技术领域technical field
本发明涉及UV固化树脂的合成领域，具体涉及一种用于UV-LED固化乙烯基超支化聚氨酯的合成方法。The invention relates to the field of synthesis of UV curable resins, in particular to a synthesis method for UV-LED curing of vinyl hyperbranched polyurethane.
背景技术Background technique
UV固化是指在紫外光的照射下物质从低分子转变为高分子的一个过程，具有节约能源、固化速度快、涂膜性能好、适用于大规模工业化生产等优点，同时UV固化材料在固化过程中不含或只含少量挥发性有机化合物(VOCs),被誉为“绿色技术”。在UV固化体系中使用的典型光源有：中高压汞灯、金属卤素灯、无极灯、氙灯和UV-LED灯。UV curing refers to a process in which a substance changes from low molecular weight to high molecular weight under the irradiation of ultraviolet light. It has the advantages of energy saving, fast curing speed, good coating performance, and is suitable for large-scale industrial production. At the same time, UV curing materials are curing The process contains no or only a small amount of volatile organic compounds (VOCs), known as "green technology". Typical light sources used in UV curing systems are: medium and high pressure mercury lamps, metal halide lamps, electrodeless lamps, xenon lamps and UV-LED lamps.
常规UV光源为高压汞灯，然而像汞灯这样的传统光固化设备发射出的光谱主要在200-400nm，输入的能量中大约只有30％的能量可用于产生紫外光，同时散发大量的热。汞灯的使用寿命短(1500-2000h)、能耗较大；另外，长时间使用汞灯容易产生大量的臭氧，而且在回收废旧汞灯的过程中，汞可能会释放到环境中，严重危害人体健康和生态安全。为降低汞污染，联合国环境规划署理事会已经在水俣公约中提倡减少汞设备的使用。因此，寻找一种可以替代汞灯的光源设备非常有必要。The conventional UV light source is a high-pressure mercury lamp. However, the spectrum emitted by traditional light curing equipment such as mercury lamps is mainly at 200-400nm. Only about 30% of the input energy can be used to generate ultraviolet light, and at the same time emit a lot of heat. Mercury lamps have a short service life (1500-2000h) and high energy consumption; in addition, long-term use of mercury lamps is likely to generate a large amount of ozone, and in the process of recycling waste mercury lamps, mercury may be released into the environment, seriously endangering Human health and ecological security. To reduce mercury pollution, the Governing Council of the United Nations Environment Program has advocated reducing the use of mercury devices in the Minamata Convention. Therefore, it is very necessary to find a light source device that can replace the mercury lamp.
在UV-LED固化体系中使用的UV-LED光源与传统UV光源相比，表现出了诸多优点：(1)使用寿命长，可达30000-40000h，更换维护周期长，节省使用费用；(2)红外辐射低，发热量小，适合液晶、薄膜等热敏感材料的固化；(3)环保安全，不含汞；(4)波峰单一，能量集中在狭窄的紫外光谱段；(5)高效节能；(6)低压直流电工作，驱动安全方便，用于便携设备时可用电池供电；(7)可近距离直接照射，结构简单，体积小巧，安装灵活；(8)照射头形式灵活多变，方便制作点、线、面光源及3D光源；(9)可瞬间启动与关闭，无需快门，无需预热就可达100％功率输出，作业效率得到提高；(10)可实现脉冲驱动与输出精确调节，有助于消除应力；(11)光电衰减特性个体差异小，光输出稳定，适合生产线批量使用PLC控制与设备管理；(12)UV-LED方式无臭氧产生，改善了工人的工作环境，无需再安装捕捉和焚化设备来消除臭氧的危害。从上述各种优势可见，UV-LED固化系统不仅明显降低了成本而且还减少了对环境的污染和能源的损耗。此外，UV-LED固化系统几乎不产生热量，适用于多种热敏介质，如塑料薄膜印刷基材。Compared with the traditional UV light source, the UV-LED light source used in the UV-LED curing system has shown many advantages: (1) Long service life, up to 30000-40000h, long replacement and maintenance cycle, saving use costs; (2) ) Low infrared radiation, low calorific value, suitable for curing heat-sensitive materials such as liquid crystals and films; (3) Environmentally friendly and safe, mercury-free; (4) Single wave peak, energy concentrated in a narrow ultraviolet spectrum; (5) High efficiency and energy saving ; (6) Low-voltage direct current operation, safe and convenient driving, and can be powered by batteries when used in portable devices; (7) Direct irradiation at close range, simple structure, small size, and flexible installation; (8) The form of the irradiation head is flexible and changeable, convenient Make point, line, surface light source and 3D light source; (9) It can be turned on and off instantly, without shutter and without preheating, it can reach 100% power output, and the work efficiency is improved; (10) It can realize pulse drive and precise adjustment of output , helps to eliminate stress; (11) The individual differences in photoelectric attenuation characteristics are small, and the light output is stable, which is suitable for batch use of PLC control and equipment management in production lines; (12) UV-LED method does not generate ozone, which improves the working environment of workers Then install capture and incineration equipment to eliminate the hazards of ozone. It can be seen from the above advantages that the UV-LED curing system not only significantly reduces the cost but also reduces environmental pollution and energy consumption. In addition, the UV-LED curing system generates almost no heat and is suitable for a variety of heat-sensitive media, such as plastic film printing substrates.
目前，UV-LED固化技术仍然面临着诸多挑战。由于UV-LED灯发出的是单色光，波峰狭窄，辐射的能量集中在狭窄的紫外光谱段，故UV-LED固化也只能集中在紫外光谱中一个狭窄的范围，目前UV-LED固化光源的波长包括365nm、375nm、385nm、395nm和405nm，每种波长光源的发射谱带宽度大约为10nm，而现在市场上大多数的光引发剂是在300-370nm有较强的吸收，在λ＞370nm的范围内吸光性能比较差，这就导致了UV-LED固化体系中光源的发射光谱与传统光引发剂的吸收光谱不相匹配的问题，最终会影响光引发剂的引发效率；此外，由于UV-LED灯功率小(尤其是短波UV-LED)，输出光强弱，发光效率低，降低了光引发剂对其的敏感度，影响光引发剂引发光化学反应的量子效率，最终导致光引发剂的引发效率降低。At present, UV-LED curing technology still faces many challenges. Since the UV-LED lamp emits monochromatic light with a narrow peak, the radiated energy is concentrated in a narrow ultraviolet spectrum, so UV-LED curing can only be concentrated in a narrow range of the ultraviolet spectrum. Currently, UV-LED curing light sources The wavelengths include 365nm, 375nm, 385nm, 395nm and 405nm. The emission bandwidth of each wavelength light source is about 10nm, and most of the photoinitiators on the market now have strong absorption at 300-370nm. The light absorption performance in the range of 370nm is relatively poor, which leads to the problem that the emission spectrum of the light source in the UV-LED curing system does not match the absorption spectrum of the traditional photoinitiator, which will eventually affect the initiation efficiency of the photoinitiator; in addition, due to The power of UV-LED lamps is small (especially short-wave UV-LED), the output light intensity is weak, and the luminous efficiency is low, which reduces the sensitivity of the photoinitiator to it, affects the quantum efficiency of the photochemical reaction initiated by the photoinitiator, and eventually leads to photoinitiation. The initiation efficiency of the agent is reduced.
以上关于引发剂与光源匹配性的问题及UV-LED光源功率小的问题无法短时间内出现较大的技术突破，因此，需要开发高反应活性的用于UV-LED固化的树脂满足市场需求。The above problems about the compatibility between the initiator and the light source and the low power of the UV-LED light source cannot make a major technological breakthrough in a short period of time. Therefore, it is necessary to develop a highly reactive resin for UV-LED curing to meet market demand.
中国发明专利申请CN102190789A公开了一种分子量分布较窄的聚氨酯丙烯酸酯树脂的制备方法。其为含单羟基单双键丙烯酸酯封端的线型聚氨酯丙烯酸树脂。此为常见的用于UV固化的聚氨酯丙烯酸酯树脂的结构，此类树脂由于双键的官能度低，固化时需要较高的能量，而UV-LED能量有限，因此不适用。Chinese invention patent application CN102190789A discloses a preparation method of polyurethane acrylate resin with narrow molecular weight distribution. It is a linear urethane acrylic resin endcapped with a single hydroxyl single double bond acrylate. This is the structure of a common polyurethane acrylate resin used for UV curing. Due to the low functionality of the double bond, this type of resin requires high energy for curing, but UV-LED energy is limited, so it is not suitable.
中国发明专利申请CN105199077A公开了一种高官能团高耐磨性可冷光源固化聚氨酯丙烯酸酯的制备方法。其采用含单羟基多双键的丙烯酸酯单体与含环状结构二异氰酸酯的两个异氰酸基反应，制得分子量小官能度高的聚氨酯丙烯酸酯，因此反应活性高，可用于冷光源固化。但该申请技术也存在收缩率高、储存稳定性差、自然光稳定性差等问题。Chinese invention patent application CN105199077A discloses a preparation method of polyurethane acrylate with high functional group and high wear resistance, which can be cured by cold light source. It uses acrylate monomers containing single hydroxyl and multiple double bonds to react with two isocyanate groups containing cyclic diisocyanate to prepare polyurethane acrylate with small molecular weight and high functionality, so it has high reactivity and can be used for cold light sources solidified. However, this application technology also has problems such as high shrinkage rate, poor storage stability, and poor natural light stability.
中国发明专利申请CN101792518A公开了一种氨酯链杆型高耐候端基多烯键光固化预聚物的制备方法。其为含单羟基多双键的中间体封端的聚氨酯丙烯酸酯树脂，整体为中间线型两段支化的结构。其与CN102190789A相比官能度有所提高，因此反应活性略高，而与CN105199077A相比分子量有所提高，因此反应活性略低。其末端的支化结构有利于其用于UV-LED固化，但存在粘度高的问题，且不易制得高硬度产品，不易制得系列产品。Chinese invention patent application CN101792518A discloses a method for preparing a urethane chain-rod type high-weather-resistant end-group polyene bond photocurable prepolymer. It is a polyurethane acrylate resin terminated by an intermediate containing a single hydroxyl group and multiple double bonds, and has a linear two-stage branched structure as a whole. Compared with CN102190789A, its functionality is improved, so its reactivity is slightly higher, and compared with CN105199077A, its molecular weight is improved, so its reactivity is slightly lower. The branched structure at its end is beneficial for its use in UV-LED curing, but it has the problem of high viscosity, and it is not easy to produce high hardness products, and it is not easy to produce series products.
发明内容Contents of the invention
本发明针对现有UV固化树脂用于UV-LED固化时存在的不足，提供一种有效解决高官能度单体固化时收缩率过高，树脂与其他成分相容性较差，反应活性高的用于UV-LED固化乙烯基超支化聚氨酯及其制备方法。The present invention aims at the deficiencies of the existing UV curable resins when used for UV-LED curing, and provides an effective solution to the high shrinkage rate when the high-functionality monomer is cured, poor compatibility between the resin and other components, and high reactivity. Used for UV-LED curing vinyl hyperbranched polyurethane and preparation method thereof.
本发明釆用三步法合成乙烯基超支化聚氨酯；步骤(1)，二异氰酸酯和二元醇进行扩链反应合成含端NCO基的中间体A2，A2中间体和支化剂在较低温度下反应合成中间体AB2，该中间体发生自缩聚反应合成不同代数羟基超支化聚氨酯；步骤(2)，二异氰酸酯和(甲基)丙稀酸羟基酯反应合成半加成产物，步骤(3)，半加成产物对超支化聚氨酯进行化学改性合成高活性乙烯基超支化聚氨酯光固化树脂。本发明在树脂活性和稳定性之间取得平衡，容易制得双键官能度可调且与常规光固化树脂有较好的相容性的系列超支化聚氨酯UV-LED固化树脂。The present invention adopts three-step method to synthesize vinyl hyperbranched polyurethane; step (1 ), diisocyanate and dibasic alcohol carry out chain extension reaction to synthesize intermediate A2 containing terminal NCO group,A2 intermediate and branching agent are compared Reaction at low temperature to synthesize intermediate AB2, which undergoes self-condensation reaction to synthesize different algebraic hydroxyl hyperbranched polyurethanes; step (2 ), diisocyanate and (meth) hydroxy acrylate react to synthesize semi-addition product, step (3), semi-addition products chemically modify hyperbranched polyurethane to synthesize highly active vinyl hyperbranched polyurethane photocurable resin. The invention achieves a balance between resin activity and stability, and can easily prepare a series of hyperbranched polyurethane UV-LED curable resins with adjustable double bond functionality and better compatibility with conventional photocurable resins.
超支化聚合物最初由ABX(X≥2)型单体进行自缩聚反应合成，超支化聚合物是一种可溶性的高度支化的聚合物，这种聚合物在结构上不是完美的树枝状大分子，而是分子结构有缺陷的聚合物。类似于树状聚合物，超支化聚合也具有独特的结构和性能，如：分子结构高度支化、分子内部存在三种类型的结构单元、具有大量可改性末端基团、粘度较低、溶解性良好等可以对其分子结构进行设计，采用ABX型单体缩聚、开环聚合、自缩合乙烯基聚合、质子转移法聚合、A2+B3型单体聚合和偶合单体聚合等方法合成超支化聚合物，目前超支化聚合物在涂料工业、加工助剂、的载体、光电材料、液晶、药物缓释剂和分子自组装等领域都进行了广泛的基础理论研究。Hyperbranched polymers are initially synthesized by the self-condensation reaction of ABX (X≥2) type monomers. Hyperbranched polymers are soluble, highly branched polymers that are not perfectly dendritic in structure. Macromolecules, but polymers with defective molecular structure. Similar to dendritic polymers, hyperbranched polymers also have unique structures and properties, such as: highly branched molecular structure, three types of structural units inside the molecule, a large number of modifiable end groups, low viscosity, solubility The molecular structure can be designed by using ABX type monomer polycondensation, ring-opening polymerization, self-condensation vinyl polymerization, proton transfer polymerization, A2 + B3 type monomer polymerization and coupling monomer polymerization, etc. Synthesis of hyperbranched polymers. At present, hyperbranched polymers have been extensively studied in the fields of coating industry, processing aids, carriers, optoelectronic materials, liquid crystals, drug sustained release agents and molecular self-assembly.
超支化聚氨酯是指超支化分子主链上含有-NHCOON-基团重复结构单元的聚合物，超支化聚氨酯除了具有超支化聚合物的特点外，还具有聚氨酯树脂较好的附着力、柔韧性和耐磨性等优点，两者结合具有优异的综合性能。对超支化聚氨酯进行改性，接入丙稀酸基团合成乙烯基超支化聚氨酯，其在光下能够进行固化反应。乙烯基超支化聚氨酯光固化树脂这一性能优异的材料近年来受到研究人员的广泛关注，它除了具有一般超支化聚合物的粘度较低、溶解能力强、反应活性高等优点外，还具有固化速度快、涂膜性能好、环境污染小等特性，在实际生产和应用中可用作涂料和胶黏剂成膜物质、活性稀释剂、增韧剂、阻尼材料等，前景广阔。Hyperbranched polyurethane refers to a polymer containing -NHCOON- group repeating structural units on the main chain of hyperbranched molecules. In addition to the characteristics of hyperbranched polymers, hyperbranched polyurethane also has good adhesion, flexibility and The combination of the two has excellent comprehensive performance. The hyperbranched polyurethane is modified, and acrylic acid groups are added to synthesize vinyl hyperbranched polyurethane, which can be cured under light. Vinyl hyperbranched polyurethane photocurable resin, a material with excellent performance, has attracted extensive attention from researchers in recent years. In addition to the advantages of low viscosity, strong solubility, and high reactivity of general hyperbranched polymers, it also has curing speed. It can be used as coating and adhesive film-forming substance, active diluent, toughening agent, damping material, etc. in actual production and application, with broad prospects.
在步骤(1)合成超支化聚氨酯时存在自缩聚的过程，合成出的超支化聚氨酯为不同代数聚合物的混合物，通过在NCO为一定值时加入封端剂终止反应，而实现聚合物代数和分子量的控制。In step (1) when hyperbranched polyurethane is synthesized, there is a process of self-condensation. The synthesized hyperbranched polyurethane is a mixture of polymers with different algebras. When the NCO is a certain value, adding an end-capping agent to terminate the reaction can realize the polymer algebra and molecular weight control.
不同代数超支化聚氨酯的理论分子结构式如下：The theoretical molecular structural formulas of different algebraic hyperbranched polyurethanes are as follows:
本发明目的通过如下技术方案实现：The object of the invention is achieved through the following technical solutions:
用于UV-LED固化乙烯基超支化聚氨酯的制备方法，包含如下步骤：The preparation method that is used for UV-LED curing vinyl hyperbranched polyurethane comprises the following steps:
1)超支化羟基聚氨酯的制备：以质量份数计，取26.0-50.0份二异氰酸酯、0-0.03份催化剂和0.03-0.05份阻聚剂加入反应釜，升温至35-45℃，取11.7-47.0份的二元醇溶于活性稀释剂，滴加入所述反应釜中，滴完后继续反应，制备出A2中间体；降温至0-5℃，取10-16.5份支化剂溶于活性稀释剂中，滴完后继续反应，制备出AB2中间体；升温至40℃-55℃，补加0.04-0.05份催化剂，继续反应，反应至NCO值为2.0％以下，加入2.2-4.7份封端剂，制备出端羟基含量为1.5％-3.0％的超支化聚氨酯树脂；1) Preparation of hyperbranched hydroxyl polyurethane: in parts by mass, take 26.0-50.0 parts of diisocyanate, 0-0.03 parts of catalyst and 0.03-0.05 parts of polymerization inhibitor into the reactor, heat up to 35-45 ° C, take 11.7- 47.0 parts of dihydric alcohol dissolved in active diluent, added dropwise into the reaction kettle, continued to react after dropping, and prepared A2 intermediate; cooled to 0-5°C, took10-16.5 parts of branching agent and dissolved in In the active diluent, continue to react after dropping to prepare the AB2 intermediate; raise the temperature to 40°C-55°C, add 0.04-0.05 parts of catalyst, continue the reaction until the NCO value is below 2.0%, add 2.2-4.7 part of end-capping agent to prepare a hyperbranched polyurethane resin with a terminal hydroxyl content of 1.5%-3.0%;
2)含NCO基与乙烯基的半加成物的制备：以质量份数计，取36.7-65.84份二异氰酸酯、0-0.06份催化剂和0-0.05份阻聚剂加入反应釜，25℃-40℃条件下滴加34.12-63.25份丙烯酸羟基酯或甲基丙烯酸羟基酯，滴完后继续反应30-40min，制备出NCO含量为7.5％-13.8％的半加成物；2) Preparation of semi-adducts containing NCO groups and vinyl groups: In terms of parts by mass, take 36.7-65.84 parts of diisocyanate, 0-0.06 parts of catalyst and 0-0.05 parts of polymerization inhibitor into the reactor. Add 34.12-63.25 parts of hydroxy acrylate or methacrylate dropwise at 40°C, and continue the reaction for 30-40 minutes after the dropping, to prepare a semi-adduct with an NCO content of 7.5%-13.8%;
3)乙烯基超支化聚氨酯的制备：以质量份数计，取12.9-16.8份活性稀释剂、0.03-0.04份阻聚剂、45.3-65.0份超支化羟基聚氨酯加入反应釜，35-40℃条件下滴加18.1-40.4份含NCO基与乙烯基的半加成物，滴加完后升温至70-75℃，加入0.06-0.07份催化剂，继续反应1.5-2.5h，至NCO值小于0.1％，得到用于UV-LED固化乙烯基超支化聚氨酯；3) Preparation of vinyl hyperbranched polyurethane: In terms of parts by mass, take 12.9-16.8 parts of reactive diluent, 0.03-0.04 parts of polymerization inhibitor, and 45.3-65.0 parts of hyperbranched hydroxyl polyurethane into the reaction kettle at 35-40°C Add dropwise 18.1-40.4 parts of semi-adducts containing NCO groups and vinyl groups. After the dropwise addition, raise the temperature to 70-75°C, add 0.06-0.07 parts of catalyst, and continue the reaction for 1.5-2.5 hours until the NCO value is less than 0.1%. , to obtain vinyl hyperbranched polyurethane for UV-LED curing;
步骤1)、步骤2)和步骤3)所述催化剂都为OMG公司的有机铋(Kat 24)、有机铋(Kat320)和二月桂酸二丁基锡(DBTL)的一种。The catalysts in step 1), step 2) and step 3) are all organic bismuth (Kat 24), organic bismuth (Kat320) and dibutyltin dilaurate (DBTL) from OMG Company.
为进一步实现本发明目的，优选地，步骤1)和步骤2)所述二异氰酸酯都为甲苯二异氰酸酯(TDI)、六亚甲基二异氰酸酯(HDI)、异佛尔酮二异氰酸酯(IPDI)二苯甲烷二异氰酸酯(MDI)和氢化苯基甲烷二异氰酸酯(HMDI)的一种或多种。以质量份数计，For further realizing the object of the present invention, preferably, the diisocyanate described in step 1) and step 2) is toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) diisocyanate (IPDI) One or more of phenylmethane diisocyanate (MDI) and hydrogenated phenylmethane diisocyanate (HMDI). In parts by mass,
优选地，所述二元醇为新戊二醇(NPG)、1,4-丁二醇(BDO)、2,4-二乙基-1,5-戊二醇(PD-9)、乙基丁基丙二醇(BEPD)、1,6-己二醇(HDO)和聚醚(PEG600)的一种。Preferably, the dihydric alcohol is neopentyl glycol (NPG), 1,4-butanediol (BDO), 2,4-diethyl-1,5-pentanediol (PD-9), ethyl One of butyl propylene glycol (BEPD), 1,6-hexanediol (HDO) and polyether (PEG600).
优选地，步骤1)中，以质量份数计，二元醇溶于5.0-11.0份活性稀释剂中；Preferably, in step 1), in parts by mass, dihydric alcohol is dissolved in 5.0-11.0 parts of active diluent;
制备出A2中间体中，滴加入所述反应釜中的时间为20-30min，滴完后继续反应的时间为30-40min；In the prepared A2 intermediate, the time for dropping into the reaction kettle is 20-30min, and the time for continuing the reaction after dropping is 30-40min;
制备出AB2中间体中，支化剂溶于8.5-16.2份活性稀释剂，25-35min滴完，然后继续反应20-30min；In the preparation of the AB2 intermediate, the branching agent was dissolved in 8.5-16.2 parts of reactive diluent, dripped in 25-35 minutes, and then continued to react for 20-30 minutes;
NCO值每间隔10-20min测一次。The NCO value was measured every 10-20min.
优选地，步骤2)滴加34.12-63.25份(甲基)丙烯酸羟基酯的时间为20-30min，滴完后继续反应30-40min。Preferably, the time for step 2) to add 34.12-63.25 parts of hydroxy (meth)acrylate dropwise is 20-30 minutes, and the reaction is continued for 30-40 minutes after the drop is completed.
优选地，所述为支化剂为二乙醇胺(DEOA)和二异丙醇胺(DIPA)的一种；所述阻聚剂为对甲氧基苯酚(MEHQ)、2-叔丁基对苯二酚(TBHQ)和甲基氢醌(THQ)的一种。Preferably, the branching agent is one of diethanolamine (DEOA) and diisopropanolamine (DIPA); the polymerization inhibitor is p-methoxyphenol (MEHQ), 2-tert-butyl-p-phenylene A kind of diphenol (TBHQ) and methyl hydroquinone (THQ).
优选地，所述封端剂为二丙胺(DNPA)、二正丁胺(DNBA)、二异丁胺(DIBA)和N-甲基环己胺(N-MCHA)的一种。Preferably, the blocking agent is one of dipropylamine (DNPA), di-n-butylamine (DNBA), diisobutylamine (DIBA) and N-methylcyclohexylamine (N-MCHA).
优选地，所述丙烯酸羟基酯或甲基丙烯酸羟基酯单体为甲基丙烯酸羟乙酯(HEMA)、丙烯酸羟丙酯(HEA)和季戊四醇三丙烯酸酯(PETA)的一种或多种。Preferably, the hydroxy acrylate or methacrylate monomer is one or more of hydroxyethyl methacrylate (HEMA), hydroxypropyl acrylate (HEA) and pentaerythritol triacrylate (PETA).
优选地，所述活性稀释剂为己二醇二丙烯酸酯(HDDA)、三丙二醇二丙烯酸酯(TPGDA)、三羟甲基丙烷三丙烯酸酯(TMPTA)和乙氧化三羟甲基丙烷三丙烯酸酯(TMP3EOTA)的一种。Preferably, the reactive diluent is hexanediol diacrylate (HDDA), tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (TMPTA) and ethoxylated trimethylolpropane triacrylate (TMP3EOTA).
一种用于UV-LED固化乙烯基超支化聚氨酯，由上述制备方法制得。A kind of UV-LED curing vinyl hyperbranched polyurethane is prepared by the above preparation method.
相对于现有技术，本发明具有如下优点和有益效果：Compared with the prior art, the present invention has the following advantages and beneficial effects:
1)本发明在乙烯基超支化聚氨酯的制备中，二异氰酸酯单体可直接作为重复单元R中的A2中间体，而本发明设计二异氰酸酯与二元醇扩链后作为A2中间体，延长了超支化结构中重复单元分子链，提高了分子链的柔性。此设计有利于超支化结构中分子链的运动，提高了超支化结构末端双键的反应活性，解决了高官能度单体固化时收缩率过高的问题，改善了树脂与其他成分的相容性。1 ) In the preparation of the vinyl hyperbranched polyurethane of the present invention, the diisocyanate monomer can be directly used as the A2 intermediate in the repeating unit R, and the present invention designs the diisocyanate and the diol chain extension as theA2 intermediate, The molecular chain of the repeating unit in the hyperbranched structure is extended, and the flexibility of the molecular chain is improved. This design is conducive to the movement of molecular chains in the hyperbranched structure, improves the reactivity of the double bond at the end of the hyperbranched structure, solves the problem of high shrinkage when the high-functionality monomer is cured, and improves the compatibility of the resin with other components sex.
2)本发明所得乙烯基超支化聚氨酯反应活性高，且通过配方和工艺微调容易制得不同分子量、不同官能度、不同硬度和不同柔韧性的系列树脂，非常适用于UV-LED固化涂料。2) The vinyl hyperbranched polyurethane obtained in the present invention has high reactivity, and it is easy to prepare a series of resins with different molecular weights, different functionalities, different hardnesses and different flexibility through formula and process fine-tuning, which is very suitable for UV-LED curing coatings.
具体实施方式Detailed ways
下面结合实施例对本发明作进一步描述，但本发明的实施方式不限于此，对于未特别注明的工艺参数，可参照常规技术进行。The present invention will be further described below in conjunction with the examples, but the embodiments of the present invention are not limited thereto, and for the process parameters not specified in particular, it can be carried out with reference to conventional techniques.
实施例1Example 1
当超支化聚氨酯的合成原料为异佛尔酮二异氰酸酯(IPDI)、新戊二醇(NPG)和二乙醇胺(DEOA)时，代数与超支化聚氨酯的NCO值、羟基数和相对分子质量的关系如表1a：When the synthetic raw materials of hyperbranched polyurethane are isophorone diisocyanate (IPDI), neopentyl glycol (NPG) and diethanolamine (DEOA), the relationship between algebra and NCO value, hydroxyl number and relative molecular mass of hyperbranched polyurethane As in Table 1a:
表1aTable 1a
(1)超支化聚氨酯的合成：(1) Synthesis of hyperbranched polyurethane:
超支化聚氨酯配方如表1b：The formula of hyperbranched polyurethane is shown in Table 1b:
表1bTable 1b
取50.0份IPDI、0.03份Kat 24和0.03份MEHQ加入反应釜，升温至35℃，取11.7份的NPG溶于11.0份HDDA，滴加，20min滴完，滴完后继续反应40min，合成出A2中间体；降温至5℃，取11.8份DEOA溶于11.0份HDDA，滴加，25min滴完，滴完后继续反应30min，合成出AB2中间体；升温至55℃，补加0.04份Kat 24，继续反应，每10min测NCO值，反应至NCO值为1.5％时，加入4.4份二正丁胺封端，合成出端羟基含量为2.5％的超支化聚氨酯树脂。Add 50.0 parts of IPDI, 0.03 parts of Kat 24 and 0.03 parts of MEHQ into the reactor, raise the temperature to 35°C, take 11.7 parts of NPG and dissolve it in 11.0 parts of HDDA, add dropwise, and finish dropping in 20 minutes. After the dropping, continue to react for 40 minutes to synthesize A2 intermediate; lower the temperature to 5°C, dissolve 11.8 parts of DEOA in 11.0 parts of HDDA, add dropwise, drop it for 25 minutes, continue to react for 30 minutes after the drop, synthesize AB2 intermediate; raise the temperature to 55°C, add 0.04 part of Kat 24. Continue the reaction, measure the NCO value every 10 minutes, and when the NCO value reaches 1.5%, add 4.4 parts of di-n-butylamine to end the reaction, and synthesize a hyperbranched polyurethane resin with a terminal hydroxyl content of 2.5%.
(2)IPDI-HEA半加成物的合成：(2) Synthesis of IPDI-HEA semi-adducts:
IPDI-HEA半加成物的配方如表1c：The formula of IPDI-HEA semi-adduct is shown in Table 1c:
表1cTable 1c
取65.6份IPDI、0.06份Kat 24和0.04份MEHQ加入反应釜，40℃条件下滴加34.3份HEA，20min滴完，滴完后继续反应40min，合成出NCO含量为12.4％的IPDI-HEA半加成物。Take 65.6 parts of IPDI, 0.06 parts of Kat 24 and 0.04 parts of MEHQ and put them into the reactor, add 34.3 parts of HEA dropwise at 40°C for 20 minutes, and then continue the reaction for 40 minutes to synthesize IPDI-HEA with an NCO content of 12.4%. adducts.
(3)乙烯基超支化聚氨酯的合成：乙烯基超支化聚氨酯的配方如表1d：取12.9份HDDA、0.03份MEHQ、58.0份步骤(1)合成的超支化聚氨酯加入反应釜，40℃条件下滴加29.0份步骤(2)合成的IPDI-HEA半加成物，滴加完后升温至70℃，加入0.07份Kat 24，继续反应约2h，至NCO值小于0.1％，得到乙烯基超支化聚氨酯。(3) Synthesis of vinyl hyperbranched polyurethane: the formula of vinyl hyperbranched polyurethane is shown in Table 1d: Take 12.9 parts of HDDA, 0.03 part of MEHQ, and 58.0 parts of hyperbranched polyurethane synthesized in step (1) into the reaction kettle, under the condition of 40 °C Add 29.0 parts of the IPDI-HEA semi-adduct synthesized in step (2) dropwise, raise the temperature to 70°C after the dropwise addition, add 0.07 part of Kat 24, and continue the reaction for about 2 hours until the NCO value is less than 0.1%, and vinyl hyperbranched Polyurethane.
表1dTable 1d
乙烯基超支化聚氨酯的参数如表1e：The parameters of vinyl hyperbranched polyurethane are shown in Table 1e:
表1eTable 1e
本实施例首先以IPDI和NPG扩链制得A2中间体，A2中间体和DEOA反应后作为重复单元AB2，AB2缩聚合成出含端羟基低粘度超支化聚氨酯。扩链后的A2中间体延长了超支化结构中重复单元分子链，提高了分子链的柔性，有利于超支化结构中分子链的运动，进而提高最终乙烯基超支化聚氨酯末端双键的反应活性，以及提高树脂与其他成分的相容性。以此树脂为核，再以IPDI-HEA半加成物封端，制得的乙烯基超支化聚氨酯的双键分布在大分子的外围，极大地提高了树脂的反应活性，从而降低涂膜固化对UV-LED光源和引发剂的要求，有利于UV-LED固化技术的推广。In this example, the A2 intermediate is firstly obtained by IPDI and NPG chain extension, and the A 2intermediate is reacted with DEOA as a repeating unit AB2 , and AB2 is condensed to synthesize a low-viscosity hyperbranched polyurethane containing terminal hydroxyl groups. The chain- extended A2 intermediate extends the molecular chain of the repeating unit in the hyperbranched structure, improves the flexibility of the molecular chain, and is beneficial to the movement of the molecular chain in the hyperbranched structure, thereby improving the reaction of the double bond at the end of the final vinyl hyperbranched polyurethane Reactivity, as well as improving the resin's compatibility with other ingredients. With this resin as the core and IPDI-HEA semi-adduct capping, the double bonds of the prepared vinyl hyperbranched polyurethane are distributed on the periphery of the macromolecule, which greatly improves the reactivity of the resin and reduces the curing rate of the coating film. The requirements for UV-LED light sources and initiators are conducive to the promotion of UV-LED curing technology.
由表1e看出与市场化产品相比本实施例的乙烯基超支化聚氨酯有较高的反应活性。当常规产品漆膜硬度较高时容易存在涂料粘度高和柔韧性差的问题，本实施例由于具有超支化结构，其在涂料粘度、漆膜硬度和漆膜柔韧性三方面取得平衡。另外，漆膜附着力是反应漆膜收缩特性的指标，漆膜收缩应力越大附着力越差，本实施例对超支化结构的末端进行扩链，减小了漆膜固化时的收缩应力，从而保证了附着力。It can be seen from Table 1e that the vinyl hyperbranched polyurethane of this example has higher reactivity compared with the marketed products. When the paint film hardness of conventional products is high, there are likely to be problems of high paint viscosity and poor flexibility. Due to the hyperbranched structure, this embodiment achieves a balance in paint viscosity, paint film hardness and paint film flexibility. In addition, the adhesion of the paint film is an index that reflects the shrinkage characteristics of the paint film. The greater the shrinkage stress of the paint film, the worse the adhesion. Guaranteed adhesion.
实施例2Example 2
当超支化聚氨酯的合成原料为异佛尔酮二异氰酸酯(IPDI)、2,4-二乙基-1,5-戊二醇(PD-9)和二异丙醇胺(DIPA)时，代数与超支化聚氨酯的NCO值、羟基数和相对分子质量的关系如表2a：When the synthetic raw materials of hyperbranched polyurethane are isophorone diisocyanate (IPDI), 2,4-diethyl-1,5-pentanediol (PD-9) and diisopropanolamine (DIPA), the algebraic The relationship with the NCO value, hydroxyl number and relative molecular mass of hyperbranched polyurethane is shown in Table 2a:
表2aTable 2a
步骤(1)，超支化聚氨酯的合成Step (1), the synthesis of hyperbranched polyurethane
超支化聚氨酯配方如表2b：The formula of hyperbranched polyurethane is shown in Table 2b:
取45.5份IPDI、0.03份Kat 320和0.03份TBHQ加入反应釜，升温至40℃，取16.5份的PD-9溶于5.0份TMP3EOTA，滴加，30min滴完，滴完后继续反应Add 45.5 parts of IPDI, 0.03 parts of Kat 320 and 0.03 parts of TBHQ into the reactor, raise the temperature to 40°C, take 16.5 parts of PD-9 and dissolve in 5.0 parts of TMP3EOTA, add dropwise, finish dropping for 30 minutes, and continue the reaction after dropping
表2bTable 2b
30min，合成出A2中间体；降温至5℃，取14.0份DIPA溶于16.2份TMP3EOTA，滴加，35min滴完，滴完后继续反应20min，合成出AB2中间体；升温至55℃，加入0.04份Kat 320，继续反应，每15min测NCO值，反应至NCO值为1.2％时，加入2.7份DNPA封端，合成出端羟基含量为2.3％的超支化聚氨酯树脂。After 30 minutes, the A2 intermediate was synthesized; the temperature was lowered to 5°C, and 14.0 parts of DIPA was dissolved in 16.2 parts of TMP3EOTA, and added dropwise, the drop was completed in 35 minutes, and the reaction was continued for 20 minutes after the drop, and the AB2 intermediate was synthesized; Add 0.04 parts of Kat 320, continue the reaction, measure the NCO value every 15 minutes, and when the NCO value is 1.2%, add 2.7 parts of DNPA to end the reaction, and synthesize a hyperbranched polyurethane resin with a terminal hydroxyl content of 2.3%.
步骤(2)，TDI-ACE半加成物的合成Step (2), the synthesis of TDI-ACE semi-adduct
TDI-HEMA半加成物的配方如表2c：The formula of TDI-HEMA semi-adduct is shown in Table 2c:
表2cTable 2c
取36.7份TDI和0.05份TBHQ加入反应釜，25℃条件下滴加63.25份HEMA，30min滴完，滴完后继续反应35min，合成出NCO含量为8.9％的TDI-HEMA半加成物。Take 36.7 parts of TDI and 0.05 parts of TBHQ into the reactor, add 63.25 parts of HEMA dropwise at 25°C, drop it in 30 minutes, continue the reaction for 35 minutes after the drop, and synthesize a TDI-HEMA semi-adduct with an NCO content of 8.9%.
步骤(3)，乙烯基超支化聚氨酯的合成Step (3), the synthesis of vinyl hyperbranched polyurethane
乙烯基超支化聚氨酯的配方如表2d：The formula of vinyl hyperbranched polyurethane is shown in Table 2d:
取14.9份TMP3EOTA、0.04份TBHQ、52.0份步骤(1)合成的超支化聚氨酯加入反应釜，35℃条件下滴加33.0份步骤(2)合成的TDI-HEMA半加成物，滴加完后升温至70℃，加入0.06份Kat 320，继续反应约2h，至NCO值小于0.1％，得到乙烯基超支化聚氨酯。Take 14.9 parts of TMP3EOTA, 0.04 parts of TBHQ, and 52.0 parts of hyperbranched polyurethane synthesized in step (1) and add them to the reactor, and add 33.0 parts of the TDI-HEMA semi-adduct synthesized in step (2) dropwise at 35°C. Raise the temperature to 70°C, add 0.06 parts of Kat 320, continue the reaction for about 2 hours until the NCO value is less than 0.1%, and obtain vinyl hyperbranched polyurethane.
表2dTable 2d
乙烯基超支化聚氨酯的参数如表2e：The parameters of vinyl hyperbranched polyurethane are shown in Table 2e:
表2eTable 2e
实施例3Example 3
当超支化聚氨酯的合成原料为甲苯二异氰酸酯(TDI)、1,4-丁二醇(BDO)和二乙醇胺(DEOA)时，代数与超支化聚氨酯的NCO值、羟基数和相对分子质量的关系如表3a：When the synthetic raw materials of hyperbranched polyurethane are toluene diisocyanate (TDI), 1,4-butanediol (BDO) and diethanolamine (DEOA), the relationship between algebra and NCO value, hydroxyl number and relative molecular mass of hyperbranched polyurethane As in Table 3a:
表3aTable 3a
步骤(1)，超支化聚氨酯的合成Step (1), the synthesis of hyperbranched polyurethane
超支化聚氨酯配方如表3b：The formula of hyperbranched polyurethane is shown in Table 3b:
取47.5份TDI和0.05份MEHQ加入反应釜，升温至45℃，取12.4份的BDO溶于5.0份TPGDA，滴加，20min滴完，滴完后继续反应40min，合成出A2中间体；降温至0℃，取14.5份DEOA溶于15.8份TPGDA，滴加，25min滴完，滴完后继续反应30min，合成出AB2中间体；升温至40℃，加入0.05份Kat 24，继续反应，每20min测NCO值，反应至NCO值为2.0％时，加入4.7份DNBAAdd 47.5 parts of TDI and 0.05 parts of MEHQ to the reactor, raise the temperature to 45°C, take 12.4 parts of BDO and dissolve in 5.0 parts of TPGDA, add dropwise, and finish dropping for 20 minutes. Continue to react for 40 minutes after dropping, and synthesize A2 intermediate; cool down To 0°C, take 14.5 parts of DEOA dissolved in 15.8 parts of TPGDA, add dropwise, drop over 25 minutes, continue to react for 30 minutes after dropping, synthesize AB2 intermediate; raise the temperature to 40°C, add 0.05 parts of Kat 24, continue the reaction, every Measure the NCO value in 20 minutes, when the NCO value is 2.0%, add 4.7 parts of DNBA
表3bTable 3b
封端，合成出端羟基含量为3.0％的超支化聚氨酯树脂。End capping, synthesized hyperbranched polyurethane resin with terminal hydroxyl content of 3.0%.
步骤(2)，MDI-HPA半加成物的合成Step (2), the synthesis of MDI-HPA semi-adduct
MDI-HPA半加成物的配方如表3c：The formula of the MDI-HPA semi-adduct is shown in Table 3c:
表3cTable 3c
取65.84份MDI和0.04份THQ加入反应釜，25℃条件下滴加34.12份HPA，25min滴完，滴完后继续反应35min，合成出NCO含量为11.1％的MDI-HPA半加成物。Take 65.84 parts of MDI and 0.04 parts of THQ into the reactor, add 34.12 parts of HPA dropwise at 25°C, drop it in 25 minutes, continue the reaction for 35 minutes after the drop, and synthesize an MDI-HPA semi-adduct with an NCO content of 11.1%.
步骤(3)，乙烯基超支化聚氨酯的合成Step (3), the synthesis of vinyl hyperbranched polyurethane
乙烯基超支化聚氨酯的配方如表3d：The formulation of vinyl hyperbranched polyurethane is shown in Table 3d:
表3dTable 3d
取13.9份TPGDA、0.03份THQ、51.5份步骤(1)合成的超支化聚氨酯加入反应釜，40℃条件下滴加34.5份步骤(2)合成的MDI-HPA半加成物，滴加完后升温至75℃，加入0.07份DBTL，继续反应约2h，至NCO值小于0.1％，得到乙烯基超支化聚氨酯。Take 13.9 parts of TPGDA, 0.03 parts of THQ, and 51.5 parts of hyperbranched polyurethane synthesized in step (1) and add them to the reactor, and add 34.5 parts of MDI-HPA semi-adducts synthesized in step (2) dropwise at 40°C. Raise the temperature to 75°C, add 0.07 parts of DBTL, continue the reaction for about 2 hours until the NCO value is less than 0.1%, and obtain vinyl hyperbranched polyurethane.
乙烯基超支化聚氨酯的参数如表3e：The parameters of vinyl hyperbranched polyurethane are shown in Table 3e:
表3eTable 3e
实施例4Example 4
当超支化聚氨酯的合成原料为六亚甲基二异氰酸酯(HDI)、聚醚(PEG600)和二异丙醇胺(DIPA)时，代数与超支化聚氨酯的NCO值、羟基数和相对分子质量的关系如表4a：When the synthetic raw materials of hyperbranched polyurethane are hexamethylene diisocyanate (HDI), polyether (PEG600) and diisopropanolamine (DIPA), the relationship between algebra and NCO value, hydroxyl number and relative molecular weight of hyperbranched polyurethane The relationship is shown in Table 4a:
表4aTable 4a
步骤(1)，超支化聚氨酯的合成Step (1), the synthesis of hyperbranched polyurethane
超支化聚氨酯配方如表4b：The formula of hyperbranched polyurethane is shown in Table 4b:
表4bTable 4b
取26.0份HDI、0.03份Kat 24和0.03份TBHQ加入反应釜，升温至35℃，取47.0份的PEG600溶于5.0份TMPTA，滴加，30min滴完，滴完后继续反应30min，合成出A2中间体；降温至0℃，取10.2份DIPA溶于9.5份TMPTA，滴加，35min滴完，滴完后继续反应20min，合成出AB2中间体；升温至55℃，补加0.04份Kat 24，继续反应，每10min测NCO值，反应至NCO值为0.8％时，加入2.2份N-MCHA封端，合成出端羟基含量为1.5％的超支化聚氨酯树脂。Add 26.0 parts of HDI, 0.03 parts of Kat 24 and 0.03 parts of TBHQ into the reactor, raise the temperature to 35°C, take 47.0 parts of PEG600 and dissolve in 5.0 parts of TMPTA, add dropwise, finish dropping for 30 minutes, continue to react for 30 minutes after dropping, and synthesize A2 intermediates; cool down to 0°C, dissolve 10.2 parts of DIPA in 9.5 parts of TMPTA, add dropwise, drop for 35 minutes, continue to react for 20 minutes after dropping, synthesize AB2 intermediates; raise the temperature to 55°C, add 0.04 parts of Kat 24. Continue the reaction, measure the NCO value every 10 minutes, and when the NCO value is 0.8%, add 2.2 parts of N-MCHA to end-cap, and synthesize a hyperbranched polyurethane resin with a terminal hydroxyl content of 1.5%.
步骤(2)，IPDI-HEA-SC1020半加成物的合成Step (2), the synthesis of IPDI-HEA-SC1020 semi-adduct
IPDI-HEA-SC1020半加成物的配方如表4c：The formula of IPDI-HEA-SC1020 semi-adduct is shown in Table 4c:
取55.2份IPDI、0.06份Kat 24和0.04份TBHQ加入反应釜，40℃条件下滴加14.4份HEA和30.3份SC1020混合液，30min滴完，滴完后继续反应40min，合成出NCO含量为13.3％的IPDI-HEA-SC1020半加成物。Take 55.2 parts of IPDI, 0.06 parts of Kat 24 and 0.04 parts of TBHQ and add them to the reactor, add 14.4 parts of HEA and 30.3 parts of SC1020 mixture dropwise at 40°C, and finish dropping in 30 minutes. % IPDI-HEA-SC1020 hemiadduct.
表4cTable 4c
步骤(3)，乙烯基超支化聚氨酯的合成Step (3), the synthesis of vinyl hyperbranched polyurethane
乙烯基超支化聚氨酯的配方如表4d：The formula of vinyl hyperbranched polyurethane is shown in Table 4d:
表4dTable 4d
取16.8份TMPTA、0.04份TBHQ、65.0份步骤(1)合成的超支化聚氨酯加入反应釜，35℃条件下滴加18.1份步骤(2)合成的IPDI-HEA-SC1020半加成物，滴加完后升温至75℃，加入0.06份Kat 24，继续反应约2h，至NCO值小于0.1％，得到乙烯基超支化聚氨酯。Take 16.8 parts of TMPTA, 0.04 parts of TBHQ, and 65.0 parts of hyperbranched polyurethane synthesized in step (1) and add them to the reactor, and add 18.1 parts of IPDI-HEA-SC1020 semi-adducts synthesized in step (2) dropwise at 35°C. After completion, the temperature was raised to 75°C, 0.06 parts of Kat 24 was added, and the reaction was continued for about 2 hours until the NCO value was less than 0.1%, to obtain vinyl hyperbranched polyurethane.
乙烯基超支化聚氨酯的参数如表4e：The parameters of vinyl hyperbranched polyurethane are shown in Table 4e:
表4eTable 4e
实施例5Example 5
当超支化聚氨酯的合成原料为甲苯二异氰酸酯(TDI)、1,6-己二醇(HDO)和二乙醇胺(DEOA)时，代数与超支化聚氨酯的NCO值、羟基数和相对分子质量的关系如表5a：When the synthetic raw materials of hyperbranched polyurethane are toluene diisocyanate (TDI), 1,6-hexanediol (HDO) and diethanolamine (DEOA), the relationship between algebra and NCO value, hydroxyl number and relative molecular mass of hyperbranched polyurethane As in Table 5a:
表5aTable 5a
步骤(1)，超支化聚氨酯的合成Step (1), the synthesis of hyperbranched polyurethane
超支化聚氨酯配方如表5b：The formula of hyperbranched polyurethane is shown in Table 5b:
表5bTable 5b
取46.8份TDI和0.05份MEHQ加入反应釜，升温至40℃，取15.9份的HDO溶于10.0份HDDA，滴加，20min滴完，滴完后继续反应40min，合成出A2中间体；降温至0℃，取14.1份DEOA溶于10.1份HDDA，滴加，25min滴完，滴完后继续反应30min，合成出AB2中间体；升温至40℃，加入0.05份Kat 24，继续反应，每15min测NCO值，反应至NCO值为1.0％时，加入3.0份DNBA封端，合成出端羟基含量为2.7％的超支化聚氨酯树脂。Take 46.8 parts of TDI and 0.05 parts of MEHQ and add them to the reactor, raise the temperature to 40°C, take 15.9 parts of HDO and dissolve in 10.0 parts of HDDA, add dropwise, finish dropping for 20 minutes, continue to react for 40 minutes after dropping, and synthesize A2 intermediate; cool down To 0°C, take 14.1 parts of DEOA dissolved in 10.1 parts of HDDA, add dropwise, drop it in 25 minutes, continue to react for 30 minutes after dropping, synthesize AB2 intermediate; raise the temperature to 40°C, add 0.05 parts of Kat 24, continue the reaction, every The NCO value was measured for 15 minutes, and when the NCO value was 1.0%, 3.0 parts of DNBA was added for end-capping, and a hyperbranched polyurethane resin with a terminal hydroxyl content of 2.7% was synthesized.
步骤(2)，HMDI-PETA半加成物的合成Step (2), the synthesis of HMDI-PETA semi-adduct
HMDI-PETA半加成物的配方如表5c：The formula of HMDI-PETA semi-adduct is shown in Table 5c:
表5cTable 5c
取46.8份HMDI和0.05份THQ加入反应釜，25℃条件下滴加53.15份PETA，30min滴完，滴完后继续反应30min，合成出NCO含量为7.5％的HMDI-PETA半加成物。Take 46.8 parts of HMDI and 0.05 parts of THQ into the reactor, add 53.15 parts of PETA dropwise under the condition of 25°C, drop it in 30 minutes, continue to react for 30 minutes after dropping, and synthesize HMDI-PETA semi-adduct with 7.5% NCO content.
步骤(3)，乙烯基超支化聚氨酯的合成Step (3), the synthesis of vinyl hyperbranched polyurethane
乙烯基超支化聚氨酯的配方如表5d：The formula of vinyl hyperbranched polyurethane is as table 5d:
表5dTable 5d
取14.2份HDDA、0.03份THQ、45.3份步骤(1)合成的超支化聚氨酯加入反应釜，40℃条件下滴加40.4份步骤(2)合成的HMDI-PETA半加成物，滴加完后升温至75℃，加入0.07份Kat 320，继续反应约2h，至NCO值小于0.1％，得到乙烯基超支化聚氨酯。Take 14.2 parts of HDDA, 0.03 parts of THQ, and 45.3 parts of hyperbranched polyurethane synthesized in step (1) and add them to the reactor, and add 40.4 parts of the HMDI-PETA semi-adduct synthesized in step (2) dropwise at 40°C. Raise the temperature to 75°C, add 0.07 parts of Kat 320, continue the reaction for about 2 hours until the NCO value is less than 0.1%, and obtain vinyl hyperbranched polyurethane.
乙烯基超支化聚氨酯的参数如表5e：The parameters of vinyl hyperbranched polyurethane are shown in Table 5e:
表5eTable 5e
实施例6Example 6
当超支化聚氨酯的合成原料为甲苯二异氰酸酯(TDI)、乙基丁基丙二醇(BEPD)和二异丙醇胺(DIPA)时，代数与超支化聚氨酯的NCO值、羟基数和相对分子质量的关系如表6a：When the synthetic raw materials of hyperbranched polyurethane are toluene diisocyanate (TDI), ethylbutylpropylene glycol (BEPD) and diisopropanolamine (DIPA), the relationship between algebra and NCO value, hydroxyl number and relative molecular weight of hyperbranched polyurethane The relationship is shown in Table 6a:
表6aTable 6a
步骤(1)，超支化聚氨酯的合成Step (1), the synthesis of hyperbranched polyurethane
超支化聚氨酯配方如表6b：The formula of hyperbranched polyurethane is shown in Table 6b:
表6bTable 6b
取42.9份TDI和0.05份TBHQ加入反应釜，升温至45℃，取19.7份的BEPD溶于10.0份HDDA，滴加，30min滴完，滴完后继续反应30min，合成出A2中间体；降温至0℃，取16.4份DIPA溶于8.5份HDDA，滴加，35min滴完，滴完后继续反应20min，合成出AB2中间体；升温至40℃，加入0.05份DBTL，继续反应，每20min测NCO值，反应至NCO值为0.8％时，加入2.4份DNBA封端，合成出端羟基含量为2.6％的超支化聚氨酯树脂。Add 42.9 parts of TDI and 0.05 parts of TBHQ to the reactor, raise the temperature to 45°C, take 19.7 parts of BEPD and dissolve it in 10.0 parts of HDDA, add dropwise, and finish dropping for 30 minutes. Continue to react for 30 minutes after dropping, and synthesize A2 intermediate; cool down To 0°C, take 16.4 parts of DIPA dissolved in 8.5 parts of HDDA, add dropwise, drop over 35 minutes, continue to react for 20 minutes after dropping, synthesize AB2 intermediate; raise the temperature to 40°C, add 0.05 parts of DBTL, continue the reaction, every 20 minutes The NCO value was measured, and when the NCO value was 0.8%, 2.4 parts of DNBA was added for end-capping, and a hyperbranched polyurethane resin with a terminal hydroxyl content of 2.6% was synthesized.
步骤(2)，IPDI-SC1020半加成物的合成Step (2), the synthesis of IPDI-SC1020 semi-adduct
IPDI-SC1020半加成物的配方如表6c：The formula of IPDI-SC1020 semi-adduct is shown in Table 6c:
取47.6份IPDI、0.06份DBTL和0.04份TBHQ加入反应釜，40℃条件下滴加52.3份SC1020，30min滴完，滴完后继续反应35min，合成出NCO含量为Take 47.6 parts of IPDI, 0.06 parts of DBTL and 0.04 parts of TBHQ and add them to the reactor, add 52.3 parts of SC1020 dropwise at 40°C, drop them in 30 minutes, and continue to react for 35 minutes after the drops, the synthesized NCO content is
表6cTable 6c
11.5％的IPDI-HAP半加成物。11.5% IPDI-HAP hemiadduct.
步骤(3)，乙烯基超支化聚氨酯的合成Step (3), the synthesis of vinyl hyperbranched polyurethane
乙烯基超支化聚氨酯的配方如表6d：The formula of vinyl hyperbranched polyurethane is as table 6d:
表6dTable 6d
取14.2份HDDA、0.04份TBHQ、55.0份步骤(1)合成的超支化聚氨酯加入反应釜，35℃条件下滴加30.7份步骤(2)合成的IPDI-HAP半加成物，滴加完后升温至75℃，加入0.06份DBTL，继续反应约2h，至NCO值小于0.1％，得到乙烯基超支化聚氨酯。Take 14.2 parts of HDDA, 0.04 parts of TBHQ, and 55.0 parts of hyperbranched polyurethane synthesized in step (1) and add them to the reactor, and add 30.7 parts of IPDI-HAP semi-adducts synthesized in step (2) dropwise at 35°C. Raise the temperature to 75°C, add 0.06 parts of DBTL, continue the reaction for about 2 hours until the NCO value is less than 0.1%, and obtain vinyl hyperbranched polyurethane.
乙烯基超支化聚氨酯的参数如表6e：The parameters of vinyl hyperbranched polyurethane are shown in Table 6e:
表6eTable 6e
本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。The implementation of the present invention is not limited by the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods, including Within the protection scope of the present invention.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810403757.3ACN108641060A (en) | 2018-04-28 | 2018-04-28 | Cure vinyl ultra-branching polyurethane and preparation method thereof for UV-LED |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810403757.3ACN108641060A (en) | 2018-04-28 | 2018-04-28 | Cure vinyl ultra-branching polyurethane and preparation method thereof for UV-LED |
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| CN108641060Atrue CN108641060A (en) | 2018-10-12 |
| Application Number | Title | Priority Date | Filing Date |
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| CN201810403757.3APendingCN108641060A (en) | 2018-04-28 | 2018-04-28 | Cure vinyl ultra-branching polyurethane and preparation method thereof for UV-LED |
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