-2,2,6,6-四甲基哌啶-4-基)十二烷基琥珀酰亚胺、2,4,6-三[N-丁基-N-(1-氧基-2,2,6,6-四甲基哌啶-4-基]三嗪、N,N'-双(1-氧基-2,2,6,6-四甲基哌啶-4-基)-N,N'-双甲酰基-1,6-二氨基己烷、4,4'-亚乙基双(1-氧基-2,2,6,6-四甲基哌嗪-3-酮)等。
适用于或适用作聚合抑制剂(D)的其他化合物包括吩噻嗪(PTZ)和具有类似结构的化合物,诸如吩噁嗪、普马嗪、N,N'-二甲基吩嗪、咔唑、N-乙基咔唑、N-苄基吩噻嗪、N-(1-苯乙基)吩噻嗪、N-烷基化吩噻嗪衍生物诸如N-苄基吩噻嗪和N-(1-苯乙基)吩噻嗪等。当然,聚合抑制剂(D)可包括任何数量的特定化合物,这些化合物可各自独立地选择并且与聚合抑制剂(D)的任何其他化合物相同或不同。
当使用时,聚合抑制剂(D)可作为分立的组分添加到反应中,或者可在组分(A)与(B)反应之前与另一组分(例如,官能化合物(B))组合。聚合抑制剂(D)可以本领域技术人员将例如取决于所选择的特定聚合抑制剂(D)、所采用的反应参数、反应规模(例如组分(A)和/或(B)的总量)、反应气氛、反应温度和/或压力等选择的任何量使用。在某些实施方案中,聚合抑制剂(D)以50ppm至2000ppm的量,诸如以50ppm、另选地100ppm、另选地250ppm、另选地500ppm、另选地1000ppm、另选地1500ppm、另选地2000ppm的量存在于反应中。然而,本领域技术人员将容易理解,也可使用这些范围和示例性量之外的量,例如,在反应规模和/或条件需要额外量的聚合抑制剂(D)的情况下。此外,除了上述量之外或作为上述量的替代,可将氧气作为单独的组分(例如,代替选自上述化合物的分立的聚合抑制剂(D)或除该聚合抑制剂之外)添加到反应中。在此类情况下,可任选地在存在其他气体(例如,以空气的形式)的情况下,将氧以氧气的形式引入到反应中。当利用时,将氧气的量选择成使得反应混合物上方的气相保持低于爆炸极限。
通常,用以制备支链有机硅化合物的组分(A)与(B)的反应在容器或反应器中进行。当如下文所述在高温下进行反应时,可以任何合适的方式,例如经由护套、加热罩、烤盘、线圈等加热容器或反应器。
组分(A)、(B)以及任选的(C)和/或(D)可一起或单独地进料到容器中,或者可以任何添加顺序以及以任何组合设置在容器中。例如,在某些实施方案中,将组分(B)和任选的组分(C)添加到盛有组分(A)和任选的组分(D)的容器中。在此类实施方案中,组分(B)和(C)可先在添加之前组合,或者可顺序地添加到容器中。一般来讲,本文中对“反应混合物”的提及通常是指包含组分(A)、(B)以及任选的(C)和/或(D)的混合物(例如,通过组合这些组分而获得,如上文所述)。
该方法还可包括搅拌反应混合物。当例如在其反应混合物中组合时,搅拌可增强组分(A)、(B)以及任选的(C)和/或(D)的混合并接触在一起。此类接触可独立地使用其他条件,并且加以搅拌(例如,同时或顺序地)或不加以搅拌(即,独立于搅拌,另选地代替搅拌)。可定制其他条件以增强官能化合物(B)与有机硅化合物(A)的接触,并且从而增强两者的反应以便形成支链有机硅化合物。其他条件可以是用于提高反应产率或最大程度减少连同支链有机硅化合物包含在反应产物内的特定反应副产物的量的对结果有效的条件。
在一些实施方案中,反应在高温下进行。将根据所选择的特定有机硅化合物(A)、所选择的特定官能化合物(B)、所利用的特定载体和/或溶剂(如果有的话)等来选择和控制高温。因此,鉴于所选择的反应条件和参数以及本文的描述,本领域中技术人员将容易地选择高温。高温通常为大于环境温度至180℃,诸如30℃至170℃、另选地40℃至170℃、另选地40℃至160℃、另选地50℃至150℃、另选地50℃至135℃、另选地60℃至135℃、另选地70℃至130℃、另选地80℃至120℃。
应当理解,高温也可不同于上文示出的范围。还应当理解,在组分(A)和(B)的反应期间可修改反应参数。例如,在反应期间可独立地选择或修改温度、压力和其他参数。这些参数中的任一个参数可独立地为环境参数(例如,室温和/或大气压)和/或非环境参数(例如,低温或高温以及/或者低压或高压)。也可动态地修改、实时地修改即在该方法期间修改任何参数,或者任何参数可为不变的(例如,在反应的持续时间内,或在其任何部分内)。
进行组分(A)与(B)的反应以制备支链有机硅化合物的时间随规模、反应参数和条件、特定组分的选择等而变化。在某些实施方案中,进行反应的时间为将组分(A)和(B)组合后(例如在存在组分(C)和/或(D)的情况下)大于0小时至48小时、另选地1小时至36小时、另选地2小时至24小时、另选地4小时至12小时。
在某些实施方案中,该方法还包括从反应产物中分离和/或纯化支链有机硅化合物。如本文所用,分离支链有机硅化合物通常被定义为增加支链有机硅化合物相比于与其组合的其他化合物(例如在反应产物中或其纯化型式)的相对浓度。因此,如本领域中所理解的,分离/纯化可包括从此类组合中去除其他化合物(即,例如在反应产物中,减少与支链有机硅化合物组合的杂质的量)以及/或者从该组合中去除支链有机硅化合物本身。可使用任何合适的分离技术和/或方案。合适的分离技术的示例包括蒸馏、汽提/蒸发、提取、过滤、洗涤、分配、相分离、色谱法等。如本领域中技术人员将理解的,这些技术中的任何技术可与任何另一种技术组合(即,顺序地)使用以分离丙烯酸酯官能支链有机硅化合物。应当理解,分离可包括并因此可被称为纯化支链有机硅化合物。然而,与用于分离支链有机硅化合物的那些技术相比,纯化支链有机硅化合物可包括另选的和/或附加的技术。无论所选择的一种多多种特定技术如何,支链有机硅化合物的分离和/或纯化都可以按反应本身依次(即,根据反应本身)进行,因此可以是自动的。在其他情况下,纯化可以是包含支链有机硅化合物的反应产物所经受的独立程序。
共聚物
还提供了一种共聚物。共聚物包含支链有机硅化合物和与支链有机硅化合物(下文称为“反应性化合物”)反应的第二化合物的反应产物。如本领域中技术人员根据本文的描述将理解的,可制备共聚物的许多形式,例如,取决于所利用的具体支链有机硅化合物、所利用的具体反应性化合物、所执行的反应的类型、所利用的组分的比率等。通常,反应性化合物为丙烯酸酯官能的。
一般来讲,共聚物包含具有下式的支链有机硅部分:
其由在与反应性化合物的反应中利用的支链有机硅化合物形成。因此,就共聚物的支链有机硅部分而言,由子式R1 3Si–X–N(R2)–D–表示的有机硅部分如以上针对支链有机硅化合物及其形成方法所定义。子式–Y2–为由支链有机硅化合物的丙烯酰氧基部分R3形成的部分(即,在支链有机硅化合物与反应性化合物的反应期间),如下文进一步详细描述的。
在一些实施方案中,共聚物具有通式:
其中由子式R1 3Si–X–N(R2)–D–表示的有机硅部分如上文针对支链有机硅化合物及其形成方法所定义。并且Z为由反应性化合物形成的聚合物部分,如下文进一步详细描述的。
在某些实施方案中,共聚物具有通式:
其中部分R1 3Si–X–N(R2)–D–和Z如以上所定义,并且下标x”≥2。在此类实施方案中,共聚物可包含直链结构,例如其中下标x”为2,并且聚合物部分Z为直链,使得共聚物具有通式结构R1 3Si–X–N(R2)–D–Z–D–N(R2)–X–Si–R1 3。另选地,共聚物可包含支链结构,诸如其中X为至少三价,并且下标x”≥2、另选地≥3。
在某些实施方案中,当制备共聚物时,将第二硅氧烷连同支链有机硅化合物一起利用。第二硅氧烷可为不同于支链有机硅化合物的树枝状硅氧烷。第二硅氧烷的具体示例包括具有以下结构的那些:
其中Me为甲基,并且Bu为丁基。
附加的示例包括甲基丙烯酰氧基丙基三(三甲基甲硅烷氧基)硅烷、α-丁基二甲基甲硅烷基和ω-3-甲基丙烯酰氧基丙基二甲基甲硅烷基封端的聚二甲基硅氧烷(CAS#149925-73-5),例如来自Gelest的MCR-M 07、MCR-M 11、MCR-M 17、MCR-M 22,以及来自JNC的Silaplane FM 0711、Silaplane FM 0721、Silaplane FM 0725。第二硅氧烷可根据JP1999-001485的实施例1的公开内容来制备。
(共聚物的)聚合物部分
所述共聚物包含聚合物部分,在上述某些实施方案中,所述聚合物部分由具体式中的部分Z表示。聚合物部分不受特别限制,并且可包含可接枝到支链有机硅化合物上或与支链有机硅化合物反应的任何聚合物或聚合物的组合,另选地可为可接枝到支链有机硅化合物上或与支链有机硅化合物反应的任何聚合物或聚合物的组合。此外,聚合物部分可在存在支链有机硅化合物的情况下原位形成,即,聚合物部分不需要在形成共聚物之前形成。
聚丙烯酸酯
通常,聚合物部分包含聚丙烯酸酯部分,另选地为聚丙烯酸酯部分。聚丙烯酸酯部分不受限制,并且可由任何丙烯酸酯化合物形成,如下文进一步详细描述的。如本文所用,术语“聚丙烯酸酯部分”意指包含至少两个丙烯酸酯官能团(例如,丙烯酸烷基酯基团,诸如丙烯酸甲酯、丙烯酸乙酯或丙烯酸丁酯基团,取代的丙烯酸酯基团,诸如2-乙基己基或羟乙基基团,以及其他基团,诸如羟甲基丙烷丙烯酸酯基团等)的部分。如根据本文的描述将理解的,聚丙烯酸酯部分可为单体的、低聚的、聚合的、脂族的、芳族的、芳脂族的等。此外,共聚物可包含许多不同的聚丙烯酸酯部分,这些丙烯酸酯官能团独立地选择。
存在于共聚物中的特定聚丙烯酸酯部分取决于共聚物的最终用途应用。例如,脂族聚丙烯酸酯部分通常提供比芳族聚丙烯酸酯部分更大的柔韧性和更小的玻璃化转变温度(Tg),所述芳族聚丙烯酸酯部分通常更具刚性且具有更大的玻璃化转变温度(Tg)。类似地,可基于共聚物的所需特性来选择分子量和粘度。
聚丙烯酸酯部分通常具有至少100的数均分子量(Mn)。在某些实施方案中,至少一种聚丙烯酸酯具有至少100、另选地至少125、另选地至少150、另选地至少200、另选地至少250、另选地至少300的Mn。在这些或其他实施方案中,每个聚丙烯酸酯部分具有至少200、另选地至少300、另选地至少400、另选地至少500、另选地至少600、另选地至少700、另选地至少1,000、另选地至少2,000、另选地至少4,000、另选地至少8,000的Mn。在某些实施方案中,每个聚丙烯酸酯部分具有20,000、另选地小于19,000、另选地小于18,000、另选地小于17,000、另选地小于16,000、另选地小于15,000的最大Mn。数均分子量可基于聚苯乙烯标准物使用凝胶渗透色谱法(GPC)技术容易地确定。
制备共聚物的方法
如以上所介绍,共聚物包含支链有机硅化合物和反应性化合物的反应产物。因此,还提供了一种制备共聚物的方法(“聚合方法”)。聚合方法包括使支链有机硅化合物和反应性化合物反应以得到共聚物。任选地,聚合方法可包括使第二硅氧烷反应,如以上所介绍。
与支链有机硅化合物反应的第二化合物
反应性化合物是与支链有机硅化合物反应的。通常,反应性化合物包含丙烯酸酯官能化合物,另选地为丙烯酸酯官能化合物。丙烯酸酯官能化合物不受限制,并且可为任何丙烯酸酯官能化合物,如下文进一步详细描述的。如本文所用,术语“丙烯酸酯官能化合物”意指包含至少一个、另选地至少两个丙烯酸酯官能团(例如,丙烯酸烷基酯基团,诸如丙烯酸甲酯、丙烯酸乙酯或丙烯酸丁酯基团,取代的丙烯酸酯基团,诸如2-乙基己基或羟乙基基团,以及其他基团,诸如羟甲基丙烷丙烯酸酯基团等)的化合物或分子。如根据本文的描述将理解的,丙烯酸酯官能化合物可为单体的、低聚的、聚合的、脂族的、芳族的、芳脂族的等。此外,共聚物可包含许多不同的丙烯酸酯官能团,这些丙烯酸酯官能团独立地选择。
丙烯酸酯化合物和制备丙烯酸酯官能化合物的方法是本领域中已知的。例如,聚丙烯酸酯可经由丙烯酸类单体的常规自由基聚合来制备。此类常规方法通常通过在存在自由基引发剂/产生剂(诸如热聚合引发剂、化学聚合引发剂和/或光聚合引发剂)的情况下将可自由基聚合的单体(例如丙烯酸酯单体、共聚单体等)组合来进行。例如,通常利用过氧化物和芳族引发剂(例如酚、苯偶姻、杂环诸如咪唑等)。这些常规方法可用于制备丙烯酸酯均聚物和共聚物,包括三元、四元和更高阶的共聚物。另外,也可利用例如二官能和/或多官能丙烯酸类单体,以制备多官能聚丙烯酸酯(和聚丙烯酸酯化合物),如根据本文合适的丙烯酸类单体的描述将会理解的。
一般来讲,制备丙烯酸酯官能化合物的方法利用至少一种具有丙烯酰氧基或烷基丙烯酰氧基的丙烯酸类单体(即,丙烯酸酯、丙烯酸烷基酯、丙烯酸、烷基丙烯酸等,以及它们的衍生物和/或组合)。此类丙烯酸类单体可为单官能或多官能丙烯酸类单体。
适用于制备聚丙烯酸酯(和聚丙烯酸酯部分)的具体单官能丙烯酸类单体的示例包括(烷基)丙烯酸类化合物,诸如丙烯酸甲酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸苯氧基-2-甲基乙酯、(甲基)丙烯酸苯氧基乙氧基乙酯、(甲基)丙烯酸3-苯氧基-2-羟丙酯、(甲基)丙烯酸2-苯基苯氧基乙酯、(甲基)丙烯酸4-苯基苯氧基乙酯、(甲基)丙烯酸3-(2-苯基苯基)-2-羟丙酯、聚氧乙烯改性的(甲基)丙烯酸对枯基苯酚酯、(甲基)丙烯酸2-溴苯氧基乙酯、(甲基)丙烯酸2,4-二溴苯氧基乙酯、(甲基)丙烯酸2,4,6-三溴苯氧基乙酯、聚氧乙烯改性的苯氧基(甲基)丙烯酸酯、聚氧丙烯改性的苯氧基(甲基)丙烯酸酯、聚氧乙烯壬基苯基醚(甲基)丙烯酸酯、(甲基)丙烯酸异冰片酯、(甲基)丙烯酸1-金刚烷基酯、(甲基)丙烯酸2-甲基-2-金刚烷基酯、(甲基)丙烯酸2-乙基-2-金刚烷基酯、(甲基)丙烯酸冰片酯、(甲基)丙烯酸三环癸酯、(甲基)丙烯酸二环戊酯、(甲基)丙烯酸二环戊烯酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸-4-丁基环己酯、丙烯酰吗啉、(甲基)丙烯酸-2-羟乙酯、(甲基)丙烯酸-2-羟丙酯、(甲基)丙烯酸-2-羟丁酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸异丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸异戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸异辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸异癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸异硬脂酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸1-萘基甲酯、(甲基)丙烯酸2-萘基甲酯、(甲基)丙烯酸四氢糠酯、(甲基)丙烯酸丁氧基乙酯、乙氧基二甘醇(甲基)丙烯酸酯、聚(乙二醇)单(甲基)丙烯酸酯、聚(丙二醇)单(甲基)丙烯酸酯、甲氧基乙二醇(甲基)丙烯酸酯、乙氧基乙基(甲基)丙烯酸酯、甲氧基聚(乙二醇)(甲基)丙烯酸酯、甲氧基聚(丙二醇)(甲基)丙烯酸酯、二丙酮(甲基)丙烯酰胺、异丁氧基甲基(甲基)丙烯酰胺、N,N-二甲基(甲基)丙烯酰胺、叔辛基(甲基)丙烯酰胺、(甲基)丙烯酸二甲基氨基乙酯、(甲基)丙烯酸二乙基氨基乙酯、(甲基)丙烯酸7-氨基-3,7-二甲基辛酯、N,N-二乙基(甲基)丙烯酰胺、N,N-二甲基氨基丙基(甲基)丙烯酰胺等,以及它们的衍生物。
适用于制备聚丙烯酸酯(和聚丙烯酸酯部分)的具体多官能丙烯酸类单体的示例包括具有两个或更多个丙烯酰基或甲基丙烯酰基的(烷基)丙烯酸类化合物,诸如三羟甲基丙烷二(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯、聚氧乙烯改性的三羟甲基丙烷三(甲基)丙烯酸酯、聚氧丙烯改性的三羟甲基丙烷三(甲基)丙烯酸酯、聚氧乙烯/聚氧丙烯改性的三羟甲基丙烷三(甲基)丙烯酸酯、二羟甲基三环癸烷二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、苯基乙二醇二(甲基)丙烯酸酯、聚(乙二醇)二(甲基)丙烯酸酯、聚(丙二醇)二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、1,3-金刚烷二甲醇二(甲基)丙烯酸酯、邻二甲苯二(甲基)丙烯酸酯、间二甲苯二(甲基)丙烯酸酯、对二甲苯二(甲基)丙烯酸酯、三(2-羟乙基)异氰脲酸酯三(甲基)丙烯酸酯、三(丙烯酰氧基)异氰脲酸酯、双(羟甲基)三环癸烷二(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、聚氧乙烯改性的2,2-双(4-(甲基)丙烯酰氧基)苯基)丙烷、聚氧丙烯改性的2,2-双(4-(甲基)丙烯酰氧基)苯基)丙烷和聚氧乙烯/聚氧丙烯改性的2,2-双(4-(甲基)丙烯酰氧基)苯基)丙烷。
应当理解,上述(烷基)丙烯酸类化合物仅为简明起见根据(甲基)丙烯酸酯物质进行描述,并且本领域中技术人员将容易理解,可等同地利用此类化合物的其它烷基和/或氢化物型式。例如,本领域中技术人员将理解,上文列出的单体“(甲基)丙烯酸2-乙基己酯”例示了(甲基)丙烯酸2-乙基己酯以及丙烯酸2-乙基己酯两者。同样,虽然在上文示例中一般将丙烯酸类单体描述为丙烯酸酯(即,α,β-不饱和酯),但应当理解,在这些描述中使用的术语“丙烯酸酯”可等同地指所例示的酯的酸、盐和/或共轭碱。例如,本领域中技术人员将理解,上面列出的单体“丙烯酸甲酯”例示了丙烯酸的甲酯以及丙烯酸、丙烯酸盐(例如丙烯酸钠)等。此外,也可利用上述丙烯酸类单体的多官能衍生物/变型。例如,上面列出的单体“(甲基)丙烯酸乙酯”例示了官能化衍生物,诸如取代的(甲基)丙烯酸乙酯和丙烯酸乙酯(例如,分别为(甲基)丙烯酸羟乙酯和丙烯酸羟乙酯)。
共聚单体(即,与上述丙烯酸类单体反应的单体)也可用于制备丙烯酸酯官能化合物或者以其他方式与丙烯酸酯官能化合物一起存在。此类单体不受限制,并且通常包括具有可自由基聚合的基团(诸如烯基、丙烯酰基和烷基丙烯酰基基团)的化合物。一般来讲,共聚单体由例如本领域中技术人员选择,以改变丙烯酸酯官能化合物和/或用丙烯酸酯官能化合物形成的共聚物的特性。例如,本领域中已知苯乙烯可与丙烯酸类单体共聚以制备聚丙烯酸酯(和聚丙烯酸酯部分),与不含此类苯乙烯共聚单体的那些相比,所述聚丙烯酸酯(和聚丙烯酸酯部分)具有增加的硬度。同样,共聚单体诸如丙烯腈可用于增加链间极性相互作用,并因此增加聚丙烯酸酯(和聚丙烯酸酯部分)的拉伸强度和极限伸长率,同时还降低此类聚丙烯酸酯(和聚丙烯酸酯部分)的低温柔韧性。此外,本领域中技术人员将易于选择所利用的单体的比例、添加顺序、反应长度、以及其它因素,以独立地调谐聚丙烯酸酯部分、包含聚丙烯酸酯部分的共聚物、和/或由其制备的组合物和/或产物的各种特性(例如柔韧性、溶解度、硬度、极性等)。合适的共聚单体的具体示例包括苯乙烯、丙烯腈、偏二氯乙烯、氯乙烯、乙烯、丙烯、丁烯、氯丁二烯、异戊二烯、四氟乙烯等,以及它们的衍生物。
应当理解,丙烯酸类单体的组合也可用作丙烯酸酯官能化合物或用于制备丙烯酸酯官能化合物,使得丙烯酸酯官能化合物可相对于其中的任何重复链段均聚或共聚。例如,上述方法可用于制备多官能聚丙烯酸酯,例如通过利用单官能丙烯酸类单体和多官能丙烯酸类单体。这些不同的官能单体通常由本领域中技术人员例如基于反应性以及聚合物间和/或聚合物内相互作用来选择,以改变用其制备的聚丙烯酸酯的机械强度。例如,与利用均聚聚丙烯酸酯部分的那些相比,可制备具有增加的机械强度的包含利用聚丙烯酸酯部分的共聚物的固化产物,所述聚丙烯酸酯部分包括单官能丙烯酸类单体和多官能丙烯酸类单体的组合。同样,与利用多官能聚丙烯酸酯部分的那些相比,可制备具有增加的柔韧性的包含利用均聚聚丙烯酸酯部分的共聚物的固化产物固化产物。
在具体的实施方案中,丙烯酸酯官能化合物包含(甲基)丙烯酸甲酯、丙烯酸甲酯、(甲基)丙烯酸丁酯、丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯、丙烯酸2-乙基己酯、(甲基)丙烯酸羟乙酯、丙烯酸羟乙酯、甲基丙烯酸、丙烯酸和/或苯乙烯单体或者由它们制备。
还将理解,相对于其中存在的非丙烯酸类官能团,如上所述制备的丙烯酸酯官能化合物可为单官能或多官能的。例如,此类方法可用于制备聚丙烯酸酯醇、二醇和/或多元醇,包括经由上述方法(例如,通过利用羟基官能单体)及其改性(例如,通过利用后聚合官能化技术,诸如封端和/或将含官能团化合物接枝到聚丙烯酸酯上)。此类含官能团化合物包含烷氧基甲硅烷基基团,例如其可经由氢化硅烷化或本领域中已知的其它方法接枝到聚丙烯酸酯上。例如,在某些实施方案中,聚丙烯酸酯部分由聚丙烯酸酯多元醇制备。在这些或其他实施方案中,聚丙烯酸酯部分由包含二甲氧基甲基侧基的聚丙烯酸酯化合物制备。在某些实施方案中,聚丙烯酸酯部分由包含至少一个可自由基聚合基团(诸如丙烯酰基官能团)的聚丙烯酸酯化合物制备。
丙烯酸酯官能化合物通常具有至少100的数均分子量(Mn)。在某些实施方案中,丙烯酸酯官能化合物具有至少100、另选地至少125、另选地至少150、另选地至少200、另选地至少250、另选地至少300的Mn。在这些或其他实施方案中,每个聚丙烯酸酯部分具有至少200、另选地至少300、另选地至少400、另选地至少500、另选地至少600、另选地至少700、另选地至少1,000、另选地至少2,000、另选地至少4,000、另选地至少8,000的Mn。在某些实施方案中,丙烯酸酯官能化合物具有100,000、另选地小于80,000、另选地小于60,000、另选地小于40,000、另选地小于20,000、另选地小于19,000、另选地小于18,000、另选地小于17,000、另选地小于16,000、另选地小于15,000的最大Mn。数均分子量可基于聚苯乙烯标准物使用凝胶渗透色谱法(GPC)技术容易地确定。
支链有机硅化合物和共聚物的组合物和用途
还提供了一种组合物。该组合物包含支链有机硅化合物(“化合物”)和共聚物中的至少一者。在各种实施方案中,组合物包含化合物,但不包含共聚物。在某些实施方案中,除了化合物之外,组合物还包含共聚物。在其他实施方案中,组合物包含共聚物,但不包含化合物。该组合物通常不受限制,并且可具有各种形式、功能、用途、最终应用等。
如果使用,该化合物可以各种量存在于该组合物中。如果用于组合物中,则共聚物也是如此。本领域中技术人员可根据例如特定组合物、化合物或共聚物以及期望的结果容易地确定该化合物和/或共聚物的合适量。
在各种实施方案中,该组合物被进一步限定为以下项中的至少一者:(i)乳液;(ii)水性组合物;(iii)表面活性剂组合物;(iv)润湿组合物;(v)水性成膜泡沫;(vi)表面张力调节剂;(vii)防粘连添加剂;(viii)农用组合物;(ix)涂料组合物;(x)油漆组合物;(xi)表面处理组合物;(xii)成膜组合物;和(xiii)化妆品组合物。本领域中技术人员理解,某些组合物可重叠以便形成和/或起作用。在下文的描述中,对该组合物和这些具体组合物中的任一者(例如乳液)的提及可以互换。
该化合物可用于多种应用。在各种实施方案中,该化合物用作表面活性剂、分散剂、润湿剂、防粘连添加剂、表面张力调节剂、表面处理剂、用于农用组合物的添加剂、用于涂料的添加剂、用于油漆的添加剂、化妆品成分、硅氧烷改性剂和水性成膜泡沫成分中的至少一者。本领域的技术人员应当理解,某些用途或应用可在功能和/或期望结果方面重叠。
共聚物也可用于许多应用,并且此类应用与上文针对化合物所述的用途相同或不同。在某些实施方案中,共聚物被用作表面处理剂、用于油漆的添加剂、用于涂料的添加剂和化妆品成分中的至少一者。
在该组合物中,任选在存在一种或多种添加剂的情况下,该化合物或共聚物可单独或一起使用,可补充至少一种辅助组分,或可充当至少一种其他组分的助剂。在各种实施方案中,该化合物或共聚物可被称为试剂、添加剂、辅助剂、成分或改性剂。
化合物或共聚物中的每一者可与该组合物中存在的其他组分反应,或相对于该组合物中存在的其他组分为惰性的。在其中组合物、化合物或共聚物接触表面或基底的组合物或应用中,可存在与表面或基底的粘结,并且此类粘结为机械粘结/物理粘结、化学粘结或它们的组合。例如,表面可具有与该化合物反应的官能团。此类官能团可以是表面固有的,或者可以通过一种或多种类型的常规表面处理形成。下文描述了某些示例性组合物及其组分。
应当理解,某些组分或添加剂可根据不同的技术条件进行分类,并且仅因为组分或添加剂被分类为此类术语并不意味着它们限于该功能。添加剂中的一种或多种添加剂可以该组合物的任何合适的重量百分比(重量%)诸如0.01重量%至65重量%、另选地0.05重量%至35重量%、另选地0.1重量%至15重量%、另选地0.5重量%至5重量%、或另选地0.1重量%或更少存在。本领域中技术人员可根据例如添加剂的类型和期望的结果容易地确定添加剂的合适量。某些任选添加剂在下文更详细地描述。
在各种实施方案中,该组合物包含或为乳液。乳液不受限制,并且通常选自有机硅/水包油(O/W)和油包水/有机硅(W/O)乳液。该乳液包含非水相和水相。通常,非水相为乳液中的不连续相,并且水相为连续相。然而,基于其中的组分的相关量,如下所述,非水相可为连续相,并且水相为不连续相。
不连续相通常在乳液的连续相中形成颗粒。颗粒是液体,并且可另选地称为液滴。颗粒的尺寸通常取决于例如其中组分的选择和它们的量。
在各种实施方案中,乳液的非水相包含本公开的化合物和/或共聚物。在某些实施方案中,非水相还包含化合物和/或共聚物的载体媒介物。载体媒介物可选自本领域理解的媒介物,诸如硅氧烷载体媒介物、无机和有机溶剂等。在其他或另外的实施方案中,非水相还包含表面活性剂,如下文进一步描述的。示例性乳液、包含乳液的组合物以及用其形成的膜描述于WO2018145069A1中。
有机溶剂的代表性非限制性示例包括甲苯、二甲苯和类似的芳族烃;己烷、庚烷、异辛烷或类似的线性或部分支化的饱和烃;环己烷和类似的脂族烃;低分子量醇,诸如甲醇、乙醇、丙醇、异丙醇等;低分子量醚,诸如二(丙二醇)单甲醚、二(乙二醇)丁醚、二(乙二醇)甲醚、二(丙二醇)丁醚、二(丙二醇)甲醚醋酸酯、二(丙二醇)丙醚、乙二醇苯醚、丙二醇丁醚、1-甲氧基-2-丙醇、乙酸-1-甲氧基-2-丙酯、丙二醇丙醚、1-苯氧基-2-丙醇、三(丙二醇)甲醚和三(丙二醇)丁醚以及其他类似的二醇。
所述水相包含水。水可以来自任何来源,并且可以任选地进行纯化,例如通过过滤、蒸馏、反渗透技术等。
在许多实施方案中,乳液还包含表面活性剂。另选地,表面活性剂可称为乳化剂,并且通常用于乳化乳液水相中的非水相。表面活性剂可以是适用于制备具有非水相和水相的乳液的任何表面活性剂。
例如,表面活性剂可包含一种或多种阴离子表面活性剂、阳离子表面活性剂、非离子表面活性剂和/或两性表面活性剂、有机改性的有机硅,诸如聚二甲基硅氧烷共聚多元醇;甘油的氧乙烯化醚和/或氧丙烯化醚;脂肪醇的氧乙烯化醚和/或氧丙烯化醚,诸如鲸蜡硬脂醇聚醚-30、C12-15链烷醇聚醚-7;聚乙二醇的脂肪酸酯,诸如PEG-50硬脂酸酯、PEG-40单硬脂酸酯;糖酯和糖醚,诸如蔗糖硬脂酸酯、蔗糖椰油酸酯和脱水山梨糖醇硬脂酸酯、及其混合物;磷酸酯及其盐,诸如油醇聚醚-10磷酸酯DEA盐;磺基琥珀酸盐,诸如PEG-5月桂醇柠檬酸酯磺基琥珀酸酯二钠和蓖麻醇酸酰胺MEA磺基琥珀酸酯二钠;烷基醚硫酸盐,诸如月桂基醚硫酸钠;羟乙基磺酸盐;甜菜碱衍生物;及其混合物。
在某些实施方案中,表面活性剂包含阴离子表面活性剂。阴离子表面活性剂包括,例如,羧酸盐(2-(2-羟基烷氧基)乙酸钠)、氨基酸衍生物(N-酰基谷氨酸盐、N-酰基甘氨酸盐或酰基肌氨酸盐)、烷基硫酸盐、烷基醚硫酸盐及其氧乙烯化衍生物、磺酸盐、羟乙基磺酸盐和N-酰基羟乙基磺酸盐、牛磺酸盐和N-酰基N-甲基牛磺酸盐、磺基琥珀酸盐、烷基磺基乙酸盐、磷酸盐和烷基磷酸盐、多肽、烷基多聚糖苷的阴离子衍生物(酰基-D-半乳糖苷糖醛酸盐)和脂肪酸皂、碱金属磺化蓖麻醇酸盐、脂肪酸的磺化甘油酯(诸如椰子油酸的磺化单甘油酯)、磺化单价醇酯的盐(诸如油烯基羟乙基磺酸钠)、氨基磺酸的酰胺(诸如油烯基甲基牛磺酸的钠盐)、脂肪酸腈的磺化产物(诸如棕榈腈磺酸盐)、磺化芳族烃(诸如α-萘单磺酸钠)、萘磺酸与甲醛的缩合产物、八氢蒽磺酸钠、碱金属烷基硫酸盐(诸如月桂基硫酸钠、月桂基硫酸铵和月桂基硫酸三乙醇胺)、具有8个或更多个碳原子的烷基基团的醚硫酸盐(诸如月桂基醚硫酸钠、月桂基醚硫酸铵、烷基芳基醚硫酸钠和烷基芳基醚硫酸铵)、具有1个或多个含8个或更多个碳原子的烷基基团的烷基芳基磺酸盐、烷基苯磺酸的碱金属盐(示例为己基苯磺酸的钠盐、辛基苯磺酸的钠盐、癸基苯磺酸的钠盐、十二烷基苯磺酸的钠盐、十六烷基苯磺酸的钠盐和十四烷基苯磺酸的钠盐)、聚氧乙烯烷基醚的硫酸酯(包括CH3(CH2)6CH2O(C2H4O)2SO3H、CH3(CH2)7CH2O(C2H4O)3.5SO3H、CH3(CH2)8CH2O(C2H4O)8SO3H、CH3(CH2)19CH2O(C2H4O)4SO3H和CH3(CH2)10CH2O(C2H4O)6SO3H)、烷基萘基磺酸的钠盐、钾盐和胺盐、及其混合物。
在这些或其他实施方案中,表面活性剂包含阳离子表面活性剂。阳离子表面活性剂包括,例如,各种脂肪酸胺和酰胺及其衍生物,以及脂肪酸胺和酰胺的盐。脂族脂肪酸胺的示例包括乙酸十二烷基胺、乙酸十八烷基胺和牛油脂肪酸胺的乙酸盐、具有脂肪酸的芳族胺的同系物诸如十二烷基甘油(dodecylanalin)、衍生自脂族二胺的脂肪酰胺诸如十一烷基咪唑啉、衍生自脂族二胺的脂肪酰胺诸如十一烷基咪唑啉、衍生自二取代胺的脂肪酰胺诸如油烯基氨基二乙胺、乙二胺的衍生物、季铵化合物及其盐(例如牛油三甲基氯化铵、双十八烷基二甲基氯化铵、双十二烷基二甲基氯化铵、双十六烷基氯化铵)、烷基三甲基氢氧化铵诸如辛基三甲基氢氧化铵、十二烷基三甲基氢氧化铵和十六烷基三甲基氢氧化铵、二烷基二甲基氢氧化铵诸如辛基二甲基氢氧化铵、癸基二甲基氢氧化铵、双十二烷基二甲基氢氧化铵、双十八烷基二甲基氢氧化铵、牛油三甲基氢氧化铵、椰子油、三甲基氢氧化铵、甲基聚氧乙烯椰油氯化铵和二棕榈酰基羟基乙基甲基硫酸铵、氨基醇的酰胺衍生物诸如β-羟基乙基硬脂酰胺、长链脂肪酸的胺盐、及其混合物。
在这些或其他实施方案中,表面活性剂包含非离子表面活性剂。非离子表面活性剂包括,例如,聚氧乙烯烷基醚(诸如月桂基、鲸蜡基、硬脂基或辛基)、聚氧乙烯烷基酚醚、聚氧乙烯月桂基醚、聚氧乙烯脱水山梨糖醇单油酸酯、聚氧乙烯烷基酯、聚氧乙烯脱水山梨糖醇烷基酯、聚乙二醇、聚丙二醇、二乙二醇、乙氧基化三甲基壬醇、聚亚氧烷基二醇改性的聚硅氧烷表面活性剂、聚亚氧烷基取代的有机硅(耙型或ABn型)、有机硅烷醇酰胺、有机硅酯、有机硅糖苷、聚二甲基硅氧烷共聚多元醇、多元醇的脂肪酸酯,例如单-、二-、三-和倍半油酸和硬脂酸山梨糖醇酯和甘油酯、月桂酸甘油酯和月桂酸聚乙二醇酯;聚乙二醇的脂肪酸酯(诸如聚乙二醇单硬脂酸酯和单月桂酸酯)、山梨糖醇的聚氧乙烯化脂肪酸酯(诸如硬脂酸酯和油酸酯)、及其混合物。
在这些或其他实施方案中,表面活性剂包括两性表面活性剂。两性表面活性剂包括,例如,氨基酸表面活性剂、甜菜碱酸表面活性剂、三甲基壬基聚乙二醇醚和含有具有11至15个碳原子的线性烷基基团的聚乙二醇醚醇,诸如2,6,8-三甲基-4-壬氧基聚乙烯氧乙醇(6EO)(由OSi Specialties,A Witco Company,Endicott,NY以TMN-6出售)、2,6,8-三甲基-4-壬氧基聚乙烯氧乙醇(10EO)(由OSi Specialties,A Witco Company,Endicott,NY以TMN-10出售)、亚烷基-氧基聚乙烯氧乙醇(C11-15仲烷基,9EO)(由OSi Specialties,A Witco Company,Endicott,NY以15-S-9出售)、亚烷基氧基聚乙烯氧乙醇(C11-15仲烷基,15EO)(由OSi Specialties,A Witco Company,Endicott,NY以15-S-15出售)、具有不同量的环氧乙烷单元的辛基苯氧基聚乙氧乙醇诸如辛基苯氧基聚乙氧基乙醇(40EO)(由Rohm and Haas Company,Philadelphia,Pa.以X405出售)、非离子乙氧基化十三烷基醚(可以商品名Trycol购自Emery Industries,Mauldin,SC)、磺基琥珀酸二烷基酯的碱金属盐(可以商品名Aerosol购自AmericanCyanamid Company,Wayne,NJ)、聚乙氧基化季铵盐和伯脂肪胺的环氧乙烷缩合产物(可以商品名Ethoquad、Ethomeen或Arquad购自Armak Company,Chicago,llinois)、聚氧亚烷基二醇改性的聚硅氧烷、N-烷基酰胺基甜菜碱及其衍生物、蛋白质及其衍生物、甘氨酸衍生物、磺基甜菜碱、烷基多氨基羧酸盐和烷基两性乙酸盐、及其混合物。这些表面活性剂也可以以不同商品名从其他供应商处获得。
表面活性剂可以以有效乳化水相中非水相的浓度包含在乳液中(或反之亦然)。此类浓度范围基于乳液的总重量为大于0重量%至10重量%,另选地0.3重量%至5重量%。表面活性剂或表面活性剂的组合可存在于乳液的水相、乳液的非水相、水相和非水相的界面、或其组合中。
乳液可还包含一种或多种各种任选的添加剂,诸如偶联剂、抗静电剂、紫外(UV)吸收剂、增塑剂、流平剂、防腐剂、表面活性物质(表面活性剂或洗涤剂或乳化剂)、泡沫促进剂、沉积剂、增稠剂、水相稳定剂、填料、悬浮剂、杀生物剂、冷冻/解冻添加剂、抗冻剂、粘度调节剂、泡沫控制剂、染料(例如颜料)、粘结剂及其组合。
作为上述的替代或补充,乳液可还包含各种添加剂化合物,用于改善由其形成的膜的性质。添加剂化合物的示例为硅烷,诸如四(二甲胺)硅烷、正硅酸四乙酯、缩水甘油氧基丙基三甲氧基硅烷、三乙基硅烷、异丁基三甲氧基硅烷;以及硅氧烷,诸如七甲基三硅氧烷、四甲基二硅氧烷等。
在一些实施方案中,乳液为涂料组合物,或者可配制成涂料组合物。此类涂料组合物通常用于通过将涂料组合物施用于基底的表面来在基底上提供连续的保护性涂层。此类基底的示例包括有机或无机组分,并且可包括家用材料,诸如皮革、纸材、木材、金属、塑料、织物、油漆等。涂料组合物也可适用于其他应用,例如用作保护性和/或装饰性涂料、用作油漆中的组分等。
在各种实施方案中,可将化合物和/或共聚物用作环氧基涂料的添加剂。许多环氧基涂料是本领域所理解的,包括在US8722148和US20060205861中描述的那些。
在各种实施方案中,该组合物包含乳液和有机粘结剂。乳液可以在组合物中原位形成,或者可以首先制备乳液,并且然后与有机粘结剂连同任何其他任选的组分组合,以得到组合物。在某些实施方案中,通过将乳液和有机粘结剂连同任何任选的组分组合来形成组合物。乳液通常存在于组合物中,即用乳液形成组合物不会破坏乳液。
有机粘结剂不受限制,并且通常基于组合物的最终用途应用来选择。虽然示例性示例在下文示出,但在组合物中可利用任何有机粘结剂。有机粘结剂可以是反应性的或非反应性的,并且可以是热塑性和/或热固性的。通常,有机粘结剂为有机聚合物和/或树脂。
在某些实施方案中,有机粘结剂包含天然胶乳。在这些或其他实施方案中,有机粘结剂包括合成胶乳。有机粘结剂也可以是天然和合成胶乳的组合。例如,当所述组合物用于制备膜或油漆时,有机粘结剂通常为天然和/或合成胶乳。天然和合成胶乳是本领域已知的。例如,取决于对有机粘结剂的选择,所述组合物可用作油漆,例如耐热油漆,其可为无溶剂的。所述油漆可用于绝缘应用、抗污应用、建筑应用、商业/工业或住宅应用、防护应用、皮革应用、纺织物应用等。
有机粘结剂的具体示例包括但不限于聚烯烃、丙烯酸类聚合物、聚乙酸乙烯酯、聚氯乙烯、苯乙烯(例如苯乙烯-丁二烯橡胶)、丙烯腈-丁二烯、环氧树脂、酚醛树脂、聚酯、聚乙烯醇缩丁醛、苯氧基、聚脲、纤维素树脂、聚氨酯、聚酰胺、聚醚、醇酸盐、有机硅、丙烯腈等。有机粘结剂可以包括此类有机粘结剂的组合,或包括一种或多种此类有机粘结剂的共聚物或三元共聚物。
组合物中有机粘结剂的含量可以根据许多因素而变化,诸如其选择、组合物中存在的乳液的类型和量,组合物的最终用途应用等。增加的有机粘结剂负载量通常导致具有更大的硬度和其他增加的物理性质的膜。在某些实施方案中,组合物包含粘结剂,其量基于组合物的总重量为大于0重量%至小于100重量%、另选地大于0重量%至50重量%、另选地0.1重量%至40重量%、另选地5重量%至15重量%。
有机粘结剂可以分散或设置在载体媒介物中。载体媒介物可以是任何合适的载体媒介物,其通常溶解有机粘结剂。载体媒介物通常是所用有机粘结剂的功能。载体媒介物可以是水,使得组合物整体上是水基的,或者可以是除水之外的溶剂,例如有机溶剂。在某些实施方案中,与乳液一样,组合物基本上不含水。基本上不含水是相对于乳液定义的。
在一些实施方案中,组合物还包含一种或多种任选的组分。该组合物可包含上文关于乳液描述的任何任选的组分。这些任选的组分可以包含在组合物中而不存在于乳液中,可以独立于乳液并入组合物中或两者。任选的组分的具体示例包括但不限于着色剂、聚结助剂、表面活性剂、增稠剂、消泡剂、增容剂、UV稳定剂、抗氧化剂、杀生物剂、阻燃剂等。这些任选的组分中的一些可存在于乳液中,如上所述,并且因此包含在组合物中,或者在形成组合物时可以并入这些任选的组分中的一种或多种。上述相对于乳液的任何任选的组分也可以通过从乳液中引入或包含附加的量的特定组分而存在于组合物中。举例来说,组合物可包含催化剂,其可与乳液中可存在的任何催化剂相同或不同。
在某些实施方案中,组合物还包含一种或多种着色剂,诸如颜料、染料等。此类着色剂可以是有机或无机的,合成的或天然的。着色剂的示例列于关于乳液的上文中。乳液和组合物本身可包括独立选择的不同着色剂。合适的着色剂的附加的示例包括镉黄、镉红、镉绿、镉橙、炭黑(包括藤黑、灯黑)、象牙黑(骨炭)、铬黄、铬绿、钴紫、钴蓝、蔚蓝、钴黄(aureolin\cobalt yellow)、石青、汉紫、汉蓝、埃及蓝、孔雀石、巴黎绿、酞菁蓝BN、酞菁绿G、铜绿、铬绿、血红、残渣、氧化红、赭红、威尼斯红、普鲁士蓝、赭黄、生赭、赭褐、棕土、烧棕土、纯铅白、拿浦黄、朱红、钛黄、钛米色、钛白(TiO2)、钛黑、群青、群青绿调、锌白、锌铁氧体、茜素(合成或天然)、茜素深红(合成或天然)、藤黄、胭脂红、茜草玫瑰红、靛蓝、印度黄、泰尔紫、喹吖啶酮、品红、酞菁绿、酞菁蓝、颜料红170、或其任何组合。
在特定实施方案中,组合物还包含聚结助剂。合适的聚结助剂包括当有机粘结剂确实形成膜时降低有机粘结剂的最低成膜温度的任何化合物,和/或当任何载体媒介物或水从组合物去除时增加从有机粘结剂形成固体膜的速率的任何化合物。合适的聚结助剂的示例包括二醇醚、异丁酸2,2,4-三甲基-1,3-戊二醇酯、及其组合。
在某些实施方案中,组合物包含表面活性剂。表面活性剂可以与乳液中利用的任何表面活性剂相同或不同,其示例如上所述。
增稠剂(或流变改性剂)也可包含在组合物中以获得所需的粘度和流动性质。取决于它们的选择,作为有机粘结剂的选择,增稠剂可以通过例如与有机粘结剂形成多个氢键起作用,由此引起链缠结、成环和/或溶胀,这导致体积限制。在某些实施方案中,可以利用增稠剂,诸如纤维素衍生物,包括羟乙基纤维素、甲基纤维素和羧甲基纤维素。
在一些实施方案中,该组合物包含消泡剂。消泡剂可以是任何合适的化学添加剂,其减少和阻碍组合物中泡沫的形成。消泡剂是本领域已知的并且通常基于组合物中存在的其他组分来选择。
当组合物包含增容剂时,增容剂可以是任何化合物或组分,其改变、另选地改善组合物中组分的润湿。此类增容剂的示例包括钛醇盐,磷酸、亚磷酸、膦酸和硅酸的酯,脂族、芳族和脂环族酸的金属盐和酯,乙烯/丙烯酸或甲基丙烯酸,乙烯/丙烯酸酯或甲基丙烯酸酯,乙烯/乙酸乙烯酯树脂,苯乙烯/马来酸酐树脂或其酯,丙烯腈-丁二烯-苯乙烯树脂,甲基丙烯酸酯/丁二烯-苯乙烯树脂(MBS),苯乙烯-丙烯腈树脂(SAN)和丁二烯丙烯腈共聚物。另选地或除此之外,增容剂可包含硅烷,例如烃氧基硅烷,诸如烷氧基硅烷、烷氧基硅烷与羟基官能性聚有机硅氧烷的组合、氨基官能化的硅烷、或其组合。硅烷可包括任何官能团,其可以是粘合促进基团,诸如氨基、环氧基、巯基和/或丙烯酸酯基团。可以利用官能团的组合,例如,(D)增容剂可包含环氧官能化的烷氧基硅烷。合适的环氧官能化的有机基团例如为3-缩水甘油氧基丙基和(环氧环己基)乙基。不饱和有机基团例如为3-甲基丙烯酰氧基丙基、3-丙烯酰氧基丙基以及不饱和单价烃基团,诸如乙烯基、烯丙基、己烯基、十一烯基。合适的环氧官能化的烷氧基硅烷的示例包括3-缩水甘油氧基丙基三甲氧基硅烷、3-缩水甘油氧基丙基三乙氧基硅烷、(环氧基环己基)乙基二甲氧基硅烷、(环氧基环己基)乙基二乙氧基硅烷及其组合。合适的不饱和烷氧基硅烷的示例包括乙烯基三甲氧基硅烷、烯丙基三甲氧基硅烷、烯丙基三乙氧基硅烷、己烯基三甲氧基硅烷、十一碳烯基三甲氧基硅烷、3-甲基丙烯酰氧基丙基三甲氧基硅烷、3-甲基丙烯酰氧基丙基三乙氧基硅烷、3-丙烯酰氧基丙基三甲氧基硅烷、3-丙烯酰氧基丙基三乙氧基硅烷、及其组合。如本领域所理解,氨基官能化的硅烷,诸如氨基官能化的烷氧基硅烷可具有各种氨基基团。增容剂的其他示例包括改性的聚乙烯和改性的聚丙烯,它们分别通过使用反应性基团改性聚乙烯和聚丙烯而获得,所述反应性基团包括极性单体诸如马来酸酐或酯、丙烯酸或甲基丙烯酸或酯、乙酸乙烯酯、丙烯腈和苯乙烯。
UV稳定剂的具体示例包括支化的和线性2-(2H-苯并三唑-2-基)-6-十二烷基-4-甲基-酚(571)。合适的UV稳定剂的附加的示例包括癸二酸双(1,2,2,6,6-五甲基-4-哌啶基)酯;癸二酸1,2,2,6,6-五甲基-4-哌啶酯/甲酯;及其组合(272)。这些和其他添加剂(诸如765)可从美国纽约州塔里敦的汽巴精化公司(Ciba Specialty Chemicals,Tarrytown,NY,U.S.A.)商购获得。其他UV和光稳定剂可商购获得,并且示例有来自科聚亚公司(Chemtura)的LowLite、来自普立万公司(PolyOne)的OnCap和来自美国特拉华州的杜邦公司(E.I.du Pont de Nemours andCompany of Delaware,U.S.A)的Light Stabilizer 210。低聚抗氧化稳定剂的示例(特别是受阻胺光稳定剂(HALS))是汽巴(Ciba)622,其是丁二酸与4-羟基-2,2,6,6-四甲基-1-哌啶乙醇共聚的二甲酯。
如果利用,抗氧化剂可以是本领域已知的任何抗氧化剂。其具体示例包括酚抗氧化剂及酚抗氧化剂与稳定剂的组合。酚抗氧化剂包括完全空间位阻酚和部分位阻酚;以及空间位阻胺,诸如四甲基哌啶衍生物。合适的酚抗氧化剂包括维生素E和来自美国汽巴精化公司(Ciba Specialty Chemicals,U.S.A.)的1010。1010包含季戊四醇四(3-(3,5-二-叔丁基-4-羟基苯基)丙酸酯)。抗氧化剂的附加的示例为乙酰基半胱氨酸、熊果苷、抗坏血酸、抗坏血酸多肽、抗坏血酸二棕榈酸酯、抗坏血酸甲基硅烷醇果胶酸酯、抗坏血酸棕榈酸酯、抗坏血酸硬脂酸酯、BHA、对羟基苯甲醚、BHT、叔丁基对苯二酚、咖啡酸、茶(Camellia sinensis)油、脱乙酰壳多糖抗坏血酸盐、脱乙酰壳多糖甘醇酸盐、脱乙酰壳多糖水杨酸盐、绿原酸、半胱氨酸、半胱氨酸盐酸盐、癸基巯甲基咪唑、异抗坏血酸、二戊基对苯二酚、二叔丁基对苯二酚、双十六烷基醇硫代二丙酸酯、二环戊二烯/叔丁基甲酚共聚物、棓酰棓酸三油酸酯、硫代二丙酸二月桂酯、硫代二丙酸二肉豆蔻醇酯、二油基生育酚甲基硅烷醇、异槲皮苷、地奥司明、抗坏血酸硫酸酯二钠、芸香亭基硫酸二钠、硫代二丙酸二硬脂醇酯、硫代二丙酸双十三醇酯、没食子酸月桂酯、阿魏酸乙酯、阿魏酸、对苯二酚、羟胺盐酸盐、羟胺硫酸盐、巯基乙酸异辛酯、曲酸、羟基积雪草苷、抗坏血酸镁、抗坏血酸磷酸酯镁、褪黑激素、甲氧基-PEG-7芸香苷琥珀酸酯、亚甲基二叔丁基甲酚、甲基硅烷醇抗坏血酸、去甲二氢愈创木酸、没食子酸辛酯、苯基巯基乙酸、间苯三酚、磷酸抗坏血酸酯生育酚钾盐、硫代二乙酰胺、亚硫酸钾、没食子酸丙酯、迷迭香酸、芦丁、抗坏血酸钠、抗坏血酸/胆甾醇磷酸酯钠、亚硫酸氢钠、异抗坏血酸钠、焦亚硫酸钠、亚硫酸钠、硫代乙醇酸钠、山梨糖醇缩糠醛、茶树(Melaleuca aftemifolia)油、醋酸生育酚、四己基癸醇抗坏血酸酯、四氢二阿魏酰甲烷、生育酚亚油酸酯/油酸酯、硫二甘醇、生育酚琥珀酸酯、硫代二乙醇酸、硫代乙醇酸、硫代乳酸、硫代水杨酸、硫代牛磺酸、视黄醇、生育酚聚醚-5、生育酚聚醚-10、生育酚聚醚-12、生育酚聚醚-18、生育酚聚醚-50、生育酚、托可索仑、生育酚亚油酸酯、生育酚烟酸酯、托可醌、邻甲苯双胍、三(壬苯基)亚磷酸酯、泛醌、二丁基二硫代氨基甲酸锌、及其混合物。
杀生物剂的示例可为杀真菌剂、除草剂、杀虫剂、抗微生物剂、或其组合。
杀真菌剂的具体示例包括N取代的苯并咪唑氨基甲酸酯、苯并咪唑基氨基甲酸酯,诸如2-苯并咪唑基氨基甲酸甲酯、2-苯并咪唑基氨基甲酸乙酯、2-苯并咪唑基氨基甲酸异丙酯、N-{2-[l-(N,N-二甲基氨甲酰基)苯并咪唑基]}氨基甲酸甲酯、N-{2-[l-(N,N-二甲基氨甲酰基)-6-甲基苯并咪唑基]}氨基甲酸甲酯、N-{2-[l-(N,N-二甲基氨甲酰基)-5-甲基苯并咪唑基]}氨基甲酸甲酯、N-{2-[l-(N-甲基氨甲酰基)苯并咪唑基]}氨基甲酸甲酯、N-{2-[l-(N-甲基氨甲酰基)-6-甲基苯并咪唑基]}氨基甲酸甲酯、N-{2-[l-(N-甲基氨甲酰基)-5-甲基苯并咪唑基]}氨基甲酸甲酯、N-{2-[l-(N,N-二甲基氨甲酰基)苯并咪唑基]}氨基甲酸乙酯、N-{2-[2-(N-甲基氨甲酰基)苯并咪唑基]}氨基甲酸乙酯、N-{2-[l-(N,N-二甲基氨甲酰基)-6-甲基苯并咪唑基]}氨基甲酸乙酯、N-{2-[l-(N-甲基氨甲酰基)-6-甲基苯并咪唑基]}氨基甲酸乙酯、N-{2-[l-(N,N-二甲基氨甲酰基)苯并咪唑基]}氨基甲酸异丙酯、N-{2-[1-(N-甲基氨甲酰基)苯并咪唑基]}氨基甲酸异丙酯、N-{2-[l-(N-丙基氨甲酰基)苯并咪唑基]}氨基甲酸甲酯、N-{2-[1-(N-丁基氨甲酰基)苯并咪唑基]}氨基甲酸甲酯、N-{2-[1-(N-丙基氨甲酰基)苯并咪唑基]}氨基甲酸甲氧基乙酯、N-{2-[1-(N-丁基氨甲酰基)苯并咪唑基]}氨基甲酸甲氧基乙酯、N-{2-[1-(N-丙基氨甲酰基)苯并咪唑基]}氨基甲酸乙氧基乙酯、N-{2-[l-(N-丁基氨甲酰基)苯并咪唑基]}氨基甲酸乙氧基乙酯、N-{l-(N,N-二甲基氨甲酰氧基)苯并咪唑基]}氨基甲酸甲酯、N-{2-[N-甲基氨甲酰氧基)苯并咪唑基]}氨基甲酸甲酯、N-{2-[l-(N-丁基氨甲酰氧基)苯并咪唑基]}氨基甲酸甲酯、N-{2-[l-(N-丙基氨甲酰基)苯并咪唑基]}氨基甲酸乙氧基乙酯、N-{2-[l-(N-丁基氨甲酰氧基)苯并咪唑基]}氨基甲酸乙氧基乙酯、N-{2-[l-(N,N-二甲基氨甲酰基)-6-氯苯并咪唑基]}氨基甲酸甲酯和N-{2-[l-(N,N-二甲基氨甲酰基)-6-硝基苯并咪唑基]}氨基甲酸甲酯;10,10'-氧双吩恶砒(其具有商品名霉克净(Vinyzene),OB PA)、二-碘甲基-对甲苯基砜、苯并噻吩-2-环己基甲酰胺-S,S-二氧化物、N-(氟二氯甲硫代)邻苯二甲酰亚胺(其具有商品名氟灭菌丹(Fluor-Folper)和备防多(Preventol)A3);甲基-苯并咪唑-2-基氨基甲酸酯(其具有商品名多菌灵(Carbendazim)和备防多(Preventol)BCM)、双(2-吡啶基硫代-l-氧化物)锌(吡啶硫酮锌)、2-(4-噻唑基)-苯并咪唑、N-苯基-碘炔丙基氨基甲酸酯、N-辛基-4-异噻唑啉-3-酮、4,5-二氯化物-2-正辛基-4-异噻唑啉-3-酮、N-丁基-l,2-苯并异噻唑啉-3-酮,和/或三唑基化合物,诸如戊唑醇(tebuconazole)与含有银的沸石组合。
另选地,杀生物剂可以包含含有硼的物质,例如硼酸酐、硼砂、或八硼酸二钠四水合物;其可用作杀虫剂、杀真菌剂和/或阻燃剂。
合适的阻燃剂的具体示例包括炭黑、水合氢氧化铝和硅酸盐(诸如硅灰石)、铂和铂化合物。另选地,如果利用,则阻燃剂可以选自基于卤素的阻燃剂,诸如十溴二苯醚、八溴二苯醚、六溴环十二烷、十溴二苯醚、二苯氧基苯、乙撑双-四溴邻苯二甲酰亚胺、五溴乙苯、丙烯酸五溴苄酯、三溴苯基马来酰亚胺、四溴双酚A、双-(三溴苯氧基)乙烷、双-(五溴苯氧基)乙烷、聚二溴苯醚、三溴苯基烯丙基醚、双-二溴丙基醚、四溴邻苯二甲酸酐、二溴新戊二醇、二溴乙基二溴环己烷、五溴二苯醚、三溴苯乙烯、五溴氯环己烷、四溴二甲苯、六溴环十二烷、溴化聚苯乙烯、十四溴二苯氧基苯、三氟丙烯和PVC。另选地,如果利用,则阻燃剂可以选自基于磷的阻燃剂,诸如(2,3-二溴丙基)-磷酸酯、磷、环磷酸酯、磷酸三芳基酯、喷替酸双-三聚氰铵(bis-melaminium pentate)、季戊四醇双环磷酸酯、磷酸二甲基甲基酯、氧化膦二醇、磷酸三苯酯、磷酸三-(2-氯乙基)酯、磷酸酯(诸如磷酸三甲苯酯、磷酸三二甲苯酯、磷酸异癸基二苯酯、磷酸乙基己基二苯酯)、各种胺的磷酸盐(诸如磷酸铵)、磷酸三辛酯、磷酸三丁酯或磷酸三-丁氧基乙基酯。其他合适的阻燃剂可包括四烷基铅化合物,诸如四乙基铅、五羰基铁、甲基环戊二烯基三羰基锰、三聚氰胺以及衍生物(诸如三聚氰胺盐)、胍、双氰胺、氨基磺酸铵、三水合氧化铝和氢氧化镁三水合氧化铝。
水性组合物包括包含水作为组分,通常作为主要组分或大部分组分(例如,作为溶剂、载体或介质)的任何组合物。在这些实施方案中,水性组合物还包含本公开的化合物和/或共聚物。
如本领域所理解的,表面活性剂是降低两种液体之间、气体与液体之间、或液体与固体之间的表面张力(或界面张力)的化合物。表面活性剂可充当洗涤剂、润湿剂、乳化剂、发泡剂和分散剂。在许多实际应用和产品中,表面活性剂可用作清洁剂、润湿剂、分散剂、乳化剂、起泡剂和消泡剂,包括但不限于洗涤剂;织物软化剂;乳液;皂;油漆;粘合剂;油墨;防雾剂;滑雪蜡;滑雪板蜡;浮选、洗涤和酶促方法中循环利用纸脱墨剂;轻泻剂等。农用化学品制剂诸如一些除草剂、杀昆虫剂、生物杀灭剂(消毒杀菌剂)和杀精子剂也可包含一种或多种表面活性剂。个人护理产品诸如化妆品、洗发剂、沐浴凝胶、毛发调理剂(洗发剂后)和牙膏常常包含一种或多种表面活性剂。
在各种实施方案中,表面活性剂组合物包含本公开的化合物和/或共聚物。在某些实施方案中,表面活性剂组合物还包含本领域理解的一种或多种添加剂,诸如水和/或其他载体、一种或多种常规表面活性剂等。本领域中技术人员应理解,表面活性剂组合物也可被称为润湿组合物、表面张力调节剂或分散剂组合物。在一些应用中,关于此类组合物的形式、功能和/或最终应用的差异可存在细微差别。
在其他实施方案中,化合物本身—和/或共聚物本身—为表面活性剂。在这些实施方案中,化合物和/或共聚物可被称为分散剂、润湿剂或表面张力调节剂。
在各种实施方案中,该组合物选自成膜组合物,包括起泡和基本上不起泡的组合物、水性和非水性组合物、以及它们的组合。下文描述了某些膜。该组合物可以是可固化的、部分可固化的,或者可以不固化。在其中该组合物为可至少部分地固化至可固化的实施方案中,该组合物可改变形式,诸如从液体变成更粘稠的液体、凝胶、半固体或固体。
在各种实施方案中,该组合物可用作防粘连(或抗粘连)添加剂(或试剂)。在这些实施方案中,该组合物还可提供耐刮擦性和低摩擦系数(COF)。在某些实施方案中,化合物本身—和/或共聚物本身—为抗粘连添加剂。
防粘连剂常常用于膜中或用于膜,例如用于聚烯烃膜中,以改善防粘连剂的各个分子之间的滑移,并且是此类膜的后处理转化(切割、折叠、焊接等)的重要成分。粘连是膜和涂层制造商遇到的常见问题。粘连是膜的两个相邻层的粘附。这是与(吹塑或浇铸)聚乙烯和聚丙烯膜最相关的问题,并且在较小程度上在挤出涂覆或层压产品中也是如此。由于在聚合物的无定形区域之间存在范德华力,因此发生相邻膜层的粘连。这些力随着两层之间距离的减小而增大,从而在两层被压在一起(例如,粘结到收卷辊上或成品转化膜的堆叠)时增加粘连。粘连的另一种可能原因是存在趋于迁移到膜表面的低分子量物质(诸如低聚物)。
解决这些处理问题的有效方法是加入防粘连添加剂。存在于树脂中的防粘连添加剂从膜表面微观上突出。这产生微凸体(“小凸块”),这些微凸体有助于使膜与膜表面接触最小化,从而增加两个层之间的距离,从而最大程度减少粘连。
相邻层之间的粘连导致摩擦增加,并且防粘连剂的加入通常有助于降低膜与膜COF。COF是一个表面在邻接表面上滑移的相对难度的量度。滑移阻力越大,COF值越高(例如,“低滑移”或“无滑移”膜,有时被称为“高COF”膜)。
在各种实施方案中,该组合物为农用组合物。可将化合物和共聚物中的至少一者用作农用组合物的添加剂。许多类型的用于促进农业的组合物是本领域所理解的,包括那些促进植物生长、控制或预防杂草、控制或预防害兽和昆虫等的组合物。无论使用植物生长调节剂还是基因改变的植物,都将任何数量的农学上合适的添加剂、辅助剂和/或植物催化剂施用于植物以支持或促进植物生长,包括:含有诸如氮、磷、钾、高二氧化碳、过氧化氢、铁和锰的元素的肥料;次要营养素,诸如硫、钙和镁的来源;微量营养素,诸如硼、钴、铜、钼、锌、镍;水溶性碳水化合物,诸如蔗糖、果糖和葡萄糖;以及各种烷基葡糖苷。
在各种实施方案中,该组合物包含至少一种杀虫剂。术语杀虫剂应理解为涵盖除草剂、杀虫剂、杀螨剂、杀线虫剂、杀外寄生虫药、杀真菌剂和植物生长调节剂。就这一点而言,该组合物不受限制。
具有除草活性的化合物类别的示例包括:咪唑啉酮,诸如灭草喹;磺酰脲,诸如氯嘧磺隆;三唑并嘧啶磺酰胺,诸如唑嘧磺草胺;芳氧基苯氧基丙酸酯,诸如喹禾灵;芳基脲,诸如异丙隆和绿麦隆;三嗪,诸如阿特拉津和西玛津;芳基羧酸,诸如毒莠定;芳氧基链烷酸,诸如MCPA;氯乙酰苯胺,诸如吡唑草胺;二硝基苯胺,诸如氨磺乐灵;吡唑类,诸如吡唑特;以及二苯基醚,诸如治草醚。具有杀虫活性的化合物类别的示例包括:苯甲酰基脲,诸如氟铃脲;双酰肼类,诸如虫酰肼;氨基甲酸酯,诸如克百威;拟除虫菊酯,诸如氯氰菊酯;有机磷酸酯,诸如亚胺硫磷;三唑;以及天然产物,诸如多杀菌素。
具有杀真菌活性的化合物类别的示例包括:吗啉类,诸如烯酰吗啉;苯基酰胺类,诸如苯霜灵;唑类,诸如己唑醇;嗜球果伞素类,诸如嘧菌酯;酞腈类,诸如百菌清;以及苯氧基喹啉类,诸如快诺芬。
杀虫剂/杀螨剂的示例为:杀草丹;除虫脲;伏虫脲;虱螨脲;丁醚脲或拟除虫菊酯,诸如联苯菊酯、生物烯丙菊酯、氟胺氰菊酯、灭虫菊、苄氯菊酯、氯氰菊酯、氟氯氰菊酯、三氟氯氰菊酯、溴氰菊酯、七氟菊酯或似虫菊;另外有吡蚜酮、杀虫环、苯氧威、烯虫酯、阿巴美丁和甲氨基阿维菌素。
在各种实施方案中,可将化合物和/或共聚物用于处理颗粒,例如用作中间体以处理金属氧化物颗粒表面。颗粒可具有各种尺寸和粒度分布,包括纳米级尺寸和微米级尺寸。
金属氧化物颗粒可为任何合适的金属氧化物颗粒。合适的金属氧化物颗粒包括例如氧化铝、氧化钛、二氧化硅、氧化锡、氧化镁、氧化锌、氧化锶颗粒、它们的混合物、以及它们的共氧化物。
颗粒可以是导电且/或导热的或者非导电且/或非导热的。在某些实施方案中,颗粒被分类为:导电填料,其可为金属或导电非金属;或者金属颗粒或具有金属外表面的非金属颗粒,并且外表面金属为贵金属诸如银、金、铂、钯以及它们的合金,或基体金属诸如镍、铝、铜或钢。颗粒还可具有金属的外表面,其中颗粒的芯由铜、实心玻璃、中空玻璃、云母、镍、陶瓷纤维或聚合物诸如聚苯乙烯和聚甲基丙烯酸甲酯构成。
在某些实施方案中,颗粒被分类为导热填料,其可为金属颗粒、金属氧化物颗粒、导热非金属粉末或它们的组合。导热填料可为铝、铜、金、镍、银、氧化铝、氧化镁、氧化铍、氧化铬、氧化钛、氧化锌、钛酸钡、金刚石、石墨、碳或硅纳米级颗粒、氮化硼、氮化铝、碳化硼、碳化钛、碳化硅和碳化钨。
可经处理的矿物填料或颜料的示例包括:二氧化钛;氢氧化铝(也称为ATH);氢氧化镁;云母;高岭土;碳酸钙;钠、钾、镁、钙和钡的非水合、部分水合或水合的氟化物、氯化物、溴化物、碘化物、铬酸盐、碳酸盐、氢氧化物、磷酸盐、磷酸氢盐、硝酸盐、氧化物和硫酸盐;氧化锌、氧化铝、五氧化二锑、三氧化锑、氧化铍、氧化铬、氧化铁、锌钡白、硼酸或硼酸盐,诸如硼酸锌、偏硼酸钡或硼酸铝,混合的金属氧化物,诸如硅铝酸盐、蛭石、二氧化硅(包括热解法二氧化硅、熔融二氧化硅、沉淀二氧化硅)、石英、砂石和硅胶;稻壳灰、陶瓷和玻璃珠、沸石、金属诸如铝薄片或粉末、青铜粉、铜、金、钼、镍、银粉或薄片、不锈钢粉末、钨、含水硅酸钙、钛酸钡、二氧化硅-炭黑复合材料、官能化碳纳米管、水泥、飞灰、板岩粉、陶瓷或玻璃珠、膨润土、粘土、滑石、无烟煤、磷灰石、硅镁土、氮化硼、方英石、硅藻土、白云石、铁氧体、长石、石墨、煅烧高岭土、二硫化钼、珍珠岩、浮石、叶蜡石、海泡石、锡酸锌、硫化锌或硅灰石。
可经处理的其他填料包括:天然纤维,诸如木粉、木纤维、棉纤维或农业纤维诸如小麦秸秆、大麻、亚麻、洋麻、木棉、黄麻、苎麻、剑麻、灰叶剑麻、玉米纤维或椰纤维、坚果壳或稻壳、木质素、淀粉、或纤维素和含纤维素产品;或某些合成纤维,诸如芳族聚酰胺纤维、尼龙纤维、棉纤维或玻璃纤维、或聚四氟乙烯或聚乙烯的塑料微球,并且本发明包括此类填料的处理。填料可为:固体有机颜料,诸如掺入偶氮、靛青类、三苯甲烷、蒽醌、氢醌或黄嘌呤染料的那些;或固体有机阻燃剂,诸如聚氯联苯或十溴二苯醚或含磷阻燃剂。
在各种实施方案中,可将化合物和/或共聚物用于对硅氧烷或包含至少一种硅氧烷的组合物进行改性。改性可为直接或间接的,例如在化合物可与硅氧烷反应的情况下改性。以下描述了该组合物的附加实施方案。
所述组合物可包含一种或多种填料。填料可为一种或多种增强填料、非增强填料、或它们的混合物。细分的增强填料的示例包括高表面积热解法和沉淀二氧化硅,其包括稻壳灰和一定程度的碳酸钙。细分的非增强填料的示例包括粉碎的石英、硅藻土、硫酸钡、氧化铁、二氧化钛和碳黑、滑石、和硅灰石。其他可单独使用或除上述之外的填料包括碳纳米管例如多壁碳纳米管矾土石、空心玻璃球、硫酸钙(硬石膏)、石膏、硫酸钙、碳酸镁、粘土诸如高岭土、三水合氧化铝、氢氧化镁(水镁石)、石墨、碳酸铜例如孔雀石、碳酸镍例如翠镍矿(zarachite)、碳酸钡例如毒重石和/或碳酸锶例如菱锶矿。另外的另选填料包括氧化铝,选自以下的硅酸盐:橄榄石类、石榴石类;硅铝酸盐;环硅酸盐;链状硅酸盐;和片状硅酸盐。在某些实施方案中,该组合物包含至少一种填料,该填料包括中空颗粒,例如中空球。此类填料可用于有助于泡沫的孔隙率和/或总体空隙率。在某些实施方案中,一些填料可用于调节所述组合物的触变特性。
填料(如果存在的话)可任选用处理剂进行表面处理。处理剂和处理方法是本领域理解的。填料的表面处理通常例如用脂肪酸或脂肪酸酯诸如硬脂酸酯,或用有机硅烷、有机硅氧烷或有机硅氮烷诸如六烷基二硅氮烷或短链硅氧烷二醇执行。通常,表面处理使得填料成为疏水的,并因此更容易处理并获得与组合物中的其它组分的均匀混合物。硅烷诸如R5 eSi(OR6)4-e也可用作填料的处理剂,其中R5为6个至20个碳原子的取代或未取代的单价烃基团,例如烷基基团,诸如己基、辛基、十二烷基、十四烷基、十六烷基和十八烷基,以及芳烷基基团,诸如苄基和苯乙基,R6为1个至6个碳原子的烷基基团,并且下标“e”等于1、2或3。在某些实施方案中,可将化合物和共聚物中的至少一者用作如上所述的处理剂,任选地与一种或多种常规处理剂组合。
在各种实施方案中,所述组合物还包含反应抑制剂。例如炔醇,诸如2-甲基-3-丁炔-2-醇、3,5-二甲基-1-己炔-3-醇、或2-苯基-3-丁炔-2-醇;烯炔化合物,诸如3-甲基-3-戊烯-1-炔或3,5-二甲基-3-己烯-1-炔;或1,3,5,7-四甲基-1,3,5,7-四乙烯基环四硅氧烷、1,3,5,7-四甲基-1,3,5,7-四己烯基环四硅氧烷、或苯并三唑作为任选的组分掺入所述组合物中。
在各种实施方案中,所述组合物还包含触变剂。合适的触变剂包括流变剂,此类试剂的具体示例可见于美国专利公布2018/0066115A1和2018/0208797A1中。
在各种实施方案中,该组合物还包含粘附赋予剂。粘附赋予剂可改善泡沫对固化期间所接触的基体材料(例如,第二表面36)的粘附性。在某些实施方案中,粘附赋予剂选自在分子中具有至少一个键合到硅原子的烷氧基基团的有机硅化合物。该烷氧基基团的示例为甲氧基基团、乙氧基基团、丙氧基基团、丁氧基基团和甲氧基乙氧基基团。此外,键合到该有机硅化合物的硅原子的非烷氧基基团的示例为:取代或未取代的单价烃基团,诸如烷基基团、烯基基团、芳基基团、芳烷基基团、卤代烷基基团等;含环氧基的一价有机基团,诸如3-环氧丙氧丙基基团、4-环氧丙氧丁基基团或类似的环氧丙氧烷基基团;2-(3,4-环氧环己基)乙基基团、3-(3,4-环氧环己基)丙基基团或类似的环氧环己烷基基团;和4-氧杂环丙丁基基团、8-氧杂环丙辛基基团或类似的氧杂环丙烷基基团;含有丙烯酸基的单价有机基团,诸如3-甲基丙烯酰氧基丙基等;以及氢原子。
该有机硅化合物通常具有硅键合的烯基基团或硅键合的氢原子。此外,由于能够赋予相对于各种类型基体材料的良好粘附性的能力,因此该有机硅化合物通常在分子中具有至少一个含有环氧基基团的一价有机基团。这种类型的有机硅化合物的示例为有机硅烷化合物、有机硅氧烷低聚物和硅酸烷基酯。有机硅氧烷低聚物或硅酸烷基酯的分子结构的示例为直链结构、部分支化的直链结构、支链结构、环状结构和网状结构。直链结构、支链结构和网状结构是典型的。这种类型的有机硅化合物的示例为:硅烷化合物,诸如3-缩水甘油氧基丙基三甲氧基硅烷、2-(3,4-环氧基环己基)乙基三甲氧基硅烷、3-甲基丙烯酰氧基丙基三甲氧基硅烷等;硅氧烷化合物,其在分子中具有至少一个硅键合的烯基基团或硅键合的氢原子和至少一个硅键合的烷氧基基团;具有至少一个硅键合的烷氧基基团的硅烷化合物或硅氧烷化合物与在分子中具有至少一个硅键合的羟基基团和至少一个硅键合的烯基基团的硅氧烷化合物的混合物;以及甲基聚硅酸盐、乙基聚硅酸盐和含有环氧基基团的乙基聚硅酸盐。
在各种实施方案中,该组合物包含至少一种发泡剂。如果利用的话,发泡剂可选自化学发泡剂、物理发泡剂以及它们的组合。发泡剂的用量可根据期望的结果而变化。例如,可改变发泡剂的用量以定制最终泡沫密度和泡沫上升曲线。
该组合物可包含载体媒介物(或稀释剂),该载体媒介物(或稀释剂)包括有机硅(直链和环状的两种)、有机油、有机溶剂以及这些的混合物。溶剂的具体示例可见于美国专利6,200,581中。载体媒介物也可为25℃下的粘度在1mm2/sec至1,000mm2/sec范围内的低粘度有机聚硅氧烷或挥发性甲基硅氧烷或挥发性乙基硅氧烷或挥发性甲基乙基硅氧烷,如六甲基环三硅氧烷、八甲基环四硅氧烷、十甲基环五硅氧烷、十二甲基环六硅氧烷、八甲基三硅氧烷、十甲基四硅氧烷、十二甲基五硅氧烷、十四甲基六硅氧烷、十六甲基七硅氧烷、七甲基-3-{(三甲基甲硅烷基)氧基)}三硅氧烷、六甲基-3,3,双{(三甲基甲硅烷基)氧基}三硅氧烷、五甲基{(三甲基甲硅烷基)氧基}环三硅氧烷以及聚二甲基硅氧烷、聚乙基硅氧烷、聚甲基乙基硅氧烷、聚甲基苯基硅氧烷、聚二苯基硅氧烷、辛酰基聚甲基硅氧烷以及它们的任何混合物。
在一些实施方案中,该组合物包含一种或多种附加组分,诸如流变改性剂、极性有机溶剂、增稠剂、无机盐(例如氯化钙)、个人护理活性物质/成分、芳香剂、或它们的组合。通常,该一种或多种附加组分基于该组合物的期望用途来选择。例如,在一些实施方案中,该组合物被配制成用作个人护理组合物,并且还包含个人护理成分。具体的个人护理成分,或具体的个人护理成分的混合物可基于该组合物被配制成的个人护理组合物的类型来选择。在这些实施方案中,个人护理成分可为液体、固体、胶囊包封的液体等。个人护理成分的各种示例如下文所述。这些个人护理成分中的任一种个人护理成分或者两种或更多种不同的个人护理成分的组合可用作个人护理成分。为了清楚和一致性,“个人护理成分”涵盖其中组合物包含但一种或两种或更多种个人护理成分的实施方案。
在具体的实施方案中,个人护理成分为止汗剂和/或除臭剂(AP/DEO)。在这些实施方案中,该组合物可被称为止汗剂和/或除臭剂(AP/DEO)组合物。止汗剂和除臭剂的示例包括氯化铝、四氯羟铝锆GLY、四氯羟铝锆PEG、氯化羟铝二元醇、四氯羟铝锆PG、氯化羟铝PEG、三氯羟铝锆、氯化羟铝PG、三氯羟铝锆GLY、六氯酚、苯扎氯铵、水合倍半氯化羟铝、碳酸氢钠、倍半氯化羟铝PEG、叶绿酸-铜络合物、三氯生、八氯羟铝锆、蓖麻醇酸锌,以及它们的混合物。
在某些实施方案中,个人护理成分包含皮肤护理成分。如果用于制备该组合物,则皮肤护理成分通常选自水相稳定剂、化妆品杀虫剂、调理剂(可为有机硅、阳离子、疏水的等)、润肤剂、保湿剂、着色剂、染料、紫外线(UV)吸收剂、防晒剂、抗氧化剂、芳香剂、抗微生物剂、抗菌剂、抗真菌剂、抗衰老活性剂、抗痤疮剂、皮肤增亮剂、颜料、防腐剂、pH控制剂、电解质、螯合剂、植物提取物、植物性提取物、皮脂吸收剂、皮脂控制剂、维生素、蜡、表面活性剂、洗涤剂、乳化剂、增稠剂、推进剂气体、皮肤保护剂、成膜聚合物、光散射剂、以及它们的组合。在这些实施方案中的一些实施方案中,基于所用的特定个人护理成分,该组合物可被称为皮肤护理组合物、化妆品组合物、防晒剂、沐浴凝胶、皂、水凝胶、霜剂、洗剂、香膏、粉底、唇膏、眼线、角质层包覆剂、腮红等。各种种类的此类皮肤护理成分如下所示,并且类似的和另选的种类是本领域普通技术人员已知的。
润肤剂的示例包括挥发性或非挥发性有机硅油;有机硅树脂,诸如聚丙基倍半硅氧烷和聚苯基三甲基硅氧烷;有机硅弹性体,诸如聚二甲基硅氧烷交联聚合物;烷基甲基硅氧烷,诸如C30-45烷基聚甲基硅氧烷;挥发性或非挥发性烃化合物,诸如角鲨烯、石蜡油、矿脂油和萘油;氢化或部分氢化聚异丁烯;异二十烷;角鲨烷;异链烷烃;异十二烷;异癸烷或异十六烷;支化的C8-C16酯;新戊酸异己酯;酯油,诸如异壬酸异壬酯、辛酸十六-十八烷酯、肉豆蔻酸异丙酯、棕榈酸酯衍生物(例如棕榈酸糊精)、硬脂酸酯衍生物、苹果酸二异硬脂基酯、异硬脂酸异硬脂醇酯以及醇或多元醇的庚酸酯、辛酸酯、癸酸酯或蓖麻醇酸酯或它们的混合物;植物源烃油,所述植物源诸如小麦胚芽、向日葵、葡萄籽、蓖麻、乳木果、鳄梨、橄榄、大豆、甜杏仁、棕榈、油菜籽、棉花籽、榛果、澳洲坚果、霍霍巴油、黑加仑、月见草;或辛酸/癸酸的甘油三酯;高级脂肪酸,诸如油酸、亚油酸或亚麻酸,以及它们的混合物。
蜡的示例包括烃蜡诸如蜂蜡、羊毛脂蜡、米蜡、巴西棕榈蜡、小烛树蜡、微晶蜡、石蜡、地蜡、聚乙烯蜡、合成蜡、纯地蜡、羊毛脂、羊毛脂衍生物、椰子油、紫胶蜡、糠蜡、木棉蜡(capok wax)、甘蔗蜡、蒙旦蜡、鲸蜡、杨梅蜡、有机硅蜡(例如聚甲基硅氧烷烷基、烷氧基和/或酯、C30-45烷基二甲基甲硅烷基聚丙基倍半硅氧烷)、硬脂基聚二甲基硅氧烷、在烷基甲基硅氧基单元中包括长链烷基基团的烷基甲基硅氧烷、以及它们的混合物。
保湿剂的示例包括低分子量的脂族二醇,诸如丙二醇和丁二醇;多元醇,诸如甘油和山梨醇;以及聚氧乙烯聚合物,诸如聚乙二醇200;透明质酸及其衍生物,以及它们的混合物。
增稠剂的示例包括丙烯酰胺共聚物、丙烯酸酯共聚物及其盐(诸如聚丙烯酸钠)、黄原胶及衍生物、纤维素胶和纤维素衍生物(诸如甲基纤维素、甲基羟丙基纤维素、羟乙基纤维素、羟丙基纤维素、聚丙基羟乙基纤维素)、淀粉和淀粉衍生物(诸如羟乙基直链淀粉和淀粉酶)、聚氧乙烯、卡波姆、海藻酸盐(诸如海藻酸钠)、阿拉伯树胶、肉桂胶、角豆胶、硬葡聚糖胶、结冷胶、鼠李糖胶、刺梧桐胶、角叉菜胶、瓜尔胶和瓜尔胶衍生物、椰油酰胺衍生物(包括椰油酰胺丙基甜菜碱和椰油酰胺MIPA)、烷基醇(诸如十六/十八醇、硬脂醇和其它脂肪醇)、明胶、PEG衍生物、糖类(诸如果糖、葡萄糖)和糖类衍生物(诸如PEG-120甲基葡萄糖二油酸酯)以及它们的混合物。
水相稳定剂的示例包括电解质(例如碱金属盐和碱土金属盐,特别是钠、钾、钙和镁的氯化物、硼酸盐、柠檬酸盐和硫酸盐,以及水合氯化铝和聚电解质,特别是透明质酸和透明质酸钠)、多元醇(甘油、丙二醇、丁二醇和山梨醇)、醇类(诸如乙醇)和水解胶体以及它们的混合物。
pH控制剂的示例包括任何水溶性酸(诸如羧酸)或矿物酸(诸如盐酸、硫酸和磷酸)、一元羧酸(诸如乙酸和乳酸)以及多元羧酸(诸如琥珀酸、己二酸、柠檬酸)以及它们的混合物。
防腐剂和化妆品杀虫剂的示例包括对羟基苯甲酸酯衍生物(例如对羟基苯甲酸甲酯、对羟基苯甲酸丙酯)、乙内酰脲衍生物、氯己定及其衍生物、咪唑烷基脲、重氮烷基脲、苯氧基乙醇、银的衍生物、水杨酸盐衍生物、三氯生、环吡酮胺盐、去氧苯比妥、羟基喹啉及其衍生物、PVP-碘、锌盐及其衍生物诸如吡啶硫酮锌、甲基氯异噻唑啉酮、甲基异噻唑啉酮、以及它们的混合物。
皮脂吸收剂或皮脂控制剂的示例包括甲硅烷基化二氧化硅、二甲基甲硅烷基化二氧化硅、聚二甲基硅氧烷/乙烯基聚二甲基硅氧烷交联聚合物、聚甲基丙烯酸甲酯、交联甲基丙烯酸甲酯和淀粉辛烯基琥珀酸铝以及它们的混合物。
颜料和着色剂的示例包括经表面处理的或未经表面处理的铁氧化物、经表面处理或未经表面处理的二氧化钛、经表面处理或未经表面处理的云母、氧化银、硅酸盐、铬氧化物、类胡萝卜素、炭黑、群青颜料、叶绿酸衍生物和黄赭色。有机颜料的示例包括芳族类型,该类型包括偶氮、靛青类、三苯甲烷、蒽醌和黄嘌呤染料(其被指定为D&C和FD&C蓝、棕、绿、橙、红、黄等)以及它们的混合物。表面处理包括基于卵磷脂、有机硅、硅烷、氟化合物以及它们的混合物的那些处理。
有机硅调理剂的示例包括有机硅油,诸如聚二甲基硅氧烷;有机硅树胶诸如聚二甲基硅氧烷醇;有机硅树脂诸如三甲基甲硅烷氧基硅酸盐、聚丙基倍半硅氧烷;有机硅弹性体;烷基甲基硅氧烷;有机改性的有机硅油,诸如氨基封端的聚二甲基硅氧烷、氨丙基聚苯基三甲基硅氧烷、聚苯基三甲基硅氧烷、三甲基五苯基三硅氧烷、有机硅季铵盐-16/环氧丙氧基聚二甲基硅氧烷交联聚合物、有机硅季铵盐-16;糖类官能化硅氧烷;甲醇官能化硅氧烷;有机硅聚醚;硅氧烷共聚物(二乙烯基聚二甲基硅氧烷/聚二甲基硅氧烷共聚物);丙烯酸酯或丙烯酸官能化硅氧烷;以及它们的混合物或乳液。
阳离子调理剂的示例包括瓜尔胶衍生物,诸如瓜耳胶的羟基丙基三甲基铵衍生物;阳离子纤维素衍生物、阳离子淀粉衍生物;纤维素醚的季氮衍生物;二甲基二烯丙基氯化铵的均聚物;丙烯酰胺和二甲基二烯丙基氯化铵的共聚物;含有通过酯或酰胺键连接到聚合物的阳离子氮官能团的、衍生自丙烯酸或甲基丙烯酸的均聚物或共聚物;与脂肪烷基二甲基铵取代的环氧化物反应的羟乙基纤维素的聚合物型季铵盐;N,N'-双-(2,3-环氧丙基)-哌嗪或哌嗪-双-丙烯酰胺与哌嗪的缩聚产物;以及乙烯基吡咯烷酮和丙烯酸酯与季氮官能团的共聚物。具体的材料包括各种聚季铵盐类,例如聚季铵盐-7、聚季铵盐-8、聚季铵盐-10、聚季铵盐-11和聚季铵盐-23。其它类别的调理剂包括阳离子表面活性剂,诸如十六烷基三甲基氯化铵、十六烷基三甲基溴化铵、硬脂基三甲基氯化铵以及它们的混合物。在某些情况下,阳离子调理剂还是经疏水改性的,诸如经疏水改性的季铵化的羟乙基纤维素聚合物;阳离子疏水改性的半乳甘露聚糖醚;以及它们的混合物。
疏水调理剂的示例包括瓜耳胶衍生物;半乳甘露聚糖凝胶衍生物;纤维素衍生物;以及它们的混合物。
紫外线吸收剂和防晒剂包括吸收在290纳米-320纳米之间(UV-B区)的紫外线的那些以及吸收在320纳米-400纳米范围(UV-A区)内的紫外线的那些。
防晒剂的一些示例为氨基苯甲酸、西诺沙酯、二乙醇胺甲氧基肉桂酸盐、棓酰棓酸三油酸酯、二羟苯腙、4-[双(羟丙基)]氨基苯甲酸乙酯、氨基苯甲酸甘油酯、胡莫柳酯、具有二羟基丙酮的指甲花醌、邻氨基苯甲酸薄荷酯、氰双苯丙烯酸辛酯、甲氧基肉桂酸乙基己酯(或甲氧基肉桂酸辛酯)、水杨酸辛酯(或水杨酸乙基己酯)、羟甲氧二苯酮、对二甲氨基苯甲酸异辛酯、苯基苯并咪唑磺酸、红矿脂、磺异苯酮、二氧化钛、水杨酸三乙醇胺,以及它们的混合物。
紫外线吸收剂的一些示例为醋氨沙洛、尿囊素PABA、亚苄基酞、二苯甲酮、二苯甲酮1-12、3-亚苄基樟脑、亚苄基樟脑水解的胶原磺酰胺、亚苄基樟脑磺酸、水杨酸苄酯、波尼酮、布美三唑、丁基甲氧基二苯甲酰基甲烷、丁基PABA、二氧化铈/二氧化硅、二氧化铈/二氧化硅滑石、西诺沙酯、甲氧基肉桂酸DEA盐、二苯并噁唑萘、二叔丁基羟基亚苄基樟脑、棓酰棓酸三油酸酯、二异丙基肉桂酸甲酯、二甲基PABA乙基鲸蜡硬脂基二甲基铵甲苯磺酸盐、二辛基丁酰胺基三嗪酮、二苯基甲氧甲酰基乙酰氧基萘并吡喃、双乙苯基三氨基三嗪茋二磺酸二钠、联苯乙烯二苯基三氨基三嗪茋二磺酸二钠、联苯乙烯二苯基二磺酸二钠、甲酚曲唑、甲酚曲唑三硅氧烷、乙基二羟基丙基PABA、二异丙基肉桂酸乙酯、甲氧基肉桂酸乙酯、乙基PABA、尿刊酸乙酯、阿魏酸氰双苯丙烯酸乙酯、甘油乙基己酸酯二甲氧基肉桂酸酯、甘油基PABA、乙二醇水杨酸酯、胡莫柳酯、对甲氧基肉桂酸异戊酯、水杨酸异丙基苄基酯、异丙基二苯甲酰甲烷、甲氧基肉桂酸异丙酯、甲氧基肉桂酸辛酯、邻氨基苯甲酸薄荷酯、薄荷醇水杨酸酯、4-甲基亚苄基、樟脑、氰双苯丙烯酸辛酯、辛酚三唑、辛基二甲基PABA、甲氧基肉桂酸乙基己酯、水杨酸辛酯、辛基三嗪酮、PABA、PEG-25PABA、戊基二甲基PABA、苯基苯并咪唑磺酸、聚丙烯酰胺甲基亚苄基樟脑、甲氧基肉桂酸钾、苯基苯并咪唑磺酸钾、红矿脂、苯基苯并咪唑磺酸钠、尿刊酸钠、TEA-苯基苯并咪唑磺酸盐、TEA-水杨酸盐、对苯二亚甲基二樟脑磺酸、二氧化钛、三PABA泛醇、咪唑丙烯酸、VA/巴豆酸酯/甲基丙烯酰氧二苯甲酮-1共聚物,以及它们的混合物。
皮肤保护剂的示例包括尿囊素、乙酸铝、氢氧化铝、硫酸铝、炉甘石、可可油、鳕鱼肝油、胶状燕麦、聚二甲基硅氧烷、甘油、高岭土、羊毛脂、矿物油、矿脂、鲨鱼肝油、碳酸氢钠、滑石、金缕梅、乙酸锌、碳酸锌、氧化锌以及它们的混合物。
染料的示例包括1-乙酰氧基-2-甲基萘;酸性染料;5-氨基-4-氯邻甲酚;5-氨基-2,6-二甲氧基-3-羟基吡啶;3-氨基-2,6-二甲基苯酚;2-氨基-5-乙基苯酚盐酸盐;5-氨基-4-氟-2-甲基苯酚硫酸盐;2-氨基-4-羟乙基氨基苯甲醚;2-氨基-4-羟乙基氨基苯甲醚硫酸盐;2-氨基-5-硝基苯酚;4-氨基-2-硝基苯酚;4-氨基-3-硝基苯酚;2-氨基-4-硝基苯酚硫酸盐;间氨基苯酚盐酸盐;对氨基苯酚盐酸盐;间氨基苯酚;邻氨基苯酚;4,6-双(2-羟乙氧基)间苯二胺盐酸盐;2,6-双(2-羟乙氧基)-3,5-吡啶二胺盐酸盐;2-氯-6-乙基氨基-4-硝基苯酚;2-氯-5-硝基-N-羟乙基对苯二胺;2-氯对苯二胺;3,4-二氨基苯甲酸;4,5-二氨基-1-((4-氯苯基)甲基)-1H-吡唑硫酸盐;2,3-二氨基二氢吡唑并吡唑啉酮二甲基硫酸盐;2,6-二氨基吡啶;2,6-二氨基-3-((吡啶-3-基)偶氮)吡啶;二羟基吲哚;羟基二氢吲哚;N,N-二甲基对苯二胺;2,6-二甲基对苯二胺;N,N-二甲基对苯二胺硫酸盐;直接染料;4-乙氧基间苯二胺硫酸盐;3-乙基氨基对甲酚硫酸盐;N-乙基-3-硝基PABA;葡糖酰氨基丙基氨基丙基聚二甲基硅氧烷;巴西彩木(Haematoxylon brasiletto wood)提取物;HC染料;指甲花(Henna)提取物;羟乙基-3,4-亚甲基二氧基苯胺盐酸盐;羟乙基-2-硝基对甲苯胺;羟乙基对苯二胺硫酸盐;2-羟乙基苦氨酸;羟基吡啶酮;羟基琥珀酰亚胺基C21-C22异烷基酸酯;靛红;欧洲菘蓝叶粉;2-甲氧基甲基对苯二胺硫酸盐;2-甲氧基对苯二胺硫酸盐;6-甲氧基-2,3-吡啶二胺盐酸盐;4,5-二氨基吡唑硫酸4-甲基苄酯;2,2'-亚甲基双4-氨基苯酚;2,2'-亚甲基双-4-氨基苯酚盐酸盐;3,4-亚甲二氧基苯胺;2-甲基间苯二酚;甲紫;1,5-萘二酚;1,7-萘二酚;3-硝基对甲酚;2-硝基-5-甘油基甲基苯胺;4-硝基愈创木酚;3-硝基对羟乙基氨基苯酚;2-硝基-N-羟乙基对茴香胺;硝基苯酚;4-硝基苯基氨基乙基脲;4-硝基邻苯二胺二盐酸盐;2-硝基对苯二胺二盐酸盐;4-硝基邻苯二胺盐酸盐;4-硝基间苯二胺;4-硝基邻苯二胺;2-硝基对苯二胺;4-硝基间苯二胺硫酸盐;4-硝基邻苯二胺硫酸盐;2-硝基对苯二胺硫酸盐;6-硝基-2,5-吡啶二胺;6-硝基邻甲苯胺;PEG-3 2,2'-二对苯二胺;对苯二胺盐酸盐;对苯二胺硫酸盐;苯基甲基吡唑啉酮;N-苯基对苯二胺盐酸盐;颜料蓝15:1;颜料紫23;颜料黄13;焦性儿茶酚;连苯三酚;间苯二酚;苦氨酸钠;对氨基苯磺酸钠;溶剂黄85;溶剂黄172;四氨基嘧啶硫酸盐;四溴酚蓝;2,5,6-三氨基-4-嘧啶醇硫酸盐;1,2,4-三羟基苯。
芳香剂的示例包括香料酮和香料醛。示例性香料酮为布枯肟(buccoxime);异茉莉酮;甲基β萘基酮;麝香二氢茚酮;优质吐纳麝香/麝香;α-二氢大马酮、β-二氢大马酮、δ-二氢大马酮、异二氢大马酮、大马烯酮、大马玫瑰、二氢茉莉酮酸甲酯、薄荷酮、香芹酮、樟脑、葑酮、α-紫罗兰酮、β-紫罗兰酮、所谓的γ-甲基紫罗兰酮、庚基环戊酮、二氢茉莉酮、顺式茉莉酮、龙涎酮、甲基柏木烯酮或甲基柏木酮、苯乙酮、甲基苯乙酮、对甲氧基苯乙酮、甲基-β-萘酮、苄基丙酮、二苯甲酮、对羟基苯基丁酮、芹菜酮或利福酮、6-异丙基十氢-2-萘酮、二甲基辛烯酮、鲜薄荷酮、4-(1-乙氧乙烯基)-3,3,5,5,-四甲基环己酮、甲基庚烯酮、2-(2-(4-甲基-3-环己烯-1-基)丙基)-环戊酮、1-(对薄荷烯-6(2)-基)-1-丙酮、4-(4-羟基-3-甲氧苯基)-2-丁酮、2-乙酰基-3,3-二甲基-降莰烷、6,7-二氢-1,1,2,3,3-五甲基-4(5H)-茚酮、4-二氢大马醇、胡椒基丙酮(Dulcinyl)或胡椒基丙酮(Cassione)、钩吻酮、己酮、异环琥珀酮E、甲基柠檬酮、甲基熏衣草酮、对叔戊基环己酮、对叔丁基环己酮、邻叔丁基环己酮、戊基环戊酮、麝香酮、新丁烯酮、大侧柏酮、凡路酮、2,4,4,7-四甲基-辛-6-烯-3-酮和特曲美安酮。芳香剂可来源于植物,海藻等的花、种子、叶片和/或根或从植物,海藻等的花、种子、叶片和/或根提取。芳香剂可从动物(例如,分泌腺)提取,并且可能为麝香或鲸油。芳香剂也可被人工合成,例如薄荷醇、醋酸酯、香草醛等。
在具体的实施方案中,香料酮为选自来自α-二氢大马酮、δ二氢大马酮、异二氢大马酮、香芹酮、γ-甲基紫罗兰酮、龙涎酮、2,4,4,7-四甲基-辛-6-烯-3-酮、苄基丙酮、β-二氢大马酮、大马烯酮、二氢茉莉酮酸甲酯、甲基柏木酮、以及它们的混合物的气味特性。
在具体的实施方案中,香料醛被选择用于来自以下的气味特性:阿道克醛;大茴香醛;西马醛(cymal);乙基香草醛;花青醛;新洋茉莉醛;胡椒醛;羟基香茅醛;寇夫醛(koavone);月桂醛;新铃兰醛;甲基壬基乙醛;P.T.兰醛;苯乙醛;十一烯醛;香草醛;2,6,10-三甲基-9-十一烯醛、3-十二碳烯-1-醛、α-正戊基肉桂醛、4-甲氧基苯甲醛、苯甲醛、3-(4-叔丁基苯基)-丙醛、2-甲基-3-(对甲氧苯基丙醛、2-甲基-4-(2,6,6-三甲基-2(1)-环己烯-1-基)丁醛、3-苯基-2-丙烯醛、顺-/反-3,7-二甲基-2,6-辛二烯-1-醛、3,7-二甲基-6-辛烯-1-醛、[(3,7-二甲基-6-辛烯基)氧]乙醛、4-异丙基苯甲醛、1,2,3,4,5,6,7,8-八氢-8,8-二甲基-2-萘醛、2,4-二甲基-3-环己烯-1-甲醛、2-甲基-3-(异丙基苯基)丙醛、1-癸醛;癸醛、2,6-二甲基-5-庚烯醛、4-(三环[5.2.1.0(2,6)]-癸亚基-8)-丁醛、八氢-4,7-亚甲基-1H-茚甲醛、3-乙氧基-4-羟基苯甲醛、对乙基-α,α-二甲基氢化肉桂醛、α-甲基-3,4-(亚甲二氧)-氢化肉桂醛、3,4-亚甲二氧基苯甲醛、α-正己基肉桂醛、间伞花烃-7-甲醛、α-甲基苯乙醛、7-羟基-3,7-二甲基辛醛、十一烯醛、2,4,6-三甲基-3-环己烯-1-甲醛、4-(3)(4-甲基-3-戊烯基)-3-环己烯-甲醛、1-十二烷醛、2,4-二甲基环己烯-3-甲醛、4-(4-羟基-4-甲基戊基)-3-环己烯-1-甲醛、7-甲氧基-3,7-二甲基辛-1-醛、2-甲基十一烷醛、2-甲基癸醛、1-壬醛、1-辛醛、2,6,10-三甲基-5,9-十一碳二烯醛、2-甲基-3-(4-叔丁基)丙醛、二氢肉桂醛、1-甲基-4-(4-甲基-3-戊烯基)-3-环己烯-1-甲醛、5或6甲氧基10六氢-4,7-亚甲基茚满-1或2-甲醛、3,7-二甲基辛-1-醛、1-十一烷醛、10-十一烯-1-醛、4-羟基-3-甲氧基苯甲醛、1-甲基-3-(4-甲基戊基)-3-环己烯甲醛、7-羟基-3,7-二甲基-辛醛、反-4-癸烯醛、2,6-壬二烯醛、对甲基苯乙醛;4-甲基苯乙醛、2-甲基-4-(2,6,6-三甲基-1-环己烯-1-基)-2-丁烯醛、邻甲氧基肉桂醛、3,5,6-三甲基-3-环己烯甲醛、3,7-二甲基-2-亚甲基-6-辛烯醛、苯氧基乙醛、5,9-二甲基-4,8-癸二烯醛、牡丹醛(6,10-二甲基-3-氧杂-5,9-十一碳二烯-1-醛)、六氢-4,7-亚甲基茚满-1-甲醛、2-甲基辛醛、α-甲基-4-(1-甲基乙基)苯乙醛、6,6-二甲基-2-降蒎烯-2-丙醛、对甲基苯氧基乙醛、2-甲基-3-苯基-2-丙烯-1-醛、3,5,5-三甲基己醛、六氢-8,8-二甲基-2-萘醛、3-丙基-二环[2.2.1]-5-庚烯-2-甲醛、9-癸烯醛、3-甲基-5-苯基-1-戊醛、甲基壬基乙醛、己醛、反式-2-己醛、1-对-薄荷烯-q-甲醛、以及它们的混合物。
抗氧化剂的示例为乙酰基半胱氨酸、熊果苷、抗坏血酸、抗坏血酸多肽、抗坏血酸二棕榈酸酯、抗坏血酸甲基硅烷醇果胶酸酯、抗坏血酸棕榈酸酯、抗坏血酸硬脂酸酯、BHA、对羟基苯甲醚、BHT、叔丁基氢醌、咖啡酸、茶(Camellia sinensis)叶油、脱乙酰壳多糖抗坏血酸盐、脱乙酰壳多糖甘醇酸盐、脱乙酰壳多糖水杨酸盐、绿原酸、半胱氨酸、半胱氨酸盐酸盐、癸基巯甲基咪唑、异抗坏血酸、二戊基氢醌、二叔丁基氢醌、二鲸蜡醇硫代二丙酸酯、二环戊二烯/叔丁基甲酚共聚物、棓酰棓酸三油酸酯、硫代二丙酸二月桂酯、二肉豆蔻醇硫代二丙酸酯、二油基生育酚甲基硅烷醇、异槲皮苷、地奥司明、抗坏血酸硫酸酯二钠、芸香亭基硫酸二钠、硫代二丙酸双十八醇酯、双十三醇硫代二丙酸酯、没食子酸月桂酯、阿魏酸乙酯、阿魏酸、氢醌、羟胺盐酸盐、羟胺硫酸盐、巯基乙酸异辛酯、曲酸、羟基积雪草苷、抗坏血酸镁、抗坏血酸磷酸酯镁、褪黑激素、甲氧基-PEG-7芸香苷琥珀酸酯、亚甲基二叔丁基甲酚、甲基硅烷醇抗坏血酸、去甲二氢愈创木酸、没食子酸辛酯、苯基巯基乙酸、间苯三酚、磷酸抗坏血酸酯生育酚酯钾、硫代二乙酰胺、亚硫酸钾、没食子酸丙酯、迷迭香酸、芦丁、抗坏血酸钠、抗坏血酸/胆甾醇磷酸酯钠、亚硫酸氢钠、异抗坏血酸钠、焦亚硫酸钠、亚硫酸钠、硫代乙醇酸钠、山梨醇缩糠醛、茶树(Melaleuca aftemifolia)油、醋酸生育酚、四己基癸醇抗坏血酸酯、四氢二阿魏酰甲烷、生育酚亚油酸酯/油酸酯、硫二甘醇、生育酚琥珀酸酯、硫代二乙醇酸、硫代乙醇酸、硫代乳酸、硫代水杨酸、硫代牛磺酸、视黄醇、生育酚聚醚-5、生育酚聚醚-10、生育酚聚醚-12、生育酚聚醚-18、生育酚聚醚-50、生育酚、托可索仑、生育酚亚油酸酯、生育酚烟酸酯、托可醌、邻甲苯基双胍、三(壬基酚)亚磷酸酯、泛醌、二丁基二硫代氨基甲酸锌以及它们的混合物。
推进剂气体的示例包括二氧化碳、氮气、一氧化二氮、挥发性的烃(诸如丁烷、异丁烷或丙烷)、以及氯化的或氟化的烃(诸如二氯二氟甲烷和二氯四氟乙烷)或二甲基醚;以及它们的混合物。
在一个具体的实施方案中,该组合物为防晒剂。在这些实施方案中,个人护理成分包含防晒剂。防晒剂可为例如防晒剂添加剂、SPF促进剂、光稳定剂、成膜聚合物等,防晒剂也可为或可替选地用于免晒美黑应用中。防晒剂的具体示例如上文所述。
在其它实施方案中,个人护理成分包含毛发护理成分。在这些实施方案中,该组合物可被称为毛发护理组合物。如果用于制备组合物,则毛发护理成分通常选自调理剂(其可为有机硅、阳离子、疏水的等)、着色剂、染料、紫外线(UV)吸收剂、防腐剂、植物提取物、脂肪醇、维生素、芳香剂、去头皮屑剂、颜色护理添加剂、珠光剂、pH控制剂、电解质、螯合剂、定型剂、神经酰胺、氨基酸衍生物、悬浮剂、表面活性剂、洗涤剂、乳化剂、增稠剂、氧化剂、还原剂、成膜聚合物、以及它们的组合。对于这些毛发护理实施方案中的一些,该组合物可称为洗发剂、洗去型调理剂、免洗型调理剂、凝胶、润发油、精华液、喷雾剂、着色产品或睫毛膏。许多这些毛发护理成分的示例如上文所示为合适的个人护理成分。
氧化剂的示例为过硫酸铵、过氧化钙、过氧化氢、过氧化镁、过氧化蜜胺、溴酸钾、卡卢酸钾(potassium caroate)、氯酸钾、过硫酸钾、溴酸钠、过碳酸钠、氯酸钠、碘酸钠、过硼酸钠、过硫酸钠、二氧化锶、过氧化锶、过氧化脲、过氧化锌以及它们的混合物。
还原剂的示例为亚硫酸氢铵、亚硫酸铵、巯基乙醇酸铵、硫代乳酸铵、半胱胺盐酸盐、半胱氨酸、半胱氨酸盐酸盐、乙醇胺巯基乙酸盐、谷胱甘肽、甘油巯基乙醇酸酯、甘油硫代丙酸酯、对苯二酚、对羟基苯甲醚、巯基乙醇酸异辛酯、巯基乙醇酸镁、巯基丙酸、焦亚硫酸钾、亚硫酸钾、巯基乙醇酸钾、亚硫酸氢钠、连二亚硫酸钠、羟甲烷磺酸钠、焦亚硫酸钠、亚硫酸钠、巯基乙醇酸钠、巯基乙醇酸锶、超氧化物歧化酶、硫甘油、巯基乙酸、硫代乳酸、硫代水杨酸、甲醛合次硫酸锌,以及它们的混合物。
去头皮屑剂的示例包括吡啶硫酮盐,诸如二硫化硒的硒化合物、以及可溶性去头皮屑剂,以及它们的混合物。
在其它实施方案中,个人护理成分包含指/趾甲护理成分。在这些实施方案中,该组合物可被称为指/趾甲护理组合物。如果用于制备该组合物,则指/趾甲护理成分可为用于指/趾甲护理组合物中的任何成分,例如指/趾甲油、指/趾甲凝胶、指/趾甲片、丙烯酸涂饰剂等。此类指/趾甲护理成分的示例包括颜料、树脂、溶剂、挥发性卤代化合物(例如,甲氧基九氟丁烷和/或乙氧基九氟丁烷)等。
更具体地,指/趾甲护理成分的示例包括乙酸丁酯;乙酸乙酯;硝化纤维;柠檬酸乙酰基三丁酯;异丙醇;己二酸/新戊二醇/偏苯三酸酐共聚物;硬脂基二甲基苄基铵膨润土;丙烯酸酯共聚物;泛酸钙;冰岛地衣(Cetraria islandica)提取物;皱波角叉菜(Chondruscrispus);苯乙烯/丙烯酸酯共聚物;三甲基戊二醇二苯甲酸酯-1;聚乙烯醇缩丁醛;正丁醇;丙二醇;丁二醇;云母;二氧化硅;氧化锡;硼硅酸钙;合成氟金云母;聚对苯二甲酸乙二醇酯;脱水山梨糖醇月桂酸酯衍生物;滑石;霍霍巴油提取物;金刚石粉;异丁苯氧基环氧树脂;丝粉;以及它们的混合物。
在其它实施方案中,个人护理成分包含牙齿护理成分。在这些实施方案中,该组合物可称为牙齿护理组合物。此类牙齿护理组合物的一个具体示例为牙膏。牙齿护理组合物的另一个示例为牙齿增白组合物。牙齿护理成分可为适用于牙齿护理组合物的任何牙齿护理成分,诸如研磨剂化合物(例如,氧化铝、碳酸钙、二氧化硅、沸石),氟化化合物,表面活性剂,调味剂,再矿化剂,抗菌剂等。
在某些实施方案中,个人护理成分包含成膜聚合物,其可用作个人护理成分,无论该组合物是否用于皮肤护理、毛发护理等。如本文所用“成膜聚合物”是指能够在存在成膜剂的情况下本身或任选地在基底上形成膜的聚合物或低聚物。成膜聚合物可在施用固化条件,例如施用热量、暴露于大气条件等时形成膜,另选地,成膜聚合物可在蒸发其中可任选地设置有成膜聚合物的任何载体时形成膜。成膜聚合物可经历反应,例如成膜聚合物可在形成膜时交联或以其它方式包括另外粘结。然而,成膜聚合物可在不存在此类反应的情况下形成膜。成膜聚合物可为胶凝剂。当组合物为防晒剂时,成膜聚合物为尤其有利的,尽管个人护理成分也可包含其它组合物中的成膜聚合物。
其上形成膜的基底可为任何基底,尽管基底通常为哺乳动物,特别是人的一部分,如下面参考处理方法更详细地描述的。合适基底的具体示例包括皮肤、毛发和指/趾甲。
一般来讲,膜为连续的,但膜可具有变化的厚度。所谓连续的,它是指膜不限定任何孔隙。膜可被称为宏观连续的。膜可由基底支撑,或可例如物理和/或化学地粘结到基底。在某些实施方案中,膜可任选地从基底上去除,例如膜可从基底剥离。在与基底分离时,膜可作为独立的膜保持完整,或者可通过施用剪切来分离,这可能损坏和/或破坏膜的连续性。
适合的成膜聚合物的具体示例包括丙烯酸类聚合物、有机硅树脂(例如聚丙基倍半硅氧烷)、聚氨酯、聚氨酯-丙烯酸类、聚酯、聚酯-聚氨酯、聚醚-聚氨酯、聚酯酰胺、醇酸树脂、聚酰胺、聚脲、聚脲-聚氨酯、基于纤维素的聚合物(例如硝化纤维)、有机硅、丙烯酸类-有机硅、聚丙烯酰胺、氟化聚合物、聚异戊二烯及其任何共聚物或三元共聚物或包括这些中的一种。如本文所用,术语“有机硅”是指合适的成膜聚合物,包括直链、支化的和树脂状有机硅,但树脂有机硅通常被称为树脂状有机硅而不是聚合物。有机硅可被改性,例如有机硅可为有机硅接枝丙烯酸类聚合物。
如以上所介绍,成膜聚合物可设置在载体中,该载体可部分或完全溶解成膜聚合物。根据成膜聚合物的选择,载体可为例如油,例如有机油和/或有机硅油、溶剂、水等,成膜聚合物可为聚合物颗粒形式,聚合物颗粒可任选地用至少一种稳定剂使表面稳定,并且聚合物颗粒可作为分散体或乳液存在。
成膜聚合物可为嵌段聚合物,其可不含苯乙烯。通常,嵌段聚合物包含至少一个第一嵌段和至少一个第二嵌段,其可经由中间嵌段连接在一起,该中间嵌段包含第一嵌段的至少一种组成单体和第二嵌段的至少一种组成单体。通常,第一嵌段和第二嵌段的玻璃化转变温度彼此不同。
可用于制备嵌段聚合物的单体包括,例如,甲基丙烯酸甲酯、(甲基)丙烯酸异丁酯和(甲基)丙烯酸异冰片酯、丙烯酸甲酯、丙烯酸异丁酯、甲基丙烯酸正丁酯、丙烯酸环癸酯、丙烯酸新戊酯、异癸基丙烯酰胺丙烯酸2-乙基己酯、以及它们的混合物。
在具体的实施方案中,成膜聚合物可经由自由基聚合获得或产生。例如,可经由至少一种丙烯酸类单体和包含可聚合端基的至少一种基于有机硅或烃的大分子单体的自由基聚合来生成成膜聚合物。
基于烃的大分子单体的具体示例包括直链或支链的C8-C22烷基丙烯酸酯或甲基丙烯酸酯的均聚物和共聚物。可聚合端基可为乙烯基或(甲基)丙烯酸酯基团,例如聚(丙烯酸2-乙基己酯)大分子单体;聚(丙烯酸十二烷基酯)或聚(甲基丙烯酸十二烷基酯)大分子单体;聚(丙烯酸硬脂基酯)或聚(甲基丙烯酸硬脂基酯)大分子单体等,此类大分子单体一般包括作为可聚合端基的一个(甲基)丙烯酸酯基团。
基于烃的大分子单体的另外的示例包括含有烯属不饱和端基(作为可聚合的端基)的聚烯烃,例如(甲基)丙烯酸酯端基。此类聚烯烃的具体示例包括聚乙烯大分子单体、聚丙烯大分子单体、聚乙烯/聚丙烯共聚物大分子单体、聚乙烯/聚丁烯共聚物大分子单体、聚异丁烯大分子单体;聚丁二烯大分子单体;聚异戊二烯大分子单体;聚丁二烯大分子单体;和聚(乙烯/丁烯)-聚异戊二烯大分子单体。
基于有机硅的大分子单体的示例包括含有可聚合端基的有机聚硅氧烷,例如(甲基)丙烯酸酯端基。有机聚硅氧烷可为直链、支化的、部分支化的或树脂状。在各种实施方案中,有机聚硅氧烷为直链。在这些实施方案中,有机聚硅氧烷可为聚二甲基硅氧烷,但除了甲基基团以外的烃基团可连同甲基基团一起存在或代替甲基基团。通常,可聚合端基为末端,但可聚合端基可任选地为侧基。基于有机硅的大分子单体的一个具体示例为单甲基丙烯酰氧基丙基聚二甲基硅氧烷。
在某些实施方案中,成膜聚合物为可溶于油作为载体的有机成膜聚合物。在这些实施方案中,成膜聚合物可被称为脂溶性聚合物。脂溶性聚合物可为任何类型的,并且它们的具体示例包括或由烯烃、环烯烃、丁二烯、异戊二烯、苯乙烯、乙烯基醚、乙烯基酯、乙烯基酰胺、(甲基)丙烯酸酯或酰胺等形成。
在一个实施方案中,脂溶性聚合物由选自如下的单体形成:(甲基)丙烯酸异辛酯、(甲基)丙烯酸异壬酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸异戊酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸十三烷酯、(甲基)丙烯酸硬脂酯、以及它们的组合。
另选地,脂溶性聚合物可为丙烯酸有机硅接枝聚合物,其通常包括有机硅主链和丙烯酸接枝,或者另选地包括丙烯酸主链和有机硅接枝。
成膜聚合物可为卤化的,例如成膜聚合物可包含氟原子。
另选地,如以上所介绍,成膜聚合物可为基于纤维素的聚合物,诸如硝化纤维、乙酸纤维素、乙酰丁酸纤维素、乙酰丙酸纤维素或乙基纤维素。或者,成膜聚合物可包括聚氨酯、丙烯酸类聚合物、乙烯基聚合物、聚乙烯醇缩丁醛、醇酸树脂、或衍生自醛缩合产物的树脂,诸如芳基磺酰胺-甲醛树脂。
此外,如以上所介绍,成膜聚合物可包含有机硅,其可为直链、支化的或树脂状。如本领域所理解的,树脂状有机硅通常包括至少一个T和/或Q单元。树脂状有机硅的示例包括倍半硅氧烷。有机硅可包括M、D、T和Q单元的任何组合,只要有机硅构成成膜聚合物即可。
当成膜聚合物包含有机硅时,成膜聚合物可包含两亲性有机硅。两亲性有机硅通常含有与有机硅介质相容的有机硅部分和亲水性部分。亲水性部分可为例如选自醇和多元醇的化合物的残基,具有1至12个羟基基团和聚氧化烯(例如含有氧丙烯单元和/或氧乙烯单元的那些)。
两亲性有机硅可为具有或不具有胶凝活性的油。此类油可包含例如聚二甲基硅氧烷共聚多元醇、双羟基乙氧基丙基聚二甲基硅氧烷等。
在一个实施方案中,成膜聚合物包含有机硅有机弹性体凝胶。有机硅有机弹性体凝胶包含经由聚氧化烯交联的直链有机聚硅氧烷链。有机硅有机弹性体凝胶可还包含来自直链有机聚硅氧烷链侧向的亲水性聚醚官能团。合适的有机硅有机弹性体凝胶的具体示例公开于国际(PCT)申请号PCT/US2010/020110。
在各种实施方案中,个人护理成分可包含或被称为个人护理活性物质、保健活性物质或它们的组合(统称为“活性物质”或“多种活性物质”)。如本文所用,“个人护理活性物质”是指本领域已知作为个人护理制剂中的添加剂通常用于提供化妆和/或美学益处的任何化合物或化合物的混合物。“保健活性剂”意指本领域已知来提供药学或医学益处的任何化合物或化合物的混合物。因而,“保健活性剂”包括如通常由美国卫生与公众服务部食品和药品管理局(United States Department of Health&Human Services Food and DrugAdministration)所使用并定义的,美国联邦法规第200-299部和第300-499部的第21篇第I章中所含有的,被视为活性成分或活性药物成分的物质。具体的个人护理活性物质和保健活性物质描述于下文中。这些个人护理活性物质和保健活性物质可构成个人护理成分,无论个人护理成分是否被用于形成例如AP/DEO组合物、皮肤护理组合物、毛发护理组合物、指/趾甲护理组合物、和/或牙齿护理组合物。例如,在各种实施方案中,可利用相同的个人护理成分来形成毛发护理组合物或皮肤护理组合物。如本领域所理解,下文所述的个人护理活性物质中至少一些是上文关于皮肤护理组合物、毛发护理组合物、指/趾甲护理组合物和牙齿护理组合物的某些个人护理成分的种类。例如,下文描述了多种植物或蔬菜提取物,其为上文所述的植物提取物作为合适的个人护理成分的示例性示例。下文所述的活性成分或活性物质可构成组合物的个人护理成分,或可与其组合利用。
用于组合物的可用活性成分包括维生素和维生素衍生物,包括“维生素原”。可用于本文的维生素包括但不限于:维生素A1、视黄醇、视黄醇的C2-C18酯、维生素E、生育酚、维生素E的酯、以及它们的混合物。视黄醇包括反式-视黄醇、1,3-顺式-视黄醇、11-顺式-视黄醇、9-顺式-视黄醇和3,4-二脱氢-视黄醇、维生素C及其衍生物、维生素B1、维生素B2、维生素B5原、泛醇、维生素B6、维生素B12、烟酸、叶酸、生物素和泛酸。视为包括在本文中的其他合适的维生素以及所述维生素的INCI名称为抗坏血酸二棕榈酸酯、抗坏血酸甲基硅烷醇果胶酸酯、抗坏血酸棕榈酸酯、抗坏血酸硬脂酸酯、抗坏血酸葡糖苷、抗坏血酸磷酸酯钠、抗坏血酸钠、抗坏血酸硫酸酯二钠、(抗坏血酸/生育酚)磷酸酯钾。一般来讲,视黄醇、所有反式视黄酸和它们的衍生物、异构体和类似物统称为“类视色素”。
应当注意,视黄醇为由华盛顿(Washington DC)的化妆品、梳洗品和芳香剂协会(CTFA)针对维生素A指定的国际化妆品原料命名(INCI)。考虑包括在本文中的其它合适的维生素以及对维生素的INCI名称为视黄醇乙酸酯、视黄醇棕榈酸酯、视黄醇丙酸酯、α-生育酚、托可索仑、生育酚乙酸酯、生育酚亚油酸酯、生育酚烟酸酯和生育酚琥珀酸酯。
适用于本发明的市售产品的一些示例为:维生素A醋酸酯和维生素C,这两种产品均为瑞士布克斯的Fluka化学股份有限公司(Fluka Chemie AG,Buchs,Switzerland)的产品;COVI-OX T-50,伊利诺伊州拉格兰奇汉高公司(Henkel Corporation,La Grange,Illinois)的维生素E产品;COVI-OX T-70,伊利诺伊州拉格兰奇汉高公司的另一种维生素E产品;和维生素E醋酸酯,新泽西州纳特利罗氏维生素和精细化学品(Roche Vitamins&FineChemicals,Nutley,New Jersey)的产品。
活性剂可以为蛋白质,诸如酶。酶包括但不限于市售类型、改善类型、重组类型、野生型、天然不存在的变体以及它们的混合物。例如,合适的酶包括水解酶、角质酶、氧化酶、转移酶、还原酶、半纤维素酶、酯酶、异构酶、果胶酶、乳糖酶、过氧化物酶、漆酶、过氧化氢酶和它们的混合物。水解酶包括但不限于:蛋白酶(细菌蛋白酶、真菌蛋白酶、酸性蛋白酶、中性蛋白酶或碱性蛋白酶)、淀粉酶(α淀粉酶或β淀粉酶)、脂肪酶、甘露聚糖酶、纤维素酶、胶原酶、溶菌酶、超氧化物歧化酶、过氧化氢酶和它们的混合物。蛋白酶包括但不限于:胰蛋白酶、胰凝乳蛋白酶、胃蛋白酶、胰酶和其它哺乳动物的酶;木瓜蛋白酶、菠萝蛋白酶和其他植物酶;枯草杆菌蛋白酶、表皮素、乳酸链球菌素、柚皮苷酶(L-鼠李糖苷酶)、尿激酶和其他细菌酶。脂酶包括但不限于:三酰甘油脂酶、单酰基甘油脂酶、脂蛋白脂酶,例如胰脂酶、肠肽酶、胃蛋白酶、其它哺乳类动物脂酶、植物脂酶、细菌脂酶以及纯化的脂酶。在一个具体的实施方案中,天然木瓜用作酶。另外,刺激激素(例如胰岛素)可与酶一起使用以加强效果。
活性物质还可为一种或多种植物或蔬菜提取物。这些组分的示例为如下:明日叶提取物、鳄梨提取物、绣球花提取物、木槿提取物、山金车花提取物、芦荟提取物、杏提取物、杏仁提取物、银杏提取物、茴香提取物、姜黄[姜黄(Curcuma)]提取物、乌龙茶提取物、玫瑰果提取物、紫锥菊提取物、黄芩根提取物、黄柏树皮提取物、日本黄连提取物、大麦提取物、金丝桃提取物、白荨麻提取物、豆瓣菜提取物、橙提取物、脱水海水、海藻提取物、水解弹性蛋白、水解小麦粉、水解蚕丝、洋甘菊提取物、胡萝卜提取物、蒿属提取物、甘草提取物、芙蓉茶提取物、火棘果提取物、猕猴桃提取物、金鸡纳树提取物、黄瓜提取物、鸟苷(guanocine)、栀子提取物、山白竹提取物、苦参根提取物、核桃提取物、葡萄柚提取物、铁线莲提取物、小球藻提取物、桑树提取物、龙胆提取物、红茶提取物、酵母提取物、牛蒡提取物、米糠发酵液提取物、米胚芽油、聚合草提取物、胶原蛋白、越橘提取物、栀子提取物、细辛根提取物、柴胡属提取物、鼠尾草提取物、肥皂草提取物、竹提取物、山楂果实提取物、花椒果实提取物、香菇提取物、地黄提取物、紫草提取物、紫苏提取物、椴树提取物、蚊子草提取物、芍药提取物、菖蒲根提取物、白桦树提取物、马尾草提取物、常春藤(Ivy)提取物、山楂提取物、西洋接骨木提取物、欧蓍草提取物、胡椒薄荷提取物、鼠尾草提取物、锦葵提取物、日本川芎根提取物、日本绿龙胆提取物、大豆提取物、大枣提取物、百里香提取物、茶叶提取物、丁香提取物、禾本科白茅提取物、温州蜜柑皮提取物、日本当归根提取物、金盏花提取物、桃仁提取物、苦橙皮提取物、鱼腥草提取物、番茄提取物、纳豆提取物、人参提取物、绿茶提取物(野茶树)、大蒜提取物、野生玫瑰提取物、木槿提取物、麦冬块茎提取物、荷花提取物、欧芹提取物、蜂蜜、金缕梅提取物、墙草提取物、溪黄草提取物、红没药醇提取物、枇杷提取物、款冬提取物、蜂斗菜提取物、茯苓提取物、假叶树提取物、葡萄提取物、蜂胶提取物、丝瓜提取物、红花提取物、薄荷提取物、椴树提取物、芍药提取物、啤酒花提取物、松树提取物、马栗树提取物、水芭蕉[观音莲]提取物、无患子果皮提取物、蜂花提取物、桃提取物、矢车菊提取物、桉树提取物、虎耳草提取物、枸橼提取物、薏苡提取物、艾蒿提取物、薰衣草提取物、苹果提取物、莴苣提取物、柠檬提取物、紫云英提取物、玫瑰提取物、迷迭香提取物、罗马洋甘菊提取物、蜂王浆提取物、以及它们的组合。
下文描述可用作本发明组合物中药物的保健活性物质的非限制性示例。一种或多种药物可单独使用或与上述活性物质和/或个人护理成分组合使用。
该组合物可包含抗寄生虫剂。抗寄生虫剂可为任何类型。抗寄生虫剂的示例包括但不限于六氯苯、氨基甲酸酯、天然存在的拟除虫菊酯、氯菊酯、丙烯菊酯、马拉硫磷、胡椒基丁醚、以及它们的组合。
该组合物可包含抗微生物剂,也称为杀菌剂。抗微生物剂可为任何类型。抗微生物剂的示例包括但不限于苯酚,包括甲酚和间苯二酚。此类组合物可用于治疗皮肤感染。非常常见的皮肤感染的示例为痤疮,其涉及痤疮丙酸杆菌(p.acnes)以及金黄色葡萄球菌(Staphylococus aurus)或假单胞菌(Pseudomonas)对皮脂腺的侵染。可用的抗痤疮活性剂的示例包括:角质离解剂,诸如水杨酸(邻羟基苯甲酸)、水杨酸的衍生物诸如5-辛酰水杨酸和间苯二酚;类视色素类,诸如视黄酸及其衍生物(如顺式和反式);含硫的D和L氨基酸以及它们的衍生物和盐,特别是它们的N-乙酰基衍生物,例如N-乙酰基-L-半胱氨酸;硫辛酸;抗生素和抗微生物剂,诸如过氧化苯甲酰、羟甲辛吡酮、四环素、2,4,4'-三氯-2'-羟基二苯基醚、3,4,4'-三氯二苯基脲、壬二酸及其衍生物、苯氧基乙醇、苯氧基丙醇、苯氧基异丙醇、乙酸乙酯、克林霉素和氯甲烯土霉素;sebostat类,诸如黄酮类;以及胆汁盐,诸如鲨胆甾醇硫酸盐及其衍生物、脱氧胆酸盐和胆酸盐;对氯间二甲苯酚;以及它们的组合。
浓度为0.2重量%、1.0重量%和1.3重量%的酚类通常分别为抑菌、杀菌和杀真菌的。若干酚衍生物比酚本身更有效,其中最重要的为卤代的酚和双酚、烷基取代的酚以及间苯二酚。疏水的抗菌剂包括三氯生、三氯卡班、桉叶油素、薄荷醇、水杨酸甲酯、百里酚以及它们的组合。
该组合物可包含抗真菌剂。抗真菌剂可为任何类型。抗真菌剂的示例包括但不限于唑类、二唑类、三唑类、咪康唑、氟康唑、酮康唑、克霉唑、伊曲康唑灰黄霉素、环吡酮、阿莫罗芬、特比萘芬、两性霉素B、碘化钾、氟胞嘧啶(5FC)、以及它们的组合。美国专利4,352,808公开了具有抗真菌和抗细菌活性的3-芳烷氧基-2,3-二氢-2-(1H-咪唑基甲基)苯并[b]噻吩化合物,该专利通过引用并入本文。
该组合物可包含甾族抗炎剂。甾族抗炎剂可为任何类型。甾族抗炎剂可包括但不限于:皮质类固醇,例如氢化可的松、羟基曲安西龙α-甲基地塞米松(hydroxyltriamcinolone alphamethyl dexamethasone)、磷酸地塞米松、二丙酸倍氯米松、戊酸氯倍他索、地奈德、去氧米松、醋酸去氧皮质酮、地塞米松、二氯松、二醋酸二氟拉松、双氟可龙戊酸酯、氟雄诺龙、氟氯缩松缩丙酮化物(fluclarolone acetonide)、氟氢可的松、新戊酸氟米松、fluosinolone acetonide、氟轻松醋酸酯、氟可丁酯(flucortinebutylester)、氟可龙、醋酸氟泼尼定(醋酸氟甲叉龙)、氟氢缩松、哈西奈德、乙酸氢化可的松、丁酸氢化可的松、甲泼尼龙、曲安奈德、可的松、去氧可的松(cortodoxone)、氟塞耐德(flucetonide)、氟氢可的松、二乙酸二氟松、氟雄诺龙缩丙酮化物(fluradrenaloneacetonide)、甲羟孕酮(medrysone)、amc、安西非特(amcinafide)、倍他米松且余量为其酯、氯泼尼松(chlorprednisone)、醋酸氯泼尼松、氯可托龙、克西诺龙(clescinolone)、二氯松、二氟泼尼酯、氟二氯松(flucloronide)、氟尼缩松、氟米龙、氟培龙、氟泼尼龙、戊酸氢化可的松、环戊基丙酸氢化可的松、氢可他酯、甲泼尼松、帕拉米松、泼尼松龙、泼尼松、二丙酸倍氯米松、二丙酸倍他米松、氟羟强的松龙(triamcinolone)、以及它们的组合。
当前可用的局部抗组织胺制剂包括:1%和2%的苯海拉明(和)、5%的多塞平霜、马来酸吡拉明(phrilamine maleate)、扑尔敏和吡苄明、酚噻嗪系、盐酸异丙嗪和马来酸吡啶茚胺。这些药物以及另外的抗组胺药也可包括在该组合物中。另外,所谓的“天然”抗炎剂可以为有用的。例如,小烛树蜡、α-红没药醇、芦荟、茜草提取物(Manjistha)(提取自茜草属(Rubia),特别是茜草(Rubiacordifolia))和穆库尔(Guggal)(提取自没药属(Commiphora),特别是印度穆库尔没药(Commiphora mukul))可用作该组合物中的活性物质。
组合物可包含非甾族抗炎药物(NSAID)。NSAID可为任何类型。NSAID的示例包括但不限于以下NSAID类别:丙酸衍生物乙酸衍生物;芬那酸衍生物;联苯甲酸衍生物;和昔康类。此类NSAID描述于美国专利4,985,459中,该专利以引用方式并入本文。另外的示例包括但不限于:乙酰水杨酸、布洛芬、萘普生、苯噁洛芬、氟比洛芬、非诺洛芬、芬布芬、酮洛芬、吲哚洛芬、吡洛芬、卡洛芬、噁丙嗪、普拉洛芬、咪洛芬(mniroprofen)、硫噁洛芬、舒洛芬、阿明洛芬、噻洛芬酸、氟洛芬、布氯酸、以及它们的组合。
组合物可包含抗氧化剂/自由基清除剂。抗氧化剂可为任何类型。抗氧化剂的示例包括但不限于:抗坏血酸(维生素C)及其盐、生育酚(维生素E)及其衍生物(诸如生育酚山梨酸酯、生育酚的其它酯)、丁基化的羟基苯甲酸及其盐、6-羟基-2,5,7,8-四甲基色满-2-羧酸(可以商品名商购获得)、没食子酸及其烷基酯(特别是没食子酸丙酯)、尿酸及其盐和烷基酯、山梨酸及其盐、脂肪酸的抗坏血酸酯、胺(例如N,N-二乙基羟基胺、氨基胍)、巯基化合物(例如谷胱甘肽)和二羟基富马酸及其盐可以使用以及EDTA、BHT等、以及它们的组合。
组合物可包括抗生素。抗生素可为任何类型。抗生素的示例包括但不限于氯霉素、四环素、合成和半合成青霉素、β-内酰胺、喹诺酮、氟喹啉、大环内酯类抗生素、肽抗生素、环孢菌素、红霉素、克林霉素、以及它们的组合。
组合物可包括局部麻醉剂。局部麻醉剂可为任何类型。局部麻醉剂的示例包括但不限于苯佐卡因、利多卡因、布比卡因、氯普鲁卡因、狄布卡因、依替卡因、马比佛卡因、丁卡因、达克罗宁、海克卡因、普鲁卡因、可卡因、开他敏、普莫卡因、苯酚、其药学上可接受的盐、以及它们的组合。
组合物可包含抗病毒剂。抗病毒剂可为任何类型。抗病毒剂的示例包括但不限于:抑制或减少病毒吸附至其受体、病毒内化进细胞中、病毒复制或病毒从细胞释放的蛋白质、多肽、肽、融合蛋白抗体、核酸分子、有机分子、无机分子和小分子。具体地,抗病毒剂包括但不限于:核苷类似物(例如齐多夫定、阿昔洛韦、阿昔洛韦前药、泛昔洛韦、更昔洛韦、阿糖腺苷、碘苷、曲氟尿苷和利巴韦林)、正二十二醇膦甲酸(n-docosanoll foscarnet)、金刚烷胺、金刚乙胺、茚地那韦、沙奎那韦、利托那韦、碘苷、α-干扰素以及其它干扰素、AZT、以及它们的组合。
活性物质的另外的示例包括止痛剂和抗高血压剂。止痛剂在本领域中为已知的并且通俗地称为止痛药。止痛剂可选自任何已知的止痛剂,并且其具体示例包括扑热息痛(对乙酰氨基酚)、吗啡、可待因、海洛因、美沙酮、蒂巴因、orpiarine、丁丙诺啡、吗啡喃类、苯吗喃类、对乙酰氨基酚、布托啡诺、二氟尼柳、非诺洛芬、芬太尼、柠檬酸芬太尼、氢可酮、阿司匹林、水杨酸钠、布洛芬、羟吗啡酮、五羟甲基乙酸(pentaxicine)、萘普生、纳布啡、甲芬那酸、哌替啶和二氢麦角胺、非甾族抗炎剂诸如水杨酸、和类鸦片制剂诸如吗啡和羟考酮。抗高血压剂在本领域已知用于治疗或减少高血压,即高血压。抗高血压剂可选自任何已知的抗高血压剂,并且它们的具体示例包括利尿药、肾上腺素受体拮抗剂(例如β阻滞剂)、苯二氮卓类、钙通道阻滞剂、肾素抑制剂等。
典型的麻醉拮抗剂为纳洛酮。示例的镇咳剂包括但不限于:苯海拉明、愈创木酚甘油醚、氢化吗啡酮、麻黄碱、苯丙醇胺、茶碱、可待因、诺司卡品、左旋丙氧芬、喷托维林、氯苯达诺(chlorpehndianol)和苯佐那酯。
可利用的镇静剂为(但不限于):水合氯醛、仲丁巴比妥、阿普唑仑、异戊巴比妥、甲氨二氮卓、安定、甲苯巴比妥、司可巴比妥、苯海拉明、凡眠特、氟胺安定、哈拉西泮、氟哌啶醇、丙氯拉嗪、奥沙西泮和他布酮。
心脏药物的示例为但不限于:奎尼丁、普萘洛尔、硝苯地平、普鲁卡因、多巴酚丁胺、洋地黄毒苷、苯妥英、硝普钠、硝酸甘油、盐酸维拉帕米、地高辛、盐酸尼卡地平和硝酸异山梨酯。
止吐剂由如下物质示例但不限于如下物质:硫乙哌丙嗪、甲氧氯普胺、苯甲嗪、氯苯甲嗪、丙氯拉嗪、琥珀酸多西拉敏、异丙嗪、三氟丙嗪和羟嗪。
典型的多巴胺受体激动剂为甲磺酸溴隐亭。示例性的氨基酸、肽和蛋白质激素包括但不限于甲状腺素、生长激素(GH)、间质细胞刺激素(ICSH)、促卵泡激素(FSH)、促甲状腺激素(TSH)、促肾上腺皮质激素(ACTH)、促性腺激素释放激素(GnRH),例如醋酸亮丙瑞林,加压素及其活性降解产物。某些产品可能具有足够高的分子量,因此通过角质层或粘膜吸收可能是困难的。因而,本发明仅适用于具有将允许穿透皮肤的分子量和立体构型的那些激素。
可使用的雌激素包括但不限于雌二醇、己烯雌酚、缀合的雌激素、雌酮、炔诺酮、甲羟孕酮、孕酮和甲基炔诺酮。可利用的代表性雄激素可由如下物质代表但不限于如下物质:睾酮、甲基睾酮和氟甲睾酮。
如以上所介绍,乳液可包含各种添加剂(例如,在乳液制备期间添加的那些),使得乳液本身用作最终用途组合物。然而,乳液也可与各种附加组分(例如,在其制备之后)诸如上文所述的那些组合,并因此配制成各种最终用途组合物,诸如个人护理组合物。此类组合物可为任何形式,诸如霜剂、凝胶、粉末、糊剂或可自由倾倒的液体。包含本公开的乳液或由本公开的乳液形成的组合物可表现出改善的施用和美容特性(包括降低的粘着性和粘性),以及改善的透明度/低残留特性。
在一些实施方案中,乳液本身为个人护理组合物,或者可配制成个人护理组合物。在此类实施方案中,个人护理组合物可配制成美容的、治疗性的、相对于身体施用个人护理组合物的一部分起作用的、或它们的一些组合。个人护理组合物的示例包括:止汗剂和除臭剂、皮肤护理霜剂、皮肤护理洗剂、保湿剂、面部处理剂(例如除痤疮剂或除皱剂)、个人和面部清洁剂、浴油、香水、古龙香水、香粉、防晒剂、剃须前和剃须后用洗液、剃须皂和剃须泡沫、洗发剂、调理剂、毛发着色剂、毛发松弛剂、发胶、摩丝、毛发凝胶、烫发剂、脱毛剂、角质层包覆剂、化妆品、有色化妆品、粉底、遮暇膏、胭脂、唇膏、眼线、睫毛膏、去油剂、彩妆去除剂、药物霜膏、糊剂或喷雾剂(例如用于抗痤疮剂、牙齿卫生剂、抗生素、愈合促进剂等)。一般来讲,包含乳液的个人护理组合物用允许以任何常规形式施用的载体配制,例如取决于预期用途,该常规形式诸如液体、冲洗剂、洗剂、霜膏、糊剂、凝胶、泡沫、摩丝、膏剂、喷雾剂、气溶胶、皂、棒、软固体、或固体凝胶。构成用于配制个人护理组合物的合适载体对于本领域的普通技术人员而言是显而易见的,并且可选自本文所例示的那些载体。
个人护理组合物可为液体或非液体(半固体、软固体、固体等)的任何形式。例如,个人护理组合物可为糊剂、固体、凝胶或霜剂。此外,无论乳液如何制备,由乳液形成的个人护理组合物本身可为乳液,诸如水包油或油包水乳液、复合乳液诸如油包水包油乳液或水包油包水乳液;或固态、刚性或柔软的凝胶,包括无水凝胶。个人护理组合物还可为选自半透明无水凝胶和透明无水凝胶的形式。个人护理组合物可例如包含外相或连续脂肪相。个人护理组合物可为无水的。在某些情况下,个人护理组合物可为模塑组合物或者浇铸成棒或盘。在具体的实施方案中,包含乳液的个人护理组合物为模塑倾注棒。在此类实施方案中,个人护理组合物(例如呈棒形式)可表现为可变形的柔性弹性固体,在施用时弹性柔软性增加。
包含乳液的个人护理组合物可通过任何方法使用,诸如通过用手或用施用装置(例如刷子或喷涂器)施用于人体(例如皮肤或毛发)。在一些实施方案中,个人护理组合物可旨在在此类施用后例如通过洗涤、擦拭、剥离等、或它们的组合被去除。
如上所提及,一般来讲,当用于或用作化妆品成分或成膜剂(包括用于准药物制剂或局部制剂)时,共聚物,并且特别是丙烯酸类共聚物的具体实施方案,具有优异的实用性。虽然不限于该特定最终用途应用,但本发明的共聚物可用于替代在现有化妆品制剂中普遍存在的具有碳硅氧烷树枝状结构的任何常规共聚物或与具有碳硅氧烷树枝状结构的任何常规共聚物组合利用。
例如,共聚物可在以下专利申请公布中的化妆品制剂中部分或完全替代具有碳硅氧烷树枝状结构的有机硅丙烯酸酯共聚物(例如FA4001 CM有机硅丙烯酸酯、FA4002 ID有机硅丙烯酸酯、FA4003有机硅丙烯酸酯等):WO2012/143344、WO2014/154701、WO2014/154700、WO2015/092632、WO2015/097110、WO2015/097103、WO2017/050699、WO2017/050922、WO2010/026538、WO2014/087183、WO2011/051323、JP2007-320960、WO2016/030842、JP2010-018612、JP2011-016734、JP2011-016732、JP2011-016733、JP2011-016734、JP 2011-126807、JP 2011-126808、JP2013-001672、JP 2014-034568、JP 2014-040388、JP 2014-227358、JP2015-098451、JP 2015-137252、JP 2016-008200、JP2016-088848、JP 2016-121095、JP 2016-160191、JP 2018-090495、JP2000-072784、JP07-309714、JP2007-320960、JP2014-040512、WO2017/061090、JP2011-149017、JP2014-040512、JP2014-040511、WO/2018/086139、WO/2018/186138、PCT/JP18/022412和PCT/JP18/022413。
本发明共聚物的具体预期最终用途应用基于以上专利申请公布的化妆品制剂,由此这些专利申请公布的具有碳硅氧烷树枝状结构的常规共聚物被本公开的本发明共聚物替代。在某些实施方案中,本发明的共聚物与具有碳硅氧烷树枝状结构的常规共聚物组合利用。在其他实施方案中,本发明的共聚物用于代替(和替代)具有碳硅氧烷树枝状结构的常规共聚物。
此外,包含共聚物的乳液组合物可用乳液中的本发明共聚物部分或完全替代。例如,以下文献中公开的化妆品制剂中的共聚物乳液可用包含本发明共聚物的乳液替代:WO2017/061090、WO/2018/086139、WO/2018/186138、PCT/JP18/022412、PCT/JP18/022413和研究公开:No.IPCOM000243971D和No.IPCOM0002457480。
通过在可用的和常规的化妆品制剂中用包含支链有机硅部分的共聚物替代具有碳硅氧烷树枝状结构的常规有机硅丙烯酸酯共聚物,本领域中技术人员可预期并设计使用包含支链有机硅部分的共聚物的类似或改善的化妆品制剂。
示出本公开的实施方案的以下实施例旨在示出而非限制本发明。
表1:制备例1中所用的组分
制备例1:
将初始有机硅化合物(A1)(657.13g)装载到连接到真空并配有两个塔顶接收器、蒸馏塔、再沸器和冷阱(干冰)的反应容器中。将容器加热至129℃,并且汽提出挥发物(29.15g;己烷/水)。然后抽真空(至10mmHg),将容器罐加热至135℃,并且去除附加的挥发物(26.91g来自塔顶;21.56g来自冷阱)。然后将抑制剂(D1)以四个部分装载到系统中,包括在两个塔顶接收器(各自为0.410g)、冷阱(0.3g)和蒸馏塔的顶部(0.50g)中。然后在再沸器流体中开始吹扫(7%O2/N2;40sccm)。然后将催化剂(C1)(2.9g)和MMA(298.77g)装载到容器中。将反应器设定点加热至回流并去除挥发物,并且塔顶温度处于64℃或低于64℃。使反应保持6小时,期间将体系保持在真空下以维持回流和103℃的罐温度,并且收集挥发物(35.4g)。测试(GC)罐中的反应混合物以确定转化率(GC;96.3%转化率)。然后抽真空至535mmHg,将罐加热至103℃,并且塔顶馏出设定至40的回流比,并且将反应器保持2.5小时。然后抽真空至10mmHg,将罐加热至118℃,并且将反应器维持1小时,同时去除挥发物(204.31g,并且在冷阱中为19.03g),以得到作为黄色且浑浊的物质的包含丙烯酰氧基官能有机硅化合物的反应产物(544.02g;100%转化成甲基丙烯酰氧基酯(GC);97.2%质量平衡),并且白色粉末沉淀出来。丙烯酰氧基官能有机硅化合物具有以下结构:
并且在本文中可称为SiN。
实施例1
单体混合物、自由基引发剂溶液的制备
在第一烧杯中,添加15.20重量份的甲基丙烯酸甲酯、4.80重量份的丙烯酸丁酯和20.00重量份的支链有机硅化合物(Si10N)并均匀混合。
在第二烧杯中,称量0.4重量份的V-601(二甲基2,2'-偶氮二(2-丙酸甲酯)),并且然后添加21.38重量份的异丙醇,并且搅拌以形成溶液。
自由基聚合和溶剂取代
在可分离的烧瓶中装入32.44重量份的异丙醇,并且在搅拌下用N2鼓泡将温度在30分钟内升至70℃,以用于从异丙醇中去除氧气。温度达到70℃后,逐渐同时滴加第一烧杯和第二烧杯的内容物,以允许反应进行。在完成第一烧杯和第二烧杯的内容物的滴加后,添加6.18重量份的异丙醇以用于冲洗第一烧杯和第二烧杯。在70℃下反应10小时后,获得澄清液体并将其用于一些测试(表2)。
比较例1:
重复以上如针对实施例1所述的相同程序,不同的是利用3-甲基丙烯酰氧基丙基三{[三(三甲基甲硅烷氧基)甲硅烷基]乙基二甲基甲硅烷氧基}硅烷代替Si10N。
表2:IPA中的共聚物
有机硅化合物为3-甲基丙烯酰氧基丙基三{[三(三甲基甲硅烷氧基)甲硅烷基]乙基二甲基甲硅烷氧基}硅烷。
实施例1仅需要6小时以满足低于0.5%的残余Si含量。另一方面,比较例1需要10小时以实现相同的Si含量。
因此,获得具有低水平杂质的有机硅丙烯酸酯共聚物溶液。还评估了膜特性(表3)。通过110℃加热和50mmHg抽真空将异丙醇替换为异十二烷。完成的聚合物溶液具有大约30%的非挥发性含量。
表3:
实施例2
单体乳化
在第一烧杯中,称量0.71重量份的90%月桂基聚氧乙烯醚-1磷酸酯,并且然后添加51.68重量份的交换过的离子和0.39重量份的20%氢氧化钠水溶液,并且搅拌以形成水溶液。在第二烧杯中,添加0.60重量份的2-苯氧基乙醇、9.90重量份的甲基丙烯酸甲酯、5.10重量份的丙烯酸丁酯和15.00重量份的Si10N树枝状体并均质化。在将第二烧杯中的混合物添加到第一烧杯中并且搅拌几分钟后,通过使用匀化器,使内容物多次通过300kg/cm2至400kg/cm2的压力,以获得无油滴的乳白色单体乳液。
自由基聚合
在可分离的烧瓶中装入4.60重量份的离子交换水和一部分所获得的单体乳液,并且在搅拌混合物的同时将温度升至80℃。在温度达到80℃后,逐渐同时滴加剩余的所得单体乳液和7.5重量份的用离子交换水制备的3%2,2'-偶氮二[N-(2-羧乙基)-2-甲基丙基脒]四水合物水溶液,以允许反应进行。反应3小时后,添加4.5重量份的用离子交换水制备的5%2,2'-偶氮二[N-(2-羧乙基)-2-甲基丙基脒]四水合物水溶液。反应后,未注意到甲基丙烯酸甲酯或丙烯酸丁酯的气味。完成的乳液具有大约30%的非挥发性含量,并且确认反应完成。
实施例3:
实施例3与实施例2相同,不同的是利用不同量的MMA、n-BuA和Si10N(如下表4中所示)。
实施例4:
实施例4与实施例2相同,不同的是利用不同量的MMA、n-BuA和Si10N(如下表4中所示)。
由实施例2-4制备膜,并且测量其物理特性并示于下表4中。
表4:
术语“包含”或“含有”在本文中以其最广泛的意义使用,意指并且涵盖“包括”、“基本上由…组成”和“由…组成”的概念。使用“例如”、“举例来说”、“诸如”和“包括”来列出示例性示例,不意味着仅限于所列出的示例。因此,“例如”或“诸如”意指“例如,但不限于”或“诸如,但不限于”并且涵盖其他类似或等同的示例。
一般来讲,如本文所用,在值的范围内的连字符“-”或破折号“–”为“至”或“到”;“>”为“高于”或“大于”;“≥”为“至少”或“大于或等于”;“<”为“低于”或“小于”;并且“≤”为“至多”或“小于或等于”。前述的专利申请、专利和/或专利申请公开中的每一者各自在一个或多个非限制性实施方案中明确地全文以引用方式并入文本。
应当理解,所附权利要求不限于具体实施方式中描述的专门和特定的化合物、组合物或方法,其可以在落入所附权利要求的范围内的特定实施方案之间变化。就本文为描述各种实施方案的特定特征或方面而依赖的任何马库什组而言,可以从独立于所有其他马库什成员的相应的马库什组的每个成员获得不同、特殊和/或意料之外的结果。马库什组的每个成员可以被单独地和/或组合地依赖,并且为所附权利要求范围内的具体实施方案提供足够的支持。
此外,在描述本发明的各种实施方案中依赖的任何范围和子范围独立地且共同地落入所附权利要求的范围内,并且应理解为描述和设想在其中包括全部和/或部分值的所有范围,即使本文未明确写出这样的值。本领域中技术人员将容易认识到,列举的范围和子范围充分地描述了本发明的各种实施方案并使它们成为可能,并且这样的范围和子范围可以被进一步描绘成相关的二分之一、三分之一、四分之一、五分之一等。仅作为一个示例,“0.1至0.9”的范围可以被进一步描绘为下三分之一(即0.1至0.3)、中三分之一(即0.4至0.6)和上三分之一(即0.7至0.9),其单独地且共同地在所附权利要求的范围内,并且可以被单独地和/或共同地依赖并为所附权利要求的范围内的具体实施方案提供足够的支持。此外,就诸如“至少”、“大于”、“小于”、“不超过”等限定或修饰范围的语言而言,应当理解,此类语言包括子范围和/或上限或下限。作为另一个示例,“至少10”的范围本质上包括至少10至35的子范围、至少10至25的子范围、25至35的子范围等,并且每个子范围可以被单独地和/或共同地依赖并为所附权利要求的范围内的具体实施方案提供足够的支持。最后,在所公开的范围内的独立数值可以被依赖并为所附权利要求的范围内的具体实施方案提供足够的支持。例如,“1至9”的范围包括诸如3的各个单个的整数,以及诸如4.1的包括小数点(或分数)的单个数,其可以被依赖并为所附权利要求的范围内的具体实施方案提供足够的支持。
已通过示例性方式对本发明进行了描述,并且应当理解已经使用的术语旨在具有描述性而不是限制性词语的性质。显然,按照上面的教导内容,本发明的许多修改形式和变型形式是可能的。可以按具体地描述之外的方式实施本发明。
Claims (16)
2.根据权利要求1所述的支链有机硅化合物,其中每个R1为-OSi(R4)3,并且其中R4中的至少一者为-[OSiR2]mOSiR3,其中每个R和m独立地选择并在上文定义。
5.根据任一项前述权利要求所述的支链有机硅化合物,其中R3具有下式:-D-O-C(O)C(R7)CH2,其中D为二价连接基团,并且R7为H或R,其中R在上文定义。
8.一种制备支链有机硅化合物的方法,所述方法包括:
使(A)有机硅化合物和(B)官能化合物任选地在存在(C)催化剂的情况下反应以得到所述支链有机硅化合物;
其中所述支链有机硅化合物为根据权利要求1-7中任一项所述的支链有机硅化合物。
11.一种共聚物,所述共聚物包含支链有机硅化合物和与所述支链有机硅化合物反应的第二化合物的反应产物;
其中所述支链有机硅化合物为根据权利要求1-7中任一项所述的支链有机硅化合物。
12.一种制备共聚物的方法,所述方法包括使支链有机硅化合物和与所述支链有机硅化合物反应的第二化合物反应以得到所述共聚物;
其中所述共聚物为根据权利要求11所述的共聚物。
13.一种组合物,所述组合物包含根据权利要求1-7中任一项所述的支链有机硅化合物和/或根据权利要求11所述的共聚物。
14.根据权利要求13所述的组合物,所述组合物被进一步限定为以下项中的至少一者:(i)乳液;(ii)水性组合物;(iii)表面活性剂组合物;(iv)润湿组合物;(v)水性成膜泡沫;(vi)表面张力调节剂;(vii)防粘连添加剂;(viii)农用组合物;(ix)涂料组合物;(x)油漆组合物;(xi)表面处理组合物;(xii)成膜组合物;和(xiii)化妆品组合物。
15.根据权利要求1-7中任一项所述的支链有机硅化合物作为表面活性剂、分散剂、润湿剂、防粘连添加剂、表面张力调节剂、表面处理剂、用于农用组合物的添加剂、用于涂料的添加剂、用于油漆的添加剂、化妆品成分、硅氧烷改性剂和水性成膜泡沫成分中的至少一者的用途。
16.根据权利要求11所述的共聚物作为表面处理剂、用于油漆的添加剂、用于涂料的添加剂和化妆品成分中的至少一者的用途。
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JP2022516126A (ja) | 2022-02-24 |
EP3906273A1 (en) | 2021-11-10 |
KR20210110843A (ko) | 2021-09-09 |
WO2020142441A1 (en) | 2020-07-09 |
US20220119597A1 (en) | 2022-04-21 |
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