Polyolefin composition and preparation method thereof

Abstract

The present application discloses a polyolefin composition and a preparation method thereof, and relates to the technical field of polymer materials. The polyolefin composition comprises polypropylene and a modifier, and the structural formula of the modifier is shown in the following formula:; wherein R is selected from. The polyolefin composition provided by the present application is a polypropylene molecular chain grafted with a dendritic molecule modifier rich in amide groups and terminal amino groups through molecular chemical structure design. Due to the high polarity and hydrophilicity of the amide groups and terminal amino groups in the modifier, the polyolefin composition has a strong force on various polar surfaces, and after the polyolefin composition is cured, the branches of the dendritic molecule modifier are interspersed with each other, and the amide groups and amino groups can form strong intermolecular hydrogen bonds. The polyolefin composition has a large cohesive energy and excellent strength after curing.

Description

Technical Field

[0001] The present application relates to the field of polymer technology, and in particular to a polyolefin composition and a preparation method thereof. Background Art

[0002] Polyolefins have been widely used in many fields such as automobile manufacturing, building construction and food packaging due to their excellent heat resistance, outstanding chemical corrosion resistance and relatively low cost-effectiveness.

[0003] However, the inherent properties of polyolefin materials, such as low surface energy, weak polarity and poor wetting ability, make this type of adhesive mainly show good adhesion to non-polar surfaces, especially polyolefin materials themselves. In addition, the solubility of polyolefin materials is extremely limited, mainly limited to harmful organic solvents such as toluene and xylene. These factors significantly restrict its practical application in a wider range of scenarios. Summary of the invention

[0004] In view of this, the present application provides a polyolefin composition and a preparation method thereof.

[0005] The embodiment of the present application is implemented in this way. The embodiment of the present application provides a polyolefin composition, wherein the polyolefin composition comprises polypropylene and a modifier, and the structural formula of the modifier is shown as follows:

[0006] ; wherein R is selected from .

[0007] Optionally, in some embodiments of the present application, the mass ratio of the polypropylene to the modifier is (70-90): (10-30); and / or

[0008] In the polyolefin composition, the polypropylene and the modifier are connected via a covalent bond.

[0009] Optionally, in some embodiments of the present application, the polyolefin composition further comprises a grafting initiator; and / or

[0010] The polyolefin composition further comprises an antioxidant; and / or

[0011] The polyolefin composition also includes water.

[0012] Optionally, in some embodiments of the present application, the grafting initiator comprises a peroxide, and the peroxide is selected from one or more of diacetyl peroxide, diisopropylbenzene peroxide, and benzoyl peroxide; and / or

[0013] The mass ratio of the polypropylene to the grafting initiator is (70-90): (0.1-1); and / or

[0014] The antioxidant is selected from one or more of antioxidant AO-1010, antioxidant 1010, and antioxidant 412S; and / or

[0015] The mass ratio of the polypropylene to the antioxidant is (70-90): (0.1-1); and / or

[0016] The solid content of the polyolefin composition is 10 wt % to 20 wt %.

[0017] The present invention also provides a method for preparing a polyolefin composition, comprising the following steps:

[0018] Provide polypropylene and a modifier, wherein the structural formula of the modifier is as shown below:

[0019] ; wherein R is selected from ;

[0020] The polypropylene and the modifier are mixed and reacted to obtain a polyolefin composition.

[0021] Optionally, in some embodiments of the present application, the method for preparing the modifier comprises the following steps:

[0022] Providing allylamine, a first methyl acrylate and a solvent, mixing and reacting them to obtain a first intermediate product;

[0023] Adding the first ethylenediamine to react to obtain a second intermediate product;

[0024] adding a second methyl acrylate, reacting to obtain a third intermediate product;

[0025] Adding a second ethylenediamine to react to obtain a fourth intermediate product;

[0026] adding a third methyl acrylate, reacting to obtain a fifth intermediate product;

[0027] A third ethylenediamine is added to react to obtain a modifier.

[0028] Optionally, in some embodiments of the present application, the solvent is selected from one or more of methanol, ethanol, propylene glycol, butanol, trimethoxymethanol, tetrahydrofuran, acetone, acetonitrile, N,N-dimethylformamide, and dimethyl sulfoxide; and / or

[0029] After the allylamine, the first methyl acrylate and the solvent are mixed, the molar concentration of the allylamine is 0.1 mol / L to 1 mol / L; and / or

[0030] After the allylamine, the first methyl acrylate and the solvent are mixed, the molar concentration of the first methyl acrylate is 0.2 mol / L to 5 mol / L; and / or

[0031] The molar ratio of the allylamine to the first methyl acrylate is 1:(2-5); and / or

[0032] The molar ratio of the first intermediate product to the first ethylenediamine is 1:(2-5); and / or

[0033] The molar ratio of the second intermediate product to the second methyl acrylate is 1:(4-8); and / or

[0034] The molar ratio of the third intermediate product to the second ethylenediamine is 1:(4-8); and / or

[0035] The molar ratio of the fourth intermediate product to the third methyl acrylate is 1:(8-12); and / or

[0036] The molar ratio of the fifth intermediate product to the third ethylenediamine is 1:(8-12); and / or

[0037] The adding of the first ethylenediamine reaction further comprises adding a first catalyst, wherein the first catalyst is selected from sodium methoxide; and / or

[0038] The adding of the second ethylenediamine reaction further comprises adding a second catalyst, wherein the second catalyst is selected from sodium methoxide; and / or

[0039] The adding of the third ethylenediamine reaction further comprises adding a third catalyst, and the third catalyst is selected from sodium methoxide.

[0040] Optionally, in some embodiments of the present application, the temperature for reacting the allylamine and the first methyl acrylate is 20° C. to 40° C., and the reaction time is 8 h to 20 h; and / or

[0041] The reaction temperature of the first intermediate product and the first ethylenediamine is 40° C. to 60° C., and the reaction time is 8 h to 20 h; and / or

[0042] The temperature of the reaction of the second intermediate product and the second methyl acrylate is 20-40° C., and the reaction time is 8-20 hours; and / or

[0043] The temperature of the reaction of the third intermediate product and the second ethylenediamine is 40° C. to 60° C., and the reaction time is 8 h to 20 h; and / or

[0044] The temperature of the reaction of the fourth intermediate product and the third methyl acrylate is 20-40° C., and the reaction time is 8-20 hours; and / or

[0045] The temperature for reacting the fifth intermediate product with the third ethylenediamine is 40° C. to 60° C., and the reaction time is 8 h to 20 h.

[0046] Optionally, in some embodiments of the present application, the structural formula of the first intermediate product is as shown below:

[0047] ; and / or

[0048] The structural formula of the second intermediate product is shown below:

[0049] ; and / or

[0050] The structural formula of the third intermediate product is shown below:

[0051] ; and / or

[0052] The structural formula of the fourth intermediate product is shown below:

[0053] ; and / or

[0054] The structural formula of the fifth intermediate product is shown below:

[0055] ; wherein R is selected from .

[0056] Optionally, in some embodiments of the present application, the mass ratio of the polypropylene to the modifier is (70-90): (10-30); and / or

[0057] The mixing of the polypropylene and the modifier further comprises: adding a grafting initiator and mixing; and / or

[0058] The mixing of the polypropylene and the modifier further comprises: adding an antioxidant and mixing; and / or

[0059] The reaction of the polypropylene and the modifier comprises banburying; the banburying temperature is 180° C. to 250° C., and the banburying time is 5 min to 20 min; and / or

[0060] After the polypropylene and the modifier react, the method further comprises: adding water.

[0061] The polyolefin composition provided in the present application is a polyolefin composition in which a dendritic molecule modifier rich in amide groups and terminal amino groups is grafted onto a polypropylene molecular chain through a molecular chemical structure design. Due to the high polarity and hydrophilicity of the amide groups and terminal amino groups in the modifier, the polyolefin composition has strong adhesion to various polar surfaces. Moreover, after the polyolefin composition is cured, the branches of the dendritic molecule modifier are interlaced with each other, and the amide groups and amino groups can form strong intermolecular hydrogen bonds. Therefore, the polyolefin composition has large cohesive energy and excellent strength after curing. BRIEF DESCRIPTION OF THE DRAWINGS

[0062] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for use in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For those skilled in the art, other drawings can be obtained based on these drawings without paying any creative work.

[0063] Figure 1 It is a flow chart of a method for preparing a polyolefin composition provided in an embodiment of the present application. DETAILED DESCRIPTION

[0064] The technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without making creative work belong to the scope of protection of the present application. In addition, it should be understood that the specific implementation methods described herein are only used to illustrate and explain the present application, and are not used to limit the present application.

[0065] In this application, unless otherwise stated, directional words such as "upper" and "lower" generally refer to the upper and lower parts of the device in actual use or working state, specifically the drawing direction in the accompanying drawings; while "inner" and "outer" refer to the outline of the device. In addition, in the description of this application, the term "including" means "including but not limited to". The terms first, second, third, etc. are used only as labels and do not impose numerical requirements or establish an order.

[0066] In this application, "and / or" describes the association relationship of associated objects, indicating that there may be three relationships. For example, A and / or B can mean: A exists alone, A and B exist at the same time, and B exists alone. A and B can be singular or plural.

[0067] In this application, "at least one" means one or more, and "plurality" means two or more. "One or several", "at least one of the following" or similar expressions refer to any combination of these items, including any combination of single or plural items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.

[0068] Various embodiments of the present application may be presented in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity, and should not be understood as a rigid limitation on the scope of the present application; therefore, the range description should be considered to have specifically disclosed all possible sub-ranges and single numerical values ​​within the range. For example, the range description from 1 to 6 should be considered to have specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5 and 6, which apply regardless of the range. In addition, whenever a numerical range is indicated herein, it is meant to include any cited number (fractional or integer) within the indicated range.

[0069] The structural formula and molecular weight of some chemical reagents used in this application are described as follows:

[0070] Allylamine: , molecular weight = 57.09;

[0071] Methyl acrylate: , molecular weight = 86.09;

[0072] Ethylenediamine: , molecular weight = 60.1.

[0073] The technical solution of this application is as follows:

[0074] In a first aspect, an embodiment of the present application provides a polyolefin composition, including polypropylene and a modifier, wherein the structural formula of the modifier is shown as follows:

[0075] ; wherein R is selected from , Represents the junction site.

[0076] The polyolefin composition provided in the present application is a polyolefin composition in which a dendritic molecular modifier rich in amide groups and terminal amino groups is grafted onto a polypropylene molecular chain through a molecular chemical structure design. Due to the high polarity and hydrophilicity of the amide groups and terminal amino groups in the modifier, the polyolefin composition has strong adhesion to various polar surfaces. Moreover, after the polyolefin composition is cured, the branches of the dendritic molecular modifier are interlaced with each other, and the amide groups and amino groups can form strong intermolecular hydrogen bonds. Therefore, the polyolefin composition has large cohesive energy and exhibits excellent strength.

[0077] In some embodiments, the mass ratio of the polypropylene to the modifier is (70-90): (10-30), for example, 70:30, 75:25, 80:20, 85:15, 90:10 or any range between two ratios, etc. Within the mass ratio range, the polypropylene and the modifier are effectively combined, thereby improving the strength and water solubility of the polyolefin composition after curing.

[0078] In some embodiments, in the polyolefin composition, the polypropylene and the modifying agent are linked by a covalent bond.

[0079] In some embodiments, the polyolefin composition further comprises a grafting initiator. It is understood that in the process of preparing the polyolefin composition, the grafting initiator can promote the full grafting of polypropylene onto polypropylene, thereby improving the overall connectivity of the polyolefin composition.

[0080] Furthermore, the grafting initiator comprises a peroxide, and the peroxide is selected from one or more of diacetyl peroxide, dicumyl peroxide (DCP), and benzoyl peroxide (BPO).

[0081] The mass ratio of the polypropylene to the grafting initiator is (70-90): (0.1-1), for example, 70:1, 75:0.8, 80:0.6, 85:0.4, 90:0.2 or any range between two ratios, etc. Within the mass ratio range, the grafting initiator is conducive to initiating a chemical reaction between the modifier and the polypropylene, so that the modifier is successfully grafted onto the polypropylene.

[0082] In some embodiments, the polyolefin composition further comprises an antioxidant. It is understood that the antioxidant can prevent the polyolefin composition from being oxidized during storage and slow down its aging rate.

[0083] Furthermore, the antioxidant is selected from one or more of antioxidant AO-1010, antioxidant 1010, and antioxidant 412S.

[0084] The mass ratio of the polypropylene to the antioxidant is (70-90): (0.1-1), for example, 70:1, 75:0.8, 80:0.6, 85:0.4, 90:0.2 or any range between two ratios, etc. Within the mass ratio range, the antioxidant is conducive to fully improving the service life of the polyolefin composition.

[0085] In some embodiments, the polyolefin composition further comprises water. In the polyolefin composition, polypropylene, a modifier, a grafting initiator, and an antioxidant are all dissolved in water.

[0086] Further, the solid content of the polyolefin composition is 10wt% to 20wt%, for example, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%, 18wt%, 19wt% or any range between two values, etc. It is understood that the solid content of the polyolefin composition can be adjusted according to actual use requirements.

[0087] Second, see Figure 1 The present invention provides a method for preparing a polyolefin composition, comprising the following steps:

[0088] S11, providing polypropylene and a modifier, wherein the structural formula of the modifier is as shown below:

[0089] ; wherein R is selected from ;

[0090] S12, mixing the polypropylene and the modifier, reacting to obtain a polyolefin composition.

[0091] The preparation method of the polyolefin composition provided in the present application is to graft a dendritic molecular modifier rich in amide groups and terminal amino groups onto the polypropylene molecular chain through molecular chemical structure design. Due to the high polarity and hydrophilicity of the amide groups and terminal amino groups, the adhesion of the polyolefin composition to various polar surfaces is improved. Moreover, after the polyolefin composition provided by the present invention is cured, the branches of the dendritic molecular modifier are interspersed with each other, and the amide groups and amino groups can form strong intermolecular hydrogen bonds, so that the prepared polyolefin composition has large cohesive energy and exhibits excellent mechanical strength.

[0092] In the S11:

[0093] In some embodiments, the synthetic route of the modifier is as follows:

[0094] ;

[0095] ;

[0096] ;

[0097] ;

[0098] ;

[0099] .

[0100] Specifically, the preparation method of the modifier comprises the following steps:

[0101] S111, providing allylamine, a first methyl acrylate and a solvent, mixing and reacting them to obtain a first intermediate product;

[0102] S112, adding the first ethylenediamine, reacting to obtain a second intermediate product;

[0103] S113, adding a second methyl acrylate, reacting to obtain a third intermediate product;

[0104] S114, adding a second ethylenediamine, reacting to obtain a fourth intermediate product;

[0105] S115, adding a third methyl acrylate, reacting to obtain a fifth intermediate product;

[0106] S116, adding a third ethylenediamine, reacting, and obtaining a modifier.

[0107] In some embodiments, the solvent is selected from one or more of methanol, ethanol, propylene glycol, butanol, trimethoxymethanol, tetrahydrofuran, acetone, acetonitrile, N,N-dimethylformamide (DMF), and dimethyl sulfoxide (DMSO).

[0108] In some embodiments, after the allylamine, the first methyl acrylate and the solvent are mixed, the molar concentration of the allylamine is 0.1 mol / L to 1 mol / L, for example, 0.1 mol / L, 0.2 mol / L, 0.3 mol / L, 0.4 mol / L, 0.5 mol / L, 0.6 mol / L, 0.7 mol / L, 0.8 mol / L, 0.9 mol / L or a range between any two values, etc. Within the molar concentration range, the allylamine is facilitated to be uniformly dissolved and dispersed.

[0109] In some embodiments, after the allylamine, the first methyl acrylate and the solvent are mixed, the molar concentration of the first methyl acrylate is 0.2 mol / L to 5 mol / L, for example, 0.2 mol / L, 0.5 mol / L, 1 mol / L, 1.5 mol / L, 2 mol / L, 3 mol / L, 4 mol / L, 59 mol / L or a range between any two values, etc. Within the molar concentration range, the allylamine is facilitated to be uniformly dissolved and dispersed.

[0110] In some embodiments, the molar ratio of the allylamine to the first methyl acrylate is 1:(2-5), for example, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, or any range between two values. Within the molar ratio range, it is beneficial for the allylamine to fully react with the first methyl acrylate.

[0111] In some embodiments, the temperature of the reaction of the allylamine and the first methyl acrylate is 20°C to 40°C, for example, 25°C, 30°C, 35°C, or any range between two values, etc.; the reaction time is 8h to 20h, for example, 10h, 12h, 15h, 18h, 20h, or any range between two values, etc. Thus, under the reaction conditions, the allylamine and the first methyl acrylate are conducive to efficient reaction.

[0112] In some embodiments, the structural formula of the first intermediate product is shown below: .

[0113] In some embodiments, the molar ratio of the first intermediate product to the first ethylenediamine is 1:(2-5), for example, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5 or any range between two values. Within the molar ratio range, it is beneficial for the first intermediate product to fully react with the first ethylenediamine.

[0114] In some embodiments, the adding of the first ethylenediamine reaction further comprises adding a first catalyst. The first catalyst is selected from sodium methoxide. The first catalyst can increase the reaction rate of the first intermediate product and the first ethylenediamine.

[0115] In some embodiments, the reaction temperature of the first intermediate product and the first ethylenediamine is 40°C to 60°C, for example, 45°C, 50°C, 55°C, or any range between two values, etc.; the reaction time is 8h to 20h, for example, 10h, 12h, 15h, 18h, 20h, or any range between two values, etc. Thus, under the reaction conditions, the first intermediate product and the first ethylenediamine are conducive to efficient reaction.

[0116] In some embodiments, the structural formula of the second intermediate product is as shown below:

[0117] .

[0118] In some embodiments, the molar ratio of the second intermediate product to the second methyl acrylate is 1:(4-8), for example, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8 or any range between two values. Within the molar ratio range, the second intermediate product is conducive to fully reacting with the second methyl acrylate.

[0119] In some embodiments, the reaction temperature of the second intermediate product and the second methyl acrylate is 20-40°C, for example, 25°C, 30°C, 35°C, or any range between two values, etc.; the reaction time is 8h-20h, for example, 10h, 12h, 15h, 18h, 20h, or any range between two values, etc. Thus, under the reaction conditions, the second intermediate product and the second methyl acrylate are conducive to efficient reaction.

[0120] In some embodiments, the third intermediate product has a structural formula as shown below:

[0121] .

[0122] In some embodiments, the molar ratio of the third intermediate product to the second ethylenediamine is 1:(4-8), for example, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8 or any range between two values. Within the molar ratio range, it is beneficial for the third intermediate product to fully react with the second ethylenediamine.

[0123] In some embodiments, the adding of the second ethylenediamine to react further comprises adding a second catalyst. The second catalyst is selected from sodium methoxide. The second catalyst can increase the reaction rate of the third intermediate product and the second ethylenediamine.

[0124] In some embodiments, the temperature of the reaction of the third intermediate product and the second ethylenediamine is 40°C to 60°C, for example, 45°C, 50°C, 55°C, or a range between any two values, etc.; the reaction time is 8h to 20h, for example, 10h, 12h, 15h, 18h, 20h, or a range between any two values, etc. Thus, under the reaction conditions, the third intermediate product and the second ethylenediamine are conducive to efficient reaction.

[0125] In some embodiments, the fourth intermediate product has a structural formula as shown below:

[0126] .

[0127] In some embodiments, the molar ratio of the fourth intermediate product to the third methyl acrylate is 1:(8-12), for example, 1:8, 1:8.5, 1:9, 1:9.5, 1:10, 1:10.5, 1:11, 1:11.5, 1:12 or any range between two values. Within the molar ratio range, it is beneficial for the fourth intermediate product to fully react with the third methyl acrylate.

[0128] In some embodiments, the temperature for the reaction of the fourth intermediate product and the third methyl acrylate is 20-40°C, for example, 25°C, 30°C, 35°C, or any range between two values, etc.; the reaction time is 8h-20h, for example, 10h, 12h, 15h, 18h, 20h, or any range between two values, etc. Thus, under the reaction conditions, the fourth intermediate product and the third methyl acrylate are conducive to efficient reaction.

[0129] In some embodiments, the structural formula of the fifth intermediate product is as shown below:

[0130] ; wherein R' is selected from .

[0131] In some embodiments, the molar ratio of the fifth intermediate product to the third ethylenediamine is 1:(8-12), for example, 1:8, 1:8.5, 1:9, 1:9.5, 1:10, 1:10.5, 1:11, 1:11.5, 1:12 or a range between any two values, etc. Within the molar ratio range, it is beneficial for the fifth intermediate product to fully react with the third ethylenediamine.

[0132] In some embodiments, the adding of the third ethylenediamine reaction further comprises adding a third catalyst. The third catalyst is selected from sodium methoxide. The third catalyst can increase the reaction rate of the fifth intermediate product and the third ethylenediamine.

[0133] In some embodiments, the reaction temperature of the fifth intermediate product and the third ethylenediamine is 40°C to 60°C, for example, 45°C, 50°C, 55°C, or a range between any two values, etc.; the reaction time is 8h to 20h, for example, 10h, 12h, 15h, 18h, 20h, or a range between any two values, etc. Thus, under the reaction conditions, the fifth intermediate product and the third ethylenediamine are conducive to efficient reaction.

[0134] It should be noted that, as shown in the synthetic route of the modifier, 1 mol of allylamine and 2 mol of the first methyl acrylate react to form 1 mol of the first intermediate product. In order to improve the reaction efficiency, an excessive amount of the first methyl acrylate can be added in an appropriate amount, but there will still be only 2 mol of the first methyl acrylate combined with 1 mol of allylamine. Therefore, after the first intermediate product is formed, the excess first methyl acrylate needs to be removed, and then the first ethylenediamine is added to react with the first intermediate product. Similarly, the first intermediate product and the first ethylenediamine, the second intermediate product and the second methyl acrylate, the third intermediate product and the second ethylenediamine, the fourth intermediate product and the third methyl acrylate, and the fifth intermediate product and the third ethylenediamine react in the same way, and the molar ratio of the combination is fixed. If an excessive amount of methyl acrylate and ethylenediamine are added, after each reaction, measures can be taken to remove the excess unreacted raw materials, such as rotary evaporation and suction filtration, and then the next raw material is added for reaction and combination to finally obtain the modifier.

[0135] In S12:

[0136] In some embodiments, the mass ratio of the polypropylene to the modifier is (70-90): (10-30), for example, 70:30, 75:25, 80:20, 85:15, 90:10 or any range between two ratios, etc. Within the mass ratio range, the polypropylene and the modifier are effectively combined, thereby improving the cured strength and water solubility of the polyolefin composition.

[0137] In some embodiments, mixing the polypropylene and the modifier further comprises: adding a grafting initiator and mixing.

[0138] In some embodiments, mixing the polypropylene and the modifier further comprises: adding an antioxidant and mixing.

[0139] The materials and proportions of the grafting initiator and antioxidant are mentioned above and will not be described in detail here.

[0140] In some embodiments, the reaction of the polypropylene and the modifier includes banburying. The banburying temperature is 180°C to 250°C, for example, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, or a range between any two values; the banburying time is 5min to 20min, for example, 6min, 8min, 10min, 12min, 15min, 18min, 20min, or a range between any two values. In this way, under the banburying conditions, it is beneficial for the modifier to be fully grafted onto the polypropylene, and the obtained polyolefin composition has good strength after curing.

[0141] In some embodiments, after the polypropylene and the modifier react, the method further comprises: adding water.

[0142] Furthermore, after adding water, heating and stirring are also performed to promote the dissolution of polypropylene, modifiers, etc. in water to obtain a polyolefin composition with a suitable solid content.

[0143] Since the polyolefin composition provided by the present invention has high strength after curing and strong bonding force with various materials such as polyolefin plastics, metal materials and inorganic non-metallic materials, the polyolefin composition provided by the present invention can be applied to the field of adhesives.

[0144] The present application is described in detail below through specific embodiments. The following embodiments are only partial embodiments of the present application and are not limitations of the present application.

[0145] Embodiment 1: This embodiment provides a polyolefin composition, and its preparation method comprises the following steps:

[0146] Step 1: Weigh 0.1 mol of allylamine, 0.2 mol of methyl acrylate and 200 g of anhydrous tetrahydrofuran into a 100 mL three-necked flask, stir and mix evenly, introduce circulating nitrogen protection, and react at 25° C. for 12 h to obtain a first intermediate product with two side chains, the specific structural formula of which is shown in the figure below:

[0147] ;

[0148] Step 2: Add 0.2 mol of ethylenediamine and 0.2 g of sodium methoxide to the reaction solution obtained in step 1, stir and mix evenly, introduce nitrogen gas for protection, and react at 50° C. for 12 h to obtain a second intermediate product having two terminal amino groups, the specific structural formula of which is shown in the figure below:

[0149] ;

[0150] Step 3: Add 0.4 mol of methyl acrylate to the reaction solution obtained in step 2, stir and mix evenly, introduce nitrogen gas for protection, and react at 25° C. for 12 hours to obtain a third intermediate product with four branches, the specific structural formula of which is shown in the figure below:

[0151] ;

[0152] Step 4: Add 0.4 mol of ethylenediamine and 0.2 g of sodium methoxide to the reaction solution obtained in step 3, stir and mix evenly, introduce nitrogen gas for protection, and react at 50° C. for 12 h to obtain a fourth intermediate product having four terminal amino groups, the specific structural formula of which is shown in the figure below:

[0153] ;

[0154] Step 5: Add 0.8 mol of methyl acrylate to the reaction solution obtained in step 4, stir and mix evenly, introduce nitrogen gas for protection, and react at 25° C. for 12 hours to obtain a fifth intermediate product with eight branches, the specific structural formula of which is shown in the figure below:

[0155] ; wherein R' is selected from ;

[0156] Step 6: Add 0.8 mol of ethylenediamine and 0.2 g of sodium methoxide to the reaction solution obtained in step 5, stir and mix evenly, introduce nitrogen gas for protection, react at 50°C for 12 hours, and after the reaction is completed, perform rotary evaporation at 60°C to remove residual tetrahydrofuran in the system to obtain a light yellow viscous liquid, which is the modifier;

[0157] Step 7: Take 135g (90wt%) of random copolymer polypropylene material (PP 5090T, purchased from Taiwan Plastics Industry Co., Ltd.), 15g (10wt%) of the modifier obtained in step 6, 0.9g of diacetyl peroxide and 0.9g of antioxidant AO-1010, add them into a high-speed stirrer, stir and mix at room temperature, set the speed to 100 rpm, and take out the premix after mixing for 10 minutes; then carry out grafting reaction on the premix in a small torque rheometer, the mixing temperature is 210°C, take out the material after reaction for 10 minutes, add it into 850g of deionized water, heat and reflux at 80°C, keep stirring until it is completely dissolved, and obtain a polyolefin composition with a solid content of 15wt%.

[0158] Example 2: This example is basically the same as Example 1, except that in step 7 of this example, the amount of each raw material used is: 127.5 g (85 wt%) random copolymer polypropylene material (PP 5090T, purchased from Taiwan Plastics Industry Co., Ltd.), 22.5 g (15 wt%) modifier, 0.9 g diacetyl peroxide and 0.9 g antioxidant AO-1010.

[0159] Example 3: This example is basically the same as Example 1, except that in step 7 of this example, the amount of each raw material used is: 120g (80wt%) random copolymer polypropylene material (PP 5090T, purchased from Taiwan Plastics Industry Co., Ltd.), 30g (20wt%) modifier, 0.9g diacetyl peroxide and 0.9g antioxidant AO-1010.

[0160] Example 4: This example is basically the same as Example 1, except that in step 7 of this example, the amount of each raw material used is: 112.5 g (75 wt%) random copolymer polypropylene material (PP 5090T, purchased from Taiwan Plastics Industry Co., Ltd.), 37.5 g (25 wt%) modifier, 0.9 g diacetyl peroxide and 0.9 g antioxidant AO-1010.

[0161] Comparative Example: This comparative example provides commercially available 2014 transparent polyolefin adhesive (purchased from Huizhou Weiligu New Material Technology Co., Ltd.).

[0162] The polyolefin compositions of Examples 1 to 4 and the 2014 transparent polyolefin adhesive of the comparative example were tested for bonding strength. The test results are shown in Table 1.

[0163] The bonding strength test is carried out in accordance with the standard GB / T 6328-2018 "Determination of shear bonding strength of adhesives";

[0164] Table 1:

[0165] .

[0166] As shown in Table 1, the polyolefin compositions provided in Examples 1 to 4 have better bonding strengths with polypropylene, stainless steel, and glass surfaces than the comparative examples, wherein the bonding strengths between the composition of Example 4 and polypropylene, stainless steel, and glass surfaces are relatively the highest, which are 44.1 MPa, 40.6 MPa, and 38.8 MPa, respectively. The polyolefin composition provided in the present application exhibits excellent bonding strength.

[0167] The technical solutions provided by the embodiments of the present application are introduced in detail above. Specific examples are used herein to illustrate the principles and implementation methods of the present application. The description of the above embodiments is only used to help understand the method of the present application and its core idea. At the same time, for technical personnel in this field, according to the idea of ​​the present application, there will be changes in the specific implementation methods and application scope. In summary, the content of this specification should not be understood as a limitation on the present application.

Claims

1. A polyolefin composition, characterized in that The polyolefin composition comprises polypropylene and a modifier. In the polyolefin composition, the polypropylene and the modifier are connected by a covalent bond. The structural formula of the modifier is shown as follows: ; wherein R is selected from , Represents the junction site.

2. The polyolefin composition according to claim 1, characterized in that The mass ratio of the polypropylene to the modifier is (70-90): (10-30).

3. The polyolefin composition according to claim 1, characterized in that The polyolefin composition further comprises a grafting initiator; and / or The polyolefin composition further comprises an antioxidant; and / or The polyolefin composition also includes water.

4. The polyolefin composition according to claim 3, characterized in that The grafting initiator comprises a peroxide, and the peroxide is selected from one or more of diacetyl peroxide, dicumyl peroxide, and benzoyl peroxide; and / or The mass ratio of the polypropylene to the grafting initiator is (70-90): (0.1-1); and / or The antioxidant is selected from one or more of antioxidant AO-1010 and antioxidant 412S; and / or The mass ratio of the polypropylene to the antioxidant is (70-90): (0.1-1); and / or The solid content of the polyolefin composition is 10 wt % to 20 wt %.

5. A method for preparing a polyolefin composition, characterized in that: The steps include: Provide polypropylene and a modifier, wherein the structural formula of the modifier is as shown below: ; wherein R is selected from , represents the junction site; The polypropylene and the modifier are mixed and reacted to obtain a polyolefin composition.

6. The preparation method according to claim 5, characterized in that: The preparation method of the modifier comprises the following steps: Providing allylamine, a first methyl acrylate and a solvent, mixing and reacting them to obtain a first intermediate product; Adding the first ethylenediamine to react to obtain a second intermediate product; adding a second methyl acrylate, reacting to obtain a third intermediate product; Adding a second ethylenediamine to react to obtain a fourth intermediate product; adding a third methyl acrylate, reacting to obtain a fifth intermediate product; A third ethylenediamine is added to react to obtain a modifier.

7. The preparation method according to claim 6, characterized in that: The solvent is selected from one or more of methanol, ethanol, propylene glycol, butanol, trimethoxymethanol, tetrahydrofuran, acetone, acetonitrile, N,N-dimethylformamide, and dimethyl sulfoxide; and / or After the allylamine, the first methyl acrylate and the solvent are mixed, the molar concentration of the allylamine is 0.1 mol / L to 1 mol / L; and / or After the allylamine, the first methyl acrylate and the solvent are mixed, the molar concentration of the first methyl acrylate is 0.2 mol / L to 5 mol / L; and / or The molar ratio of the allylamine to the first methyl acrylate is 1:(2-5); and / or The molar ratio of the first intermediate product to the first ethylenediamine is 1:(2-5); and / or The molar ratio of the second intermediate product to the second methyl acrylate is 1:(4-8); and / or The molar ratio of the third intermediate product to the second ethylenediamine is 1:(4-8); and / or The molar ratio of the fourth intermediate product to the third methyl acrylate is 1:(8-12); and / or The molar ratio of the fifth intermediate product to the third ethylenediamine is 1:(8-12); and / or The adding of the first ethylenediamine reaction further comprises adding a first catalyst, wherein the first catalyst is selected from sodium methoxide; and / or The adding of the second ethylenediamine reaction further comprises adding a second catalyst, wherein the second catalyst is selected from sodium methoxide; and / or The adding of the third ethylenediamine reaction further comprises adding a third catalyst, wherein the third catalyst is selected from sodium methoxide; and / The temperature of the reaction of the allylamine and the first methyl acrylate is 20° C. to 40° C., and the reaction time is 8 h to 20 h; and / or The reaction temperature of the first intermediate product and the first ethylenediamine is 40° C. to 60° C., and the reaction time is 8 h to 20 h; and / or The temperature of the reaction of the second intermediate product and the second methyl acrylate is 20-40° C., and the reaction time is 8-20 hours; and / or The temperature of the reaction of the third intermediate product and the second ethylenediamine is 40° C. to 60° C., and the reaction time is 8 h to 20 h; and / or The temperature of the reaction of the fourth intermediate product and the third methyl acrylate is 20-40° C., and the reaction time is 8-20 hours; and / or The temperature for reacting the fifth intermediate product with the third ethylenediamine is 40° C. to 60° C., and the reaction time is 8 h to 20 h.

8. The preparation method according to claim 6, characterized in that: The structural formula of the first intermediate product is shown below: ; and / or The structural formula of the second intermediate product is shown below: ; and / or The structural formula of the third intermediate product is shown below: ; and / or The structural formula of the fourth intermediate product is shown below: ; and / or The structural formula of the fifth intermediate product is shown below: ; wherein R' is selected from .

9. The preparation method according to claim 5, characterized in that: The mass ratio of the polypropylene to the modifier is (70-90): (10-30); and / or The mixing of the polypropylene and the modifier further comprises: adding a grafting initiator and mixing; and / or The mixing of the polypropylene and the modifier further comprises: adding an antioxidant and mixing; and / or The reaction of the polypropylene and the modifier comprises banburying; the banburying temperature is 180° C. to 250° C., and the banburying time is 5 min to 20 min; and / or After the polypropylene and the modifier react, the method further comprises: adding water.

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