CN114716640A - Aqueous polyurethane-polyurea dispersion and preparation method thereof - Google Patents
Aqueous polyurethane-polyurea dispersion and preparation method thereof Download PDFInfo
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Abstract
本发明涉及高分子技术领域，更具体地，本发明涉及一种水性聚氨酯‑聚脲分散体及其制备方法。所述分散体的制备原料按重量份计，包括20～90份羟基化合物、10～30份仲胺基化合物、20～60份多异氰酸酯和75～300份水。使用含有氨基硅氧烷改性环氧大豆油，得到聚氨酯高聚物，可有效提高耐水性，且部分硅氧键水解缩聚，提高聚合物的交联密度，提高力学和抗冲击性能。添加仲胺基化合物和多异氰酸酯形成聚脲结构，从而生成聚氨酯‑聚脲交叉网络，可进一步提高耐水性、力学性能和抗冲击性能。控制分散体的制备原料的添加顺序，得到聚氨酯‑聚脲主链、硅氧烷侧链的结构后使用扩链剂进行扩链，更有利于减少粘度的增加，提高力学、耐水性和抗冲击。The present invention relates to the technical field of polymers, and more particularly, to an aqueous polyurethane-polyurea dispersion and a preparation method thereof. The raw materials for preparing the dispersion include, in parts by weight, 20-90 parts of hydroxyl compounds, 10-30 parts of secondary amine-based compounds, 20-60 parts of polyisocyanate and 75-300 parts of water. Using aminosiloxane-containing modified epoxy soybean oil to obtain a polyurethane polymer, which can effectively improve water resistance, and hydrolyze and polycondensate part of the silicon-oxygen bond, improve the crosslinking density of the polymer, and improve the mechanical and impact resistance properties. Adding secondary amine-based compounds and polyisocyanates to form a polyurea structure, resulting in a polyurethane-polyurea cross-network, can further improve water resistance, mechanical properties and impact resistance. Controlling the order of adding the raw materials for the preparation of the dispersion, obtaining the structure of the polyurethane-polyurea main chain and the siloxane side chain, using a chain extender to extend the chain is more conducive to reducing the increase in viscosity and improving mechanics, water resistance and impact resistance. .
Description
技术领域technical field
本发明涉及高分子技术领域，更具体地，本发明涉及一种水性聚氨酯-聚脲分散体及其制备方法。The present invention relates to the technical field of polymers, and more particularly, to an aqueous polyurethane-polyurea dispersion and a preparation method thereof.
背景技术Background technique
随着国内环保要求日益加强，水性聚氨酯备受关注。水性聚氨酯环保、无毒，是一种嵌段聚合物，可通过调整分子结构中软硬段比例及合成所用原料来获得不同性能，满足不同应用场景，但仍存在耐水性不好，硬度低等问题，需对其进行改性，获得性能的提升。With the increasing domestic environmental protection requirements, waterborne polyurethane has attracted much attention. Waterborne polyurethane is environmentally friendly and non-toxic. It is a block polymer. Different properties can be obtained by adjusting the ratio of soft and hard segments in the molecular structure and the raw materials used for synthesis to meet different application scenarios. However, there are still problems such as poor water resistance and low hardness. problem, it needs to be modified to obtain performance improvement.
此外，传统聚氨酯的合成原料主要为石油的下游产品，使得其生产过程不可避免会带来石油枯竭、环境污染和温室效应等问题，环保可再生型聚合物，如向植物油分子中引入羟基，制备出植物油多元醇已受到越来越多的关注，但由于植物油本身的缺陷，得到的聚氨酯的机械性能，热稳定性和耐候性差，具有硬脆的特点。In addition, the synthetic raw materials of traditional polyurethane are mainly the downstream products of petroleum, which makes its production process inevitably bring about problems such as oil depletion, environmental pollution and greenhouse effect. Vegetable oil polyols have received more and more attention, but due to the defects of vegetable oil itself, the obtained polyurethane has poor mechanical properties, thermal stability and weather resistance, and has the characteristics of hard and brittle.
有机硅、聚脲等拥有优异的疏水性和较好的耐热稳定性，可以添加到聚氨酯制备过程中，改善聚合物整体性能，但因为聚氨酯、聚脲、有机硅等结构差异，在制备过程中往往造成粘度大幅度增加，力学和耐水性难以得到提高。Silicone, polyurea, etc. have excellent hydrophobicity and good thermal stability, and can be added to the preparation process of polyurethane to improve the overall performance of the polymer. It often results in a substantial increase in viscosity, and it is difficult to improve the mechanics and water resistance.
发明内容SUMMARY OF THE INVENTION
为了解决上述问题，本发明第一个方面提供了一种水性聚氨酯-聚脲分散体，所述分散体的制备原料按重量份计，包括20～90份羟基化合物、10～30份仲胺基化合物、20～60份多异氰酸酯和75～300份水。In order to solve the above problems, the first aspect of the present invention provides an aqueous polyurethane-polyurea dispersion, the preparation raw materials of the dispersion include, in parts by weight, 20-90 parts of hydroxyl compounds, 10-30 parts of secondary amine groups compound, 20-60 parts polyisocyanate and 75-300 parts water.
作为本发明一种优选的技术方案，所述羟基化合物包括多元醇低聚物、改性环氧大豆油、多元醇小分子和亲水单体，重量比为(15～50)：(2～20)：(0.1～10)：(3～8)。As a preferred technical solution of the present invention, the hydroxyl compound includes polyol oligomer, modified epoxidized soybean oil, polyol small molecule and hydrophilic monomer, and the weight ratio is (15-50): (2- 20): (0.1 to 10): (3 to 8).
作为本发明一种优选的技术方案，所述多元醇低聚物的数均分子量为500～5000。As a preferred technical solution of the present invention, the number average molecular weight of the polyol oligomer is 500-5000.
作为本发明一种优选的技术方案，所述多元醇低聚物选自聚乙二醇、聚丙二醇、聚四氢呋喃二醇、聚碳酸酯二醇、聚己内酯二醇、聚己内酯三元醇、聚己二酸乙二醇酯二醇、聚己二酸-1，4-丁二醇酯二醇、聚己二酸己二醇酯二醇中的至少一种。As a preferred technical solution of the present invention, the polyol oligomer is selected from polyethylene glycol, polypropylene glycol, polytetrahydrofuran diol, polycarbonate diol, polycaprolactone diol, polycaprolactone triglyceride At least one of polyhydric alcohol, polyethylene adipate diol, poly-1,4-butanediol adipate diol, and polyhexylene adipate diol.
作为本发明一种优选的技术方案，所述改性环氧大豆油的制备原料包括环氧大豆油和氨基硅氧烷。As a preferred technical solution of the present invention, the preparation raw materials of the modified epoxidized soybean oil include epoxidized soybean oil and aminosiloxane.
作为本发明一种优选的技术方案，所述多元醇小分子选自乙二醇、二甘醇、三乙二醇、1，4-丁二醇、1，6-己二醇、1，4-环己烷二甲醇、3-甲基-1，5戊二醇、1，5戊二醇、1，2-丙二醇、二丙二醇、三丙二醇、氢化双酚A二醇、丙三醇、三羟甲基丙烷、蓖麻油中的至少一种。As a preferred technical solution of the present invention, the polyol small molecule is selected from ethylene glycol, diethylene glycol, triethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4 - Cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 1,5-pentanediol, 1,2-propanediol, dipropylene glycol, tripropylene glycol, hydrogenated bisphenol A glycol, glycerol, tripropylene glycol At least one of methylolpropane and castor oil.
作为本发明一种优选的技术方案，所述仲胺基化合物选自N,N’-二乙基乙二胺、N,N’-二甲基乙二胺、N,N’-二乙基己二胺、聚天门冬氨酸酯中的一种或多种。As a preferred technical solution of the present invention, the secondary amine compound is selected from N,N'-diethylethylenediamine, N,N'-dimethylethylenediamine, N,N'-diethylethylenediamine One or more of hexamethylenediamine and polyaspartate.
作为本发明一种优选的技术方案，所述多异氰酸酯为脂环族多异氰酸酯和/或芳香族多异氰酸酯。As a preferred technical solution of the present invention, the polyisocyanate is an alicyclic polyisocyanate and/or an aromatic polyisocyanate.
作为本发明一种优选的技术方案，所述分散体的制备原料还包括扩链剂。As a preferred technical solution of the present invention, the raw materials for preparing the dispersion also include a chain extender.
本发明第二个方面提供了一种所述的水性聚氨酯-聚脲分散体的制备方法，包括：A second aspect of the present invention provides a method for preparing the aqueous polyurethane-polyurea dispersion, comprising:
滴加多异氰酸酯到羟基化合物后，在70～85℃反应，降温至50～60℃，滴加仲胺基化合物反应，加入扩链剂、水混合，得到所述水性聚氨酯-聚脲分散体。After dropping the polyisocyanate to the hydroxyl compound, react at 70-85° C., cool down to 50-60° C., drop the secondary amine compound for reaction, add a chain extender and mix with water to obtain the aqueous polyurethane-polyurea dispersion.
本发明与现有技术相比具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
(1)本发明使用含有氨基硅氧烷改性环氧大豆油的羟基化合物和多异氰酸酯反应，得到聚氨酯高聚物，可有效提高耐水性，且部分硅氧键水解缩聚，提高聚合物的交联密度，提高力学和抗冲击性能。(1) The present invention uses a hydroxyl compound containing aminosiloxane modified epoxidized soybean oil to react with a polyisocyanate to obtain a polyurethane polymer, which can effectively improve water resistance, and hydrolyze and polycondensate part of the silicon-oxygen bond to improve the cross-linking of the polymer. Link density, improve mechanical and impact resistance.
(2)添加仲胺基化合物，尤其是聚天门冬氨酸酯参与反应，可和多异氰酸酯形成聚脲结构，从而生成聚氨酯-聚脲交叉网络，可进一步提高耐水性、力学性能和抗冲击性能。(2) Adding secondary amine-based compounds, especially polyaspartate, can form a polyurea structure with polyisocyanate to form a polyurethane-polyurea cross network, which can further improve water resistance, mechanical properties and impact resistance. .
(3)相比于直接添加氨基硅氧烷，本发明发现，使用氨基硅氧烷改性环氧大豆油时，可避免氨基硅氧烷的伯胺与异氰酸酯反应活性太高导致反应胶凝。(3) Compared with the direct addition of aminosiloxane, the present invention finds that when using aminosiloxane to modify epoxidized soybean oil, it can avoid the reaction gelation caused by too high reactivity of the primary amine of aminosiloxane and isocyanate.
(4)使用仲胺基化合物，尤其是聚天门冬氨酸酯作为原料，利用仲胺的空间位阻和多元醇低聚物的较长分子链遮蔽异氰酸根，来调整反应活性，形成均匀的网状结构的同时，在分散体分子中形成稳定的氢键结构，进一步避免粘度的过度增加，甚至出现凝胶现象。(4) Using secondary amine-based compounds, especially polyaspartic acid esters as raw materials, using the steric hindrance of secondary amines and the longer molecular chains of polyol oligomers to shield isocyanate groups to adjust the reactivity and form a uniform At the same time of the network structure, a stable hydrogen bond structure is formed in the dispersion molecules, which further avoids excessive increase in viscosity and even gel phenomenon.
(5)控制分散体的制备原料的添加顺序，得到聚氨酯-聚脲主链、硅氧烷侧链的结构后使用扩链剂进行扩链，相比于共同添加，更有利于减少粘度的增加，提高分散体制备得到的涂膜力学、耐水性和抗冲击性能。(5) Control the order of adding the raw materials for the preparation of the dispersion, and then use a chain extender to extend the chain after obtaining the structure of the polyurethane-polyurea main chain and the siloxane side chain. Compared with co-adding, it is more conducive to reducing the increase in viscosity , to improve the mechanical, water resistance and impact resistance properties of the coating film prepared from the dispersion.
具体实施方式Detailed ways
参选以下本发明的优选实施方法的详述以及包括的实施例可更容易地理解本发明的内容。除非另有限定，本文使用的所有技术以及科学术语具有与本发明所属领域普通技术人员通常理解的相同的含义。当存在矛盾时，以本说明书中的定义为准。The content of the present invention may be more readily understood by reference to the following detailed description of the preferred embodiments of the invention and the included examples. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the definitions in this specification will control.
如本文所用术语“由…制备”与“包含”同义。本文中所用的术语“包含”、“包括”、“具有”、“含有”或其任何其它变形，意在覆盖非排它性的包括。例如，包含所列要素的组合物、步骤、方法、制品或装置不必仅限于那些要素，而是可以包括未明确列出的其它要素或此种组合物、步骤、方法、制品或装置所固有的要素。As used herein, the term "prepared from" is synonymous with "comprising". As used herein, the terms "comprising," "including," "having," "containing," or any other variation thereof, are intended to cover non-exclusive inclusion. For example, a composition, step, method, article or device comprising the listed elements is not necessarily limited to those elements, but may include other elements not expressly listed or inherent to such composition, step, method, article or device elements.
连接词“由…组成”排除任何未指出的要素、步骤或组分。如果用于权利要求中，此短语将使权利要求为封闭式，使其不包含除那些描述的材料以外的材料，但与其相关的常规杂质除外。当短语“由…组成”出现在权利要求主体的子句中而不是紧接在主题之后时，其仅限定在该子句中描述的要素；其它要素并不被排除在作为整体的所述权利要求之外。The conjunction "consisting of" excludes any unspecified element, step or component. If used in a claim, this phrase would make the claim closed to the exclusion of materials other than those described, but with the exception of conventional impurities associated therewith. When the phrase "consisting of" appears in a clause in the body of a claim rather than immediately following the subject matter, it is limited only to the elements described in that clause; other elements are not excluded from the claim as a whole beyond the requirements.
当量、浓度、或者其它值或参数以范围、优选范围、或一系列上限优选值和下限优选值限定的范围表示时，这应当被理解为具体公开了由任何范围上限或优选值与任何范围下限或优选值的任一配对所形成的所有范围，而不论该范围是否单独公开了。例如，当公开了范围“1至5”时，所描述的范围应被解释为包括范围“1至4”、“1至3”、“1至2”、“1至2和4至5”、“1至3和5”等。当数值范围在本文中被描述时，除非另外说明，否则该范围意图包括其端值和在该范围内的所有整数和分数。When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a series of upper preferred values and lower preferred values, this should be understood as specifically disclosing any upper range limit or preferred value and any lower range limit or all ranges formed by any pairing of preferred values, whether or not the ranges are individually disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be construed to include the ranges "1 to 4," "1 to 3," "1 to 2," "1 to 2, and 4 to 5." , "1 to 3 and 5", etc. When numerical ranges are described herein, unless stated otherwise, the ranges are intended to include the endpoints and all integers and fractions within the range.
单数形式包括复数讨论对象，除非上下文中另外清楚地指明。“任选的”或者“任意一种”是指其后描述的事项或事件可以发生或不发生，而且该描述包括事件发生的情形和事件不发生的情形。The singular form includes the plural object of discussion unless the context clearly dictates otherwise. "Optional" or "either" means that the subsequently described item or event may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
说明书和权利要求书中的近似用语用来修饰数量，表示本发明并不限定于该具体数量，还包括与该数量接近的可接受的而不会导致相关基本功能的改变的修正的部分。相应的，用“大约”、“约”等修饰一个数值，意为本发明不限于该精确数值。在某些例子中，近似用语可能对应于测量数值的仪器的精度。在本申请说明书和权利要求书中，范围限定可以组合和/或互换，如果没有另外说明这些范围包括其间所含有的所有子范围。Approximate terms in the specification and claims are used to modify a quantity, indicating that the invention is not limited to the specific quantity, but also includes acceptable amendments close to the quantity without causing a change in the relevant basic function. Accordingly, modification of a numerical value with "about", "about", etc. means that the invention is not limited to the precise numerical value. In some instances, the term of approximation may correspond to the precision of the instrument measuring the value. In the present specification and claims, range definitions may be combined and/or interchanged, and unless otherwise stated, these ranges include all subranges subsumed therebetween.
此外，本发明要素或组分前的不定冠词“一种”和“一个”对要素或组分的数量要求(即出现次数)无限制性。因此“一个”或“一种”应被解读为包括一个或至少一个，并且单数形式的要素或组分也包括复数形式，除非所述数量明显旨指单数形式。Furthermore, the indefinite articles "a" and "an" preceding an element or component of the invention are not limiting on the quantitative requirement (ie, the number of occurrences) of the element or component. Thus "a" or "an" should be read to include one or at least one, and elements or components in the singular also include the plural unless the number is clearly intended to be in the singular.
以下通过具体实施方式说明本发明，但不局限于以下给出的具体实施例。The present invention is described below through specific embodiments, but is not limited to the specific examples given below.
本发明第一个方面提供了一种水性聚氨酯-聚脲分散体，所述分散体的制备原料按重量份计，包括20～90份羟基化合物、10～30份仲胺基化合物、20～60份多异氰酸酯和75～300份水。A first aspect of the present invention provides an aqueous polyurethane-polyurea dispersion. The preparation raw materials of the dispersion include, in parts by weight, 20-90 parts of hydroxyl compounds, 10-30 parts of secondary amine-based compounds, 20-60 parts of parts of polyisocyanate and 75 to 300 parts of water.
在一种实施方式中，所述分散体的制备原料按重量份计，包括30～50份羟基化合物、10～30份仲胺基化合物、30～50份多异氰酸酯和100～300份水。In one embodiment, the raw materials for preparing the dispersion include, in parts by weight, 30-50 parts of hydroxyl compounds, 10-30 parts of secondary amine-based compounds, 30-50 parts of polyisocyanate and 100-300 parts of water.
羟基化合物Hydroxy compound
在一种实施方式中，本发明所述羟基化合物包括多元醇低聚物、改性环氧大豆油、多元醇小分子和亲水单体，重量比为(15～50)：(2～20)：(0.1～10)：(3～8)；优选地为(15～40)：(2～10)：(1～5)：(3～8)。In one embodiment, the hydroxyl compound of the present invention includes polyol oligomer, modified epoxidized soybean oil, polyol small molecule and hydrophilic monomer, and the weight ratio is (15-50): (2-20 ): (0.1-10): (3-8); preferably (15-40): (2-10): (1-5): (3-8).
优选地，本发明所述多元醇低聚物的数均分子量为500～5000，可列举的有，500、1000、2000、3000、4000、5000。按分子数目统计平均，则称为数均分子量。Preferably, the polyol oligomer of the present invention has a number average molecular weight of 500-5000, which can be exemplified as 500, 1000, 2000, 3000, 4000, and 5000. According to the statistical average of the number of molecules, it is called the number average molecular weight.
更优选地，本发明所述多元醇低聚物选自聚乙二醇、聚丙二醇、聚四氢呋喃二醇、聚碳酸酯二醇、聚己内酯二醇、聚己内酯三元醇、聚己二酸乙二醇酯二醇、聚己二酸-1，4-丁二醇酯二醇、聚己二酸己二醇酯二醇中的至少一种。More preferably, the polyol oligomer of the present invention is selected from polyethylene glycol, polypropylene glycol, polytetrahydrofuran diol, polycarbonate diol, polycaprolactone diol, polycaprolactone triol, poly At least one of ethylene adipate diol, poly-1,4-butanediol adipate diol, and polyhexylene adipate diol.
进一步优选地，本发明所述改性环氧大豆油的制备原料包括环氧大豆油和氨基硅氧烷。改性环氧大豆油通过环氧大豆油中的环氧基和酯基与氨基硅烷中的伯胺进行开环和胺/酯交换反应制得。在一种实施方式中，所述环氧大豆油的环氧基和氨基硅氧烷的氨基的摩尔比为1：(0.9～1.1)。Further preferably, the raw materials for preparing the modified epoxidized soybean oil of the present invention include epoxidized soybean oil and aminosiloxane. Modified epoxidized soybean oil is prepared by ring-opening and amine/ester exchange reaction between epoxy and ester groups in epoxidized soybean oil and primary amine in aminosilane. In one embodiment, the molar ratio of the epoxy group of the epoxidized soybean oil to the amino group of the aminosiloxane is 1:(0.9-1.1).
环氧大豆油(epoxidized soybean oil，简称ESO)，是一类有机物，化学式为(RC2H2OR'COO)3C3H5，常温下为浅黄色黏稠油状液体。无毒。沸点150℃(0.53kPa)。溶于大多数有机溶剂和烃类，不溶于水。在一种实施方式中，所述环氧大豆油的环氧值为4～7，可列举的有，4、5、6、7。环氧大亚油的环氧值是指100克环氧大豆油中含有的环氧基团中氧元素的质量分数。Epoxidized soybean oil (epoxidized soybean oil, referred to as ESO) is a kind of organic matter, the chemical formula is (RC 2 H 2 OR'COO) 3 C 3 H 5 , and it is a light yellow viscous oily liquid at room temperature. Nontoxic. The boiling point is 150°C (0.53kPa). Soluble in most organic solvents and hydrocarbons, insoluble in water. In one embodiment, the epoxy value of the epoxidized soybean oil is 4 to 7, and examples thereof include 4, 5, 6, and 7. The epoxy value of epoxidized large linseed oil refers to the mass fraction of oxygen elements in the epoxy group contained in 100 grams of epoxidized soybean oil.
本发明不对改性环氧大豆油的制备方法做具体限定，在一种实施方式中，所述改性环氧大豆油的制备方法包括，将环氧大豆油和氨基硅氧烷在于100～120℃下反应5～8h，得到所述改性环氧大豆油。为了提高改型环氧大豆油和其他制备原料的相容性，在制备分散体的过程中可以添加溶剂，作为溶剂的实例，可列举的有，N-甲基吡咯烷酮、二甲基甲酰胺。The present invention does not specifically limit the preparation method of the modified epoxidized soybean oil. In one embodiment, the preparation method of the modified epoxidized soybean oil includes: mixing the epoxidized soybean oil and the aminosiloxane at a concentration of 100-120 The modified epoxidized soybean oil is obtained by reacting at ℃ for 5-8 hours. In order to improve the compatibility between the modified epoxidized soybean oil and other preparation materials, a solvent can be added during the preparation of the dispersion. Examples of the solvent include N-methylpyrrolidone and dimethylformamide.
氨基硅氧烷为含有氨基(NH2)的硅氧烷，可列举的有，γ-氨丙基三甲氧基硅烷(KH-540)、γ-氨丙基甲基二甲氧基硅烷(KH-530)、γ-氨丙基三乙氧基硅烷(KH-550)、N-(β氨乙基)-γ-氨丙基甲基二甲氧基硅烷(KH-602)、N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷(KH-792)。The aminosiloxane is a siloxane containing an amino group (NH 2 ), and examples thereof include γ-aminopropyltrimethoxysilane (KH-540), γ-aminopropylmethyldimethoxysilane (KH -530), γ-aminopropyltriethoxysilane (KH-550), N-(βaminoethyl)-γ-aminopropylmethyldimethoxysilane (KH-602), N-( β-Aminoethyl)-γ-aminopropyltrimethoxysilane (KH-792).
更进一步优选地，本发明所述多元醇小分子选自乙二醇、二甘醇、三乙二醇、1，4-丁二醇、1，6-己二醇、1，4-环己烷二甲醇、3-甲基-1，5戊二醇、1，5戊二醇、1，2-丙二醇、二丙二醇、三丙二醇、氢化双酚A二醇、丙三醇、三羟甲基丙烷、蓖麻油中的至少一种。More preferably, the polyol small molecule of the present invention is selected from ethylene glycol, diethylene glycol, triethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexane Alkane dimethanol, 3-methyl-1,5-pentanediol, 1,5-pentanediol, 1,2-propanediol, dipropylene glycol, tripropylene glycol, hydrogenated bisphenol A glycol, glycerol, trimethylol At least one of propane and castor oil.
在一种优选的实施方式中，本发明所述亲水单体为二羟基烷基酸，可列举的优，2,2-二羟甲基丙酸、2,2-二羟甲基丁酸。In a preferred embodiment, the hydrophilic monomer of the present invention is a dihydroxyalkanoic acid, such as 2,2-dimethylolpropionic acid and 2,2-dimethylolbutyric acid. .
仲胺基化合物Secondary Amino Compounds
在一种实施方式中，本发明所述仲胺基化合物选自N,N’-二乙基乙二胺、N,N’-二甲基乙二胺、N,N’-二乙基己二胺、聚天门冬氨酸酯中的一种或多种，优选地为聚天门冬氨酸酯。In one embodiment, the secondary amine compound of the present invention is selected from N,N'-diethylethylenediamine, N,N'-dimethylethylenediamine, N,N'-diethylhexanediamine One or more of diamine and polyaspartate, preferably polyaspartate.
聚天门冬氨酸酯是一种空间位阻的脂肪族仲二胺，其结构中的胺基受到屏蔽基团的电子诱导效应和位阻屏蔽效应的协同作用，活性大大降低，使得其与多异氰酸酯的反应速度明显降低。作为聚天门冬氨酸酯的实例，包括但不限于，飞扬骏研F420、飞扬骏研F520、飞扬骏研F220、飞扬骏研F330、Desmophen NH1420、Desmophen NH1520、Desmophen NH1220。Polyaspartate is a sterically hindered aliphatic secondary diamine. The amine group in its structure is affected by the synergistic effect of the electronic induction effect of the shielding group and the steric shielding effect, and the activity is greatly reduced, which makes it difficult to interact with polyaspartic acid. The reaction rate of isocyanates is significantly reduced. Examples of polyaspartic acid esters include, but are not limited to, Feiyang Junyan F420, Feiyang Junyan F520, Feiyang Junyan F220, Feiyang Junyan F330, Desmophen NH1420, Desmophen NH1520, Desmophen NH1220.
多异氰酸酯polyisocyanate
在一种实施方式中，本发明所述多异氰酸酯选自脂环族多异氰酸酯、芳香族多异氰酸酯、脂肪族多异氰酸酯中的一种或多种，优选地，本发明所述多异氰酸酯为脂环族多异氰酸酯和/或芳香族多异氰酸酯。In one embodiment, the polyisocyanates of the present invention are selected from one or more of alicyclic polyisocyanates, aromatic polyisocyanates, and aliphatic polyisocyanates, preferably, the polyisocyanates of the present invention are alicyclic polyisocyanates aromatic polyisocyanates and/or aromatic polyisocyanates.
作为脂环族多异氰酸酯的实例，包括但不限于，二环己基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、环己烷二亚甲基二异氰酸酯。Examples of alicyclic polyisocyanates include, but are not limited to, dicyclohexylmethane diisocyanate, isophorone diisocyanate, and cyclohexane dimethylene diisocyanate.
作为芳香族多异氰酸酯的实例，包括但不限于，甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、苯二亚甲基二异氰酸酯、四甲基苯二亚甲基二异氰酸酯。Examples of aromatic polyisocyanates include, but are not limited to, toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, and tetramethyl xylylene diisocyanate.
作为脂肪族多异氰酸酯的实例，包括但不限于，六亚甲基二异氰酸酯。Examples of aliphatic polyisocyanates include, but are not limited to, hexamethylene diisocyanate.
在一种实施方式中，本发明所述分散体的制备原料还包括中和剂。In one embodiment, the raw material for preparing the dispersion of the present invention further includes a neutralizing agent.
中和剂Neutralizer
为中和分散体中亲水单体羧酸官能团，可添加中和剂，本发明不对中和剂的具体用量进行限定，将分散体中亲水单体的羧酸官能团中和即可。在一种实施方式中，本发明所述中和剂选自三乙胺、二甲基乙醇胺、二乙醇胺中的一种。优选地，本发明所述中和剂和亲水单体的重量比为(2～6)：(3～8)。In order to neutralize the carboxylic acid functional group of the hydrophilic monomer in the dispersion, a neutralizing agent can be added, and the specific amount of the neutralizing agent is not limited in the present invention, and the carboxylic acid functional group of the hydrophilic monomer in the dispersion can be neutralized. In one embodiment, the neutralizing agent of the present invention is selected from one of triethylamine, dimethylethanolamine, and diethanolamine. Preferably, the weight ratio of the neutralizing agent and the hydrophilic monomer in the present invention is (2-6): (3-8).
在一种实施方式中，本发明所述分散体的制备原料还包括扩链剂。In one embodiment, the raw material for the preparation of the dispersion of the present invention further includes a chain extender.
扩链剂chain extender
在一种实施方式中，本发明所述扩链剂选自乙二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺、五乙烯六胺、六乙烯七胺、己二胺、聚醚胺D230、聚醚胺D400中的至少一种。优选地，本发明所述多异氰酸酯和扩链剂的重量比为(1～25)：(20～60)，优选为(1～5)：(30～50)。In one embodiment, the chain extender of the present invention is selected from the group consisting of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, hexamethylenediamine, poly At least one of etheramine D230 and polyetheramine D400. Preferably, the weight ratio of the polyisocyanate and the chain extender in the present invention is (1-25):(20-60), preferably (1-5):(30-50).
在一种实施方式中，本发明所述分散体的制备原料还包括催化剂。In one embodiment, the raw material for the preparation of the dispersion of the present invention further comprises a catalyst.
催化剂catalyst
作为催化剂的实例，包括但不限于，二月桂酸二丁基锡、辛基亚锡；在一种实施方式中，所述催化剂占多异氰酸酯的1～10wt‰。Examples of the catalyst include, but are not limited to, dibutyltin dilaurate and octylstannous; in one embodiment, the catalyst accounts for 1-10wt‰ of the polyisocyanate.
本发明第二个方面提供一种如上所述的水性聚氨酯-聚脲分散体的制备方法，包括：A second aspect of the present invention provides a method for preparing the above-mentioned aqueous polyurethane-polyurea dispersion, comprising:
滴加多异氰酸酯到羟基化合物后，在70～85℃反应，降温至50～60℃，滴加仲胺基化合物反应，加入扩链剂、水混合，得到所述水性聚氨酯-聚脲分散体。After dropping the polyisocyanate to the hydroxyl compound, react at 70-85° C., cool down to 50-60° C., drop the secondary amine compound for reaction, add a chain extender and mix with water to obtain the aqueous polyurethane-polyurea dispersion.
在一种实施方式中，本发明所述水性聚氨酯-聚脲分散体的制备方法，包括：In one embodiment, the preparation method of the aqueous polyurethane-polyurea dispersion of the present invention comprises:
滴加0.5～2h多异氰酸酯到羟基化合物后，加入催化剂，在70～85℃反应，降温至50～60℃，滴加0.5～2h仲胺基化合物反应，降温至35～45℃，加入中和剂混合后，加入扩链剂、水混合，得到所述水性聚氨酯-聚脲分散体。After adding 0.5-2h polyisocyanate dropwise to the hydroxyl compound, add catalyst, react at 70-85°C, cool down to 50-60°C, add dropwise 0.5-2h secondary amine compound for reaction, cool down to 35-45°C, add neutralization After mixing of the agent, a chain extender is added, and water is mixed to obtain the aqueous polyurethane-polyurea dispersion.
在一种实施方式中，本发明所述滴加多异氰酸酯到羟基化合物前，将多元醇低聚物、多元醇小分子、亲水单体在90～110℃，-0.1～-0.08MPa条件下脱水2h后，加入溶剂和环氧大豆油，得到羟基化合物。In one embodiment, before adding the polyisocyanate dropwise to the hydroxyl compound, the polyol oligomer, the polyol small molecule and the hydrophilic monomer are heated at 90～110℃ and -0.1～-0.08MPa. After dehydration for 2 h, solvent and epoxidized soybean oil were added to obtain a hydroxyl compound.
实施例Example
下面通过实施例对本发明进行具体描述。有必要在此指出的是，以下实施例只用于对本发明作进一步说明，不能理解为对本发明保护范围的限制，该领域的专业技术人员根据上述本发明的内容做出的一些非本质的改进和调整，仍属于本发明的保护范围。The present invention will be specifically described below by means of examples. It is necessary to point out here that the following examples are only used to further illustrate the present invention, and should not be construed as limiting the scope of protection of the present invention, and some non-essential improvements made by those skilled in the art according to the above-mentioned content of the present invention and adjustment, still belong to the protection scope of the present invention.
实施例1Example 1
本例提供一种水性聚氨酯-聚脲分散体，所述分散体的制备原料按重量份计，包括29.5份PPG2000(数均分子量为2000)、3份1，4-丁二醇、4.5份二羟甲基丙酸、25份N-甲基吡咯烷酮、5份改性环氧大豆油、40.3份异佛尔酮二异氰酸酯、18份飞扬骏研F420、3.2份三乙胺、3.4份乙二胺、187份水、二月桂酸二丁基锡，所述二月桂酸二丁基锡占异佛尔酮二异氰酸酯1wt‰。This example provides an aqueous polyurethane-polyurea dispersion, and the raw materials for the preparation of the dispersion, in parts by weight, include 29.5 parts of PPG2000 (number average molecular weight is 2000), 3 parts of 1,4-butanediol, 4.5 parts of dimethicone Methylolpropionic acid, 25 parts of N-methylpyrrolidone, 5 parts of modified epoxidized soybean oil, 40.3 parts of isophorone diisocyanate, 18 parts of Feiyang Junyan F420, 3.2 parts of triethylamine, 3.4 parts of ethylenediamine , 187 parts of water, dibutyltin dilaurate, the dibutyltin dilaurate accounts for 1wt‰ of isophorone diisocyanate.
所述改性环氧大豆油的制备原料包括100份环氧大豆油(环氧值为6)、82.8份γ-氨丙基三乙氧基硅烷；所述改性环氧大豆油的制备方法包括：惰性气体保护下，环氧大豆油与γ-氨丙基三乙氧基硅烷于110℃下反应6h，降温即得。测得改性环氧大豆油的羟基、仲胺和伯胺总含量为：248mg KOH/g。The preparation raw materials of the modified epoxidized soybean oil include 100 parts of epoxidized soybean oil (epoxy value of 6) and 82.8 parts of γ-aminopropyltriethoxysilane; the preparation method of the modified epoxidized soybean oil Including: under the protection of inert gas, epoxidized soybean oil and γ-aminopropyl triethoxysilane are reacted at 110° C. for 6 hours, and then the temperature is lowered. The total content of hydroxyl groups, secondary amines and primary amines in the modified epoxidized soybean oil was measured to be 248 mg KOH/g.
本例还提供如上所述的水性聚氨酯-聚脲分散体的制备方法，包括：This example also provides the above-mentioned preparation method of the aqueous polyurethane-polyurea dispersion, including:
将PPG2000、1，4-丁二醇、二羟甲基丙酸于反应瓶中，在110℃，-0.095MPa条件下脱水2h；Put PPG2000, 1,4-butanediol and dimethylolpropionic acid in a reaction flask, dehydrate at 110°C and -0.095MPa for 2h;
惰性气体保护下，往上述反应瓶中加入N-甲基吡咯烷酮和改性环氧大豆油，室温下滴加异佛尔酮二异氰酸酯，1h内滴完，加入二月桂酸二丁基锡后升温至80℃反应至-NCO值为6.9～7.1％；Under the protection of inert gas, N-methylpyrrolidone and modified epoxidized soybean oil were added to the above reaction flask, and isophorone diisocyanate was added dropwise at room temperature. ℃ Reaction to -NCO value of 6.9 to 7.1%;
惰性气体保护下，待上述反应物料降温至55℃，滴加飞扬骏研F420，1h内滴完，保温反应至-NCO值为3.7～3.9％，降温至40℃，加入三乙胺搅拌30min，再加入乙二胺、冰水高速分散30min，即得水性聚氨酯-聚脲分散体。Under the protection of inert gas, after the above reaction material was cooled to 55 ℃, Feiyang Junyan F420 was added dropwise, the dripping was completed within 1 h, the reaction was kept warm until the -NCO value was 3.7-3.9%, the temperature was lowered to 40 ℃, triethylamine was added and stirred for 30 min, Then, ethylenediamine and ice water were added to disperse at high speed for 30min to obtain water-based polyurethane-polyurea dispersion.
实施例2Example 2
本例提供一种水性聚氨酯-聚脲分散体，所述分散体的制备原料按重量份计，包括25.3份PPG2000、3份1，4-丁二醇、4.5份二羟甲基丙酸、25份N-甲基吡咯烷酮、8份改性环氧大豆油、41.2份异佛尔酮二异氰酸酯、18份飞扬骏研F420、3.2份三乙胺、3.4份乙二胺、187份水、二月桂酸二丁基锡，所述二月桂酸二丁基锡占异佛尔酮二异氰酸酯1wt‰。This example provides an aqueous polyurethane-polyurea dispersion, and the raw materials for the preparation of the dispersion, in parts by weight, include 25.3 parts of PPG2000, 3 parts of 1,4-butanediol, 4.5 parts of dimethylolpropionic acid, 25 parts of Parts of N-methylpyrrolidone, 8 parts of modified epoxidized soybean oil, 41.2 parts of isophorone diisocyanate, 18 parts of Feiyang Junyan F420, 3.2 parts of triethylamine, 3.4 parts of ethylenediamine, 187 parts of water, dilaurin Dibutyltin dilaurate, the dibutyltin dilaurate accounts for 1wt‰ of isophorone diisocyanate.
所述改性环氧大豆油的制备原料包括100份环氧大豆油(环氧值为6)、82.8份γ-氨丙基三乙氧基硅烷；所述改性环氧大豆油的制备方法包括：惰性气体保护下，环氧大豆油与γ-氨丙基三乙氧基硅烷于110℃下反应6h，降温即得。测得改性环氧大豆油的羟基、仲胺和伯胺总含量为：248mg KOH/g。The preparation raw materials of the modified epoxidized soybean oil include 100 parts of epoxidized soybean oil (epoxy value of 6) and 82.8 parts of γ-aminopropyltriethoxysilane; the preparation method of the modified epoxidized soybean oil Including: under the protection of inert gas, epoxidized soybean oil and γ-aminopropyl triethoxysilane are reacted at 110° C. for 6 hours, and then the temperature is lowered. The total content of hydroxyl groups, secondary amines and primary amines in the modified epoxidized soybean oil was measured to be 248 mg KOH/g.
本例还提供如上所述的水性聚氨酯-聚脲分散体的制备方法，包括：This example also provides the above-mentioned preparation method of the aqueous polyurethane-polyurea dispersion, including:
将PPG2000、1，4-丁二醇、二羟甲基丙酸于反应瓶中，在110℃，-0.095MPa条件下脱水2h；Put PPG2000, 1,4-butanediol and dimethylolpropionic acid in a reaction flask, dehydrate at 110°C and -0.095MPa for 2h;
惰性气体保护下，往上述反应瓶中加入N-甲基吡咯烷酮、改性环氧大豆油，室温下滴加异佛尔酮二异氰酸酯，1h内滴完，加入二月桂酸二丁基锡后升温至80℃反应至-NCO值为6.8～7％；Under the protection of inert gas, N-methylpyrrolidone and modified epoxidized soybean oil were added to the above reaction flask, and isophorone diisocyanate was added dropwise at room temperature. ℃ Reaction to -NCO value of 6.8 to 7%;
惰性气体保护下，待上述反应物料降温至55℃，滴加飞扬骏研F420，1h内滴完，保温反应至-NCO值为3.7～3.9％，降温至40℃，加入三乙胺搅拌30min，再加入乙二胺、冰水高速分散30min，即得水性聚氨酯-聚脲分散体。Under the protection of inert gas, after the above reaction material was cooled to 55 ℃, Feiyang Junyan F420 was added dropwise, the dripping was completed within 1 h, the reaction was kept warm until the -NCO value was 3.7-3.9%, the temperature was lowered to 40 ℃, triethylamine was added and stirred for 30 min, Then, ethylenediamine and ice water were added to disperse at high speed for 30min to obtain water-based polyurethane-polyurea dispersion.
实施例3Example 3
本例提供一种水性聚氨酯-聚脲分散体，所述分散体的制备原料按重量份计，包括28.3份聚己内酯二醇(数均分子量为2000)、3.1份1，4-环己烷二甲醇、4.4份二羟甲基丙酸、25份N-甲基吡咯烷酮、8份改性环氧大豆油、38.3份异佛尔酮二异氰酸酯、18份飞扬骏研F420、3.1份三乙胺、3.2份乙二胺、187份水、二月桂酸二丁基锡，所述二月桂酸二丁基锡占异佛尔酮二异氰酸酯1wt‰。This example provides an aqueous polyurethane-polyurea dispersion. The raw materials for the preparation of the dispersion, in parts by weight, include 28.3 parts of polycaprolactone diol (number average molecular weight is 2000), 3.1 parts of 1,4-cyclohexane Alkane dimethanol, 4.4 parts of dimethylolpropionic acid, 25 parts of N-methylpyrrolidone, 8 parts of modified epoxidized soybean oil, 38.3 parts of isophorone diisocyanate, 18 parts of Feiyang Junyan F420, 3.1 parts of triethyl Amine, 3.2 parts of ethylenediamine, 187 parts of water, dibutyltin dilaurate, the dibutyltin dilaurate accounts for 1wt‰ of isophorone diisocyanate.
所述改性环氧大豆油的制备原料包括100份环氧大豆油(环氧值为6)、82.8份γ-氨丙基三乙氧基硅烷；所述改性环氧大豆油的制备方法包括：惰性气体保护下，环氧大豆油与γ-氨丙基三乙氧基硅烷于110℃下反应6h，降温即得。测得改性环氧大豆油的羟基、仲胺和伯胺总含量为：248mg KOH/g。The preparation raw materials of the modified epoxidized soybean oil include 100 parts of epoxidized soybean oil (epoxy value of 6) and 82.8 parts of γ-aminopropyltriethoxysilane; the preparation method of the modified epoxidized soybean oil Including: under the protection of inert gas, epoxidized soybean oil and γ-aminopropyl triethoxysilane are reacted at 110° C. for 6 hours, and then the temperature is lowered. The total content of hydroxyl groups, secondary amines and primary amines in the modified epoxidized soybean oil was measured to be 248 mg KOH/g.
本例还提供如上所述的水性聚氨酯-聚脲分散体的制备方法，包括：This example also provides the above-mentioned preparation method of the aqueous polyurethane-polyurea dispersion, including:
将聚己内酯二醇、1，4-环己烷二甲醇、二羟甲基丙酸于反应瓶中，在110℃，-0.095MPa条件下脱水2h；Put polycaprolactone diol, 1,4-cyclohexanedimethanol and dimethylolpropionic acid in a reaction flask, dehydrate at 110°C and -0.095MPa for 2h;
惰性气体保护下，往上述反应瓶中加入N-甲基吡咯烷酮和改性环氧大豆油，室温下滴加异佛尔酮二异氰酸酯，1h内滴完，加入二月桂酸二丁基锡后升温至80℃反应至-NCO为6.7～6.8％；Under the protection of inert gas, N-methylpyrrolidone and modified epoxidized soybean oil were added to the above reaction flask, and isophorone diisocyanate was added dropwise at room temperature. ℃ Reaction to -NCO is 6.7～6.8%;
惰性气体保护下，待上述反应物料降温至55℃，滴加飞扬骏研F420，1h内滴完，保温反应至-NCO值为3.5～3.7％，降温至40℃，加入三乙胺搅拌30min，再加入乙二胺、冰水高速分散30min，即得水性聚氨酯-聚脲分散体。Under the protection of inert gas, after the above reaction material was cooled to 55 ℃, Feiyang Junyan F420 was added dropwise, the dripping was completed within 1 hour, the reaction was kept warm until the -NCO value was 3.5-3.7%, the temperature was lowered to 40 ℃, triethylamine was added and stirred for 30 min, Then, ethylenediamine and ice water were added to disperse at high speed for 30min to obtain water-based polyurethane-polyurea dispersion.
实施例4Example 4
本例提供一种水性聚氨酯-聚脲分散体，所述分散体的制备原料按重量份计，包括24.4份PPG1000(数均分子量为1000)、3份1，6-己二醇、4.5份二羟甲基丙酸、25份N-甲基吡咯烷酮、6份改性环氧大豆油、42.2份异佛尔酮二异氰酸酯、20份飞扬骏研F520、3.2份三乙胺、3.6份乙二胺、187份水、二月桂酸二丁基锡，所述二月桂酸二丁基锡占异佛尔酮二异氰酸酯1wt‰。This example provides an aqueous polyurethane-polyurea dispersion. The raw materials for the preparation of the dispersion, in parts by weight, include 24.4 parts of PPG1000 (number-average molecular weight is 1000), 3 parts of 1,6-hexanediol, 4.5 parts of diethylene glycol Methylolpropionic acid, 25 parts N-methylpyrrolidone, 6 parts modified epoxidized soybean oil, 42.2 parts isophorone diisocyanate, 20 parts Feiyang Junyan F520, 3.2 parts triethylamine, 3.6 parts ethylenediamine , 187 parts of water, dibutyltin dilaurate, the dibutyltin dilaurate accounts for 1wt‰ of isophorone diisocyanate.
所述改性环氧大豆油的制备原料包括100份环氧大豆油(环氧值为6)、82.8份γ-氨丙基三乙氧基硅烷；所述改性环氧大豆油的制备方法包括：惰性气体保护下，环氧大豆油与γ-氨丙基三乙氧基硅烷于110℃下反应6h，降温即得。测得改性环氧大豆油的羟基、仲胺和伯胺总含量为：248mg KOH/g。The preparation raw materials of the modified epoxidized soybean oil include 100 parts of epoxidized soybean oil (epoxy value of 6) and 82.8 parts of γ-aminopropyltriethoxysilane; the preparation method of the modified epoxidized soybean oil Including: under the protection of inert gas, epoxidized soybean oil and γ-aminopropyl triethoxysilane are reacted at 110° C. for 6 hours, and then the temperature is lowered. The total content of hydroxyl groups, secondary amines and primary amines in the modified epoxidized soybean oil was measured to be 248 mg KOH/g.
本例还提供如上所述的水性聚氨酯-聚脲分散体的制备方法，包括：This example also provides the above-mentioned preparation method of the aqueous polyurethane-polyurea dispersion, including:
将PPG1000、1，6-己二醇、二羟甲基丙酸于反应瓶中，在110℃，-0.095MPa条件下脱水2h；Put PPG1000, 1,6-hexanediol and dimethylolpropionic acid in a reaction flask, dehydrate at 110°C and -0.095MPa for 2h;
惰性气体保护下，往上述反应瓶中加入N-甲基吡咯烷酮和改性环氧大豆油，室温下滴加异佛尔酮二异氰酸酯，1h内滴完，加入二月桂酸二丁基锡后升温至80℃反应至-NCO为7.4～7.6％；Under the protection of inert gas, N-methylpyrrolidone and modified epoxidized soybean oil were added to the above reaction flask, and isophorone diisocyanate was added dropwise at room temperature. ℃ Reaction to -NCO is 7.4～7.6%;
惰性气体保护下，待上述反应物料降温至55℃，滴加飞扬骏研F520，1h内滴完，保温反应至-NCO值为3.9～4.1％，降温至40℃，加入三乙胺搅拌30min，再加入乙二胺、冰水高速分散30min，即得水性聚氨酯。Under the protection of inert gas, after the reaction material was cooled to 55°C, Feiyang Junyan F520 was added dropwise, the dropping was completed within 1 hour, the reaction was kept warm until the -NCO value was 3.9-4.1%, the temperature was lowered to 40°C, triethylamine was added and stirred for 30min, Then add ethylenediamine and ice water to disperse at high speed for 30min to obtain water-based polyurethane.
实施例5Example 5
本例提供一种水性聚氨酯-聚脲分散体，所述分散体的制备原料按重量份计，包括19.2份PPG1000、3份1，6-己二醇、4.5份二羟甲基丙酸、25份N-甲基吡咯烷酮和10份改性环氧大豆油、43.4份异佛尔酮二异氰酸酯、20份飞扬骏研F520、3.2份三乙胺、3.6份乙二胺、187份水、二月桂酸二丁基锡，所述二月桂酸二丁基锡占异佛尔酮二异氰酸酯1wt‰。This example provides an aqueous polyurethane-polyurea dispersion. The raw materials for the preparation of the dispersion, in parts by weight, include 19.2 parts of PPG1000, 3 parts of 1,6-hexanediol, 4.5 parts of dimethylolpropionic acid, 25 parts of Parts of N-methylpyrrolidone and 10 parts of modified epoxidized soybean oil, 43.4 parts of isophorone diisocyanate, 20 parts of Feiyang Junyan F520, 3.2 parts of triethylamine, 3.6 parts of ethylenediamine, 187 parts of water, dilaurin Dibutyltin dilaurate, the dibutyltin dilaurate accounts for 1wt‰ of isophorone diisocyanate.
所述改性环氧大豆油的制备原料包括100份环氧大豆油(环氧值为6)、82.8份γ-氨丙基三乙氧基硅烷；所述改性环氧大豆油的制备方法包括：惰性气体保护下，环氧大豆油与γ-氨丙基三乙氧基硅烷于110℃下反应6h，降温即得。测得改性环氧大豆油的羟基、仲胺和伯胺总含量为：248mg KOH/g。The preparation raw materials of the modified epoxidized soybean oil include 100 parts of epoxidized soybean oil (epoxy value of 6) and 82.8 parts of γ-aminopropyltriethoxysilane; the preparation method of the modified epoxidized soybean oil Including: under the protection of inert gas, epoxidized soybean oil and γ-aminopropyl triethoxysilane are reacted at 110° C. for 6 hours, and then the temperature is lowered. The total content of hydroxyl groups, secondary amines and primary amines in the modified epoxidized soybean oil was measured to be 248 mg KOH/g.
本例还提供如上所述的水性聚氨酯-聚脲分散体的制备方法，包括：This example also provides the above-mentioned preparation method of the aqueous polyurethane-polyurea dispersion, including:
将PPG1000、1，6-己二醇、二羟甲基丙酸于反应瓶中，在110℃，-0.095MPa条件下脱水2h；Put PPG1000, 1,6-hexanediol and dimethylolpropionic acid in a reaction flask, dehydrate at 110°C and -0.095MPa for 2h;
惰性气体保护下，往上述反应瓶中加入N-甲基吡咯烷酮和改性环氧大豆油，室温下滴加异佛尔酮二异氰酸酯，1h内滴完，加入二月桂酸二丁基锡后升温至80℃反应至-NCO值为7.5～7.7％；Under the protection of inert gas, N-methylpyrrolidone and modified epoxidized soybean oil were added to the above reaction flask, and isophorone diisocyanate was added dropwise at room temperature. ℃ Reaction to -NCO value of 7.5 to 7.7%;
惰性气体保护下，待上述反应物料降温至55℃，滴加飞扬骏研F520，1h内滴完，保温反应至-NCO值为3.9～4.1％，降温至40℃，加入三乙胺搅拌30min，再加入乙二胺、冰水高速分散30min，即得水性聚氨酯-聚脲分散体。Under the protection of inert gas, after the reaction material was cooled to 55°C, Feiyang Junyan F520 was added dropwise, the dropping was completed within 1 hour, the reaction was kept warm until the -NCO value was 3.9-4.1%, the temperature was lowered to 40°C, triethylamine was added and stirred for 30min, Then, ethylenediamine and ice water were added to disperse at high speed for 30min to obtain water-based polyurethane-polyurea dispersion.
实施例6Example 6
本例提供一种水性聚氨酯-聚脲分散体，所述分散体的制备原料按重量份计，包括30份PPG2000、3份1，4-丁二醇、4.5份二羟甲基丙酸、25份N-甲基吡咯烷酮、6份改性环氧大豆油、36份环己烷二亚甲基二异氰酸酯、22份飞扬骏研F520、3.2份三乙胺、3.4份乙二胺、187份水、二月桂酸二丁基锡，所述二月桂酸二丁基锡占环己烷二亚甲基二异氰酸酯1wt‰。This example provides an aqueous polyurethane-polyurea dispersion. The preparation raw materials of the dispersion include, in parts by weight, 30 parts of PPG2000, 3 parts of 1,4-butanediol, 4.5 parts of dimethylolpropionic acid, 25 parts of Parts of N-methylpyrrolidone, 6 parts of modified epoxidized soybean oil, 36 parts of cyclohexane dimethylene diisocyanate, 22 parts of Feiyang Junyan F520, 3.2 parts of triethylamine, 3.4 parts of ethylenediamine, 187 parts of water , Dibutyltin dilaurate, the dibutyltin dilaurate accounts for 1wt‰ of cyclohexane dimethylene diisocyanate.
所述改性环氧大豆油的制备原料包括100份环氧大豆油(环氧值为6)、77.2份N-(β氨乙基)-γ-氨丙基甲基二甲氧基硅烷(KH-602)；所述改性环氧大豆油的制备方法包括：惰性气体保护下，环氧大豆油与γ-氨丙基甲基二甲氧基硅烷于110℃下反应6h，降温即得。测得改性环氧大豆油的羟基、仲胺和伯胺总含量为：248mg KOH/g。The preparation raw materials of the modified epoxidized soybean oil include 100 parts of epoxidized soybean oil (epoxy value of 6), 77.2 parts of N-(β aminoethyl)-γ-aminopropyl methyldimethoxysilane ( KH-602); the preparation method of the modified epoxidized soybean oil includes: under the protection of an inert gas, the epoxidized soybean oil and γ-aminopropyl methyldimethoxysilane are reacted at 110 ° C for 6 hours, and then the temperature is lowered to obtain . The total content of hydroxyl groups, secondary amines and primary amines in the modified epoxidized soybean oil was measured to be 248 mg KOH/g.
本例还提供如上所述的水性聚氨酯-聚脲分散体的制备方法，包括：This example also provides the above-mentioned preparation method of the aqueous polyurethane-polyurea dispersion, including:
将PPG2000、1，4-丁二醇、二羟甲基丙酸于反应瓶中，在110℃，-0.095MPa条件下脱水2h；Put PPG2000, 1,4-butanediol and dimethylolpropionic acid in a reaction flask, dehydrate at 110°C and -0.095MPa for 2h;
惰性气体保护下，往上述反应瓶中加入N-甲基吡咯烷酮和改性环氧大豆油，室温下滴加环己烷二亚甲基二异氰酸酯，1h内滴完，加入二月桂酸二丁基锡后升温至80℃反应至-NCO值为6.8～7.1％；Under the protection of inert gas, N-methylpyrrolidone and modified epoxidized soybean oil were added to the above reaction flask, and cyclohexane dimethylene diisocyanate was added dropwise at room temperature. The temperature was raised to 80°C and the reaction was performed until the -NCO value was 6.8-7.1%;
惰性气体保护下，待上述反应物料降温至55℃，滴加飞扬骏研F520，1h内滴完，保温反应至-NCO值为3.7～3.9％，降温至40℃，加入三乙胺搅拌30min，再加入乙二胺、冰水高速分散30min，即得水性聚氨酯-聚脲分散体。Under the protection of inert gas, after the above reaction material was cooled to 55 ℃, Feiyang Junyan F520 was added dropwise, the dripping was completed within 1 hour, the reaction was kept warm until the -NCO value was 3.7-3.9%, the temperature was lowered to 40 ℃, triethylamine was added and stirred for 30 minutes, Then, ethylenediamine and ice water were added to disperse at high speed for 30min to obtain water-based polyurethane-polyurea dispersion.
对比例1Comparative Example 1
本例提供一种分散体，所述分散体的制备原料按重量份计，包括：117.4份PPG2000、7份1，4-丁二醇、8.6份二羟甲基丙酸、50份N-甲基吡咯烷酮、66.7份异佛尔酮二异氰酸酯、6.4份三乙胺、5.9份乙二胺、375份水、二月桂酸二丁基锡，所述二月桂酸二丁基锡占异佛尔酮二异氰酸酯1wt‰。This example provides a dispersion, and the raw materials for the preparation of the dispersion, in parts by weight, include: 117.4 parts of PPG2000, 7 parts of 1,4-butanediol, 8.6 parts of dimethylolpropionic acid, and 50 parts of N-methylpropionic acid. pyrrolidone, 66.7 parts of isophorone diisocyanate, 6.4 parts of triethylamine, 5.9 parts of ethylenediamine, 375 parts of water, dibutyltin dilaurate, the dibutyltin dilaurate accounts for 1wt‰ of isophorone diisocyanate .
本例还提供如上所述的分散体的制备方法，包括：This example also provides a method for preparing a dispersion as described above, comprising:
将PPG2000、1，4-丁二醇、二羟甲基丙酸于反应瓶中，在110℃，-0.095MPa条件下脱水2h；Put PPG2000, 1,4-butanediol and dimethylolpropionic acid in a reaction flask, dehydrate at 110°C and -0.095MPa for 2h;
惰性气体保护下，往上述反应瓶中加入N-甲基吡咯烷酮，控温60℃，滴加异佛尔酮二异氰酸酯，1h左右滴完，加入二月桂酸二丁基锡，继续升温至80℃反应至-NCO值为3.2～3.4％，降温至40℃，加入三乙胺中和30min，再加入乙二胺、冰水高速分散30min，即得分散体。Under the protection of inert gas, N-methylpyrrolidone was added to the above reaction flask, the temperature was controlled at 60 °C, isophorone diisocyanate was added dropwise, after about 1 h, dibutyltin dilaurate was added, and the temperature was continued to rise to 80 °C to react to -NCO value is 3.2-3.4%, cooling to 40°C, adding triethylamine for neutralization for 30min, then adding ethylenediamine and ice water for high-speed dispersion for 30min to obtain a dispersion.
对比例2Comparative Example 2
本例提供一种分散体，所述分散体的制备原料按重量份计，包括：66份PPG2000、8.3份1，4-丁二醇、10.1份二羟甲基丙酸、58.7份N-甲基吡咯烷酮、101.3份异佛尔酮二异氰酸酯、49.4份飞扬骏研F420、7.6份三乙胺、10.1份乙二胺、440.5份水、二月桂酸二丁基锡，所述二月桂酸二丁基锡占异佛尔酮二异氰酸酯1wt‰。This example provides a dispersion, and the raw materials for the preparation of the dispersion, in parts by weight, include: 66 parts of PPG2000, 8.3 parts of 1,4-butanediol, 10.1 parts of dimethylolpropionic acid, and 58.7 parts of N-methylolpropionic acid. pyrrolidone, 101.3 parts of isophorone diisocyanate, 49.4 parts of Feiyang Junyan F420, 7.6 parts of triethylamine, 10.1 parts of ethylenediamine, 440.5 parts of water, dibutyltin dilaurate, the Phorone diisocyanate 1wt‰.
本例还提供如上所述的分散体的制备方法，包括：This example also provides a method for preparing a dispersion as described above, comprising:
将PPG2000、1，4-丁二醇、二羟甲基丙酸于反应瓶中，在110℃，-0.095MPa条件下脱水2h；Put PPG2000, 1,4-butanediol and dimethylolpropionic acid in a reaction flask, dehydrate at 110°C and -0.095MPa for 2h;
惰性气体保护下，往上述反应瓶中加入N-甲基吡咯烷酮，控温60℃，滴加异佛尔酮二异氰酸酯，1h左右滴完，加入二月桂酸二丁基锡，继续升温至80℃反应至-NCO值为8.7～8.9％；Under the protection of inert gas, N-methylpyrrolidone was added to the above reaction flask, the temperature was controlled at 60 °C, isophorone diisocyanate was added dropwise, after about 1 h, dibutyltin dilaurate was added, and the temperature was continued to rise to 80 °C to react to -NCO value is 8.7～8.9%;
惰性气体保护下，待上述反应物料降温至55℃，滴加飞扬骏研F420，1h内滴完，保温反应至-NCO值为4.7～4.9％，降温至40℃，加入三乙胺中和30min，再加入乙二胺、冰水高速分散30min，即得水性聚氨酯-聚脲分散体。Under the protection of inert gas, after the above reaction material is cooled to 55 ℃, Feiyang Junyan F420 is added dropwise, the dripping is completed within 1 hour, the reaction is kept warm until the -NCO value is 4.7-4.9%, the temperature is lowered to 40 ℃, and triethylamine is added for neutralization for 30 minutes. , and then add ethylenediamine and ice water to disperse at high speed for 30min to obtain water-based polyurethane-polyurea dispersion.
性能评价Performance evaluation
将实施例和对比例提供的分散体分别涂敷于马口铁，放置室温下干燥48h，再放置于60℃烘箱中干燥24h，得到的涂膜进行硬度(根据GB/T6739-2006测试)、耐冲击性能(根据GB/T 1732-93测试)、拉伸性能(断裂伸长率和拉伸强度，根据国家标准GB/T 1040.1-2006测试)、耐水性(根据GB/T 1733-93测试)，结果见表1。The dispersions provided in the examples and comparative examples were respectively coated on tinplate, dried at room temperature for 48h, and then placed in an oven at 60°C for 24h, and the obtained coating films were tested for hardness (tested according to GB/T6739-2006), impact resistance Properties (tested according to GB/T 1732-93), tensile properties (elongation at break and tensile strength, tested according to national standard GB/T 1040.1-2006), water resistance (tested according to GB/T 1733-93), The results are shown in Table 1.
表1性能表征测试Table 1 Performance Characterization Test
由上述测试结果可知，本发明提供的水性聚氨酯-聚脲分散体具有合适的粘度，制得的涂膜具有高的耐水性的同时，具有好的力学性能和抗冲击性能，可用于多种基材，如金属、非金属、高分子基材上。It can be seen from the above test results that the waterborne polyurethane-polyurea dispersion provided by the present invention has suitable viscosity, and the obtained coating film has high water resistance, good mechanical properties and impact resistance, and can be used for various bases. materials, such as metal, non-metal, and polymer substrates.
前述的实例仅是说明性的，用于解释本发明所述方法的一些特征。所附的权利要求旨在要求可以设想的尽可能广的范围，且本文所呈现的实施例仅是根据所有可能的实施例的组合的选择的实施方式的说明。因此，申请人的用意是所附的权利要求不被说明本发明的特征的示例的选择限制。在权利要求中所用的一些数值范围也包括了在其之内的子范围，这些范围中的变化也应在可能的情况下解释为被所附的权利要求覆盖。The foregoing examples are illustrative only and serve to explain some of the features of the methods described herein. The appended claims are intended to claim the broadest conceivable scope and the embodiments presented herein are merely illustrative of selected implementations according to a combination of all possible embodiments. Accordingly, it is the applicant's intention that the appended claims not be limited by the selection of examples that characterize the invention. Some numerical ranges used in the claims also include sub-ranges within them, and variations within these ranges should also be construed, where possible, to be covered by the appended claims.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4582873A (en) * | 1984-05-21 | 1986-04-15 | Ppg Industries, Inc. | Process for producing aqueous dispersions, internally silylated and dispersed polyurethane resins, and surfaces containing same |
| CN102585200A (en) * | 2005-04-06 | 2012-07-18 | 拜尔材料科学有限公司 | Polyuratethane foams made with alkoxylated vegetable oil hydroxylate |
| CN108250390A (en) * | 2016-12-29 | 2018-07-06 | 万华化学集团股份有限公司 | The aqueous dispersion of a kind of polyurethane or polyurethane-urea, preparation method and purposes |
| CN109467571A (en) * | 2018-09-29 | 2019-03-15 | 万华化学集团股份有限公司 | A kind of silicone-modified aspartate and its preparation method and application |
| CN110358065A (en) * | 2019-08-05 | 2019-10-22 | 美瑞新材料股份有限公司 | A kind of polysiloxanes -ester polyalcohol, preparation method and application |
| CN110951029A (en) * | 2019-11-27 | 2020-04-03 | 中国林业科学研究院林产化学工业研究所 | A kind of organosilicon modified vegetable oil-based polyol and its preparation method and application |
-
2021
- 2021-03-12 CN CN202110267891.7A patent/CN114716640A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4582873A (en) * | 1984-05-21 | 1986-04-15 | Ppg Industries, Inc. | Process for producing aqueous dispersions, internally silylated and dispersed polyurethane resins, and surfaces containing same |
| CN102585200A (en) * | 2005-04-06 | 2012-07-18 | 拜尔材料科学有限公司 | Polyuratethane foams made with alkoxylated vegetable oil hydroxylate |
| CN108250390A (en) * | 2016-12-29 | 2018-07-06 | 万华化学集团股份有限公司 | The aqueous dispersion of a kind of polyurethane or polyurethane-urea, preparation method and purposes |
| CN109467571A (en) * | 2018-09-29 | 2019-03-15 | 万华化学集团股份有限公司 | A kind of silicone-modified aspartate and its preparation method and application |
| CN110358065A (en) * | 2019-08-05 | 2019-10-22 | 美瑞新材料股份有限公司 | A kind of polysiloxanes -ester polyalcohol, preparation method and application |
| CN110951029A (en) * | 2019-11-27 | 2020-04-03 | 中国林业科学研究院林产化学工业研究所 | A kind of organosilicon modified vegetable oil-based polyol and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| 张彪等: "水性聚氨酯−聚脲的合成及其性能研究", 《中国涂料》, vol. 34, no. 5, pages 35 - 39 * |
| 马克义等: "氨基硅烷化环氧大豆油基水性聚氨酯的制备及性能表征", 《山东化工》, vol. 49, no. 13, pages 14 - 16 * |
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