CN108384022A - A kind of preparation improving uncured rubber asphalt high temperature resistance hyperbranched resin - Google Patents

The present invention relates to uncured rubber asphalt waterproof coating field, more specifically to a kind of preparation for the hyperbranched resin improving uncured rubber asphalt waterproof coating high temperature resistance.A kind of isocyanate terminated dissaving polymer has been synthesized first, then by the way that amino is introduced into the hyperbranched resin end with amino-modified silicone, to synthesize a kind of amine-terminated hyperbrancedization resin.The amine-terminated hyperbrancedization resin is applied into uncured rubber asphalt waterproof coating field, uncured rubber asphalt waterproof coating high temperature resistance can be improved well, synthesis technology is easy, easily industrializes, is a kind of uncured rubber asphalt waterproof coating modifying agent of function admirable.

一种提高非固化橡胶沥青耐高温性能超支化树脂的制备Preparation of a hyperbranched resin to improve the high temperature resistance of non-cured rubber asphalt

技术领域technical field

本发明涉及非固化橡胶沥青防水涂料技术领域，特别涉及一种用于提高非固化橡胶沥青防水涂料耐高温性能超支化树脂，还涉及其制备方法。The invention relates to the technical field of non-cured rubber asphalt waterproof coatings, in particular to a hyperbranched resin used to improve the high temperature resistance of non-cured rubber asphalt waterproof coatings, and to a preparation method thereof.

背景技术Background technique

非固化橡胶沥青防水涂料是一种高固含量的聚合物改性沥青防水涂料。具有长期不固化，自愈能力强，难以剥离，低温粘结性能好等特点。能解决因基层应力变化导致的防水层断裂等问题。同时可作为底层附着涂料与防水卷材配合使用构成复合防水层，此防水层可解决单独使用防水卷材所难以解决的串水问题。Non-curing rubber bitumen waterproof coating is a kind of high solid content polymer modified bitumen waterproof coating. It has the characteristics of long-term non-curing, strong self-healing ability, difficult to peel off, and good low-temperature bonding performance. It can solve the problems such as the breakage of the waterproof layer caused by the stress change of the base layer. At the same time, it can be used as the bottom attachment paint and waterproof membrane to form a composite waterproof layer. This waterproof layer can solve the problem of water stringing that is difficult to solve by using waterproof membrane alone.

传统的非固化橡胶沥青防水涂料的主要成分是由沥青、橡胶、软化剂、增粘剂、稳定剂、填料等制成。为了便于施工，传统的非固化橡胶沥青防水涂料一般会设计成高温下有较大的流淌性，这就容易导致产品耐热性差，高温易滑动、流淌等问题。The main components of traditional non-curing rubber asphalt waterproof coatings are made of asphalt, rubber, softeners, tackifiers, stabilizers, fillers, etc. In order to facilitate construction, traditional non-curing rubber asphalt waterproof coatings are generally designed to have greater fluidity at high temperatures, which can easily lead to problems such as poor heat resistance of the product, and easy sliding and flowing at high temperatures.

本发明专利旨在引入含有大量端氨基硅氧烷的超支化树脂，使得非固化橡胶沥青防水涂料与超支化树脂发生化学交联，提高其耐高温性能。The patent of the present invention aims to introduce a hyperbranched resin containing a large amount of amino-terminated siloxane, so that the non-curing rubber asphalt waterproof coating and the hyperbranched resin can be chemically cross-linked to improve its high temperature resistance.

超支化聚合物具有三维立体网状结构，活性位点多，粘度小，与基体融合性好，具有广阔的应用前景，目前在光电材料、涂料、粘合剂、纳米科技、药物运载等领域都表现出了巨大的应用价值。Hyperbranched polymers have a three-dimensional network structure, many active sites, low viscosity, good integration with the matrix, and broad application prospects. Currently, they are widely used in optoelectronic materials, coatings, adhesives, nanotechnology, and drug delivery It shows great application value.

发明内容Contents of the invention

为了解决非固化橡胶沥青防水涂料耐热性差，高温易滑动、流淌等问题，本发明提供了一种用于提高非固化橡胶沥青防水涂料耐热性能的端氨基超支化树脂。In order to solve the problems of poor heat resistance of non-cured rubber asphalt waterproof coating, easy sliding and flow at high temperature, etc., the invention provides an amino-terminated hyperbranched resin for improving the heat resistance of non-cured rubber asphalt waterproof coating.

本发明还提供了所述端氨基超支化树脂的制备方法。The invention also provides a preparation method of the amino-terminated hyperbranched resin.

本发明是通过以下措施实现的：The present invention is achieved through the following measures:

一种端氨基超支化树脂在提高非固化橡胶沥青防水涂料耐热性能中的应用，所述的端氨基超支化树脂是通过以下步骤得到的：Application of a kind of amino-terminated hyperbranched resin in improving the heat resistance of non-cured rubber asphalt waterproof coating, described amino-terminated hyperbranched resin is obtained by the following steps:

将多元醇和多元醇摩尔数3~4.5倍的2,2—二羟甲基丙酸混合均匀后在氮气保护下加热至140~170℃，常压反应1.5~2h；然后加入异氰酸酯和三乙醇胺在氮气保护下加热至60~70℃，反应4h；然后再加入端氨基硅油在室温下搅拌3h。Mix the polyol and 2,2-dimethylolpropionic acid with 3~4.5 times the molar number of polyol evenly, heat to 140~170℃ under the protection of nitrogen, and react at normal pressure for 1.5~2h; then add isocyanate and triethanolamine in the Heated to 60~70°C under nitrogen protection, reacted for 4h; then added amino-terminated silicone oil and stirred at room temperature for 3h.

所述的多元醇为三元醇或四元醇。The polyhydric alcohols are trihydric alcohols or tetrahydric alcohols.

所述的三元醇为三羟甲基丙烷、丙三醇、丁三醇、三乙醇胺中的一种或两种以上。The trihydric alcohol is one or more of trimethylolpropane, glycerol, butanetriol and triethanolamine.

所述的四元醇为季戊四醇。Described tetrahydric alcohol is pentaerythritol.

所述的异氰酸酯为2,4—二异氰酸甲苯酯、4,4—二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯中的一种或两种以上。The isocyanate is one or more of 2,4-toluene diisocyanate, 4,4-diphenylmethane diisocyanate and isophorone diisocyanate.

所述不同代数端异氰酸酯超支化树脂，其中第一代、第二代、第三代、第四代多元醇与异氰酸酯投料摩尔比为1:6~8、1:18~24、1:42~56、1:90~120。The different algebra terminal isocyanate hyperbranched resins, wherein the molar ratios of the first generation, second generation, third generation, and fourth generation polyols to isocyanates are 1:6~8, 1:18~24, 1:42~ 56. 1:90~120.

所述不同代数端异氰酸酯超支化树脂，其中第一代、第二代、第三代、第四代多元醇与三乙醇胺投料摩尔比为1:0、1:6~8、1:18~24、1:42~56。The different algebra terminal isocyanate hyperbranched resins, wherein the molar ratios of the first generation, second generation, third generation, and fourth generation polyols to triethanolamine are 1:0, 1:6~8, 1:18~24 , 1:42~56.

所述不同代数端异氰酸酯超支化树脂，其中第一代、第二代、第三代、第四代多元醇与端异氰酸酯摩尔比为1:6~8、1:12~16、1:24~32、1:48~64。The different algebra terminal isocyanate hyperbranched resins, wherein the first generation, second generation, third generation, and fourth generation polyols and terminal isocyanate molar ratios are 1:6~8, 1:12~16, 1:24~ 32. 1:48~64.

所述不同代数端异氰酸酯超支化树脂，以第二代为例，可能但不仅限于如下式所示：The different algebraic terminal isocyanate hyperbranched resins, taking the second generation as an example, may, but not limited to, be shown in the following formula:

所述的端氨基硅油的重均分子量为300~1000，且含有0.1~2w%的氨基。The weight-average molecular weight of the amino-terminated silicone oil is 300-1000, and contains 0.1-2w% amino groups.

所述的端氨基硅油与端异氰酸酯摩尔比为1:1。The molar ratio of amino-terminated silicone oil to isocyanate-terminated is 1:1.

所述的端氨基硅油为道康宁CM-226、道康宁OFX-8040A、道康宁OFX-8803中的一种或两种以上。The amino-terminated silicone oil is one or more of Dow Corning CM-226, Dow Corning OFX-8040A, and Dow Corning OFX-8803.

相对于现有技术，本发明所述的方法制备的用于提高非固化橡胶沥青耐高温性能端氨基超支化树脂，具有以下优点：Compared with the prior art, the amino-terminated hyperbranched resin prepared by the method for improving the high temperature resistance of non-cured rubber asphalt has the following advantages:

首先将多元醇与2,2—二羟甲基丙酸反应制备端羟基中心核，然后引入异氰酸酯与羟基反应，同时引入三乙醇胺增加支链，形成多异氰酸酯的超支化聚合物，为氨基硅油的接入提供了大量的活性基团。First, polyols are reacted with 2,2-dimethylolpropionic acid to prepare a hydroxyl-terminated central core, and then isocyanate is introduced to react with hydroxyl groups, and triethanolamine is introduced at the same time to increase the branched chain to form a hyperbranched polymer of polyisocyanate, which is the base of amino silicone oil. Access provides a large number of reactive groups.

同时硅氧烷的引入也有利于提高树脂的耐热性能和柔顺性；端氨基超支化树脂中大量的氨基可以与沥青中的酯基等基团交联，形成网状结构提高非固化橡胶沥青防水涂料的耐高温性能。At the same time, the introduction of siloxane is also conducive to improving the heat resistance and flexibility of the resin; a large number of amino groups in the amino-terminated hyperbranched resin can cross-link with groups such as ester groups in asphalt to form a network structure to improve the performance of non-cured rubber asphalt. High temperature resistance performance of waterproof coating.

本发明的有益效果：Beneficial effects of the present invention:

本发明所制备的树脂采用超支化结构，制备方法简单，原料易得，末端含有大量的活性官能团可减少投料量，降低成本；同时对非固化橡胶沥青防水涂料的耐高温性能有较大提高，与非固化橡胶沥青防水涂料共混搅拌均匀即可，不增加额外的工艺流程，有利于控制成本。The resin prepared by the present invention adopts a hyperbranched structure, the preparation method is simple, the raw materials are easy to obtain, and the terminal contains a large number of active functional groups, which can reduce the amount of feed and reduce the cost; at the same time, the high temperature resistance of the non-cured rubber asphalt waterproof coating is greatly improved. It can be blended and stirred evenly with the non-curing rubber asphalt waterproof coating, and no additional process is added, which is conducive to cost control.

具体实施方式Detailed ways

以下是对本发明具体实施方法更为详尽的陈述，目的在于阐述本发明的构思以及特点，并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。The following is a more detailed statement of the specific implementation methods of the present invention, the purpose of which is to illustrate the concept and characteristics of the present invention, and not to limit the protection scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention shall fall within the protection scope of the present invention.

实施方法一Implementation method one

（1）称取13.60g（0.1mol）季戊四醇、53.65g（0.4mol）2,2—二羟甲基丙酸，首先将季戊四醇和2,2—二羟甲基丙酸加入带有磁力搅拌器的四口烧瓶中，再加入适量N,N—二甲基甲酰胺使其溶解，再加入0.80g对甲基苯磺酸，升温至140℃，常压反应1.5h；降温至65℃，然后加入139.20g（0.8mol）2,4—二异氰酸甲苯酯，在二月桂酸二丁基锡催化和氮气保护下反应4h；将至室温，缓慢加入240.00g氨基硅油，反应3h既得端氨基超支化树脂。(1) Weigh 13.60g (0.1mol) of pentaerythritol and 53.65g (0.4mol) of 2,2-dimethylolpropionic acid, first add pentaerythritol and 2,2-dimethylolpropionic acid to a magnetic stirrer In a four-necked flask, add an appropriate amount of N,N-dimethylformamide to dissolve it, then add 0.80g of p-toluenesulfonic acid, heat up to 140°C, and react under normal pressure for 1.5h; cool down to 65°C, and then Add 139.20g (0.8mol) of toluene 2,4-diisocyanate, and react for 4 hours under the catalysis of dibutyltin dilaurate and nitrogen protection; when it reaches room temperature, slowly add 240.00g of amino silicone oil, and react for 3 hours to obtain the amino-terminated hyperbranched resin.

（2）取一定量的非固化橡胶沥青防水涂料加入坩埚中，加热熔融，再取质量分数占非固化橡胶沥青防水涂料5%的第一步得到的端氨基超支化树脂加入到坩埚中，然后在温度为150℃的条件下搅拌均匀，之后将其涂抹到长宽厚分别为100mm*50mm*2mm的铝板上，冷却24h，然后与水平面成45°角的烘箱中处理2h±15min，记录最先出现滑动、流淌、滴落的温度。(2) Take a certain amount of non-curing rubber asphalt waterproof coating and add it to the crucible, heat and melt it, and then take the amino-terminated hyperbranched resin obtained in the first step with a mass fraction of 5% of the non-curing rubber asphalt waterproof coating and add it to the crucible, and then Stir evenly at a temperature of 150°C, then spread it on an aluminum plate with a length, width, and thickness of 100mm*50mm*2mm, cool for 24 hours, and then treat it in an oven at an angle of 45° to the horizontal plane for 2 hours ± 15 minutes, and record first Slip, run, drip temperature.

实施方法二Implementation method two

（1）称取13.60g（0.1mol）季戊四醇、53.65g（0.4mol）2,2—二羟甲基丙酸，首先将季戊四醇和2,2—二羟甲基丙酸加入带有磁力搅拌器的四口烧瓶中，再加入适量N,N—二甲基甲酰胺使其溶解，再加入0.80g对甲基苯磺酸，升温至140℃，常压反应1.5h；降温至65℃，然后加入139.20g（0.8mol）2,4—二异氰酸甲苯酯，在二月桂酸二丁基锡催化和氮气保护下反应4h；再加入119.20g（0.8mol）的三乙醇胺，反应4h，再加入278.40g（1.6mol）2,4—二异氰酸甲苯酯，反应4h；将至室温，缓慢加入480.00g氨基硅油，反应3h既得端氨基超支化树脂。(1) Weigh 13.60g (0.1mol) of pentaerythritol and 53.65g (0.4mol) of 2,2-dimethylolpropionic acid, first add pentaerythritol and 2,2-dimethylolpropionic acid to a magnetic stirrer In a four-neck flask, add an appropriate amount of N,N-dimethylformamide to dissolve it, then add 0.80g of p-toluenesulfonic acid, heat up to 140°C, and react under normal pressure for 1.5h; cool down to 65°C, and then Add 139.20g (0.8mol) of toluene 2,4-diisocyanate, react for 4h under the catalysis of dibutyltin dilaurate and nitrogen protection; then add 119.20g (0.8mol) of triethanolamine, react for 4h, then add 278.40 g (1.6mol) 2,4-cresyl diisocyanate, react for 4 hours; when the room temperature is reached, slowly add 480.00g of amino silicone oil, and react for 3 hours to obtain an amino-terminated hyperbranched resin.

（2）取一定量的非固化橡胶沥青防水涂料加入坩埚中，加热熔融，再取质量分数占非固化橡胶沥青防水涂料5%的第一步得到的端氨基超支化树脂加入到坩埚中，然后在温度为150℃的条件下搅拌均匀，之后将其涂抹到长宽厚分别为100mm*50mm*2mm的铝板上，冷却24h，然后与水平面成45°角的烘箱中处理2h±15min，记录最先出现滑动、流淌、滴落的温度。(2) Take a certain amount of non-curing rubber asphalt waterproof coating and add it to the crucible, heat and melt it, and then take the amino-terminated hyperbranched resin obtained in the first step with a mass fraction of 5% of the non-curing rubber asphalt waterproof coating and add it to the crucible, and then Stir evenly at a temperature of 150°C, then spread it on an aluminum plate with a length, width, and thickness of 100mm*50mm*2mm, cool for 24 hours, and then treat it in an oven at an angle of 45° to the horizontal plane for 2 hours ± 15 minutes, and record first Slip, run, drip temperature.

实施方法三Implementation method three

（1）称取13.60g（0.1mol）季戊四醇、53.65g（0.4mol）2,2—二羟甲基丙酸，首先将季戊四醇和2,2—二羟甲基丙酸加入带有磁力搅拌器的四口烧瓶中，再加入适量N,N—二甲基甲酰胺使其溶解，再加入0.80g对甲基苯磺酸，升温至140℃，常压反应1.5h；降温至65℃，然后加入139.20g（0.8mol）2,4—二异氰酸甲苯酯，在二月桂酸二丁基锡催化和氮气保护下反应4h；再加入119.20g（0.8mol）的三乙醇胺，反应4h，再加入278.40g（1.6mol）2,4—二异氰酸甲苯酯，反应4h；将至室温，缓慢加入480.00g氨基硅油，反应3h既得端氨基超支化树脂。(1) Weigh 13.60g (0.1mol) of pentaerythritol and 53.65g (0.4mol) of 2,2-dimethylolpropionic acid, first add pentaerythritol and 2,2-dimethylolpropionic acid to a magnetic stirrer In a four-necked flask, add an appropriate amount of N,N-dimethylformamide to dissolve it, then add 0.80g of p-toluenesulfonic acid, heat up to 140°C, and react under normal pressure for 1.5h; cool down to 65°C, and then Add 139.20g (0.8mol) of toluene 2,4-diisocyanate, react for 4h under the catalysis of dibutyltin dilaurate and nitrogen protection; then add 119.20g (0.8mol) of triethanolamine, react for 4h, then add 278.40 g (1.6mol) 2,4-cresyl diisocyanate, react for 4 hours; when the room temperature is reached, slowly add 480.00g of amino silicone oil, and react for 3 hours to obtain an amino-terminated hyperbranched resin.

（2）取一定量的非固化橡胶沥青防水涂料加入坩埚中，加热熔融，再取质量分数占非固化橡胶沥青防水涂料10%的第一步得到的端氨基超支化树脂加入到坩埚中，然后在温度为150℃的条件下搅拌均匀，之后将其涂抹到长宽厚分别为100mm*50mm*2mm的铝板上，冷却24h，然后与水平面成45°角的烘箱中处理2h±15min，记录最先出现滑动、流淌、滴落的温度。(2) Take a certain amount of non-cured rubber asphalt waterproof coating and add it to the crucible, heat and melt it, then take the amino-terminated hyperbranched resin obtained in the first step with a mass fraction accounting for 10% of the non-cured rubber asphalt waterproof coating, and add it to the crucible, and then Stir evenly at a temperature of 150°C, then spread it on an aluminum plate with a length, width, and thickness of 100mm*50mm*2mm, cool for 24 hours, and then treat it in an oven at an angle of 45° to the horizontal plane for 2 hours ± 15 minutes, and record first Slip, run, drip temperature.

实施方法四Implementation method four

（1）称取13.60g（0.1mol）季戊四醇、53.65g（0.4mol）2,2—二羟甲基丙酸，首先将季戊四醇和2,2—二羟甲基丙酸加入带有磁力搅拌器的四口烧瓶中，再加入适量N,N—二甲基甲酰胺使其溶解，再加入0.80g对甲基苯磺酸，升温至140℃，常压反应1.5h；降温至65℃，然后加入139.20g（0.8mol）2,4—二异氰酸甲苯酯，在二月桂酸二丁基锡催化和氮气保护下反应4h；再加入119.20g（0.8mol）的三乙醇胺，反应4h，再加入278.40g（1.6mol）2,4—二异氰酸甲苯酯，反应4h；将至室温，缓慢加入480.00g氨基硅油，反应3h既得端氨基超支化树脂。(1) Weigh 13.60g (0.1mol) of pentaerythritol and 53.65g (0.4mol) of 2,2-dimethylolpropionic acid, first add pentaerythritol and 2,2-dimethylolpropionic acid to a magnetic stirrer In a four-neck flask, add an appropriate amount of N,N-dimethylformamide to dissolve it, then add 0.80g of p-toluenesulfonic acid, heat up to 140°C, and react under normal pressure for 1.5h; cool down to 65°C, and then Add 139.20g (0.8mol) of toluene 2,4-diisocyanate, react for 4h under the catalysis of dibutyltin dilaurate and nitrogen protection; then add 119.20g (0.8mol) of triethanolamine, react for 4h, then add 278.40 g (1.6mol) 2,4-cresyl diisocyanate, react for 4 hours; when the room temperature is reached, slowly add 480.00g of amino silicone oil, and react for 3 hours to obtain an amino-terminated hyperbranched resin.

（2）取一定量的非固化橡胶沥青防水涂料加入坩埚中，加热熔融，再取质量分数占非固化橡胶沥青防水涂料15%的第一步得到的端氨基超支化树脂加入到坩埚中，然后在温度为150℃的条件下搅拌均匀，之后将其涂抹到长宽厚分别为100mm*50mm*2mm的铝板上，冷却24h，然后与水平面成45°角的烘箱中处理2h±15min，记录最先出现滑动、流淌、滴落的温度。(2) Take a certain amount of non-cured rubber asphalt waterproof coating and add it to the crucible, heat and melt it, then take the amino-terminated hyperbranched resin obtained in the first step with a mass fraction of 15% of the non-cured rubber asphalt waterproof coating, and add it to the crucible, and then Stir evenly at a temperature of 150°C, then spread it on an aluminum plate with a length, width, and thickness of 100mm*50mm*2mm, cool for 24 hours, and then treat it in an oven at an angle of 45° to the horizontal plane for 2 hours ± 15 minutes, and record first Slip, run, drip temperature.

对比实施Compare implementation

取一定量的非固化橡胶沥青防水涂料加入坩埚中，加热熔融，之后将其涂抹到长宽厚分别为100mm*50mm*2mm的铝板上，冷却24h，然后与水平面成45°角的烘箱中处理2h±15min，记录最先出现滑动、流淌、滴落的温度。Take a certain amount of non-curing rubber asphalt waterproof paint and add it to the crucible, heat and melt it, and then apply it to an aluminum plate with a length, width and thickness of 100mm*50mm*2mm, cool for 24 hours, and then treat it in an oven at an angle of 45° to the horizontal plane for 2 hours ±15min, record the temperature at which sliding, flowing and dripping first appear.

性能测试Performance Testing

为了说明本发明的实际效果，下面就是将本发明实施方法中得到的超支化树脂加入到非固化橡胶沥青防水涂料中，进行耐高温性能检测。In order to illustrate the actual effect of the present invention, the hyperbranched resin obtained in the implementation method of the present invention is added into the non-cured rubber asphalt waterproof coating, and the high temperature resistance performance is detected.

测试性能如下表1。The test performance is shown in Table 1 below.

表1. 非固化橡胶沥青防水涂料流淌温度 超支化树脂 流淌温度/℃ 对比实施 71 实施方法一（5%） 83 实施方法二（5%） 85 实施方法三（10%） 100 实施方法四（15%） 117 Table 1. Flow temperature of non-curing rubber bitumen waterproof coating hyperbranched resin Flow temperature/℃ Compare implementation 71 Implementation method one (5%) 83 Implementation method two (5%) 85 Implementation method three (10%) 100 Implementation method four (15%) 117

由表1可知，在掺加本发明所制的端氨基超支化树脂后，制备出的非固化橡胶沥青防水涂料与未加入超支化树脂的相比耐高温性能有了明显的改善。其中在掺加量为5%时，第二代超支化树脂略好于第一代；随着第二代超支化树脂掺加量的增加，非固化橡胶沥青防水涂料耐高温性能有了较大提高。 It can be seen from Table 1 that after adding the amino-terminated hyperbranched resin prepared by the present invention, the prepared non-cured rubber asphalt waterproof coating has significantly improved high temperature resistance compared with that without adding hyperbranched resin. Among them, when the addition amount is 5%, the second-generation hyperbranched resin is slightly better than the first generation; with the increase of the second-generation hyperbranched resin addition amount, the high temperature resistance of non-curing rubber asphalt waterproof coating has a greater improve.

上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受实施例的限制，其它任何未背离本发明的精神实质与原理下所做的改变、修饰、组合、替代、简化均应为等效替换方式，都包含在本发明的保护范围之内。The above-mentioned embodiment is a preferred embodiment of the present invention, but the embodiment of the present invention is not limited by the embodiment, and any other changes, modifications, combinations, substitutions, and simplifications that do not deviate from the spirit and principles of the present invention All should be equivalent replacements, and all are included in the protection scope of the present invention.