Acrylic acid modified polyurethane epoxy flexibilizer and production process thereof

Abstract

The invention relates to the technical field of chemical engineering, and particularly discloses an acrylic acid modified polyurethane epoxy flexibilizer and a production process thereof, and the acrylic acid modified polyurethane epoxy flexibilizer comprises macromolecular diol, hyperbranched polyol, polycarbonate diol, an end-capping reagent, a nano material and a fiber composite material. According to the invention, the hyperbranched polyol is arranged, so that the acrylic acid modified polyurethane epoxy flexibilizer can be obviously influenced under the condition of a relatively low addition amount, gaps exist in hyperbranched polyol molecules, and the gaps provide storage spaces for some small molecular substances, so that energy can be absorbed when the hyperbranched polyol is impacted; according to the invention, the hyperbranched polyol is added to improve the intermolecular interaction and steric hindrance effect, the toughness and impact resistance of the material are improved, and the hyperbranched polyol has good fluidity, dissolvability and low viscosity, so that the mobility of internal molecules can be improved, and the tolerance of a product can be improved. Materials with different hardness and flexibility can be obtained by adjusting the proportion by matching polycarbonate diol with other polyols.

Description

Technical Field

[0001] The present invention relates to the technical field of chemical engineering, and particularly to an acrylic modified polyurethane epoxy toughening agent and its production process. Background Art

[0002] Chemical engineering is an abbreviation of "chemical technology", "chemical industry", "chemical engineering", etc. All technologies that use chemical methods to change the composition, structure of substances or synthesize new substances belong to chemical production technologies, that is, chemical processes, and the obtained products are called chemical products or chemical industrial products. The relationship between humans and chemical engineering is very close. Some chemical industrial products play an epoch-making important role in the history of human development. Their production and application even represent a certain historical stage of human civilization.

[0003] Polyurethane, whose full name is polycarbamate, the existing polyurethane is a polymer material formed by the polycondensation reaction of polyols and polyisocyanates and has excellent mechanical properties. However, polyisocyanates are irritating and corrosive to the skin and eyes. Secondly, in the use and processing of polyisocyanates, if there are no sufficient protective measures, there will be risks of explosion and fire. We have proposed an acrylic modified polyurethane epoxy toughening agent and its production process. Summary of the Invention

[0004] The purpose of the present invention is to solve the deficiencies existing in the prior art, and to propose an acrylic modified polyurethane epoxy toughening agent and its production process.

[0005] In order to achieve the above purpose, the present invention adopts the following technical solutions:

[0006] An acrylic modified polyurethane epoxy toughening agent, comprising macromolecular diol, hyperbranched polyol, polycarbonate diol, capping agent, nano material and fiber composite material.

[0007] Preferably, the macromolecular diol is at least one of polypropylene glycol, polytetrahydrofuran diol, polyester diol, polycaprolactone diol and polycarbonate diol, the molecular weight of the macromolecular diol is 500 - 3000, and the capping agent is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, caprolactone acrylate, pentaerythritol triacrylate and dipentaerythritol pentaacrylate.

[0008] Preferably, the nano material is at least one of nano silicon dioxide and carbon nanotubes, and the fiber composite material is at least one of glass fiber and carbon fiber.

[0009] A production process of an acrylic modified polyurethane epoxy toughening agent, the production process includes the above-mentioned acrylic modified polyurethane epoxy toughening agent and the production process further includes the following steps:

[0010] Step 1: Take 30 - 70 parts of macromolecular diol, 10 - 40 parts of hyperbranched polyol, and 10 - 40 parts of polycarbonate diol. Add the above macromolecular diol, hyperbranched polyol, and polycarbonate diol into a reaction vessel.

[0011] Step 2: Turn on the heating device and slowly raise the temperature of the reaction system to a predetermined reaction temperature, generally 80 - 150 °C. After the temperature reaches the set value, add an appropriate amount of catalyst.

[0012] Step 3: During the reaction, the hydroxyl groups in the reaction system will undergo polycondensation reaction, and the reaction time is 2 - 10 hours to form a prepolymer.

[0013] Step 4: When the temperature of the prepolymer cools to 65 - 75 °C, add 4 - 8 parts of a capping agent, and keep stirring during the addition process. After adding the capping agent, add 2 - 4 parts of nanomaterials and 2 - 4 parts of fiber composite materials.

[0014] Preferably, in Step 1: During the addition of macromolecular diol, hyperbranched polyol, and polycarbonate diol, stir to make them preliminarily mixed evenly, and control the stirring speed at 10 - 15 r / min.

[0015] Preferably, in Step 2: The catalyst is dibutyltin dilaurate, and its addition amount is usually 0.1% - 1% of the total mass of the reactants.

[0016] Preferably, in Step 3: As the reaction progresses, the viscosity of the reaction system will gradually increase. The progress of the reaction can be monitored by observing the change in viscosity of the reaction system and sampling analysis. When the reaction reaches the expected degree, stop heating and end the reaction.

[0017] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0018] By setting hyperbranched polyol in the present invention, it can have a significant impact on the acrylic - modified polyurethane epoxy toughening agent at a relatively low addition amount. There are voids inside the hyperbranched polyol molecules, which provide storage space for some small - molecule substances. When subjected to impact, it can absorb energy, increase the intermolecular interaction and steric hindrance effect, improve the toughness and impact resistance of the material. At the same time, hyperbranched polyol has good fluidity, solubility and low viscosity, which can increase the mobility of internal molecules and improve the tolerance of the product. In the synthesis of polyurethane elastomers with higher requirements for hydrolysis resistance and flexibility of materials, by using polycarbonate diol in combination with other polyols, different hardness and flexibility materials can be obtained by adjusting the ratio, and products with excellent performance can be obtained to meet diverse application requirements. Detailed implementation mode

[0019] Next, in combination with the embodiments of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments.

[0020] Please refer to an acrylic-modified polyurethane epoxy toughening agent, which includes macromolecular diol, hyperbranched polyol, polycarbonate diol, capping agent, nanomaterial, and fiber composite material.

[0021] As a technical optimization scheme of the present invention, the macromolecular diol is at least one of polypropylene glycol, polytetrahydrofuran diol, polyester diol, polycaprolactone diol, and polycarbonate diol. The molecular weight of the macromolecular diol is 500 - 3000, and the capping agent is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, caprolactone acrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate.

[0022] As a technical optimization scheme of the present invention, the nanomaterial is at least one of nano-silica and carbon nanotubes, and the fiber composite material is at least one of glass fiber and carbon fiber.

[0023] A production process of an acrylic-modified polyurethane epoxy toughening agent, which includes the above-mentioned acrylic-modified polyurethane epoxy toughening agent and also includes the following steps:

[0024] Step 1: Take 30 - 70 parts of macromolecular diol, 10 - 40 parts of hyperbranched polyol, and 10 - 40 parts of polycarbonate diol. Add the above macromolecular diol, hyperbranched polyol, and polycarbonate diol into a reaction vessel.

[0025] Step 2: Turn on the heating device and slowly raise the temperature of the reaction system to a predetermined reaction temperature, generally 80 - 150 °C. When the temperature reaches the set value, add an appropriate amount of catalyst.

[0026] Step 3: During the reaction, the hydroxyl groups in the reaction system will undergo a polycondensation reaction, and the reaction time is 2 - 10 hours to form a prepolymer.

[0027] Step 4: When the temperature of the prepolymer cools to 65 - 75 °C, add 4 - 8 parts of the capping agent thereto, and keep stirring during the addition process. After adding the capping agent, add 2 - 4 parts of the nanomaterial and 2 - 4 parts of the fiber composite material thereto.

[0028] As a technical optimization scheme of the present invention, in Step 1: During the addition of macromolecular diol, hyperbranched polyol, and polycarbonate diol, stir them to make them preliminarily mixed evenly, and control the stirring speed at 10 - 15 r / min; avoid overly intense stirring from generating a large amount of foam, and also avoid overly slow stirring from resulting in uneven mixing.

[0029] As a technical optimization solution of the present invention, in step two: the catalyst is dibutyltin dilaurate, and its addition amount is usually 0.1%-1% of the total mass of the reactants. The addition of the catalyst can promote the polycondensation reaction between hydroxyl groups.

[0030] As a technical optimization solution of the present invention, in step three: as the reaction proceeds, the viscosity of the reaction system will gradually increase. The progress of the reaction can be monitored by observing the viscosity change of the reaction system and the method of sampling and analysis. For example, samples are taken every once in a while (such as 30 minutes), and the molecular weight and its distribution of the product are analyzed by gel permeation chromatography (GPC), or the change of the hydroxyl peak is detected by infrared spectroscopy (IR) to judge the reaction degree. When the reaction reaches the expected degree, for example, when the molecular weight of the product reaches a predetermined value or the hydroxyl conversion rate reaches a certain proportion, stop heating and end the reaction.

[0031] Example one:

[0032] An acrylic-modified polyurethane epoxy toughening agent, comprising macroglycol, hyperbranched polyol, polycarbonate diol, capping agent, nanomaterial and fiber composite material.

[0033] As a technical optimization solution of the present invention, the macroglycol is at least one of polypropylene glycol, polytetrahydrofuran diol, polyester diol, polycaprolactone diol and polycarbonate diol, the molecular weight of the macroglycol is 500, and the capping agent is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, caprolactone acrylate, pentaerythritol triacrylate and dipentaerythritol pentaacrylate.

[0034] As a technical optimization solution of the present invention, the nanomaterial is at least one of nano-silica and carbon nanotubes, and the fiber composite material is at least one of glass fiber and carbon fiber.

[0035] A production process of an acrylic-modified polyurethane epoxy toughening agent, the production process includes the above-mentioned acrylic-modified polyurethane epoxy toughening agent and the production process further includes the following steps:

[0036] Step 1: Take 30 parts of macromolecular diol, 10 parts of hyperbranched polyol, and 10 parts of polycarbonate diol. Add the above macromolecular diol, hyperbranched polyol, and polycarbonate diol into a reaction vessel; by adding the hyperbranched polyol, with its unique and highly branched three-dimensional spherical molecular structure, a large number of terminal hydroxyl functional groups are provided. A large number of terminal hydroxyl groups react with reactive groups such as isocyanate. The highly branched structure occupies more space in the system. When the toughening agent is added, the structure formed by the hyperbranched polyol can be dispersed in the matrix like "microspheres", playing a physical barrier role to prevent crack propagation and improve the toughness of the material; furthermore, there are voids inside the hyperbranched polyol molecules, and these voids provide storage space for some small molecule substances, which can buffer external forces and absorb energy when the material is impacted, improving the toughening effect.

[0037] Step 2: Turn on the heating device and slowly raise the temperature of the reaction system to the predetermined reaction temperature, generally 80 °C. When the temperature reaches the set value, add an appropriate amount of catalyst.

[0038] Step 3: During the reaction, the hydroxyl groups in the reaction system will undergo polycondensation reaction, and the reaction time is 2 hours to form a prepolymer.

[0039] Step 4: When the temperature of the prepolymer cools to 65 °C, add 4 parts of capping agent, and keep stirring during the addition process. After adding the capping agent, add 2 parts of nanomaterials and 2 parts of fiber composites to it.

[0040] As a technical optimization scheme of the present invention, in Step 1: During the addition of macromolecular diol, hyperbranched polyol, and polycarbonate diol, stir them to make a preliminary uniform mixture, and control the stirring speed at 10 r / min; avoid excessive stirring to generate a large amount of foam, and do not stir too slowly to cause uneven mixing.

[0041] As a technical optimization scheme of the present invention, in Step 2: The catalyst is dibutyltin dilaurate, and its addition amount is usually 0.1% of the total mass of the reactants. The addition of the catalyst can promote the polycondensation reaction between hydroxyl groups.

[0042] As a technical optimization scheme of the present invention, in Step 3: As the reaction progresses, the viscosity of the reaction system will gradually increase. The progress of the reaction can be monitored by observing the change in the viscosity of the reaction system and the method of sampling and analysis. For example, sample at regular intervals (such as every 30 minutes), analyze the molecular weight and its distribution of the product by gel permeation chromatography (GPC), or detect the change in the hydroxyl peak by infrared spectroscopy (IR) to judge the reaction degree. When the reaction reaches the expected degree, such as when the molecular weight of the product reaches the predetermined value or the hydroxyl conversion rate reaches a certain proportion, stop heating and end the reaction.

[0043] Embodiment Column Two:

[0044] An acrylic-modified polyurethane epoxy toughening agent, comprising macroglycol, hyperbranched polyol, polycarbonate diol, capping agent, nanomaterials and fiber composites.

[0045] As a technical optimization scheme of the present invention, the macroglycol is at least one of polypropylene glycol, polytetrahydrofuran glycol, polyester diol, polycaprolactone diol and polycarbonate diol, the molecular weight of the macroglycol is 2000, and the capping agent is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, caprolactone acrylate, pentaerythritol triacrylate and dipentaerythritol pentaacrylate.

[0046] As a technical optimization scheme of the present invention, the nanomaterials are at least one of nano-silica and carbon nanotubes, and the fiber composites are at least one of glass fiber and carbon fiber.

[0047] A production process of an acrylic-modified polyurethane epoxy toughening agent, which production process includes the above-mentioned acrylic-modified polyurethane epoxy toughening agent and also includes the following steps:

[0048] Step 1: Take 50 parts of macroglycol, 25 parts of hyperbranched polyol and 25 parts of polycarbonate diol. Add the above-mentioned macroglycol, hyperbranched polyol and polycarbonate diol into a reaction vessel.

[0049] Step 2: Turn on the heating device, slowly raise the temperature of the reaction system to a predetermined reaction temperature, generally at 115°C. When the temperature reaches the set value, add an appropriate amount of catalyst.

[0050] Step 3: During the reaction, the hydroxyl groups in the reaction system will undergo a polycondensation reaction, and the reaction time is 6 hours to form a prepolymer.

[0051] Step 4: When the temperature of the prepolymer cools to 70°C, add 6 parts of the capping agent thereto, and keep stirring during the addition. After the capping agent is added, add 3 parts of nanomaterials and 3 parts of fiber composites thereto; the addition of the fiber composites can provide high strength and high modulus, and improve the toughness and impact resistance of the toughening agent; the nanomaterials are nano-silica or carbon nanotubes. The addition of nano-silica, due to its high specific surface area and high activity, can improve the strength, hardness and wear resistance of the toughening agent, and at the same time form a good interfacial bond with the epoxy resin, improving the compatibility and bonding force between the toughening agent and the epoxy resin; when carbon nanotubes are added, due to their excellent mechanical properties, electrical conductivity and thermal properties, the mechanical properties and thermal stability can be improved after addition. The carbon nanotubes can also form a network structure in the epoxy resin to hinder the propagation of cracks.

[0052] As a technical optimization solution of the present invention, in step one: during the addition of macromolecular diol, hyperbranched polyol and polycarbonate diol, they are preliminarily mixed evenly by stirring, and the stirring speed is controlled at 13 r / min; it is necessary to avoid excessive stirring generating a large amount of foam, nor can the stirring be too slow to cause uneven mixing.

[0053] As a technical optimization solution of the present invention, in step two: the catalyst is dibutyltin dilaurate, and its addition amount is usually 0.5% of the total mass of the reactants. The addition of the catalyst can promote the polycondensation reaction between hydroxyl groups.

[0054] As a technical optimization solution of the present invention, in step three: as the reaction proceeds, the viscosity of the reaction system will gradually increase. The progress of the reaction can be monitored by observing the change in the viscosity of the reaction system and the method of sampling and analysis. For example, samples are taken at regular intervals (such as every 30 minutes), and the molecular weight and its distribution of the product are analyzed by gel permeation chromatography (GPC), or the change in the hydroxyl peak is detected by infrared spectroscopy (IR) to judge the reaction degree. When the reaction reaches the expected degree, for example, when the molecular weight of the product reaches a predetermined value or the hydroxyl conversion rate reaches a certain proportion, stop heating and end the reaction.

[0055] Example three:

[0056] An acrylic-modified polyurethane epoxy toughening agent, comprising macromolecular diol, hyperbranched polyol, polycarbonate diol, end-capping agent, nanomaterial and fiber composite material.

[0057] As a technical optimization solution of the present invention, the macromolecular diol is at least one of polypropylene glycol, polytetrahydrofuran diol, polyester diol, polycaprolactone diol and polycarbonate diol, the molecular weight of the macromolecular diol is 3000, and the end-capping agent is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, caprolactone acrylate, pentaerythritol triacrylate and dipentaerythritol pentaacrylate.

[0058] As a technical optimization solution of the present invention, the nanomaterial is at least one of nano-silica and carbon nanotubes, and the fiber composite material is at least one of glass fiber and carbon fiber.

[0059] A production process of an acrylic-modified polyurethane epoxy toughening agent, the production process includes the above-mentioned acrylic-modified polyurethane epoxy toughening agent and the production process further includes the following steps:

[0060] Step one: Take 70 parts of macromolecular diol, 40 parts of hyperbranched polyol and 40 parts of polycarbonate diol. Add the above-mentioned macromolecular diol, hyperbranched polyol and polycarbonate diol into the reaction vessel.

[0061] Step 2: Turn on the heating device and slowly raise the temperature of the reaction system to the predetermined reaction temperature, generally at 80 - 150 °C. After the temperature reaches the set value, add an appropriate amount of catalyst.

[0062] Step 3: During the reaction, the hydroxyl groups in the reaction system will undergo a polycondensation reaction for 2 - 10 hours to form a prepolymer.

[0063] Step 4: When the temperature of the prepolymer cools to 75 °C, add 8 parts of the capping agent while continuously stirring during the addition process. After adding the capping agent, add 4 parts of the nanomaterial and 4 parts of the fiber composite material.

[0064] As a technical optimization scheme of the present invention, in Step 1: During the addition of the macromolecular diol, hyperbranched polyol, and polycarbonate diol, initially mix them evenly by stirring, and control the stirring speed at 15 r / min; avoid excessive stirring that generates a large amount of foam, and also avoid too slow stirring that leads to uneven mixing; by stirring during the reaction, the uniform mixing of multiple raw materials enables the reaction to proceed evenly, avoiding too fast or too slow local reactions; stirring can also increase the contact probability between reactants. During stirring, the molecules constantly collide with each other, which is beneficial to the contact between the isocyanate group (-NCO) and the hydroxyl group (-OH) to accelerate the reaction and improve the uniformity of the reaction; since the mixing reaction between the raw materials is exothermic, stirring can timely dissipate this heat to the outside, and side reactions caused by too high local temperature will not occur, such as the formation of products with too high crosslinking degree, abnormal increase in the viscosity of the toughening agent, or even gelation.

[0065] As a technical optimization scheme of the present invention, in Step 2: The catalyst is dibutyltin dilaurate, and its addition amount is usually 1% of the total mass of the reactants. The addition of the catalyst can promote the polycondensation reaction between hydroxyl groups.

[0066] As a technical optimization scheme of the present invention, in Step 3: As the reaction proceeds, the viscosity of the reaction system will gradually increase. The progress of the reaction can be monitored by observing the viscosity change of the reaction system and sampling analysis methods. For example, sample at regular intervals (such as every 30 minutes), analyze the molecular weight and its distribution of the product by gel permeation chromatography (GPC), or detect the change of the hydroxyl peak by infrared spectroscopy (IR) to judge the reaction degree. When the reaction reaches the expected degree, such as the molecular weight of the product reaches the predetermined value or the hydroxyl conversion rate reaches a certain proportion, stop heating and end the reaction.

[0067] Analysis table of acrylic - modified polyurethane epoxy toughening agent after adding hyperbranched polyol

[0068]

[0069] When the present invention is in use, by setting hyperbranched polyol, it can have a significant impact on the acrylic modified polyurethane epoxy toughening agent at a relatively low addition amount. It can improve the toughness and impact resistance of the material by increasing the intermolecular interaction and steric hindrance effect. In the synthesis of polyurethane elastomers with relatively high requirements for hydrolysis resistance and flexibility of the material, by using polycarbonate diol in combination with other polyols, products with excellent properties can be obtained. Nanomaterials have a very high specific surface area and surface activity. When it is introduced into the acrylic modified polyurethane epoxy system and interacts with the polymer matrix, for example, through hydrogen bonding and other interaction methods, the toughness of the material is enhanced to a certain extent. The fiber composite material undergoes chemical bonding with the organic polymer, improving the compatibility and interfacial bonding force of the system, thereby enhancing the mechanical properties of the toughening agent.

[0070] The above are only the preferred specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, according to the technical solution and inventive concept of the present invention, making equivalent substitutions or changes should be covered within the protection scope of the present invention.

Claims

1. An acrylic acid modified polyurethane epoxy toughening agent, characterized in that: Including macromolecular diols, hyperbranched polyols, polycarbonate diols, end-capping agents, nanomaterials and fiber composite materials.

2. The acrylic acid-modified polyurethane epoxy toughening agent according to claim 1, characterized in that: The macromolecular diol is at least one of polypropylene glycol, polytetramethylene glycol, polyester diol, polycaprolactone diol and polycarbonate diol, the molecular weight of the macromolecular diol is 500-3000, and the end-capping agent is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, caprolactone acrylate, pentaerythritol triacrylate and dipentaerythritol pentaacrylate.

3. The acrylic modified polyurethane epoxy toughening agent according to claim 1, characterized in that: The nano material is at least one of nano silicon dioxide and carbon nanotubes, and the fiber composite material is at least one of glass fiber and carbon fiber.

4. A production process of acrylic acid modified polyurethane epoxy toughening agent, characterized in that: The production process comprises an acrylic modified polyurethane epoxy toughening agent as claimed in claims 1 to 3 above and the production process further comprises the following steps: Step 1: Take 30-70 parts of macromolecular diol, 10-40 parts of hyperbranched polyol and 10-40 parts of polycarbonate diol. Add the macromolecular diol, hyperbranched polyol and polycarbonate diol into a reaction container. Step 2: Turn on the heating device and slowly heat the reaction system to the predetermined reaction temperature, generally 80-150°C. When the temperature reaches the set value, add an appropriate amount of catalyst. Step 3: During the reaction, the hydroxyl groups in the reaction system will undergo a condensation reaction, and the reaction time is 2-10 hours to form a prepolymer. Step 4: When the temperature of the prepolymer is cooled to 65-75°C, add 4-8 parts of the end-capping agent into it, stirring continuously during the addition process. After the end-capping agent is added, add 2-4 parts of the nanomaterial and 2-4 parts of the fiber composite material into it.

5. The production process of an acrylic modified polyurethane epoxy toughening agent and its production process according to claim 4, characterized in that: In the step 1: during the addition of the macromolecular diol, the hyperbranched polyol and the polycarbonate diol, they are preliminarily mixed uniformly by stirring, and the stirring speed is controlled at 10-15 r / min.

6. The production process of an acrylic modified polyurethane epoxy toughening agent and its production process according to claim 4, characterized in that: In the step 2, the catalyst is dibutyltin dilaurate, and the amount added is usually 0.1%-1% of the total mass of the reactants.

7. The production process of an acrylic modified polyurethane epoxy toughening agent and its production process according to claim 4, characterized in that: In step 3: as the reaction proceeds, the viscosity of the reaction system will gradually increase, and the progress of the reaction can be monitored by observing the viscosity change of the reaction system and sampling and analyzing the reaction. When the reaction reaches the expected level, stop heating and end the reaction.

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