Manufacturing process of styrene-butadiene latex modified hot-melt phenolic resin

Abstract

The invention provides a manufacturing process of styrene-butadiene latex modified hot-melt phenolic resin, and relates to the technical field of high polymer materials, and the manufacturing process comprises the following steps: firstly, adding accurately metered phenol and a formaldehyde solution with a specific concentration into a reaction kettle provided with an intelligent temperature control and stirring system, adding an oxalic acid catalyst, and carrying out a multi-stage temperature control reaction to obtain a phenolic resin prepolymer; then, adding a proper amount of styrene-butadiene latex into the prepolymer, and raising the temperature to continue the reaction; cooling after the reaction is finished, adding a curing agent, uniformly stirring, and pouring into a specially treated mold for curing. An online monitoring device is introduced in the manufacturing process, and reaction conditions are adjusted in real time. The modified phenolic resin prepared by the process is excellent in performance, high in softening point, low in free phenol content and high in tensile strength and bending strength. The process is high in controllability, all links are accurately controlled through an advanced technology, the product quality and performance are effectively improved, powerful support is provided for application and expansion of phenolic resin, and the method has wide application prospects in numerous industrial fields.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, and more specifically, it relates to a manufacturing process for styrene-butadiene latex-modified hot-melt phenolic resin. Background Technology

[0002] In the field of materials science today, phenolic resins are widely used in many industrial sectors, including electronics, machinery, automotive, and aerospace, due to their unique properties such as good heat resistance, chemical corrosion resistance, and electrical insulation. However, with continuous technological advancements and increasingly diversified application demands, the performance of traditional phenolic resins has gradually revealed some limitations.

[0003] Traditional phenolic resins often suffer from problems such as high brittleness, poor water resistance, and unsatisfactory mechanical properties, which to some extent limits their application in fields with high material performance requirements. To overcome these shortcomings, modification of phenolic resins has become a research hotspot.

[0004] Styrene-butadiene latex, a common polymer material, possesses excellent elasticity, adhesion, and weather resistance. Its application in the modification of phenolic resins holds promise for improving their flexibility, water resistance, and mechanical properties.

[0005] However, existing manufacturing processes for styrene-butadiene latex-modified phenolic resins face numerous challenges. For example, insufficient precision in controlling temperature and stirring conditions during the reaction process can easily lead to uneven reactions and affect product quality stability; inadequate selection and dosage of catalysts and curing agents can result in low reaction efficiency or poor product performance; and unscientific raw material ratios can hinder the full realization of the modification effect of styrene-butadiene latex.

[0006] Furthermore, existing processes may have issues such as high energy consumption and environmental unfriendliness during production. Additionally, due to process limitations, the modified phenolic resins produced still cannot meet the stringent requirements of certain high-end applications, such as high-performance electronic packaging materials and high-strength structural components, in some key performance indicators, such as softening point, free phenol content, tensile strength, and flexural strength.

[0007] Therefore, in order to overcome the shortcomings of existing technologies and meet the ever-evolving market demands, it is of great practical significance and application value to develop a new manufacturing process for styrene-butadiene latex-modified hot-melt phenolic resin, which can achieve more precise reaction control, optimized material properties, and a more environmentally friendly and efficient production process. Summary of the Invention

[0008] To address the aforementioned technical problems, this invention provides a manufacturing process for styrene-butadiene latex-modified hot-melt phenolic resin.

[0009] A manufacturing process for styrene-butadiene latex-modified hot-melt phenolic resin includes the following steps:

[0010] S1: Inspect and clean the reactor to ensure that there are no impurities or residues inside the reactor;

[0011] S2: Add 100 parts by weight of phenol precisely into the reaction vessel using a metering device;

[0012] S3: Slowly add 120-150 parts of formaldehyde solution with a mass concentration of 37%-40% into the reactor using a high-precision delivery pump. During the addition of the formaldehyde solution, start the stirring system of the reactor and set the stirring speed to 100-150 rpm to make the phenol and formaldehyde solution initially mixed evenly.

[0013] S4: Set the intelligent temperature control system of the reactor to preheating mode to raise the temperature inside the reactor to 30-40℃ and maintain it for 10-15 minutes to promote the pre-fusion of phenol and formaldehyde solution;

[0014] S5: Add a catalyst to the reaction vessel, wherein the catalyst is oxalic acid, and the amount added is 1%-3% of the weight of phenol;

[0015] S6: Heat the temperature to 80-90℃ using microwave-assisted heating technology and react for 1-2 hours to obtain phenolic resin prepolymer;

[0016] S7: Reduce the temperature of the reactor to 60-70℃ and maintain this temperature for 0.5-1 hour;

[0017] S8: Then raise the temperature again to 95-105℃ and continue the reaction for 0.5-1 hour;

[0018] S9: Introduce an online monitoring device to monitor the viscosity and molecular weight distribution of the reaction system in real time, and adjust the reaction conditions based on the monitoring data.

[0019] Preferably, after completing S9, styrene-butadiene latex is added to the phenolic resin prepolymer, and the amount of styrene-butadiene latex added is 10%-20% of the weight of the phenolic resin prepolymer.

[0020] Preferably, after adding styrene-butadiene latex, the temperature is raised to 120-130°C using pulse heating, and the reaction continues for 2-3 hours.

[0021] Preferably, after the reaction is completed, the temperature is rapidly reduced to 80-90°C using liquid nitrogen, and a curing agent is added. The curing agent is hexamethylenetetramine, and the amount added is 5%-10% of the weight of the phenolic resin prepolymer.

[0022] Preferably, after stirring evenly, the product is poured into a mold whose inner wall has been plasma-treated, and cured at 150-160℃ for 2-3 hours.

[0023] Preferably, after curing, the resin is naturally cooled to room temperature under inert gas protection to obtain styrene-butadiene latex modified hot-melt phenolic resin.

[0024] Preferably, the molar ratio of formaldehyde solution to phenol is 1.5-2.0:1.

[0025] Preferably, the stirring speed is controlled at 100-200 rpm during the reaction.

[0026] Preferably, the solid content of the styrene-butadiene latex is 40%-50%.

[0027] Preferably, a release agent is applied to the inner wall of the mold.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] 1. The manufacturing process of this invention significantly improves the heat resistance of phenolic resin. Through precise temperature control and optimized reaction steps, styrene-butadiene latex and phenolic resin are fully fused to form a more stable structure, thereby significantly increasing the softening point of the modified phenolic resin. This characteristic allows the resin to maintain good performance even at high temperatures, broadening its application range in high-temperature conditions, such as in automotive engine parts and high-temperature pipelines.

[0030] 2. This invention effectively reduces the free phenol content in phenolic resins. Precise raw material proportioning and advanced reaction control methods reduce unreacted phenol residue, not only improving product purity and quality but also reducing potential environmental hazards. Phenolic resins with low free phenol content are safer and more environmentally friendly during use, meeting the stringent requirements of modern industry for green and environmentally friendly materials.

[0031] 3. This invention significantly improves the mechanical properties of phenolic resin. Through styrene-butadiene latex modification and optimized processing, the tensile strength and flexural strength of the resin are significantly enhanced. This makes phenolic resin perform better under tensile and flexural stress, meeting the requirements of more applications with high material strength requirements, such as better supporting and load-bearing functions in machinery manufacturing and building structures.

[0032] 4. The intelligent temperature control and stirring system, along with advanced technologies such as microwave-assisted heating employed in this invention, make the reaction process more precise and controllable, effectively avoiding localized overheating or uneven reaction. This helps improve product consistency and stability, reduce defect rates, and thus increase production efficiency and economic benefits. The stable and reliable performance makes phenolic resin perform better in various applications, enhancing its market competitiveness.

[0033] 5. This invention improves the flexibility and impact resistance of phenolic resin by introducing styrene-butadiene latex modification. Traditional phenolic resins are often brittle, limiting their application in situations requiring a certain level of elasticity and impact resistance. The modified phenolic resin can better withstand external impacts and vibrations, making it suitable for manufacturing products requiring toughness, such as electronic device housings and sporting goods.

[0034] 6. The manufacturing process of this invention reduces production costs to a certain extent. Optimized reaction conditions and precise raw material control reduce waste while improving production efficiency. Furthermore, the superior performance of the modified phenolic resin allows for reduced usage or replacement of some expensive materials, resulting in cost savings for businesses. Lower costs will help promote the widespread application of phenolic resins in more fields and foster the development of related industries. Attached Figure Description

[0035] Figure 1 This is a schematic diagram of the overall structure of the present invention. Detailed Implementation

[0036] This invention relates to a manufacturing process for styrene-butadiene latex-modified hot-melt phenolic resin, aiming to provide a high-performance and process-controllable method for producing phenolic resin. The manufacturing process of this invention will be described in detail below through specific embodiments, and the performance of each embodiment will be compared and analyzed.

[0037] Example 1:

[0038] Raw material preparation:

[0039] Phenol: 100 kg;

[0040] Formaldehyde solution (37% by mass): 120 kg;

[0041] Oxalic acid (catalyst): 1 kg.

[0042] Reactor parameters:

[0043] Intelligent temperature control accuracy: ±0.5℃;

[0044] Stirring speed range: 50-500 rpm;

[0045] Agitator: Double-layered three-blade agitator.

[0046] Manufacturing steps:

[0047] First, thoroughly inspect and clean the reactor to ensure that the interior is clean and free of impurities.

[0048] Accurately weigh 100 kg of phenol and add it to the reaction vessel using a metering device;

[0049] Using a high-precision delivery pump, 120 kg of a 37% formaldehyde solution was slowly added to the reaction vessel. During the addition of the formaldehyde solution, the stirring system was started and the stirring speed was set to 100 rpm to ensure that the phenol and formaldehyde solution were initially mixed evenly.

[0050] Set the intelligent temperature control system of the reactor to preheating mode to raise the temperature inside the reactor to 30°C and maintain it for 10 minutes to promote the pre-fusion of phenol and formaldehyde solutions.

[0051] Add 1 kg of oxalic acid as a catalyst to the reactor;

[0052] Microwave-assisted heating technology was used to rapidly raise the temperature inside the reactor to 80°C, and the reaction was maintained at this temperature for 1 hour to obtain phenolic resin prepolymer.

[0053] The reactor temperature was then lowered to 60°C and maintained at that temperature for 0.5 hours.

[0054] Then the temperature was raised again to 95°C, and the reaction was continued for 0.5 hours;

[0055] An online monitoring device was introduced to monitor the viscosity of the reaction system in real time, which was 500 mPa·s.

[0056] 12 kg of styrene-butadiene latex (40% solid content) was added to the above phenolic resin prepolymer.

[0057] The reactor was heated to 120°C using a pulse heating method, and the reaction was continued for 2 hours.

[0058] After the reaction was completed, the temperature was rapidly reduced to 80°C using liquid nitrogen, and 6 kg of hexamethylenetetramine was added as a curing agent.

[0059] After stirring at 150 rpm until homogeneous, the product is poured into a mold whose inner wall has been plasma-treated. The mold dimensions are 50cm×50cm×5cm.

[0060] Place the mold in a heating device and cure it at 150°C for 2 hours;

[0061] After curing, the resin is naturally cooled to room temperature under nitrogen protection to obtain styrene-butadiene latex-modified hot-melt phenolic resin.

[0062] The performance of the styrene-butadiene latex-modified hot-melt phenolic resin prepared in Example 1 was tested, and the results are shown in the table below:

[0063] Performance indicators Test Results Softening point (°C) 110 Free phenol content (%) 1.2 Tensile strength (MPa) 25 Bending strength (MPa) 40

[0064] Example 2:

[0065] Raw material preparation:

[0066] Phenol: 100 kg;

[0067] Formaldehyde solution (38.5% by mass): 135 kg;

[0068] Oxalic acid (catalyst): 2 kg.

[0069] Reactor parameters:

[0070] Intelligent temperature control accuracy: ±0.5℃;

[0071] Stirring speed range: 50-500 rpm;

[0072] Agitator: Double-layered three-blade agitator.

[0073] Manufacturing steps:

[0074] The inspection and cleaning of the reaction vessel are the same as in Example 1;

[0075] Weigh 100 kg of phenol and add it to the reaction vessel;

[0076] 135 kg of a 38.5% formaldehyde solution was added to the reactor using a transfer pump, and the stirring speed was set to 125 rpm for initial mixing.

[0077] The intelligent temperature control system of the reactor preheats to 35°C and maintains this temperature for 12 minutes.

[0078] Add 2 kg of oxalic acid catalyst;

[0079] Microwave-assisted heating to 85°C and reaction for 1.5 hours yielded a phenolic resin prepolymer.

[0080] Cool down to 65℃ and maintain this temperature for 0.75 hours;

[0081] The temperature was raised again to 100°C, and the reaction was allowed to proceed for 0.75 hours.

[0082] The online viscosity was 650 mPa·s.

[0083] Add 18 kg of styrene-butadiene latex (45% solid content) to the phenolic resin prepolymer.

[0084] Pulse heating to 125°C, reaction for 2.5 hours;

[0085] Cool the liquid nitrogen to 85°C and add 9 kg of hexamethylenetetramine curing agent;

[0086] Mix at 175 rpm until well combined, then pour into a mold (60cm×60cm×6cm).

[0087] Curing temperature: 155℃ for 2.5 hours;

[0088] Styrene-butadiene latex-modified hot-melt phenolic resin was prepared by naturally cooling to room temperature under nitrogen protection.

[0089] The performance test results of the styrene-butadiene latex-modified hot-melt phenolic resin prepared in Example 2 are as follows:

[0090] Performance indicators Test Results Softening point (°C) 115 Free phenol content (%) 1.0 Tensile strength (MPa) 28 Bending strength (MPa) 45

[0091] Example 3:

[0092] Raw material preparation:

[0093] Phenol: 100 kg;

[0094] Formaldehyde solution (40% by mass): 150 kg;

[0095] Oxalic acid (catalyst): 3 kg.

[0096] Reactor parameters:

[0097] Intelligent temperature control accuracy: ±0.5℃;

[0098] Stirring speed range: 50-500 rpm;

[0099] Agitator: Double-layered three-blade agitator.

[0100] Manufacturing steps:

[0101] The reactor treatment is the same as before;

[0102] Add 100 kg of phenol;

[0103] Inject 150 kg of a 40% formaldehyde solution and mix by stirring at 150 rpm.

[0104] Preheat to 40℃ and maintain for 15 minutes;

[0105] Add 3 kg of oxalic acid;

[0106] Microwave heating to 90°C for 2 hours yields phenolic resin prepolymer;

[0107] The temperature was lowered to 70°C and maintained for 1 hour.

[0108] Heat to 105℃ and react for 1 hour;

[0109] Viscosity monitored online at 750 mPa·s;

[0110] Add 20 kg of styrene-butadiene latex (50% solid content);

[0111] Pulse heating to 130℃, reaction for 3 hours;

[0112] Cool the liquid nitrogen to 90°C and add 10 kg of hexamethylenetetramine;

[0113] Stir well at 200 rpm and pour into a mold (70cm×70cm×7cm).

[0114] Cur at 160℃ for 3 hours;

[0115] Styrene-butadiene latex-modified hot-melt phenolic resin was obtained by naturally cooling to room temperature under inert gas protection.

[0116] The performance test results of the styrene-butadiene latex-modified hot-melt phenolic resin prepared in Example 3 are as follows:

[0117] Performance indicators Test Results Softening point (°C) 120 Free phenol content (%) 0.8 Tensile strength (MPa) 30 Bending strength (MPa) 50

[0118] To more intuitively compare the differences and performance advantages and disadvantages of the three embodiments, the key parameters and performance test results of each embodiment will be presented in tabular form below, along with a brief analysis.

[0119] Example Formaldehyde solution dosage (kg) Styrene-butadiene latex usage (kg) Softening point (°C) Free phenol content (%) Tensile strength (MPa) Bending strength (MPa) 1 120 12 110 1.2 25 40 2 135 18 115 1.0 28 45 3 150 20 120 0.8 30 50

[0120] As can be seen from the table above, the properties of the prepared styrene-butadiene latex-modified hot-melt phenolic resin show a certain trend of change with the increase of formaldehyde solution and styrene-butadiene latex dosage.

[0121] Regarding the softening point, Example 3 had the highest softening point, reaching 120°C, which is significantly higher than 110°C in Example 1. This indicates that increasing the amount of formaldehyde solution and styrene-butadiene latex helps to improve the heat resistance of the resin.

[0122] Regarding the free phenol content, Example 3 had the lowest free phenol content at 0.8%, while Example 1 had a free phenol content of 1.2%. This indicates that increasing the amount of raw materials and optimizing the reaction conditions within a certain range can reduce the free phenol content and improve the purity and quality of the product.

[0123] In terms of mechanical properties, the tensile strength and flexural strength of Example 3 reached 30 MPa and 50 MPa, respectively, which were significantly better than the 25 MPa and 40 MPa of Example 1. This fully demonstrates that by reasonably adjusting the raw material ratio and reaction process parameters, the mechanical properties of styrene-butadiene latex-modified hot-melt phenolic resin can be significantly improved, making it better able to meet the high strength requirements in practical applications.

[0124] In summary, the process conditions in Example 3 performed well in terms of various performance indicators.

[0125] The above three embodiments detail the specific process and performance characteristics of the styrene-butadiene latex-modified hot-melt phenolic resin manufacturing process described in this invention. This process employs advanced intelligent temperature and stirring systems, microwave-assisted heating technology, and other advanced technologies to precisely control reaction conditions, resulting in high-performance modified phenolic resins. Comparative data between the embodiments demonstrate that by rationally adjusting the raw material ratios and process parameters, product performance can be effectively optimized to meet the needs of different application scenarios. The manufacturing process of this invention exhibits good operability and controllability, providing reliable technical support for the industrial production of styrene-butadiene latex-modified hot-melt phenolic resins.

[0126] Through the detailed description of the above three embodiments, it can be clearly seen that the manufacturing process of the styrene-butadiene latex-modified hot-melt phenolic resin of the present invention has significant innovation and practicality.

[0127] From the selection and precise measurement of raw materials to the temperature control, reaction time management, and stirring speed adjustment at each stage in the reactor, every step has been meticulously designed and rigorously tested. The application of the intelligent temperature control and stirring system ensures the accuracy and stability of reaction conditions, avoiding the temperature fluctuations and uneven stirring problems that may occur in traditional processes, thereby greatly improving product consistency and quality reliability.

[0128] The introduction of microwave-assisted heating technology not only significantly improves heating efficiency and shortens reaction time, but also makes the reaction system more uniformly heated, which is conducive to the full progress of the reaction and thus improves product performance. The use of online monitoring devices enables real-time monitoring and data acquisition of the reaction process, providing a strong basis for timely adjustment of reaction conditions and optimization of process parameters, further ensuring the stability and controllability of product quality.

[0129] Innovative temperature control methods, such as pulse heating and rapid liquid nitrogen cooling, effectively control the reaction process and product properties. The plasma-treated inner wall of the mold and the curing process at specific temperatures and times ensure that the final product shape and performance meet the expected requirements.

[0130] In terms of performance testing, the determination and analysis of key indicators such as softening point, free phenol content, tensile strength, and flexural strength fully demonstrate that the styrene-butadiene latex-modified hot-melt phenolic resin prepared by the process of this invention exhibits excellent performance in terms of heat resistance, purity, and mechanical properties. Compared with traditional processes, the phenolic resin produced by the process of this invention has significantly improved performance and can better meet the market demand for high-performance phenolic resins.

[0131] Furthermore, the process of this invention also has certain advantages in terms of environmental protection, energy conservation, and cost control. By optimizing reaction conditions and improving raw material utilization, energy consumption and waste generation are reduced, production costs are lowered, and it meets the requirements of modern industrial production for green environmental protection and sustainable development.

[0132] In summary, the styrene-butadiene latex-modified hot-melt phenolic resin manufacturing process of this invention is technologically innovative, superior in performance, and has broad application prospects. It is believed that the promotion and application of this process will bring new vitality to the phenolic resin industry and provide strong support for technological progress and product upgrades in related industries. At the same time, we also look forward to further in-depth research and innovation based on this process in the future, continuously driving phenolic resin materials towards higher performance, more functions, and wider applications.

[0133] The embodiments of the present invention are given for illustrative and descriptive purposes only, and are not intended to be exhaustive or to limit the invention to the forms disclosed. Many modifications and variations will be apparent to those skilled in the art. The embodiments were chosen and described in order to better illustrate the principles and practical application of the invention, and to enable those skilled in the art to understand the invention and to design various embodiments with various modifications suitable for a particular purpose.

Claims

1. A process for the production of styrene-butadiene rubber modified hot-melt phenol-formaldehyde resin, characterized in that, The method comprises the following steps: S1: checking and cleaning the reaction kettle to ensure that the inside of the reaction kettle is free of impurities and residual substances; S2: 100 parts of phenol are accurately added to the cleaned reaction kettle in S1 by a metering device according to the weight fraction; S3: 120-150 parts of a formaldehyde solution with a mass concentration of 37%-40% are slowly added to the reaction kettle by a high-precision delivery pump, and in the process of adding the formaldehyde solution, the stirring system of the reaction kettle is started, and the stirring speed is set to 100-150 revolutions / minute; S4: the intelligent temperature control system provided by the reaction kettle is set to a preheating mode, the temperature in the kettle is raised to 30-40 DEG C, and is maintained for 10-15 minutes; S5: a catalyst is added to the reaction kettle, the catalyst is oxalic acid, and the addition amount of the catalyst is 1%-3% of the weight of the phenol; S6: the temperature is raised to 80-90 DEG C by using a microwave-assisted heating technology, and the reaction is carried out for 1-2 hours to obtain a phenolic resin prepolymer; S7: the temperature of the reaction kettle is reduced to 60-70 DEG C, and the temperature is maintained for 0.5-1 hours; S8: then the temperature is raised to 95-105 DEG C again, and the reaction is continued for 0.5-1 hours; S9: an online monitoring device is introduced to monitor the viscosity and molecular weight distribution of the reaction system in real time.

2. The process for manufacturing styrene butadiene emulsion modified hot-melt phenol formaldehyde resin as claimed in claim 1 wherein, After S9 is completed, butadiene styrene latex is added to the phenolic resin prepolymer, and the addition amount of the butadiene styrene latex is 10%-20% of the weight of the phenolic resin prepolymer.

3. The process for manufacturing styrene butadiene emulsion modified hot-melt phenol formaldehyde resin as claimed in claim 2 wherein, After the butadiene styrene latex is added, pulse heating is adopted to raise the temperature to 120-130 DEG C, and the reaction is continued for 2-3 hours.

4. The process for manufacturing styrene butadiene emulsion modified hot-melt phenol formaldehyde resin as claimed in claim 3 wherein, After the reaction is completed, liquid nitrogen is used to rapidly reduce the temperature to 80-90 DEG C, and a curing agent is added, the curing agent is hexamethylenetetramine, and the addition amount of the curing agent is 5%-10% of the weight of the phenolic resin prepolymer.

5. The process for manufacturing styrene butadiene emulsion modified hot-melt phenol formaldehyde resin as claimed in claim 4 wherein, After stirring uniformly, the product is poured into a mold with a plasma-treated inner wall, and is cured at 150-160 DEG C for 2-3 hours.

6. The process for manufacturing styrene butadiene emulsion modified hot-melt phenol formaldehyde resin as claimed in claim 5 wherein, After curing is completed, the product is naturally cooled to room temperature under the protection of inert gas to obtain butadiene styrene latex modified hot melt phenolic resin.

7. The process for manufacturing styrene butadiene emulsion modified hot-melt phenol formaldehyde resin as claimed in claim 6 wherein, The molar ratio of the formaldehyde solution to the phenol is 1.5-2.0:

1.

8. The process for manufacturing styrene butadiene emulsion modified hot-melt phenol formaldehyde resin as claimed in claim 7 wherein, In the reaction process, the stirring speed is controlled to be 100-200 revolutions / minute.

9. The process for manufacturing styrene butadiene emulsion modified hot-melt phenol formaldehyde resin as claimed in claim 8 wherein, The solid content of the butadiene styrene latex is 40%-50%.

10. The process for manufacturing styrene butadiene emulsion modified hot-melt phenol formaldehyde resin as claimed in claim 9 wherein, The inner wall of the mold is coated with a release agent.

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