Migration-resistant ABS resin lubricant as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of fine chemistry, and discloses a migration-resistant ABS resin lubricant and a preparation method and application thereof.The migration-resistant ABS resin lubricant is prepared by taking levulinic acid and fatty alcohol as raw materials, obtaining levulinic acid ester through esterification reaction and then conducting ketalation reaction. The migration-resistant ABS resin lubricant has better intermiscibility with ABS resin, and a corresponding ABS product has good mechanical properties, melt flowability and migration resistance; and the migration-resistant ABS resin lubricant takes the bio-based compound levulinic acid as the main raw material, so that the dependence on petrochemical raw materials is avoided, and the use of the bio-based raw materials is improved.

Description

Technical Field

[0001] The invention belongs to the technical field of fine chemistry, and in particular relates to a migration-resistant ABS resin lubricant and a preparation method and application thereof. Background Art

[0002] Acrylonitrile-butadiene-styrene (ABS) is one of the most prominent and widely used rubber-toughened amorphous thermoplastics. Due to the synergistic effect between the three components, ABS resin can resist impact loads even at low temperatures and has high rigidity, chemical resistance, heat resistance and recyclability. Therefore, ABS resin is widely used in industrial fields such as automobiles, transportation, electronics and construction, and is developed for use as engineering plastics.

[0003] Due to insufficient melt fluidity during processing, impurities are entrained and obvious flow marks appear on the surface of injection molded parts. These problems seriously damage the appearance quality and performance of the products, thereby greatly reducing their competitiveness in the white appliance market. The melt flow rate can be significantly improved by adjusting the ratio of rubber phase to resin phase. The lower the rubber phase content, the better the fluidity. However, this improvement in fluidity is usually at the expense of impact strength, which poses a challenge to the sustainability of its practical application. Therefore, improving the fluidity of ABS resin without affecting its mechanical properties has become an important research challenge.

[0004] As a small molecule additive, lubricant can significantly change the processing properties of ABS resin and maintain the stability of its mechanical properties. So far, lubricants that can be used for ABS resin can be mainly divided into three categories according to their chemical structure: fatty acids, fatty amides and fatty metal soaps. In particular, fatty diamides represented by EBA are widely used due to their excellent lubrication properties and good processing adaptability. However, the compatibility between traditional lubricants and the matrix is ​​limited, and they are easy to migrate out of the matrix. The migration resistance is not good enough, which greatly reduces the flow properties of the material. In addition, the migration of traditional lubricants from the matrix is ​​easy to cause damage to human health and is not green and environmentally friendly.

[0005] As a green biomass acid, levulinic acid has significant advantages in environmental protection and sustainable development. It is mainly derived from biomass raw materials, especially through fermentation or extraction from agricultural waste, which is in line with the basic concept of green chemistry. The green characteristics of levulinic acid are reflected in its renewability, low environmental load and biodegradability. Compared with traditional petroleum-based chemicals, levulinic acid is obtained through bioconversion processes, which reduces dependence on fossil fuels and reduces pollutant emissions during the production process. In addition, the degradation products of levulinic acid are environmentally friendly, meet the requirements of the circular economy, and are potential sustainable chemicals. Therefore, the effective use of levulinic acid to synthesize lubricants with excellent comprehensive performance is a direction worthy of research. Summary of the invention

[0006] In view of this, the present invention provides a migration-resistant ABS resin lubricant and a preparation method and application thereof.

[0007] To achieve the above object, the technical solution of the present invention is as follows: a migration-resistant ABS resin lubricant, the structural formula of which is as follows:

[0008]

[0009] In the formula, R is -C n H 2n Straight chain alkyl, n=4-12.

[0010] The invention provides a method for preparing the migration-resistant ABS resin lubricant, which uses levulinic acid and dihydric fatty alcohol as raw materials, obtains levulinic ester through esterification reaction, and then obtains the ABS resin lubricant through ketalization reaction.

[0011] The present invention is further configured that the preparation method specifically comprises the following steps:

[0012] (1) Esterification reaction: levulinic acid, dihydric fatty alcohol, and catalyst are added to a reactor equipped with a reflux device, and then a water-carrying agent is added. After mixing, the temperature is raised to 150-170° C. and refluxed for 8-10 hours. The water generated during the reaction will be azeotropically carried out of the system with the water-carrying agent. When the water level in the water separator no longer rises, the reaction system is naturally cooled to room temperature, and an alkali solution is added to a pH of ≥7. The reaction is carried out at room temperature for 20-60 minutes, and then washed with deionized water until neutral, and filtered to obtain the intermediate product, dihydric alcohol levulinic acid;

[0013] (2) Ketalization reaction: Add the diol levulinate prepared by the esterification reaction and ethylene glycol into a reactor, introduce nitrogen, heat to 100-120° C. and react for 5-8 hours. After the reaction is completed, add solvent extraction, wash with deionized water until neutral, distill the organic phase under reduced pressure, and vacuum dry to obtain ketalized levulinate ester, i.e., the ABS resin lubricant.

[0014] The present invention is further configured such that, in step (1), the molar ratio of levulinic acid, dihydric fatty alcohol and catalyst is 2:(1-1.5):(0.06-0.1); and in step (2), the molar ratio of dihydric alcohol levulinic acid ester to ethylene glycol is 1:(2-2.5).

[0015] The present invention is further configured such that, in step (1), the water-carrying agent is selected from one or a combination of benzene, toluene or n-hexane; and the amount of the water-carrying agent added is 15 to 18 times the total mass of levulinic acid, dihydric fatty alcohol and catalyst.

[0016] The present invention is further configured such that, in step (1), the catalyst is selected from one or more of phosphoric acid, sulfuric acid, p-toluenesulfonic acid or sodium bisulfate.

[0017] The present invention is further configured that the dihydric fatty alcohol is selected from one of C6-C12 aliphatic straight-chain diols. Preferably, the dihydric fatty alcohol is selected from at least one of 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol or 1,11-undecanediol.

[0018] The present invention is further configured such that, in step (1), the alkali solution is one of a sodium carbonate solution, a sodium bicarbonate solution or a sodium hydroxide solution.

[0019] The present invention is further configured such that, in step (2), the solvent is selected from one of toluene, benzene, dichloromethane or ethyl acetate.

[0020] The present invention also provides an application of the migration-resistant ABS resin lubricant in the preparation of ABS plastic products.

[0021] The present invention also provides an ABS resin, which is a modified ABS resin lubricated by the migration-resistant ABS resin lubricant.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] (1) The migration-resistant ABS resin lubricant provided by the present invention has excellent compatibility with ABS resin without phase separation, and the corresponding ABS products have good mechanical properties, melt fluidity and migration resistance.

[0024] (2) The migration-resistant ABS resin lubricant provided by the present invention uses the bio-based compound levulinic acid as the main raw material, thereby avoiding dependence on petrochemical raw materials and improving the utilization of bio-based raw materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 This is the infrared spectra of the ABS resin lubricants prepared in Examples 1 to 3.

[0026] Figure 2 The melt flow rate diagram of the ABS resin samples prepared in Application Examples 1 to 3 and Comparative Application Examples 1 to 2.

[0027] Figure 3 The figure is a migration resistance test result diagram of the ABS resin samples prepared in Application Examples 1 to 3 and Comparative Application Examples 1 to 2.

[0028] Figure 4 The tensile properties of the ABS resin samples prepared in Application Examples 1 to 3 and Comparative Application Examples 1 to 2 are shown in FIG. DETAILED DESCRIPTION

[0029] The present invention is further described below by way of examples. The following examples are only used to illustrate the present invention, but are not intended to limit the scope of the present invention.

[0030] The raw materials used in the following examples were all purchased directly, wherein the ABS grafted powder and SAN resin were purchased from Jilin Petrochemical Company of China National Petroleum Corporation.

[0031] The present invention discloses a migration-resistant ABS resin lubricant, the structural formula of which is as follows:

[0032]

[0033] In the formula, R is -C n H 2n Straight chain alkyl, n=4-12, for example, n=4, 5, 6, 7, 8, 9, 10, 11 or 12.

[0034] The invention discloses a method for preparing the migration-resistant ABS resin lubricant. The method uses levulinic acid and divalent fatty alcohol as raw materials, obtains levulinic ester through esterification reaction, and then obtains the ABS resin lubricant through ketalization reaction.

[0035] In an embodiment of the present invention, the preparation method specifically comprises the following steps:

[0036] (1) Esterification reaction: levulinic acid, dihydric fatty alcohol, and catalyst are added to a reactor equipped with a reflux device, and then a water-carrying agent is added. After mixing, the temperature is raised to 150-170° C. and refluxed for 8-10 hours. The water generated during the reaction will be azeotropically carried out of the system with the water-carrying agent. When the water level in the water separator no longer rises, the reaction system is naturally cooled to room temperature, and an alkali solution is added to a pH of ≥7. The reaction is carried out at room temperature for 20-60 minutes, and then washed with deionized water until neutral, and filtered to obtain the intermediate product, dihydric alcohol levulinic acid;

[0037] (2) Ketalization reaction: Add the diol levulinate prepared by the esterification reaction and ethylene glycol into a reactor, introduce nitrogen, heat to 100-120° C. and react for 5-8 hours. After the reaction is completed, add solvent extraction, wash with deionized water until neutral, distill the organic phase under reduced pressure, and vacuum dry to obtain ketalized levulinate ester, i.e., the ABS resin lubricant.

[0038] In an embodiment of the present invention, in step (1), the molar ratio of levulinic acid, dihydric fatty alcohol and catalyst is 2:(1-1.5):(0.06-0.1); in step (2), the molar ratio of levulinic acid diol ester and ethylene glycol is 1:(2-2.5).

[0039] In an embodiment of the present invention, in step (1), the water-carrying agent is selected from one or a combination of benzene, toluene or n-hexane; and the amount of the water-carrying agent added is 15 to 18 times the total mass of levulinic acid, dihydric fatty alcohol and catalyst.

[0040] In an embodiment of the present invention, in step (1), the catalyst is selected from one or more of phosphoric acid, sulfuric acid, p-toluenesulfonic acid or sodium bisulfate.

[0041] In an embodiment of the present invention, the dihydric fatty alcohol is selected from one of C6-C12 aliphatic straight-chain diols. Preferably, the dihydric fatty alcohol is selected from at least one of 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol or 1,11-undecanediol.

[0042] In an embodiment of the present invention, in step (1), the alkali solution is one of a sodium carbonate solution, a sodium bicarbonate solution or a sodium hydroxide solution.

[0043] In an embodiment of the present invention, in step (2), the solvent is selected from one of toluene, benzene, dichloromethane or ethyl acetate.

[0044] The invention also discloses application of the migration-resistant ABS resin lubricant in the preparation of ABS plastic products.

[0045] The invention also discloses an ABS resin, which is a modified ABS resin lubricated by the migration-resistant ABS resin lubricant.

[0046] Example 1

[0047] This embodiment provides an ABS resin lubricant, which is ketalized hexanediol levulinate, and its structural formula is as follows:

[0048]

[0049] The preparation method thereof comprises the following steps:

[0050] (1) In a three-necked round-bottom flask equipped with a thermometer, a water separator and a condenser, 10 g of levulinic acid, 5.1 g of hexanediol and 0.54 g of sodium bisulfate were added, and then 200 mL of n-hexane was added as a water-carrying agent. The temperature was raised to 150°C and refluxed until the water level in the water separator no longer rose. After the reaction was completed, the reaction system was naturally cooled to room temperature, and then 5 wt% sodium carbonate solution was added to pH ≥ 7, and the reaction was carried out for 30 minutes; then the mixture was washed with deionized water until neutral, and the intermediate product hexanediol levulinate was obtained by suction filtration.

[0051] (2) Add hexanediol levulinate obtained in step (1) and ethylene glycol in a molar ratio of 1:2 into a three-necked round-bottom flask, introduce nitrogen, heat to 120°C, and react for 8 hours. After the reaction is completed, add ethyl acetate for extraction, wash with deionized water until neutral, distill the organic phase under reduced pressure, and dry under vacuum to obtain ketalized hexanediol levulinate. The infrared spectrum of the product is shown in FIG. Figure 1 shown.

[0052] Example 2

[0053] This embodiment provides an ABS resin lubricant, which is ketalized octanediol levulinate, and its structural formula is as follows:

[0054]

[0055] The preparation method thereof comprises the following steps:

[0056] (1) In a three-necked round-bottom flask equipped with a thermometer, a water separator and a condenser, 10 g of levulinic acid, 6.29 g of 1,8-octanediol, 0.44 g of phosphoric acid, and 200 mL of n-hexane as a water-carrying agent were added, and the temperature was raised to 160° C. for reaction. The reaction was terminated when the water level in the water separator no longer rose. After the reaction system was naturally cooled to room temperature, 5 wt % sodium carbonate solution was added until the pH was ≥ 7, and the reaction was carried out at room temperature for 30 min. The product was washed with deionized water and filtered to obtain the intermediate product levulinic acid octanediol ester.

[0057] (2) The prepared octanediol levulinate and ethylene glycol were added to a three-necked round-bottom flask at a molar ratio of 1:2.1, nitrogen was introduced, and the mixture was heated to 110°C and reacted for 7 hours. After the reaction, ethyl acetate was added for extraction, and the mixture was washed with deionized water until neutral. The organic phase was distilled under reduced pressure and dried under vacuum to obtain ketalized octanediol levulinate. The infrared spectrum of the product is shown in FIG. Figure 1 shown.

[0058] Example 3

[0059] This embodiment provides an ABS resin lubricant, which is ketalized undecanediol levulinate, and its structural formula is as follows:

[0060]

[0061] The preparation method thereof comprises the following steps:

[0062] (1) In a three-necked round-bottom flask equipped with a thermometer, a water separator and a condenser, 10 g of levulinic acid, 8.1 g of 1,11-undecanediol, and 0.45 g of phosphoric acid were added, and 200 mL of toluene was added as a water-carrying agent. The temperature was raised to 160° C. for reaction, and reflux reaction was performed until the liquid level of water in the water separator no longer rose, and the reaction was terminated; after the reaction system was naturally cooled to room temperature, 5 wt % sodium carbonate solution was added to pH ≥ 7, and the reaction was carried out at room temperature for 30 min, and the intermediate product, levulinic acid undecanediol ester, was obtained by suction filtration.

[0063] (2) The prepared levulinic acid undecanediol ester and ethylene glycol were added to a three-necked flask at a molar ratio of 1:2.2, nitrogen was introduced, and the mixture was heated to 115°C and reacted for 8 hours. After the reaction, ethyl acetate was added for extraction, and the mixture was washed with deionized water until neutral. The organic phase was distilled under reduced pressure and dried under vacuum to obtain ketalized levulinic acid undecanediol ester. The infrared spectrum of the product is shown in FIG. Figure 1 shown.

[0064] like Figure 1 As shown, from top to bottom are the infrared spectra of ketalized hexanediol levulinate, ketalized octanediol levulinate and ketalized undecanediol levulinate prepared in Examples 1 to 3. Figure 1 Medium, 2850~2919cm -1 The signal peaks are the vibration peaks of methyl and methylene, 1727cm -1 The vibration peak of the carbonyl group in levulinic acid was not observed, which indicated that the ketal levulinic acid ester was successfully synthesized.

[0065] Application Example 1

[0066] 1 g of the ABS resin lubricant prepared in Example 1, 250 g of ABS grafted powder (PB-g-SAN, PB content of 60%), 750 g of SAN resin and 2 g of antioxidant 618 were blended by a twin-screw extruder at a melt temperature of 200° C. and a screw speed of 200 rpm to prepare a ketalized levulinic ester-modified ABS resin.

[0067] Application Examples 2-3

[0068] Compared with Application Example 1, the only difference is that the ABS resin lubricant in Application Example 1 is replaced by the ABS resin lubricants prepared in Examples 2 and 3, respectively, to prepare ketalized levulinic ester-modified ABS resin.

[0069] Comparative application example 1

[0070] Compared with Application Example 1, the only difference is that no ABS resin lubricant is added.

[0071] Comparative Application Example 2

[0072] Compared with Application Example 1, the only difference is that the ABS resin lubricant in Application Example 1 is replaced by the lubricant ethylene bis stearamide (EBA) in the prior art.

[0073] Performance Testing

[0074] The following performance tests were performed on the ABS resins prepared in the above Application Examples 1 to 3 and Comparative Application Examples 1 to 2.

[0075] (1) Melt flow rate (MFR) test

[0076] According to the test standard of GB / T 3682-2000 "Determination of melt mass flow rate and melt volume flow rate of thermoplastics", the melt flow rate (MFR) of ABS resin samples prepared in the application example and the comparative application example was tested respectively. The results are as follows: Figure 2 As shown. Figure 2 The test results show that the MFR of the ABS resin sample lubricated with the ketalized levulinate lubricant is significantly increased compared with the ABS resin sample of Comparative Application Example 1 and the ABS resin sample lubricated with EBA of Comparative Application Example 2. This shows that the ketalized levulinate ABS resin lubricant has good compatibility with ABS and can greatly improve the melt fluidity of the ABS sample.

[0077] (2) Migration resistance test

[0078] The test method is: soak the ABS resin samples prepared in Application Examples 1 to 3 and Comparative Application Examples 1 to 2 in n-hexane at 23±2°C and 50±5% relative humidity for 24 hours. Take out and wipe clean, and dry in a 50°C oven for 24 hours. Record the mass of the sample before and after the test, and calculate the mass loss rate.

[0079] The mass loss curves of 5 groups of ABS resin samples are as follows: Figure 3 As shown. Figure 3 It can be seen that for the mass loss rate in n-hexane, the ABS sample with ketal levulinate lubricant is significantly lower than that of the ABS sample with EBA lubrication, indicating that the ketal levulinate ABS resin lubricant has a stronger migration resistance and is better than the EBA lubricant.

[0080] (3) Tensile performance test

[0081] The test method is: according to GB / T 1040.1-2018 "Determination of Tensile Properties of Plastics", the tensile properties are tested at a test temperature of 23±2°C and a tensile rate of 5mm / min.

[0082] Application Examples and Comparative Examples The stress-strain curves of 5 groups of ABS resin samples in the application example are as follows: Figure 4 As shown. Figure 4 It can be seen that the elongation at break of the ABS sample with ketal levulinate lubricant is significantly higher than that of the ABS sample with EBA lubrication, indicating that the ketal levulinate ABS resin lubricant can improve the tensile properties of ABS better than the EBA lubricant.

[0083] (4) The glass transition temperatures of the ABS samples tested by the dynamic thermomechanical analyzer are shown in Table 1. Application Examples and Comparative Examples The glass transition temperatures of 5 groups of ABS resin samples in the application examples are shown in Table 1 below.

[0084] Table 1 Glass transition temperature

[0085]

[0086]

[0087] As can be seen from Table 1, the glass transition temperature of the ABS sample with ketal levulinate lubricant is significantly lower than that of the ABS sample with EBA lubricant, indicating that the ketal levulinate ABS resin lubricant has better compatibility with ABS resin than EBA lubricant.

[0088] The above embodiments are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with the technology to understand the content of the present invention and implement it accordingly, and they cannot be used to limit the protection scope of the present invention. Any equivalent transformation or modification made according to the spirit of the present invention should be included in the protection scope of the present invention.

Claims

1. A migration-resistant ABS resin lubricant, characterized in that: The structural formula is as follows: In the formula, R is -C n H 2n Straight chain alkyl, n=4-12.

2. A method for preparing the migration-resistant ABS resin lubricant according to claim 1, characterized in that: Levulinic acid and divalent fatty alcohol are used as raw materials, levulinic acid ester is obtained through esterification reaction, and then through ketalization reaction, the ABS resin lubricant is obtained.

3. The method for preparing the migration-resistant ABS resin lubricant according to claim 2, characterized in that: The specific steps include: (1) Esterification reaction: levulinic acid, dihydric fatty alcohol, and catalyst are added to a reactor equipped with a reflux device, and then a water-carrying agent is added. After mixing, the temperature is raised to 150-170° C. and refluxed for 8-10 hours. The water generated during the reaction will be azeotropically carried out of the system with the water-carrying agent. When the water level in the water separator no longer rises, the reaction system is naturally cooled to room temperature, and an alkali solution is added to a pH of ≥7. The reaction is carried out at room temperature for 20-60 minutes, and then washed with deionized water until neutral, and filtered to obtain the intermediate product, dihydric alcohol levulinic acid; (2) Ketalization reaction: Add the diol levulinate prepared by the esterification reaction and ethylene glycol into a reactor, introduce nitrogen, heat to 100-120° C. and react for 5-8 hours. After the reaction is completed, add solvent extraction, wash with deionized water until neutral, distill the organic phase under reduced pressure, and vacuum dry to obtain ketalized levulinate ester, i.e., the ABS resin lubricant.

4. The method for preparing the migration-resistant ABS resin lubricant according to claim 3, characterized in that: In step (1), the molar ratio of levulinic acid, dihydric fatty alcohol and catalyst is 2:(1-1.5):(0.06-0.1); in step (2), the molar ratio of dihydric alcohol levulinic acid ester and ethylene glycol is 1:(2-2.5).

5. The method for preparing the migration-resistant ABS resin lubricant according to claim 3, characterized in that: In step (1), the water-carrying agent is selected from one or a combination of benzene, toluene or n-hexane; the amount of the water-carrying agent added is 15 to 18 times the total mass of levulinic acid, divalent fatty alcohol and catalyst.

6. The method for preparing the migration-resistant ABS resin lubricant according to claim 3, characterized in that: In step (1), the catalyst is selected from one or more of phosphoric acid, sulfuric acid, p-toluenesulfonic acid or sodium bisulfate.

7. The method for preparing the migration-resistant ABS resin lubricant according to claim 2, characterized in that: The dihydric fatty alcohol is selected from at least one of C6-C12 aliphatic straight-chain dihydric alcohols.

8. The method for preparing the migration-resistant ABS resin lubricant according to claim 3, characterized in that: In step (2), the solvent is selected from one of toluene, benzene, dichloromethane or ethyl acetate.

9. Use of the migration-resistant ABS resin lubricant as claimed in claim 1 in the preparation of ABS plastic products.

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