CN107849163B - 衣康酸酯的乳液聚合 - Google Patents
衣康酸酯的乳液聚合 Download PDFInfo
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- CN107849163B CN107849163B CN201680036039.6A CN201680036039A CN107849163B CN 107849163 B CN107849163 B CN 107849163B CN 201680036039 A CN201680036039 A CN 201680036039A CN 107849163 B CN107849163 B CN 107849163B
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- 238000007720 emulsion polymerization reaction Methods 0.000 title abstract description 41
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical class OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 title abstract description 13
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- 238000000034 method Methods 0.000 claims abstract description 19
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 12
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- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 claims description 11
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- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 5
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- 150000003254 radicals Chemical class 0.000 claims description 4
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- 125000001072 heteroaryl group Chemical group 0.000 claims description 3
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- -1 alkyl itaconates Chemical class 0.000 abstract description 10
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 abstract description 8
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- OGVXYCDTRMDYOG-UHFFFAOYSA-N dibutyl 2-methylidenebutanedioate Chemical compound CCCCOC(=O)CC(=C)C(=O)OCCCC OGVXYCDTRMDYOG-UHFFFAOYSA-N 0.000 description 23
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- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 11
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 11
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 9
- DTPCFIHYWYONMD-UHFFFAOYSA-N decaethylene glycol Polymers OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO DTPCFIHYWYONMD-UHFFFAOYSA-N 0.000 description 9
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- 230000015572 biosynthetic process Effects 0.000 description 8
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- 238000004458 analytical method Methods 0.000 description 7
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- 230000010354 integration Effects 0.000 description 6
- JYMCPGMXHKUZGC-UHFFFAOYSA-N bis(2-methylpropyl) 2-methylidenebutanedioate Chemical compound CC(C)COC(=O)CC(=C)C(=O)OCC(C)C JYMCPGMXHKUZGC-UHFFFAOYSA-N 0.000 description 5
- WLHQHAUOOXYABV-UHFFFAOYSA-N lornoxicam Chemical compound OC=1C=2SC(Cl)=CC=2S(=O)(=O)N(C)C=1C(=O)NC1=CC=CC=N1 WLHQHAUOOXYABV-UHFFFAOYSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
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- 238000005481 NMR spectroscopy Methods 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 3
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- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
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- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
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- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
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- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000001902 propagating effect Effects 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229910018830 PO3H Inorganic materials 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
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- 239000012736 aqueous medium Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
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- 238000004090 dissolution Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
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- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
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- 230000002794 monomerizing effect Effects 0.000 description 1
- 238000000569 multi-angle light scattering Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000001208 nuclear magnetic resonance pulse sequence Methods 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000001448 refractive index detection Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
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- C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
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Abstract
本发明的公开内容涉及含酯官能团的衣康酸,例如称为衣康酸烷酯的衣康酸的烷基酯的乳液聚合方法。更具体地,借助乳液聚合,生产聚衣康酸聚合物的酯,并且含有50wt%衣康酸酯以及所选的粒度和分子量水平与间同立构规整度。
Description
相关申请的交叉参考
本申请要求2015年5月11日提交的美国临时申请序列号No.62/159,514的权益,在本文中通过参考将其全文引入。
发明领域
本发明涉及聚合含酯官能团的衣康酸,例如称为衣康酸烷酯的衣康酸的烷基酯。更具体地,借助乳液聚合生产聚衣康酸聚合物的酯,且它含有大于50wt%衣康酸酯以及选择的粒度和分子量水平与间同立构规整度。
背景技术
美国专利No.8,227,560报道了聚合含有侧挂羧酸基和酯基官能团的基于乙烯基类单体的方法与聚合物,例如聚合衣康酸。在部分中和的选择条件下制备聚合物,提供相对高的转化率和/或相对高的分子量值和/或选择量的重复单元立构规整度。
美国专利No.8,410,232报道了衣康酸酯适合于在水性介质中在种子粒子存在下聚合。种子粒子表示为吸附单体并聚合到所需的粒度。
Hirano等人已经评价了衣康酸酯聚合对其聚合介质的敏感度,它报道了在衣康酸二丁酯(DBI)的自由基聚合中立体特异性对聚合温度的突出依赖性。T.Hirano,S.Tateiwa,M.Seno和T.Sato,Journal of Polymer Science Part A:Polymer Chemistry,第38卷,第13期,第2487-2491页,2000年7月1日。更具体地,研究了本体聚合和形成聚(衣康酸二丁酯),且表明立构规整度的温度依赖性。在随后的研究中,确定了自由基聚合衣康酸二正丁酯表明在高于60℃的温度下,在13C NMR谱图内预料不到的共振(C-共振),存在分子内的链转移(这在高温下在聚合具有比较庞大酯基的衣康酸酯中更加频繁地发生)。参见,Tomohiro Hirano,Kazuhiro Furuya,Makiko Seno and Tsuneyuki Sato,Journal ofPolymer Science Part A:Polymer Chemistry,第40卷,第24期,第4513-4522页,2002年12月15日,“13C NMR and Electron Spin Resonance Analyses of the RadicalPolymerization of Diisopropyl Itaconate”和Tomohiro Hirano,Ryoko Takeyoshi,Makiko Seno和Tsuneyuki Sato,Journal of Polymer Science Part A:PolymerChemistry,第40卷第14期,第2415-2426页,2002年7月15日,“Chain-Transfer Reactionin the Radical Polymerization of Di-n-butyl Itaconate at High Temperatures”。另外,检验了在借助氢-键合相互作用,可与DBI单体络合的酰胺化合物存在下,自由基聚合衣康酸二丁酯,它被描述为导致具有间同立构序列的增长基团数量的变化。参见,TomohiroHirano,Kousuke Higashi,Makiko Seno和Tsuneyuki Sato,Journal of Polymer SciencePart A:Polymer Chemistry,第41卷第21期,第3463-3467页,2003年11月1日,“Effect ofHydrogen-Bonding Interaction on Radical Polymerization of Di-n-butylItaconate”和Tomohiro Hirano*,Kousuke Higashi,Makiko Seno和Tsuneyuki Sato,Journal of Polymer Science Part A:Polymer Chemistry,第42卷第19期,第4895-4905页,2004年10月1日,“Reaction Control in Radical Polymerization of Di-n-butylItaconate Utilizing a Hydrogen-Bonding Interaction”。
鉴于在本体中衣康酸酯单体对聚合条件的相对高敏感性质,本文的一个目的是考虑使用乳液聚合和相关的温度控制,以决定乳液环境是否可在所选粒度,游离酸含量,相对高分子量,相对高转化率和/或相对高水平的间同立构位置下提供聚(衣康酸烷酯)。
发明概述
聚合方法包括:
(a)供应具有下述结构的第一单体:
其中R1和R2选自烷基或芳基或环烷基,及其组合,和R3选自烷基,芳基官能团,杂芳基官能团,环烷基,杂环基或其组合;
(b)具有下述结构的第二单体:
其中R4选自氢,烷基,芳基或其本身提供羧酸官能团;
(c)任选地,含自由基可聚合的乙烯基类型单体的一种或多种单体;
通过将所述单体与表面活性剂和水溶性自由基引发剂一起置于水中,形成(a),(b),和任选地(c)的乳液,和聚合所述单体并形成相应的无规共聚物结构:
其中R5是氢原子或烷基或含有乙烯基的取代基,和R6是芳环,酯基,腈基,含有乙烯基和/或乙酸酯基的取代基,"a"的数值使得所指的重复单元以大于50wt%的水平存在,"b"的数值使得所指的重复单元以0.05至5.0wt%的水平存在,和余量是重复单元"c",它可以以0.0wt%至49.85wt%的水平存在;和
其中所述聚合物结构为粒度10nm至900nm和重均分子量数值大于或等于30,000g/mol的粒子形式。
附图简述
图1是对于通过乳液聚合,在80℃下聚合聚衣康酸二正丁酯来说,顺时转化率(wt%聚合物)对聚合时间的图表。
图2是对于通过乳液聚合,在60℃下在接种体系中聚合聚衣康酸二正丁酯来说,顺时转化率(wt%聚合物)对聚合时间的图表。
详细说明
可在本发明的乳液聚合工序中聚合的单一结构之一如下所述:
在上述中,R1和R2二者可选自烷基或芳基或环烷基,及其组合,和R3选自烷基,芳基官能团,杂芳基官能团,环烷基,杂环基或其组合。因此,上述单体提供确定羧酸酯基中酯类官能团的单体,其中特定的酯官能团可随R1和R2的选择而变化。优选地,R1和R2选自正烷基和/或异烷基,其中包括例如甲基,乙基,丙基,丁基,戊基,己基,庚基和辛基类型的官能团。在(以下描述的)后续的聚合物组合物中这种第一共聚单体的水平优选大于50wt%。因此,以上描述的第一共聚单体可优选以50.1wt%至99.95wt%的水平存在。
在本文描述的乳液聚合工序中使用的一种尤其优选的单体是具有下述结构的衣康酸二正丁酯(DnBI),其中R3是亚甲基:
另外,本发明的公开内容考虑在乳液聚合中使用第二共聚单体,所述第二共聚单体优选是提供乙烯基酸官能团的那种。它因此可包括提供酸性官能团的任何乙烯基单体,所述酸性官能团可包括有机酸官能团(-COOH)和/或无机酸度(-SO3H,-PO3H)。优选地,人们因此可包括选自丙烯酸,甲基丙烯酸酯,衣康酸,富马酸,乙烯基膦酸和/或苯乙烯磺酸中的第二共聚单体。另外,优选使用这种第二共聚单体,使得它以0.05wt%至5.0wt%的水平存在于后续的最终聚合物组合物内。更优选这种共聚单体可在最终的聚合物组合物内以0.1wt%至4.0wt%的水平,和最优选以0.15wt%至3.0wt%的水平存在。
提供乙烯基-基酸官能团的一种优选的第二共聚单体可具有下述结构:
其中R4可以是氢,烷基,芳基,或本身提供羧酸官能团的基团,例如-CH2COOH。因此,值得注意的是,选择使用以上提到的提供酸性官能团的乙烯基单体,使得当作为例如涂层使用后续的聚合物胶乳且在相对高剪切,例如大于或等于1,000sec-1或在1,000sec-1至lxlO6sec-1范围内施加到给定表面上时,这种胶乳显示出剪切稳定性。提到剪切稳定性应当理解为避免胶乳凝结,使得聚合物和水环境相分离和分散不存在(los t)。另外,存在所指的酸官能团独立地促进粘合到给定表面,例如玻璃,金属,纤维等上,其中该表面具有吸引酸性基团的极性官能团。此外,高于5.0wt%提供酸性官能团的乙烯基单体的操作将导致吸湿并吸收过量水的聚合物体系。
此外,本发明的公开内容进一步考虑任选地、可在后续的乳液聚合中包括一种或多种共聚单体,所述共聚单体可包括任何自由基可聚合的乙烯基单体,其中包括,但不限于,一种或多种苯乙烯,丙烯腈,乙酸乙烯酯,丙烯酸酯类,甲基丙烯酸酯类和/或双官能团乙烯基单体,例如二乙烯基苯或乙二醇二甲基丙烯酸酯。在后续的聚合物内这种额外的共聚单体的水平可优选在0.0wt%至49.85wt%的水平下。
因此,根据上面可理解,通过本文描述的乳液工序形成的后续的聚合物结构可具有下述通式结构:
在上述中,R1,R2,R3和R4如前所述,R5可以是氢原子或烷基,和R6可以是芳环,丙烯酸酯基,和/或乙酸酯基。"a"的数值优选使得所指的重复单元以大于50wt%的水平存在,"b"的数值使得所指的含一个或多个酸取代基的乙烯基单体优选以0.05至5.0wt%的水平存在,和余量是重复单元"c",它可以以0.0wt%至49.85wt%的水平存在。因此,重复单元"c"应当理解为任选的。优选地,重复单元"c"选自苯乙烯,丙烯腈,丙烯酸酯类,甲基丙烯酸酯类和乙酸乙烯酯。另外,当所指的重复单元"c"包括两个含有乙烯基官能团的取代基时,重复单元"c"仅仅以最多10.0wt%的水平存在,和更优选范围为0.1至10.0wt%,和甚至更优选0.1至5.0wt%。
一种尤其优选的组合物如下所述:
在上述中,"a"的数值优选在大于60%至99.95wt%的水平下,"b"的数值优选在0.5至2.0wt%的水平下,和余量是重复单元"c",它优选以低于39.5%至0.0wt%的水平存在。另外,R5和R6分别优选是氢或甲基和羧酸烷酯。
接下来注意到,本文的乳液聚合是提供控制粒度而进行的聚合,这意味着粒度优选落在10nm至900nm,更优选30nm至600nm范围内,和最优选在50nm至500nm范围内。而且,发现控制粒度在这一范围内提供相对快速的聚合动力学,和特别地,比相应本体聚合工序相对快速的聚合动力学。这将在本文中更加充分地讨论。
本文的乳液聚合还是通过NMR技术,相对于三单元组结构的分析,以可促进所需水平的立构规整度的方式进行的聚合。更具体地,使用本文的乳液聚合技术,已发现,人们可形成相对更多的13C NMR间同立构三单元组,当乳液聚合温度在相对低温下时。优选地,当温度从例如80℃下降到60℃时,观察到相对较大量的间同立构13C NMR三单元组。因此,在本发明公开内容的宽的上下文中,当前述单体在本文引证的组成选项(options)下,在等于或低于60℃的温度下结合前述单体,促进相对较高水平的间同立构位置时,将促进相对较大量的间同立构规整度。
本文的乳液聚合也是已发现提供相对低水平残留单体含量的聚合。特别地,已发现,应用到本文所描述的组合物上的乳液聚合工序提供范围为0.001wt%至15.0wt%的残留单体含量。
工作例
以下讨论了许多实验,这些实验涉及与本发明公开内容的乳液聚合技术相比,利用本体聚合的对比例。尽管聚(衣康酸二正丁酯)用作例举单体,但考虑本文的结构应用到本文描述的一般组合物上,其中包括前述共聚物类型结构。
实施例1
在80℃下本体聚合并形成PDnBI
在20ml小瓶中,向10g衣康酸二正丁酯中添加0.05g AIBN。经48小时加热样品到80℃。将该样品溶解在99.9%异丙醇中,且随后在水中沉淀。回收0.4g聚合物并分析。通过GPC积分测定的转化率:56%。
实施例2
在80℃下乳液聚合并形成PDnBI
向1升圆底烧瓶中添加233g水,62.6g衣康酸二正丁酯,2.4g十二烷基二苯基氧化物二磺酸钠,2.4g聚氧乙烯(10)油基醚,1.45g低分子量预蒸煮的水溶性淀粉,和1.2g过硫酸钠。在80℃下经2小时分批投料该混合物。在随后12小时内连续供料58.3g水,208.6g衣康酸二正丁酯,4.9g十二烷基二苯基氧化物二磺酸钠,4.9g聚氧乙烯(10)油基醚,和1.2g过硫酸钠。在供料之后,在80℃下保持该混合物另外7小时。在2天内通过3.5K MWCO透析盒,清洁2g胶乳。回收0.4g聚合物并分析。通过动态光散射(UPA),测定粒度:平均粒径,体均Dv=133nm,平均粒径,数均Dn=86nm。固体含量:45%,通过湿气分析。通过GPC积分测定的转化率:85.4%。
实施例3
在60℃下本体聚合并形成PDnBI
在20ml小瓶中,向10g衣康酸二正丁酯中添加0.05g AIBN。经48小时加热样品到60℃。将该样品溶解在99.9%异丙醇中,且随后在水中沉淀。回收0.4g聚合物并分析。通过GPC积分测定的转化率:52%。
实施例4
在60℃下乳液聚合并形成PDnBI
向1升圆底烧瓶中添加233g水,62.6g衣康酸二正丁酯,2.4g十二烷基二苯基氧化物二磺酸钠,2.4g聚氧乙烯(10)油基醚,1.45g低分子量预蒸煮的水溶性淀粉,和1.2g过硫酸钠。在60℃下经2小时分批投料该混合物。在随后12小时内连续供料58.3g水,208.6g衣康酸二正丁酯,4.9g十二烷基二苯基氧化物二磺酸钠,4.9g聚氧乙烯(10)油基醚,和1.2g过硫酸钠。在供料之后,在60℃下保持该混合物另外7小时。在2天内通过3.5K MWCO透析盒,清洁2g胶乳。回收0.4g聚合物并分析。通过UPA,测定粒度:Dv=127nm,Dn=100nm。固体含量:41%,通过湿气分析。通过GPC积分测定的转化率:91.6%。
实施例5
在60℃下本体聚合并形成PDnBI和PDiBI的共聚物
在20ml小瓶中,向4g衣康酸二正丁酯和6g衣康酸二异丁酯的混合物中添加0.05gAIBN。经48小时加热样品到60℃。将该样品溶解在99.9%异丙醇中,且随后在水中沉淀。回收0.4g聚合物并分析。本文中这一样品鉴定为COP 60C Bulk。
实施例6
在60℃下乳液聚合并形成PDnBI和PDiBI的共聚物
向1升圆底烧瓶中添加233g水,25g衣康酸二正丁酯,37.6g衣康酸二异丁酯,2.5g甲基丙烯酸,2.4g十二烷基二苯基氧化物二磺酸钠,1.2g聚氧乙烯(10)油基醚,1.45g低分子量预蒸煮的水溶性淀粉,和1.2g过硫酸钠。在60℃下经2小时分批投料该混合物。在随后12小时内连续供料58.3g水,83.4g衣康酸二正丁酯,125.2g衣康酸二异丁酯,4.9g甲基丙烯酸,4.9g十二烷基二苯基氧化物二磺酸钠,2.45g聚氧乙烯(10)油基醚,和1.2g过硫酸钠。在供料之后,在60℃下保持该混合物另外7小时。在2天内通过3.5K MWCO透析盒,清洁2g胶乳。回收0.4g聚合物并分析。通过UPA,测定粒度:Dv=140nm,Dn=82nm。固体含量:39%,通过湿气分析。通过GPC积分测定的转化率88.7%。这一样品鉴定为COP 60C LTX。
实施例7
在60℃下乳液聚合并形成聚(nBI,iBI,BA,MAA)的共聚物
向5L夹套式反应器中添加1337.1g种子胶乳(配方如下)。在60℃下保持反应器。在12小时内连续进料628.6g水,720g衣康酸二正丁酯,480g衣康酸二异丁酯,32g甲基丙烯酸,28g十二烷基二苯基氧化物二磺酸钠,14.3g聚氧乙烯(10)油基醚,和6.9g过硫酸钠。在供料之后,在60℃下保持该混合物另外2.5小时,并升温至73.6℃。向该反应器中添加1.71g过硫酸钠和57g水。在随后的2小时内连续进料171.4g丙烯酸导致到该反应器中。在73.6℃下保持反应另外4小时以完成。通过UPA,测定粒度:Dv=81nm,Dn=64nm。固体含量:46%,通过湿气分析。通过GPC积分测定的转化率87.2%。这一样品表示为COP+BA 60CLTX。
种子胶乳的配方:向5L夹套式反应器中添加2812g水,253g衣康酸二正丁酯,168.8g衣康酸二异丁酯,28.2g乙二醇二甲基丙烯酸酯,33.8g十二烷基二苯基氧化物二磺酸钠,16.8g聚氧乙烯(10)油基醚,和8.4g过硫酸钠。在60℃下经12小时分批投料该混合物。
实施例8
向1L圆底烧瓶中添加234g种子胶乳(参见实施例7),0.6g过硫酸钠和60g水。在60℃下保持该反应器。在12小时内连续进料50g水,240g衣康酸二正丁酯,4.8g甲基丙烯酸,4.9g十二烷基二苯基氧化物二磺酸钠,2.5g聚氧乙烯(10)油基醚,和0.6g过硫酸钠。在供料完成之后,在60℃下保持该混合物另外7小时。通过UPA,测定粒度:Dv=84nm。Dn=71nm。固体含量:42.3%,通过湿气分析。
13C NMR分析
使用13C NMR分析,测定上述提到样品的立构规整度。在5mm NMR管中,将每一样品溶解在作为溶剂的CDCl3中。所使用的仪器是在100.52MHz的碳频下操作的Varian Mercury400。探针是适合于13C和1H(ATB_PFG400)的宽带探针。该实验是1D,其中脉冲序列是s2pul。接收器增益设定为24。样品温度为55℃。松弛延迟设定为12秒和脉冲宽度设定为2.4毫秒。总的扫描次数在18小时内为4728次。将数据输入到Varian Mnova NMR处理软件版本10.0中。处理的数据包含64K数据点和10Hz指数倍频(线变宽),和在线拟合之前,采用聚合的标称(polynomial)基线校正。去旋(de-convolution)软件赋予峰高和峰宽,且对于168至178ppm的光谱区域来说,具有最小残留(误差)。计算外消旋三单元组分数所使用的峰面积。
13C NMR说明:根据本文描述的Hirano的工作,迄今为止,下述立体规整的三单元组归于聚合物主链的α位置上的羰基:来自174.9至175.9ppm的间同立构三单元组"rr",来自174.3至174.9的杂同立构三单元组"mr",和来自173.4至174.3ppm的全同立构三单元组"mm"。通过Bernoulli方法,基于内消旋二单元组"mm":P间同立构=(1-mm)^2的可能性,计算间同立构规整度。显示出间同立构规整度大于0.5625的聚合物被认为优先间同立构。
C13 NMR结果
根据上述可看出,使用本文的乳液聚合技术,已发现,人们可形成相对更多的13CNMR间同立构三单元组,当乳液聚合温度为相对低温时。特别地,在60℃下的乳液聚合表明13C NMR间同立构三单元组的水平大于或等于67%。因此,本文认为人们可容易地从60℃升温到较高温度(例如70℃),以实现较低的13C NMR间同立构三单元组水平,但仍然等于或高于58%,或者等于或高于61%,或者如所描述的,等于或高于67%。
分子量分析
通过多角光散射结合凝胶渗透色谱法(MALS-GPC),分析分子量。通过在四氢呋喃中溶解,制备WYATT Technology miniDAWN TREOS.dn/dc(mL/g)=0.068。洗脱剂流速:0.350ml/min。使用折射指数检测。Mn是指数均分子量。Mp是指峰值分子量(即在分子量vs洗脱体积的图表上的最高峰值分子量)。Mw是指重均分子量。
MW分析
样品 | Dn/Dc(ml/g) | Mn(g/mol) | Mp(g/mol) | Mw(g/mol) |
PDnBI Bulk 80℃ | 0.068 | 23,680 | 26,030 | 28,940 |
PDnBI 80℃LTX | 0.068 | 17,420 | 18,950 | 22,600 |
PDnBI Bulk 60℃ | 0.068 | 134,600 | 150,500 | 161,500 |
PDnBI 60℃LTX | 0.068 | 69,330 | 77,860 | 112,200 |
COP 60℃Bulk | 0.068 | 70,900 | 200,000 | 240,000 |
COP 60℃LTX | 0.068 | 50,300 | 100,000 | 152,000 |
COP+BA60℃LTX | 0.068 | 45,400 | 83,000 | 170,000 |
根据上述可看出,应用到含有酯官能团的衣康酸单体的所指聚合上的本文的乳液聚合工序表明当聚合温度下降时,MW值增加。更具体地,当乳液聚合的温度从例如80℃下降到60℃时,可看出,样品PDnBI 80C LTX表明对于所有测量的分子量参数Mn,Mp和Mw来说,MW值突出地增加。因此可理解,通过采用本文的乳液聚合工序,人们可聚合所指的具有酯官能团的衣康酸单体,使得所获得的MW值大于或等于30,000。因此,考虑通过本文的乳液聚合工序获得的MW值可落在30,000-1,000,000范围内,优选40,000至1,000,000,最优选50,000至500,000。同样值得注意的是在本文的乳液聚合单体包括二乙烯基单体的情况下,本文后续形成的聚合物可使得它们以微凝胶(即交联离子)形式形成,所述微凝胶通常不可溶且在本文报道的分子量范围内没有考虑,但仍然落在本发明公开内容的范围内。
接下来的注意力涉及图1,它是下表中针对在80℃下乳液聚合衣康酸二正丁酯(PDnBI)而鉴定的数据来说,顺时转化率(wt%聚合物)vs聚合时间的图表。提到顺时转化率是指在任何给定的时间点处,聚合物对结合的聚合物和单体之比,而与随后在所描述的分批乳液聚合期间添加进一步的单体的意图无关。
聚合时间vs顺时转化率(PDnBI)
接下的注意力涉及图2,它是下表中根据实施例8,针对在60℃下在种子粒子体系中,乳液聚合衣康酸二正丁酯(PDnBI)而鉴定的数据来说,顺时转化率(wt%聚合物)vs聚合时间的图表。
根据上表可看出,在接种粒子乳液中,人们始于种子形式的100%聚合物。一旦添加单体,则聚合开始,和观察到顺时转化率相对高(0.75),这意味着75%引入的单体聚合。这一顺时转化率然后下降到0.57,这意味着57%现引入的所有单体聚合。可观察到顺时转化率然后下降到约0.56,这意味着56%所添加的单体转化成聚合物。进一步添加单体通常没有改变这一数值。在12小时处,添加单体完成,在这一点处,顺时转化率增加,这意味着聚合进行且开始消耗可获得的单体。
在典型的本体间歇聚合中,例如这一公开内容的本体实例中,采用100%单体引发聚合。衣康酸二烷酯单体是相对缓慢聚合的单体,它花费长时间段达到可注意到的转化率。更具体地,在48本体聚合时间之后,转化率典型地低于56%,这在用于本体聚合DnBI的实施例1和3中观察到。
在本文报道的乳液聚合中,例如这一申请的所有胶乳实例中,在水相中引发聚合,然后快速地增长的聚合物自由基进入溶胀胶束或聚合物纳米粒子内。在这一聚合的大致头10-15分钟内,在聚合速度(R聚合物)和单体添加速度(R单体添加)之间产生平衡。在连续(典型地均匀)添加单体到反应中的乳液聚合情况下,在纳米粒子内的聚合和单体添加到反应器之间实现平衡。这导致在乳液聚合工序期间,单体浓度典型地维持在等于或低于反应聚合物纳米粒子组合物的44.0wt%下。例如,若形成10个图表的聚合物粒子,则单体浓度维持在等于或小于4.4g的水平存在。
因此,当在本文公开的乳液聚合中聚合进展时,单体浓度优选保持在20wt%至40wt%之间,相对于所存在的聚合物。也就是说,相对于增长或已有的聚合物链,存在过量单体,但仅仅达到20%至40wt%的水平。当停止单体进料时,单体被消耗,和单体浓度朝0进展,更典型地约5%至10wt%,相对于所存在的聚合物链。
在图2中列出了相当的趋势,其中观察到在60℃下,在接种乳液聚合DnBI情况下的所有时间,顺时转化率大于56.0wt%,这对应于在所有时间处单体浓度低于44.0wt%。
因此,在本文的乳液聚合工序中,最终以纳米粒子形式生产90.0wt%至100wt%聚合物,其中单体浓度小于44.0wt%。这导致增长的聚合物自由基的微环境显著不同(本体内富含单体vs本文公开的乳液聚合中贫单体)。认为这一微环境是独特的,和主要地在这些条件下仍然生产间同立构的聚衣康酸烷酯聚合物,和主要还在相对高分子量值下制造聚衣康酸烷酯聚合物(Mw值大于30,000和在30,000至1,000,000g/mol范围内)。
用另一方式描述,对于本文描述的乳液聚合来说,单体的添加速度(RM-添加)可以等于Rpoly,和另外,RM-添加也可增加到比Rpoly大最多50%,且可实现相对高的MW(Mw>30,000)和相对高的间同立构规整度(13C NMR间同立构三单元组大于或等于58%)。
Claims (3)
1.一种聚合方法,该方法包括:
(a)供应具有下述结构的第一单体:
其中R1和R2选自烷基或芳基或环烷基,及其组合,且R3选自烷基,芳基官能团,杂芳基官能团,环烷基,杂环基或其组合;
(b)供应具有下述结构的第二单体:
其中R4选自氢,烷基,芳基或其本身提供的羧酸官能团;
(c)任选地供应含自由基可聚合的乙烯基类型单体的一种或多种单体;
(d)通过将所述单体与表面活性剂和水溶性自由基引发剂一起置于水中,形成(a)、(b)和任选地(c)的乳液,和在等于或低于60℃的温度下聚合所述单体并形成相应的无规共聚物结构:
其中R5是氢原子或烷基或含有乙烯基的取代基,且R6是芳环,酯基,腈基,含有乙烯基和/或乙酸酯基的取代基,"a"的数值使得所指的重复单元以大于50wt%的水平存在,"b"的数值使得所指的重复单元以0.05至5.0wt%的水平存在,且余量是重复单元"c",它可以以0.0wt%至49.85wt%的水平存在;且
其中所述聚合物结构为粒度10nm至900nm且重均分子量数值大于或等于30,000g/mol的粒子形式,和所述聚合物结构含有等于或高于58%的13C NMR间同立构三单元组水平。
2.权利要求1的方法,其中所述聚合物粒子的Mw范围为30,000至1,000,000。
3.权利要求1的方法,其中在单体(a)、(b)和任选地(c)的浓度维持在等于或低于44.0wt%所形成的聚合物粒子的条件下进行所述聚合。
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