CN113698855A - 一种丙烯酸/有机硅纳米复合改性水性聚氨酯船舶防污涂料及其制备方法 - Google Patents
一种丙烯酸/有机硅纳米复合改性水性聚氨酯船舶防污涂料及其制备方法 Download PDFInfo
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- CN113698855A CN113698855A CN202111055467.2A CN202111055467A CN113698855A CN 113698855 A CN113698855 A CN 113698855A CN 202111055467 A CN202111055467 A CN 202111055467A CN 113698855 A CN113698855 A CN 113698855A
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- Prior art keywords
- acrylic acid
- antifouling paint
- waterborne polyurethane
- modified waterborne
- agent
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- Polyurethanes Or Polyureas (AREA)
Abstract
本发明公开了一种丙烯酸/有机硅纳米复合改性水性聚氨酯船舶防污涂料及其制备方法,以二异氰酸酯、低聚多元醇组分和羟烷基封端聚硅氧烷,制得嵌段式聚硅氧烷聚氨酯预聚体;将亲水扩链剂、小分子二醇催化剂加入进行扩链反应,然后加入TMP、PETA进行封端处理,通过点击化学法在端基引入反应位点,通过迈克尔加成反应接入MPTES;加入三乙胺成盐后,高速搅拌分散到去离子水中,得到成膜乳液;将成膜乳液与纳米SiO2颗粒、助剂等混合均匀,置于干净的四氟乙烯板中干燥成膜。本发明所制备的防污涂料表面能低,不存在毒料释放造成的污染问题,同时掺杂的纳米二氧化硅不需要表面修饰,即可与硅氧烷形成交联网络,成本降低。
Description
技术领域
本发明涉及一种丙烯酸/有机硅纳米复合改性水性聚氨酯船舶防污涂料及其制备方法,应用于低表面能防水、防污方面,为涂料技术领域。
背景技术
船舶是海洋运输业中重要的载运工具,在海洋环境中服役的过程中,船底会受到海洋生物和微生物的附着,使船壳等海洋设施受到污损,生物污损会导致船舶航行阻力增加、船体金属腐蚀:加速、海洋仪器损坏等。传统的船舶防污涂料采用释放有毒物质在服役过程中制造不利于生物附着的表面环境或杀死附着的海洋生物。这不仅会对环境造成污染,更为严重的是,有毒物质会在鱼类和贝类身体中积聚,并通过食物链进入到人类体内,对人类的健康产生直接危害。
目前在新型防污涂料中,低表面能防污涂料研究的比较成功,而水性聚氨酯涂层具有出色的机械强度、耐磨性和柔韧性,同时聚氨酯结构可设计产生的微相分离结构使其有很好的抗蛋白吸附性,能够抑制污损生物的附着,这些优良的性能使相对于其他低表面能防污涂料在机械性能方面具有明显的优势,但是其结构中亲水基团的引入导致水性聚氨酯在耐水性方面有所下降,限制了水性聚氨酯的应用。
专利CN 102633983 B公开了一种羟基封端硅氧烷改性水性聚氨酯的方法,通过加入过量的异氰酸酯组分,将羟基封端聚硅氧烷作为软段,共聚形成嵌段聚合物,在主链中形成Si-O-C键,但Si-O-C相对Si-C-O键易水解,得到的乳液稳定性较差。
专利CN 104356342 A公开了一种单组份有机硅改性水性聚氨酯的方法,通过羟基硅油与异氰酸酯组份反应形成一种主链结构的预聚物,扩链分散后乳液均一稳定,合成的乳液在耐水性、耐寒性方面明显改善,但交联程度不高,机械强度受到限制。
发明内容
本发明的目的在于提供一种低表面能丙烯酸/有机硅纳米水性聚氨酯防污涂料及其制备方法,利用结构设计与未经修饰纳米粒子形成交联网络,开发出一种无毒、耐水、低表面能、稳定性好、合成工艺简单的新型防污涂料。
为实现上述目的,本发明采用以下技术方案:
一种丙烯酸/有机硅纳米复合改性水性聚氨酯船舶防污涂料,
由以下质量百分比的原料制备而成:
成膜乳液 70-80%
助剂 4-7%
填料 5-8%
固化剂 8-15%;
所述成膜乳液包括A组分和去离子水;
所述A组分由以下质量百分比的原料制备而成:
二异氰酸酯 20-30%
聚醚多元醇 45-55%
羟烷基封端聚硅氧烷 1-10%
扩链剂 5-10%
催化剂 0.5-1%
封端剂 2.5-7.5%
接枝剂 2.5-7.5%
中和剂 1-4%
溶剂 10-15%。
优选的,所述A组分和去离子水的质量比为3:7。
优选的,所述的二异氰酸酯为:异佛尔酮二异氰酸酯(IPDI)、二苯基甲烷二异氰酸酯(MDI)和六亚甲基二异氰酸酯(HDI)中的一种;
所述的聚醚多元醇为聚四氢呋喃二醇(PTMG)或聚丙二醇(PPG);
所述的羟烷基封端硅氧烷为信越KF-6001或信越X-22-176-DX;
所述的扩链剂包括亲水扩链剂和小分子扩链剂,所述亲水扩链剂为二羟甲基丙酸(DMPA)或二羟甲基丁酸(DMBA),所述小分子扩链剂为1,4-丁二醇(BDO);
所述的催化剂为二月桂酸二丁基锡(DBTDL)或辛酸亚锡;
所述的封端剂为季戊四醇三丙烯酸酯(PETA),或三羟甲基丙烷(TMP)和季戊四醇三丙烯酸酯(PETA)的混合物;
所述的接枝剂为3-巯丙基三乙氧基硅烷(MPTES);所述接枝剂和季戊四醇三丙烯酸酯(PETA)摩尔比为1:0.9-1;
所述的中和剂为三乙胺(TEA);
所述的溶剂为丙酮(AC)或N-甲基吡咯烷酮(NMP)。
优选的,所述的助剂为润湿分散剂、防沉增稠剂和消泡剂中的一种或几种的组合;
所述的填料为纳米二氧化硅和功能填料;
所述的固化剂为亲水性异氰酸酯固化剂,亲水性异氰酸酯固化剂优选BayhydurXP2547或Bayhydur XP2655;
优选的,所述功能填料为氧化亚铜、氧化锌和氧化铁红中的一种或几种的组合。
优选的,所述润湿分散剂为BYK-345。
所述增稠剂为: TAFIGEL PUR 62。
所述消泡剂为:BYK-024。
优选的,所述羟烷基封端硅氧烷结构为:
一种丙烯酸/有机硅纳米复合改性水性聚氨酯船舶防污涂料的制备方法,成膜乳液的制备包括如下步骤:
步骤A 反应底物的预处理:将聚醚多元醇在氮气保护氛围下,升温至105~120℃,0.07MPa下减压蒸馏2~3h,得到脱水聚醚多元醇;
步骤B 预聚体的制备:待温度将至70~95℃时,向反应器中加入全部二异氰酸、脱水聚醚多元醇、羟烷基封端聚硅氧烷,机械搅拌混合均匀后,反应2-3h;
步骤C 预聚体扩链反应:升高温度至80~100℃,加入亲水扩链剂、催化剂、小分子扩链剂,继续反应1-2h;
步骤D 预聚体封端:扩链完成后,继续保持温度在80~100℃,加入封端剂,反应1~2h,后降温至30~40℃;
步骤E 点击化学反应:加入接枝剂,使-SH与引入的C=C加成反应,然后加入溶剂稀释粘度;
步骤F中和分散:将中和剂加入到封端完成的聚氨酯中,中和度控制在80%-110%之间,搅拌15min,之后分散到去离子水中,搅拌30min;
步骤G溶剂回收:在45~55℃、0.07MPa减压蒸馏,将制备的乳液中的溶剂蒸出;称量损失的去离子水质量,补加回分散体中,搅拌10分钟,得到成膜乳液。
一种丙烯酸/有机硅纳米复合改性水性聚氨酯船舶防污涂料的制备方法,包括以下步骤:
步骤H涂料互配:将制备的成膜乳液中,加入计量的填料、助剂,机械分散均匀后,按照NCO/OH=1.2:1加入固化剂,搅拌均匀,涂抹于物体表面干燥成膜。
所述步骤E点击化学反应的化学反应式为:
本发明与现有技术相比具有以下有益效果:
本发明选择羟烷基聚硅氧烷聚氨酯作为软段,预聚过程形成嵌段共聚物,引入Si-C-O、Si-O-Si结构,采用季戊四醇三丙烯酸酯(PETA)作为封端剂,一方面能够结合丙烯酸的优点有效提高水性聚氨酯涂层的耐水性及耐热性能,另一方面,能够在链端提供3个C=C反应位点, MPTES的-SH可以与丙烯酸酯的C=C发生反应,与纳米SiO2混合后MPTES的-OC2H5基团与纳米SiO2的-OH反应,以纳米SiO2为交联点合成丙烯酸/有机硅纳米复合水性聚氨酯材料。
本发明通过共聚改性的方法,采用羟烷基聚硅氧烷接入获得更多的反应位点,解决了引入量有限、分布不均匀的问题。采用PETA作为封端剂用于提供C=C,基于点击化学反应接入3-巯基丙基-三乙氧基硅烷(MPTES),MPTES的-OC2H5基团与纳米SiO2的-OH反应,以纳米SiO2为交联点合成交联网络结构,增强漆膜表面力学性能和凝结强度,阻拦水分子的进入,显著提升涂层耐水性能。
本发明硅氧烷具有“有机基团”和“无机链段”独特的化学结构,侧链上的甲基疏水且基团向外伸展包覆了结构中唯一具有较好亲水性的氧原子,使其具有很好的稳定性和疏水性。通过共聚改性在结构中引入嵌段式结构的-Si-O-Si-主链,能提供良好柔韧性的同时,防止硅氧烷链段水解,提升了改性乳液稳定性。
具体表现在以下几点:
1. 本发明主链采用羟烷基聚硅氧烷改性,主链中引入Si-C-O结构具有更好的耐水性,通过双官能团共聚反应形成一种嵌段结构,提高了了硅氧烷与聚氨酯结构的相容性,减少了水解带来的凝胶问题,增强了乳液的稳定性的。
2. 本发明加入季戊四醇三丙烯酸酯(PETA)与聚氨酯预聚体反应,制得有机硅/丙烯酸复合改性的乳液,结合了丙烯酸耐水性能好、机械强度高的特点,且共聚改性稳定性好。
3. 本发明采用点击化学法,通过在结构中引入丙烯酸酯单体(PETA)的C=C键,3-巯基丙基-三乙氧基硅烷(MPTES)充当中间媒介, MPTES的-SH可以与丙烯酸酯的C=C发生反应,引入接枝硅氧烷结构。
4. 本发明接枝的MPTES硅氧烷结构中,MPTES的-OC2H5基团可以与纳米SiO2的-OH反应,以纳米SiO2为交联点形成交联网络。
5. 本发明使用的纳米SiO2表面无需修饰,极大的降低了制造的成本,和施工的难度。
6.本发明制备流程简单,所使用的有机硅为市场售产品,所使用的溶剂易于脱除和回收,具有较高的市场应用价值。
附图说明
图1为本发明实施例1的IPDI- PPG谱图。
图2为本发明实施例1和对比例1-3产品稳定性对比图。
具体实施方式
为更好理解本发明,结合实施例进行阐述,但实施例不构成对本发明权利要求保护范围的限定。
实施例1
一种丙烯酸/有机硅纳米复合改性水性聚氨酯船舶防污涂料,包括以下步骤:
1)将聚醚多元醇在氮气保护氛围下,升温至105~120℃,0.07MPa下减压蒸馏2~3h,得到脱水聚醚多元醇;
丙烯酸/有机硅合改性水性聚氨酯乳液制备:以质量份计,将20份脱水的异佛尔酮二异氰酸酯(IPDI)、45份脱水聚丙二醇(PPG-2000) 、1份的信越KF-6001加入到三口烧瓶中,搅拌混合均匀,80℃反应3h;
再将5份二羟甲基丙酸(DMPA)、4份1,4-丁二醇(BDO)和0.5份二月桂酸二丁基锡(DBTDL)加入到反应器中,85℃反应2h,得到硅氧烷嵌段预聚体;
取3份三羟甲基丙烷(TMP)使用5份N-甲基吡咯烷酮(NMP)溶解后加入三口烧瓶中,再取5份季戊四醇三丙烯酸酯(PETA),85℃反应1小时。
降温至40℃以下加入4份3-巯丙基三乙氧基硅烷(MPTES)反应30min,加入5份丙酮稀释剂;
再加入3.5份三乙胺TEA,中和15min,机械分散到30%固含量所需的去离子水中,分散30分钟;
在45~55℃、0.07MPa减压蒸馏,减压蒸馏去除丙酮,再把损失的水补回去,搅拌10分钟,得到成膜乳液。
2)丙烯酸/有机硅纳米复合改性水性聚氨酯船舶防污涂料制备:取成膜乳液80份,加入1份BYK-345、1份BYK-024、1份TAFIGEL PUR 62,与3份氧化亚铜、1份氧化锌,1份纳米二氧化硅,在1000r/min高速搅拌下混合40min,经丝绢过滤后加入12份亲水性异氰酸酯固化剂,搅拌均匀后,涂抹于物体表面干燥成膜。
由图1 IPDI- PPG谱图可见,出现氨基甲酸酯的特征C=O的吸收峰1713 cm-1、N-H的特征峰3327 cm-1,同时NCO特征峰2270 cm-1没有出现,谱图中1102 cm-1、807 cm-1处出现Si-O-Si拉伸波动和Si-C特征峰,表明结构里存在了硅氧烷结构,羟烷基聚硅氧烷结构成功接入结构中,并且742cm-1位置出现C-S-C特征锋,Si-OH的3600-3700cm-1和-SH的2250-2600cm-1的峰消失了,表明接枝剂和偶联剂完全参与了反应。
实施例2
一种丙烯酸/有机硅纳米复合改性水性聚氨酯船舶防污涂料,包括以下步骤:
1) 将聚醚多元醇在氮气保护氛围下,升温至105~120℃,0.07MPa下减压蒸馏2~3h,得到脱水聚醚多元醇;
丙烯酸/有机硅合改性水性聚氨酯乳液制备:以质量份计,将30份脱水的六亚甲基二异氰酸酯(HDI)、45份脱水聚四氢呋喃二醇(PTMG)、5份的信越信越X-22-167-DX加入到三口烧瓶中,搅拌混合均匀, 85℃反应3h;
再将3份二羟甲基丙酸(DMPA)、2份1,4-丁二醇(BDO)和0.5份辛酸亚锡加入到反应器中,85℃反应2h,得到硅氧烷嵌段预聚体;
加5份季戊四醇三丙烯酸酯(PETA),80℃反应1小时,降温至40℃以下;
加入5份3-巯丙基三乙氧基硅烷(MPTES)反应30min,加入10份丙酮稀释剂;
后加入1.5份三乙胺TEA,中和15min,机械分散到30%固含量所需的去离子水中,搅拌30min,在45~55℃、0.07MPa减压蒸馏去除丙酮,称量损失的去离子水的质量,补加回去,搅拌10分钟,得到成膜乳液。
丙烯酸/有机硅纳米复合改性水性聚氨酯船舶防污涂料制备:取成膜乳液组分70份,加入2份BYK-345、2份BYK-024、2份TAFIGEL PUR 62,与2份氧化亚铜、2份氧化锌,5份纳米二氧化硅,在1000r/min高速搅拌下混合40min,经丝绢过滤后加入15份亲水性异氰酸酯固化剂,搅拌均匀后,涂抹于物体表面干燥成膜。
实施例3
一种丙烯酸/有机硅纳米复合改性水性聚氨酯船舶防污涂料,包括以下步骤:
1) 将聚醚多元醇在氮气保护氛围下,升温至105~120℃,0.07MPa下减压蒸馏2~3h,得到脱水聚醚多元醇;
丙烯酸/有机硅合改性水性聚氨酯乳液制备:以质量份计,将20份脱水的二苯基甲烷二异氰酸酯(MDI)、45份聚四氢呋喃二醇(PTMG) 、5份的信越X-22-167-DX加入到三口烧瓶中,搅拌混合均匀,80℃反应3h;
再将5份二羟甲基丁酸(DMBA)、5份1,4-丁二醇(BDO)和0.5份辛酸亚锡加入到反应器中,80℃反应2h,得到硅氧烷嵌段预聚体;
加3份季戊四醇三丙烯酸酯(PETA),95℃反应1小时,降温至40℃以下;
加入2份3-巯丙基三乙氧基硅烷(MPTES)反应30min,加入13份丙酮稀释剂;
后加入1.5份三乙胺TEA,中和15min,机械分散到30%固含量所需的去离子水中,搅拌30分钟;
在45~55℃、0.07MPa减压蒸馏去除丙酮,,称量损失的去离子水的质量,补加回去,搅拌10分钟,得到成膜乳液。
2) 丙烯酸/有机硅纳米复合改性水性聚氨酯船舶防污涂料制备:取成膜物质A组分80份,加入1份BYK-345、2份BYK-024、1份TAFIGEL PUR 62,与1份氧化亚铜、1份氧化锌,6份纳米二氧化硅,在1000r/min高速搅拌下混合40min,经丝绢过滤后加入8份亲水性异氰酸酯固化剂,搅拌均匀后,涂抹于物体表面干燥成膜。
对比例1
羟烷基聚硅氧烷KF-6001改性涂层包括以下步骤:
1)将聚醚多元醇在氮气保护氛围下,升温至105~120℃,0.07MPa下减压蒸馏2~3h,得到脱水聚醚多元醇;
丙烯酸/有机硅合改性水性聚氨酯乳液制备:以质量份计,将20份脱水的异佛尔酮二异氰酸酯(IPDI)、45份脱水聚丙二醇(PPG-2000) 、1份的信越KF-6001加入到三口烧瓶中,搅拌混合均匀,80℃反应3h;
再将5份二羟甲基丙酸(DMPA)、4份1,4-丁二醇(BDO)和0.5份二月桂酸二丁基锡(DBTDL)加入到反应器中,85℃反应2h,得到硅氧烷嵌段预聚体;
取3份三羟甲基丙烷(TMP)使用5份N-甲基吡咯烷酮(NMP)溶解后加入三口烧瓶中,85℃反应1小时。
降温至40℃以下加入5份丙酮稀释剂;再加入3.5份三乙胺TEA,中和15min,机械分散到30%固含量所需的去离子水中,分散30分钟;
在45~55℃、0.07MPa减压蒸馏,减压蒸馏去除丙酮,再把损失的水补回去,搅拌10分钟,得到成膜乳液。
2)羟烷基聚硅氧烷改性水性聚氨酯船舶防污涂料制备:取成膜乳液80份,加入1份BYK-345、1份BYK-024、1份TAFIGEL PUR 62,与3份氧化亚铜、1份氧化锌,1份纳米二氧化硅,在1000r/min高速搅拌下混合40min,经丝绢过滤后加入12份亲水性异氰酸酯固化剂,搅拌均匀后,涂抹于物体表面干燥成膜。
对比例2
季戊四醇三丙烯酸酯(PETA)改性涂层,包括以下步骤:
1)将聚醚多元醇在氮气保护氛围下,升温至105~120℃,0.07MPa下减压蒸馏2~3h,得到脱水聚醚多元醇;
丙烯酸/有机硅合改性水性聚氨酯乳液制备:以质量份计,将20份脱水的异佛尔酮二异氰酸酯(IPDI)、45份脱水聚丙二醇(PPG-2000)加入到三口烧瓶中,搅拌混合均匀,80℃反应3h;
再将5份二羟甲基丙酸(DMPA)、4份1,4-丁二醇(BDO)和0.5份二月桂酸二丁基锡(DBTDL)加入到反应器中,85℃反应2h,得到预聚体;
取3份三羟甲基丙烷(TMP)使用5份N-甲基吡咯烷酮(NMP)溶解后加入三口烧瓶中,再取5份季戊四醇三丙烯酸酯(PETA),85℃反应1小时。
降温至40℃以下加入5份丙酮稀释剂;
再加入3.5份三乙胺TEA,中和15min,机械分散到30%固含量所需的去离子水中,分散30分钟;
在45~55℃、0.07MPa减压蒸馏,减压蒸馏去除丙酮,再把损失的水补回去,搅拌10分钟,得到成膜乳液。
2)季戊四醇三丙烯酸酯(PETA)改性涂料制备:取成膜乳液80份,加入1份BYK-345、1份BYK-024、1份TAFIGEL PUR 62,与3份氧化亚铜、1份氧化锌,1份纳米二氧化硅,在1000r/min高速搅拌下混合40min,经丝绢过滤后加入12份亲水性异氰酸酯固化剂,搅拌均匀后,涂抹于物体表面干燥成膜。
对比例3
季戊四醇三丙烯酸酯(PETA)\3-巯丙基三乙氧基硅烷(MPTES)复合改性,包括以下步骤:
1)将聚醚多元醇在氮气保护氛围下,升温至105~120℃,0.07MPa下减压蒸馏2~3h,得到脱水聚醚多元醇;
丙烯酸/有机硅合改性水性聚氨酯乳液制备:以质量份计,将20份脱水的异佛尔酮二异氰酸酯(IPDI)、45份脱水聚丙二醇(PPG-2000)加入到三口烧瓶中,搅拌混合均匀,80℃反应3h;
再将5份二羟甲基丙酸(DMPA)、4份1,4-丁二醇(BDO)和0.5份二月桂酸二丁基锡(DBTDL)加入到反应器中,85℃反应2h,得到预聚体;
取3份三羟甲基丙烷(TMP)使用5份N-甲基吡咯烷酮(NMP)溶解后加入三口烧瓶中,再取5份季戊四醇三丙烯酸酯(PETA),85℃反应1小时。
降温至40℃以下加入4份3-巯丙基三乙氧基硅烷(MPTES)反应30min,加入5份丙酮稀释剂;
再加入3.5份三乙胺TEA,中和15min,机械分散到30%固含量所需的去离子水中,分散30分钟;
季戊四醇三丙烯酸酯(PETA)\3-巯丙基三乙氧基硅烷(MPTES)复合改性涂料制备:取成膜乳液80份,加入1份BYK-345、1份BYK-024、1份TAFIGEL PUR 62,与3份氧化亚铜、1份氧化锌,1份纳米二氧化硅,在1000r/min高速搅拌下混合40min,经丝绢过滤后加入12份亲水性异氰酸酯固化剂,搅拌均匀后,涂抹于物体表面干燥成膜。
实施例1-3结果说明丙烯酸\有机硅纳米复合改性后涂层接触角明显提高,主要是纳米二氧化硅和羟丙基聚硅氧烷能够降低表面自由能;对比案例1-3说明嵌段式硅氧烷结构和末端接枝的结构分布更均匀,与纳米二氧化硅共混后,减少了团聚现象的发生,稳定性提升。
本发明实施例1-3和对比例1-3的实验结果见表1。从表1可知,接触角角度本申请实施例1-3大于对比例1-3,吸水率申请实施例1-3小于对比例1-3,说明本申请具有良好的耐水性。
本发明实施例1和对比例1-3的稳定性对比见图2。
表1
Claims (10)
1.一种丙烯酸/有机硅纳米复合改性水性聚氨酯船舶防污涂料,其特征在于,
由以下质量百分比的原料制备而成:
成膜乳液 70-80%
助剂 4-7%
填料 5-8%
固化剂 8-15%;
所述成膜乳液包括A组分和去离子水;
所述A组分由以下质量百分比的原料制备而成:
二异氰酸酯 20-30%
聚醚多元醇 45-55%
羟烷基封端聚硅氧烷 1-10%
扩链剂 5-10%
催化剂 0.5-1%
封端剂 2.5-7.5%
接枝剂 2.5-7.5%
中和剂 1-4%
溶剂 10-15%。
2.根据权利要求1所述的一种丙烯酸/有机硅纳米复合改性水性聚氨酯船舶防污涂料,其特征在于,所述A组分和去离子水的质量比为3:7。
3.根据权利要求1所述的一种丙烯酸/有机硅纳米复合改性水性聚氨酯船舶防污涂料,其特征在于,所述的二异氰酸酯为:异佛尔酮二异氰酸酯(IPDI)、二苯基甲烷二异氰酸酯(MDI)和六亚甲基二异氰酸酯(HDI)中的一种;
所述的聚醚多元醇为聚四氢呋喃二醇(PTMG)或聚丙二醇(PPG);
所述的羟烷基封端硅氧烷为信越KF-6001或信越X-22-176-DX;
所述的扩链剂包括亲水扩链剂和小分子扩链剂,所述亲水扩链剂为二羟甲基丙酸(DMPA)或二羟甲基丁酸(DMBA),所述小分子扩链剂为1,4-丁二醇(BDO);
所述的催化剂为二月桂酸二丁基锡(DBTDL)或辛酸亚锡;
所述的封端剂为季戊四醇三丙烯酸酯(PETA),或三羟甲基丙烷(TMP)和季戊四醇三丙烯酸酯(PETA)的混合物;
所述的接枝剂为3-巯丙基三乙氧基硅烷(MPTES);所述接枝剂和季戊四醇三丙烯酸酯(PETA)摩尔比为1:0.9-1;
所述的中和剂为三乙胺(TEA);
所述的溶剂为丙酮(AC)或N-甲基吡咯烷酮(NMP)。
4.根据权利要求1所述的一种丙烯酸/有机硅纳米复合改性水性聚氨酯船舶防污涂料,其特征在于,所述的助剂为润湿分散剂、防沉增稠剂和消泡剂中的一种或几种的组合;
所述的填料为纳米二氧化硅和功能填料;
所述的固化剂为亲水性异氰酸酯固化剂。
5.根据权利要求4所述的一种丙烯酸/有机硅纳米复合改性水性聚氨酯船舶防污涂料,其特征在于,所述功能填料为氧化亚铜、氧化锌和氧化铁红中的一种或几种的组合。
6.根据权利要求4所述的一种丙烯酸/有机硅纳米复合改性水性聚氨酯船舶防污涂料,其特征在于,所述润湿分散剂为BYK-345;
所述增稠剂为: TAFIGEL PUR 62;
所述消泡剂为:BYK-024。
8.一种丙烯酸/有机硅纳米复合改性水性聚氨酯船舶防污涂料的制备方法,其特征在于,成膜乳液的制备包括如下步骤:
步骤A 反应底物的预处理:将聚醚多元醇在氮气保护氛围下,升温至105~120℃,0.07MPa下减压蒸馏2~3h,得到脱水聚醚多元醇;
步骤B 预聚体的制备:待温度将至70~95℃时,向反应器中加入全部二异氰酸、脱水聚醚多元醇、羟烷基封端聚硅氧烷,机械搅拌混合均匀后,反应2-3h;
步骤C 预聚体扩链反应:升高温度至80~100℃,加入亲水扩链剂、催化剂、小分子扩链剂,继续反应1-2h;
步骤D 预聚体封端:扩链完成后,继续保持温度在80~100℃,加入封端剂,反应1~2h,后降温至30~40℃;
步骤E 点击化学反应:加入接枝剂,使-SH与引入的C=C加成反应,然后加入溶剂稀释粘度;
步骤F中和分散:将中和剂加入到封端完成的聚氨酯中,中和度控制在80%-110%之间,搅拌15min,之后分散到去离子水中,搅拌30min;
步骤G溶剂回收:在45~55℃、0.07MPa减压蒸馏,将制备的乳液中的溶剂蒸出;称量损失的去离子水质量,补加回分散体中,搅拌10分钟,得到成膜乳液。
9.根据权利要求8所述的一种丙烯酸/有机硅纳米复合改性水性聚氨酯船舶防污涂料的制备方法,其特征在于,包括以下步骤:
步骤H涂料互配:将制备的成膜乳液中,加入计量的填料、助剂,机械分散均匀后,按照NCO/OH=1.2:1加入固化剂,搅拌均匀,涂抹于物体表面干燥成膜。
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