High-barrier polyolefin nylon composite material as well as preparation method and application thereof

Abstract

The invention discloses a high-barrier polyolefin nylon composite material as well as a preparation method and application thereof. The composite material comprises the following components: a) 80-99 parts of polyolefin; b) 1-25 parts of nylon; c) 0.01 to 0.5 part of a nucleating agent; and d) 0.1-3 parts of an antioxidant. The high-barrier nylon containing alkyl side groups is copolymerized, so that the compatibility with a polyolefin material is improved, and the polyolefin composite material with high barrier property is obtained by blending with the antioxidant and the nucleating agent, and is used in polyolefin container packaging.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to a high-barrier polyolefin nylon composite material, its preparation method, and its applications. Background Technology

[0002] Polyolefin materials such as polypropylene and polyethylene, as general-purpose thermoplastics, are widely used in automobiles, home appliance parts, packaging, and other fields due to their advantages such as non-toxicity, low price, low relative density, and resistance to chemical corrosion. However, polyolefin materials have poor barrier properties against substances such as oxygen and carbon dioxide, limiting their use in fields with high barrier requirements. Poly(m-phenylene caproyl)dimethylamine (MXD6) is a semi-aromatic nylon polymerized from m-phenylene dimethylamine (MXDA) and adipic acid. Due to its high density of benzene rings and small intermolecular gaps, it possesses excellent barrier properties and can be used in barrier films and containers.

[0003] There are many solutions to improve the barrier properties of polyolefin materials. CN107513257A prepared PET / MXD6 or PP / MXD6 multilayer materials through a multilayer co-extrusion process, with MXD6 addition ranging from 10-50%. This process is complex and does not consider the adhesion between adjacent PP and MXD6 layers, leading to delamination and failure of the product during use. Patent CN110845793B improves the barrier properties of polypropylene by blending 2-20% nylon with graphene, elastomers, solubilizers, and other additives. The nylons used include nylon 6, nylon 12, nylon 1010, and nylon 610. These nylons are mainly used in automotive piping, gas tanks, and gas transmission lines where barrier properties are required. The barrier properties of this aliphatic nylon have room for further improvement. CN118222060A describes the preparation of a high-barrier polyolefin masterbatch by blending polyolefin, styrene, maleic anhydride as a graft modifier, peroxide as an initiator, and montmorillonite as a multilayer barrier material. However, the preparation process cannot guarantee the complete reaction of maleic anhydride and peroxide, and the residues may affect its application in food packaging.

[0004] Downstream food customers have reported that existing polyolefin packaging solutions have a short shelf life and their barrier properties urgently need further improvement. Therefore, it is of great significance to further improve the barrier properties of polyolefin materials so that they can have a wider range of applications. Summary of the Invention

[0005] The purpose of this invention is to provide a high-barrier polyolefin nylon composite material, its preparation method, and its applications. The composite material of this invention has better barrier properties.

[0006] To solve the above technical problems, the present invention provides the following technical solution:

[0007] A high-barrier polyolefin nylon composite material comprises the following parts by weight:

[0008]

[0009] As a preferred embodiment, the polyolefins described in this invention include polypropylene and / or polyethylene.

[0010] As a preferred embodiment, the comonomers of the nylon described in this invention include m-phenylenediamine, adipic acid, other diamines and / or other dicarboxylic acids.

[0011] As a preferred embodiment, the comonomer of the nylon described in this invention includes: m-phenylenediamine, adipic acid, and other diamines; or, m-phenylenediamine + adipic acid and other diamines.

[0012] As a preferred embodiment, the other diamines described in this invention include any one or more compounds having the structure shown in Formula I (containing a straight-chain or branched aliphatic side group) and Formula II (containing a straight-chain or branched aliphatic side group):

[0013]

[0014] In Formula I, the R group is a C4-C18 alkyl group, such as butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, octadecyl and their corresponding isomers; in Formula II, the R1 group is a C6-C8 alkyl group, such as isohexyl, isoheptyl, isooctyl, and the -CH2-NH2 group in Formula II is located in the meta (1,3-) or para (1,4-) position.

[0015] Preferably, the method for preparing the diamine of formula I containing straight-chain or branched aliphatic side groups includes the following steps:

[0016] (1) R-NH2, acrylonitrile and catalyst are reacted in water at 80-100℃ for 4-8h, and then distilled under reduced pressure at 100-130℃ and 5-15kPa for 2-5h to obtain bis(nitrile) ethyl compound.

[0017] (2) The bis(nitrile) ethyl compound obtained in step (1) is subjected to hydrogenation to obtain a diamine of formula I containing straight-chain or branched aliphatic side groups.

[0018] Preferably, in step (1), the catalyst comprises glycolic acid.

[0019] Preferably, in step (1), the molar ratio of acrylonitrile to R-NH2 is (2.2-2.6):1.

[0020] Preferably, in step (1), the molar ratio of acrylonitrile to catalyst is 1:(0.025-0.05).

[0021] Preferably, in step (2), the hydrogenation reaction is carried out in the presence of a metal-supported catalyst, preferably a Ru / Al2O3 catalyst, and the amount of catalyst used is 0.1-0.5 wt% of the bis(nitrile) ethyl compound.

[0022] Preferably, in step (2), the hydrogenation reaction is carried out in a mixed solvent consisting of anhydrous ethanol and an aqueous solution of potassium carbonate with a mass fraction of 0.4-0.5 wt%.

[0023] Preferably, in step (2), the hydrogen pressure of the hydrogenation reaction is 2-3 MPa, the reaction temperature is 100-130℃, and the reaction time is 1-3 h.

[0024] Preferably, the method for preparing cyclohexanedimethylamine of Formula II containing straight-chain or branched aliphatic side groups includes the following steps:

[0025] (a) Neutralize 1,3-cyclohexanedimethylamine or 1,4-cyclohexanedimethylamine with a C2-C4 organic acid to obtain a first mixture; mix the first mixture with a C6-C8 olefin to obtain a second mixture; react the second mixture with 0.1%-1% of aluminum trichloride by mass, crystallize and separate to obtain a crude product, and dissolve the crude product in a MIBK solution to obtain a third mixture;

[0026] (b) The third mixture is reacted with sodium hydroxide solution, separated to obtain the product oil phase, washed with water, and distilled.

[0027] Preferably, in step (a), the C2-C4 organic acid is selected from one or more of acetic acid, propionic acid, and butyric acid.

[0028] Preferably, in step (a), the molar ratio of 1,3-cyclohexanedimethylamine or 1,4-cyclohexanedimethylamine to C2-C4 organic acids is 1:(2-2.2).

[0029] Preferably, in step (a), the temperature of neutralization is 10-40°C.

[0030] Preferably, in step (a), the C6-C8 olefin is selected from one or more of n-hexene, n-heptene, and n-octene.

[0031] Preferably, in step (a), the molar ratio of 1,3-cyclohexanedimethylamine or 1,4-cyclohexanedimethylamine to C6-C8 olefins in the first mixture is 1:(3-5).

[0032] Preferably, in step (a), the reaction temperature is 100-200℃, the reaction pressure is 1-10 MPa, and the reaction time is 8-20 h.

[0033] Preferably, in step (a), the crystallization and separation steps include: controlling the cooling rate at 1-5 K / min, reducing the temperature from the reaction temperature to 10-20°C, and filtering the reaction solution after crystallization.

[0034] Preferably, in step (a), the mass ratio of crude product to MIBK is 1:(3-5).

[0035] Preferably, in step (b), the concentration of the sodium hydroxide solution is 20-40 wt%.

[0036] Preferably, in step (b), the mass ratio of the third mixture to the sodium hydroxide solution is 1:(1-2).

[0037] Preferably, in step (b), the reaction temperature of the third mixture with the sodium hydroxide solution is 80-120°C, and the reaction time is 1-2 hours.

[0038] Preferably, in step (b), the water washing is a countercurrent water washing of the oil phase, and the number of water washing stages is 2-4 stages.

[0039] Preferably, in step (b), the water washing temperature is 10-20°C, and the mass ratio of oil phase to water washing water is 1:(2-3).

[0040] Preferably, in step (b), the bottom temperature of the distillation column is 70-90℃, the top temperature is 40-50℃, and the pressure is 10-50Kpa.

[0041] As a preferred embodiment, the other dicarboxylic acid is a C3-C14 dicarboxylic acid containing branched alkanes, wherein the branched alkanes are C2-C10 alkyl groups, and the number of branches in the dicarboxylic acid can be an integer from 1 to 3. Suitable examples include, but are not limited to, one or more of the following: butylmalonic acid, dibutylmalonic acid, ethylsuccinic acid, propylsuccinic acid, butylsuccinic acid, 2,3-diethylsuccinic acid, 2-ethylglutaric acid, 3-ethylglutaric acid, 3-ethyl-3-methylglutaric acid, 2-propylglutaric acid, 3-propylglutaric acid, 3-butylglutaric acid, 3-isobutylglutaric acid, 2,4-diethylglutaric acid, 2-ethylhexanoic acid, 2-butylhexanoic acid, 3-tert-butylhexanoic acid, 2,5-dibutylhexanoic acid, 2-butyloctanoic acid, 2-ethyloctanoic acid, etc.

[0042] As a preferred embodiment, the amount of the other diamines and / or other diacids added is 0.25-1.5 wt%, preferably 0.4-1.1 wt%, based on the mass of the comonomers; the molar ratio of all diamines and diacids in the nylon is 1:(1.005-1.01); and the relative viscosity of the nylon is 1.8-3.5, preferably 2.1-3.0.

[0043] As a preferred embodiment, the method for preparing the nylon includes the following steps:

[0044] m-Phenylenediamine, adipic acid, other diamines and / or other dicarboxylic acids, catalyst and water are added to a reaction vessel. After nitrogen purging, the temperature is raised to 50-120℃ for 30-60 min for salt formation reaction. Then, the mixture is transferred to a prepolymerization reaction vessel, and the temperature is raised to 150-230℃ for 60-120 min for prepolymerization reaction. Finally, the temperature is raised to 260-280℃ for 30-120 min for melt polycondensation reaction to obtain the nylon.

[0045] As a preferred embodiment, the method for preparing the composite material includes the following steps: mixing the polyolefin, nylon, nucleating agent, and antioxidant evenly according to a ratio, and then adding them into the extruder through the main feed port of the twin-screw extruder; the processing temperature is 240-280℃; and extruding and granulating.

[0046] As a preferred embodiment, the nucleating agent of the present invention is selected from sorbitol-based nucleating agents, Brügmann P22, Brügmann P32, NAV101 nucleating agent, etc. Suitable examples of sorbitol-based nucleating agents include, but are not limited to, one or more of di(p-ethylbenzyl)sorbitol (EDBS), 1,3-2,4-di(p-hydroxy)benzyl sorbitol (DHDBS), 1,3-2,4-di(p-nitro)benzyl sorbitol (DNDBS), and 1,3-2,4-di(3,4-dimethylbenzyl)-D-sorbitol (DMDBS).

[0047] As a preferred embodiment, the composite material can be used in polyolefin barrier containers such as jelly cups, yogurt cups, and sauce containers.

[0048] The beneficial effects of this invention are as follows: The high-barrier polyolefin nylon composite material provided by this invention introduces other diamines containing alkyl side groups and / or other dicarboxylic acids containing alkyl side groups into the preparation of barrier nylon raw materials, combined with m-phenylenediamine and adipic acid, successfully introducing alkyl side groups into the molecular chain of nylon resin. This increases the compatibility and distribution uniformity of non-polar polyolefin and polar nylon materials when combined with a specific amount of polyolefin, thereby improving the barrier properties of the polyolefin material and the barrier properties of food packaging containers made of polyolefin material. Detailed Implementation

[0049] The following examples further illustrate preferred embodiments within the scope of the present invention. These examples are merely illustrative and not intended to limit the scope of the invention, as many variations can be made to the invention without departing from its essence and scope.

[0050] The main raw materials used in the embodiments of the present invention are all obtained from common commercially available raw materials.

[0051] The performance testing method used in this embodiment of the invention:

[0052] Relative viscosity: Prepare a concentrated sulfuric acid solution with a nylon chip concentration of 0.01 g / ml, and measure the relative viscosity using an Ubbelohde viscometer.

[0053] Mechanical property testing: Mechanical properties were tested according to ISO standards. Tensile strength was tested according to ISO 527-2:2012 standard at a tensile speed of 50 mm / min. Impact strength was measured as the impact strength of a simply supported beam.

[0054] Monomer Preparation Example 1

[0055] A diamine containing a dodecyl side group, the structure of which is as follows:

[0056]

[0057] Its preparation method includes the following steps:

[0058] (1) 125g (2.356mol) of acrylonitrile was added to a high-pressure reactor containing 7.5g of glycolic acid aqueous solution (75wt%, based on the total weight of the solution), and 170g (0.917mol) of dodecylamine was added. The mixture was heated to 90℃ and reacted for 8h to obtain a reaction solution. The reaction solution was then subjected to vacuum distillation at 130℃ and 10kPa for 5h to remove low-boiling-point acrylonitrile and other substances to obtain bis(nitrile) ethyl compound.

[0059] (2) 200g of the bis(nitrile) ethyl compound obtained in step (1) and 15g of Ru / Al2O3 catalyst with a mass percentage of 5% were added to a mixed solvent consisting of 400g of anhydrous ethanol and 300g of potassium carbonate aqueous solution (0.5wt%). The mixture was reacted for 2h under the conditions of hydrogen pressure of 2.3MPa and temperature of 100℃, and then cooled to obtain the diamine containing dodecyl side groups.

[0060] Monomer Preparation Example 2

[0061] A diamine containing a butyl side group has the following structure:

[0062]

[0063] Its preparation method includes the following steps:

[0064] (1) 93g (1.271mol) acrylonitrile was added to a high-pressure reactor containing 7.3g glycolic acid aqueous solution (75wt%, based on the total weight of the solution), and 150g (2.827mol) butylamine was added. The mixture was heated to 80℃ and reacted for 4h to obtain a reaction solution. The reaction solution was then distilled under reduced pressure at 100℃ and 5kPa for 2h to remove low-boiling-point acrylonitrile and other substances to obtain bis(nitrile) ethyl compound.

[0065] (2) 210g of the bis(nitrile) ethyl compound obtained in step (1) and 12g of Ru / Al2O3 catalyst with a mass percentage of 5% were added to a mixed solvent consisting of 400g of anhydrous ethanol and 300g of potassium carbonate aqueous solution (0.5wt%). The mixture was reacted for 1.5h under the conditions of hydrogen pressure of 2.5MPa and temperature of 110℃. After cooling, the diamine containing the butyl side group was obtained.

[0066] Monomer Preparation Example 3

[0067] A diamine containing a nonyl side group has the following structure:

[0068]

[0069] Its preparation method includes the following steps:

[0070] (1) 157g (1.096mol) of acrylonitrile was added to a high-pressure reactor containing 12.1g of glycolic acid aqueous solution (75wt%, based on the total weight of the solution), and 140g (2.639mol) of nonylamine was added. The mixture was heated to 100℃ and reacted for 6h to obtain a reaction solution. The reaction solution was then distilled under reduced pressure at 115℃ and 15kPa for 3.5h to remove low-boiling-point acrylonitrile and other substances to obtain a dicyandiamide ethyl compound.

[0071] (2) 190g of the bis(nitrile) ethyl compound obtained in step (1) and 5g of Ru / Al2O3 catalyst with a mass percentage of 5% were added to a mixed solvent consisting of 400g of anhydrous ethanol and 300g of potassium carbonate aqueous solution (0.5wt%). The mixture was reacted for 3h under the conditions of hydrogen pressure of 2.8MPa and temperature of 120℃, and then cooled to obtain the diamine containing the nonyl side group.

[0072] Monomer Preparation Example 4

[0073] A cyclohexanedimethylamine containing alkyl side groups has the following structure:

[0074]

[0075] Its preparation method includes the following steps;

[0076] 142 g (0.998 mol) of 1,3-cyclohexanedimethylamine and 120 g (1.998 mol) of acetic acid were mixed at 10 °C to obtain a first mixture. The first mixture was then mixed with 336 g (3.01 mol) of n-octene to obtain a second mixture. 2.99 g of aluminum trichloride was added to the second mixture to react and obtain a reaction solution. The reaction temperature was controlled at 100 °C, the reaction pressure at 1 MPa, and the reaction time at 20 h, with a reaction yield of 0.95. The obtained reaction solution was crystallized, with a cooling rate controlled at 5 K / min, from the reaction temperature to 10 °C. After crystallization, the reaction solution was filtered to obtain a crude product of 355.12 g. The crude product was dissolved in 1065.36 g of MIBK solution to obtain a third mixture. The third mixture was then mixed with 1420.48 g of 20% sodium hydroxide solution in a reactor under stirring. The stirring temperature was controlled at 80 °C, and the stirring time was controlled at 1 h. After the reaction was complete, the lower aqueous phase was discharged to obtain the product oil phase. The product oil phase was then subjected to a four-stage countercurrent water wash to obtain the refined product. The water washing temperature was 10℃, and the mass of the washing water was 2841.0g.

[0077] The washed oil phase was subjected to continuous distillation. The distillation column had 8 trays, a bottom temperature of 70°C, a top temperature of 40°C, a top pressure of 10 kPa, and a reflux ratio of 2. The purified product was obtained at the bottom of the column, yielding 210.1 g of product with a yield of 91% and a purity of 99.1%.

[0078] Monomer Preparation Example 5

[0079] A cyclohexanedimethylamine containing alkyl side groups has the following structure:

[0080]

[0081] Its preparation method includes the following steps;

[0082] 142g of 1,4-cyclohexanedimethylamine and 193.8g of n-butyric acid were mixed at 40℃ to obtain a first mixture. The first mixture was then mixed with 420g of 1-hexene to obtain a second mixture. 0.1% aluminum trichloride was added to the second mixture to react and obtain a reaction solution. The reaction temperature was controlled at 200℃, the reaction pressure at 10MPa, and the reaction time at 8h. The obtained reaction solution was crystallized, with a cooling rate controlled at 1K / min, from the reaction temperature down to 20℃. After crystallization, the reaction solution was filtered to obtain 390.4g of crude product. The crude product was dissolved in 1952g of MIBK solution to obtain a third mixture. The third mixture was mixed with 4684.9g of 30% sodium hydroxide solution in a reactor under stirring. The stirring temperature was controlled at 120℃, and the stirring time at 2h. After the reaction was completed, the lower aqueous phase was discharged to obtain the product oil phase. The product oil phase was subjected to a two-stage countercurrent water washing to obtain the purified product. The washing temperature is 20℃, and the mass of water used for washing is 7027g.

[0083] The washed oil phase was subjected to continuous distillation. The distillation column had 5 trays, a bottom temperature of 90℃, a top temperature of 50℃, a top pressure of 50 kPa, and a reflux ratio of 3. 197.28 g of the refined product was obtained at the bottom of the column, with a product yield of 93% and a purity of 98%.

[0084] Monomer Preparation Example 6

[0085] A cyclohexanedimethylamine containing alkyl side groups has the following structure:

[0086]

[0087] Its preparation method includes the following steps;

[0088] 142g of 1,4-cyclohexanedimethylamine and 155.6g of n-propionic acid were mixed at 30℃ to obtain the first mixture. The first mixture was then mixed with 392g of 1-n-heptene to obtain the second mixture. 2.97g of aluminum trichloride was added to the second mixture to react and obtain the reaction solution. The reaction temperature was controlled at 150℃, the reaction pressure at 5MPa, and the reaction time at 14h. The obtained reaction solution was crystallized, and the cooling rate was controlled at 3K / min. After cooling from the reaction temperature to 15℃, the crystallized reaction solution was filtered to obtain 379.8g of crude product. The crude product was dissolved in 1519g of MIBK solution to obtain the third mixture. The third mixture was mixed with 2848.3g of 30% sodium hydroxide solution in a reactor under stirring. The stirring temperature was controlled at 100℃, and the stirring time was controlled at 1.5h. After the reaction was completed, the lower aqueous phase was discharged to obtain the product oil phase. The product oil phase was subjected to two-stage countercurrent water washing to obtain the purified product. The washing temperature was 15℃, and the mass of water used for washing was 4747.2g.

[0089] The washed oil phase was subjected to continuous distillation. The distillation column had 6 trays, a bottom temperature of 80℃, a top temperature of 45℃, a top pressure of 45 kPa, and a reflux ratio of 2.5. The purified product 209.29 was obtained at the bottom of the column, with a product yield of 92% and a purity of 98.5%.

[0090] Barrier Nylon Preparation Example 1

[0091] Preparation of barrier MX nylon: 2000.00g (14.685mol) of m-phenylenediamine, 2171.52g (14.859mol) of adipic acid, 30.00g (0.100mol) of monomer (prepared from the product of Example 1), 21.008g of phosphoric acid and 1260g of water were added to a reactor. After nitrogen purging, the temperature was raised to 50℃ for 60min of salt formation reaction. Then, the temperature was raised to 150℃ and the pressure was maintained for 120min of prepolymerization reaction. Then, the pressure was released to atmospheric pressure, and the temperature was raised to 265℃ for melt polycondensation and nitrogen purging reaction for 70min to obtain barrier nylon with a relative viscosity of 2.73.

[0092] Barrier Nylon Preparation Example 2

[0093] Preparation of barrier MX nylon: 2400.00g (17.622mol) of m-phenylenediamine, 2658.40g (18.191mol) of adipic acid, 80.00g (0.427mol) of monomer (prepared as the product of Example 2), 25.692g of sodium hypophosphite and 1542g of water were added to a reactor. After nitrogen purging, the temperature was raised to 120℃ for 30min of salt formation reaction. Then the temperature was raised to 190℃ and held under pressure for 100min of prepolymerization reaction. Then the pressure was released to atmospheric pressure and the temperature was raised to 270℃ for melt polycondensation and nitrogen purging reaction for 80min to obtain barrier nylon with a relative viscosity of 2.26.

[0094] Barrier Nylon Preparation Example 3

[0095] Preparation of barrier MX nylon: 2100.00g (15.420mol) of m-phenylenediamine, 2338.47g (16.001mol) of adipic acid, 110.00g (0.428mol) of monomer (prepared as the product of Example 3), 22.742g of phosphoric acid and 1364.54g of water were added to a reactor. After nitrogen purging, the temperature was raised to 70℃ for 45min for salt formation reaction. Then, the temperature was raised to 200℃ and held under pressure for 65min for prepolymerization reaction. Then, the pressure was released to atmospheric pressure and the temperature was raised to 280℃ for melt polycondensation and nitrogen purging reaction for 35min to obtain barrier nylon with a relative viscosity of 2.13.

[0096] Barrier Nylon Preparation Example 4

[0097] Preparation of barrier MX nylon: 2200.00g (16.154mol) of m-phenylenediamine, 2428.72g (16.619mol) of adipic acid, 85g (0.368mol) of monomer (prepared from the product of Example 4), 23.569g of phosphoric acid and 1885g of water were added to a reactor. After nitrogen purging, the temperature was raised to 90℃ for 55min of salt formation reaction. Then, the temperature was raised to 230℃ and the pressure was maintained for 60min of prepolymerization reaction. Then, the pressure was released to atmospheric pressure and the temperature was raised to 275℃ for melt polycondensation and nitrogen purging reaction for 55min to obtain barrier nylon with a relative viscosity of 2.53.

[0098] Barrier Nylon Preparation Example 5

[0099] Preparation of barrier MX nylon: 2500.00g (18.357mol) of m-phenylenediamine, 2808.17g (19.215mol) of adipic acid, 160g (0.368mol) of monomer (prepared as the product of Example 5), 2.341g of phosphoric acid and 2187g of water were added to the reactor. After nitrogen purging, the temperature was raised to 100℃ for 50min of salt formation reaction. Then the temperature was raised to 170℃ and the pressure was maintained for 80min of prepolymerization reaction. Then the pressure was released to atmospheric pressure and the temperature was raised to 265℃ for melt polycondensation and nitrogen purging reaction for 100min to obtain barrier nylon with a relative viscosity of 2.45.

[0100] Barrier Nylon Preparation Example 6

[0101] Preparation of barrier MX nylon: 2300.00g (16.888mol) of m-phenylenediamine, 2512.51g (17.192mol) of adipic acid, 50.00g (0.220mol) of monomer (prepared as the product of Example 6), 24.313g of phosphoric acid and 1945g of water were added to a reactor. After nitrogen purging, the temperature was raised to 110℃ for 35min of salt formation reaction. Then, the temperature was raised to 180℃ and held under pressure for 70min of prepolymerization reaction. Then, the pressure was released to atmospheric pressure and the temperature was raised to 260℃ for melt polycondensation and nitrogen purging reaction for 120min to obtain barrier nylon with a relative viscosity of 2.95.

[0102] Barrier Nylon Preparation Example 7

[0103] Preparation of barrier MX nylon: 2270.00g (16.68mol) of m-phenylenediamine, 2372.55g (16.235mol) of adipic acid, 132.7g (0.514mol) of 2,5-dibutyl adipic acid, 23.876g of phosphoric acid and 2388g of water were added to a reaction vessel. After nitrogen purging, the temperature was raised to 80℃ for 45min of salt formation reaction. Then, the temperature was raised to 200℃ and the pressure was maintained for 100min of prepolymerization reaction. Then, the pressure was released to atmospheric pressure and the temperature was raised to 260℃ for melt polycondensation and nitrogen purging reaction for 90min to obtain barrier nylon with a relative viscosity of 2.81.

[0104] Barrier Nylon Preparation Example 8

[0105] Preparation of barrier MX nylon: 2524.00g (18.533mol) of m-phenylenediamine, 2698.76g (18.467mol) of adipic acid, 30.70g (0.176mol) of 3-propylglutaric acid, 26.267g of phosphoric acid and 2627g of water were added to a reaction vessel. After nitrogen purging, the temperature was raised to 95℃ for 50min of salt formation reaction. Then, the temperature was raised to 210℃ and the pressure was maintained for 90min of prepolymerization reaction. Then, the pressure was released to atmospheric pressure and the temperature was raised to 270℃ for melt polycondensation and nitrogen purging reaction for 80min to obtain barrier nylon with a relative viscosity of 2.66.

[0106] Barrier Nylon Preparation Example 9

[0107] Preparation of barrier MX nylon: 2365.00g (17.365mol) of m-phenylenediamine, 2485.33g (17.006mol) of adipic acid, 103.2g (0.477mol) of dibutylmalonic acid, 24.768g of phosphoric acid and 2477g of water were added to a reaction vessel. After nitrogen purging, the temperature was raised to 115℃ for 35min of salt formation reaction. Then, the temperature was raised to 220℃ and the pressure was maintained for 60min of prepolymerization reaction. Then, the pressure was released to atmospheric pressure and the temperature was raised to 280℃ for melt polycondensation and nitrogen purging reaction for 50min to obtain barrier nylon with a relative viscosity of 2.32.

[0108] According to the proportions shown in the table below, the polyolefin, barrier MX nylon, nucleating agent, and antioxidant are mixed evenly and then fed into the extruder through the feed port of the twin-screw extruder. The processing temperature is set within the range of 240-280℃. Finally, the mixture is extruded and granulated, and then processing tests are conducted.

[0109] Table 1. Experimental formulations for examples and comparative examples.

[0110]

[0111] Table 2. Test results for the examples and comparative examples.

[0112]

[0113] As can be seen from the examples, the mechanical properties and barrier properties of the product gradually increase with the increase of the amount of barrier nylon used; as can be seen from the comparative examples and examples, the polyolefin / nylon composite material obtained by the present invention has better mechanical and barrier properties and better formability.

[0114] The above embodiments are only for illustrating the technical concept and features of the present invention and should not be construed as limiting the scope of protection of the present invention. All changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A high barrier polyolefin-nylon composite, comprising the following components by weight:

2. The composite material of claim 1, wherein, The polyolefin comprises polypropylene and / or polyethylene.

3. The composite material according to claim 1 or 2, characterized in that, The comonomer of the nylon comprises m-xylylenediamine, adipic acid, other diamines and / or other diacids.

4. The composite material of claim 3, wherein, The other diamines comprise any one or more of the following compounds having linear or branched aliphatic side groups, as shown in the following formula I or formula II: wherein the R group of formula I is a C4-C18 alkyl group, preferably butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, octadecyl and their corresponding isomer groups; the R1 group of formula II is a C6-C8 alkyl group, preferably isohexyl, isohexyl, isooctyl, and the -CH2-NH2 group of formula II is located at the meta or para position.

5. The composite material of claim 4, wherein, The preparation method of the formula I diamine with linear or branched aliphatic side groups comprises the following steps: (1) reacting R-NH2, acrylonitrile and a catalyst in solvent water at 80-100°C for 4-8h, and then distilling under reduced pressure at 100-130°C and 5-15kPa absolute pressure for 2-5h to obtain a dinitrile ethyl compound; (2) hydrogenating the dinitrile ethyl compound obtained in step (1) to obtain the formula I diamine with linear or branched aliphatic side groups.

6. The composite material according to any one of claims 1 to 5, wherein, The preparation method of the formula II cyclohexanedimethylamine with linear or branched aliphatic side groups comprises the following steps: (1) neutralizing 1,3-cyclohexanedimethylamine or 1,4-cyclohexanedimethylamine with a C2-C4 organic acid to obtain a first mixture; mixing the first mixture with a C6-C8 olefin to obtain a second mixture; reacting the second mixture with 0.1%-1% aluminum trichloride based on the mass of the second mixture, crystallizing and separating to obtain a crude product, dissolving the crude product in a MIBK solution to obtain a third mixture; (2) mixing and reacting the third mixture with a sodium hydroxide solution, separating to obtain a product oil phase, washing with water and rectifying.

7. The composite material according to any one of claims 1 to 6, wherein The other diacids are C3-C14 diacids containing branched alkanes, the branched alkanes are C2-C10 alkyl groups, and the number of branched alkanes in the diacids can be an integer from 1 to 3; preferably one or more of butylmalonic acid, dibutylmalonic acid, ethylsuccinic acid, propylsuccinic acid, butylsuccinic acid, 2,3-diethylsuccinic acid, 2-ethylpentanedioic acid, 3-ethylpentanedioic acid, 3-ethyl-3-methylpentanedioic acid, 2-propylpentanedioic acid, 3-propylpentanedioic acid, 3-butylpentanedioic acid, 3-isobutylpentanedioic acid, 2,4-diethylpentanedioic acid, 2-ethylhexanedioic acid, 2-butylhexanedioic acid, 3-tert-butylhexanedioic acid, 2,5-dibutylhexanedioic acid, 2-butyloctanedioic acid, 2-ethyloctanedioic acid, and the like.

8. The composite material of any one of claims 1-7, wherein, The addition amount of the other diamines and / or other diacids is 0.25-1.5wt%, preferably 0.4-1.1wt%, based on the mass of the comonomer; the molar ratio of all diamines and diacids in the nylon is 1:(1.005-1.01); the relative viscosity of the nylon is 1.8-3.5, preferably 2.1-3.

0.

9. A method of making the composite material of any one of claims 1-8, comprising the steps of: The polyolefin, the nylon, the nucleating agent and the antioxidant are mixed uniformly in proportion, and then added into the extruder from the main feeding port of the twin-screw extruder, with the processing temperature being 240-280 ℃, and then extruded and granulated.

10. Use of the composite material according to any one of claims 1-8 or the composite material prepared by the method according to claim 9 for barrier containers, including jelly cups, yogurt cups, sauce boxes.

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