WO2021068275A1 - 一种深色体系光聚合组合物 - Google Patents

一种深色体系光聚合组合物 Download PDF

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WO2021068275A1
WO2021068275A1 PCT/CN2019/111547 CN2019111547W WO2021068275A1 WO 2021068275 A1 WO2021068275 A1 WO 2021068275A1 CN 2019111547 W CN2019111547 W CN 2019111547W WO 2021068275 A1 WO2021068275 A1 WO 2021068275A1
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dark
parts
acrylate
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colored
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刘仁
邹修成
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江南大学
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/064—Polymers containing more than one epoxy group per molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C08K5/3417—Five-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing compounds

Definitions

  • the invention relates to the technical field of photopolymerization materials, in particular to a dark-color system photopolymer composition.
  • the polymerization of dark-colored systems is currently mainly realized by thermal polymerization, which requires thermal baking treatment, and the curing efficiency is low.
  • thermal polymerization which requires thermal baking treatment, and the curing efficiency is low.
  • light curing technology has been developed rapidly in recent years.
  • the current commercial photoinitiator has a relatively short maximum absorption wavelength (mostly less than 500nm), and the penetration of light in this wavelength range in the resin system is limited.
  • the introduction of pigments, fillers and functional materials, especially black pigments The system makes the light basically unable to penetrate and cannot realize the photopolymerization, which limits the application of light curing technology in the dark system.
  • the present invention provides a photopolymerizable composition of a dark color system.
  • the photopolymerizable prepolymer and/or the photopolymerizable monomer have a polar group, and the polar group includes a hydroxyl group and an amino group.
  • the photopolymerizable prepolymer and/or photopolymerizable monomer with polar groups can significantly improve the dispersion effect of the dark pigment, and at the same time can increase the force between the prepolymer/monomer and the dark pigment, thereby increasing Mechanical properties of materials.
  • the photopolymerizable prepolymer includes one or more of urethane acrylate, epoxy acrylate, polyester acrylate, amino acrylate, epoxy resin, and vinyl resin; preferably It is one or more of urethane acrylate, epoxy acrylate, and epoxy resin.
  • the photopolymerizable monomers include monofunctional acrylate monomers, difunctional acrylate monomers, multifunctional acrylate monomers, ester ring epoxy monomers, oxa One or more of cyclobutane monomers; preferably isobornyl acrylate, neopentyl glycol diacrylate, dipentaerythritol hexaacrylate, 1-vinyl-2-pyrrolidone, tetrahydrofuran acrylate, o-benzene Phenoxyethyl acrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, 3,4-epoxycyclohexylmethyl-3,4-ring One or more of oxycyclohexyl formate.
  • the up-conversion material includes one or more of NaYF 4 , BaYF 5 , NaGdF 4 , LiYF 4 , NaYbF 4 , Na 3 ScF 6 , YF 3, and GdOF.
  • the dark pigment includes natural melanin.
  • the dark pigment includes a substance having the following structure:
  • the dark pigment is prepared by oxidation of 4-(2-aminoethyl)-1,2-benzenediol hydrochloride.
  • the photoinitiator includes 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethyl Ethyl benzoyl phenyl phosphonate, bis 2,6-difluoro-3-pyrrole phenyl titanocene, phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide, 2-iso Propylthioxanthone, 2-hydroxy-2-methyl-1-phenylpropanone, 2-methyl-2-(4-morpholinylphenyl)-1-[4-(methylthio)benzene Base)-1-acetone, 1,7,7'-trimethyl-bicyclo(2,2,1)heptane-1,3-dione, methyl diphenylsulfonium tetrafluoroborate, 4, One or more of 4'-dimethyl diphenyl iodonium salt hexafluor
  • Another object of the present invention is to provide the application of the aforementioned dark-colored system photopolymerization composition, which undergoes photopolymerization under near-infrared light irradiation to form a dark-colored crosslinked polymer.
  • the curing depth of the dark cross-linked polymer is 0.01-30 mm
  • the wavelength of the near-infrared light is 800-1100 nm; the energy density of the near-infrared light is greater than 1 W/cm 2 and less than 20 W/cm 2 .
  • the present invention uses dark pigments to replace the carbon black filler in the black resin system, and selects up-conversion materials, dark pigments, and photoinitiators of a certain concentration and proportion to be added to the photopolymerization system. It realizes that the maximum curing depth of dark system reaches centimeter level.
  • the method of the present invention is simple and efficient, breaks through the difficult problem of traditional dark system photopolymerization, broadens the application field of photopolymerization technology, and is suitable for dark light curing coatings and photocuring Composite materials and other technical fields.
  • the dark pigment used in the present invention can avoid the absorption of near-infrared light, and the up-conversion material can absorb near-infrared light with good penetrating ability and emit ultraviolet or visible light, which induces the decomposition of free radicals or ionic photoinitiators in the composition and excites
  • the other components in the composition act synergistically to realize the photopolymerization reaction of the photopolymerizable material, thereby realizing the polymerization of the dark color composition, and increasing the photopolymerization depth of the dark color composition.
  • the interaction between the components can also act as a physical cross-linking point and improve the mechanical properties of the polymer.
  • Figure 1 is a schematic diagram of the photopolymerization reaction of the composition of the present invention.
  • Figure 2 shows the curing depth of Examples 1-4 and Comparative Example 5 of the present invention.
  • Figure 3 is the test data curve of Examples 1-4 and Comparative Example 5 of the present invention.
  • Figure 4 is a test curve of Examples 1-4 of the present invention.
  • the photopolymerizable prepolymer, monomer, photoinitiator, melanin, and upconversion material are mixed uniformly and put into a test tube. After being irradiated with near-infrared light, the absorption of melanin can be avoided.
  • the upconversion material absorbs and emits ultraviolet light or visible light, and promotes the decomposition of the photoinitiator to initiate a photopolymerization reaction to obtain the final crosslinked product.
  • Synthesis of melanin 180 mg of dopamine hydrochloride was dissolved in 90 mL of deionized water. Under vigorous stirring at 50°C, 760 ⁇ L of 1 mol/L NaOH solution was added to the above solution.
  • the color of the solution changed to light yellow and gradually changed to dark brown.
  • the melanin-like nanoparticles were recovered by centrifugation at 18000 rpm, washed with deionized water three times, and dried.
  • the structure is as follows:
  • n is in the range of 50-400
  • a composition for realizing deep-layer photopolymerization of a black system the components contained in the composition and the mass parts of each component are:
  • a composition for realizing deep-layer photopolymerization of a black system The components and the mass parts of each component are the same as those in Example 1. The difference is that the melanin content is changed to 0.3 parts, and the composition is obtained under the same light conditions.
  • the length of the column is 22 mm as shown in Figure 2, and the double bond conversion is about 56% as shown in Figure 3.
  • the above composition was used to prepare tensile specimens and subjected to mechanical testing.
  • the tensile strength is as shown in Figure 4, which is about 34 MPa.
  • a composition for realizing deep-layer photopolymerization of a black system The components and the mass parts of each component are the same as those in Example 1. The difference is that the melanin content is changed to 0.5 part, and the composition is obtained under the same light conditions.
  • the length of the column is 17 mm as shown in Figure 2, and the double bond conversion rate is about 52% as shown in Figure 3.
  • the above composition was used to prepare tensile specimens and subjected to mechanical testing. The tensile strength is shown in Figure 4, which is approximately 36 MPa.
  • a composition for realizing deep-layer photopolymerization of a black system The components and the mass parts of each component are the same as those in Example 1. The difference is that the content of melanin is changed to 1 part, and the composition is obtained under the same light conditions.
  • the length of the column is 9 mm as shown in Fig. 2, and the double bond conversion rate is as shown in Fig. 3, which is about 45%.
  • a tensile test strip was prepared from the above composition and subjected to a mechanical test. The tensile strength is shown in Figure 4, which is about 41 MPa.
  • melanin acts as a physical cross-linking point, and the tensile strength gradually increases.
  • composition of traditional carbon black black filler system photopolymerization the components and the mass parts of each component contained in the composition are:
  • the blocking ability of carbon black to near-infrared is higher than melanin, making it difficult for near-infrared to penetrate the sample, the curing depth is limited, and the conversion rate is lower than that of the melanin system.
  • a composition for realizing deep-layer photopolymerization of a black system the components contained in the composition and the mass parts of each component are:
  • the above composition was mixed using a film applicator applied to the surface of the iron plate 200 micron coating thickness, the use of the emission wavelength 1000nm, the energy density of the irradiation light 15W / cm 2, and curing for 1 minute, the bottom bis
  • the bond conversion rate is greater than 65%, and the paint film hardness is 4H.
  • a composition for realizing deep-layer photopolymerization of a black system the components contained in the composition and the mass parts of each component are:
  • the above composition was mixed using a film applicator applied to the surface of the iron plate 200 micron coating thickness, the use of emission wavelength 980nm, an energy density of the irradiation light 8W / cm 2 to 0.5 minutes after curing, the underlying bis
  • the bond conversion rate is greater than 60%, and the paint film hardness is 5H.
  • a composition for realizing deep-layer photopolymerization of a black system the components contained in the composition and the mass parts of each component are:
  • Up-conversion material LiYF 4 0.05 parts.
  • the above composition was mixed using a film applicator applied to the surface of the iron plate 200 micron coating thickness, the use of the emission wavelength 1000nm, the energy density of the irradiation light source 1W / cm 2 in 5 minutes after curing, the underlying bis The bond conversion rate is greater than 60%, and the paint film hardness is 2H.

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Abstract

本发明公开了一种深色体系光聚合的组合物，属于光聚合材料技术领域。该组合物所含组分及各组分质量份数为：可光聚合预聚体20-80份，可光聚合单体5-60份，光引发剂0.2-8份，黑色素0.1-5份，上转换材料0.05-5份。所述组合物在近红外光的直接辐照下能够发生光聚合反应。深色色素能够避开对近红外光的强吸收，利用上转换材料能够吸收穿透性较好近红外光并发射紫外光或可见光，诱导组合物中自由基或离子型光引发剂分解，进而实现可光聚合物质的光聚合反应，从而实现深色组合物的聚合，并提升深色组合物的光聚合深度，提高聚合物的力学性能，拓宽了应用领域。

Description

一种深色体系光聚合组合物 技术领域
本发明涉及光聚合材料技术领域，尤其是涉及一种深色体系光聚合物组合物。
背景技术
深色体系聚合目前主要通过热聚合实现，需要采用热烘处理，固化效率较低。光固化技术作为一项高效环保的绿色技术，近年来得到飞速发展。但是，现阶段商品化光引发剂最大吸收波长较短(大部分小于500nm)，而这一波段的光在树脂体系的穿透能力有限，加上颜填料和功能材料的引入，尤其是黑色颜料体系，造成光基本无法穿透，无法实现光聚合，限制了光固化技术在深色体系的应用。
因此，有必要研究开发一种可进行光固化的深色材料体系。
发明内容
为了解决上述问题，本发明提供了一种深色体系的光聚合的组合物。
本发明的技术方案如下：
一种深色体系光聚合组合物所含组分及各组分质量份数为：
可光聚合预聚体20-80份；
可光聚合单体5-60份；
光引发剂0.2-8份；
深色色素0.1-5份；
上转换材料0.05-5份。
在一种实施方案中，所述可光聚合预聚体和/或可光聚合单体带有极性基团，所述极性基团包括羟基、氨基。
所述带极性基团的可光聚合预聚体和/或可光聚合单体能够明显提升对深色素的分散效果，同时可增加预聚体/单体与深色素间作用力，提高了材料力学性能。
在一种实施方案中，所述可光聚合预聚体包括聚氨酯丙烯酸酯、环氧丙烯酸酯、聚酯丙烯酸酯、氨基丙烯酸酯、环氧树脂、乙烯基树脂中的一种或多种；优选为聚氨酯丙烯酸酯、环氧丙烯酸酯、环氧树脂的一种或多种。
在一种实施方案中，所述可光聚合单体包括单官能丙烯酸酯类单体、双官能丙烯酸酯类单体、多官能丙烯酸酯类单体、酯环族环氧类单体、氧杂环丁烷类单体中的一种或多种；优选为丙烯酸异冰片酯、新戊二醇二丙烯酸酯、二季戊四醇六丙烯酸酯、1-乙烯基-2-吡咯烷酮、 四氢呋喃丙烯酸酯、邻苯基苯氧基乙基丙烯酸酯、1,6-已二醇双丙烯酸酯、三羟甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、3,4-环氧环己基甲基-3,4-环氧环已基甲酸酯的一种或多种。
在一种实施方案中，所上转换材料包括NaYF 4、BaYF 5、NaGdF 4、LiYF 4、NaYbF 4、Na 3ScF 6、YF 3、GdOF中的一种或多种。
在一种实施方案中，所述深色色素包括天然黑色素。
在一种实施方案中，所述深色色素包括具有如下结构的物质：
Figure PCTCN2019111547-appb-000001
其中n的范围为50-400；m的范围为50-400。
在一种实施方案中，所述深色色素由4-(2-氨基乙基)-1,2-苯二酚盐酸盐氧化制备所得。
在一种实施方案中，所述光引发剂包括2,4,6-三甲基苯甲酰二苯基氧化膦、1-羟基环己基苯基甲酮、2,4,6-三甲基苯甲酰基苯基膦酸乙酯、双2,6-二氟-3-吡咯苯基二茂钛、苯基双(2,4,6-三甲基苯甲酰基)氧化膦、2-异丙基硫杂蒽酮、2-羟基-2-甲基-1-苯基丙酮、2-甲基-2-(4-吗啉基苯基)-1-[4-(甲硫基)苯基]-1-丙酮、1,7,7'-三甲基-双环(2,2,1)庚烷-1,3-二酮、四氟硼酸甲基二苯基硫鎓盐、4,4'-二甲基二苯基碘鎓盐六氟磷酸盐中的一种或多种；优选为2,4,6-三甲基苯甲酰二苯基氧化膦、双2,6-二氟-3-吡咯苯基二茂钛、4,4'-二甲基二苯基碘鎓盐六氟磷酸盐的一种或多种。
本发明的另一个目的在于提供上述一种深色体系光聚合组合物的应用，在近红外光的辐照下发生光聚合反应形成深色交联聚合物。
在一种实施方案中，所述深色交联聚合物的固化深度为0.01～30mm
在一种实施方案中，所述近红外光的波长为800-1100nm；所述近红外光的能量密度大于1W/cm 2，小于20W/cm 2。
本发明的有益效果：
本发明使用深色色素代替了黑色树脂体系中的炭黑填料，并且选用一定的浓度和比例的上转换材料、深色色素、光引发剂添加至光聚合体系中，在近红外光的辐照下实现深色体系最大固化深度达到厘米级，本发明方法简单高效，突破了传统深色体系光聚合难以固化的难题，拓宽了光聚合技术的应用领域，适用于深色光固化涂料、光固化复合材料等技术领域。
本发明所用深色色素能够避开吸收近红外光，利用上转换材料能够吸收穿透性较好近红 外光并发射紫外光或可见光，诱导组合物中自由基或离子型光引发剂分解，激发组合物中其他组分相互协同作用，进而实现可光聚合物质的光聚合反应，从而实现深色组合物的聚合，并提升深色组合物的光聚合深度。与此同时，各组分之间的相互作用，还能起到物理交联点的作用，提高了聚合物的力学性能。
附图说明
图1为本发明组合物发生光聚合反应示意图。
图2为本发明实施例1-4以及对比例5的固化深度。
图3为本发明实施例1-4以及对比例5的测试数据曲线。
图4为本发明实施例1-4的测试曲线。
具体实施方式：
下面结合附图和实施例，对本发明进行具体描述。
如图1所示，将可光聚合的预聚体、单体、光引发剂、黑色素、上转换材料混合均匀后放入试管中，经过近红外光辐照后，避开黑色素的吸收，能够被上转换材料吸收并发射紫外光或可见光，促使光引发剂分解引发光聚合反应得到最终交联产物。黑色素的合成：180mg多巴胺盐酸盐溶解在90mL去离子水中。50℃剧烈搅拌下，将760μL1mol/L的NaOH溶液加入上述溶液中。溶液的颜色变为浅黄色，并逐渐变为深棕色。老化5小时后，通过18000rpm离心回收黑色素样纳米颗粒，并用去离子水洗涤三次，烘干。结构如下：
Figure PCTCN2019111547-appb-000002
其中n的范围为50-400
实施例1
一种实现黑色体系的深层光聚合的组合物，所述组合物所含组分及各组分质量份数为：
聚氨酯丙烯酸酯75份，
三羟甲基丙烷三丙烯酸酯20份，
双2,6-二氟-3-吡咯苯基二茂钛3份，
黑色素0.1份，
上转换材料NaYF 4 2份。
将上述组合物混合均匀加入到试管中，竖直放置后使用发射波长980nm，能量密度为10W/cm 2的光源在试管顶部朝下进行辐照，5分钟后固化获得一定长度的柱状物，当黑色素含 量为0.1份时，测试结果见图2所示，柱状物长度为29mm，双键转化率如图3所示，约为60％。上述组合物制备拉伸样条，进行力学测试，拉伸强度如图4，约为27MPa。
实施例2
一种实现黑色体系的深层光聚合的组合物，所述组合物所含组分及各组分质量份数同实施例1，不同点在于改变黑色素的含量为0.3份，采用相同光照条件下所得柱状物长度，如图2所示22mm，双键转化率如图3所示，约为56％。上述组合物制备拉伸样条，进行力学测试，拉伸强度如图4，约为34MPa。
实施例3
一种实现黑色体系的深层光聚合的组合物，所述组合物所含组分及各组分质量份数同实施例1，不同点在于改变黑色素的含量为0.5份，采用相同光照条件下所得柱状物长度，如图2所示17mm，双键转化率如图3所示，约为52％。上述组合物制备拉伸样条，进行力学测试，拉伸强度如图4，约为36MPa。
实施例4
一种实现黑色体系的深层光聚合的组合物，所述组合物所含组分及各组分质量份数同实施例1，不同点在于改变黑色素的含量为1份，采用相同光照条件下所得柱状物长度，如图2所示9mm，双键转化率如图3所示，约为45％。上述组合物制备拉伸样条，进行力学测试，拉伸强度如图4，约为41MPa。
由此，随着黑色素含量的增加，由于黑色素和样品之间的氢键作用，黑色素作为物理交联点，拉伸强度逐渐增强。
对比例5
传统炭黑黑色填料体系光聚合的组合物，所述组合物所含组分及各组分质量份数为：
聚氨酯丙烯酸酯75份，
三羟甲基丙烷三丙烯酸酯20份，
双2,6-二氟-3-吡咯苯基二茂钛3份，
炭黑0.1份，
上转换材料NaYF 4 2份。
将上述组合物混合均匀加入到试管中，竖直放置后使用发射波长980nm，能量密度为10 W/cm 2的光源在试管顶部朝下进行辐照，5分钟后固化获得一定长度的柱状物，当炭黑含量为0.1份时，测试结果见图2所示，柱状物长度为2mm，双键转化率如图3所示，约为40％。
由此，炭黑对近红外的阻隔能力高于黑色素，使得近红外难以穿透样品，固化深度有限，转化率较黑色素体系也较低。
实施例6
一种实现黑色体系的深层光聚合的组合物，所述组合物所含组分及各组分质量份数为：
环氧丙烯酸酯60份，
季戊四醇三丙烯酸酯30份，
2,4,6-三甲基苯甲酰二苯基氧化膦8份，
黑色素2份，
上转换材料BaYF 5 0.05份。
将上述组合物混合均匀，利用漆膜涂布器在铁板表面涂布厚度为200微米涂层，使用发射波长1000nm，能量密度为15W/cm 2的光源辐照，1分钟后固化，底层双键转化率大于65％，漆膜硬度4H。
实施例7
一种实现黑色体系的深层光聚合的组合物，所述组合物所含组分及各组分质量份数为：
环氧树酯50份，
3,4-环氧环己基甲基-3,4-环氧环已基甲酸酯40份，
4,4'-二甲基二苯基碘鎓盐六氟磷酸盐3份，
黑色素5份，
上转换材料NaGdF 4 2份。
将上述组合物混合均匀，利用漆膜涂布器在铁板表面涂布厚度为200微米涂层，使用发射波长980nm，能量密度为8W/cm 2的光源辐照，0.5分钟后固化，底层双键转化率大于60％，漆膜硬度5H。
实施例8
一种实现黑色体系的深层光聚合的组合物，所述组合物所含组分及各组分质量份数为：
环氧树酯70份，
3,4-环氧环己基甲基-3,4-环氧环已基甲酸酯20份，
4,4'-二甲基二苯基碘鎓盐六氟磷酸盐8份，
黑色素2份，
上转换材料LiYF 4 0.05份。
将上述组合物混合均匀，利用漆膜涂布器在铁板表面涂布厚度为200微米涂层，使用发射波长1000nm，能量密度为1W/cm 2的光源辐照，5分钟后固化，底层双键转化率大于60％，漆膜硬度2H。

Claims (12)

  1. 一种深色体系光聚合组合物，其特征在于，所述组合物所含组分及各组分质量份数为：
    可光聚合预聚体20-80份；
    可光聚合单体5-60份；
    光引发剂0.2-8份；
    深色色素0.1-5份；
    上转换材料0.05-5份。
  2. 根据权利要求1所述的一种深色体系光聚合组合物，其特征在于，所述可光聚合预聚体和/或可光聚合单体带有极性基团，所述极性基团包括羟基、氨基。
  3. 根据权利要求1或2所述的一种深色体系光聚合组合物，其特征在于，所述可光聚合预聚体包括聚氨酯丙烯酸酯、环氧丙烯酸酯、聚酯丙烯酸酯、氨基丙烯酸酯、环氧树脂、乙烯基树脂中的一种或多种；优选为聚氨酯丙烯酸酯、环氧丙烯酸酯、环氧树脂的一种或多种。
  4. 根据权利要求1或2所述的一种深色体系光聚合组合物，其特征在于，所述可光聚合单体包括单官能丙烯酸酯类单体、双官能丙烯酸酯类单体、多官能丙烯酸酯类单体、酯环族环氧类单体、氧杂环丁烷类单体中的一种或多种；优选为丙烯酸异冰片酯、新戊二醇二丙烯酸酯、二季戊四醇六丙烯酸酯、1-乙烯基-2-吡咯烷酮、四氢呋喃丙烯酸酯、邻苯基苯氧基乙基丙烯酸酯、1,6-已二醇双丙烯酸酯、三羟甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、3,4-环氧环己基甲基-3,4-环氧环已基甲酸酯的一种或多种。
  5. 根据权利要求1所述的一种深色体系光聚合组合物，其特征在于，所述上转换材料包括NaYF 4、BaYF 5、NaGdF 4、LiYF 4、NaYbF 4、Na 3ScF 6、YF 3、GdOF中的一种或多种。
  6. 根据权利要求1所述的一种深色体系光聚合组合物，其特征在于，所述深色色素包括天然黑色素。
  7. 根据权利要求1或7所述的一种深色体系光聚合组合物，其特征在于，所述深色色素包括具有如下结构的物质：
    Figure PCTCN2019111547-appb-100001
    其中n的范围为50-400；m的范围为50-400。
  8. 根据权利要求1或7所述的一种深色体系光聚合组合物，其特征在于，所述深色色素 由4-(2-氨基乙基)-1,2-苯二酚盐酸盐氧化制备所得。
  9. 根据权利要求1所述的一种深色体系光聚合组合物，其特征在于，所述光引发剂包括2,4,6-三甲基苯甲酰二苯基氧化膦、1-羟基环己基苯基甲酮、2,4,6-三甲基苯甲酰基苯基膦酸乙酯、双2,6-二氟-3-吡咯苯基二茂钛、苯基双(2,4,6-三甲基苯甲酰基)氧化膦、2-异丙基硫杂蒽酮、2-羟基-2-甲基-1-苯基丙酮、2-甲基-2-(4-吗啉基苯基)-1-[4-(甲硫基)苯基]-1-丙酮、1,7,7'-三甲基-双环(2,2,1)庚烷-1,3-二酮、四氟硼酸甲基二苯基硫鎓盐、4,4'-二甲基二苯基碘鎓盐六氟磷酸盐中的一种或多种；优选为2,4,6-三甲基苯甲酰二苯基氧化膦、双2,6-二氟-3-吡咯苯基二茂钛、4,4'-二甲基二苯基碘鎓盐六氟磷酸盐的一种或多种。
  10. 根据权利要求1所述的一种深色体系光聚合组合物的应用，其特征在于，在近红外光的辐照下发生光聚合反应形成深色交联聚合物。
  11. 根据权利要求11所述的一种深色体系光聚合组合物的应用，其特征在于，所述组合物的固化深度为0.01～30mm。
  12. 根据权利要求11所述的一种深色体系光聚合组合物的应用，其特征在于，所述近红外光的波长为800-1100nm；所述近红外光的能量密度大于1W/cm 2，小于20W/cm 2。
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