CN107936158A - A kind of light-initiated high molecular polymer and preparation method thereof - Google Patents
A kind of light-initiated high molecular polymer and preparation method thereof Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000011941 photocatalyst Substances 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 11
- 238000001556 precipitation Methods 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical group O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 claims description 7
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229940043267 rhodamine b Drugs 0.000 claims description 5
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 4
- NJDNXYGOVLYJHP-UHFFFAOYSA-L disodium;2-(3-oxido-6-oxoxanthen-9-yl)benzoate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=CC(=O)C=C2OC2=CC([O-])=CC=C21 NJDNXYGOVLYJHP-UHFFFAOYSA-L 0.000 claims description 4
- 238000005286 illumination Methods 0.000 claims description 4
- 229940047670 sodium acrylate Drugs 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- 229960001483 eosin Drugs 0.000 claims description 3
- SEACYXSIPDVVMV-UHFFFAOYSA-L eosin Y Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 SEACYXSIPDVVMV-UHFFFAOYSA-L 0.000 claims description 3
- GRONZTPUWOOUFQ-UHFFFAOYSA-M sodium;methanol;hydroxide Chemical compound [OH-].[Na+].OC GRONZTPUWOOUFQ-UHFFFAOYSA-M 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 2
- VYXSBFYARXAAKO-WTKGSRSZSA-N chembl402140 Chemical compound Cl.C1=2C=C(C)C(NCC)=CC=2OC2=C\C(=N/CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-WTKGSRSZSA-N 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract 1
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 abstract 1
- 239000000047 product Substances 0.000 description 16
- 239000011521 glass Substances 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 3
- OALHHIHQOFIMEF-UHFFFAOYSA-N 3',6'-dihydroxy-2',4',5',7'-tetraiodo-3h-spiro[2-benzofuran-1,9'-xanthene]-3-one Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 OALHHIHQOFIMEF-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000012698 light-induced step-growth polymerization Methods 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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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
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/04—Acids; Metal salts or ammonium salts thereof
- C08F120/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- 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
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerization Catalysts (AREA)
Abstract
一种光引发的高分子聚合物及其制备方法，这种高分子聚合物的重均分子量从1000到1,000,000g/mol。制备方法中的使用单体是丙烯酸及其酯类、甲基丙烯酸及其酯类、苯乙烯衍生物、乙酸乙烯酯，其转化率大于等于60％。在方法中使用光催化剂与聚合物对应单体的混合物在可见光照射下，于室温进条件下进行聚合反应。
A light-initiated high molecular polymer and a preparation method thereof. The weight average molecular weight of the high molecular polymer is from 1,000 to 1,000,000 g/mol. The monomers used in the preparation method are acrylic acid and its esters, methacrylic acid and its esters, styrene derivatives and vinyl acetate, and the conversion rate is greater than or equal to 60%. In the method, the mixture of the photocatalyst and the corresponding monomer of the polymer is used to carry out the polymerization reaction under the condition of room temperature under the irradiation of visible light.
Description
技术领域technical field
本发明属于溶液聚合技术领域，涉及一种光引发的高分子聚合物及其制备方法。The invention belongs to the technical field of solution polymerization, and relates to a photoinitiated high molecular polymer and a preparation method thereof.
背景技术Background technique
光聚合是一种十分常用的技术，通常可分为光直接引发聚合，或光通过光引发剂引发聚合。丙烯酸树脂在紫外光照射下固化就属于前者，后者往往需要特定的光引发剂。而光引发剂通常难以合成或成本很高，而且多为消耗品。因此需要发展出其他的途径来实现光聚合。Photopolymerization is a very commonly used technique, which can usually be divided into direct photopolymerization or photopolymerization via photoinitiators. The curing of acrylic resin under ultraviolet light belongs to the former, and the latter often requires a specific photoinitiator. However, photoinitiators are usually difficult or expensive to synthesize, and most of them are consumables. Therefore, it is necessary to develop other ways to achieve photopolymerization.
荧光素类与罗丹明类都属于十分常见的荧光物质，经常被用于生物切片的染色。相对于传统光引发剂而言，二者使用可见光、日光进行聚合，这毫无疑问会极大地改善施工条件，减少紫外光对于人体的伤害。另外一方面，荧光素与罗丹明都易于溶解在水中、甲醇中，在聚合反应之后可以轻易的通过多次沉淀溶解的方法除净光催化剂本身的颜色，更不会产生其他光引发聚合中泛黄现象。Both fluoresceins and rhodamines are very common fluorescent substances and are often used for staining biological sections. Compared with traditional photoinitiators, the two use visible light and sunlight for polymerization, which will undoubtedly greatly improve the construction conditions and reduce the harm of ultraviolet light to the human body. On the other hand, both fluorescein and rhodamine are easy to dissolve in water and methanol. After the polymerization reaction, the color of the photocatalyst itself can be easily removed by multiple precipitation and dissolution methods, and it will not produce other light-induced polymerization. yellow phenomenon.
发明内容Contents of the invention
本发明的目的是提供一种光引发聚合的方法。另一目的是提供上述方法制备的聚合物。The object of the present invention is to provide a method for photoinitiated polymerization. Another object is to provide polymers prepared by the above method.
为实现上述目的，本发明的技术方案如下：To achieve the above object, the technical scheme of the present invention is as follows:
一种光引发的高分子聚合物的制备方法，包含以下步骤，A method for preparing a light-induced high molecular polymer, comprising the following steps,
a)在容器中将单体与溶剂配置成一种混合溶液，并加入光催化剂；a) configuring the monomer and the solvent into a mixed solution in the container, and adding a photocatalyst;
b)在容器中通入氮气并保持密闭；b) Infuse nitrogen into the container and keep it airtight;
c)在光照条件下混合溶液发生聚合反应；c) a polymerization reaction occurs by mixing the solution under light conditions;
d)向步骤c)的溶液中加入不良溶剂，沉淀出产品后过滤并干燥，干燥后得到固体；d) adding a poor solvent to the solution in step c), filtering and drying the product after precipitation, and obtaining a solid after drying;
e)使用溶剂将步骤d)的产品溶解后，重复步骤d)的沉淀、干燥、溶解过程，直至得到无色的高分子聚合物；e) After dissolving the product in step d) with a solvent, repeat the process of precipitation, drying, and dissolution in step d), until a colorless polymer is obtained;
所述步骤c)的光照条件用420-600nm的可见光，光照时间是6-24小时。The illumination condition of the step c) is 420-600nm visible light, and the illumination time is 6-24 hours.
优选的，所述步骤a)的光催化剂的化学结构包含共轭体系，所述光催化剂是荧光素、荧光素钠、四溴荧光素、四碘荧光素、罗丹明B、罗丹明6G。Preferably, the chemical structure of the photocatalyst in step a) includes a conjugated system, and the photocatalyst is fluorescein, sodium fluorescein, tetrabromofluorescein, tetraiodofluorescein, rhodamine B, rhodamine 6G.
优选的，所述步骤a)的单体是丙烯酸、甲基丙烯酸、苯乙烯、乙酸乙烯酯、丙烯酰胺、丙烯腈、N,N-二甲基丙烯酰胺、丁二烯、氯乙烯、丙烯酸钠、甲基丙烯酸甲酯中的至少一种。Preferably, the monomer in step a) is acrylic acid, methacrylic acid, styrene, vinyl acetate, acrylamide, acrylonitrile, N,N-dimethylacrylamide, butadiene, vinyl chloride, sodium acrylate , at least one of methyl methacrylate.
优选的，所述步骤a)的溶剂是水、四氢呋喃、N,N-二甲基甲酰胺、丙酮、甲苯、石油醚、二甲亚砜中的至少一种。Preferably, the solvent in step a) is at least one of water, tetrahydrofuran, N,N-dimethylformamide, acetone, toluene, petroleum ether, and dimethyl sulfoxide.
优选的，所述步骤b)在容器中通入氮气15-40分钟。Preferably, in the step b), nitrogen gas is passed into the container for 15-40 minutes.
优选的，所述步骤c)的光照强度范围是400-4000勒克斯，所述聚合反应的温度范围是0℃至40℃。Preferably, the light intensity range of step c) is 400-4000 lux, and the temperature range of the polymerization reaction is 0°C to 40°C.
优选的，所述步骤d)的不良溶剂是氢氧化钠甲醇、甲醇。Preferably, the poor solvent of step d) is sodium hydroxide methanol, methanol.
优选的，步骤d)得到的固体中的光催化剂含量应小于等于100ppm。Preferably, the photocatalyst content in the solid obtained in step d) should be less than or equal to 100ppm.
上述方法制备得到的高分子聚合物，所述高分子聚合物的重均分子量范围是从1000到1,000,000g/mol。In the high molecular polymer prepared by the above method, the weight average molecular weight of the high molecular polymer ranges from 1000 to 1,000,000 g/mol.
优选的，所述高分子聚合物的重均分子量范围是在1000到400,000g/mol。Preferably, the weight average molecular weight of the high molecular weight polymer is in the range of 1000 to 400,000 g/mol.
本发明的优点和有益效果：Advantages and beneficial effects of the present invention:
1、可见光引发聚合，避免了紫外光对人体的危害，改善施工条件。1. Visible light triggers polymerization, which avoids the harm of ultraviolet light to the human body and improves construction conditions.
2、本发明所描述方法可广泛应用于多种单体、溶剂，具有广泛适用性。2. The method described in the present invention can be widely applied to various monomers and solvents, and has wide applicability.
3、本发明所描述方法可实现在阳光下快速聚合，可用于特殊用途。3. The method described in the present invention can realize rapid polymerization under sunlight, and can be used for special purposes.
4、本发明最后得到的聚合产物转化率高，大于等于60％。聚合物重均分子量从1000到1,000,000g/mol，得到单体转化率大于等于60％的丙烯酸及其酯类、甲基丙烯酸及其酯类、苯乙烯衍生物、乙酸乙烯酯的均聚物或共聚物。4. The conversion rate of the polymer product finally obtained in the present invention is high, greater than or equal to 60%. The weight-average molecular weight of the polymer is from 1,000 to 1,000,000 g/mol, and the homopolymer of acrylic acid and its esters, methacrylic acid and its esters, styrene derivatives, and vinyl acetate with a monomer conversion rate greater than or equal to 60% or copolymer.
5、为了克服光引发剂光照易变色等特点。本发明采用廉价易得的荧光物质作为可循环使用的光催化剂代替了光引发剂。荧光素与罗丹明等有机荧光物质分子中含有比较大的共轭体系，这会对光产生比较明显的吸收，吸收光的分子变成激发态，再变回基态的过程中放出荧光。5. In order to overcome the characteristics of photoinitiators that are easy to change color under light. The invention adopts cheap and easy-to-obtain fluorescent substances as recyclable photocatalysts instead of photoinitiators. The molecules of organic fluorescent substances such as fluorescein and rhodamine contain relatively large conjugated systems, which will produce more obvious absorption of light. The molecules that absorb light become excited states, and then emit fluorescence during the process of returning to the ground state.
附图说明Description of drawings
图1是荧光素的化学结构图(a)与罗丹明B的化学结构图(b)。Figure 1 is the chemical structure diagram (a) of fluorescein and the chemical structure diagram (b) of rhodamine B.
图2是较低分子量的聚合物GPC测试结果图。Figure 2 is a graph of the GPC test results of lower molecular weight polymers.
图3是重均分子量210,000g/mol的聚合物测试结果图。Figure 3 is a graph showing the test results of a polymer with a weight average molecular weight of 210,000 g/mol.
图4是一些含有共轭结构的物质的化学结构图。Figure 4 is a diagram of the chemical structures of some substances containing conjugated structures.
具体实施方式Detailed ways
下面结合具体实施例对本发明作进一步的说明。The present invention will be further described below in conjunction with specific examples.
实施例1Example 1
将5g丙烯酸，10g水，加入到透明玻璃烧瓶中，再加入0.01g罗丹明B，向瓶内通入氮气同时搅拌均匀。20分钟后，用玻璃塞盖住防止氧气进入。在550nm绿光照射下发生聚合反应，24h后取出，把产品溶液逐滴加入50ml 0.2mol/L氢氧化钠甲醇溶液中，得到聚合物沉淀，过滤干燥后重复溶解-沉淀最后得到产品。Add 5g of acrylic acid and 10g of water into a transparent glass flask, then add 0.01g of rhodamine B, feed nitrogen into the bottle and stir evenly. After 20 minutes, cover with a glass stopper to prevent oxygen ingress. Polymerization occurs under the irradiation of 550nm green light, take it out after 24 hours, add the product solution dropwise to 50ml 0.2mol/L sodium hydroxide methanol solution, obtain polymer precipitate, filter and dry, repeat dissolution-precipitation and finally obtain the product.
实施例2Example 2
将5g丙烯酸钠，10g水，加入到透明玻璃烧瓶中，再加入0.01g荧光素钠，向瓶内通入氮气同时搅拌均匀。20分钟后，用玻璃塞盖住防止氧气进入。在480nm蓝光照射下发生聚合反应，24h后取出，把产品溶液逐滴加入50ml甲醇中，得到聚合物沉淀，过滤干燥后重复溶解-沉淀最后得到产品。Add 5g of sodium acrylate and 10g of water into a transparent glass flask, then add 0.01g of sodium fluorescein, pass nitrogen gas into the bottle and stir evenly. After 20 minutes, cover with a glass stopper to prevent oxygen ingress. The polymerization reaction occurred under the irradiation of 480nm blue light, and it was taken out after 24 hours. The product solution was added dropwise to 50ml of methanol to obtain a polymer precipitate. After filtration and drying, the dissolution-precipitation was repeated to obtain the product.
实施例3Example 3
将5g丙烯酸，10g水，加入到透明玻璃烧瓶中，再加入0.01g罗丹明B，向瓶内通入氮气同时搅拌均匀。20分钟后，用玻璃塞盖住防止氧气进入。在日光照射下发生聚合反应，依据阳光强度照射6h，把产品溶液逐滴加入50ml甲醇中，得到聚合物沉淀，过滤干燥后重复溶解-沉淀最后得到产品。Add 5g of acrylic acid and 10g of water into a transparent glass flask, then add 0.01g of rhodamine B, feed nitrogen into the bottle and stir evenly. After 20 minutes, cover with a glass stopper to prevent oxygen ingress. Polymerization occurs under sunlight irradiation. According to the intensity of sunlight for 6 hours, the product solution is added dropwise to 50ml of methanol to obtain a polymer precipitate. After filtration and drying, the dissolution-precipitation is repeated to obtain the product.
实施例4Example 4
将5g丙烯酸钠，10g水，加入到透明玻璃烧瓶中，再加入0.01g荧光素钠，向瓶内通入氮气同时搅拌均匀。20分钟后，用玻璃塞盖住防止氧气进入。在日光照射下发生聚合反应，依据阳光强度照射6h，把产品溶液逐滴加入50ml甲醇中，得到聚合物沉淀，过滤干燥后重复溶解-沉淀最后得到产品。Add 5g of sodium acrylate and 10g of water into a transparent glass flask, then add 0.01g of sodium fluorescein, pass nitrogen gas into the bottle and stir evenly. After 20 minutes, cover with a glass stopper to prevent oxygen ingress. Polymerization occurs under sunlight irradiation. According to the intensity of sunlight for 6 hours, the product solution is added dropwise to 50ml of methanol to obtain a polymer precipitate. After filtration and drying, the dissolution-precipitation is repeated to obtain the product.
实施例5Example 5
将5g甲基丙烯酸甲酯，10ml二甲亚砜，加入到透明玻璃烧瓶中，再加入0.01g荧光素与0.003g三乙胺，向瓶内通入氮气同时搅拌均匀。20分钟后，用玻璃塞盖住防止氧气进入。在480nm蓝光照射下发生聚合反应，24h后取出，把产品溶液逐滴加入50ml甲醇中，得到聚合物沉淀，过滤干燥后重复溶解-沉淀最后得到产品。Add 5g of methyl methacrylate and 10ml of dimethyl sulfoxide into a transparent glass flask, then add 0.01g of fluorescein and 0.003g of triethylamine, blow nitrogen into the bottle and stir evenly. After 20 minutes, cover with a glass stopper to prevent oxygen ingress. The polymerization reaction occurred under the irradiation of 480nm blue light, and it was taken out after 24 hours. The product solution was added dropwise to 50ml of methanol to obtain a polymer precipitate. After filtration and drying, the dissolution-precipitation was repeated to obtain the product.
实施例6Example 6
将5g甲基丙烯酸甲酯，10ml二甲亚砜，加入到透明玻璃烧瓶中，再加入0.01g荧光素与0.003g三乙胺，向瓶内通入氮气同时搅拌均匀。20分钟后，用玻璃塞盖住防止氧气进入。在日光照射下发生聚合反应，依据阳光强度照射6h，把产品溶液逐滴加入50ml甲醇中，得到聚合物沉淀，过滤干燥后重复溶解-沉淀最后得到产品。Add 5g of methyl methacrylate and 10ml of dimethyl sulfoxide into a transparent glass flask, then add 0.01g of fluorescein and 0.003g of triethylamine, blow nitrogen into the bottle and stir evenly. After 20 minutes, cover with a glass stopper to prevent oxygen ingress. Polymerization occurs under sunlight irradiation. According to the intensity of sunlight for 6 hours, the product solution is added dropwise to 50ml of methanol to obtain a polymer precipitate. After filtration and drying, the dissolution-precipitation is repeated to obtain the product.
表1实施例的产品及其效果对比表The product of the embodiment of table 1 and its effect comparison table
注：重均分子量高于500,000g/mol的聚合物因为检测原因没有测试结果。Note: There are no test results for polymers with a weight average molecular weight higher than 500,000 g/mol due to detection reasons.
本发明的实施方式不限于此，按照本发明的上述内容，利用本领域的普通技术知识和惯用手段，在不脱离本发明上述基本技术思想前提下，本发明还可以做出其它多种形式的修改、替换或变更，均落在本发明权利保护范围之内。The embodiments of the present invention are not limited thereto. According to the above content of the present invention, using ordinary technical knowledge and conventional means in this field, without departing from the above-mentioned basic technical ideas of the present invention, the present invention can also make other various forms. Amendment, replacement or alteration all fall within the protection scope of the present invention.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01138203A (en) * | 1987-07-17 | 1989-05-31 | Toray Ind Inc | Photopolymerizable composition |
| US20040086493A1 (en) * | 1992-04-20 | 2004-05-06 | Board Of Regents, The University Of Texas System | Gels for encapsulation of biological materials |
| WO2005042591A1 (en) * | 2003-11-03 | 2005-05-12 | University Of Iowa Research Foundation | Method for producing polymers with controlled molecular weight and end group functionality using photopolymerization in microemulsions |
| US20070287764A1 (en) * | 2003-11-21 | 2007-12-13 | 3M Innovative Properties Company | Photoinitiator systems with anthracene-based electron donors for curing cationically polymerizable resins |
| CN101307122A (en) * | 2008-06-27 | 2008-11-19 | 北京化工大学 | A photopolymerization method for preparing block or graft polymer |
| JP2011074180A (en) * | 2009-09-30 | 2011-04-14 | Taiyo Holdings Co Ltd | Resin composition and printed-wiring board using the same |
| US20110166306A1 (en) * | 2008-07-01 | 2011-07-07 | Stansbury Jeffrey W | Methods For Extensive Dark Curing Based on Visible-Light Initiated, Controlled Radical Polymerization |
| WO2015184551A1 (en) * | 2014-06-04 | 2015-12-10 | Klox Technologies Inc. | Biophotonic hydrogels |
| WO2016028237A1 (en) * | 2014-08-22 | 2016-02-25 | Koç Üniversitesi | A novel ph responsive hydrogel and method of synthesis |
| CN106118579A (en) * | 2016-06-23 | 2016-11-16 | 唐天 | A kind of visible-light curing glue and preparation method thereof |
| CN106317263A (en) * | 2016-08-23 | 2017-01-11 | 浙江理工大学 | Visible light initiating system in medical photo-curing hydrogel and photo-curing method thereof |
| CN106420366A (en) * | 2016-08-31 | 2017-02-22 | 哈尔滨工业大学 | Ultralow-shrinkage composite resin and preparation method thereof |
-
2017
- 2017-12-22 CN CN201711402308.9A patent/CN107936158A/en active Pending
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01138203A (en) * | 1987-07-17 | 1989-05-31 | Toray Ind Inc | Photopolymerizable composition |
| US20040086493A1 (en) * | 1992-04-20 | 2004-05-06 | Board Of Regents, The University Of Texas System | Gels for encapsulation of biological materials |
| WO2005042591A1 (en) * | 2003-11-03 | 2005-05-12 | University Of Iowa Research Foundation | Method for producing polymers with controlled molecular weight and end group functionality using photopolymerization in microemulsions |
| US7226957B1 (en) * | 2003-11-03 | 2007-06-05 | University Of Iowa Research Foundation | Method for producing polymers with controlled molecular weight and end group functionality using photopolymerization in microemulsions |
| US20070287764A1 (en) * | 2003-11-21 | 2007-12-13 | 3M Innovative Properties Company | Photoinitiator systems with anthracene-based electron donors for curing cationically polymerizable resins |
| CN101307122A (en) * | 2008-06-27 | 2008-11-19 | 北京化工大学 | A photopolymerization method for preparing block or graft polymer |
| US20110166306A1 (en) * | 2008-07-01 | 2011-07-07 | Stansbury Jeffrey W | Methods For Extensive Dark Curing Based on Visible-Light Initiated, Controlled Radical Polymerization |
| JP2011074180A (en) * | 2009-09-30 | 2011-04-14 | Taiyo Holdings Co Ltd | Resin composition and printed-wiring board using the same |
| WO2015184551A1 (en) * | 2014-06-04 | 2015-12-10 | Klox Technologies Inc. | Biophotonic hydrogels |
| CN107075127A (en) * | 2014-06-04 | 2017-08-18 | 克洛克斯科技公司 | bio-photon hydrogel |
| WO2016028237A1 (en) * | 2014-08-22 | 2016-02-25 | Koç Üniversitesi | A novel ph responsive hydrogel and method of synthesis |
| CN106118579A (en) * | 2016-06-23 | 2016-11-16 | 唐天 | A kind of visible-light curing glue and preparation method thereof |
| CN106317263A (en) * | 2016-08-23 | 2017-01-11 | 浙江理工大学 | Visible light initiating system in medical photo-curing hydrogel and photo-curing method thereof |
| CN106420366A (en) * | 2016-08-31 | 2017-02-22 | 哈尔滨工业大学 | Ultralow-shrinkage composite resin and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 薛巍，张渊明: "《生物医用水凝胶》", 31 December 2012, 暨南大学出版社 * |
| 郑春满 等: "《有机与高分子化学实验》", 31 May 2014, 国防工业出版社 * |
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