Nucleating agent compositions, polyolefin compositions, and methods of making and use

Abstract

The present application discloses a nucleating agent composition, a polyolefin composition, a preparation method and an application. The nucleating agent composition comprises a polyol diacetal nucleating agent shown in formula (I) and a hydrocarbon compound; the hydrocarbon compound is selected from one or more of alkane, alkene and polyolefin; the hydrocarbon compound is solid at 20-35 DEG C; and the melting point of the hydrocarbon compound is less than or equal to 200 DEG C. The nucleating agent composition can reduce the processing temperature of the polyolefin resin.

Description

TECHNICAL FIELD

[0001] The present application relates to a nucleating agent composition, a polyolefin composition and a method for preparing the same, and a use of a hydrocarbon compound. BACKGROUND

[0002] Sorbitol nucleating agents can improve the mechanical and optical properties of polyolefin resins, but the solubility of sorbitol nucleating agents in polyolefin resins is relatively low, which can cause the polyolefin material to have poor haze and transparency. In addition, the processing temperature of the polyolefin resin added with the sorbitol nucleating agent is also relatively high, which increases the production energy consumption.

[0003] CN103391966B discloses a method for preparing a thermoplastic polymer composition, comprising the following steps: (a) providing a thermoplastic polymer; (b) providing an additive composition comprising: (i) at least one clarifying agent selected from the group consisting of triamide, 2,2'-methylenebis-(4,6-di-tert-butylphenyl) aluminum phosphate, 2,2'-methylenebis(4,6-di-tert-butylphenyl) lithium phosphate, monocarboxylic acid compound and acetal compound conforming to the structure of formula (I); (ii) colorant; and (c) mixing the thermoplastic polymer and the additive composition to prepare a thermoplastic polymer composition. The method requires injection molding at 230℃, and the processing temperature is relatively high.

[0004] CN115141411A discloses a complex transparent nucleating agent, which comprises 1,3:2,4-di(3,4-dimethylbenzyl) sorbitol, a chelating agent and a sorbitol ester emulsifier. The chelating agent is one or more of metal salts of calcium, magnesium, copper, zinc and zirconium, and the sorbitol ester emulsifier is a Tween emulsifier or a Span emulsifier. The complex nucleating agent requires a relatively high injection molding temperature when applied to polypropylene resin.

[0005] CN111892766A discloses a PP material injection molding process, comprising the following steps: S1 external agent preparation: weighing external agent raw materials and mixing uniformly to prepare an external agent. The external agent raw materials include acetylated distarch phosphate, a nucleating agent and a dispersing agent. The dispersing agent includes stearic acid amide and microcrystalline wax. Weighing PP particles, adding the external agent and mixing uniformly to prepare a powder. The powder is heated to 185-210℃ to prepare a molten liquid. The molten liquid is injected into a mold, pressure is maintained, and a thermoplastic product is obtained. The thermoplastic product is cooled to obtain a PP plastic product. The method improves the mechanical properties of the plastic product by adding microcrystalline wax. SUMMARY

[0006] In view of the above, an object of the present application is to provide a nucleating agent composition which is used in combination with a polyolefin resin and has a low processing temperature. Further, the nucleating agent composition is capable of reducing the haze of the polyolefin resin. Another object of the present application is to provide a polyolefin composition. Still another object of the present application is to provide a method of producing a polyolefin composition. Yet another object of the present application is to provide a use of a hydrocarbon compound.

[0007] In one aspect, the present application provides a nucleating agent composition comprising a polyol acetal nucleating agent represented by Formula (I) and a hydrocarbon compound.

[0008] The hydrocarbon compound is selected from one or more of an alkane, an alkene, and a polyolefin, the hydrocarbon compound is in a solid state at 20 to 35°C, and the hydrocarbon compound has a melting point of ≤ 200°C.

[0009]

[0010] wherein R1 to R 10 are each independently selected from hydrogen, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, and a halogen, R 11 is selected from -CH2OH and -CHOHCH2OH.

[0011] According to the nucleating agent composition of the present application, preferably, the mass ratio of the polyol acetal nucleating agent to the hydrocarbon compound is 1 : (2 to 20).

[0012] According to the nucleating agent composition of the present application, preferably, the nucleating agent composition further comprises a salt material selected from one or more of a stearate, a benzoate, and a hydrotalcite.

[0013] The polyol acetal nucleating agent is used in an amount of 0.01 to 0.4 parts by weight, the hydrocarbon compound is used in an amount of 0.1 to 10 parts by weight, and the salt material is used in an amount of 0.01 to 0.1 parts by weight.

[0014] According to the nucleating agent composition of the present application, preferably, the nucleating agent composition further comprises an antioxidant and / or a pigment.

[0015] The antioxidant is used in an amount of 0.05 to 1 parts by weight, and the pigment is used in an amount of 0.0005 to 0.005 parts by weight.

[0016] According to the nucleating agent composition of the present application, preferably, the antioxidant is selected from one or more of a phenolic antioxidant and a phosphite antioxidant, and the pigment is selected from one or more of a quinacridone, a perylene, a dioxazine pigment, an isoindolinone, a diketopyrrolopyrrole, a phthalocyanine blue, a cyanine blue, and a cyanine violet.

[0017] According to the nucleating agent composition of the present application, preferably, the polyol dialkyl acetal nucleating agent is selected from one or more of 1,3:2,4-dibenzylidene sorbitol, 1,3:2,4-bis(p-methylbenzylidene)-sorbitol and 1,3:2,4-bis(3,4-dimethylbenzylidene)-sorbitol.

[0018] The hydrocarbon compound is selected from one or more of solid paraffin wax, polyethylene wax.

[0019] In another aspect, the present application provides a polyolefin composition comprising a polyolefin resin and the above-mentioned nucleating agent composition.

[0020] According to the polyolefin composition of the present application, preferably, the polyolefin resin is selected from one or more of polyethylene, polypropylene, polybutylene, and the amount of the polyolefin resin is 100 parts by weight.

[0021] In still another aspect, the present application provides a method for preparing the above-mentioned polyolefin composition, comprising the following steps:

[0022] (1) granulating the polyolefin resin and the nucleating agent composition to obtain polyolefin resin granules;

[0023] (2) injection molding the polyolefin resin granules at 150-240℃ to obtain the polyolefin composition.

[0024] In still another aspect, the present application provides a use of a hydrocarbon compound in reducing the processing temperature and / or haze of a composition, the hydrocarbon compound is selected from one or more of alkanes, alkenes, polyolefins, the hydrocarbon compound is solid at 20-35℃, the melting point of the hydrocarbon compound is ≤200℃; the composition comprises a polyolefin resin and a polyol dialkyl acetal nucleating agent represented by formula (I);

[0025]

[0026] wherein, R1-R 10 are independently selected from hydrogen, alkyl, alkoxy, alkenyl, aryl and halogen, R 11 is selected from -CH2OH and -CHOHCH2OH.

[0027] The nucleating agent composition of the present application has a lower processing temperature when combined with a polyolefin resin. Further, the nucleating agent composition of the present application can reduce the haze of the polyolefin resin. DETAILED DESCRIPTION

[0028] The present application will be further described in conjunction with specific examples, but the scope of protection of the present application is not limited thereto.

[0029] <Nucleating agent composition>

[0030] The nucleating agent composition of the present invention comprises a polyol diacetal nucleating agent of formula (I) and a hydrocarbon compound. In some embodiments, the nucleating agent composition of the present invention further comprises a salt. In some embodiments, the nucleating agent composition of the present invention further comprises an antioxidant and / or a pigment. In some embodiments, the nucleating agent composition of the present invention consists only of the above-mentioned substances. The applicant has unexpectedly discovered that the hydrocarbon compound of the present invention can increase the solubility of the polyol diacetal nucleating agent in polyolefin resins, reduce the processing temperature of polyolefin resins, and the resulting polyolefin composition has low haze.

[0031] The polyol diacetal nucleating agent of the present invention is shown in formula (I):

[0032]

[0033] Among them, R1~R 10 Each is independently selected from hydrogen, alkyl, alkoxy, alkenyl, aryl, and halogen, R 11 Selected from -CH2OH and -CHOHCH2OH. Preferably, R1 to R2 are... 10 Each is independently selected from hydrogen, alkyl, and alkoxy groups, R 11 Selected from -CH2OH and -CHOHCH2OH. More preferably, R1 to R 10 Each is independently selected from hydrogen and alkyl groups, R 11 Selected from -CH2OH and -CHOHCH2OH. In some embodiments, at least three of R1 to R5 are hydrogen substituents, and R6 to R... 10 It has at least three substituents that are hydrogen.

[0034] In this invention, the aryl group can be selected from phenyl, naphthyl, and anthracene. The aryl group may have substituents. Substituents on the aryl group include, but are not limited to, alkyl, alkoxy, and halogen groups.

[0035] In this invention, the alkyl group is preferably an alkyl group containing 1 to 8 carbon atoms; more preferably an alkyl group containing 1 to 6 carbon atoms. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, neopentyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 2,3-dimethylbutyl, 2,2-dimethylbutyl, n-heptyl, and n-octyl.

[0036] In the present application, the alkyl group is preferably an alkyl group containing 1 to 8 carbon atoms; more preferably an alkyl group containing 1 to 6 carbon atoms. Examples of the alkyl group include, but are not limited to, methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, isobutyl, n-pentyl, isopentyl, neopentyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 2,3-dimethylbutyl, 2,2-dimethylbutyl, n-heptyl, n-octyl.

[0037] In the present application, the alkenyl group is preferably an alkenyl group containing 1 to 8 carbon atoms; more preferably an alkenyl group containing 1 to 6 carbon atoms. Preferably, the alkenyl group contains one or two unsaturated double bonds. More preferably, the alkenyl group contains one unsaturated double bond. Examples of the alkenyl group include, but are not limited to, ethenyl, propenyl, allyl, 1-butenyl, 2-butenyl, 3-butenyl, 1,3-dibutenyl, 2-methylpropenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl.

[0038] In the present application, examples of the halogen include, but are not limited to, fluorine, chlorine, bromine, iodine.

[0039] when R 11 is -CH2OH, formula (I) represents a five-membered alcohol diacetal nucleating agent, such as a diacetal nucleating agent of xylitol. When R 11 is -CHOHCH2OH, formula (I) represents a six-membered alcohol diacetal nucleating agent, such as a diacetal nucleating agent of sorbitol, a diacetal nucleating agent of glucose.

[0040] According to one embodiment of the present application, the polyol diacetal nucleating agent is a diacetal of sorbitol. Examples of the polyol diacetal nucleating agent include, but are not limited to, 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol, 1,3:2,4-bis(p-methylbenzylidene)sorbitol, 1,3:2,4-bisbenzylidene sorbitol, 1,3:2,4-(3,4-dimethylbenzylidene / p-methylbenzylidene)sorbitol, 1,3:2,4-bis(p-ethylbenzylidene)sorbitol, 1,3:2,4-(p-ethylbenzylidene / 3,4-dimethylbenzylidene)sorbitol, 1,3:2,4-(p-methylbenzylidene / p-ethylbenzylidene)sorbitol, 1,3:2,4-bis(p-chlorobenzylidene)sorbitol, 1,3:2,4-(p-chlorobenzylidene / p-methylbenzylidene)sorbitol, 1,3:2,4-(p-chlorobenzylidene / 3,4-dimethylbenzylidene)sorbitol, 1,3:2,4-bis(m-bromobenzylidene)sorbitol, 1,3:2,4-(3,4-dimethylbenzylidene / benzylidene)sorbitol, 1,3:2,4-(p-chlorobenzylidene / m-bromobenzylidene)sorbitol, or any combination of the above polyol diacetals.

[0041] According to one embodiment of the present application, the polyol dialkyl acetal nucleating agent is selected from 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol (nucleating agent 3988), 1,3:2,4-bis(p-methylbenzylidene)sorbitol (nucleating agent 3940), 1,3:2,4-bisbenzylidene sorbitol (nucleating agent 3905). According to one preferred embodiment of the present application, the polyol dialkyl acetal nucleating agent is 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol.

[0042] The above-mentioned nucleating agent in combination with the hydrocarbon compound of the present application is more helpful to reduce the processing temperature and the haze.

[0043] The hydrocarbon compound of the present application is selected from one or more of alkane, alkene, polyalkene. The hydrocarbon compound is solid at 20-35°C. The melting point of the hydrocarbon compound is ≤200°C.

[0044] In the present application, the alkane can be a chain alkane or a cyclic alkane. The chain alkane can be a straight chain alkane or a branched chain alkane. The alkane can be an alkane containing 18-36 carbon atoms.

[0045] In the present application, the alkene can be a chain alkene or a cyclic alkene. The chain alkene can be a straight chain alkene or a branched chain alkene.

[0046] In the present application, the monomer forming polyalkene can be a chain alkene or a cyclic alkene. The chain alkene can be a straight chain alkene or a branched chain alkene. In some embodiments, the monomer forming polyalkene can contain 2-10 carbon atoms; preferably, 2-5 carbon atoms.

[0047] The hydrocarbon compound is solid at room temperature. Room temperature refers to 20-35°C. Specifically, room temperature refers to 25-30°C.

[0048] The melting point of the hydrocarbon compound is ≤200°C; preferably, ≤100°C; more preferably, ≤80°C. In some embodiments, the melting point of the hydrocarbon compound is ≥40°C; preferably, ≥45°C.

[0049] Examples of the hydrocarbon compound include, but are not limited to, solid paraffin, polyethylene paraffin.

[0050] The above-mentioned hydrocarbon compound has better promoting effect on the nucleating agent of the present application, and is more helpful to reduce the processing temperature and the haze of the polyalkene resin.

[0051] The mass ratio of the polyol dialkyl acetal nucleating agent to the hydrocarbon compound can be 1:(2-20); preferably, 1:(5-15); more preferably, 1:(7-12). Using such ratio can reduce the processing temperature and the haze of the polyalkene composition on the basis of reducing the amount of the hydrocarbon compound.

[0052] The salt substance is selected from one or more of stearate, benzoate and hydrotalcite. Examples of stearate include, but are not limited to, calcium stearate, zinc stearate, lithium stearate, sodium stearate. Examples of benzoate include, but are not limited to, sodium benzoate. According to one embodiment of the present application, the salt substance is calcium stearate.

[0053] The antioxidant is selected from one or more of phenolic antioxidant and phosphite antioxidant. In some embodiments, the antioxidant is a combination of phenolic antioxidant and phosphite antioxidant. The mass ratio of the phenolic antioxidant and the phosphite antioxidant can be 1 : (0.5-4); preferably 1 : (1-3); more preferably 1 : (1-2). In other embodiments, the antioxidant is a phenolic antioxidant. Examples of phenolic antioxidant include, but are not limited to, antioxidant 1010, antioxidant 1076, antioxidant 330, antioxidant 3114, antioxidant 1790, antioxidant 508, antioxidant 535, antioxidant 541, antioxidant 545, antioxidant 590. Examples of phosphite antioxidant include, but are not limited to, antioxidant 618, antioxidant 168, antioxidant 626, antioxidant PEPQ, antioxidant 624, antioxidant PEP-36, antioxidant HP-10. Preferably, the phenolic antioxidant is selected from one or more of antioxidant 1010, antioxidant 1076, antioxidant 330. Preferably, the phosphite antioxidant is selected from one or more of antioxidant 168, antioxidant 624, antioxidant 626. In some embodiments of the present application, the antioxidant comprises antioxidant 1010 and antioxidant 168.

[0054] The pigment is selected from one or more of quinacridone, perylene, dioxazine, isoindolinone, diketopyrrolopyrrole, phthalocyanine blue, ultramarine blue, ultramarine violet. According to one embodiment of the present application, the pigment is ultramarine blue.

[0055] In the present application, the amount of polyol dialkyl acetal nucleating agent is 0.01-0.4 parts by weight; preferably 0.1-0.35 parts by weight; more preferably 0.2-0.3 parts by weight.

[0056] In the present application, the amount of hydrocarbon compound is 0.1-10 parts by weight; preferably 0.5-5 parts by weight; more preferably 2.5-4 parts by weight.

[0057] In the present application, the amount of salt substance is 0.01-0.1 parts by weight; preferably 0.02-0.08 parts by weight; more preferably 0.04-0.07 parts by weight.

[0058] In the present application, the amount of antioxidant is 0.05-1 parts by weight; preferably 0.1-0.5 parts by weight. In some embodiments, the amount of antioxidant is 0.15-0.3 parts by weight.

[0059] In the present application, the amount of the pigment is 0.0005 to 0.005 parts by weight; preferably, 0.001 to 0.004 parts by weight. In some embodiments, the amount of the pigment is 0.002 to 0.003 parts by weight.

[0060] Controlling the amount of each component within the above range helps to improve the synergistic effect between the components, so that the nucleating agent composition can be used in combination with the polyolefin resin to obtain a polyolefin resin composition with lower haze at a lower processing temperature.

[0061] <The polyolefin composition>

[0062] The polyolefin composition of the present application comprises a polyolefin resin and a nucleating agent composition. In some embodiments, the polyolefin composition consists of a polyolefin resin and a nucleating agent composition.

[0063] In the present application, the amount of the polyolefin resin is 100 parts by weight. The composition of the nucleating agent composition and the amount of each component are as described above. Such a combination can effectively reduce the processing temperature and haze of the polyolefin composition, and has less adverse effect on other properties of the polyolefin resin.

[0064] The polyolefin resin of the present application can be selected from one or more of polyethylene, polypropylene, and polybutylene. Preferably, the polyolefin resin is a polypropylene resin. The polypropylene resin can be isotactic polypropylene, atactic polypropylene, or syndiotactic polypropylene. The polypropylene has better compatibility with the nucleating agent composition of the present application, and can better exert the effect of the nucleating agent composition.

[0065] The haze of the polyolefin composition of the present application is less than or equal to 11%, preferably less than or equal to 9%, and more preferably less than or equal to 7.5%. In some embodiments, the haze is 6% to 11%, preferably 6.5% to 9%, and more preferably 7% to 8%. The haze is measured according to GB / T 2410-2008 using a haze meter, and the sample is a 1 mm thick sheet.

[0066] <Method for preparing the polyolefin composition>

[0067] The method for preparing the polyolefin composition of the present application comprises the following steps: (1) a granulation step; and (2) an injection molding step.

[0068] The step of granulating

[0069] The polyolefin resin and the nucleating agent composition are pelletized to obtain polyolefin resin pellets. Specifically, the polyolefin resin is mixed with the nucleating agent composition, and then the mixture is melt-kneaded and pelletized. In some embodiments, the components in the nucleating agent composition need to be mixed uniformly before mixing with the polyolefin resin.

[0070] The temperature for pelletization can be 200-250°C; preferably 210-240°C; more preferably 210-230°C.

[0071] The step of injection molding

[0072] The polyolefin resin pellets are injection molded at 150-240°C to obtain the polypropylene composition. The injection molding can be done in an injection molding machine.

[0073] The temperature for injection molding can be 150-240°C; preferably 170-210°C; more preferably 180-200°C. The polyolefin resin composition of the present application can obtain a low haze when injection molded at a temperature range of 150-240°C. In particular, the haze can be further reduced at a lower temperature. This not only can obtain a polyolefin resin composition with low haze, but also can reduce the energy consumption in production, and has a broad industrial application prospect.

[0074] <Use of hydrocarbon compounds>

[0075] It is surprisingly found that adding a specific hydrocarbon compound to a composition containing a polyolefin resin and a polyol dialkyl acetal nucleating agent can reduce the processing temperature of the composition and can reduce the haze of the composition. Therefore, the present application provides a use of a hydrocarbon compound in reducing the processing temperature and / or haze of a composition. The processing temperature is preferably the injection molding temperature.

[0076] The hydrocarbon compound of the present application is selected from one or more of alkanes, alkenes, and polyolefins. The hydrocarbon compound is solid at 20-35°C. The melting point of the hydrocarbon compound is ≤200°C. The selection and amount of the hydrocarbon compound are as described above and will not be repeated here.

[0077] The composition of the present application contains a polyolefin resin and a polyol dialkyl acetal nucleating agent. In some embodiments, it also contains one or more of a salt, an antioxidant, and a pigment. The selection and amount of the polyolefin resin, the polyol dialkyl acetal nucleating agent, the salt, the antioxidant, and the pigment are as described above and will not be repeated here.

[0078] The haze of the composition of the present application is less than or equal to 11%, preferably less than or equal to 9%, more preferably less than or equal to 7.5%. In some embodiments, the haze is 6% to 11%, preferably 6.5% to 9%, more preferably 7% to 8%. The haze is measured according to GB / T 2410-2008 using a haze meter, and the sample is a 1mm thick sheet.

[0079] The processing temperature of the composition of the present application is 150 to 240°C; preferably 170 to 210°C; more preferably 180 to 200°C.

[0080] The test methods used in the following examples and comparative examples are described below:

[0081] Haze: tested according to the method specified in GB / T 2410-2008.

[0082] The raw materials used are described below:

[0083] Polypropylene resin: MT20 powder produced by Sinopec Zhongyuan Petrochemical Co., Ltd. The melt index is 18 to 22 g / 10 min, and the ethylene content is less than 5%.

[0084] Solid paraffin: melting point range (melting range) is 45 to 65°C.

[0085] Pigment: ultramarine blue.

[0086] Examples 1 to 10 and Comparative Examples 1 to 10

[0087] 1,3:2,4-di(3,4-dimethylbenzylidene)-sorbitol (nucleating agent 3988), solid paraffin (if any), pigment, antioxidant 1010 (tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester), antioxidant 168 (tris[2.4-di-tert-butylphenyl]phosphite) (if any), and calcium stearate were mixed to obtain a nucleating agent composition.

[0088] 100 parts by weight of polypropylene resin and the nucleating agent composition were uniformly mixed in a blender, then melted and kneaded, and pelletized at 220°C to obtain polyolefin pellets.

[0089] The polyolefin pellets were injection molded into polyolefin compositions in an injection molding machine at a T temperature. The polyolefin composition was a 1mm thick sheet.

[0090] The composition of the nucleating agent composition, the injection molding temperature, and the haze of the polyolefin composition are shown in Table 1.

[0091] Table 1

[0092]

[0093] From the above table, it can be seen that the addition of solid paraffin can indeed reduce the haze of the polypropylene and can reduce the injection molding temperature. The polyolefin composition of the present application can obtain a product with lower haze at a lower injection molding temperature. This not only improves the quality of the product, but also reduces the production energy consumption, which has significant significance.

[0094] The present application is not limited to the above-described embodiments, and any modification, improvement, or replacement that can be conceived by those skilled in the art without departing from the essential content of the present application falls within the scope of the present application.

Claims

1. A polyolefin composition, characterized in that, The polyolefin composition comprises 100 parts by weight of polypropylene resin, 0.3-0.35 parts by weight of 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol, 2.5-4 parts by weight of solid paraffin, 0.003-0.004 parts by weight of ultramarine blue, 0.15-0.3 parts by weight of antioxidant, and 0.07-0.08 parts by weight of calcium oxalate; the antioxidant comprises antioxidant 1010 and antioxidant 168, and the mass ratio of the antioxidant 1010 to the antioxidant 168 is 1:(1-2); The melting point of the solid paraffin is greater than or equal to 40 DEG C and less than or equal to 80 DEG C.

2. The process for the preparation of a polyolefin composition according to claim 1, characterized in that, The method comprises the following steps: (1) granulating the polypropylene resin, 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol, solid paraffin, ultramarine blue, antioxidant, and calcium oxalate to obtain polyolefin resin granules; (2) injection molding the polyolefin resin granules at 150-240 DEG C to obtain the polyolefin composition.

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