CN108559390A - 一种不饱和超支化聚酯改性木器涂料的制备方法 - Google Patents
一种不饱和超支化聚酯改性木器涂料的制备方法 Download PDFInfo
- Publication number
- CN108559390A CN108559390A CN201810460944.5A CN201810460944A CN108559390A CN 108559390 A CN108559390 A CN 108559390A CN 201810460944 A CN201810460944 A CN 201810460944A CN 108559390 A CN108559390 A CN 108559390A
- Authority
- CN
- China
- Prior art keywords
- unsaturated
- modified
- coating
- polyester
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4286—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones prepared from a combination of hydroxycarboxylic acids and/or lactones with polycarboxylic acids or ester forming derivatives thereof and polyhydroxy compounds
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/675—Low-molecular-weight compounds
- C08G18/676—Low-molecular-weight compounds containing the unsaturation at least partially in a non-aromatic carbocyclic ring
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- C—CHEMISTRY; METALLURGY
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明公开了一种不饱和超支化聚酯改性木器涂料的制备方法,利用羟基与‑CNO基团的反应,添加表面带有高反应活性‑NCO基团的SiO2中间体,参与到三羟甲基丙烷二烯丙基醚和二异氰酸酯聚合物与端羟基超支化聚酯的反应中,制得二氧化硅接枝超支化的不饱和树脂,再用所得的超支化不饱和树脂对线性不饱和聚酯进行改性,得到不饱和聚酯涂料;本发明结合了纳米技术与超支化技术,添加纳米二氧化硅接枝的超支化聚合物后,可提高涂层与基体之间的结合强度、光洁度、抗污性等性能,超支化的多支链结构可以与线性不饱和聚酯分子链形成互穿网络,具有更高的交联密度,得到的不饱和树脂涂料具有固化快、韧性好等优异性能。
Description
技术领域
本发明涉及不饱和聚酯涂料技术领域,具体涉及一种不饱和超支化聚酯改性木器涂料的制备方法。
背景技术
不饱和聚酯涂料因其硬度高、光泽高、丰满度好、耐化学品性优异,并且成本低廉和易于加工,被广泛应用于高档家具和乐器等木器表面,然而其存在涂膜脆性大,耐冲击性差,固化收缩率大,低温固化表面易发黏等缺陷,国内外研究人员做了很多工作来克服这些缺陷,如在分子链中引入烯丙基醚、桐油、亚麻油等气干性基团,使得涂料在空气中表面固化良好;使用聚氨酯等柔韧性较好的材料改性,克服不饱和聚酯脆性大的缺陷。
不饱和超支化低聚物一般是由多官能团的核与不饱和支化单元接枝反应合成,常见的方法有马来酸酐体系封端法、丙烯酸及其衍生物封端法和二异氰酸酯+甲基丙烯酸羟乙酯封端法。异氰酸酯基反应活性高,反应时间短,产物易分离,因此第3种合成方法是不错的选择。超支化聚氨酯含有大量的氨基甲酸酯基团,能形成强的氢键,具有粘附性好、耐刮擦、高强度等特征,被广泛地用于涂装木器基材。
发明内容
本发明提供了一种不饱和超支化聚酯改性木器涂料的制备方法,克服了传统不饱和聚酯木器底漆涂膜脆性大,固化时间长,低温固化表面易发黏等缺陷。
为达到上述目的,本发明采用以下技术方案:
一种不饱和超支化聚酯改性木器涂料的制备方法,利用二异氰酸酯对纳米SiO2粒子表面进行化学修饰,得到表面带有高反应活性-NCO基团的SiO2中间体,之后利用羟基与-CNO基团的反应,参与三羟甲基丙烷二烯丙基醚与二异氰酸酯聚合物与端羟基超支化聚酯进行改性,制得二氧化硅接枝超支化的不饱和树脂,再用所得的超支化不饱和树脂对线性不饱和聚酯进行改性,得到不饱和聚酯涂料;
具体步骤如下:
(1)改性SiO2中间体:
将纳米二氧化硅分散在DMF中,超声分散15-25min,得到分散均匀的悬浮液,在恒压滴液漏斗中加入适量DMF、二异氰酸酯和DBTDL,在65-75℃条件下逐滴缓慢加入到二氧化硅悬浮液中,搅拌反应2-4h;
(2)在装有回流冷凝管、温度计、搅拌器的四口瓶中加入62-68份IPDI(异佛尔酮二异氰酸酯)和0.3-0.6份DBTDL催化剂,用滴液漏斗缓慢滴加58-62份TMPDE(三羟甲基丙烷二烯丙基醚),于32-38℃反应3-4h,至-NCO值为初始值的一半,即停止反应,制得IPDI-TMPDE预聚物;
(3)纳米二氧化硅接枝超支化不饱和树脂:
将40-48份端羟基超支化聚酯充分溶解于丙酮中,升温至72-78℃,缓慢滴加上述制备的IPDI-TMPDE预聚物、改性SiO2中间体,每隔 30min测定反应体系中的-NCO值,直至-NCO值<0.2%时停止反应,减压蒸馏,得到超支化不饱和树脂;
(4)涂料的制备:
将上述超支化不饱和树脂以涂料总质量的10-35%的比例加入到线性不饱和聚酯中搅拌混合,得到改性不饱和聚酯涂料。
其中,所述纳米二氧化硅粒径在300 nm,表面羟基含量为1.0mmol/g,使用前在110℃真空干燥。
其中,所述步骤(1)中二氧化硅与异氰酸酯按照1:2-4的摩尔比添加。
其中,所述涂料中纳米二氧化硅的质量分数在0.8-1.2%。
其中,所述端羟基超支化聚酯是以三羟甲丙烷为核,二羟甲基丙酸为支化单元,合成的二代端羟基超支化聚酯。
本发明的有益效果如下:
本发明中利用SiO2表面的活性-OH与二异氰酸酯的-CNO发生缩合反应,对纳米SiO2粒子表面进行化学修饰,得到表面带有高反应活性-NCO基团和不同键合状态的羟基的功能化SiO2粒子,再以高活性的改性二氧化硅为中间体,参与IPDI-TMPDE预聚物与对端羟基超支化聚酯的反应,利用-CNO基团与端羟基之间的反应,把纳米二氧化硅引入超支化结构中,结合纳米技术与超支化技术得到了超支化的不饱和树脂,添加少量的纳米二氧化硅改性的超支化聚合物后,涂料的悬浮稳定性、触变性、涂层与基体之间的结合强度、光洁度等性能均获得显著提高,涂膜固化后涂层的抗污性明显改善;再用所得的超支化不饱和树脂对线性不饱和聚酯进行改性,烯丙基气干性基团分布在超支化结构的外层,可加快固化速度,同时引入了大量韧性较强的氨基甲酸酯结构,且三维体型的多支链结构可以与线性不饱和聚酯分子链形成互穿网络,使得涂膜固化后具有更高的交联密度,制备的超支化不饱和树脂涂料具有固化快、收缩率低、韧性好等优异性能。
具体实施方式
实施例1
一种不饱和超支化聚酯改性木器涂料的制备方法,具体步骤如下:
(1)改性SiO2中间体:
取2g 粒径在300 nm的纳米二氧化硅,表面羟基含量为1.0mmol/g,在110℃真空干燥后,分散在DMF中,超声分散20min,得到悬浮液;在恒压滴液漏斗中加入适量DMF、3.5g二异氰酸酯和0.2g DBTDL,在70℃条件下逐滴缓慢加入到二氧化硅悬浮液中,搅拌反应3h;
(2)在装有回流冷凝管、温度计、搅拌器的四口瓶中加入65g IPDI(异佛尔酮二异氰酸酯)和0.4g DBTDL催化剂,用滴液漏斗缓慢滴加62g TMPDE(三羟甲基丙烷二烯丙基醚),于35℃反应4h,至-NCO值为初始值的一半,即停止反应,制得IPDI-TMPDE预聚物;
(3)纳米二氧化硅接枝超支化不饱和树脂:
以三羟甲丙烷为核,二羟甲基丙酸为支化单元合成二代端羟基超支化聚酯,取44g端羟基超支化聚酯充分溶解于丙酮中,升温至75℃,缓慢滴加上述制备的IPDI-TMPDE预聚物、改性SiO2中间体,每隔 30min测定反应体系中的-NCO值,直至-NCO值<0.2%时停止反应,减压蒸馏,得到超支化不饱和树脂;
(4)涂料的制备:
将上述超支化不饱和树脂以涂料总质量的20%的比例加入到线性不饱和聚酯中搅拌混合,得到改性不饱和聚酯涂料。
Claims (5)
1.一种不饱和超支化聚酯改性木器涂料的制备方法,其特征在于,利用二异氰酸酯对纳米SiO2粒子表面进行化学修饰,得到表面带有高反应活性-NCO基团的SiO2中间体,之后利用羟基与-CNO基团的反应,参与三羟甲基丙烷二烯丙基醚与二异氰酸酯聚合物与端羟基超支化聚酯进行改性,制得二氧化硅接枝超支化的不饱和树脂,再用所得的超支化不饱和树脂对线性不饱和聚酯进行改性,得到不饱和聚酯涂料;
具体步骤如下:
(1)改性SiO2中间体:
将纳米二氧化硅分散在DMF中,超声分散15-25min,得到分散均匀的悬浮液,在恒压滴液漏斗中加入适量DMF、二异氰酸酯和DBTDL,在65-75℃条件下逐滴缓慢加入到二氧化硅悬浮液中,搅拌反应2-4h;
(2)在装有回流冷凝管、温度计、搅拌器的四口瓶中加入62-68份IPDI(异佛尔酮二异氰酸酯)和0.3-0.6份DBTDL催化剂,用滴液漏斗缓慢滴加58-62份TMPDE(三羟甲基丙烷二烯丙基醚),于32-38℃反应3-4h,至-NCO值为初始值的一半,即停止反应,制得IPDI-TMPDE预聚物;
(3)纳米二氧化硅接枝超支化不饱和树脂:
将40-48份端羟基超支化聚酯充分溶解于丙酮中,升温至72-78℃,缓慢滴加上述制备的IPDI-TMPDE预聚物、改性SiO2中间体,每隔 30min测定反应体系中的-NCO值,直至-NCO值<0.2%时停止反应,减压蒸馏,得到超支化不饱和树脂;
(4)涂料的制备:
将上述超支化不饱和树脂以涂料总质量的10-35%的比例加入到线性不饱和聚酯中搅拌混合,得到改性不饱和聚酯涂料。
2.根据权利要求1所述的一种不饱和超支化聚酯改性木器涂料的制备方法,其特征在于,所述纳米二氧化硅粒径在300 nm,表面羟基含量为1.0mmol/g,使用前在110℃真空干燥。
3.根据权利要求1所述的一种不饱和超支化聚酯改性木器涂料的制备方法,其特征在于,所述步骤(1)中二氧化硅与异氰酸酯按照1:2-4的摩尔比添加。
4.根据权利要求1所述的一种不饱和超支化聚酯改性木器涂料的制备方法,其特征在于,所述涂料中纳米二氧化硅的质量分数在0.8-1.2%。
5.根据权利要求1所述的一种不饱和超支化聚酯改性木器涂料的制备方法,其特征在于,所述端羟基超支化聚酯是以三羟甲丙烷为核,二羟甲基丙酸为支化单元,合成的二代端羟基超支化聚酯。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810460944.5A CN108559390A (zh) | 2018-05-15 | 2018-05-15 | 一种不饱和超支化聚酯改性木器涂料的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810460944.5A CN108559390A (zh) | 2018-05-15 | 2018-05-15 | 一种不饱和超支化聚酯改性木器涂料的制备方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN108559390A true CN108559390A (zh) | 2018-09-21 |
Family
ID=63538775
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810460944.5A Withdrawn CN108559390A (zh) | 2018-05-15 | 2018-05-15 | 一种不饱和超支化聚酯改性木器涂料的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108559390A (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109705398A (zh) * | 2018-12-17 | 2019-05-03 | 汕头市贝斯特科技有限公司 | 一种聚烯烃薄膜用非迁移性亲水防雾母料及其制备 |
-
2018
- 2018-05-15 CN CN201810460944.5A patent/CN108559390A/zh not_active Withdrawn
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109705398A (zh) * | 2018-12-17 | 2019-05-03 | 汕头市贝斯特科技有限公司 | 一种聚烯烃薄膜用非迁移性亲水防雾母料及其制备 |
CN109705398B (zh) * | 2018-12-17 | 2020-08-07 | 汕头市贝斯特科技有限公司 | 一种聚烯烃薄膜用非迁移性亲水防雾母料及其制备 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN112778886B (zh) | 一种光固化双组份聚脲防水涂料及其制备方法 | |
TWI535746B (zh) | 水性輻射硬化型聚胺基甲酸酯組成物及其應用方法 | |
JPS6254716A (ja) | 空乾性樹脂組成物 | |
CN106543877B (zh) | 含有机硅水性聚丙烯酸酯改性聚氨酯木器涂料及其制法与应用 | |
US20060142459A1 (en) | Aqueous binders containing layered silicate, process for the production thereof and use thereof in aqueous coating compositions | |
US6811825B1 (en) | Aqueous dispersion comprising polyurethane-based resins and water-insoluble cellulose ester, methods for preparing and using same, and articles coated with same | |
TW201335294A (zh) | 水分散性可自交聯的預聚物組成物 | |
CN113272349A (zh) | 赋予改善的耐污性的涂料组合物 | |
CN104710578B (zh) | 一种新型水性双组份聚氨酯胶黏剂用丙烯酸改性树脂及包含该树脂的聚氨酯胶黏剂 | |
CN108559390A (zh) | 一种不饱和超支化聚酯改性木器涂料的制备方法 | |
CN109810220B (zh) | 一种羟基丙烯酸树脂的制备方法 | |
JP2012017404A (ja) | 光硬化型樹脂組成物及びそれを用いた光硬化型コーティング剤 | |
KR940011197B1 (ko) | 2성분계 폴리우레탄 도료 | |
CN110016143B (zh) | 一种多官能度混杂固化树脂及其制备方法 | |
TW570935B (en) | Curable unsaturated resin composition | |
JP4915042B2 (ja) | 光硬化型樹脂組成物及びそれを用いた光硬化型コーティング剤、光硬化型フィルム | |
JP2001064543A (ja) | 硬化型被覆材用樹脂組成物 | |
CN110003480A (zh) | 具有协同水溶作用的阳离子紫外光固化树脂的制备方法 | |
CN109504267A (zh) | 一种有机硅改性水性复合木器涂料及其制备方法与应用 | |
EP2155801A1 (en) | Polysiloxane and urethane modified water-reducible alkyd resins | |
JPH11181041A (ja) | 光硬化性樹脂組成物及び塗料 | |
JPH01261450A (ja) | 常温乾燥型非水分散性樹脂液及び形成方法 | |
JPH029608B2 (zh) | ||
JP4608259B2 (ja) | 水性樹脂組成物 | |
JPS5821459A (ja) | 塗料用樹脂組成物の調整方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WW01 | Invention patent application withdrawn after publication |
Application publication date: 20180921 |
|
WW01 | Invention patent application withdrawn after publication |