An oil shale semi-coke-based masterbatch, its preparation method and application

Abstract

The present invention discloses an oil shale semi-coke-based masterbatch, which is mainly composed of modified oil shale semi-coke and a resin carrier. The modified oil shale semi-coke is oil shale semi-coke modified by N,N-diethylphosphoramidite di-tert-butyl ester and / or 2-methacryloyloxyethyl phosphorylcholine. Compared with the existing oil shale ash-filled masterbatch, the modified oil shale semi-coke of the present invention can improve the mechanical properties and flame retardancy of resin products while increasing the filling amount.

Description

Technical Field

[0001] The present invention belongs to the field of functional resin masterbatches, and particularly relates to an oil shale semi-coke-based masterbatch. Background Art

[0002] Oil shale semi-coke is a by-product after extracting shale oil from oil shale ore. Although it can be burned, it has low calorific value and high transportation cost, which poses certain restrictions. Xiao Qihai disclosed in "Research and Development of Oil Shale Ash Filled Masterbatch" (Plastics Science and Technology, No. 2, 1995 (Total No. 106), pp. 5-8) that compared with the traditional filler CaCO3, the filled masterbatch made from oil shale waste residue has the characteristics of good fluidity and aging resistance, and can significantly reduce the deterioration of the tensile strength and impact strength of plastic products. However, with the increase of the filling amount, the mechanical properties of the products decline rapidly. Summary of the Invention

[0003] Based on the above deficiencies of the prior art, the present invention provides an improved oil shale semi-coke-based masterbatch.

[0004] An oil shale semi-coke-based masterbatch mainly consists of modified oil shale semi-coke and a resin carrier, and is characterized in that: the modified oil shale semi-coke is oil shale semi-coke modified by N, N-diethylphosphoramidite di-tert-butyl ester and / or 2-methacryloyloxyethyl phosphorylcholine.

[0005] Preferably, the content of N, N-diethylphosphoramidite di-tert-butyl ester and / or 2-methacryloyloxyethyl phosphorylcholine is 1% - 5% of the mass of the oil shale semi-coke.

[0006] More preferably, the modified oil shale semi-coke is obtained by mechanochemical modification.

[0007] Preferably, the mass percentage content of the modified oil shale semi-coke in the oil shale semi-coke-based masterbatch is 65% - 80%.

[0008] Preferably, the resin carrier is polybutylene terephthalate / adipate resin.

[0009] More preferably, the polybutylene terephthalate / adipate resin is modified by dimethyl-2-epoxyethyl phosphate.

[0010] More preferably, the temperature for modifying the polybutylene terephthalate / adipate resin with dimethyl-2-epoxyethyl phosphate is 110 - 130 °C.

[0011] More preferably, the dosage of dimethyl-2-epoxyethyl phosphate is 3% - 7% of the mass of the polybutylene terephthalate / adipate resin.

[0012] The preparation method of the above oil shale semi-coke-based masterbatch includes:

[0013] (1) High-speed stirring of N,N-diethyl phosphoramidite di-tert-butyl ester and / or 2-methacryloyloxyethyl phosphorylcholine with oil shale semicoke to obtain modified oil shale semicoke;

[0014] (2) Mixing and kneading the modified oil shale semicoke with a resin carrier to obtain the oil shale semicoke-based masterbatch.

[0015] Preferably, the time of high-speed stirring in step (1) is 10 - 50 minutes.

[0016] Preferably, before high-speed stirring in step (1), the particle size of the oil shale semicoke is not less than 5000 mesh.

[0017] Preferably, the temperature of kneading in step (2) is 150 - 170 °C and the time is 5 - 10 minutes.

[0018] A modified oil shale semicoke, which is an oil shale semicoke modified by N,N-diethyl phosphoramidite di-tert-butyl ester and / or 2-methacryloyloxyethyl phosphorylcholine.

[0019] Preferably, the content of N,N-diethyl phosphoramidite di-tert-butyl ester and / or 2-methacryloyloxyethyl phosphorylcholine is 1% - 5% of the mass of the oil shale semicoke.

[0020] More preferably, the modified oil shale semicoke is obtained by mechanochemical modification.

[0021] Application of the above-mentioned modified oil shale semicoke as a filler in the preparation of resin masterbatch or resin products.

[0022] Preferably, the resin is a flame-retardant resin.

[0023] Compared with the existing oil shale ash-filled masterbatch mentioned above, the modified oil shale semicoke of the present invention can improve the mechanical properties and flame-retardant properties of resin products while increasing the filling amount. Description of the Drawings

[0024] Figure 1 It is the infrared spectrum of the oil shale semicoke modified by N,N-diethyl phosphoramidite di-tert-butyl ester and 2-methacryloyloxyethyl phosphorylcholine. Among them, C 12 H 28 NO2P is N,N-diethyl phosphoramidite di-tert-butyl ester; C 11 H 22 NO6P is 2-methacryloyloxyethyl phosphorylcholine, SC is the oil shale semicoke before modification, and Mixture is the modified oil shale semicoke. Detailed Embodiments

[0025] Poly(butylene adipate-co-terephthalate) (PBAT) belongs to thermoplastic biodegradable plastics, combining the characteristics of PBA and PBT. It has good ductility and elongation at break, as well as good heat resistance and impact performance. In addition, it also has excellent biodegradability and is one of the most popular and best-applied biodegradable materials in the research of biodegradable plastics. Under the background of "dual carbon", it is widely used in fields such as packaging and film materials. Taking PBAT as an example, the technical solution of the present invention will be further described in detail below.

[0026] Dimethyl 2-oxiranylphosphate: , English name: Dimethyl 2-oxiranylphosphate, CAS number: 1071080-01-7, the synthesis method refers to the reference: Adam, Wa., Saha-Moeller, C. R., Zhao, C.-G. Dioxirane epoxidation of alkenes. Org. React. 2002, 61, 220-516.

[0027] (I) Preparation of modified oil shale semicoke

[0028] 1. Grind the oil shale semicoke into powder, and the particle size of the powder is not less than 5000 mesh, denoted as BJ-0.

[0029] 2. Mix N,N-diethylphosphoramidite di-tert-butyl ester (CAS number: 117924-33-1) and 2-methacryloyloxyethyl phosphorylcholine (CAS number: 67881-98-5) in a mass ratio of 1:1 to 1:5 to prepare a composite modifier, denoted as OR-1.

[0030] 3. Dry BJ-0 at 110 °C for 2 hours, then add OR-1 to it and stir at high speed for 10 - 50 minutes. The addition amount of OR-1 is 1% - 5% (mass ratio) of BJ-0, and the obtained product is denoted as BJ-1.

[0031] The infrared spectrum characterization of BJ-1 is shown in Figure 1 . It can be seen from the curves in the figure that the characteristic peaks of N,N-diethylphosphoramidite di-tert-butyl ester and 2-methacryloyloxyethyl phosphorylcholine (see the places circled by squares, triangles, and circles in the figure) all appear in the modified oil shale semicoke, indicating that these two organic compounds are successfully grafted onto the surface of the oil shale semicoke powder under the action of mechanical force.

[0032] BJ-2: Use the same amount of coupling agent KH-550 to replace OR-1, and the other preparation conditions of the modified oil shale semicoke are the same as those of BJ-1.

[0033] BJ-3: The oil shale semicoke is modified solely with di-tert-butyl N,N-diethylphosphoramidite in the same amount as OR-1, and other preparation conditions are the same as BJ-1.

[0034] BJ-4: The oil shale semicoke is modified solely with 2-methacryloyloxyethyl phosphorylcholine in the same amount as OR-1, and other preparation conditions are the same as BJ-1.

[0035] (II) Preparation of oil shale semicoke-based masterbatch

[0036] 1. PBAT is mixed with 2-(2-oxiranylmethoxy)dimethyl phosphate and granulated by single-screw extrusion at 120 °C. The amount of 2-(2-oxiranylmethoxy)dimethyl phosphate accounts for 3% - 7% of the mass of PBAT, and PBAT-1 is prepared.

[0037] 2. PBAT-1 is mixed with BJ-1, and after high-speed stirring, it is kneaded in a kneader at a temperature of 150 - 170 °C for 5 - 10 minutes. The mass percentage of PBAT-1 is 20% - 35%, and the mass percentage of BJ-1 is 80% - 65%. After kneading, it enters a single-screw granulator for granulation, and the oil shale semicoke-based masterbatch, denoted as PBAT&BJ-1, is obtained.

[0038] Replacing BJ-1 with BJ-2, BJ-3, and BJ-4 respectively, and other preparation processes and conditions are the same as PBAT&BJ-1, to obtain PBAT&BJ-2, PBAT&BJ-3, and PBAT&BJ-4 masterbatches.

[0039] (III) Applications

[0040] Masterbatches: PBAT&BJ-1 (BJ-1 content is 75%), PBAT&BJ-2 (BJ-2 content is 75%), PBAT&BJ-3 (BJ-3 content is 75%), PBAT&BJ-4 (BJ-4 content is 75%)

[0041] 1. PBAT is mixed with PBAT&BJ-1 and granulated by a twin-screw extruder. The temperatures of each section of the twin-screw extruder are set as follows: the first section: 165 °C, the second section: 170 °C, the third section: 175 °C, the fourth section: 175 °C. The mixing mass ratio of PBAT to PBAT&BJ-1 is 2:3, and granulation is carried out. The product is denoted as PBAT-BJ-1.

[0042] 2. PBAT-BJ-1 is added to an injection molding machine to be injection molded into standard test samples respectively. The injection molding temperature is set at 165 °C, the mold temperature is 50 °C, and the injection molding pressure is set at 0.6 MPa.

[0043] 3. Replace PBAT&BJ-1 with PBAT&BJ-2, PBAT&BJ-3, and PBAT&BJ-4, and repeat the above steps to obtain PBAT-BJ-2, PBAT-BJ-3, and PBAT-BJ-4 samples in sequence.

[0044] For the PBAT-BJ-5 sample, direct filling is adopted, that is, replace PBAT&BJ-1 in Step 1 with BJ-1 and dimethyl phosphate-2-epoxyethyl ester. The mass percentage dosage of BJ-1 is 45%, and the extrusion process conditions and injection molding process conditions are the same as those of PBAT-BJ-1.

[0045] The preparation of the PBAT-BJ-6 sample is the same as that of the PBAT-BJ-1 sample, except that dimethyl phosphate-2-epoxyethyl ester is not added when preparing the oil shale semicoke-based masterbatch.

[0046] Control sample: PBAT-BJ-0, whose preparation is the same as that of the PBAT-BJ-1 sample, except that when preparing the oil shale semicoke-based masterbatch, the same amount of unmodified oil shale semicoke is used to replace BJ-1.

[0047] The performance test results of each sample are shown in Table 1.

[0048] Tensile property: Test according to GB / T 1040-2018, and the tensile rate is 20 mm / min.

[0049] Impact property: Test according to GB / T 1843-2008, and the pendulum impact energy is 2.75 J.

[0050] LOI test: Determine the oxygen index of the sample with reference to GB / T 2406-1993, and take the average value after parallel determination of each sample 5 times.

[0051] UL-94 test: Determine the combustion grade of the composite material sample with reference to GB / T 2408-2008, and take the average value after parallel determination of each sample 5 times.

[0052] Cone calorimeter test: Test according to the standard ISO 5660-1-2015. The sample size is 100 mm×100 mm×2 mm, and the irradiation intensity is 50 kW / m 2 .

[0053] Table 1 Performance test data of PBAT plastic products after filling and modifying oil shale semicoke

[0054]

[0055] As can be seen from PBAT-BJ-0 and PBAT, the unmodified oil shale semicoke is filled in the form of a masterbatch. When the filling amount of the unmodified oil shale semicoke in the plastic product reaches 45%, the flame retardant performance of the product is improved, but the mechanical properties decrease significantly, which is similar to that reported in the prior art.

[0056] From the comparison of PBAT-BJ-1, PBAT-BJ-3, PBAT-BJ-4, PBAT-BJ-2 and PBAT-BJ-0, it can be seen that by using the modified oil shale semicoke, both the flame retardant performance and the mechanical properties of the plastic product are significantly improved. Compared with the fact that the mechanical properties of PBAT still decrease to a certain extent after being filled with the oil shale semicoke modified by silane coupling agent KH-550, the oil shale semicoke modified by N, N-diethylphosphoramidite di-tert-butyl ester and 2-methacryloyloxyethyl phosphorylcholine can improve the mechanical properties of PBAT, avoid the deterioration of the mechanical properties, and also improve the various indexes of the flame retardant performance.

[0057] From PBAT-BJ-5 and PBAT-BJ-1, it can be seen that making the modified oil shale semicoke of the present invention into a filled masterbatch and then filling it into the plastic product has a better use effect than directly filling the modified oil shale semicoke into the plastic product. And from the comparison of PBAT-BJ-2 and PBAT-BJ-0, it can be seen that even if the modified oil shale semicoke of the present invention is directly filled into the plastic product, the mechanical properties of the product can reach the effect of filling the KH-550 modified oil shale semicoke into the plastic product in the form of a masterbatch, and is significantly better than the plastic product prepared by using the unmodified oil shale semicoke filled masterbatch.

[0058] The performance test results of PBAT-BJ-6 show that adding 2-epoxyethyl dimethyl phosphate can effectively improve the mechanical properties and flame retardant performance of PBAT.

[0059] Example 1

[0060] The oil shale semicoke is pulverized, and the particle size of the powder is not less than 5000 mesh. Then N, N-diethylphosphoramidite di-tert-butyl ester is added thereto and stirred at high speed for 20 minutes. The addition amount of N, N-diethylphosphoramidite di-tert-butyl ester is 3% (mass ratio) of the oil shale semicoke to obtain the modified oil shale semicoke.

[0061] Example 2

[0062] The oil shale semicoke is pulverized, and the particle size of the powder is not less than 5000 mesh. Then 2-methacryloyloxyethyl phosphorylcholine is added thereto and stirred at high speed for 20 minutes. The addition amount of 2-methacryloyloxyethyl phosphorylcholine is 3% (mass ratio) of the oil shale semicoke to obtain the modified oil shale semicoke.

[0063] Example 3

[0064] 1. Pulverize the oil shale semicoke, with the particle size of the powder being not less than 5000 mesh, and reserve it for later use.

[0065] 2. Mix N, N - diethylphosphoramidite di - tert - butyl ester and 2 - methacryloyloxyethyl phosphorylcholine in a mass ratio of 1:1 to prepare a composite modifier.

[0066] 3. Dry the oil shale semicoke at 110 °C for 2 hours, then add the composite modifier into it and stir at high speed for 10 minutes. The addition amount of the composite modifier is 1% (mass ratio) of the oil shale semicoke to obtain modified oil shale semicoke.

[0067] Example 4

[0068] 1. Pulverize the oil shale semicoke, with the particle size of the powder being not less than 5000 mesh, and reserve it for later use.

[0069] 2. Mix N, N - diethylphosphoramidite di - tert - butyl ester and 2 - methacryloyloxyethyl phosphorylcholine in a mass ratio of 1:3 to prepare a composite modifier.

[0070] 3. Dry the oil shale semicoke at 110 °C for 2 hours, then add the composite modifier into it and stir at high speed for 30 minutes. The addition amount of the composite modifier is 3% (mass ratio) of the oil shale semicoke to obtain modified oil shale semicoke.

[0071] Example 5

[0072] 1. Pulverize the oil shale semicoke, with the particle size of the powder being not less than 5000 mesh, and reserve it for later use.

[0073] 2. Mix N, N - diethylphosphoramidite di - tert - butyl ester and 2 - methacryloyloxyethyl phosphorylcholine in a mass ratio of 1:5 to prepare a composite modifier.

[0074] 3. Dry the oil shale semicoke at 110 °C for 2 hours, then add the composite modifier into it and stir at high speed for 30 minutes. The addition amount of the composite modifier is 5% (mass ratio) of the oil shale semicoke to obtain modified oil shale semicoke.

[0075] Example 6

[0076] 1. Pulverize the oil shale semicoke, with the particle size of the powder being not less than 5000 mesh, and reserve it for later use.

[0077] 2. Mix N, N - diethylphosphoramidite di - tert - butyl ester and 2 - methacryloyloxyethyl phosphorylcholine in a mass ratio of 1:1 to prepare a composite modifier.

[0078] 3. Dry the oil shale semicoke at 110 °C for 2 hours, then add the composite modifier to it and stir at high speed for 30 minutes. The addition amount of the composite modifier is 4% (mass ratio) of the oil shale semicoke to obtain the modified oil shale semicoke.

[0079] Example 7

[0080] 1. Pulverize the oil shale semicoke, and the particle size of the powder is not less than 5000 mesh for standby.

[0081] 2. Mix N, N - diethylphosphoramidite di - tert - butyl ester and 2 - methacryloyloxyethyl phosphorylcholine according to a mass ratio of 1:2 to prepare a composite modifier.

[0082] 3. Dry the oil shale semicoke at 110 °C for 2 hours, then add the composite modifier to it and stir at high speed for 50 minutes. The addition amount of the composite modifier is 5% (mass ratio) of the oil shale semicoke to obtain the modified oil shale semicoke.

[0083] Example 8

[0084] 1. Mix PBAT and 2 - epoxyethyl dimethyl phosphate, and 2 - epoxyethyl dimethyl phosphate accounts for 3% of the mass of PBAT. Extrude and pelletize with a single - screw extruder at 120 °C to prepare PBAT - 1.

[0085] 2. Mix PBAT - 1 with the modified oil shale semicoke of Example 1, stir at high speed and then place it in a mixer for mixing. The temperature is 150 - 170 °C, and mix for 5 - 10 minutes. The mass percentage of PBAT - 1 is 20%, and the mass percentage of the modified oil shale semicoke is 80%. After mixing, enter a single - screw pelletizer for pelletizing to obtain the oil shale semicoke - based masterbatch.

[0086] Example 9

[0087] 1. Mix PBAT and 2 - epoxyethyl dimethyl phosphate, and 2 - epoxyethyl dimethyl phosphate accounts for 4% of the mass of PBAT. Extrude and pelletize with a single - screw extruder at 120 °C to prepare PBAT - 1.

[0088] 2. Mix PBAT - 1 with the modified oil shale semicoke of Example 5, stir at high speed and then place it in a mixer for mixing. The temperature is 150 - 170 °C, and mix for 5 - 10 minutes. The mass percentage of PBAT - 1 is 20%, and the mass percentage of the modified oil shale semicoke is 80%. After mixing, enter a single - screw pelletizer for pelletizing to obtain the oil shale semicoke - based masterbatch.

[0089] Example 10

[0090] 1. Mix PBAT with 2-(2-methoxyethoxy)ethyl phosphate, where 2-(2-methoxyethoxy)ethyl phosphate accounts for 5% of the mass of PBAT, and granulate by single-screw extrusion at 120 °C to obtain PBAT-1.

[0091] 2. Mix PBAT-1 with the modified oil shale semicoke of Example 6, stir at high speed and then conduct internal mixing in an internal mixer at a temperature of 150 - 170 °C for 5 - 10 minutes. The mass percentage of PBAT-1 is 35%, and the mass percentage of the modified oil shale semicoke is 65%. After internal mixing, granulate in a single-screw granulator to obtain the oil shale semicoke-based masterbatch.

[0092] Example 11

[0093] 1. Mix PBAT with 2-(2-methoxyethoxy)ethyl phosphate, where 2-(2-methoxyethoxy)ethyl phosphate accounts for 7% of the mass of PBAT, and granulate by single-screw extrusion at 120 °C to obtain PBAT-1.

[0094] 2. Mix PBAT-1 with the modified oil shale semicoke of Example 7, stir at high speed and then conduct internal mixing in an internal mixer at a temperature of 150 - 170 °C for 5 - 10 minutes. The mass percentage of PBAT-1 is 30%, and the mass percentage of the modified oil shale semicoke is 70%. After internal mixing, granulate in a single-screw granulator to obtain the oil shale semicoke-based masterbatch.

[0095] Example 12

[0096] Mix PBAT with the modified oil shale semicoke of Example 5, stir at high speed and then conduct internal mixing in an internal mixer at a temperature of 150 - 170 °C for 5 - 10 minutes. The mass percentage of PBAT is 30%, and the mass percentage of the modified oil shale semicoke is 70%. After internal mixing, granulate in a single-screw granulator to obtain the oil shale semicoke-based masterbatch.

[0097] Finally, it should be noted that the above are only the preferred embodiments of the present invention and are not used to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, for those skilled in the art, they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements for some of the technical features. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. An oil shale semi-coke-based masterbatch, mainly composed of modified oil shale semi-coke and a resin carrier, characterized in that: The modified oil shale semicoke is the oil shale semicoke modified by N,N - diethylphosphoramidite di - tert - butyl ester and / or 2 - methacryloyloxyethyl phosphorylcholine.

2. The oil shale semi-coke-based masterbatch according to claim 1, characterized in that: The content of N,N - diethylphosphoramidite di - tert - butyl ester and / or 2 - methacryloyloxyethyl phosphorylcholine is 1% - 5% of the mass of the oil shale semicoke.

3. The oil shale semi-coke-based masterbatch according to claim 2, characterized in that: The mass ratio of N,N - diethylphosphoramidite di - tert - butyl ester to 2 - methacryloyloxyethyl phosphorylcholine is 1:1 - 1:

5.

4. The oil shale semi-coke-based masterbatch according to claim 2, characterized in that: The modified oil shale semicoke is obtained by mechanochemical modification.

5. The oil shale semi-coke-based masterbatch according to claim 1, characterized in that: The mass percentage content of the modified oil shale semicoke in the oil shale semicoke - based masterbatch is 65% - 80%.

6. The oil shale semi-coke-based masterbatch according to claim 1, characterized in that: The resin carrier is poly(butylene terephthalate / adipate) resin.

7. The oil shale semi-coke-based masterbatch according to claim 6, characterized in that: The poly(butylene terephthalate / adipate) resin is modified by 2 - epoxyethyl dimethyl phosphate.

8. The oil shale semi-coke-based masterbatch according to claim 7, characterized in that: The temperature of the modification treatment is 110 - 130 °C.

9. The oil shale semi-coke-based masterbatch according to claim 7, characterized in that: The dosage of 2 - epoxyethyl dimethyl phosphate is 3% - 7% of the mass of the poly(butylene terephthalate / adipate) resin.

10. A method for preparing the oil shale semi-coke-based masterbatch according to claim 1, comprising: (1) High - speed stirring of N,N - diethylphosphoramidite di - tert - butyl ester and / or 2 - methacryloyloxyethyl phosphorylcholine with the oil shale semicoke to obtain the modified oil shale semicoke; (2) Mixing and internal - mixing the modified oil shale semicoke with the resin carrier to obtain the oil shale semicoke - based masterbatch.

11. The preparation method according to claim 10, characterized in that: The time of high - speed stirring in step (1) is 10 - 50 minutes.

12. The preparation method according to claim 10, characterized in that: Before high - speed stirring in step (1), the particle size of the oil shale semicoke is not less than 5000 mesh.

13. The preparation method according to claim 10, characterized in that: The temperature of internal - mixing in step (2) is 150 - 170 °C and the time is 5 - 10 minutes.

14. A modified oil shale semi-coke, characterized in that: The modified oil shale semicoke is the oil shale semicoke modified by N,N - diethylphosphoramidite di - tert - butyl ester and / or 2 - methacryloyloxyethyl phosphorylcholine.

15. The modified oil shale semi-coke according to claim 14, characterized in that: The content of N,N - diethylphosphoramidite di - tert - butyl ester and / or 2 - methacryloyloxyethyl phosphorylcholine is 1% - 5% of the mass of the oil shale semicoke.

16. The modified oil shale semi-coke according to claim 15, characterized in that: The mass ratio of N,N - diethylphosphoramidite di - tert - butyl ester to 2 - methacryloyloxyethyl phosphorylcholine is 1:1 - 1:

5.

17. The modified oil shale semi-coke according to claim 15, characterized in that: The modified oil shale semicoke is obtained by mechanochemical modification.

18. Use of the modified oil shale semi-coke according to any one of claims 14 to 17 as a filler in the preparation of a resin masterbatch or a resin product.

19. The application according to claim 18, wherein: The resin is a flame - retardant resin.

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