CN116041739A - A kind of multi-arm polyethylene glycol gel and preparation method thereof - Google Patents
A kind of multi-arm polyethylene glycol gel and preparation method thereofDownload PDFInfo
- Publication number
- CN116041739A CN116041739ACN202310073437.7ACN202310073437ACN116041739ACN 116041739 ACN116041739 ACN 116041739ACN 202310073437 ACN202310073437 ACN 202310073437ACN 116041739 ACN116041739 ACN 116041739A
- Authority
- CN
- China
- Prior art keywords
- polyethylene glycol
- arm polyethylene
- gel
- unit
- dicyclohexylcarbodiimide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002202Polyethylene glycolSubstances0.000titleclaimsabstractdescription105
- 229920001223polyethylene glycolPolymers0.000titleclaimsabstractdescription105
- 238000002360preparation methodMethods0.000titleclaimsabstractdescription15
- 238000001879gelationMethods0.000titledescription2
- QTBSBXVTEAMEQO-UHFFFAOYSA-NAcetic acidChemical compoundCC(O)=OQTBSBXVTEAMEQO-UHFFFAOYSA-N0.000claimsabstractdescription93
- QOSSAOTZNIDXMA-UHFFFAOYSA-NDicylcohexylcarbodiimideChemical compoundC1CCCCC1N=C=NC1CCCCC1QOSSAOTZNIDXMA-UHFFFAOYSA-N0.000claimsabstractdescription31
- 238000006243chemical reactionMethods0.000claimsabstractdescription19
- YMWUJEATGCHHMB-UHFFFAOYSA-NDichloromethaneChemical compoundClCClYMWUJEATGCHHMB-UHFFFAOYSA-N0.000claimsdescription27
- 239000002994raw materialSubstances0.000claimsdescription22
- 238000000034methodMethods0.000claimsdescription12
- 150000001875compoundsChemical class0.000claimsdescription9
- 229920000642polymerPolymers0.000claimsdescription9
- LMDZBCPBFSXMTL-UHFFFAOYSA-N1-ethyl-3-(3-dimethylaminopropyl)carbodiimideChemical compoundCCN=C=NCCCN(C)CLMDZBCPBFSXMTL-UHFFFAOYSA-N0.000claimsdescription4
- 239000005457ice waterSubstances0.000claimsdescription3
- 239000007788liquidSubstances0.000claimsdescription3
- 239000008346aqueous phaseSubstances0.000abstractdescription9
- 239000000126substanceSubstances0.000abstractdescription7
- 230000009257reactivityEffects0.000abstractdescription6
- 125000002843carboxylic acid groupChemical group0.000abstractdescription5
- 239000000499gelSubstances0.000description68
- 238000012360testing methodMethods0.000description7
- 150000008064anhydridesChemical group0.000description6
- 239000000017hydrogelSubstances0.000description6
- 238000001228spectrumMethods0.000description6
- 230000006835compressionEffects0.000description5
- 238000007906compressionMethods0.000description5
- 238000009413insulationMethods0.000description5
- WFDIJRYMOXRFFG-UHFFFAOYSA-NAcetic anhydrideChemical compoundCC(=O)OC(C)=OWFDIJRYMOXRFFG-UHFFFAOYSA-N0.000description3
- 230000000694effectsEffects0.000description3
- 150000002148estersChemical class0.000description3
- 230000007062hydrolysisEffects0.000description3
- 238000006460hydrolysis reactionMethods0.000description3
- 238000012986modificationMethods0.000description3
- 230000004048modificationEffects0.000description3
- 238000007711solidificationMethods0.000description3
- 230000008023solidificationEffects0.000description3
- BDNKZNFMNDZQMI-UHFFFAOYSA-N1,3-diisopropylcarbodiimideChemical compoundCC(C)N=C=NC(C)CBDNKZNFMNDZQMI-UHFFFAOYSA-N0.000description2
- 23800000164413C nuclear magnetic resonance spectroscopyMethods0.000description2
- 2380000051601H NMR spectroscopyMethods0.000description2
- 2380000101463D printingMethods0.000description2
- 101001121408Homo sapiens L-amino-acid oxidaseProteins0.000description2
- UFHFLCQGNIYNRP-UHFFFAOYSA-NHydrogenChemical compound[H][H]UFHFLCQGNIYNRP-UHFFFAOYSA-N0.000description2
- 102100026388L-amino-acid oxidaseHuman genes0.000description2
- 238000010521absorption reactionMethods0.000description2
- 238000004132cross linkingMethods0.000description2
- 229910052739hydrogenInorganic materials0.000description2
- 239000001257hydrogenSubstances0.000description2
- 230000008439repair processEffects0.000description2
- 238000007789sealingMethods0.000description2
- 230000035939shockEffects0.000description2
- 238000009864tensile testMethods0.000description2
- 101000827703Homo sapiens Polyphosphoinositide phosphataseProteins0.000description1
- 102100023591Polyphosphoinositide phosphataseHuman genes0.000description1
- 101100012902Saccharomyces cerevisiae (strain ATCC 204508 / S288c) FIG2 geneProteins0.000description1
- 101100233916Saccharomyces cerevisiae (strain ATCC 204508 / S288c) KAR5 geneProteins0.000description1
- 238000007792additionMethods0.000description1
- 230000009286beneficial effectEffects0.000description1
- 125000002915carbonyl groupChemical group[*:2]C([*:1])=O0.000description1
- 238000005266castingMethods0.000description1
- 239000004568cementSubstances0.000description1
- 239000003153chemical reaction reagentSubstances0.000description1
- 238000012669compression testMethods0.000description1
- 238000009833condensationMethods0.000description1
- 230000005494condensationEffects0.000description1
- 238000010276constructionMethods0.000description1
- 238000000635electron micrographMethods0.000description1
- 238000004519manufacturing processMethods0.000description1
- 230000007246mechanismEffects0.000description1
- 231100000252nontoxicToxicity0.000description1
- 230000003000nontoxic effectEffects0.000description1
- 238000006116polymerization reactionMethods0.000description1
- 239000011148porous materialSubstances0.000description1
- 230000008569processEffects0.000description1
- 238000006467substitution reactionMethods0.000description1
- 229920003169water-soluble polymerPolymers0.000description1
Images
Classifications
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/02—Polyalkylene oxides
- 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
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
Translated fromChinese技术领域Technical Field
本发明涉及凝胶制备技术领域，具体涉及一种多臂聚乙二醇凝胶及其制备方法。The invention relates to the technical field of gel preparation, and in particular to a multi-arm polyethylene glycol gel and a preparation method thereof.
背景技术Background Art
聚乙二醇(PEG)是一种常见的水溶性高分子，其制得的水凝胶无毒，同时具有良好的生物相容性，广泛的应用在生物医学和药学领域。此外，在PEG分子链的两端有功能性的基团羟基，易于修饰，易于发生化学反应，PEG也很容易结晶。因而采用PEG制备结构均一的水凝胶具有显著的优势。但是常见的PEG水凝胶所选用的PEG活性末端多数是NHS酯，并且它的反应体系一般是在水相体系中，在该反应体系中PEG的活性末端NHS酯会有一定程度的水解，水解后的末端活性基团即丧失了反应活性，从而使得PEG水凝胶交联度降低。Polyethylene glycol (PEG) is a common water-soluble polymer. The hydrogel obtained by it is non-toxic and has good biocompatibility. It is widely used in biomedicine and pharmaceutical fields. In addition, there are functional group hydroxyls at both ends of the PEG molecular chain, which are easy to modify and easy to chemically react. PEG is also easy to crystallize. Therefore, it has significant advantages to prepare hydrogels with uniform structure using PEG. However, most of the PEG active ends selected by common PEG hydrogels are NHS esters, and its reaction system is generally in an aqueous phase system. In this reaction system, the active end NHS ester of PEG will have a certain degree of hydrolysis, and the terminal active groups after hydrolysis have lost their reactivity, thereby reducing the cross-linking degree of PEG hydrogel.
发明内容Summary of the invention
本发明要解决现有技术中PEG水凝胶在水相体系中活性末端NHS酯会因水解而失去反应活性，从而使PEG水凝胶交联度降低的技术问题，提供一种多臂聚乙二醇凝胶及其制备方法。本发明的多臂聚乙二醇凝胶的末端是羧酸基团，且是在非水相的体系制备得到，因而不存在活性末端失去反应活性的情况。The present invention aims to solve the technical problem that the active terminal NHS ester of PEG hydrogel in the aqueous phase system loses its reactivity due to hydrolysis, thereby reducing the crosslinking degree of the PEG hydrogel, and provides a multi-arm polyethylene glycol gel and a preparation method thereof. The terminal of the multi-arm polyethylene glycol gel of the present invention is a carboxylic acid group, and it is prepared in a non-aqueous phase system, so there is no situation where the active terminal loses its reactivity.
为了实现上述目的，本发明的技术方案具体如下：In order to achieve the above object, the technical solution of the present invention is as follows:
本发明提供一种多臂聚乙二醇凝胶，其结构式如式1所示：The present invention provides a multi-arm polyethylene glycol gel, the structural formula of which is shown in Formula 1:
其中，x的值为2、4、6或者8，m值为1-20；Where x is 2, 4, 6 or 8, and m is 1-20;
所述凝胶是一种高分子化合物，其结构单元如式1，每个A单元连接x个B单元，每个B单元连接两个A单元；The gel is a polymer compound, and its structural unit is as shown in Formula 1, where each A unit is connected to x B units, and each B unit is connected to two A units;
A单元的结构式如下所示结构中的一种：The structural formula of unit A is one of the following structures:
其中，n值为55-110；Among them, the value of n is 55-110;
B单元的结构式如下：The structural formula of unit B is as follows:
在上述技术方案中，优选的是：A单元的结构式如下：In the above technical solution, it is preferred that the structural formula of unit A is as follows:
本发明还提供一种多臂聚乙二醇凝胶的制备方法，包括以下步骤：The present invention also provides a method for preparing a multi-arm polyethylene glycol gel, comprising the following steps:
将多臂聚乙二醇乙酸和二环己基碳二亚胺(DCC)反应制备得到所述多臂聚乙二醇凝胶；The multi-arm polyethylene glycol gel is prepared by reacting multi-arm polyethylene glycol acetic acid and dicyclohexylcarbodiimide (DCC);
反应式如下：The reaction formula is as follows:
其中，x的值为2、4、6或者8，m值为1-20；Where x is 2, 4, 6 or 8, and m is 1-20;
所述凝胶是一种高分子化合物，其结构单元如式1，每个A单元连接x个B单元，每个B单元连接两个A单元；The gel is a polymer compound, and its structural unit is as shown in Formula 1, where each A unit is connected to x B units, and each B unit is connected to two A units;
A单元的结构式如下：The structural formula of unit A is as follows:
其中，n值为55-110；Among them, the value of n is 55-110;
B单元的结构式如下：The structural formula of unit B is as follows:
在上述技术方案中，优选的是，所述多臂聚乙二醇乙酸为四臂聚乙二醇乙酸，其分子量为10000-20000。In the above technical solution, preferably, the multi-arm polyethylene glycol acetic acid is four-arm polyethylene glycol acetic acid, and its molecular weight is 10000-20000.
在上述技术方案中，优选的是，所述二环己基碳二亚胺还可以替换为1-乙基-(3-二甲基氨基丙基)碳酰二亚胺(EDC)或者N-二异丙基碳二亚胺(DIC)。In the above technical solution, preferably, the dicyclohexylcarbodiimide can also be replaced by 1-ethyl-(3-dimethylaminopropyl)carbodiimide (EDC) or N-diisopropylcarbodiimide (DIC).
在上述技术方案中，优选的是，所述多臂聚乙二醇乙酸与二环己基碳二亚胺的摩尔比为1:13.2～20。In the above technical solution, preferably, the molar ratio of the multi-arm polyethylene glycol acetic acid to dicyclohexylcarbodiimide is 1:13.2-20.
在上述技术方案中，进一步优选的是，所述多臂聚乙二醇乙酸与二环己基碳二亚胺的摩尔比为1:13.2或者1:20。In the above technical solution, it is further preferred that the molar ratio of the multi-arm polyethylene glycol acetic acid to dicyclohexylcarbodiimide is 1:13.2 or 1:20.
在上述技术方案中，优选的是，所述制备方法的一种具体实施方式为：In the above technical solution, preferably, a specific implementation of the preparation method is:
将原料多臂聚乙二醇乙酸，用5倍的二氯甲烷溶解，当原料全部溶解之后，将溶解后的原料液放入冰水浴，开始降温，当温度降到5℃以下之后，加入二环己基碳二亚胺，反应完全后获得所述多臂聚乙二醇凝胶。The raw material multi-arm polyethylene glycol acetic acid is dissolved with 5 times dichloromethane. When the raw material is completely dissolved, the dissolved raw material liquid is placed in an ice water bath and begins to cool down. When the temperature drops below 5°C, dicyclohexylcarbodiimide is added. After the reaction is complete, the multi-arm polyethylene glycol gel is obtained.
在上述技术方案中，进一步优选的是，当温度降到3℃，加入二环己基碳二亚胺。In the above technical solution, it is further preferred that when the temperature drops to 3°C, dicyclohexylcarbodiimide is added.
在上述技术方案中，优选的是，所述制备方法的一种具体实施方式为：In the above technical solution, preferably, a specific implementation of the preparation method is:
将原料多臂聚乙二醇乙酸，用5倍的二氯甲烷溶解，当原料全部溶解之后，加入二环己基碳二亚胺，于室温25摄氏度下反应完全后获得所述多臂聚乙二醇凝胶。The raw material multi-arm polyethylene glycol acetic acid is dissolved in 5 times dichloromethane. When the raw material is completely dissolved, dicyclohexylcarbodiimide is added, and the multi-arm polyethylene glycol gel is obtained after the reaction is completed at room temperature of 25 degrees Celsius.
本发明的有益效果是：The beneficial effects of the present invention are:
本发明提供的多臂聚乙二醇凝胶，是由多臂聚乙二醇乙酸和二环己基碳二亚胺反应制备得到的新型结构的凝胶，其末端是羧酸基团，且是在非水相的体系制备得到，因而不存在活性末端失去反应活性的情况，制得的凝胶具有较好的力学性能，化学性质稳定，应用领域广泛。The multi-arm polyethylene glycol gel provided by the present invention is a gel of a novel structure prepared by reacting multi-arm polyethylene glycol acetic acid and dicyclohexylcarbodiimide, the ends of which are carboxylic acid groups, and are prepared in a non-aqueous phase system, so there is no situation where the active ends lose their reactivity. The prepared gel has good mechanical properties, stable chemical properties, and a wide range of applications.
本发明提供的多臂聚乙二醇凝胶的成胶的机理为：PEG末端的两个或多个羧酸基团，经DCC缩合脱水形成酸酐结构，引起PEG的聚合，从而形成凝胶。The gelling mechanism of the multi-arm polyethylene glycol gel provided by the present invention is that two or more carboxylic acid groups at the end of PEG are dehydrated by DCC condensation to form anhydride structures, which cause the polymerization of PEG, thereby forming a gel.
本发明提供的多臂聚乙二醇凝胶的制备方法，反应体系为非水相，成胶速率快。The preparation method of the multi-arm polyethylene glycol gel provided by the invention has a non-aqueous phase reaction system and a fast gelling rate.
本发明提供的多臂聚乙二醇凝胶因具有凝固快、不挥发、化学性质稳定、绝缘性好的优点，因此可以用于绝缘设备，电气设备漏电的快速修复。The multi-arm polyethylene glycol gel provided by the present invention has the advantages of fast solidification, non-volatility, stable chemical properties and good insulation, and can therefore be used for insulating equipment and rapid repair of electrical equipment leakage.
本发明提供的多臂聚乙二醇凝胶由于绝缘性好，化学性质稳定，有减震效果所以对于新能源汽车电池外皮的保护有很好的作用。The multi-arm polyethylene glycol gel provided by the present invention has good insulation, stable chemical properties and shock absorption effect, so it plays a good role in protecting the outer skin of new energy vehicle batteries.
本发明提供的多臂聚乙二醇凝胶由于凝固快，不挥发、化学性质稳定，所以可以用作模具的制备，也可用在工艺品等贵重物品的封存。The multi-arm polyethylene glycol gel provided by the present invention can be used for preparing molds and can also be used for sealing valuable items such as handicrafts because of its fast solidification, non-volatility and stable chemical properties.
本发明提供的多臂聚乙二醇凝胶也可应用于3D打印，如概念汽车设计以及大型雕塑甚至是水泥建筑模具，这种工艺在混凝土施工中的优势也越来越明显地体现出来，包括混凝土浇注模具和全尺寸模板的生产。The multi-arm polyethylene glycol gel provided by the present invention can also be applied to 3D printing, such as concept car design, large sculptures and even cement building molds. The advantages of this process in concrete construction are also becoming increasingly apparent, including the production of concrete casting molds and full-size templates.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
下面结合附图和具体实施方式对本发明作进一步详细说明。The present invention is further described in detail below in conjunction with the accompanying drawings and specific embodiments.
图1为本发明实施例1制备的四臂聚乙二醇凝胶的核磁氢谱图。FIG1 is a hydrogen nuclear magnetic spectrum of the four-arm polyethylene glycol gel prepared in Example 1 of the present invention.
图2为本发明实施例1制备的四臂聚乙二醇凝胶的电镜图。FIG. 2 is an electron micrograph of the four-arm polyethylene glycol gel prepared in Example 1 of the present invention.
图3为本发明实施例5制备的两臂聚乙二醇凝胶的核磁氢谱图。FIG3 is a hydrogen nuclear magnetic spectrum of the two-arm polyethylene glycol gel prepared in Example 5 of the present invention.
图4为本发明实施例5制备的两臂聚乙二醇凝胶的核磁碳谱图。FIG4 is a carbon NMR spectrum of the two-arm polyethylene glycol gel prepared in Example 5 of the present invention.
具体实施方式DETAILED DESCRIPTION
以下通过具体实施例对本发明做进一步说明，但实施例具体细节仅是为了说明本发明，并不代表本发明构思下的全部的技术方案，因此不应理解为对本发明总的技术方案的限定，一些在技术人员看来，不偏离本发明的非实质性增加和改动，例如以具有相同或相似效果的技术特征简单改换或替换，均属于本发明保护范围。The present invention is further described below through specific embodiments, but the specific details of the embodiments are only for illustrating the present invention and do not represent all the technical solutions conceived by the present invention. Therefore, they should not be understood as limiting the overall technical solution of the present invention. Some non-substantial additions and modifications that do not deviate from the present invention in the opinion of technical personnel, such as simple replacement or substitution of technical features with the same or similar effects, all fall within the scope of protection of the present invention.
以下实施例所用试剂均为市售商品。The reagents used in the following examples are all commercially available products.
实施例1Example 1
将原料四臂聚乙二醇乙酸(分子量20000)，用5倍的二氯甲烷溶解，当原料全部溶解之后，将溶解后的原料液放入冰水浴，开始降温，当温度降到3℃，加入二环己基碳二亚胺，1分钟左右即可成胶，四臂聚乙二醇乙酸与二环己基碳二亚胺的摩尔比为1:20，获得所述四臂聚乙二醇凝胶。The raw material four-arm polyethylene glycol acetic acid (molecular weight 20000) was dissolved with 5 times dichloromethane. When the raw material was completely dissolved, the dissolved raw material liquid was placed in an ice water bath and began to cool down. When the temperature dropped to 3°C, dicyclohexylcarbodiimide was added. It took about 1 minute to form a gel. The molar ratio of four-arm polyethylene glycol acetic acid to dicyclohexylcarbodiimide was 1:20, and the four-arm polyethylene glycol gel was obtained.
所得四臂聚乙二醇凝胶为白色凝胶，有弹性，其结构式如式1所示：The obtained four-arm polyethylene glycol gel is a white gel with elasticity, and its structural formula is shown in Formula 1:
其中，x的值为4，m值为10；Among them, the value of x is 4, and the value of m is 10;
所述凝胶是一种高分子化合物，其结构单元如式1，每个A单元连接4个B单元，每个B单元连接两个A单元；The gel is a polymer compound, and its structural unit is as shown in Formula 1, where each A unit is connected to four B units, and each B unit is connected to two A units;
反应式如下：The reaction formula is as follows:
A单元的结构式如下：The structural formula of unit A is as follows:
B单元的结构式如下：The structural formula of unit B is as follows:
图1为所得四臂聚乙二醇凝胶的核磁氢谱图，因分子量原因，所以酸酐的峰形显示较弱在4.24处，由该图可知本实施例成功制备了多臂聚乙二醇凝胶。FIG1 is a H-NMR spectrum of the obtained four-arm polyethylene glycol gel. Due to the molecular weight, the peak of the anhydride is weaker at 4.24. It can be seen from the figure that the multi-arm polyethylene glycol gel was successfully prepared in this example.
本发明的四臂聚乙二醇凝胶具有蜂窝状多孔结构，孔孔相连且均匀分布，参见图2。The four-arm polyethylene glycol gel of the present invention has a honeycomb porous structure, and the pores are connected and evenly distributed, see FIG2 .
本实施例的四臂聚乙二醇凝胶，成胶速度快，常温放置两天不挥发，且结构上无活性基团化学性质稳定，凝胶不导电绝缘性好。The four-arm polyethylene glycol gel of this embodiment has a fast gelling speed, does not volatilize after being placed at room temperature for two days, has no active groups in the structure, is chemically stable, and has good non-conductive insulation properties.
实施例2Example 2
将原料四臂聚乙二醇乙酸(分子量20000)，用5倍的二氯甲烷溶解，当原料全部溶解之后，加入二环己基碳二亚胺，于室温25摄氏度下1分钟左右即可成胶，四臂聚乙二醇乙酸与二环己基碳二亚胺的摩尔比为1:20，获得所述四臂聚乙二醇凝胶。The raw material four-arm polyethylene glycol acetic acid (molecular weight 20000) is dissolved in 5 times dichloromethane. When the raw material is completely dissolved, dicyclohexylcarbodiimide is added. It can form a gel at room temperature of 25 degrees Celsius for about 1 minute. The molar ratio of four-arm polyethylene glycol acetic acid to dicyclohexylcarbodiimide is 1:20, and the four-arm polyethylene glycol gel is obtained.
所得四臂聚乙二醇凝胶为白色凝胶，有弹性，其结构式如式1所示：The obtained four-arm polyethylene glycol gel is a white gel with elasticity, and its structural formula is shown in Formula 1:
其中，x的值为4，m值为10；Among them, the value of x is 4, and the value of m is 10;
所述凝胶是一种高分子化合物，其结构单元如式1，每个A单元连接4个B单元，每个B单元连接两个A单元；The gel is a polymer compound, and its structural unit is as shown in Formula 1, where each A unit is connected to four B units, and each B unit is connected to two A units;
反应式如下：The reaction formula is as follows:
A单元的结构式如下：The structural formula of unit A is as follows:
B单元的结构式如下：The structural formula of unit B is as follows:
实施例3Example 3
将原料四臂聚乙二醇乙酸(分子量20000)，用5倍的二氯甲烷溶解，当原料全部溶解之后，加入二环己基碳二亚胺，于室温25摄氏度下1分钟左右即可成胶，四臂聚乙二醇乙酸与二环己基碳二亚胺的摩尔比为1:13.2，获得所述四臂聚乙二醇凝胶。The raw material four-arm polyethylene glycol acetic acid (molecular weight 20000) was dissolved with 5 times dichloromethane. When the raw material was completely dissolved, dicyclohexylcarbodiimide was added and gel was formed at room temperature of 25 degrees Celsius in about 1 minute. The molar ratio of four-arm polyethylene glycol acetic acid to dicyclohexylcarbodiimide was 1:13.2, and the four-arm polyethylene glycol gel was obtained.
所得四臂聚乙二醇凝胶为白色凝胶，有弹性，其结构式如式1所示：The obtained four-arm polyethylene glycol gel is a white gel with elasticity, and its structural formula is shown in Formula 1:
其中，x的值为4，m值为16；Among them, the value of x is 4, and the value of m is 16;
所述凝胶是一种高分子化合物，其结构单元如式1，每个A单元连接4个B单元，每个B单元连接两个A单元；The gel is a polymer compound, and its structural unit is as shown in Formula 1, where each A unit is connected to four B units, and each B unit is connected to two A units;
反应式如下：The reaction formula is as follows:
A单元的结构式如下：The structural formula of unit A is as follows:
B单元的结构式如下：The structural formula of unit B is as follows:
实施例4Example 4
将原料四臂聚乙二醇乙酸(分子量10000)，用5倍的二氯甲烷溶解，当原料全部溶解之后，加入二环己基碳二亚胺，于室温25摄氏度下1分钟左右即可成胶，四臂聚乙二醇乙酸与二环己基碳二亚胺的摩尔比为1:13.2，获得所述四臂聚乙二醇凝胶。The raw material four-arm polyethylene glycol acetic acid (molecular weight 10000) was dissolved with 5 times dichloromethane. When the raw material was completely dissolved, dicyclohexylcarbodiimide was added. It took about 1 minute to form a gel at room temperature of 25 degrees Celsius. The molar ratio of four-arm polyethylene glycol acetic acid to dicyclohexylcarbodiimide was 1:13.2, and the four-arm polyethylene glycol gel was obtained.
所得四臂聚乙二醇凝胶为白色凝胶，有弹性，其结构式如式1所示：The obtained four-arm polyethylene glycol gel is a white gel with elasticity, and its structural formula is shown in Formula 1:
其中，x的值为4，m值为12；Among them, the value of x is 4, and the value of m is 12;
所述凝胶是一种高分子化合物，其结构单元如式1，每个A单元连接4个B单元，每个B单元连接两个A单元；The gel is a polymer compound, and its structural unit is as shown in Formula 1, where each A unit is connected to four B units, and each B unit is connected to two A units;
反应式如下：The reaction formula is as follows:
A单元的结构式如下：The structural formula of unit A is as follows:
B单元的结构式如下：The structural formula of unit B is as follows:
实施例5Example 5
将原料两臂聚乙二醇乙酸(分子量5000)，用5倍的二氯甲烷溶解，当原料全部溶解之后，加入二环己基碳二亚胺，于室温25摄氏度下1分钟左右即可成胶，两臂聚乙二醇乙酸与二环己基碳二亚胺的摩尔比为1:20，获得所述两臂聚乙二醇凝胶。The raw material two-arm polyethylene glycol acetic acid (molecular weight 5000) is dissolved in 5 times dichloromethane. When the raw material is completely dissolved, dicyclohexylcarbodiimide is added and gel is formed at room temperature of 25 degrees Celsius in about 1 minute. The molar ratio of two-arm polyethylene glycol acetic acid to dicyclohexylcarbodiimide is 1:20, and the two-arm polyethylene glycol gel is obtained.
所得两臂聚乙二醇凝胶为白色凝胶，有弹性，其结构式如式1所示：The obtained two-arm polyethylene glycol gel is a white gel with elasticity, and its structural formula is shown in Formula 1:
其中，x的值为2，m值为10；Among them, the value of x is 2, and the value of m is 10;
所述凝胶是一种高分子化合物，其结构单元如式1，每个A单元连接2个B单元，每个B单元连接两个A单元；The gel is a polymer compound, and its structural unit is as shown in Formula 1, where each A unit is connected to two B units, and each B unit is connected to two A units;
反应式如下：The reaction formula is as follows:
A单元的结构式如下：The structural formula of unit A is as follows:
B单元的结构式如下：The structural formula of unit B is as follows:
图3为本实施例5制备的两臂聚乙二醇凝胶的核磁氢谱图，4.31处为酸酐的出峰位置，可以清晰的看到酸酐的出峰位置，并可以确定凝胶的连接位置基团为酸酐。图4为本实施例5制备的两臂聚乙二醇凝胶的核磁碳谱图，166.22为乙酸酐的羰基峰，同样也可以证明连接处基团是酸酐。Figure 3 is the H-NMR spectrum of the two-arm polyethylene glycol gel prepared in Example 5. The peak position of the anhydride is at 4.31. The peak position of the anhydride can be clearly seen, and it can be determined that the connecting position group of the gel is anhydride. Figure 4 is the C-NMR spectrum of the two-arm polyethylene glycol gel prepared in Example 5. The carbonyl peak of acetic anhydride is 166.22, which can also prove that the connecting position group is anhydride.
上述实施例中所用的多臂聚乙二醇乙酸原料还可以替换为六臂聚乙二醇乙酸或八臂聚乙二醇乙酸，二环己基碳二亚胺还可以替换为EDC或者DIC，同样可以获得本发明所述技术效果的凝胶，这里不再一一举例。The multi-arm polyethylene glycol acetic acid raw material used in the above embodiments can also be replaced by six-arm polyethylene glycol acetic acid or eight-arm polyethylene glycol acetic acid, and dicyclohexylcarbodiimide can also be replaced by EDC or DIC. The gel with the technical effect described in the present invention can also be obtained, and examples are not given one by one here.
实施例6Example 6
对实施例1-5制备的多臂聚乙二醇凝胶的力学性能进行测试如下：The mechanical properties of the multi-arm polyethylene glycol gel prepared in Examples 1-5 were tested as follows:
参考国标，采用万能力学实验机对实施例1-5制备的多臂聚乙二醇凝胶进行机械拉伸实验和压缩实验。With reference to the national standard, a universal mechanical testing machine was used to carry out mechanical tensile and compression tests on the multi-arm polyethylene glycol gels prepared in Examples 1-5.
拉伸实验：试样规格：宽8.0mm、厚1.5mm、长度25mm，测试标距为15mm；测试条件：室温，拉伸速率为50mm/min。多次测试取平均值，结果如表1。Tensile test: Sample specifications: width 8.0mm, thickness 1.5mm, length 25mm, test gauge length 15mm; test conditions: room temperature, tensile rate 50mm/min. Multiple tests were averaged and the results are shown in Table 1.
压缩模量测定：试样规格：使用模具制成为直径8mm，高度6mm的圆柱体，脱模，然后测试凝胶的压缩模量，测试过程中压缩速率为4mm/min，多次测试取平均值，结果如表1。Compression modulus determination: Sample specifications: Use a mold to make a cylinder with a diameter of 8 mm and a height of 6 mm, demold, and then test the compression modulus of the gel. The compression rate during the test is 4 mm/min, and the average value is taken from multiple tests. The results are shown in Table 1.
表1Table 1
由表1结果可知：本发明实施例1-5制备的多臂聚乙二醇凝胶的压缩模量分别为185Kpa、182Kpa、175Kpa、170Kpa、172Kpa，拉伸率分别为92％、90％、85％、80％、82％，说明本发明的多臂聚乙二醇凝胶具有很好的力学性能。From the results in Table 1, it can be seen that the compression moduli of the multi-arm polyethylene glycol gel prepared in Examples 1-5 of the present invention are 185 Kpa, 182 Kpa, 175 Kpa, 170 Kpa, and 172 Kpa, respectively, and the elongation rates are 92%, 90%, 85%, 80%, and 82%, respectively, indicating that the multi-arm polyethylene glycol gel of the present invention has good mechanical properties.
综上所述，本发明提供的多臂聚乙二醇凝胶，是由多臂聚乙二醇乙酸和二环己基碳二亚胺反应制备得到的新型结构的凝胶，其末端是羧酸基团，且是在非水相的体系制备得到，因而不存在活性末端失去反应活性的情况，制得的凝胶具有较好的力学性能，化学性质稳定，应用领域广泛。本发明提供的多臂聚乙二醇凝胶的制备方法，反应体系为非水相，成胶速率快。In summary, the multi-arm polyethylene glycol gel provided by the present invention is a gel of a novel structure prepared by the reaction of multi-arm polyethylene glycol acetic acid and dicyclohexylcarbodiimide, the end of which is a carboxylic acid group, and is prepared in a non-aqueous phase system, so there is no situation where the active end loses its reactivity, and the prepared gel has good mechanical properties, stable chemical properties, and a wide range of applications. The preparation method of the multi-arm polyethylene glycol gel provided by the present invention has a non-aqueous phase reaction system and a fast gelation rate.
本发明提供的多臂聚乙二醇凝胶因具有凝固快、不挥发、化学性质稳定、绝缘性好、减震等优点，因此在绝缘设备和电气设备漏电的快速修复、模具的制备、工艺品贵重物品的封存、3D打印等领域具有广泛的应用前景。The multi-arm polyethylene glycol gel provided by the present invention has the advantages of fast solidification, non-volatility, stable chemical properties, good insulation, shock absorption, etc., and therefore has broad application prospects in the fields of rapid repair of insulation equipment and electrical equipment leakage, mold preparation, sealing of handicrafts and valuables, 3D printing, etc.
显然，上述实施例仅仅是为清楚地说明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。Obviously, the above embodiments are merely examples for the purpose of clear explanation, and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived therefrom are still within the scope of protection of the present invention.
Claims (10)
Translated fromChinese
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310073437.7ACN116041739B (en) | 2023-02-07 | 2023-02-07 | A multi-arm polyethylene glycol gel and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310073437.7ACN116041739B (en) | 2023-02-07 | 2023-02-07 | A multi-arm polyethylene glycol gel and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116041739Atrue CN116041739A (en) | 2023-05-02 |
| CN116041739B CN116041739B (en) | 2025-01-07 |
Family
ID=86114536
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310073437.7AActiveCN116041739B (en) | 2023-02-07 | 2023-02-07 | A multi-arm polyethylene glycol gel and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116041739B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101724144A (en)* | 2008-11-03 | 2010-06-09 | 北京键凯科技有限公司 | Novel multi-arm polyethylene glycol, preparation method and application thereof |
| CN103755949A (en)* | 2009-12-25 | 2014-04-30 | 天津键凯科技有限公司 | Dobby polyethylene glycol derivative and conjugate thereof with drug and gel |
| CN109517162A (en)* | 2018-11-20 | 2019-03-26 | 南京工业大学 | Injectable hydrogel and preparation method thereof |
| US20200131109A1 (en)* | 2017-06-30 | 2020-04-30 | Jenkem Technology Co., Ltd. (Tianjin) | Multi-arm single molecular weight polyethylene glycol, active derivative thereof, and preparation and application thereof |
| EP3985046A1 (en)* | 2020-10-15 | 2022-04-20 | Essilor International | Crosslinked gel formulation |
- 2023
- 2023-02-07CNCN202310073437.7Apatent/CN116041739B/enactiveActive
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101724144A (en)* | 2008-11-03 | 2010-06-09 | 北京键凯科技有限公司 | Novel multi-arm polyethylene glycol, preparation method and application thereof |
| US20110286956A1 (en)* | 2008-11-03 | 2011-11-24 | Beijing Jenkem Technology Co. Ltd. | Novel multi-arm polyethylene glycol, preparation method and uses thereof |
| CN103755949A (en)* | 2009-12-25 | 2014-04-30 | 天津键凯科技有限公司 | Dobby polyethylene glycol derivative and conjugate thereof with drug and gel |
| US20200131109A1 (en)* | 2017-06-30 | 2020-04-30 | Jenkem Technology Co., Ltd. (Tianjin) | Multi-arm single molecular weight polyethylene glycol, active derivative thereof, and preparation and application thereof |
| CN109517162A (en)* | 2018-11-20 | 2019-03-26 | 南京工业大学 | Injectable hydrogel and preparation method thereof |
| EP3985046A1 (en)* | 2020-10-15 | 2022-04-20 | Essilor International | Crosslinked gel formulation |
Non-Patent Citations (1)
| Title |
|---|
| 吉练权等: "《生物有机化学》", vol. 1, 30 June 1998, 高等教育出版社, pages: 56 - 57* |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116041739B (en) | 2025-01-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106633111A (en) | Method for preparing high-strength polyvinyl alcohol-based dual-network hydrogel | |
| CN108341977B (en) | A kind of citric acid cross-linked chitosan hydrogel and preparation method thereof | |
| JPH0286606A (en) | Production of polyvinyl alcohol hydrogel | |
| CN112851979B (en) | Preparation method and application of polyvinyl alcohol gel | |
| CN109705373B (en) | A kind of high-strength three-network hydrogel and preparation method thereof | |
| CN107200855A (en) | A kind of preparation method of polyvinyl alcohol hydrogel | |
| WO2019095610A1 (en) | Method for quick gelation of silk fibroin solution under physiological conditions | |
| CN109942755B (en) | Synthetic method of cellulose-based ionic liquid self-repairing gel | |
| CN112521655B (en) | High-strength multi-level hydrogel and preparation method and application thereof | |
| CN109503491B (en) | A kind of imidazolyl phosphotungstate, preparation method and application thereof in preparation of proton exchange membrane for high temperature fuel cell | |
| CN105646894A (en) | Preparation method of hydrogel based on polyamide-amine dendritic molecule | |
| CN107459637B (en) | Polybutylene succinate ionomer with low molecular weight and high melt viscosity and its preparation and microcellular foaming material based on it and its application | |
| CN115068671B (en) | Preparation method of sodium alginate hydrogel dressing | |
| CN116041739A (en) | A kind of multi-arm polyethylene glycol gel and preparation method thereof | |
| CN109776817B (en) | Photo-curing self-repairing conductive hydrogel and preparation method thereof | |
| CN110885463A (en) | A kind of preparation method of PVA hydrogel with three-dimensional network structure | |
| CN112280092A (en) | A kind of high toughness porous composite hydrogel material and its preparation and application | |
| CN115449119B (en) | Freeze-drying preparation method of chitosan-silicon dioxide hybrid aerogel | |
| CN117551302A (en) | Preparation method of highly water-absorbent and hydrolysis-resistant polysaccharide-based porous material | |
| CN106519261A (en) | Method for preparing polymer extended-chain crystal under low pressure | |
| CN106866980B (en) | Semi-aromatic polyamide resin and preparation method thereof | |
| CN116640256B (en) | A method for preparing a low-hysteresis, high-stretch, self-adhesive double-chemical cross-linked structure hydrogel | |
| CN116253673B (en) | Indole sulfonated monomer, indole sulfonated polymer, proton exchange membrane and preparation method thereof | |
| CN115304806B (en) | Hydrophobic amidated cellulose film and preparation method thereof | |
| CN116396525B (en) | Alginate-lignin composite aerogel material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |