Nucleating agent for polyolefin and preparation method thereof

Abstract

The invention relates to the technical field of nucleating agents, in particular to a nucleating agent for polyolefin and a preparation method of the nucleating agent. The nucleating agent is prepared from the following raw materials: an organic carrier, a sulfydryl silane coupling agent modified organic-inorganic hybrid material, ionic liquid, a ketone solvent and a photoinitiator. When the nucleating agent is used for polyolefin, the crystallization temperature and the light transmittance of the polyolefin can be better increased, and the polyolefin can have excellent antistatic property.

Description

Technical Field

[0001] The present invention relates to the technical field of nucleating agents, and in particular to a nucleating agent for polyolefins and a preparation method thereof. Background Art

[0002] Nucleating agents are often used during the processing of polyolefins (such as polyethylene and polypropylene) to improve their crystallization properties, increase processing efficiency, and optimize the mechanical properties and appearance of the final product. Nucleating agents accelerate the crystallization process by promoting the formation of more crystal nuclei during the cooling process, allowing the polyolefin to achieve a higher degree of crystallinity at lower temperatures, thereby improving its physical properties such as rigidity and heat distortion temperature.

[0003] Existing nucleating agents primarily fall into the following categories: 1. Organic nucleating agents, such as fatty acid nucleating agents and aromatic compounds; 2. Inorganic nucleating agents, such as glass fiber, inorganic salts, and nanomaterials. However, existing nucleating agents may be incompatible with polyolefin substrates, resulting in suboptimal nucleation or uneven dispersion. For example, some nucleating agents may interact with the polyolefin's molecular structure, leading to uneven dispersion or precipitation within the matrix, thus compromising nucleation effectiveness and ultimate performance.

[0004] In addition, the high crystallization temperature of polyolefins has the following advantages: 1. Improved thermal stability and heat resistance, 2. Enhanced hot workability, 3. Improved wear resistance, 4. Improved surface quality, etc. However, existing nucleating agents can only increase the crystallization temperature of polyolefins by a maximum of 10-15°C. Summary of the Invention

[0005] The present invention aims to provide a nucleating agent for polyolefin and a preparation method thereof. The nucleating agent has good compatibility with polyolefin and can better increase the crystallization temperature of polyolefin.

[0006] To achieve the above objectives, the first aspect of the present invention provides a nucleating agent for polyolefins. The raw materials of the nucleating agent include: an organic carrier, a mercaptosilane coupling agent modified organic-inorganic hybrid material, an ionic liquid, a ketone solvent, and a photoinitiator.

[0007] As a preferred technical solution of the present invention, the raw materials of the nucleating agent include, by weight: 100 parts of ketone solvent, 40-60 parts of organic carrier, 20-45 parts of mercaptosilane coupling agent modified organic-inorganic hybrid material, 20-30 parts of ionic liquid, and 1-5 parts of photoinitiator.

[0008] As a preferred technical solution of the present invention, the raw materials of the nucleating agent include, by weight: 100 parts of ketone solvent, 65-70 parts of organic carrier, 25-30 parts of mercaptosilane coupling agent modified organic-inorganic hybrid material, 12-15 parts of ionic liquid, and 2-3 parts of photoinitiator.

[0009] In the present invention, the preparation method of the organic-inorganic hybrid material comprises: S1: ethanol and hydroxyaluminum p-tert-butylbenzoate are first mixed to obtain a first mixture; S2. The first mixed material is mixed with ethyl orthosilicate for a second time to obtain a second mixed material; S3: adjusting the pH value of the second mixture to be alkaline, and then performing a third reaction to obtain a third mixture; S4 spray-drying the third mixed material to obtain a fourth material; S5: the fourth material is passed through a 10000-20000 mesh sieve to obtain an organic-inorganic hybrid material; S6: The ethanol aqueous solution and the mercaptosilane coupling agent are hydrolyzed, and then the organic-inorganic hybrid material is added to carry out the sixth modification reaction, followed by filtration, filter cake washing, and drying to obtain the mercaptosilane coupling agent-modified organic-inorganic hybrid material.

[0010] In the prior art, hydroxyaluminum p-tert-butylbenzoate can be used as a nucleating agent to increase the crystallization temperature of polyolefins, such as polypropylene, to 10-15°C. However, hydroxyaluminum p-tert-butylbenzoate has poor dispersibility in polyolefins. Currently, grinding is generally used to increase the dispersibility of organic carboxylates in polyolefins (such as polypropylene). At the same time, it can be reacted with talc to increase the crystallization temperature of polyolefins such as polypropylene to 10-15°C. However, in the process production, the amount of polyolefin used is very large, while the amount of organic carboxylates added is only 0.3wt%. The grinding method is not only time-consuming, but also has a great impact on the quality of the product. However, it is laborious and industrially unavailable to better disperse hydroxyaluminum p-tert-butylbenzoate in a polyolefin system to achieve the goal of increasing the crystallization temperature. However, the present invention utilizes a specific organic-inorganic hybrid material containing hydroxyaluminum p-tert-butylbenzoate dispersed in an organic carrier, enabling the nucleating agent of the present invention to be better dispersed in a polyolefin system, particularly a polypropylene system, when used. Furthermore, the specific mercaptosilane coupling agent-modified organic-inorganic hybrid material of the present invention can not only better increase the light transmittance of polyolefins, particularly polypropylene, but also better increase the crystallization temperature of polyolefins. It is speculated that this is because the specific mercaptosilane coupling agent-modified organic-inorganic hybrid material of the present invention acts as a nucleating particle, allowing the polyolefin to exhibit a multidimensional crystal growth state during the crystallization process, thereby better increasing the crystallization temperature of the polyolefin. Simultaneously, the mercaptosilane coupling agent-modified organic-inorganic hybrid material can better increase the crystallization rate of the polyolefin and reduce the size of the polyolefin spherulites, resulting in more dense and uniform small spherulites.

[0011] As a preferred technical solution of the present invention, in step S1, the weight ratio of ethanol to hydroxyaluminum p-tert-butylbenzoate is 100:(30-50), preferably 100:(35-40).

[0012] In the present invention, there is no special limitation on the conditions of the first mixing, as long as hydroxyaluminum 4-tert-butylbenzoate can be uniformly dispersed in ethanol. As a preferred technical solution of the present invention, in step S1, the conditions of the first mixing include: a temperature of 30-40°C and a time of 20-30 minutes.

[0013] As a preferred technical solution of the present invention, in step S2, the weight ratio of the first mixture to tetraethyl orthosilicate is 100:(30-50), preferably 100:(35-40).

[0014] As a preferred technical solution of the present invention, in step S2, the second mixing conditions include: temperature of 30-40°C and time of 20-30 minutes.

[0015] In the present invention, the pH of the second mixture can be adjusted to alkaline using any method known in the art. Preferably, in step S3, the pH of the second mixture is adjusted to 9-12, preferably 10-11. As a preferred technical solution of the present invention, aqueous ammonia is used to adjust the pH of the second mixture to 10-11. The aqueous ammonia in the present invention is an aqueous solution of gaseous ammonia, wherein the concentration of the aqueous ammonia is 25-28 wt%.

[0016] As a preferred technical solution of the present invention, the conditions of the third reaction include: temperature of 30-40° C. and time of 2-3 hours.

[0017] The spray drying molding conditions in step S4 of the present invention can be conventional spray drying molding conditions in the art. As a preferred technical solution of the present invention, in step S4, the spray drying molding conditions include: a drying air inlet temperature of 210-220°C and an air outlet temperature of 100-105°C.

[0018] In the present invention, the ethanol aqueous solution refers to a mixed liquid of ethanol and water. As a preferred technical solution of the present invention, in step S6, the volume ratio of ethanol to water in the ethanol aqueous solution is (8-20):1, preferably (10-12):1.

[0019] As a preferred technical solution of the present invention, the mercaptosilane coupling agent is selected from at least one of 3-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, and mercaptopropylmethyldimethoxysilane, preferably mercaptopropylmethyldimethoxysilane.

[0020] As a preferred technical solution of the present invention, in step S6, the weight ratio of the ethanol aqueous solution to the mercaptosilane coupling agent is (150-200):1.

[0021] As a preferred technical solution of the present invention, in step S6, the weight ratio of the mercaptosilane coupling agent to the organic-inorganic hybrid material is 1:(1.5-3), preferably 1:(2-2.5).

[0022] As a preferred technical solution of the present invention, in step S6, the hydrolysis conditions include: temperature of 25-30° C. and time of 5-10 minutes.

[0023] As a preferred technical solution of the present invention, in step S6, the conditions of the sixth modification reaction include: temperature of 65-75° C. and time of 2-3 hours.

[0024] The filter cake washing method in step S6 of the present invention is a conventional method in the art, for example, washing with water and ethanol alternately 4-6 times.

[0025] As a preferred technical solution of the present invention, in step S6, the drying conditions include: a temperature of 100-120° C. and a time of 10-48 hours.

[0026] As a preferred technical solution of the present invention, the ionic liquid is selected from alkenyl functionalized ionic liquids.

[0027] The inventors of the present invention unexpectedly discovered alkenyl functionalized ionic liquids during their research, which enabled the nucleating agent in the present invention to increase the antistatic properties of polyolefin products.

[0028] As a preferred technical solution of the present invention, the alkenyl functionalized ionic liquid is selected from at least one of 1-allyl-3-methylimidazolium chloride, 1-allyl-3-methylimidazolium bromide, 1-allyl-3-methylimidazolium tetrafluoroborate, 1-allyl-3-methylimidazolium trifluoromethanesulfonate, 1-allyl-3-methylimidazolium acetate, 1-allyl-3-methylimidazolium p-toluenesulfonate, 1-allyl-3-butylimidazolium chloride, 1-allyl-3-butylimidazolium tetrafluoroborate, 1-allyl-3-butylimidazolium hexafluorophosphate, 1-allyl-3-vinylimidazole tetrafluoroborate and 1-allyl-3-vinylimidazole hexafluorophosphate, preferably 1-allyl-3-vinylimidazole hexafluorophosphate.

[0029] Furthermore, the present invention has found that the use of 1-allyl-3-vinylimidazole hexafluorophosphate can better enhance the antistatic properties of polyolefins and further increase the light transmittance and crystallization temperature of polyolefins when used as a nucleating agent.

[0030] As a preferred technical solution of the present invention, the organic carrier is selected from maleic anhydride polybutadiene and cycloolefin copolymer.

[0031] As a preferred technical solution of the present invention, the weight ratio of the maleic anhydride polybutadiene to the cycloolefin copolymer is 1:(4-25), for example, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:13, 1:15, 1:18, 1:20, 1:25, preferably 1:(8-10).

[0032] As a preferred technical solution of the present invention, the number average molecular weight of the maleic anhydride polybutadiene is 2000-3000, preferably 2500.

[0033] As a preferred technical solution of the present invention, the mass content of maleic anhydride in the maleic anhydride polybutadiene is 10-25wt%, preferably 15-20wt%.

[0034] The maleic anhydride polybutadiene in the present invention can be obtained from the market, and its preferred model is Riconbond 1756 from American Rayville.

[0035] As a preferred technical solution of the present invention, the melt flow rate of the cycloolefin copolymer at 190°C / 2.16 kg is 1-5 g / 10 min, preferably 1-3 g / 10 min, and more preferably 2.7 g / 10 min.

[0036] The cyclic olefin copolymer in the present invention is commercially available, for example, TOPAS® Elastomer E-140 from TOPAS, Germany.

[0037] As a preferred technical solution of the present invention, the ketone solvent is selected from at least one of acetone, butanone, cyclohexanone, isophorone, methyl isobutyl ketone, N-methylpyrrolidone, N-ethylpyrrolidone and N-cyclohexylpyrrolidone, preferably acetone.

[0038] As a preferred technical solution of the present invention, the photoinitiator is selected from at least one of diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, benzoin diethyl ether, 2-ethylanthraquinone, 5,7-dimethoxy-3-(4-dodecylbenzoyl)coumarin, 1-hydroxycyclohexylphenyl ketone and diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, preferably benzoin diethyl ether.

[0039] The second aspect of the present invention provides a method for preparing the polyolefin nucleating agent according to the first aspect of the present invention, the preparation method comprising: (1) mixing a mercaptosilane coupling agent-modified organic-inorganic hybrid material, an ionic liquid, a photoinitiator, and a ketone solvent, performing a photoinitiation reaction, filtering, and drying the filter cake to obtain an ionic liquid-modified organic-inorganic hybrid material; (2) premixing the ionic liquid modified organic-inorganic hybrid material with an organic carrier to obtain a premix; (3) The premix is ​​extruded in a twin-screw extruder, stretched into strands, passed through water, and pelletized.

[0040] There is no special limitation on the mixing in step (1) of the present invention, as long as the mixing is uniform. The present invention will not be described in detail here.

[0041] As a preferred technical solution of the present invention, the conditions for the light-induced reaction include: a light source power density of 850-950 mW / cm2, a wavelength of 280-350 nm, and a reaction time of 40-60 minutes.

[0042] As a preferred technical solution of the present invention, in step (1), the drying conditions include: a temperature of 100-120° C. and a time of 10-48 hours.

[0043] In the present invention, the premixing conditions in step (2) are not particularly limited, for example, mixing at 30-40° C. and 200-400 rpm for 3-5 minutes.

[0044] In the present invention, the twin-screw extruder in step (2) can be a conventional twin-screw extruder in the art, for example, with a length-to-diameter ratio of 40:1 and a screw diameter of 35 mm.

[0045] As a preferred technical solution of the present invention, the extrusion conditions include: a screw speed of 300-400 rpm; a temperature of each section of the extruder of 172-208°C. For example, the screw temperature during extrusion of a twin-screw extruder is divided into 6 sections, with the temperature of zone 1 being set to 172-175°C, zone 2 being 180-185°C, zone 3 being 188-190°C, zone 4 being 195-200°C, zone 5 being 195-200°C, and zone 6 being 205-208°C.

[0046] In the present invention, the size of the pellets is generally selected according to needs, and is generally 1-3 mm.

[0047] When the nucleating agent of the present invention is used in polyolefin, its usage is generally 0.1-5 wt %, preferably 0.5-2 wt % of the mass of the polyolefin. The polyolefin may be at least one of polyethylene, polypropylene and polybutene, preferably polypropylene.

[0048] Compared with the prior art, the present invention has at least the following beneficial effects: 1. The nucleating agent in the present invention is based on an organic carrier, has good compatibility with polyolefins, and can fully exert its effect.

[0049] 2. The nucleating agent in the present invention can simultaneously increase the crystallization temperature and light transmittance of polyolefin, and also make it have excellent antistatic effect. DETAILED DESCRIPTION

[0050] The present invention is described in detail below through examples. The following examples are merely illustrative of the specific technical solutions of the present invention and do not limit the scope of the present invention. That is, it should be understood that non-essential simple corrections, adjustments and combinations made by those skilled in the art based on the inventive concept of the present invention are all within the scope of protection claimed by the present invention.

[0051] Preparation Example 1 Preparation of mercaptosilane coupling agent modified organic-inorganic hybrid material A: S1: mixing ethanol and hydroxyaluminum p-tert-butylbenzoate in a weight ratio of 100:38 at 35° C. for 25 minutes to obtain a first mixture; S2: the first mixed material and ethyl orthosilicate in a weight ratio of 100:38 are mixed at 35° C. for 25 minutes to obtain a second mixed material; S3: adjusting the pH value of the second mixture to 10.4 using 26 wt % ammonia water, and then reacting at 35° C. for 2.5 hours to obtain a third mixture; S4 spray-drying the third mixed material (conditions include: drying air inlet temperature of 215° C., air outlet temperature of 102° C.) to obtain a fourth material; S5 The fourth material is passed through an 18000 mesh sieve to obtain an organic-inorganic hybrid material; S6 An ethanol-water solution with a weight ratio of 180:1 (the volume ratio of ethanol to water is 10:1) and mercaptopropylmethyldimethoxysilane are hydrolyzed at 25°C for 8 minutes, and then an organic-inorganic hybrid material (the weight ratio of mercaptopropylmethyldimethoxysilane to organic-inorganic hybrid material is 1:2.3) is added to react at 70°C for 2.5 hours. After the reaction, the material is filtered, and the filter cake is washed alternately with water and ethanol for 5 times. Finally, it is dried at 110°C for 24 hours to obtain a mercaptosilane coupling agent-modified organic-inorganic hybrid material A.

[0052] Preparation Example 2 Preparation of mercaptosilane coupling agent modified organic-inorganic hybrid material B: S1: mixing ethanol and hydroxyaluminum p-tert-butylbenzoate in a weight ratio of 100:40 at 30° C. for 30 minutes to obtain a first mixture; S2: the first mixed material and ethyl orthosilicate in a weight ratio of 100:35 are mixed at 40° C. for 20 minutes to obtain a second mixed material; S3: adjusting the pH value of the second mixture to 11 using 26 wt % ammonia water, and then reacting at 35° C. for 2 hours to obtain a third mixture; S4 spray-drying the third mixed material (conditions include: drying air inlet temperature of 210° C., air outlet temperature of 100° C.) to obtain a fourth material; S5 The fourth material is passed through an 18000 mesh sieve to obtain an organic-inorganic hybrid material; S6 An ethanol-water solution with a weight ratio of 200:1 (the volume ratio of ethanol to water is 10:1) and mercaptopropylmethyldimethoxysilane are hydrolyzed at 25°C for 10 minutes, and then an organic-inorganic hybrid material (the weight ratio of mercaptopropylmethyldimethoxysilane to organic-inorganic hybrid material is 1:2.5) is added to react at 75°C for 2 hours. After the reaction, the material is filtered, and the filter cake is washed alternately with water and ethanol for 5 times. Finally, it is dried at 110°C for 24 hours to obtain a mercaptosilane coupling agent-modified organic-inorganic hybrid material B.

[0053] Example 1 Preparation of nucleating agent raw materials: Prepare, by weight, 100 parts of acetone, 7 parts of maleic anhydride-modified polybutadiene (Riconbond 1756, manufactured by American Rayville), 61 parts of cycloolefin copolymer (TOPAS® Elastomer E-140, manufactured by German TOPAS), 28 parts of mercaptosilane coupling agent-modified organic-inorganic hybrid material A, 14 parts of 1-allyl-3-vinylimidazole hexafluorophosphate, and 2.5 parts of benzoin diethyl ether.

[0054] Preparation of nucleating agent: (1) The mercaptosilane coupling agent modified organic-inorganic hybrid material A, 1-allyl-3-vinylimidazole hexafluorophosphate, benzoin diethyl ether and acetone were mixed, and then photoinduced at a light source power density of 900 mW / cm2 and a wavelength of 320 nm for 50 minutes, and then filtered and the filter cake was dried at 110°C for 24 hours to obtain an ionic liquid modified organic-inorganic hybrid material; (2) mixing the ionic liquid modified organic-inorganic hybrid material with maleic anhydride-modified polybutadiene and cycloolefin copolymer at 35°C and 300 rpm for 5 minutes to obtain a premix; (3) The premix was extruded in a twin-screw extruder (length-to-diameter ratio 40:1, screw diameter 35 mm), stranded, water-dried, and pelletized to obtain a 2 mm nucleating agent; Among them, the extrusion conditions include: the screw speed is 320 rpm; the screw temperature during extrusion of the twin-screw extruder is divided into 6 sections in sequence, with the temperature of zone 1 set to 173°C, zone 2 to 182°C, zone 3 to 188°C, zone 4 to 198°C, zone 5 to 198°C, and zone 6 to 206°C.

[0055] Example 2 Prepare, by weight, 100 parts of acetone, 7 parts of maleic anhydride-modified polybutadiene (Riconbond 1756, manufactured by American company TOPAS), 63 parts of cycloolefin copolymer (TOPAS® Elastomer E-140, manufactured by German company TOPAS), 30 parts of mercaptosilane coupling agent-modified organic-inorganic hybrid material B, 12 parts of 1-allyl-3-vinylimidazole hexafluorophosphate, and 3 parts of benzoin diethyl ether.

[0056] Preparation of nucleating agent: (1) The mercaptosilane coupling agent modified organic-inorganic hybrid material B, 1-allyl-3-vinylimidazole hexafluorophosphate, benzoin diethyl ether and acetone were mixed, and then photoinduced at a light source power density of 900 mW / cm2 and a wavelength of 320 nm for 50 minutes, and then filtered and the filter cake was dried at 110°C for 24 hours to obtain an ionic liquid modified organic-inorganic hybrid material; (2) The ionic liquid modified organic-inorganic hybrid material was mixed with maleic anhydride polybutadiene and cycloolefin copolymer at 40°C and 320 rpm for 3 minutes to obtain a premix; (3) The premix was extruded in a twin-screw extruder (length-to-diameter ratio 40:1, screw diameter 35 mm), stranded, water-dried, and pelletized to obtain a 2 mm nucleating agent; Among them, the extrusion conditions include: the screw speed is 320 rpm; the screw temperature during extrusion of the twin-screw extruder is divided into 6 sections in sequence, with the temperature of zone 1 set to 185°C, zone 2 to 185°C, zone 3 to 190°C, zone 4 to 200°C, zone 5 to 200°C, and zone 6 to 208°C.

[0057] Example 3 Prepare, by weight, 100 parts of acetone, 6 parts of maleic anhydride-modified polybutadiene (Riconbond 1756, manufactured by American Rayville), 59 parts of cycloolefin copolymer (TOPAS® Elastomer E-140, manufactured by German TOPAS), 25 parts of mercaptosilane coupling agent-modified organic-inorganic hybrid material A, 15 parts of 1-allyl-3-vinylimidazole hexafluorophosphate, and 3 parts of benzoin diethyl ether.

[0058] Preparation of nucleating agent: (1) The mercaptosilane coupling agent modified organic-inorganic hybrid material A, 1-allyl-3-vinylimidazole hexafluorophosphate, benzoin diethyl ether and acetone were mixed, and then photoinduced at a light source power density of 900 mW / cm2 and a wavelength of 320 nm for 50 minutes, and then filtered and the filter cake was dried at 110°C for 24 hours to obtain an ionic liquid modified organic-inorganic hybrid material; (2) mixing the ionic liquid modified organic-inorganic hybrid material with maleic anhydride-modified polybutadiene and cycloolefin copolymer at 40°C and 400 rpm for 3 minutes to obtain a premix; (3) The premix was extruded in a twin-screw extruder (length-to-diameter ratio 40:1, screw diameter 35 mm), stranded, water-dried, and pelletized to obtain a 2 mm nucleating agent; Among them, the extrusion conditions include: the screw speed is 320 rpm; the screw temperature during extrusion of the twin-screw extruder is divided into 6 sections in sequence, with the temperature of zone 1 set to 173°C, zone 2 to 182°C, zone 3 to 188°C, zone 4 to 198°C, zone 5 to 198°C, and zone 6 to 206°C.

[0059] Example 4 Preparation of nucleating agent raw materials: Prepare, by weight, 100 parts of acetone, 7 parts of maleic anhydride-modified polybutadiene (Riconbond 1756, manufactured by American Rayville), 61 parts of cyclic olefin copolymer (TOPAS® Elastomer E-140, manufactured by German TOPAS), 28 parts of mercaptosilane coupling agent-modified organic-inorganic hybrid material A, 14 parts of N-butylpyridinium hexafluorophosphate, and 2.5 parts of benzoin diethyl ether.

[0060] Preparation of nucleating agent: (1) The mercaptosilane coupling agent modified organic-inorganic hybrid material A, N-butylpyridinium hexafluorophosphate, benzoin diethyl ether and acetone were mixed, and then photoinduced at a light source power density of 900 mW / cm2 and a wavelength of 320 nm for 50 minutes, and then filtered and the filter cake was dried at 110°C for 24 hours to obtain an ionic liquid modified organic-inorganic hybrid material; (2) mixing the ionic liquid modified organic-inorganic hybrid material with maleic anhydride-modified polybutadiene and cycloolefin copolymer at 35°C and 300 rpm for 5 minutes to obtain a premix; (3) The premix was extruded in a twin-screw extruder (length-to-diameter ratio 40:1, screw diameter 35 mm), stranded, water-dried, and pelletized to obtain a 2 mm nucleating agent; Among them, the extrusion conditions include: the screw speed is 320 rpm; the screw temperature during extrusion of the twin-screw extruder is divided into 6 sections in sequence, with the temperature of zone 1 set to 173°C, zone 2 to 182°C, zone 3 to 188°C, zone 4 to 198°C, zone 5 to 198°C, and zone 6 to 206°C.

[0061] Example 5 Preparation of nucleating agent raw materials: Prepare, by weight, 100 parts of acetone, 7 parts of maleic anhydride-modified polybutadiene (Riconbond 1756, manufactured by American Rayville), 61 parts of cycloolefin copolymer (TOPAS® Elastomer E-140, manufactured by German TOPAS), 28 parts of mercaptosilane coupling agent-modified organic-inorganic hybrid material A, 14 parts of 1-allyl-3-butylimidazole hexafluorophosphate, and 2.5 parts of benzoin diethyl ether.

[0062] Preparation of nucleating agent: (1) The mercaptosilane coupling agent modified organic-inorganic hybrid material A, 1-allyl-3-butylimidazole hexafluorophosphate, benzoin diethyl ether and acetone were mixed, and then photoinduced at a light source power density of 900 mW / cm2 and a wavelength of 320 nm for 50 minutes, and then filtered and the filter cake was dried at 110°C for 24 hours to obtain an ionic liquid modified organic-inorganic hybrid material; (2) mixing the ionic liquid modified organic-inorganic hybrid material with maleic anhydride-modified polybutadiene and cycloolefin copolymer at 35°C and 300 rpm for 5 minutes to obtain a premix; (3) The premix was extruded in a twin-screw extruder (length-to-diameter ratio 40:1, screw diameter 35 mm), stranded, water-dried, and pelletized to obtain a 2 mm nucleating agent; Among them, the extrusion conditions include: the screw speed is 320 rpm; the screw temperature during extrusion of the twin-screw extruder is divided into 6 sections in sequence, with the temperature of zone 1 set to 173°C, zone 2 to 182°C, zone 3 to 188°C, zone 4 to 198°C, zone 5 to 198°C, and zone 6 to 206°C.

[0063] Example 6 Preparation of nucleating agent raw materials: Prepare, by weight, 100 parts of acetone, 7 parts of maleic anhydride-modified polybutadiene (Riconbond 1756, manufactured by American Rayville), 61 parts of cycloolefin copolymer (TOPAS® Elastomer E-140, manufactured by German TOPAS), 28 parts of mercaptosilane coupling agent-modified organic-inorganic hybrid material A, 14 parts of 1-allyl-3-methylimidazole p-toluenesulfonate, and 2.5 parts of benzoin diethyl ether.

[0064] Preparation of nucleating agent: (1) The mercaptosilane coupling agent modified organic-inorganic hybrid material A, 1-allyl-3-methylimidazole p-toluenesulfonate, benzoin diethyl ether and acetone were mixed, and then photoinduced at a light source power density of 900 mW / cm2 and a wavelength of 320 nm for 50 minutes, and then filtered and the filter cake was dried at 110°C for 24 hours to obtain an ionic liquid modified organic-inorganic hybrid material; (2) mixing the ionic liquid modified organic-inorganic hybrid material with maleic anhydride-modified polybutadiene and cycloolefin copolymer at 35°C and 300 rpm for 5 minutes to obtain a premix; (3) The premix was extruded in a twin-screw extruder (length-to-diameter ratio 40:1, screw diameter 35 mm), stranded, water-dried, and pelletized to obtain a 2 mm nucleating agent; Among them, the extrusion conditions include: the screw speed is 320 rpm; the screw temperature during extrusion of the twin-screw extruder is divided into 6 sections in sequence, with the temperature of zone 1 set to 173°C, zone 2 to 182°C, zone 3 to 188°C, zone 4 to 198°C, zone 5 to 198°C, and zone 6 to 206°C.

[0065] Comparative Example 1 Preparation of nucleating agent raw materials: Prepare, by weight, 7 parts of maleic anhydride-modified polybutadiene (Riconbond 1756, manufactured by American Rayville), 61 parts of cyclic olefin copolymer (TOPAS® Elastomer E-140, manufactured by German TOPAS), and 28 parts of mercaptosilane coupling agent-modified organic-inorganic hybrid material A.

[0066] Preparation of nucleating agent: (1) The mercaptosilane coupling agent-modified organic-inorganic hybrid material A, maleic anhydride-modified polybutadiene and cycloolefin copolymer were mixed at 35° C. and 300 rpm for 5 minutes to obtain a premix; (2) The premix was extruded in a twin-screw extruder (length-to-diameter ratio 40:1, screw diameter 35 mm), stranded, water-dried, and pelletized to obtain a 2 mm nucleating agent; Among them, the extrusion conditions include: the screw speed is 320 rpm; the screw temperature during extrusion of the twin-screw extruder is divided into 6 sections in sequence, with the temperature of zone 1 set to 173°C, zone 2 to 182°C, zone 3 to 188°C, zone 4 to 198°C, zone 5 to 198°C, and zone 6 to 206°C.

[0067] Comparative Example 2 Preparation of nucleating agent raw materials: Prepare, by weight, 7 parts of maleic anhydride polybutadiene (Riconbond 1756, USA), 61 parts of cyclic olefin copolymer (TOPAS® Elastomer E-140, German TOPAS), 14 parts of hydroxyaluminum p-tert-butylbenzoate, 14 parts of fumed silica (Cabot Nano Silica CAB-O-SIL LM150), and 14 parts of 1-allyl-3-vinylimidazolium hexafluorophosphate.

[0068] Preparation of nucleating agent: (1) Mixing the raw materials of the nucleating agent at 35°C and 300 rpm for 5 minutes to obtain a premix; (2) The premix was extruded in a twin-screw extruder (length-to-diameter ratio 40:1, screw diameter 35 mm), stranded, water-dried, and pelletized to obtain a 2 mm nucleating agent; Among them, the extrusion conditions include: the screw speed is 320 rpm; the screw temperature during extrusion of the twin-screw extruder is divided into 6 sections in sequence, with the temperature of zone 1 set to 173°C, zone 2 to 182°C, zone 3 to 188°C, zone 4 to 198°C, zone 5 to 198°C, and zone 6 to 206°C.

[0069] Test Case Preparation of polypropylene strips: Under the same conditions, a polypropylene base material (grade T36F, crystallization temperature of 109.3°C) and a nucleating agent (the polypropylene composite additive in the examples and comparative examples, respectively) were mixed, with the mass of the nucleating agent being 1 wt% of the mass of the polypropylene base material. The mixture was melt-extruded using a twin-screw extruder at a barrel temperature of 200-230°C, and then injection-molded into strips (100 mm × 3 mm × 3 mm) using an injection molding machine.

[0070] Preparation of polypropylene film: Polypropylene strips were melted at 230 °C, extruded into cast films, cooled on a cooling roller at 45 °C to form a 0.85 mm cast film, and finally stretched under the same conditions to obtain a 25 μm polypropylene film.

[0071] 1. Measure the light transmittance of polypropylene film according to GB / T2410.

[0072] 2. Determine the crystallization temperature of the injection molded specimen according to ASTM D3418-03.

[0073] 3. Conduct antistatic test on polypropylene film according to GB / T 1410-2006 "Test method for volume resistivity and surface resistivity of solid insulating materials". Use digital high resistance meter PC68 to test surface resistivity. Repeat the test 5 times and calculate the average value.

[0074] The test results are shown in Table 1.

[0075] Table 1: Test results of polypropylene composite additives in Examples and Comparative Examples Light transmittance (%) Crystallization temperature (℃) <![CDATA[Surface resistance (Ω) * 10 8 > 96.6% 130.9 2.86 95.8% 130.2 3.12 96.2% 130.5 2.95 90.8% 123.6 20.6 92.7% 125.5 8.03 91.7% 124.4 8.52 88.8% 121.8 45.18 86% 117.9 37.75 From the results in Table 1, it can be seen that the nucleating agent of the present invention, when used in polyolefin, can better increase the crystallization temperature and light transmittance of the polyolefin, and can also make the polyolefin have excellent antistatic properties.

Claims

1. A nucleating agent for polyolefins, characterized in that The raw materials of the nucleating agent include: organic carrier, mercaptosilane coupling agent modified organic-inorganic hybrid material, ionic liquid, ketone solvent and photoinitiator.

2. The nucleating agent according to claim 1, characterized in that The raw materials of the nucleating agent include: 100 parts of ketone solvent, 40-60 parts of organic carrier, 20-45 parts of mercaptosilane coupling agent modified organic-inorganic hybrid material, 20-30 parts of ionic liquid, and 1-5 parts of photoinitiator.

3. The nucleating agent according to claim 1 or 2, characterized in that The preparation method of the organic-inorganic hybrid material comprises: S1: ethanol and hydroxyaluminum p-tert-butylbenzoate are first mixed to obtain a first mixture; S2. The first mixed material is mixed with ethyl orthosilicate for a second time to obtain a second mixed material; S3: adjusting the pH value of the second mixture to be alkaline, and then performing a third reaction to obtain a third mixture; S4 spray-drying the third mixed material to obtain a fourth material; S5: the fourth material is passed through a 10000-20000 mesh sieve to obtain an organic-inorganic hybrid material; S6: The ethanol aqueous solution and the mercaptosilane coupling agent are hydrolyzed, and then the organic-inorganic hybrid material is added to carry out the sixth modification reaction, followed by filtration, filter cake washing, and drying to obtain the mercaptosilane coupling agent-modified organic-inorganic hybrid material.

4. The nucleating agent according to claim 3, characterized in that In step S1, the weight ratio of ethanol to hydroxyaluminum p-tert-butylbenzoate is 100:(30-50); in step S2, the weight ratio of the first mixture to tetraethyl orthosilicate is 100:(30-50); in step S3, the pH value of the second mixture is adjusted to 9-12; The conditions for the third reaction include: a temperature of 30-40°C and a time of 2-3 hours; in step S4, the conditions for the spray drying molding include: a drying air inlet temperature of 210-220°C and an air outlet temperature of 100-105°C.

5. The nucleating agent according to claim 3, characterized in that In step S6, the volume ratio of ethanol to water in the ethanol aqueous solution is (8-20):1; the mercaptosilane coupling agent is selected from at least one of 3-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, and mercaptopropylmethyldimethoxysilane; in step S6, the weight ratio of the ethanol aqueous solution to the mercaptosilane coupling agent is (150-200):1; in step S6, the weight ratio of the mercaptosilane coupling agent to the organic-inorganic hybrid material is 1:(1.5-3); in step S6, the conditions for the hydrolysis include: a temperature of 25-30°C and a time of 5-10 minutes; in step S6, the conditions for the sixth modification reaction include: a temperature of 65-75°C and a time of 2-3 hours.

6. The nucleating agent according to claim 1 or 2, characterized in that The ionic liquid is selected from alkenyl functionalized ionic liquids; the alkenyl functionalized ionic liquid is selected from at least one of 1-allyl-3-methylimidazolium chloride, 1-allyl-3-methylimidazolium bromide, 1-allyl-3-methylimidazolium tetrafluoroborate, 1-allyl-3-methylimidazolium trifluoromethanesulfonate, 1-allyl-3-methylimidazolium acetate, 1-allyl-3-methylimidazolium p-toluenesulfonate, 1-allyl-3-butylimidazolium chloride, 1-allyl-3-butylimidazolium tetrafluoroborate, 1-allyl-3-butylimidazolium hexafluorophosphate, 1-allyl-3-vinylimidazole tetrafluoroborate and 1-allyl-3-vinylimidazole hexafluorophosphate.

7. The nucleating agent according to claim 1 or 2, characterized in that The organic carrier is selected from maleic anhydride polybutadiene and cycloolefin copolymer, and the weight ratio of the maleic anhydride polybutadiene to the cycloolefin copolymer is 1:(4-25).

8. The nucleating agent according to claim 7, characterized in that The number average molecular weight of the maleic anhydride polybutadiene is 2000-3000; the mass content of maleic anhydride in the maleic anhydride polybutadiene is 10-25wt%; and the melt flow rate of the cycloolefin copolymer at 190°C / 2.16 kg is 1-5g / 10 min.

9. The nucleating agent according to claim 1 or 2, characterized in that The ketone solvent is selected from at least one of acetone, butanone, cyclohexanone, isophorone, methyl isobutyl ketone, N-methylpyrrolidone, N-ethylpyrrolidone and N-cyclohexylpyrrolidone; the photoinitiator is selected from at least one of diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, benzoin diethyl ether, 2-ethylanthraquinone, 5,7-dimethoxy-3-(4-dodecylbenzoyl)coumarin, 1-hydroxycyclohexylphenyl ketone and diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide.

10. A method for preparing the nucleating agent according to any one of claims 1 to 9, characterized in that: The preparation method comprises: (1) mixing a mercaptosilane coupling agent-modified organic-inorganic hybrid material, an ionic liquid, a photoinitiator, and a ketone solvent, performing a photoinitiation reaction, filtering, and drying the filter cake to obtain an ionic liquid-modified organic-inorganic hybrid material; (2) premixing the ionic liquid modified organic-inorganic hybrid material with an organic carrier to obtain a premix; (3) The premix is ​​extruded in a twin-screw extruder, stretched into strands, passed through water, and pelletized.