CN117800860A - Aromatic secondary amine resin and preparation method thereof - Google Patents
Aromatic secondary amine resin and preparation method thereof Download PDFInfo
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- CN117800860A CN117800860A CN202311807238.0A CN202311807238A CN117800860A CN 117800860 A CN117800860 A CN 117800860A CN 202311807238 A CN202311807238 A CN 202311807238A CN 117800860 A CN117800860 A CN 117800860A
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
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- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
- C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
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- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
- C07C229/18—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to carbon atoms of six-membered aromatic rings
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Abstract
The application relates to the field of resin synthesis, and particularly discloses an aromatic secondary amine resin and a preparation method thereof. The aromatic secondary amine resin comprises the following preparation raw materials: aniline, polyfunctional acrylate, catalyst and polymerization inhibitor; wherein the molar ratio of aniline to the multifunctional acrylate calculated as c=c is 1 (0.9-1.0); the preparation method comprises the following steps: s1, uniformly mixing aniline and polyfunctional acrylate, adding a polymerization inhibitor and a catalyst, heating to 75-105 ℃, and reacting for 24-96 hours at a temperature maintaining condition to obtain a crude product; s2, decompressing the crude product to remove low-boiling-point substances to obtain the aromatic secondary amine resin. The polyurethane resin has good flexibility and strength, has proper gel time, can be directly mixed and sprayed with an isocyanate curing agent, does not need to be additionally added with flexible resin like 4,4' -di-sec-butylamino-diphenyl-Methane (MDBA), and greatly expands the application space of aromatic secondary amine resin.
Description
Technical Field
The application relates to the technical field of resin synthesis, in particular to an aromatic secondary amine resin with a flexible structure and a preparation method thereof.
Background
The polyurea elastomer is a compound generated by the reaction of isocyanate component and amine component, has good adhesive force, can be spray-molded on any substrate such as steel, wood, concrete and the like, and is a novel solvent-free and pollution-free green construction technology developed and developed for adapting to the environment protection requirement after low (pollution-free) coating technology such as high solid coating, water-based coating, radiation-cured coating, powder coating and the like in recent ten years abroad.
Aromatic secondary amines are a class of low reactivity secondary amines known at the present stage, which are substantially equivalent in nucleophilicity to secondary aspartyl amines. A representative secondary aromatic amine is 4,4' -di-sec-butylamino-diphenyl-Methane (MDBA) which has a reaction gel time of about 10-20min with typical HDI trimer curing agents, is substantially similar to the gel time of conventional polyaspartic acid ester resins, and can be used as an amine component of polyurea elastomers to reduce the curing rate of the polyurea elastomers, improve the workability of the polyurea elastomers and the overall properties of the coating, and extend the pot life.
However, since the MDBA has a high-rigidity structure, if the MDBA is directly mixed with an isocyanate curing agent to prepare a polyurea coating, the brittleness of the coating is high, the hardness is high, cracking, brittle failure and other conditions are easy to occur, and the mechanical properties are poor, so that the MDBA is usually used together with flexible resins such as polyetheramine or other auxiliary agents. In addition, in industry, MDBA is generally prepared by hydrogenation reduction of ketimine intermediate, and the process not only requires high-temperature and high-pressure process conditions (the temperature is about 200-400 ℃ and the pressure is 1-10MPa generally), but also has higher requirements on equipment and facilities and higher production cost, and meanwhile, the process operation also has great potential safety hazard, and belongs to dangerous chemical processes under national key supervision.
Disclosure of Invention
In order to solve the technical problems, the application provides an aromatic secondary amine resin with a flexible structure and a preparation method thereof, so as to achieve the effect of directly mixing the aromatic secondary amine resin with an isocyanate curing agent to prepare a polyurea coating.
In a first aspect, the present application provides an aromatic secondary amine resin, which adopts the following technical scheme:
an aromatic secondary amine resin, comprising the following preparation raw materials: aniline, polyfunctional acrylate, catalyst and polymerization inhibitor; wherein the molar ratio of the aniline to the polyfunctional acrylate as c=c is 1 (0.9-1.0).
Through adopting above-mentioned technical scheme, this application adopts aniline and polyfunctional acrylate as the reaction raw materials, reacts according to specific ratio to add a small amount of catalyst and polyfunctional acrylate's polymerization inhibitor, made the polyfunctional aromatic secondary amine resin product that has the soft chain segment, this polyfunctional aromatic secondary amine resin can be directly with the mixed spraying of isocyanate curing agent, need not to add the polyurea coating that flexible resin etc. is good and intensity is high again in addition like 4,4' -di-sec-butylamine diphenylmethane (MDBA), very big degree has widened aromatic secondary amine resin's application space.
Preferably, the polyfunctional acrylate has a functionality of 2 to 3.
By adopting the technical scheme, the functionality of the polyfunctional acrylic ester is further controlled to be 2-3, so that the functionality of the prepared polyfunctional aromatic secondary amine resin product is 2-3, the prepared polyfunctional aromatic secondary amine resin and isocyanate curing agent are ensured to have proper gel time after being mixed, the curing rate of the polyurea coating is moderate, and the sufficient operable time is provided. The functionality of the polyfunctional acrylate in this application is the number of carbon-carbon double bonds in the acrylate, and the functionality of the polyfunctional aromatic secondary amine resin product is the number of secondary amine groups in the aromatic secondary amine resin product.
The multifunctional acrylates of the present application include, but are not limited to, dipropylene glycol diacrylate (DPGDA), dipropylene glycol dimethacrylate (DPGDMA), tripropylene glycol diacrylate (TPGDA), tripropylene glycol dimethacrylate (TPGDMA), trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate (TMPTMA), ethoxylated trimethylolpropane triacrylate (TMP (EO) nTA), ethoxylated trimethylolpropane trimethacrylate (TMP (EO) nTMA), ethoxylated bisphenol A diacrylate (BPA (EO) nDA) and ethoxylated bisphenol A dimethacrylate (BPA (EO) nDMA).
In one embodiment of the present application, using tripropylene glycol diacrylate (TPGDA) having a functionality of 2 as a starting material, an aromatic secondary amine resin is produced which has a gel time of about 55 minutes after mixing with a calculated amount of HDI trimer curing agent HT-600. In one embodiment of the present application, using trimethylolpropane triacrylate (TMPTA) having a functionality of 3 as a starting material, the aromatic secondary amine resin was prepared to have a gel time of about 8 minutes after mixing with a calculated amount of HDI trimer curative HT-600. In another embodiment of the present application, a tetraethoxylated bisphenol A diacrylate (BPA (EO) having a functionality of 2 is used 4 DA) as a starting material, the resulting aromatic secondary amine resin was mixed with a calculated amount of HDI trimer curing agent HT-600 and the gel time was about 33 minutes.
Preferably, the multifunctional acrylate is an ethoxylated multifunctional acrylate.
Through adopting above-mentioned technical scheme, this application further selects the ethoxylation polyfunctional acrylate as the reaction raw materials and reacts with aniline, compares in dipropylene glycol diacrylate, dipropylene glycol dimethacrylate, tripropylene glycol diacrylate, tripropylene glycol dimethacrylate, trimethylol propane triacrylate, trimethylol propane trimethacrylate etc. non-ethoxylation polyfunctional acrylate reacts with aniline, can make the tensile strength of the polyurea coating who makes improve more than 10.4%, and tensile elongation improves more than 40.1%, has further improved the pliability and the intensity of polyurea coating.
Preferably, the multifunctional acrylate is an ethoxylated bisphenol a multifunctional acrylate.
By adopting the technical scheme, the application further selects the ethoxylated bisphenol A multifunctional acrylate as the reaction raw material to react with the aniline, and compared with the common type of ethoxylated multifunctional acrylate which is used as the reaction raw material to react with the aniline, the tensile strength and the tensile elongation of the prepared polyurea coating are respectively improved by 7.1-9.4% and 24.2-26.0%, and the flexibility and the strength of the polyurea coating are further improved.
Preferably, the multifunctional acrylate is an ethoxylated bisphenol a diacrylate or an ethoxylated bisphenol a dimethacrylate.
By adopting the technical scheme, the application further selects the ethoxylated bisphenol A polyfunctional acrylate with the functionality of 2 as the reaction raw material, so that the prepared aromatic secondary amine resin has more proper gel time on the basis of good flexibility and strength, and the curing rate of the prepared polyurea coating is moderate and has enough operable time.
Preferably, the catalyst is one or more of triethylamine, tripropylamine and N, N-diisopropylethylamine.
By adopting the technical scheme, the catalyst can correspondingly select one or more of triethylamine, tripropylamine and N, N-diisopropylethylamine according to actual production conditions. In one embodiment of the present application, the catalyst is triethylamine.
Preferably, the catalyst is used in an amount of 0.3 to 0.5wt% based on the total amount of aniline and polyfunctional acrylate.
Through adopting above-mentioned technical scheme, this application has optimized the quantity of catalyst, can make the quantity of catalyst can satisfy the demand of reaction, fully promotes the reaction and goes on, improves the product yield, can not increase manufacturing cost because of its quantity is too much again.
Preferably, the polymerization inhibitor is para-hydroxyanisole or hydroquinone.
By adopting the technical scheme, the polymerization inhibitor is one of common polymerization inhibitors for acrylic ester, and can be p-hydroxyanisole or hydroquinone. In one embodiment of the present application, the polymerization inhibitor is para-hydroxyanisole.
Preferably, the polymerization inhibitor is used in an amount of 0.2 to 0.3wt% based on the amount of the polyfunctional acrylate.
Through adopting above-mentioned technical scheme, the application has optimized the quantity of polymerization inhibitor for it both can prevent the emergence of polyfunctional acrylate self-polymerization phenomenon, thereby makes polyfunctional acrylate react with aniline as far as possible, improves the product yield, can not increase manufacturing cost because of its excessive quantity again.
In a second aspect, the preparation method of the aromatic secondary amine resin provided by the application adopts the following technical scheme:
a method for preparing aromatic secondary amine resin, comprising the following steps:
s1, uniformly mixing aniline and polyfunctional acrylate, adding a polymerization inhibitor and a catalyst, heating to 75-105 ℃, and reacting for 24-96 hours at a temperature maintaining condition to obtain a crude product;
s2, decompressing and removing low-boiling-point substances from the crude product for 0.5-1.0h under the condition that the vacuum degree is 0.094-0.1MPa, and obtaining the aromatic secondary amine resin.
By adopting the technical scheme, compared with the catalytic hydrogenation method for preparing MDBA, the preparation method has simpler steps, can obtain the aromatic secondary amine resin product with higher yield by only one-step reaction, has mild reaction conditions, can reduce the reaction temperature by more than 95 ℃ compared with the prior art, and has easily obtained raw materials and low cost. Meanwhile, the preparation method does not need catalytic hydrogenation, so that the requirements on process equipment are low, the risk of major production safety hazards caused by special equipment facilities and a catalytic hydrogenation operation process is reduced, meanwhile, high equipment investment and management cost are reduced, and the production cost is obviously reduced.
In summary, the present application has the following beneficial technical effects:
1. the aromatic secondary amine resin has good flexibility and strength, has proper gel time, can be directly mixed and sprayed with an isocyanate curing agent, does not need to be additionally added with flexible resin like 4,4' -di-sec-butylamino-diphenyl-Methane (MDBA), and greatly expands the application space of the aromatic secondary amine resin;
2. as the basic component of the polyurea coating, the aromatic secondary amine resin can prepare a polyurea coating with excellent flexibility, strength and mechanical property;
3. compared with the catalytic hydrogenation method for preparing MDBA, the preparation method has the advantages that the steps are simpler, the aromatic secondary amine product with higher yield can be obtained through single-step reaction, the reaction condition is mild, the raw materials are easy to obtain, and the cost is low;
4. the preparation method has lower requirements on process equipment, reduces the risk of major production safety hazards caused by special equipment facilities and a catalytic hydrogenation operation process, reduces high equipment investment and management cost, and obviously reduces the production cost.
Detailed Description
The present application is described in further detail below with reference to examples.
Since there is no significant difference in the effects of p-hydroxyanisole and hydroquinone as polymerization inhibitors, the examples of the present application will be described by taking p-hydroxyanisole as an example; since there is no significant difference in the effect of triethylamine, tripropylamine and N, N-diisopropylethylamine as catalysts, triethylamine is exemplified in the examples of the present application.
Since dipropylene glycol diacrylate, dipropylene glycol dimethacrylate, and tripropylene glycol dimethacrylate achieve similar effects to tripropylene glycol diacrylate, trimethylolpropane trimethacrylate and trimethylolpropane triacrylate achieve similar effects, and ethoxylated trimethylolpropane trimethacrylate and ethoxylated trimethylolpropane triacrylate, the examples of the present application are described with tripropylene glycol diacrylate, trimethylolpropane triacrylate, and ethoxylated trimethylolpropane triacrylate as representative of various types of multifunctional acrylates.
The raw materials used in the application are all commercial products, and specifically are: 4,4' -bis-sec-butylaminodiphenyl Methane (MDBA), available from North Chengfeng chemical Co., ltd;
para-hydroxyanisole, available from atanan de joe chemical technology limited;
triethylamine, purchased from shandongde norhong chemical industry limited;
HDI trimer curative HT-600, produced from vancomic chemistry;
aniline, available from beijing enoki technologies limited, cat# GC88988;
tripropylene glycol diacrylate (TPGDA), available from changxing specialty materials (zhuhai) limited, trade mark: eteremer 233;
trimethylolpropane triacrylate (TMPTA), available from Changxing specialty materials (Zhuhai Co., ltd., brand name): eteremer 231;
ethoxylated trimethylolpropane triacrylate (TMP (EO) 3 TA), available from changxing specialty materials (pearl sea) limited, brand: eteremer 2380;
tetraethoxylated bisphenol A diacrylate (BPA (EO) 4 DA), changxing special materials (pearl sea) limited, brand: eteremer 2261;
tetraethoxylated bisphenol A dimethacrylate (BPA (EO) 4 DMA), changxing special materials (pearl sea) limited, brand: eteremer 3261.
Example 1
A method for preparing aromatic secondary amine resin, comprising the following steps:
s1, uniformly mixing aniline and tripropylene glycol diacrylate (calculated by C=C) according to a molar ratio of 1:0.9, adding para-hydroxyanisole and triethylamine, heating to 75 ℃, and carrying out heat preservation reaction for 96 hours to obtain a crude product; wherein the addition amount of the para-hydroxyanisole is 0.2 percent of the total weight of the tripropylene glycol diacrylate and the addition amount of the triethylamine is 0.3 percent of the total weight of the tripropylene glycol diacrylate and the aniline;
s2, decompressing and removing low-boiling-point substances from the crude product for 1.0h under the condition of the vacuum degree of 0.094MPa to obtain brown yellow transparent liquid with the functionality of 2, the viscosity of 1280cps and the yield of 93.3%.
Example 2
A method for preparing aromatic secondary amine resin, comprising the following steps:
s1, uniformly mixing aniline and trimethylolpropane triacrylate (calculated by C=C) according to a molar ratio of 1:1, adding para-hydroxyanisole and triethylamine, heating to 105 ℃, and carrying out heat preservation reaction for 24 hours to obtain a crude product; wherein the addition amount of the para-hydroxyanisole is 0.3 percent of the total weight of the trimethylolpropane triacrylate, and the addition amount of the triethylamine is 0.5 percent of the total weight of the trimethylolpropane triacrylate and the aniline;
s2, decompressing and removing low-boiling-point substances from the crude product for 0.5h under the condition of 0.1MPa of vacuum degree to obtain brown yellow transparent liquid with the functionality of 3, the viscosity of 66000cps and the yield of 97.6%.
Example 3
A method for preparing aromatic secondary amine resin, comprising the following steps:
s1, uniformly mixing aniline and ethoxylated trimethylolpropane triacrylate (calculated by C=C) according to a molar ratio of 1:1, adding para-hydroxyanisole and triethylamine, heating to 105 ℃, and carrying out heat preservation reaction for 24 hours to obtain a crude product; wherein the addition amount of the para-hydroxyanisole is 0.3 percent of the total weight of the ethoxylated trimethylolpropane triacrylate, and the addition amount of the triethylamine is 0.5 percent of the total weight of the ethoxylated trimethylolpropane triacrylate and the aniline;
s2, decompressing and removing low-boiling-point substances from the crude product for 0.5h under the condition of 0.1MPa of vacuum degree to obtain brown yellow transparent liquid with the functionality of 3, the viscosity of 73000cps and the yield of 97.5%.
Example 4
A method for preparing aromatic secondary amine resin, comprising the following steps:
s1, uniformly mixing aniline and tetraethoxybisphenol A diacrylate (calculated by C=C) according to a molar ratio of 1:1, adding para-hydroxyanisole and triethylamine, heating to 105 ℃, and carrying out heat preservation reaction for 24 hours to obtain a crude product; wherein the addition amount of the para-hydroxyanisole is 0.3 percent of the total weight of the tetraethoxybisphenol A diacrylate and the addition amount of the triethylamine is 0.5 percent of the total weight of the tetraethoxybisphenol A diacrylate and the aniline;
s2, decompressing and removing low-boiling-point substances from the crude product for 0.5h under the condition of 0.1MPa of vacuum degree to obtain brown yellow transparent liquid with the functionality of 2, the viscosity of 27000cps and the yield of 97.3%.
Example 5
A method for preparing aromatic secondary amine resin, comprising the following steps:
s1, uniformly mixing aniline and tetraethoxybisphenol A dimethacrylate (calculated by C=C) according to a molar ratio of 1:1, adding para-hydroxyanisole and triethylamine, heating to 105 ℃, and carrying out heat preservation reaction for 24 hours to obtain a crude product; wherein the addition amount of the para-hydroxyanisole is 0.3 percent of the total weight of the tetraethoxybisphenol A dimethacrylate, and the addition amount of the triethylamine is 0.5 percent of the total weight of the tetraethoxybisphenol A dimethacrylate and the aniline;
s2, decompressing and removing low-boiling-point substances from the crude product for 0.5h under the condition of 0.1MPa of vacuum degree to obtain brown yellow transparent liquid with the functionality of 2, the viscosity of 28000cps and the yield of 97.6%.
Example 6
A method for preparing aromatic secondary amine resin, comprising the following steps:
s1, uniformly mixing aniline and tripropylene glycol diacrylate (calculated by C=C) according to a molar ratio of 1:0.95, adding para-hydroxyanisole and triethylamine, heating to 75 ℃, and reacting for 96 hours under heat preservation to obtain a crude product; wherein the addition amount of the para-hydroxyanisole is 0.2 percent of the total weight of the tripropylene glycol diacrylate and the addition amount of the triethylamine is 0.3 percent of the total weight of the tripropylene glycol diacrylate and the aniline;
s2, decompressing and removing low-boiling-point substances from the crude product for 1.0h under the condition of the vacuum degree of 0.094MPa to obtain brown yellow transparent liquid with the functionality of 2, the viscosity of 1310cps and the yield of 93.9%.
Example 7
A method for preparing aromatic secondary amine resin, comprising the following steps:
s1, uniformly mixing aniline and tripropylene glycol diacrylate (calculated by C=C) according to a molar ratio of 1:0.9, adding para-hydroxyanisole and triethylamine, heating to 75 ℃, and carrying out heat preservation reaction for 96 hours to obtain a crude product; wherein the addition amount of the para-hydroxyanisole is 0.2 percent of the total weight of the tripropylene glycol diacrylate and the addition amount of the triethylamine is 0.5 percent of the total weight of the tripropylene glycol diacrylate and the aniline;
s2, decompressing and removing low-boiling-point substances from the crude product for 1.0h under the condition of the vacuum degree of 0.094MPa to obtain brown yellow transparent liquid with the functionality of 2, the viscosity of 1280cps and the yield of 94.5%.
Comparative example 1
The difference from example 1 is that an aromatic secondary amine resin having a conversion of 91.5% was produced by the following steps; the method comprises the following steps:
s1, uniformly mixing aniline and tripropylene glycol diacrylate (calculated by C=C) according to a molar ratio of 1:0.6, adding para-hydroxyanisole and triethylamine, heating to 75 ℃, and carrying out heat preservation reaction for 96 hours to obtain a crude product; wherein the addition amount of the para-hydroxyanisole is 0.2 percent of the total weight of the tripropylene glycol diacrylate and the addition amount of the triethylamine is 0.3 percent of the total weight of the tripropylene glycol diacrylate and the aniline;
s2, decompressing and removing low-boiling-point substances from the crude product for 1.0h under the condition that the vacuum degree is 0.094MPa, and obtaining brown yellow transparent liquid.
Comparative example 2
The difference from example 1 is that an aromatic secondary amine resin having a conversion of 93.3% was produced by the following steps; the method comprises the following steps:
s1, uniformly mixing aniline and tripropylene glycol diacrylate (calculated by C=C) according to a molar ratio of 1:1.5, adding para-hydroxyanisole and triethylamine, heating to 75 ℃, and carrying out heat preservation reaction for 96 hours to obtain a crude product; wherein the addition amount of the para-hydroxyanisole is 0.2 percent of the total weight of the tripropylene glycol diacrylate and the addition amount of the triethylamine is 0.3 percent of the total weight of the tripropylene glycol diacrylate and the aniline;
s2, decompressing and removing low-boiling-point substances from the crude product for 1.0h under the condition that the vacuum degree is 0.094MPa, and obtaining brown yellow transparent liquid.
Comparative example 3
The difference from example 1 was that an aromatic secondary amine resin was produced with a conversion of 88.7% in the following steps; the method comprises the following steps:
s1, uniformly mixing aniline and tripropylene glycol diacrylate (calculated by C=C) according to a molar ratio of 1:0.9, adding para-hydroxyanisole and triethylamine, heating to 75 ℃, and carrying out heat preservation reaction for 96 hours to obtain a crude product; wherein the addition amount of the para-hydroxyanisole is 0.2 percent of the total weight of the tripropylene glycol diacrylate and the addition amount of the triethylamine is 0.1 percent of the total weight of the tripropylene glycol diacrylate and the aniline;
s2, decompressing and removing low-boiling-point substances from the crude product for 1.0h under the condition that the vacuum degree is 0.094MPa, and obtaining brown yellow transparent liquid.
Comparative example 4
The difference from example 1 is that an aromatic secondary amine resin having a conversion of 93.1% was produced by the following steps; the method comprises the following steps:
s1, uniformly mixing aniline and tripropylene glycol diacrylate (calculated by C=C) according to a molar ratio of 1:0.9, adding para-hydroxyanisole and triethylamine, heating to 75 ℃, and carrying out heat preservation reaction for 96 hours to obtain a crude product; wherein the addition amount of the para-hydroxyanisole is 0.2 percent of the total weight of the tripropylene glycol diacrylate and the addition amount of the triethylamine is 0.8 percent of the total weight of the tripropylene glycol diacrylate and the aniline;
s2, decompressing and removing low-boiling-point substances from the crude product for 1.0h under the condition that the vacuum degree is 0.094MPa, and obtaining brown yellow transparent liquid.
Performance detection
1. Referring to the method of 7.6 in GB/T23446-2009 "spray polyurea waterproof paint", 4' -di-sec-butylamino-diphenyl-methane, examples 1-7 and comparative examples 1-4 were respectively weighed with about 6g of a sample of HDI trimer curing agent HT-600 according to the ratio of NCO: NH (OH) =1.05:1, and were rapidly and uniformly mixed, and the time from mixing to test non-flowing was recorded, namely the gel time, and the results are shown in Table 1.
2. The 4,4' -bis-sec-butylaminodiphenyl methane, the aromatic secondary amine resins prepared in examples 1 to 7 and comparative examples 1 to 4 were mixed with the HDI trimer curing agent HT-600 in the ratio of NCO: NH (OH) =1.05:1, and then a coating film having a thickness of 20 to 30 μm was formed by spraying using a spraying polyurea dedicated spraying apparatus according to the requirements of GB/T23446-2009 "spray polyurea waterproof coating", the sample substrate was subjected to a flexibility test, a cross-hatch test and an impact resistance test after curing for 7d, wherein the flexibility test was represented by bending test pieces on shaft rods having different diameters in a shaft rod diameter that does not cause the coating to be broken after bending, and the smaller the shaft rod diameter, the better the flexibility of the coating layer was under the condition that the coating layer was not broken; the standard cross-hatch method is adopted in the cross-hatch test, and the higher the grade is, the worse the coating adhesive force is; the impact resistance test is carried out by adopting an impact instrument, and under the condition that the diameter of an impact head and the mass of a drop hammer are the same, the larger the maximum impact height which can be born, the better the impact resistance of the coating is, and the specific results are shown in table 1.
3. The aromatic secondary amine resins prepared in examples 1 to 7 and comparative examples 1 to 4 were mixed with HDI trimer curing agent HT-600 in the ratio of NCO: NH (OH) =1.05:1, respectively, and then sprayed to form a coating film having a thickness of 1 to 2mm using a spray polyurea dedicated spraying apparatus according to the requirements of GB/T23446-2009 "spray polyurea waterproof coating", the base material of the template was a HDPE plate, and after curing for 7d, the tensile strength and tensile elongation of the coating film were measured, and the results are shown in table 1.
Table 1 table of performance test results
As can be seen from Table 1, the coating prepared from the aromatic secondary amine resin prepared in examples 1-7 of the present application as a base material has a minimum bent mandrel diameter of 1mm, an adhesion of 0 grade, a maximum impact height of 50cm, a tensile strength of 4.8-9.3MPa, and a tensile elongation of 155-286% after a flexibility test; the coating prepared by taking MDBA as a basic raw material has the minimum bending shaft rod diameter of only 5mm, the adhesive force of only 4 levels, the maximum impact height capable of bearing of only 10cm, the tensile strength of 5.6MPa and the tensile elongation of 0 after a flexibility test. Test data show that the coating prepared by directly mixing MDBA as a basic raw material with isocyanate component is hard and brittle, is easy to brittle fracture during stretching, has poor flexibility and strength, and needs to be mixed with other flexible resins to be used as the basic raw material of polyurea coating together during use; the coating prepared from the aromatic secondary amine resin prepared by the application as a basic raw material has excellent flexibility and strength, can be directly mixed and sprayed with an isocyanate curing agent, and greatly widens the application space of the aromatic secondary amine resin.
The data of examples 1-2 show that the application of the polyfunctional acrylic resin with the functionality of 2-3 can ensure that the prepared aromatic resin has proper gel time under the condition of good flexibility, and the curing rate of the polyurea coating is moderate and has enough operable time. If acrylic resin with high functionality is further selected, the gel time is too fast and the operation time is short.
The tensile strength and the tensile elongation of the coating of the embodiment 3-5 are both greater than those of the embodiment 1-2, which means that the further use of the ethoxylated polyfunctional acrylate as the reaction raw material in the embodiment 3-5 can improve the tensile strength of the prepared polyurea coating by more than 10.4% and the tensile elongation by more than 40.1% compared with the use of the non-ethoxylated polyfunctional acrylate as the reaction raw material in the embodiment 1-2, and the flexibility and the strength of the coating are remarkably improved. Wherein, the tensile strength and tensile elongation of the coatings of examples 4-5 are respectively improved by 7.1-9.4% and 24.2-26.0% compared with example 3, which shows that the flexibility and strength of the polyurea coating are further improved by further adopting the ethoxylated bisphenol A polyfunctional acrylate as a reaction raw material in examples 4-5. And further, the ethoxylated bisphenol A polyfunctional acrylate with the functionality of 2 is selected as a reaction raw material, so that the prepared aromatic secondary amine resin has better flexibility and strength and more proper gel time, and the curing rate of the prepared polyurea coating is moderate and the enough operable time is provided.
Example 6 differs from example 1 only in the molar ratio of aniline and tripropylene glycol diacrylate (c=c), the product yield of example 6 is 93.9%, the product yield of example 1 is 93.3%, and example 6 is 0.64% higher than example 1, which means that further optimization of the ratio of the two raw materials allows more complete reaction and further improves the product yield.
Example 7 differs from example 1 only in the amount of catalyst used, the product yield of example 6 was 94.5%, the product yield of example 1 was 93.3%, and example 7 was 1.29% higher than example 1, which means that further optimization of the amount of catalyst used allows more complete reaction and further increases the product yield.
Comparative examples 1-2 differ from example 1 only in the molar ratio of aniline to tripropylene glycol diacrylate (c=c), the product yield of comparative examples 1-2 is 91.5-93.3% and the product yield of example 1 is 93.3%, which means that the reaction can be made more complete by optimizing the ratio of the two starting materials, and the product yield can be further improved without additional cost.
The comparative examples 3 to 4 differ from example 1 only in the amount of catalyst used, the product yield of comparative examples 3 to 4 was 88.7 to 93.1% and the product yield of example 1 was 93.3%, which shows that the reaction can be made more complete by optimizing the amount of catalyst used in the present application, and when the amount of catalyst used reaches a certain level, the increase in the amount of catalyst is continued, so that the yield is not further improved, and even the decrease trend occurs.
The embodiments of the present invention are all preferred embodiments of the present application, and are not intended to limit the scope of the present application in this way, therefore: all equivalent changes in structure, shape and principle of this application should be covered in the protection scope of this application.
Claims (10)
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| JPH07278398A (en) * | 1994-04-05 | 1995-10-24 | Sekisui Chem Co Ltd | Conductive resin composition |
| CN102834372A (en) * | 2010-03-25 | 2012-12-19 | 太阳化学有限公司 | Amine Synergist and Its Application in Radiation Curing |
| CN109053999A (en) * | 2018-05-31 | 2018-12-21 | 广东省建筑材料研究院 | A kind of aromatic amine curing agent and preparation method thereof |
| CN116023286A (en) * | 2022-12-26 | 2023-04-28 | 山东科技大学 | A kind of tertiary amino reactive diluent and its preparation method and application |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07278398A (en) * | 1994-04-05 | 1995-10-24 | Sekisui Chem Co Ltd | Conductive resin composition |
| CN102834372A (en) * | 2010-03-25 | 2012-12-19 | 太阳化学有限公司 | Amine Synergist and Its Application in Radiation Curing |
| CN109053999A (en) * | 2018-05-31 | 2018-12-21 | 广东省建筑材料研究院 | A kind of aromatic amine curing agent and preparation method thereof |
| CN116023286A (en) * | 2022-12-26 | 2023-04-28 | 山东科技大学 | A kind of tertiary amino reactive diluent and its preparation method and application |
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