CN101490120A - 自分散硅氧烷共聚物及其制备方法及其用途 - Google Patents
自分散硅氧烷共聚物及其制备方法及其用途 Download PDFInfo
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- CN101490120A CN101490120A CNA2007800276607A CN200780027660A CN101490120A CN 101490120 A CN101490120 A CN 101490120A CN A2007800276607 A CNA2007800276607 A CN A2007800276607A CN 200780027660 A CN200780027660 A CN 200780027660A CN 101490120 A CN101490120 A CN 101490120A
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- Prior art keywords
- organosiloxane copolymer
- highly transparent
- acid
- water
- solvent
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Abstract
本发明涉及高度透明的有机官能硅氧烷共聚物,其可在水中自分散而无需乳化剂或保护胶体,可通过a)一种或多种烯键式不饱和有机单体和b)一种或多种硅氧烷大分子单体的自由基引发的溶液聚合获得,其特征在于c)一种或多种水溶性共聚单体在有机溶剂或溶剂混合物中共聚。
Description
本发明涉及可在水中自分散的高度透明的有机硅氧烷共聚物,也涉及利用自由基引发的溶液聚合由有机单体、硅氧烷大分子单体和水溶性共聚单体制备所述有机硅氧烷共聚物。
通过在水介质中的乳液聚合可获得可分散的有机硅氧烷共聚物的组合物,所得分散体的稳定化进一步需要乳化剂或保护胶体,例如在EP-A 1308468或EP-A 771826中所述。
EP-A 614924也描述了利用加入表面活性物质的在水中的乳液聚合制备有机硅氧烷共聚物。本文描述的方法仅适用于自由基可聚合的低分子量硅氧烷单体,因为若使用高分子量硅氧烷单体,聚合速率会降低,而且,在聚合过程中聚合物会聚集,或者共聚物乳状液的稳定性会降低。
EP-A 352339描述了利用溶液聚合制备有机硅氧烷共聚物的方法,其中硅氧烷部分包含于溶剂中的初始进料,且连续计量单体和油可溶性引发剂的混合物。然而,可以这种方式获得的共聚物在水中不可分散。这些共聚物的分散需要如乳化剂或保护胶体的分散助剂。
在EP-A 810243和JP-A 05-009248中,硅氧烷大分子单体在水乳状液中与有机单体聚合,所述聚合的操作只能使用油可溶性引发剂。涉及使用油可溶性引发剂的引发的方法的缺点是所得分散体的不充分的稳定性,所述分散体具有相分离的强烈倾向。
US-A 5618879描述了在阴离子型乳化剂和水溶性引发剂的存在下硅氧烷大分子单体和烯键式不饱和单体的混合物在水中的乳液共聚。在JP-A 05-140255中硅氧烷大分子单体溶解于有机单体中,使用阴离子型乳化剂,乳化在水中发生,且使用水溶性引发剂引发聚合。同样在此情况中的不利特征是必须使用表面活性物质,且相当大部分(超过20%)的硅氧烷大分子单体未共聚。
可分散的有机硅氧烷共聚物的已知组合物的共同特征是通过硅氧烷大分子单体与有机单体共聚制备它们需要乳化剂或保护胶体的存在。然而,可以这种方式获得的有机硅氧烷共聚物组合物具有相分离的倾向。聚合过程中的相分离导致浑浊的聚合物膜。已知在有机硅氧烷共聚物组合物中乳化剂或保护胶体的迁移对有机硅氧烷共聚物组合物的耐水性、粘合性或稳定性能具有反作用。
进一步的问题在于提供具有高硅氧烷部分的高度透明的可分散的有机硅氧烷共聚物组合物。特别地,当制备具有高于20重量%的硅氧烷部分的有机硅氧烷共聚物时,烯烃单体和硅氧烷之间的差的相容性在自由基聚合过程中由于相分离或胶凝作用而导致问题,从而使得有机硅氧烷共聚物变得浑浊。
在此背景下,本发明的目的是提供自分散、高度透明的硅氧烷共聚物,所述硅氧烷共聚物甚至在≥20重量%的硅氧烷含量下能在水中分散而无需乳化剂或保护胶体。
本发明提供了高度透明的有机硅氧烷共聚物,所述有机硅氧烷共聚物在无乳化剂或保护胶体下可在水中自分散,并可利用a)一种或多种烯键式不饱和有机单体和b)一种或多种硅氧烷大分子单体的自由基引发的溶液聚合获得,其特征在于
c)一种或多种水溶性共聚单体
在有机溶剂或溶剂混合物中共聚。
可以这种方式获得的有机硅氧烷共聚物能在水中分散而无需乳化剂或保护胶体。
优选的溶剂或在溶剂混合物中优选的溶剂组分为具有1至6个C原子的脂族醇,例如,甲醇、乙醇或丙醇,特别优选异丙醇。特别优选由异丙醇和一种或多种选自具有1至6个C原子的醇的溶剂组成的溶剂混合物。最优选的溶剂混合物为异丙醇和乙醇或者异丙醇和丙醇。
也优选水和一种或多种具有1至6个C原子的醇的混合物。特别优选异丙醇和水的混合物,优选具有2-35重量%的水部分且最优选具有10-25重量%的水部分,在每种情况下以溶剂混合物总重量计。
在制备具有以组分a)至c)的总重量计≥20重量%的硅氧烷含量的有机硅氧烷共聚物的过程中,优选使用对于硅氧烷大分子单体b)为非溶剂且对于单体a)和c)为溶剂的溶剂或溶剂混合物。在根据DIN50014的标准条件(23/50)下,硅氧烷大分子单体b)以低于5重量%在其中可溶,且在单体a)至c)中的每一个以高于5重量%在其中可溶。
在制备硅氧烷含量≥20重量%的有机硅氧烷共聚物的过程中的一个优选的溶剂为异丙醇。为了该目的,也优选由异丙醇和一种或多种选自具有1至6个C原子的醇和水的溶剂组成的溶剂混合物。特别优选的溶剂混合物为异丙醇和乙醇或异丙醇和丙醇或异丙醇和水。
在聚合中优选使用的烯键式不饱和有机单体a)为一种或多种选自具有1至15个C原子的非支化或支化脂肪酸的乙烯基酯、具有1至15个C原子的非支化或支化的醇的甲基丙烯酸酯和丙烯酸酯、芳乙烯、烯烃、二烯,或卤化乙烯的单体。
通常使用5重量%至95重量%,优选20重量%至95重量%,且更优选35-75重量%的烯键式不饱和有机单体a),在每种情况下以组分a)至c)的总重量计。
优选的乙烯酯为具有1至15个C原子的非支化或支化羧酸的乙烯酯。特别优选的乙烯酯为醋酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、2-乙基己酸乙烯酯、月桂酸乙烯酯、醋酸1-甲基乙烯酯、三甲基醋酸乙烯酯,和具有5至13个C原子的α-支化单羧酸的乙烯酯,例子为VeoVa5R、VeoVa9R、VeoVa10R或VeoVa11R(Shell的商标)。最优选的是醋酸乙烯酯。
选自丙烯酸或甲基丙烯酸的酯的优选的有机单体a)为具有1至15个C原子的非支化或支化醇的酯。特别优选的甲基丙烯酸酯或丙烯酸酯为丙烯酸甲酯、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、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸叔丁酯、甲基丙烯酸正丁酯、甲基丙烯酸异丁酯、甲基丙烯酸叔丁酯、丙烯酸2-乙基己酯,和丙烯酸降冰片酯。最优选丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸叔丁酯、丙烯酸2-乙基己酯,和丙烯酸降冰片酯(norbornyl acrylate)。
优选的二烯为1,3-丁二烯和异戊二烯。可共聚烯烃的例子为乙烯和丙烯。可共聚的芳乙烯包括苯乙烯和甲苯乙烯。在卤化乙烯中通常使用氯乙烯、偏二氯乙烯或氟乙烯,优选氯乙烯。
优选共聚的有机单体a)为醋酸乙烯酯和选自月桂酸乙烯酯、三甲基醋酸乙烯酯、乙烯基2-乙基己酸酯、如叔碳酸的乙烯酯(VeoVa9R、VeoVa10R)的α-支化羧酸的乙烯酯的其他乙烯酯;
为醋酸乙烯酯和乙烯,其任选地进一步共聚选自月桂酸乙烯酯、三甲基醋酸乙烯酯、乙烯基2-乙基己酸酯、富马酸二酯、马来酸二酯、如叔碳酸的乙烯酯(VeoVa9R、VeoVa10R)的α-支化羧酸的乙烯酯;
为乙烯和氯乙烯和一种或多种选自醋酸乙烯酯、丙酸乙烯酯、月桂酸乙烯酯、三甲基醋酸乙烯酯、乙烯基2-乙基己酸酯、如叔碳酸的乙烯酯(VeoVa9R、VeoVa10R)的α-支化羧酸的乙烯酯的乙烯酯;
为一种或多种乙烯酯和一种或多种丙烯酸酯和任选的乙烯、选自醋酸乙烯酯、月桂酸乙烯酯、叔碳酸的乙烯酯(VeoVa9R、VeoVa10R)的乙烯酯和选自丙烯酸丁酯、丙烯酸2-乙基己酯的丙烯酸酯;
为两种或两种以上丙烯酸酯和任选的1,3-丁二烯、选自甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸正丁酯、丙烯酸2-乙基己酯的丙烯酸酯;
为苯乙烯和一种或多种选自1,3-丁二烯、(甲基)丙烯酸酯、甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸2-乙基己酯、丙烯酸正丁酯、丙烯酸异丁酯或丙烯酸叔丁酯的单体。
优选的硅氧烷大分子单体b)为具有至少10个重复硅氧烷单元并具有至少一个自由基可聚合官能团的线性、支化的、环状的,和三维交联的硅氧烷(聚硅氧烷)。链长优选为10至1000个重复硅氧烷单元。链长特别优选为25至1000个重复硅氧烷单元。如链烯基的烯键式不饱和基团优选作为可聚合官能团。共聚物中的硅氧烷部分优选为5重量%至70重量%,更优选为15重量%至60重量%,最优选为25重量%至60重量%,在每种情况下以组分a)至c)的总重量计。
优选的硅氧烷大分子单体b)为具有通式R1 aR3-aSiO(SiR2O)nSiR3-aR1 a的硅氧烷,其中每个R类似或不同,且为一价,任选地取代的,在每种情况下具有1至18个C原子的烷基或烷氧基,R1为可聚合基团,a为0或1,且n为10至1000。
在通式R1 aR3-aSiO(SiR2O)nSiR3-aR1 a中,基团R的例子为甲基、乙基、正丙基、异丙基、1-正丁基、2-正丁基、异丁基、叔丁基、正戊基、异戊基、新戊基、叔戊基、如正己基的己基、如正庚基的庚基、如正辛基和异辛基(如2,2,4-三甲基戊基)的辛基、如正壬基的壬基、如正癸基的癸基、如正十二烷基的十二烷基、和如正十八烷基的十八烷基、如环戊基、环己基、环庚基的环烷基,和甲基环己基。基团R优选为具有1至6个碳原子的一价烃基,如甲基、乙基、正丙基、异丙基、正丁基、仲丁基、戊基和己基,特别优选甲基。
优选的烷氧基R为具有1至6个碳原子的那些,如甲氧基、乙氧基、丙氧基、正丁氧基,当合适时,所述烷氧基R也可被如氧化乙烯基或氧化亚甲基的氧化烯基取代。特别优选甲氧基和乙氧基。所述烷基和烷氧基R也可任选地被取代,例如被卤素、巯基、环氧官能团、羧基、酮基、烯胺基、氨基、氨基乙基氨基、异氰酸基、芳氧基、烷氧基甲硅烷基,和羟基取代。
合适的可聚合基团R1为具有2至8个C原子的链烯基。这种可聚合基团的例子为乙烯基、烯丙基、丁烯基,也为丙烯酰氧烷基和甲基丙烯酰氧烷基(其中烷基含有1至4个C原子)。优选乙烯基、3-甲基丙烯酰氧丙基、丙烯酰氧甲基,和3-丙烯酰氧丙基。
优选α,ω-二乙烯基-聚二甲基硅氧烷、α,ω-二(3-丙烯酰氧丙基)-聚二甲基硅氧烷、α,ω-二(3-甲基丙烯酰氧丙基)-聚二甲基硅氧烷。在硅氧烷仅被不饱和基团取代一次的情况中,优选α-单乙烯基-聚二甲基硅氧烷、α-单(3-丙烯酰氧丙基)-聚二甲基硅氧烷、α-单(丙烯酰氧甲基)聚二甲基硅氧烷、α-单(3-甲基丙烯酰氧丙基)-聚二甲基硅氧烷。在单官能聚二甲基硅氧烷的情况中,烷基或烷氧基位于链的另一端,例如甲基或丁基。
也优选线性或支化的二乙烯基-聚二甲基硅氧烷和线性或支化的单乙烯基-聚二甲基硅氧烷和/或未官能化的聚二甲基硅氧烷(后者不具有可聚合基团)的混合物。乙烯基位于链端。这种混合物的例子为来自Wacker Chemie AG的无溶剂 6系列(支化的)或 9系列(非支化的)的硅氧烷。在二元或三元混合物的情况中,非官能聚二烷基硅氧烷的部分高至15重量%,优选高至5重量%;单官能聚二烷基硅氧烷的部分高至50重量%;且双官能聚二烷基硅氧烷的部分至少为50重量%,优选至少为60重量%,在每种情况下以硅氧烷大分子单体总重量计。
最优选的硅氧烷大分子单体b)为α,ω-二乙烯基-聚二甲基硅氧烷。
优选的水溶性共聚单体c)为烯键式不饱和单羧酸和二羧酸或它们的盐,优选巴豆酸、丙烯酸、甲基丙烯酸、富马酸、马来酸;烯键式不饱和羰酰胺和腈类,优选丙烯酰胺和丙烯腈;富马酸和马来酸的单酯和双酯(如二乙基酯和二异丙基酯,也如马来酸酐);烯键式不饱和磺酸和/或它们的盐,优选乙烯基磺酸、2-甲基-2-丙烯-1-磺酸、2-丙烯-1-磺酸、2-丙烯酰胺-2-甲基丙磺酸;烯键式不饱和阳离子型单体,优选二烯丙基二甲基氯化铵(DADMAC)、氯化3-三甲基铵丙基(甲基)-丙烯酰胺(MAPTAC)、氯化2-三甲基铵乙基(甲基)丙烯酸酯;烯键式不饱和磷酸和/或它们的盐,优选乙烯基磷酸;烯键式不饱和羟基酯,优选甲基丙烯酸2-羟乙酯、甲基丙烯酸羟丙酯、丙烯酸2-羟乙酯、丙烯酸羟丙酯、1-烯丙基甘油醚;烯键式不饱和氨基官能单体,优选甲基丙烯酸2-二甲基氨乙酯、3-二甲基氨丙基甲基丙烯酰胺、氯化3-三甲基铵-丙基甲基丙烯酰胺、甲基丙烯酸2-叔丁基氨乙酯、盐酸烯丙基N-(2-氨乙基)氨基甲酸酯、盐酸烯丙基N-(6-氨己基)氨基甲酸酯、烯丙基N-(3-氨丙基)盐酸、烯丙胺、乙烯基吡啶。
特别优选的水溶性共聚单体c)为巴豆酸、丙烯酸、甲基丙烯酸、二烯丙基-二甲基氯化铵(DADMAC)、2-甲基-2-丙烯-1-磺酸、2-丙烯-1-磺酸或2-丙烯酰胺-2-甲基丙磺酸。
通常使用以所用的组分a)至c)的总重量计1重量%至30重量%,优选2重量%至10重量%,且更优选2-5重量%的水溶性共聚单体c)。
有机硅氧烷共聚物在水中的可分散性由共聚单体单元c)的极性官能团的相互作用引起,并取决于占有机硅氧烷共聚物的总重量的比例的共聚单体单元c)的部分。包含酸性或碱性共聚单体单元c)的有机硅氧烷共聚物的可分散性能通过加入酸、碱和/或缓冲剂提高,其中所述酸性或碱性共聚单体单元c)在中性水中不足以离子形式存在。在具有含羧基的共聚单体单元c)的有机硅氧烷共聚物的情况中,优选≥7.5的pH值。
优选有机硅氧烷共聚物,其包含一种或多种选自醋酸乙烯酯、月桂酸乙烯酯、VeoVa9R、VeoVa10R,或VeoVa11R的有机单体单元a),和一种或多种选自α,ω-二乙烯基-聚二甲基硅氧烷、α,ω-二(3-丙烯酰氧丙基)-聚二甲基硅氧烷,或α,ω-二(3-甲基丙烯酰氧丙基)-聚二甲基硅氧烷的硅氧烷大分子单体单元b),和一种或多种选自巴豆酸、乙烯基磺酸,或二烯丙基二甲基氯化铵(DADMAC)的共聚单体单元c),和,若需要,另外的辅助单体单元和,若需要,乙烯,单个单体的重量分数合计达100重量%。
合适的辅助单体为水解形式的可聚合的硅烷和巯基硅烷。优选γ-丙烯酰-和γ-甲基丙烯酰氧丙基-三(烷氧基)硅烷、α-甲基丙烯酰氧甲基三(烷氧基)硅烷、γ-甲基丙烯酰氧丙基甲基二(烷氧基)硅烷、乙烯基烷基二(烷氧基)硅烷,和乙烯基三(烷氧基)硅烷,能使用的烷氧基例如甲氧基、乙氧基、甲氧基乙烯、乙氧基乙烯、甲氧基丙二醇醚或乙氧基丙二醇醚基团。其例子为乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三丙氧基硅烷、乙烯基三异丙氧基硅烷、乙烯基三(1-甲氧基)异丙氧基硅烷、乙烯基三丁氧基硅烷、乙烯基三乙酰氧基硅烷、3-甲基丙烯酰氧丙基三甲氧基硅烷、3-甲基丙烯酰氧丙基甲基二甲氧基硅烷、甲基丙烯酰氧甲基三甲氧基硅烷、3-甲基丙烯酰氧丙基三(2-甲氧基乙氧基)硅烷、乙烯基三氯硅烷、乙烯基甲基二氯硅烷、乙烯基三(2-甲氧基乙氧基)硅烷、三乙酰氧基乙烯基硅烷、3-(三乙氧基甲硅烷基)丙基琥珀酐硅烷。也优选3-巯丙基三乙氧基硅烷、3-巯丙基三甲氧基硅烷和3-巯丙基甲基二甲氧基硅烷。
进一步合适的辅助单体为官能化的(甲基)丙烯酸酯和官能化的烯丙基醚和乙烯基醚,特别为羟烷基官能化的,如羟乙基(甲基)丙烯酸酯,或取代或未取代的氨烷基(甲基)丙烯酸酯,或如N-乙烯吡咯烷酮的环状单体,或N-乙烯甲酰胺。
通常所用的辅助单体的部分以有机单体a)的总重量计高至10重量%。
本发明进一步提供了制备高度透明的有机硅氧烷共聚物的方法,所述有机硅氧烷共聚物在无乳化剂或保护胶体下可在水中自分散,并可利用a)一种或多种烯键式不饱和有机单体和b)一种或多种硅氧烷大分子单体的自由基引发的溶液聚合获得,其特征在于
c)一种或多种水溶性共聚单体
在有机溶剂或溶剂混合物中共聚。
通常在20℃至130℃,更特别在60℃至90℃的温度间隔内进行所述聚合。
在初始进料中包括反应混合物的所有或单独组分,或在初始进料中包括它们的一些并随后计量加入反应混合物的组分的剩余部分或反应混合物的单独组分的剩余部分,或通过无初始进料的计量方法进行所述聚合。优选的程序为在初始进料中包括所有的硅氧烷大分子单体b)、共聚单体c)的部分和溶剂,并一起或分别地计量加入单体的剩余部分。进一步优选在初始进料中包括一些引发剂(优选为3重量%至50重量%)并计量加入剩余部分。特别优选在初始进料中包括所有的溶剂、硅氧烷大分子单体b)和一部分有机单体a)和共聚单体c),并计量加入剩余单体。
以分批过程的形式,在初始进料中包括所有的单体、溶剂和一部分引发剂,并计量加入或按份加入剩余引发剂。
当使用由例如异丙醇和水组成的溶剂混合物时,优选在初始进料中包括所有共聚单体和一部分引发剂,并计量加入水溶性共聚单体的剩余部分和引发剂的剩余部分。
如单独组分的计量、计量速率或引发剂数量的加工参数能以已知的方式影响有机硅氧烷共聚物的分子量和在有机硅氧烷共聚物中水溶性共聚单体单元c)的分布。
通过本发明的方法也可能获得有机硅氧烷共聚物的高固体含量的聚合物溶液,其中固体含量为25%至90%,固体含量优选为30%至75%,且固体含量更优选为30%至70%。
当聚合终止时,能使用已知方法通过后聚合去除残余单体。也能利用蒸馏或汽提法,优选在减压下去除挥发性残余单体和其他挥发性组分。
所用的引发剂为油可溶性引发剂,如过氧化-2-乙基己酸叔丁酯(TBPEH)、过氧化三甲基醋酸叔丁酯(PPV)、过氧化新癸酸叔丁酯(TBPND)、过氧化二苯甲酰、过氧化三甲基醋酸叔戊酯(TAPPI)、过氧化二碳酸二(2-乙基己)酯(EHPC)、过氧化1,1-双(叔丁基)-3,3,5-三甲基环己烷,和过氧化二碳酸二(4-叔丁基环己)酯。其他合适的油可溶性引发剂为如偶氮二异丁腈(AIBN)的偶氮引发剂。
与如乙烯和氯乙烯的气体单体的共聚通常在1和100barabs之间的压力下操作。
在适于使用通常的调节剂时可能控制分子量,所述调节剂的例子为如异丙醇的醇、如乙醛的醛、氯化合物、如正十二硫醇、叔十二硫醇的硫醇、巯基丙酸(酯)。
优选利用蒸馏,特别优选在真空和/或高温下完成通过从溶剂中以及,适当时,从反应混合物的其他组分中分离的有机硅氧烷共聚物的分离。所述有机硅氧烷共聚物以固体形式获得。或者能通过蒸汽蒸馏(汽提)去除溶剂,由此直接制得水分散体形式的有机硅氧烷共聚物。
本发明进一步提供了高度透明的有机硅氧烷共聚物的水分散体,所述有机硅氧烷共聚物在无乳化剂或保护胶体下可在水中自分散,并可利用a)一种或多种烯键式不饱和有机单体和b)一种或多种硅氧烷大分子单体的自由基引发的溶液聚合获得,其特征在于
c)一种或多种水溶性共聚单体
在有机溶剂或溶剂混合物中共聚,
所述共聚物无溶剂,
且剩余的固体分散于水中。
通过将固体形式的有机硅氧烷共聚物在搅拌下掺入水中制备有机硅氧烷共聚物的水分散体。持续剧烈搅拌和混合直至形成稳定的分散体。为了此目的,优选使用热水,所述热水更优选具有20-95℃的水温,最优选具有50-80℃的水温。在分散操作过程中,维持混合物在10-95℃的温度下。所用的搅拌器优选为锚式搅拌器。
所述有机硅氧烷共聚物的水分散体能与酸、碱或缓冲剂混合以设定pH值。
所述水分散体具有10%至40%且优选具有20%至35%的有机硅氧烷共聚物含量。
可在水中再分散的有机硅氧烷共聚物适用于粘合剂、涂层材料的用途,包括作为例如金属、膜、木材或释包衣的保护涂层,或纸处理的保护涂层(例如在织物领域(tissue sector)),作为固结纤维或其他粒状材料的粘合剂。它们也能用于纺织领域以进行织物处理、织物涂层、织物整理或作为织物涂饰剂,也能用于织物维护领域。此外它们也适合作为改性剂和作为疏水化试剂。另外,也可在擦亮剂领域中使用它们以得益。此外,所述分散体也能用作隔离剂。它们也适合用作油漆制造领域的粘结剂、粘合剂,和涂层材料,例如瓷砖粘合剂和用于一体化防热体系的粘合剂,特别是用于低排放聚合物粘合乳胶漆和聚合物粘合分散体基炼油,两者均用于内部领域和外部领域。或者它们能用作添加剂,例如在清漆中,或在如发胶、发乳或香波的化妆品制剂中。
如下的实施例用于进一步说明本发明,而不以任何方式局限本发明。
原料:
具有大约100、133,和177个重复SiOMe2单元的α,ω-二乙烯基-官能化的(VIPO 200、300、500)聚二甲基硅氧烷(PDMS)。制造商:Wacker Chemie AG
实施例1:具有羧基的有机硅氧烷共聚物(2重量%的巴豆酸)
将407.0克异丙醇、274.0克PDMS混合物、529.0克醋酸乙烯酯、91.0克月桂酸乙烯酯、18克巴豆酸,和1.6克PPV(过氧化新戊酸叔丁酯、在脂肪族中的75%强度的溶液)装入带有锚式搅拌器、回流冷凝器,和计量设备的2升玻璃搅拌罐。然后将所述初始装料在200rpm的搅拌速度下加热至75℃。当达到75℃的内部温度时,开始引发剂进料(70克异丙醇和4.1克PPV)(计量时间:2小时)。在引发剂进料结束后,在75℃进行后聚合超过2小时。这生成具有65重量%的固体含量和30重量%的聚合物中的硅氧烷部分的澄清聚合物溶液。在真空和高温下蒸出异丙醇。
再分散:将20克分离的共聚物引入带有80克热水(温度50-80℃)和氨的玻璃烧杯,且用锚式搅拌器搅拌该装料。在均化过程中监测pH。在该情况中pH必须高于8。约3小时之后获得稳定分散体。
对比实施例1:0.8重量%巴豆酸
进行的程序类似于实施例1,但巴豆酸的浓度以单体总含量计从2重量%降低至0.8重量%。使用该共聚物未获得分散体。
实施例2:具有季铵化氮基团的有机硅氧烷共聚物(4重量%的DADMAC)
将407.0克异丙醇、228.0克PDMS混合物、152.0克醋酸乙烯酯,和1.6克PPV(过氧化新戊酸叔丁酯、在脂肪族中的75%强度的溶液)装入带有锚式搅拌器、回流冷凝器,和计量设备的2升玻璃搅拌罐。然后将所述初始装料在200rpm的搅拌速度下加热至75℃。当达到75℃的内部温度时,计量如下溶液:
进料1:385克醋酸乙烯酯+110克月桂酸乙烯酯
进料2:57克DADMAC(二甲基二烯丙基氯化铵)(在水中64%强度)
进料3:13克PPV+50克异丙醇
进料1和2的计量时间为2小时且进料3的计量时间为3小时。在进料3之后,在75℃再发生后聚合1小时。这生成具有65重量%的固体含量和25重量%的聚合物中的硅氧烷部分的澄清聚合物溶液。在真空和高温下蒸出异丙醇和水。
再分散:将20克分离的共聚物引入带有80克热水(50-80℃)的玻璃烧杯,并用锚式搅拌器搅拌。约3小时之后获得稳定分散体。
实施例3:具有季铵化氮基团的有机硅氧烷共聚物(4重量%的DADMAC)
将377.0克异丙醇、30克水、228.0克PDMS混合物、537.0克醋酸乙烯酯、110克月桂酸乙烯酯,和1.6克PPV(过氧化新戊酸叔丁酯、在脂肪族中的75%强度的溶液)装入带有锚式搅拌器、回流冷凝器,和计量设备的2升玻璃搅拌罐。然后将所述初始装料在200rpm的搅拌速度下加热至75℃。当达到75℃的内部温度时,计量如下溶液:
进料1:57克DADMAC(二甲基二烯丙基氯化铵)(在水中64%强度)
进料2:13克PPV+50克异丙醇
进料1的计量时间为2小时且进料2的计量时间为3小时。在进料2之后,在75℃再发生后聚合1小时。这生成具有65重量%的固体含量和24重量%的聚合物中的硅氧烷部分的几乎澄清的聚合物溶液。在真空和高温下蒸出异丙醇和水。
再分散:将20克分离的共聚物引入带有80克热水(50-80℃)的玻璃烧杯,并用锚式搅拌器搅拌。约3小时之后获得稳定分散体。
对比实施例2:0.8重量%的DADMAC
进行的程序类似于实施例2,但DADMAC的浓度从4重量%(以单体总含量计)降低至0.8重量%。使用该共聚物未获得分散体。
实施例4:具有砜基团的有机硅氧烷共聚物(4重量%的2-甲基-2-丙烯-1-磺酸)
将373.0克异丙醇、229.0克PDMS混合物、153.0克醋酸乙烯酯,和1.6克PPV(过氧化新戊酸叔丁酯、在脂肪族中的75%强度的溶液)装入带有锚式搅拌器、回流冷凝器,和计量设备的2升玻璃搅拌罐。然后将所述初始装料在200rpm的搅拌速度下加热至75℃。当达到75℃的内部温度时,计量如下溶液:
进料1:386克醋酸乙烯酯+110克月桂酸乙烯酯
进料2:91克2-甲基-2-丙烯-1-磺酸(在水中40%强度)
进料3:13克PPV+50克异丙醇
进料1和2的计量时间为2小时且进料3的计量时间为3小时。在进料3之后,在75℃再发生后聚合1小时。这生成具有65重量%的固体含量和25重量%的聚合物中的硅氧烷部分的澄清聚合物溶液。在真空和高温下蒸出异丙醇和水。
再分散:将20克分离的共聚物引入带有80克热水(50-80℃)的玻璃烧杯,并用锚式搅拌器搅拌。在室温下约3小时之后获得稳定分散体。
对比实施例3:具有0.8重量%的2-甲基-2-丙烯-1-磺酸的有机硅氧烷共聚物
进行的程序类似于实施例1,但2-甲基-2-丙烯-1-磺酸的浓度从4重量%降低至0.8重量%(以单体总含量计)。使用该共聚物未获得分散体。
Claims (22)
1、一种高度透明的有机硅氧烷共聚物,所述有机硅氧烷共聚物在无乳化剂或保护胶体下可在水中自分散,并可利用a)一种或多种烯键式不饱和有机单体和b)一种或多种硅氧烷大分子单体的自由基引发的溶液聚合获得,其特征在于
c)一种或多种水溶性共聚单体
在有机溶剂或溶剂混合物中共聚。
2、根据权利要求1所述的高度透明的有机硅氧烷共聚物,其特征在于使用具有1至6个C原子的醇,优选异丙醇作为溶剂或作为溶剂混合物中的组分。
3、根据权利要求2所述的高度透明的有机硅氧烷共聚物,其特征在于将水加入所述溶剂或所述溶剂混合物。
4、根据权利要求1至3所述的高度透明的有机硅氧烷共聚物,其特征在于在溶剂或溶剂混合物中发生聚合,其中所述硅氧烷大分子单体b)在标准条件下具有低于5重量%的溶解度。
5、根据权利要求1至4所述的高度透明的有机硅氧烷共聚物,其特征在于存在的硅氧烷大分子单体b)的含量以组分a-c)的总重量计为≥20重量%。
6、根据权利要求1至5所述的高度透明的有机硅氧烷共聚物,其特征在于所用的烯键式不饱和有机单体a)为具有1至15个C原子的非支化或支化的脂肪酸的乙烯酯或甲基丙烯酸或丙烯酸与具有1至15个C原子的非支化或支化的醇的酯、芳乙烯、烯烃、二烯或卤化乙烯。
7、根据权利要求1至6所述的高度透明的有机硅氧烷共聚物,其特征在于所用的烯键式不饱和有机单体a)为醋酸乙烯酯,或醋酸乙烯酯和乙烯,或醋酸乙烯酯和具有5至11个C原子的α-支化单羧酸的乙烯酯,或醋酸乙烯酯和VeoVa9R和任选的乙烯,或醋酸乙烯酯和VeoVa10R和任选的乙烯,或醋酸乙烯酯和月桂酸乙烯酯和任选的乙烯,或乙烯和具有5至11个C原子的α-支化单羧酸的乙烯酯。
8、根据权利要求1至7所述的高度透明的有机硅氧烷共聚物,其特征在于所用的烯键式不饱和有机单体a)为来自丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丙酯、甲基丙烯酸丙酯、甲基丙烯酸正丁酯、甲基丙烯酸异丁酯、甲基丙烯酸叔丁酯,且更优选丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸叔丁酯、丙烯酸2-乙基己酯,或丙烯酸降冰片酯的一种或多种。
9、根据权利要求1至8所述的高度透明的有机硅氧烷共聚物,其特征在于所用的硅氧烷大分子单体b)为具有至少10个重复硅氧烷单元并具有至少一个自由基可聚合官能团的线性、支化的、环状的,和三维交联的硅氧烷。
10、根据权利要求1至9所述的高度透明的有机硅氧烷共聚物,其特征在于所用的硅氧烷大分子单体b)为具有通式R1 aR3-aSiO(SiR2O)nSiR3-aR1 a的硅氧烷,其中每个R类似或不同,且为一价,任选地取代的,在每种情况下具有1至18个C原子的烷基或烷氧基,R1为可聚合基团,a为0或1,且n为10至1000。
11、根据权利要求1至10所述的高度透明的有机硅氧烷共聚物,其特征在于所用的硅氧烷大分子单体b)为来自α,ω-二乙烯基-聚二甲基硅氧烷、α,ω-二(3-丙烯酰氧丙基)-聚二甲基硅氧烷、α,ω-二(3-甲基丙烯酰氧丙基)-聚二甲基硅氧烷、α-单乙烯基-聚二甲基硅氧烷、α-单(3-丙烯酰氧丙基)-聚二甲基硅氧烷、α-单(丙烯酰氧甲基)-聚二甲基硅氧烷、α-单(3-甲基丙烯酰氧丙基)-聚二甲基硅氧烷α,ω-二乙烯基-聚二甲基硅氧烷的一种或多种。
12、根据权利要求1至11所述的高度透明的有机硅氧烷共聚物,其特征在于所用的水溶性共聚单体c)为烯键式不饱和单羧酸或二羧酸或它们的盐,或烯键式不饱和羰酰胺或腈类,或富马酸的单酯或二酯,或马来酸的单酯或二酯,或烯键式不饱和磺酸或它们的盐,或烯键式不饱和四烷基卤化铵,或烯键式不饱和磷酸和/或它们的盐,或烯键式不饱和羟基酯,或烯键式不饱和氨基化合物。
13、根据权利要求1至12所述的高度透明的有机硅氧烷共聚物,其特征在于所用的水溶性共聚单体c)为来自巴豆酸、丙烯酸、甲基丙烯酸、二烯丙基二甲基氯化铵(DADMAC)、2-甲基-2-丙烯-1-磺酸、2-丙烯-1-磺酸或2-丙烯酰胺-2-甲基丙磺酸的一种或多种。
14、一种制备高度透明的有机硅氧烷共聚物的方法,所述有机硅氧烷共聚物在无乳化剂或保护胶体下可在水中自分散,并可利用a)一种或多种烯键式不饱和有机单体和b)一种或多种硅氧烷大分子单体的自由基引发的溶液聚合获得,其特征在于
c)一种或多种水溶性共聚单体
在有机溶剂或溶剂混合物中共聚。
15、根据权利要求14所述的制备高度透明的有机硅氧烷共聚物的方法,其特征在于在初始进料中包括所有的单体、溶剂、和一部分引发剂,并计量加入或按份加入剩余引发剂。
16、根据权利要求14所述的制备高度透明的有机硅氧烷共聚物的方法,其特征在于在溶剂中的初始进料中包括所需比例的全部硅氧烷大分子单体b)和部分共聚单体c),并一起或分别地计量加入单体的剩余部分。
17、一种高度透明的有机硅氧烷共聚物的水分散体,所述有机硅氧烷共聚物在无乳化剂或保护胶体下可在水中自分散,并可利用a)一种或多种烯键式不饱和有机单体和b)一种或多种硅氧烷大分子单体的自由基引发的溶液聚合获得,其特征在于
c)一种或多种水溶性共聚单体
在有机溶剂或溶剂混合物中共聚,
所述共聚物无溶剂,
且剩余的固体分散于水中。
18、根据权利要求1至13所述的高度透明的有机硅氧烷共聚物作为制备粘合涂料的隔离剂和涂层材料的用途。
19、根据权利要求1至13所述的高度透明的有机硅氧烷共聚物作为涂布织物、纸张、膜、木材和金属的涂层材料的用途。
20、根据权利要求1至13所述的高度透明的有机硅氧烷共聚物在制备耐候性涂料或密封剂的建筑保护中的用途。
21、根据权利要求1至13所述的高度透明的有机硅氧烷共聚物作为改性剂、疏水化试剂和擦亮剂的用途。
22、根据权利要求1至13所述的高度透明的有机硅氧烷共聚物作为清漆的添加剂,也作为化妆品的添加剂,特别是发胶和发定型剂的用途。
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JP2004075755A (ja) * | 2002-08-13 | 2004-03-11 | Mitsubishi Chemicals Corp | ポリシロキサン基含有重合体 |
DE10338479A1 (de) * | 2003-08-21 | 2005-04-14 | Wacker Polymer Systems Gmbh & Co. Kg | Silikonhaltige Polyvinylacetale |
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2006
- 2006-08-09 DE DE102006037270A patent/DE102006037270A1/de not_active Withdrawn
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2007
- 2007-08-07 KR KR1020097003757A patent/KR101197412B1/ko active IP Right Grant
- 2007-08-07 EP EP07788287.6A patent/EP2049580B8/de not_active Not-in-force
- 2007-08-07 JP JP2009523278A patent/JP2010500436A/ja active Pending
- 2007-08-07 CN CN2007800276607A patent/CN101490120B/zh not_active Expired - Fee Related
- 2007-08-07 WO PCT/EP2007/058187 patent/WO2008017671A1/de active Application Filing
- 2007-08-07 US US12/375,154 patent/US8637613B2/en not_active Expired - Fee Related
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105899584A (zh) * | 2014-01-15 | 2016-08-24 | 庄臣及庄臣视力保护公司 | 包含磺酸基团的聚合物 |
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US20100010165A1 (en) | 2010-01-14 |
KR101197412B1 (ko) | 2012-11-05 |
EP2049580B8 (de) | 2015-07-15 |
JP2010500436A (ja) | 2010-01-07 |
EP2049580B1 (de) | 2015-06-03 |
US8637613B2 (en) | 2014-01-28 |
KR20090042279A (ko) | 2009-04-29 |
CN101490120B (zh) | 2013-04-10 |
WO2008017671A1 (de) | 2008-02-14 |
DE102006037270A1 (de) | 2008-02-14 |
EP2049580A1 (de) | 2009-04-22 |
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