CN104053697B - 用于乳液聚合的新的活性表面活性剂、颜料分散体和uv涂料 - Google Patents
用于乳液聚合的新的活性表面活性剂、颜料分散体和uv涂料 Download PDFInfo
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- CN104053697B CN104053697B CN201280053044.XA CN201280053044A CN104053697B CN 104053697 B CN104053697 B CN 104053697B CN 201280053044 A CN201280053044 A CN 201280053044A CN 104053697 B CN104053697 B CN 104053697B
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- surfactant
- water
- monomer
- latex
- pigment
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- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 230000026731 phosphorylation Effects 0.000 description 1
- 238000006366 phosphorylation reaction Methods 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
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- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
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- 230000009467 reduction Effects 0.000 description 1
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- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 235000010352 sodium erythorbate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
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- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
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- 238000006886 vinylation reaction Methods 0.000 description 1
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Classifications
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- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/07—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton
- C07C309/09—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing etherified hydroxy groups bound to the carbon skeleton
- C07C309/10—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing etherified hydroxy groups bound to the carbon skeleton with the oxygen atom of at least one of the etherified hydroxy groups further bound to an acyclic carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/14—Unsaturated oxiranes
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2612—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aromatic or arylaliphatic hydroxyl groups
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
- C08G65/3344—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing oxygen in addition to sulfur
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/335—Polymers modified by chemical after-treatment with organic compounds containing phosphorus
- C08G65/3353—Polymers modified by chemical after-treatment with organic compounds containing phosphorus containing oxygen in addition to phosphorus
- C08G65/3355—Polymers modified by chemical after-treatment with organic compounds containing phosphorus containing oxygen in addition to phosphorus having phosphorus bound to carbon and oxygen
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
- C09D171/02—Polyalkylene oxides
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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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
本发明提供式R1O‑(CH2CHR2O)x‑(CH2CH2O)y‑(CH2CHR3O)z‑R4的活性表面活性剂,其中R1为含8‑30个碳原子的烷基、芳基、烷芳基或芳烷基芳基,R2为‑CH2OCH2CH=CH2(AGE);R3为H、CH3或CH2CH3;R4为H或‑SO3M或‑PO3M,其中M为H或K、Na、NH4、NR4、烷醇胺或其他阳离子种类,并且x=2‑100;y=4‑200并且z=0‑50。
Description
根据35U.S.C.第119部分,本申请要求2011年8月29日提交的名称为"ReactiveSurfactants For Emulsion Polymerization,Pigment Dispersion,And UV Coatings"的美国临时专利申请第61/573,084号的优先权权益,其全文以引用的方式纳入本说明书。
技术领域
本发明涉及聚合烯键式不饱和单体的乳液。本发明还涉及通过使用含有多个烯丙基缩水甘油醚基团的苯乙烯化表面活性剂作为主乳化剂(primary emulsifier)的烯键式不饱和单体的乳液聚合。本发明还涉及通过水性单体乳液的自由基聚合而制备聚合物分散体的方法。本发明还涉及制备含有衍生自至少一种可聚合的烯键式不饱和单体的单体单元的水性聚合物和共聚物分散体的方法。聚合物和共聚物分散体是通过自由基乳液聚合方法得到的,所述方法在水性介质中并且在至少一种含有多个烯丙基缩水甘油醚基团的苯乙烯化表面活性剂的存在下进行。另一方面,本发明涉及所述聚合物或共聚物分散体的用途。
背景技术
乳液聚合是制造水性分散体聚合物的最重要的工业方法。乳液聚合通常在水性介质中且在表面活性剂和水溶性引发剂的存在下进行,并且通常快速生成高固含量和低分散粘度的高分子量均聚物或共聚物。其应用需要通过使用乳化剂而使单体在介质(通常为水)中乳化。乳化剂是除其他参与聚合的组分(如引发剂和链转移剂)之外另外提供的。乳化剂的使用和类型决定了所制备的聚合物或共聚物的许多特性,所述聚合物或共聚物通常为胶乳(聚合物颗粒在连续相通常是水中的稳定的胶体悬浮液)。此外,乳化剂通常不能从胶乳中完全移除。为此,并且由于在聚合中所给定的表面活性剂作为乳化剂的效率有很大的不可预测性,许多理论上可以使用的化合物实际上并不可行。
还已知乳液聚合需要使用表面活性剂以形成稳定的单体乳液并且防止产物聚合物的聚结。表面活性剂通常分为两类:不可聚合型,或可聚合型,可聚合型表面活性剂可与用于形成聚合物的单体共聚合。表面活性剂还根据其化学组成而分为阴离子型、阳离子型、非离子型或两性离子型。使用不可聚合型表面活性剂引发的问题是其作为残留物而保持在产物聚合物中,并且由于其可以被水萃取,所以其使产品对水敏感。
名称“乳液聚合”是由历史误解所产生的使用不当的名称。聚合在聚合过程的前几分钟自发形成的胶乳颗粒中进行,而不是在乳液液滴中进行。这些胶乳颗粒的尺寸通常为100nm,并且由许多单独的聚合物链构成。这些颗粒不再彼此聚结,这是因为每个颗粒被表面活性剂(“肥皂(soap)”)所包围;表面活性剂上的电荷静电排斥其他颗粒。当水溶性聚合物用作稳定剂而不使用肥皂时,产生颗粒之间的排斥,这是因为这些水溶性聚合物在颗粒周围形成“毛层”而排斥其他颗粒,因为将颗粒推在一起会涉及压缩这些链。
乳液聚合用于制造一些具有重要商业价值的聚合物。这些聚合物中的许多被用作固体材料并且在聚合后必须从水性分散体中分离。在其它情况下,分散体本身为终产品。由乳液聚合得到的分散体通常称为胶乳(特别是如果衍生自合成橡胶)或乳液(即使“乳液”严格来讲是指水不混溶的液体在水中的分散体)。这些乳液用于粘合剂、油漆、纸张涂料和织物涂料。它们得到越来越多的认可并且在这些应用中由于其生态友好特性(其不含VOC(挥发性有机化合物))而相对于溶剂基产物是优选的。
乳液聚合物的优点包括:
可以在快的聚合速率下制备高分子量聚合物。相比之下,在本体聚合和溶液自由基聚合中,分子量和聚合速率之间存在一个折衷关系。
连续水相为热的优良导体并且使热从体系中移除,使得许多反应方法可提高其速率。
由于聚合物分子包括于颗粒中,反应介质的粘度保持与水的粘度相近并且不依赖于分子量。
最终产物可以如其本身使用并且通常不需要改变或加工。
所得的胶乳通常用于涂料应用如油漆、染色等。
一旦含胶乳的产品已被应用于表面作为保护性或装饰性涂层部分,则不再需要表面活性剂。事实上,表面活性剂的存在通常降低涂层的湿气敏感性。其他涂层性能如对基底表面的粘合性也被不利地影响。这主要是由于表面活性剂聚合物的流动性。例如,由于表面活性剂涂覆的胶束球的聚结,可在涂层中形成局部高浓度的表面活性剂分子。当涂层暴露至水时,这些未结合的表面活性剂分子可以由涂层提取,留下薄弱点或到基底表面的路径。这可以导致针孔效应并且基底被水腐蚀。
活性表面活性剂含有可参与自由基乳液聚合反应的可聚合部分。当所述表面活性剂被用于乳液聚合时,大部分表面活性剂分子不可逆地连接至乳液聚合物链和液滴。然后当将胶乳纳入至涂料如油漆时,存在更少游离的表面活性剂以干扰所需的涂层性能或降低对基底的粘合性。
许多活性非离子型和阴离子型表面活性剂是市售可得的,包括:聚氧乙烯烷基苯基醚、烯丙氧基羟丙基磺酸钠、烯基官能化非离子型surfimers、烯丙基甲氧基三乙二醇醚、甲代烯丙基磺酸钠、磺丙基丙烯酸酯、乙烯基磺酸盐、乙烯基磷酸盐、乙基磺酸一钠、单十二烷基马来酸酯盐、山梨糖醇丙烯酸酯、山梨糖醇甲基丙烯酸酯、全氟庚氧基聚(丙氧基)甲基丙烯酸酯、苯氧基聚(乙烯氧基)丙烯酸酯,苯氧基聚(乙烯氧基)甲基丙烯酸酯、壬基苯氧基聚(乙烯氧基)巴豆酸酯、壬基苯氧基聚(乙烯氧基)富马酸酯、壬基苯氧基聚(乙烯氧基)丙烯酸酯、壬基苯氧基聚(乙烯氧基)甲基丙烯酸酯、单十二烷基马来酸酯盐和烯丙基磺基琥珀酸酯盐衍生物。
另外,阴离子型活性表面活性剂已经尤其公开于日本专利公开第46-12472号、日本特许专利公开第54-144317号、日本专利公开第46-34894号、日本专利公开第56-29657号、日本特许专利公开第51-30285号、US4,814,514和US5,324,862。活性表面活性剂的综述可见于"Reactive Surfactants in Emulsion Polymerization"Guyot,A.and Tauer,K.,in Advances in Polymer Science,卷III,Springer-Verlag,Berlin,第43-65页。
这些活性表面活性剂没有在其结构中纳入多于一个活性部分。事实上,在US4,814,514中公开的苯乙烯化酚基材料通过将烯丙基缩水甘油醚(AGE)加成至表面活性剂基分子(如羟基官能化脂族醇或取代的酚)而制备,其将AGE的量特别限制至1.0摩尔。
附图说明
图1示出水浸泡测试结果。
图2示出随着一天后不透明度的变化测得的吸水。
图3描述了随着两天后不透明度的变化测得的吸水。
图4示出了随着四天后不透明度的变化测得的吸水。
图5示出了未处理松木板的染色。
图6描述了在染色的松木板上的水滴的接触角测试。
发明内容
本发明提供改进的如下式I-IV所示的非离子型和阴离子型活性表面活性剂,其作为颜料分散剂用于常规水性乳液聚合物,和用于UV固化的涂料。这些新的活性表面活性剂是两摩尔或更多摩尔的烯丙基缩水甘油醚(AGE)与环氧乙烷的共聚物,所述共聚物的一端用疏水部分封端。第二当量的AGE的加入显著降低了产品中非活性表面活性剂的量,以实现涂层疏水性的提高。
式(I)活性表面活性剂为以下结构的阴离子表面活性剂:
其中,R=CH3、CH2CH3、C6H5或C14H29;n=1、2或3;x为2-10,y为0-200,z为4-200、更优选约5至60、最优选约5至40;Z可以为SO3 -或PO3 2-,并且M+为Na+、K+、NH4 +,或烷醇胺。
本发明还涉及烯键式不饱和单体在式(II)非离子型表面活性剂存在下的乳液聚合
其中R=CH3、CH2CH3、C6H5或C14H29;n=1、2、3;x为2-10,y为0-200,z为4-200、更优选约5至60、最优选约5至40。
本发明还涉及式III和IV的阴离子型和非离子型表面活性剂
其中R1为C10-24烷基、烷芳基、烯基或环烷基,R2=CH3、CH2CH3、C6H5或C14H29;x为2-10,y为0-200,z为4-200、更优选约5至60、最优选约5至40;并且Z可以为SO3 -或PO3 2-,并且M+为Na+、K+、NH4 +,或烷醇胺。
其中R1为C10-24烷基、烷芳基、烯基或环烷基,R2=CH3、CH2CH3、C6H5或C14H29;x为2-10,y为0-200,z为4-200、更优选约5至60、最优选约5至40。
这些新的活性表面活性剂可以含有各种疏水部分如苯乙烯化苯酚醚、烷基醚(如十三烷醇),或烷基酚醚。改变乙氧基化或丙氧基化的程度和调节疏水部分的大小使得能够调整结构以获得最优性能。
除AGE和EO外在共聚物中可以包含其他单体。这些单体包括环氧丙烷(PO)和其他环氧化物如1,2-环氧丁烷、氧化苯乙烯,或1,2-环氧十四烷。
这些非离子型共聚物还可以任选地衍生化以将其转化为阴离子型表面活性剂。这些的实例包括磺酸盐(sulfonates)、磷酸酯(phosphate esters)、羧酸盐(carboxylates),和磺基琥珀酸盐(sulfosuccinates)。
这些新的表面活性剂赋予木甲板染色用的涂料以及用这些新的表面活性剂获得的直接施用于金属的涂料改善的性能。这些性能包括小的粒径、改进的疏水性、冻融稳定性、改进的光泽、耐水性和其他的油墨和涂料特性。
通常,胶乳颗粒通过使单体混合在一起以形成单体混合物而制备。然后将一种或多种表面活性剂加入至单体混合物并且在混合下加入至水中以形成乳液。表面活性剂可以包括活性表面活性剂、非活性表面活性剂,或活性和非活性表面活性剂的结合。在本发明的一个实施方案中,可以使用非活性表面活性剂以形成胶乳颗粒,并且可以一起使用活性表面活性剂,或在第二步中加入活性表面活性剂。或者,聚合可以无皂聚合进行,活性表面活性剂在聚合的末期加入。
具体实施方式
本发明涉及新的活性表面活性剂,涉及所述表面活性剂在乳液聚合中的用途,以及涉及所得的组合物的用途。
本发明提供具有下式的活性表面活性剂:
其中,R=CH3、CH2CH3、C6H5或C14H29;n=1、2或3;x为2-10,y为0-200,z为4-200、更优选约5至60、最优选约5至40;Z可以为SO3 -或PO3 2-,并且M+为Na+、K+、NH4 +,或烷醇胺;。
其中R=CH3、CH2CH3、C6H5或C14H29;n=1、2、3;x为2-10,y为0-200,z为4-200、更优选约5至60、最优选约5至40;
其中R1为C10-24烷基、烷芳基、链烯基或环烷基,R2=CH3、CH2CH3、C6H5或C14H29;x为2-10,y为0-200,z为4-200、更优选约5至60、最优选约5至40;并且Z可以为SO3 -或PO3 2-,并且M+为Na+、K+、NH4 +,或烷醇胺;
和
其中R1为C10-24烷基、烷芳基、烯基或环烷基,R2=CH3、CH2CH3、C6H5或C14H29;x为2-10,y为0-200,z为4-200、更优选约5至60、最优选约5至40。
在高压釜中在100-110℃的温度范围内使用氢氧化钾催化剂通过使1当量的二苯乙烯化苯酚或三苯乙烯化苯酚或其他含羟基的原料与2或更大当量的烯丙基缩水甘油醚反应以制备具有至少2当量的烯丙基缩水甘油醚的加成物而制造活性表面活性剂。然后,所得的加成物与环氧烷烃、环氧烷烃和氧化苯乙烯的混合物在碱性催化剂如氢氧化钾或碱金属醇盐(如甲醇钠或甲醇钾)的存在下反应。
更具体地,烷氧基化的方法包括以下步骤:将催化剂加入至含有至少一个羟基的有机化合物中;将包含含有羟基的有机化合物的反应器加热和加压;在加工温度为50℃至250℃并且压力为100至700kpa下将环氧烷烃提供至所述有机化合物和催化剂,以及分离出烷氧基化产物。
用于烷氧基化反应的环氧烷烃选自环氧乙烷、环氧丙烷、环氧丁烷、C5-C18氧化物和氧化苯乙烯。环氧烷烃基团(alkylene oxide group)可以无规排列或嵌段排列。特别优选与相当疏水基团如环氧丙烷或环氧丁烷嵌段排列。视需要调节环氧乙烷基团与其他疏水性环氧烷烃基团的摩尔比以实现所需的性能。
本发明的新的活性表面活性剂的性能特性对于具体的应用而言可以通过合适的改性如烷氧基化程度和使用的不同的环氧烷烃,用作端基的基团的选择而最优化。这些因素之间的相互作用看起来复杂并且不好理解。然而,清楚的是通过操作这些变量可以得到作为优异的乳化剂的材料。
本发明还涉及烯键式不饱和单体在式(I)的阴离子表面活性剂存在下的乳液聚合
其中,R=CH3、CH2CH3、C6H5或C14H29;n=1、2或3;x为2-10,y为0-200,z为4-200、更优选约5至60、最优选约5至40;Z可以为SO3 -或PO3 2-,并且M+为Na+、K+、NH4 +,或烷醇胺。
本发明还提供烯键式不饱和单体在式(II)的非离子型表面活性剂存在下的乳液聚合
其中R=CH3或CH2CH3;n=1、2、3;x为2-10,y为0-200,z为4-200、更优选约5至60、最优选约5至40。
在另一个实施方案中,本发明还涉及烯键式不饱和单体在式(III)或(IV)的表面活性剂存在下的乳液聚合。
其中R1为C10-24烷基、烷芳基、烯基或环烷基,R2=CH3、CH2CH3、C6H5或C14H29;x为2-10,y为0-200,z为4-200、更优选约5至60、最优选约5至40;并且Z可以为SO3 -或PO3 2-,并且M+为Na+、K+、NH4 +,或烷醇胺;
其中R1为C10-24烷基、烷芳基、烯基或环烷基,R2=CH3、CH2CH3、C6H5或C14H29;x为2-10,y为0-200,z为4-200、更优选约5至60、最优选约5至40。
式(I)-(IV)化合物在乳液聚合中可以单独使用或结合使用。当结合使用时,式(I)化合物与式(IV)化合物的比例不受限制,但是由所需的乳液性能所决定。式(I)至式(IV)表面活性剂还可以与本领域中通常使用的其他表面活性剂结合使用。当结合使用时,表面活性剂的比例不具体,但是通常基于给定的制剂中存在的烯键式不饱和单体的性质而最优化。可用于本发明的式(I)至(IV)的表面活性剂的总量优选为约0.1%至约20%,基于单体的总重量计,更优选约0.2%至约10%,最优选约0.5%至约7%,基于单体的总重量计。式(I)至(IV)化合物还可以与常规的表面活性剂结合使用,以改进乳液性能。
通常用于乳液聚合方法的其他表面活性剂包括阴离子型分子和非离子型分子。在乳液聚合方法中通常使用的阴离子型表面活性剂包括烷基苯磺酸钠、烷基二苯醚二磺酸盐、乙氧基化烷基酚硫酸盐和磷酸盐、烷基磺基琥珀酸盐、和脂族醇的硫酸盐和磷酸盐等。通常使用的非离子型表面活性剂包括直链和支化醇乙氧基化物,和烷基酚乙氧基化物,特别是辛基酚乙氧基化物。当与其他表面活性剂结合使用时,比例不受限制,但是也由所需的乳液性能而决定。
可以通过本发明惯例聚合的合适的单体包括各种烯键式不饱和单体,如乙烯基单体或丙烯酸单体。适于本发明的常规的乙烯基单体包括但不限于乙烯基酯,例如乙酸乙烯酯、丙酸乙烯酯、苯甲酸乙烯酯等;乙烯基芳族烃,例如苯乙烯、甲基苯乙烯、其他乙烯基芳族化合物(如乙烯基甲苯、乙烯基萘、二乙烯基苯)等。还可以使用卤代乙烯基单体如氯乙烯、偏二氯乙烯等。
可以根据本发明使用的合适的丙烯酸类单体包括具有丙烯酸官能的化合物,例如丙烯酸烷基酯和甲基丙烯酸烷基酯、丙烯酸和甲基丙烯酸以及丙烯酰胺和丙烯腈。常用的丙烯酸类单体包括但不限于丙烯酸甲酯和甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丙酯、甲基丙烯酸丙酯、丙烯酸丁酯和甲基丙烯酸丁酯、丙烯酸苯甲酯和甲基丙烯酸苯甲酯、丙烯酸环己酯和甲基丙烯酸环己酯、丙烯酸癸酯和甲基丙烯酸癸酯、丙烯酸十二烷基酯和甲基丙烯酸十二烷基酯等。其他常用的丙烯酸类单体包括丙烯酸羟基烷基酯和甲基丙烯酸羟基烷基酯,例如丙烯酸羟基丙基酯和甲基丙烯酸羟基丙基酯、丙烯酸羟基乙基酯和甲基丙烯酸羟基乙基酯;丙烯酸类,例如甲基丙烯酸和丙烯酸;和氨基丙烯酸酯和氨基甲基丙烯酸酯。本领域技术人员应认识到根据本发明也可以使用适于自由基加成聚合的其他不饱和单体。
在乳液聚合方法中各种形成自由基的化合物被用作催化剂。通常用作催化剂的化合物为通过热分解而形成自由基的那些化合物(所述化合物在本领域中称为“热引发剂”)或通过氧化/还原反应而形成自由基的化合物的结合。该催化剂是氧化剂与还原剂的结合并且在本领域中通常称为“氧化还原引发剂”。热催化剂或氧化还原催化剂可以用于进行本发明。
用作热引发剂的常用催化剂包括过硫酸盐,特别是过硫酸钾、过硫酸钠、过硫酸铵等。常用的氧化还原引发剂包括氧化剂或引发剂的结合,例如过氧化物,特别是过氧化苯甲酰、叔丁基过氧化氢、月桂酰基过氧化物、过氧化氢、2,2'-偶氮二异丁腈等。常用的还原剂包括亚硫酸氢钠、甲醛次硫酸氢钠、连二亚硫酸钠,和抗坏血酸和异抗坏血酸。催化剂或引发剂的用量优选为单体总重量的0.1至3重量%,最优选为单体总重量的约0.1至1重量%。
根据本发明还可以使用本领域技术人员已知的其他添加剂或组分。这些包括链转移剂(其用于控制分子量),调节pH的添加剂,和用作为胶乳颗粒提供额外稳定性的保护胶体的化合物。
在乳液聚合中使用的常用的组分列于以下常用配方中:
组分 | %-湿基 |
单体 | 30-50 |
表面活性剂 | 1-3 |
保护胶体 | 0-3 |
引发剂 | 1-3 |
改性剂 | 0-1 |
缓冲剂 | 0-1 |
水 | 50-70 |
乳化剂悬浮单体液滴和聚合物颗粒。改性剂可以为控制聚合反应的醛、硫醇或氯化烃,其限制交联和控制分子量。保护胶体如聚乙烯醇或甲基纤维素用于稳定最终的胶乳。缓冲盐控制乳液聚合浴(emulsion polymerization batch)的pH。这些盐(如磷酸盐、柠檬酸盐、乙酸盐和碳酸盐)是重要的,因为pH影响反应速率、粒径和其他反应条件。
在某些情况下,向单体乳液加入聚合物颗粒晶种。加入晶种的乳液聚合的目的在于避免颗粒引发阶段的不确定性,获得更好地批次间的再现性,并且给出所需粒径的稳定胶乳。在水中聚合的原因包括:在相同的温度下与本体聚合相比聚合更快速,且具有更大的平均分子量;在水中良好的传热,更好地控制聚合热;在聚合中所有的单体被消耗并且所得的胶乳可以直接用于涂料应用;并且水相降低了乳液的总体粘度。
单体乳液由通过表面活性剂分子、空胶束(胶态表面活性剂囊泡(colloidalsurfactant vesicles))和单体溶胀的胶束稳定的与水不混溶的单体液滴组成。单体液滴尺寸为小于1微米至10微米。胶束的尺寸为约10至15纳米。在反应过程中,单体分子从液滴储囊(reservoir)扩散至进行聚合的胶束中。聚合物链在胶束中生长。随着聚合进行,单体液滴尺寸减小并且最后消失。当聚合物颗粒变大时,胶束中的表面活性剂分子使聚合物颗粒悬浮。最终聚合物颗粒生长到十分之几微米至一微米的尺寸。最终聚合物的物理性质取决于反应温度、配方和反应条件的控制,如组分加入至反应器的时机和量。
在乳液聚合中使用匀化器以将单体乳化为预混合料加入至反应器。在所有乳液单体中,氯乙烯聚合为最通常使用均化器以制备混合物的单体。在常规的方法中,将制备聚合物的组分以合适的顺序加入至排空的、搅拌的、加压的罐中(用氮气加压)。将组分混合并且调节混合物的温度后,将乳液匀化以制备所需的单体液滴尺寸。匀化压力为1000至5000psi,取决于单体和单体储囊所需的液滴尺寸。该单体液滴尺寸可以影响最终胶乳颗粒的物理性质。乳液从匀化器进入至反应器,在反应器中在控制的温度下进行聚合,直至达到所需的转化率。反应完成后,将胶乳冷却并且从反应器中移出。
根据本发明也可以使用在乳液聚合方法中使用的任何其他常规方法。这些方法包括标准乳液单体添加技术和预乳化单体添加技术以及分阶段的单体添加方法。
本发明还提供适于制备涂料组合物的颜料分散体,其中颜料以高浓度在水溶液和非水溶液中细分散并且稳定地分散,用于油墨、油漆、染色、颜料光致刻蚀剂等工业领域。
更具体而言,本发明还提供一种颜料分散体,其含有:(a)颜料;(b)溶剂;和(c)如上所述式I-IV的分散的表面活性剂。
本发明的分散体的颜料可以选自无机颜料(例如炭黑颜料,如炉黑、导电炭黑颜料、体质颜料和腐蚀抑制颜料);有机颜料;分散染料;及其混合物。可以存在于颜料分散体中的有机颜料的实例包括但不限于二萘嵌苯、酞菁绿、酞菁蓝、亚硝基颜料、单偶氮颜料、重氮颜料、重氮缩合颜料、碱性染料颜料、碱性蓝颜料、蓝色淀颜料、根皮红颜料、喹吖啶酮颜料、酸性黄1和3色淀颜料(lake pigment)、咔唑二噁嗪紫色颜料、茜素色淀颜料、瓮颜料、邻苯二甲酰氧胺(phthaloxy amine)颜料、胭脂红色淀颜料、四氯异吲哚颜料及其混合物。可以存在于颜料分散体中的无机颜料包括例如二氧化钛、导电二氧化钛和氧化铁,例如红色氧化铁、黄色氧化铁、黑色氧化铁和透明氧化铁。可以存在于颜料分散体中的体质颜料包括但不限于二氧化硅、粘土、碱土金属硫酸盐和碳酸盐,如硫酸钙、硫酸镁、硫酸钡和碳酸钙。颜料分散体可以含有腐蚀抑制颜料,如磷酸铝和钙改性的二氧化硅。有机颜料和无机颜料的混合物还适于制备本发明的分散体。
颜料的平均初级粒径为8至80nm,优选10至35nm,并且DBP数为40至200ml/100g,优选60至150ml/100g,可以用作炭黑。在本发明的一个优选的实施方案中,可以使用平均初级粒径为8至30nm,优选10至25nm的气黑。
实施例
本发明通过以下实施例进行解释,但是不应限于此。在实施例中,除非另做说明,“份”和“%”均为重量份或重量%。
实施例1
表面活性剂的制备
将二苯乙烯化苯酚(DSP)(694g,1当量)与烯丙基缩水甘油醚(AGE)(494g,2当量)和氢氧化钾KOH(2.3g)一起加入至不锈钢高压釜中并且将高压釜密封并且加热至105℃。当所有的AGE被消耗时,将反应物料冷却,并且将产物排出。这是AGE2DSP加成物。
将1680g该AGE2DSP加成物(1当量)加入至另一高压釜并且加热至105℃。然后在数小时内加入环氧乙烷(2026g,15当量)。在所有EO被消耗后,将反应物料冷却并且催化剂通过加入少量酸而中和。该材料为实施例1。
实施例1A
将二苯乙烯化苯酚(DSP)(1388g,2当量)与烯丙基缩水甘油醚(AGE)(988g,4当量)和氢氧化钾KOH(4.6g)一起加入至不锈钢高压釜中并且将高压釜密封并且加热至105℃。当所有的AGE被消耗时,将反应物料冷却,并且将产物排出。这是AGE2DSP加成物。
将3360g该AGE2DSP加成物(2当量)加入至另一高压釜并且加热至105℃。然后在数小时内加入环氧乙烷(4052g,30当量)。在所有EO被消耗后,将反应物料冷却并且催化剂通过加入少量酸而中和。
实施例1B
将二苯乙烯化苯酚(DSP)(347g,0.5当量)与烯丙基缩水甘油醚(AGE)(247g,1当量)和氢氧化钾KOH(1.15g)一起加入至不锈钢高压釜中并且将高压釜密封并且加热至105℃。当所有的AGE被消耗时,将反应物料冷却,并且将产物排出。这是AGE2DSP加成物。
将940g该AGE2DSP加成物(0.5当量)加入至另一高压釜并且加热至105℃。然后在数小时内加入环氧乙烷(1013g,7.5当量)。在所有EO被消耗后,将反应物料冷却并且催化剂通过加入少量酸而中和。
实施例1C
将二苯乙烯化苯酚(DSP)(2776g,4当量)与烯丙基缩水甘油醚(AGE)(1976g,8当量)和氢氧化钾KOH(9.2g)一起加入至不锈钢高压釜中并且将高压釜密封并且加热至105℃。当所有的AGE被消耗时,将反应物料冷却,并且将产物排出。这是AGE2DSP加成物。
将6720g该AGE2DSP加成物(4当量)加入至另一高压釜并且加热至105℃。然后在数小时内加入环氧乙烷(8104g,60当量)。在所有EO被消耗后,将反应物料冷却并且催化剂通过加入少量酸而中和。
实施例2
在装有搅拌器、温度计和回流冷凝器的玻璃反应器中通过加热至120℃使用氨基磺酸对实施例1进行硫酸化,直至硫酸盐%>90%。将产物作为铵盐分离出。
实施例3
在装有搅拌器、温度计和回流冷凝器的玻璃反应器中通过加热至70℃使用1摩尔的五氧化二磷(P2O5)对3摩尔的实施例1进行磷酸化,直至反应完全。产物磷酸酯(单酯和二酯的混合物)用氢氧化铵水溶液中和。将产物作为铵盐水溶液分离出。
以类似于实施例1,2或3的步骤,制备实施例4-24:
实施例4-24:
实施例编号 | 疏水物 | AGE(当量) | EO(当量) | 端基 |
4 | DSP | 1 | 16 | -OH |
5 | DSP | 1 | 16 | -OSO3-NH4+ |
6 | DSP | 2 | 15 | -OSO3-NH4+ |
7 | DSP | 2 | 15 | -OPO3-NH4+ |
8 | DSP | 2 | 15 | -OPO3-K+ |
9 | 十三烷醇 | 1 | 17 | -OH |
10 | 十三烷醇 | 1 | 17 | -OSO3-NH4+ |
11 | 十三烷醇 | 2 | 36 | -OH |
12 | 十三烷醇 | 2 | 36 | -OPO3-NH4+ |
13 | 壬基苯酚 | 2 | 4 | -OH |
14 | 壬基苯酚 | 2 | 4 | -OS03-NH4+ |
15 | 壬基苯酚 | 2 | 38 | -OH |
16 | 壬基苯酚 | 2 | 38 | -OSO3-NH4+ |
17 | DSP | 2 | 15 | -OPO3-NH4+ |
18 | DSP | 1 | 5 | -OH |
19 | DSP | 1 | 5 | -OSO3-NH4+ |
20 | DSP | 2 | 5 | -OSO3-NH4+ |
21 | TSP | 1 | 10 | -OH |
22 | TSP | 1 | 10 | -OSO3-NH4+ |
23 | TSP | 2 | 10 | -OH |
24 | TSP | 2 | 10 | -OSO3-NH4+ |
TSP为三苯乙烯化苯酚,其是单苯乙烯化苯酚、二苯乙烯化苯酚和三苯乙烯化苯酚的混合物(三苯乙烯化苯酚为主要组分)
DSP为二苯乙烯化苯酚,其是单苯乙烯化苯酚、二苯乙烯化苯酚和三苯乙烯化苯酚的混合物(二苯乙烯化苯酚为主要组分)
实施例25-28
胶乳对水渗透的抗性
所有胶乳实施例25-28在套管玻璃反应器中使用以下配方而制备。各个实施例仅改变胶乳制备中使用的表面活性剂。
通过外置循环水加热器调节温度。反应器装有热电偶和进料管线。通过不锈钢管将单体进料至表面下。在胶乳的表面上加入引发剂(氧化剂和还原剂)。将单体和引发剂泵入反应溶液中。
胶乳配方:
*叔碳酸乙烯酯(VV10-Momentive)
步骤:
1.开启循环水加热器
2.配制起始的和延迟的氧化剂溶液
3.配制初始进料
4.配制以所示顺序的单体进料
5.加入初始进料
6.提高温度至80℃
7.加入初始氧化剂
8.开始单体进料
9.开始延迟的氧化剂进料
10.在进料末期,等待1小时
11.在60分钟内开始后氧化剂和后还原剂
12.移除热并且使之冷却
13.调节pH
14.测量特性
将每个胶乳25-28的五毫米厚的膜涂布至玻璃和Leneta片材并且使其完全干燥。然后将水滴置于干燥的胶乳薄膜上并且用倒置的烧杯覆盖以防止蒸发。静置24小时后,检查干燥的胶乳薄膜的耐水白(雾浊)性。越白或越模糊则表明被胶乳薄膜吸收的水越多。吸水对于保护性涂层而言是不希望的。
以下表格示出在玻璃上的各个干燥的胶乳薄膜在暴露至水后的相对变白量。这通过视觉示于图1。
表1
通过将干燥的样品在水中浸泡而进行类似于水滴试验的研究。将样品涂布在聚乙烯片材上并且使其干燥4天,每天将样品正反倒置以有助于干燥过程。最终的样品厚度为1/8英吋。然后将这些样品置于600ml烧杯中并且用200ml水覆盖。
实施例26,含有具有两个活性基团的表面活性剂的胶乳(实施例2),在所研究的四个乳胶中具有最好的耐水白性(通过最少水白确定)。实施例25中的胶乳耐水性最差,所述乳胶基于实施例5表面活性剂,实施例5表面活性剂与实施例2表面活性剂具有相同的结构和聚氧乙烯链长但是仅含有一个活性基团。这两种表面活性剂与实施例27和28的表面活性剂相比具有更长的聚氧乙烯链(这提高水白)。然而,具有两个活性基团和长的聚氧乙烯链的实施例26与具有一个活性基团的表面活性剂(实施例25和28)相比示出更好的性能,并且与包含具有非常短的聚氧乙烯链的表面活性剂的实施例27相比更好。随不透明度的变化而测量的吸水标记为随时间(1天,2天,和4天)的变化。薄膜更白表明胶乳的水敏感性越高。数据分别示于以下图2、图3和图4中。
在浸泡4天后没有发现进一步的变化。水白(水敏感性)的顺序如下并且与水点测试良好相关:
最好实施例25>实施例28>实施例27>实施例26最差
含有活性表面活性剂的木板染色制剂
将实施例25-28胶乳配制为木板染色剂。
表2(在该研究中使用的表面活性剂)
实施例 | 表面活性剂 | |
29 | POE(4)壬基苯酚硫酸铵盐 | |
30 | POE(10)烯丙基取代的壬基苯酚硫酸NH4盐 | |
31 | Ex5POE(16){DSP/1AGE}硫酸盐 | |
32 | Ex2POE(15){DSP/2AGE}硫酸盐 |
木板染色制剂的试验步骤
木板染色的配方步骤如下所示
组分 | #1 | #2 |
实施例1胶乳 | 97.5 | 97.5 |
水 | 111.2 | 111.2 |
Byk023[1] | 0.1 | 0.1 |
TINT-AYD CW5600Transpsrent RedOxide[2] | 1.2 | 1.2 |
Aqua Bead525[3] | 0.0 | 2.5 |
丁基CARBITOL溶剂[4] | 1.7 | 1.7 |
总计 | 211.7 | 214.2 |
[1]BYK-Chemie
[2]Elementis Specialties
[3]Michelman
[4]DOW
胶乳固体 | 41.9 |
凝结水平,phr | 4.1 |
总固体,重量% | 17.7 |
以体积计 | 16.3 |
每加仑重量,lb | 8.5 |
在搅拌下,以上述所列顺序将组分加入至不锈钢烧杯中。将油漆再混合15分钟。将油漆储存于1/2品脱罐中。
用Aqua Bead525蜡使用由POE(4)壬基苯酚硫酸铵盐和实施例2制成的胶乳来制备油漆,以确定该组分对水结珠(water beading)性能的影响(随着表面活性剂类型的变化)。
表面活性剂类型对水结珠的影响
木板染色性能通常通过当用水喷洒时其产生水珠的能力来说明。本质更疏水的胶乳提供优异的水结珠性。为确定配制为木板染色剂的胶乳的水结珠特性,将染色剂施加至南方黄松木板。将3g的染色剂施加至面积为3X5"的木料并且使其干燥过夜(见图5)。
第二天将水滴置于各个板的上面。拍摄照片并且测量接触角。结果示于图6。水接触角更高表明染色制剂疏水性越高。
接触角测量
POE(4)壬基苯酚硫酸铵盐的接触角是最小的,并且因此为最不疏水的涂层。这是由于表面活性剂没有连接至胶乳并且自由迁移至空气/涂层界面,从而降低了水滴的表面张力所导致的。用活性表面活性剂制备的其他三个胶乳说明具有显著更高的接触角,且实施例32具有最高接触角。实施例31和32的接触角的对比示出第二活性基团大大提高了涂层的疏水性。
实施例30和31之间的对比示出实施例31的更长的聚环氧乙烷链降低了接触角和涂层的疏水性。实施例32——具有与实施例31相同长度的聚环氧乙烷链但是含有两个活性基团——具有更大的接触角,甚至比实施例30的接触角还高,实施例30具有更短的聚环氧乙烷链。
加入Aqua Bead蜡,实施例29的接触角显著提高,但是没有提高至不含Aqua Bead蜡的两个最好的表面活性剂的水平,最好的表面活性剂是POE(IO)烯丙基取代的壬基苯酚硫酸NH4盐(实施例30)和实施例2(在实施例32的胶乳中)。这说明可聚合的表面活性剂可以赋予胶乳优异的水结珠性能。这使得提高耐久性时制剂中可含有较少的蜡添加剂。
染色剂气味
对最终的染色剂进行简单的气味测试。将染色剂置于1/2品脱罐中并且使其静置1小时。从顶部空间取样并且评估相对气味。结果示于以下:
最强气味Ex29>>Ex30>Ex31=Ex32最弱气味
本说明书中所引用的所有文献的内容和那些文献中所引用的文献,如果那些引用在本文中注明,则其全文以引用的方式纳入本说明书。
虽然本发明的许多实施方案已在上面公开并且包括目前优选的实施方案,但是许多其他的实施方案和变型实施方案可以落在本申请和以下所附权利要求的范围内。因此,所提供的优选的实施方案和实施例的细节不应理解为限制作用。应理解在此使用的术语仅为描述性的而不是限制性的并且可以在不偏离所请求保护的本发明的实质或范围下做出各种变型、大量的等价方案。
本申请由Isaac A.Angres提交,注册号为29,765。
Claims (8)
1.一种化合物,选自以下:
其中,R=CH3或CH2CH3,n=1、2、3;x为2-10,y为0-200,z为5-40;Z为SO3 -或PO3 2-,并且M+为Na+、K+、NH4 +,或烷醇胺;
其中R=CH3或CH2CH3,n=1、2、3;x为2-10,y为0-200,z为5-40;
其中R1为C10-24烯基或环烷基,R2=CH3、CH2CH3、C6H5或C14H29;x为2-10,y为0-200,z为5-40;Z为SO3 -或PO3 2-,并且M+为Na+、K+、NH4 +,或烷醇胺;和
其中R1为C10-24烯基或环烷基,R2=CH3、CH2CH3、C6H5或C14H29;x为2-10,y为0-200,z为5-40。
2.一种聚合物胶乳,其中结合了一种或多种权利要求1中的化合物。
3.一种涂料制剂,其中结合了一种或多种权利要求1中的化合物。
4.一种涂料制剂,结合了权利要求2的胶乳。
5.一种可UV固化的涂料制剂,其中结合了一种或多种权利要求1中的化合物。
6.一种颜料分散体,其中结合了一种或多种权利要求1中的化合物。
7.一种颜料,其中结合了一种或多种权利要求1的化合物。
8.一种二氧化钛颜料,其中结合了一种或多种权利要求1的化合物。
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PCT/US2012/052919 WO2013033256A1 (en) | 2011-08-29 | 2012-08-29 | New reactive surfactants for emulsion polymerization, pigment dispersion, and uv coatings |
US13/598,437 US9051341B2 (en) | 2011-08-29 | 2012-08-29 | Reactive surfactants for emulsion polymerization, pigment dispersion, and UV coatings |
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CN (1) | CN104053697B (zh) |
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CA2847280A1 (en) | 2013-03-07 |
US9051341B2 (en) | 2015-06-09 |
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CN104053697A (zh) | 2014-09-17 |
EP2751166A4 (en) | 2015-04-08 |
EP2751166B1 (en) | 2018-01-24 |
WO2013033256A1 (en) | 2013-03-07 |
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CA2847280C (en) | 2019-09-24 |
KR20140117344A (ko) | 2014-10-07 |
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