ACR plasticizer with high plasticizing efficiency and preparation method thereof

Abstract

The invention discloses an ACR plasticizer with high plasticizing efficiency and a preparation method thereof, and belongs to the field of ACR auxiliaries. Comprising the following substances in parts by weight: 30 to 50 parts of styrene, 20 to 30 parts of butyl acrylate, 15 to 25 parts of methyl methacrylate, 10 to 20 parts of dibutyl sebacate, 10 to 20 parts of acetyl tributyl citrate, 8 to 16 parts of trioctyl trimellitate, 9 to 15 parts of epoxidized soybean oil acrylate, 6 to 10 parts of maleic anhydride grafted polyether polyol and 0.2 to 0.4 part of polyoxyethylene sorbitan monopalmitate. The invention relates to a high-temperature-resistant coating which is prepared from the following components in parts by weight: 0.2 to 0.4 part of sucrose acetate isobutyrate, 0.1 to 0.3 part of polyethylene glycol monomethyl ether, 0.1 to 0.3 part of triallyl isocyanurate, 0.1 to 0.2 part of 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane and 0.1 to 0.2 part of dicumyl peroxide. According to the invention, the performance of the ACR auxiliary agent is improved while the plasticizing efficiency is improved.

Description

Technical Field

[0001] This invention belongs to the field of ACR additives, specifically a high plasticizing efficiency ACR plasticizer and its preparation method. Background Technology

[0002] Traditional PVC plasticizers are mostly phthalate compounds. While these substances can significantly improve the processing performance of PVC materials to a certain extent, making them easier to mold and use, they also bring some problems that cannot be ignored. For example, these plasticizers are prone to migration during use and have high volatility. These problems not only affect the long-term performance stability of the product but may also pose potential hazards to human health and the natural environment. In addition, traditional plasticizers are characterized by slow plasticizing speed in practical applications, which directly leads to low processing efficiency and often leaves defects such as flow marks on the surface of the final product, affecting the appearance quality and performance.

[0003] In recent years, with increasing environmental awareness and rising demand for high-performance materials, ACR plasticizers have gradually attracted widespread attention in the industry. This new type of plasticizer is considered a very promising alternative due to its non-toxic and highly efficient characteristics. However, current ACR products on the market still have some problems that urgently need to be solved, especially in terms of plasticizing speed and flowability, which limits their further promotion and application. Summary of the Invention

[0004] This invention provides an ACR plasticizer with high plasticizing efficiency and its preparation method, thereby overcoming the deficiencies in the prior art.

[0005] This invention is achieved through the following technical solution: A high-efficiency ACR plasticizer comprises the following substances in parts by weight: 30-50 parts styrene, 20-30 parts butyl acrylate, 15-25 parts methyl methacrylate, 10-20 parts dibutyl sebacate, 10-20 parts tributyl acetylacetonate, 8-16 parts trioctyl trimellitate, 9-15 parts epoxidized soybean oil acrylate, 6-10 parts maleic anhydride-grafted polyether polyol, 0.2-0.4 parts polyoxyethylene sorbitan monopalmitate, 0.2-0.4 parts sucrose isobutyrate, 0.1-0.3 parts polyethylene glycol monomethyl ether, 0.1-0.3 parts triallyl isocyanurate, 0.1-0.2 parts 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, and 0.1-0.2 parts dicumyl peroxide.

[0006] The ACR plasticizer with high plasticizing efficiency described above has a molecular weight of 4000-5000 for the maleic anhydride-grafted polyether polyol.

[0007] The ACR plasticizer with high plasticizing efficiency described above has a molecular weight of polyethylene glycol monomethyl ether of 2000-3000.

[0008] A method for preparing an ACR plasticizer with high plasticizing efficiency includes the following steps: Step 1: Weigh out the following ingredients according to the specified ratio: styrene, butyl acrylate, methyl methacrylate, dibutyl sebacate, tributyl acetylacetonate, trioctyl trimellitate, epoxidized soybean oil acrylate, maleic anhydride-grafted polyether polyol, polyoxyethylene sorbitan monopalmitate, sucrose isobutyrate, polyethylene glycol monomethyl ether, triallyl isocyanurate, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, and dicumyl peroxide. Step 2: Add styrene, butyl acrylate, tributyl acetyl citrate, polyoxyethylene sorbitan monopalmitate, polyethylene glycol monomethyl ether, and dicumyl peroxide to the mixer and carry out a sealed reaction. Step 3: Add trioctyl trimellitate, epoxidized soybean oil acrylate, and maleic anhydride-grafted polyether polyol to the mixer and continue the sealed reaction. Step 4: Add methyl methacrylate, dibutyl sebacate, sucrose isobutyrate acetate, polyethylene glycol monomethyl ether, and triallyl isocyanurate to the mixer to continue the reaction; Step 5: After mixing, the mixture is fed into a twin-screw extruder for granulation. Step 6: After granulation, crushing, drying, and packaging, ACR plasticizer with high plasticizing efficiency is obtained.

[0009] In the preparation method of the ACR plasticizer with high plasticizing efficiency as described above, the mixing temperature in step two is 80-90℃, the mixing speed is 300-400r / min, the mixing time is 2-3h, and nitrogen gas is introduced for protection during the mixing process.

[0010] In the preparation method of the ACR plasticizer with high plasticizing efficiency described above, the mixing temperature in step three is 70-80℃, the mixing speed is 200-300r / min, the mixing time is 50-90min, and nitrogen gas is introduced for protection during the mixing process.

[0011] In the preparation method of the ACR plasticizer with high plasticizing efficiency as described above, the mixing temperature in step four is 90-100℃, the mixing speed is 300-400r / min, the mixing time is 1-2h, and nitrogen gas is introduced for protection during the mixing process.

[0012] In the preparation method of the high plasticizing efficiency ACR plasticizer described above, in step five, the rotation speed of the twin-screw extruder is 200-300 r / min, the temperature of each section is 140-150℃, 150-160℃, 160-170℃, 170-180℃, 180-190℃, 170-180℃, and the die head temperature is 160-170℃, and the granules are cooled by water after granulation.

[0013] In the preparation method of the ACR plasticizer with high plasticizing efficiency described above, in step six, after pulverization, the material is passed through a 200-mesh sieve, and the material on the sieve is further pulverized until all of it passes through the sieve.

[0014] In the preparation method of the ACR plasticizer with high plasticizing efficiency as described above, the drying temperature in step six is ​​60-70℃, the drying negative pressure is 0.05-0.1MPa, and the drying time is 30-50min.

[0015] The advantages of this invention are: This invention improves plasticizing efficiency while also effectively enhancing the performance of ACR additives, thereby expanding the application scenarios of ACR additives. In this invention, the appropriate ratio of styrene to butyl acrylate can regulate the glass transition temperature of the copolymer. Different ratios of styrene and butyl acrylate will cause corresponding changes in the glass transition temperature of the copolymer, thereby meeting different performance requirements. Tributyl acetylic acid citrate can improve the processing fluidity of the material, allowing the material to flow more smoothly, reducing resistance during processing, and improving processing efficiency. Polyoxyethylene sorbitan monopalmitate and polyethylene glycol monomethyl ether can play a role in interfacial compatibility in this system, effectively promoting the uniform dispersion of each component throughout the system and avoiding component separation or uneven distribution. Dicumyl peroxide can effectively initiate the polymerization reaction of monomers. Through the synergistic effect of the above substances, a stable system can be polymerized to form a stable structural support, thereby ensuring the performance stability and functionality of the final material. In this invention, trioctyl trimellitate can fully interact with polymer molecular chains, improving the flexibility and ductility of the material; epoxidized soybean oil acrylate, with its epoxy groups in its molecular structure, can enhance the compatibility of ACR plasticizer, while also increasing the heat resistance and weather resistance of ACR plasticizer; maleic anhydride-grafted polyether polyol, utilizing the reactivity of its grafted maleic anhydride groups with other components, helps to improve the cross-linking structure of the system, enhancing the thermal stability and mechanical properties of ACR plasticizer during processing. The synergistic effect of these three components significantly improves the plasticizing efficiency, compatibility, and stability of ACR plasticizer. In this invention, methyl methacrylate can improve the hardness and rigidity of the copolymer, and synergistically regulate the mechanical properties of the material with styrene, butyl acrylate, dibutyl sebate, tributyl acetylacetonate, trioctyl trimellitate, epoxidized soybean oil acrylate, and maleic anhydride-grafted polyether polyol; dibutyl sebate can further enhance the softness of the ACR plasticizer and improve the plasticizing effect when combined with other substances; sucrose isobutyrate acetate has good compatibility and plasticizing properties, which can promote the uniform mixing of various components in the ACR plasticizer and reduce phase separation; polyethylene glycol monomethyl ether can further optimize the interfacial properties and improve the overall system stability; triallyl isocyanurate reacts with active groups to form a three-dimensional network structure, thereby improving the heat resistance, aging resistance, and mechanical strength of the ACR plasticizer. The combined effect of these substances improves the physicochemical properties of the ACR plasticizer, better meeting the diverse needs of practical applications. Detailed Implementation

[0016] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0017] Example 1 Step 1: Weigh out the following ingredients according to the specified ratio: 30 kg styrene, 20 kg butyl acrylate, 15 kg methyl methacrylate, 10 kg dibutyl sebate, 10 kg tributyl acetylacetonate, 8 kg trioctyl trimellitate, 9 kg epoxidized soybean oil acrylate, 6 kg maleic anhydride-grafted polyether polyol (molecular weight 4000-5000), 0.2 kg polyoxyethylene sorbitan monopalmitate, 0.2 kg sucrose isobutyrate acetate, 0.1 kg polyethylene glycol monomethyl ether (molecular weight 2000-3000), 0.1 kg triallyl isocyanurate, 0.1 kg 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, and 0.1 kg dicumyl peroxide. Step 2: Add styrene, butyl acrylate, tributyl acetyl citrate, polyoxyethylene sorbitan monopalmitate, polyethylene glycol monomethyl ether, and dicumyl peroxide to the mixer and carry out a sealed reaction. The mixing temperature is 80℃, the mixing speed is 400r / min, and the mixing time is 3h. Nitrogen gas is introduced for protection during the mixing process. Step 3: Add trioctyl trimellitate, epoxidized soybean oil acrylate and maleic anhydride-grafted polyether polyol to the mixer and continue the sealed reaction. The mixing temperature is 70℃, the mixing speed is 300r / min, and the mixing time is 90min. Nitrogen gas is introduced for protection during the mixing process. Step 4: Add methyl methacrylate, dibutyl sebacate, sucrose isobutyrate acetate, polyethylene glycol monomethyl ether, and triallyl isocyanurate to the mixer and continue the reaction. The mixing temperature is 90℃, the mixing speed is 400r / min, and the mixing time is 2h. Nitrogen gas is introduced for protection during the mixing process. Step 5: After mixing, the mixture is fed into a twin-screw extruder for granulation. The twin-screw extruder rotates at 200 r / min, and the temperatures of each section are 140-150℃, 150-160℃, 160-170℃, 170-180℃, 180-190℃, and 170-180℃ respectively. The die head temperature is 160-170℃. After granulation, the granules are cooled by water. Step 6: After granulation, the material is crushed through a 200-mesh sieve. The material on the sieve is then crushed again until all of it passes through the sieve. After crushing and sieving, the granules are dried at a temperature of 60℃, a negative pressure of 0.05MPa, and a drying time of 50min. After drying, the high plasticizing efficiency ACR plasticizer is obtained by packaging.

[0018] Example 2 Step 1: Weigh out the following ingredients according to the specified ratio: 50 kg styrene, 30 kg butyl acrylate, 25 kg methyl methacrylate, 20 kg dibutyl sebate, 20 kg tributyl acetylacetonate, 16 kg trioctyl trimellitate, 15 kg epoxidized soybean oil acrylate, 10 kg maleic anhydride-grafted polyether polyol (molecular weight 4000-5000), 0.4 kg polyoxyethylene sorbitan monopalmitate, 0.4 kg sucrose isobutyrate acetate, 0.3 kg polyethylene glycol monomethyl ether (molecular weight 2000-3000), 0.3 kg triallyl isocyanurate, 0.2 kg 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, and 0.2 kg dicumyl peroxide. Step 2: Add styrene, butyl acrylate, tributyl acetyl citrate, polyoxyethylene sorbitan monopalmitate, polyethylene glycol monomethyl ether, and dicumyl peroxide to the mixer and carry out a sealed reaction. The mixing temperature is 90℃, the mixing speed is 300r / min, and the mixing time is 2h. Nitrogen gas is introduced for protection during the mixing process. Step 3: Add trioctyl trimellitate, epoxidized soybean oil acrylate and maleic anhydride-grafted polyether polyol to the mixer and continue the sealed reaction. The mixing temperature is 80℃, the mixing speed is 200r / min, and the mixing time is 50min. Nitrogen gas is introduced for protection during the mixing process. Step 4: Add methyl methacrylate, dibutyl sebacate, sucrose isobutyrate acetate, polyethylene glycol monomethyl ether and triallyl isocyanurate to the mixer and continue the reaction. The mixing temperature is 100℃, the mixing speed is 300r / min, and the mixing time is 1h. Nitrogen gas is introduced for protection during the mixing process. Step 5: After mixing, the mixture is fed into a twin-screw extruder for granulation. The twin-screw extruder rotates at 300 r / min, and the temperatures of each section are 140-150℃, 150-160℃, 160-170℃, 170-180℃, 180-190℃, and 170-180℃ respectively. The die head temperature is 160-170℃. After granulation, the granules are cooled by water. Step 6: After granulation, the material is crushed through a 200-mesh sieve. The material on the sieve is then crushed again until all of it passes through the sieve. After crushing and sieving, the granules are dried at a temperature of 70°C, a negative pressure of 0.1 MPa, and a drying time of 30 minutes. After drying, the high plasticizing efficiency ACR plasticizer is packaged.

[0019] Example 3 Step 1: Weigh out the following ingredients according to the specified ratio: 40 kg styrene, 25 kg butyl acrylate, 20 kg methyl methacrylate, 15 kg dibutyl sebate, 15 kg tributyl acetylacetonate, 12 kg trioctyl trimellitate, 12 kg epoxidized soybean oil acrylate, 8 kg maleic anhydride-grafted polyether polyol (molecular weight 4000-5000), 0.3 kg polyoxyethylene sorbitan monopalmitate, 0.3 kg sucrose isobutyrate acetate, 0.2 kg polyethylene glycol monomethyl ether (molecular weight 2000-3000), 0.2 kg triallyl isocyanurate, 0.15 kg 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, and 0.15 kg dicumyl peroxide. Step 2: Add styrene, butyl acrylate, tributyl acetyl citrate, polyoxyethylene sorbitan monopalmitate, polyethylene glycol monomethyl ether, and dicumyl peroxide to the mixer and carry out a sealed reaction. The mixing temperature is 85℃, the mixing speed is 350r / min, and the mixing time is 2.5h. Nitrogen gas is introduced for protection during the mixing process. Step 3: Add trioctyl trimellitate, epoxidized soybean oil acrylate and maleic anhydride-grafted polyether polyol to the mixer and continue the sealed reaction. The mixing temperature is 75℃, the mixing speed is 250r / min, and the mixing time is 70min. Nitrogen gas is introduced for protection during the mixing process. Step 4: Add methyl methacrylate, dibutyl sebacate, sucrose isobutyrate acetate, polyethylene glycol monomethyl ether, and triallyl isocyanurate to the mixer and continue the reaction. The mixing temperature is 95℃, the mixing speed is 350r / min, and the mixing time is 1.5h. Nitrogen gas is introduced for protection during the mixing process. Step 5: After mixing, the mixture is fed into a twin-screw extruder for granulation. The twin-screw extruder rotates at 250 r / min, and the temperatures of each section are 140-150℃, 150-160℃, 160-170℃, 170-180℃, 180-190℃, and 170-180℃ respectively. The die head temperature is 160-170℃. After granulation, the granules are cooled by water. Step 6: After granulation, the material is crushed through a 200-mesh sieve. The material on the sieve is then crushed again until all of it passes through the sieve. After crushing and sieving, the granules are dried at a temperature of 65℃, a negative pressure of 0.08MPa, and a drying time of 40 minutes. After drying, the high plasticizing efficiency ACR plasticizer is obtained by packaging.

[0020] The high plasticizing efficiency ACR plasticizer prepared in Examples 1-3 was added to PVC material at a ratio of 5% and mixed at 300 r / min while heating to 120°C. The plasticizing speed was then tested (the plasticizing model was 100 mm × 100 mm × 3 mm). ACR-401 was used as Comparative Example 1, and another ACR plasticizer was used as Comparative Example 2. The same ratio and method were followed, and the properties after plasticization were tested. The results showed that the plasticizing times of the ACR plasticizers prepared in Examples 1-3 were 45 s, 42 s, and 43 s, respectively, all shorter than the 73 s of Comparative Example 1 and the 82 s of Comparative Example 2, indicating that the ACR plasticizer of this invention has higher plasticizing efficiency. Regarding mechanical properties, the tensile strengths of Examples 1-3 were 25.3 MPa, 26.1 MPa, and 25.7 MPa, respectively, which were superior to the 22.1 MPa of Comparative Example 1 and the 25.7 MPa of Comparative Example 2. The tensile strength of Examples 1-3 was 320%, 335%, and 328%, respectively, which were superior to 280% of Comparative Example 1 and 295% of Comparative Example 2. Regarding heat resistance, the heat distortion temperatures of Examples 1-3 were 85℃, 88℃, and 86℃, respectively, which were higher than 78℃ of Comparative Example 1 and 80℃ of Comparative Example 2. Regarding weather resistance, after 1000 hours of UV aging test, the tensile strength retention rates of Examples 1-3 were 89%, 91%, and 90%, respectively, which were higher than 75% of Comparative Example 1 and 78% of Comparative Example 2. The elongation at break retention rates of Examples 1-3 were 85%, 87%, and 86%, respectively, which were higher than 70% of Comparative Example 1 and 73% of Comparative Example 2. These test results fully demonstrate that the present invention, through the synergistic effect of each component and the optimization of preparation process parameters, effectively improves the plasticizing efficiency and physicochemical properties of ACR plasticizer, and can better meet the needs of processing and application of polymer materials such as PVC.

[0021] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A high-efficiency ACR plasticizer, characterized in that: The substance comprises the following components in parts by weight: 30-50 parts styrene, 20-30 parts butyl acrylate, 15-25 parts methyl methacrylate, 10-20 parts dibutyl sebacate, 10-20 parts tributyl acetylacetonate, 8-16 parts trioctyl trimellitate, 9-15 parts epoxidized soybean oil acrylate, 6-10 parts maleic anhydride-grafted polyether polyol, 0.2-0.4 parts polyoxyethylene sorbitan monopalmitate, 0.2-0.4 parts sucrose isobutyrate, 0.1-0.3 parts polyethylene glycol monomethyl ether, 0.1-0.3 parts triallyl isocyanurate, 0.1-0.2 parts 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, and 0.1-0.2 parts dicumyl peroxide.

2. The ACR plasticizer with high plasticizing efficiency according to claim 1, characterized in that: The molecular weight of the maleic anhydride-grafted polyether polyol is 4000-5000.

3. The ACR plasticizer with high plasticizing efficiency according to claim 1, characterized in that: The molecular weight of the polyethylene glycol monomethyl ether is 2000-3000.

4. A method for preparing an ACR plasticizer with high plasticizing efficiency, characterized in that: Includes the following steps: Step 1: Weigh out the following ingredients according to the specified ratio: styrene, butyl acrylate, methyl methacrylate, dibutyl sebacate, tributyl acetylacetonate, trioctyl trimellitate, epoxidized soybean oil acrylate, maleic anhydride-grafted polyether polyol, polyoxyethylene sorbitan monopalmitate, sucrose isobutyrate, polyethylene glycol monomethyl ether, triallyl isocyanurate, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, and dicumyl peroxide. Step 2: Add styrene, butyl acrylate, tributyl acetyl citrate, polyoxyethylene sorbitan monopalmitate, polyethylene glycol monomethyl ether, and dicumyl peroxide to the mixer and carry out a sealed reaction. Step 3: Add trioctyl trimellitate, epoxidized soybean oil acrylate, and maleic anhydride-grafted polyether polyol to the mixer and continue the sealed reaction. Step 4: Add methyl methacrylate, dibutyl sebacate, sucrose isobutyrate acetate, polyethylene glycol monomethyl ether, and triallyl isocyanurate to the mixer to continue the reaction; Step 5: After mixing, the mixture is fed into a twin-screw extruder for granulation. Step 6: After granulation, crushing, drying, and packaging, ACR plasticizer with high plasticizing efficiency is obtained.

5. The method for preparing a high-plasticizing-efficiency ACR plasticizer according to claim 4, characterized in that: In step two, the mixing temperature is 80-90℃, the mixing speed is 300-400r / min, the mixing time is 2-3h, and nitrogen gas is introduced for protection during the mixing process.

6. The method for preparing a high-plasticizing-efficiency ACR plasticizer according to claim 4, characterized in that: In step three, the mixing temperature is 70-80℃, the mixing speed is 200-300r / min, the mixing time is 50-90min, and nitrogen gas is introduced for protection during the mixing process.

7. The method for preparing a high-plasticizing-efficiency ACR plasticizer according to claim 4, characterized in that: In step four, the mixing temperature is 90-100℃, the mixing speed is 300-400r / min, the mixing time is 1-2h, and nitrogen gas is introduced for protection during the mixing process.

8. The method for preparing a high-plasticizing-efficiency ACR plasticizer according to claim 4, characterized in that: In step five, the twin-screw extruder operates at a speed of 200-300 r / min, with temperatures in each section ranging from 140-150℃, 150-160℃, 160-170℃, 170-180℃, 180-190℃, and 170-180℃, respectively. The die head temperature is 160-170℃, and the granules are cooled by water after granulation.

9. The method for preparing a high-plasticizing-efficiency ACR plasticizer according to claim 4, characterized in that: In step six, after pulverizing, the material is passed through a 200-mesh sieve. The material remaining on the sieve is then pulverized again until it is completely sieved.

10. The method for preparing a high-plasticizing-efficiency ACR plasticizer according to claim 4, characterized in that: The drying temperature in step six is ​​60-70℃, the drying negative pressure is 0.05-0.1MPa, and the drying time is 30-50min.