Aniline polymer and polypropylene product as well as preparation method and application thereof

Abstract

The invention relates to the field of nucleating agents, and discloses an aniline polymer, a polypropylene product and a preparation method and application of the aniline polymer and the polypropylene product. Wherein the polymer comprises structural units as shown in formulas 1-3; the polymer is introduced into a polypropylene product as a polypropylene nucleating agent, so that the optical property and the mechanical property of the polypropylene product can be improved. # imgabs0 #

Description

Technical Field

[0001] The invention relates to the field of nucleating agents, and in particular to an aniline polymer and a polypropylene product, and a preparation method and application thereof. Background Art

[0002] With the rapid development of technology and market at home and abroad, the market currently has higher requirements for the transparency of polypropylene. Highly transparent polypropylene has high heat deformation temperature, good rigidity, high tensile strength, and high cost performance. It has broad application prospects in microwave ovens, baby products, medical materials, food-grade packaging and other fields.

[0003] However, since polypropylene is a semi-crystalline polymer, it has the disadvantages of slow crystallization rate, high crystallinity, and easy formation of large-sized spherulites during the molding process, which leads to poor light transmittance and low transparency of polypropylene materials. In actual production, the method of adding transparent nucleating agents is often used to improve the transparency of polypropylene. This method uses a small amount of nucleating agents, has high stability, and can achieve adjustable transparency by changing the type and amount of nucleating agents. It has high cost performance and low cost. While adjusting the transparency of polypropylene, it can make the material crystallize more uniformly and improve the mechanical properties of the material to a certain extent.

[0004] At present, the commonly used polypropylene transparent nucleating agents are mainly organic small molecules, including organic phosphate nucleating agents and sorbitol derivative nucleating agents. In recent years, amide nucleating agents have also gradually entered the market. However, since these nucleating agents have problems such as dispersibility and high-temperature stability in the polypropylene matrix, the application range of polypropylene material products is limited.

[0005] Therefore, a new polymer and polypropylene material are needed to solve the above problems. Summary of the invention

[0006] The purpose of the present invention is to overcome the problem of poor optical and mechanical properties of polypropylene products in the prior art, and to provide an aniline polymer and a polypropylene product, and a preparation method and application thereof.

[0007] In order to achieve the above object, the present invention provides an aniline polymer on one hand, wherein the polymer comprises a structural unit shown in Formula 1-3;

[0008]

[0009] Among them, R 1 is selected from substituted or unsubstituted C 1 -C 10 alkylene, substituted or substituted non-aromatic heterocyclic group;

[0010] R 2 is selected from H, substituted or unsubstituted C 1 -C10 A hydrocarbon group, a substituted or substituted non-aromatic heterocyclic group;

[0011] Wherein, the weight average molecular weight of the polymer is 400-5000.

[0012] The second aspect of the present invention provides a method for preparing an aniline polymer, characterized in that the method comprises: mixing 1,3,5-triaminobenzene, an acyl halide and a diacyl halide for acylation reaction in the presence of a catalyst and a solvent;

[0013] Wherein, the acyl halide and diacyl halide have the chemical structures shown in Formula 4 and Formula 5 respectively:

[0014]

[0015] Among them, X 1 , X 2 and X 3 are each independently selected from fluorine, chlorine, bromine or iodine;

[0016] Among them, R 1 and R 2 The definition of is the same as that described in the first aspect of the present invention.

[0017] The third aspect of the present invention provides an aniline polymer prepared by the method described in the second aspect of the present invention.

[0018] The fourth aspect of the present invention provides a polypropylene product, wherein the polypropylene product comprises a polypropylene resin, a polypropylene nucleating agent and an auxiliary agent; wherein the polypropylene nucleating agent is the aniline polymer described in the first aspect of the present invention.

[0019] The fifth aspect of the present invention provides a method for preparing a polypropylene product, the method comprising: melt-blending and molding a polypropylene resin, a polypropylene nucleating agent and an auxiliary agent to obtain the polypropylene product; wherein the polypropylene nucleating agent is the aniline polymer described in the first and third aspects of the present invention, and the definitions of the polypropylene resin and the auxiliary agent are the same as those described in the fourth aspect of the present invention.

[0020] The sixth aspect of the present invention provides an application of the polypropylene product described in the fourth aspect of the present invention in at least one of the fields of automobile industry, household appliances, electronic packaging and building materials and home furnishings.

[0021] Through the above technical solution, the beneficial effects of the present invention at least include:

[0022] The polypropylene nucleating agent provided by the present invention has a highly branched benzamide structure. The polypropylene nucleating agent is introduced into the polypropylene product to make it have excellent optical properties and mechanical properties. Compared with the polypropylene product without the nucleating agent, when the polypropylene matrix resin is homopolymerized polypropylene, the haze of the 1mm thin sheet is reduced by 10%-50%, the yellow index is reduced by 0.3-2.5, the tensile yield modulus is increased by 2%-35%, and the bending modulus is increased by 2%-37%.

[0023] In addition, in a preferred embodiment of the present invention, the optical properties and mechanical properties of the polypropylene product are further improved by selecting appropriate polypropylene matrix resin, nucleating agent, antioxidant type and calcium stearate type and ratio, as well as melt blending conditions. DETAILED DESCRIPTION

[0024] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0025] As mentioned above, the present invention provides an aniline polymer in one aspect, wherein the polymer comprises

[0026] The structural unit shown in formula 1-3:

[0027]

[0028] Among them, R 1 Selected from substituted or unsubstituted C 1 -C 10 alkylene, substituted or substituted non-aromatic heterocyclic group;

[0029] R 2 is selected from H, substituted or unsubstituted C 1 -C 10 A hydrocarbon group, a substituted or substituted non-aromatic heterocyclic group;

[0030] Wherein, the weight average molecular weight of the polymer is 400-5000.

[0031] In some embodiments of the present invention, preferably, R 1 Selected from substituted or unsubstituted C 1 -C 10 Alkylene, substituted or unsubstituted C 1 -C 10 The invention further comprises an alkenylene group, a substituted or unsubstituted aryl group, a substituted or substituted non-aromatic heterocyclic group.

[0032] In some embodiments of the present invention, preferably, R 2 is selected from H, substituted or unsubstituted C 1 -C 10 Alkyl, substituted or unsubstituted C 1 -C 10 The invention further comprises an alkenyl group, a substituted or unsubstituted aryl group, a substituted or substituted non-aromatic heterocyclic group.

[0033] In some embodiments of the present invention, preferably, R 1 is selected from substituted or unsubstituted C 1 -C 10 alkylene, substituted or unsubstituted phenyl.

[0034] In some embodiments of the present invention, preferably, R 2 is selected from H, substituted or unsubstituted C 1 -C 10 alkyl, substituted or unsubstituted phenyl.

[0035] In the present invention, the substituted group may be methyl, ethyl, vinyl, halogen, hydroxyl, methoxy, or the like.

[0036] In some embodiments of the present invention, preferably, R 1 Selected from methylene,

[0037] In some embodiments of the present invention, preferably, R 2 Selected from ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, isopentyl, isobutyl, isopropyl, secondary pentyl, neopentyl,

[0038]

[0039] In some embodiments of the present invention, preferably, R 1 Selected from methylene, These groups can provide grafting sites within the molecule, achieving the effect of branching the chemical structure of the polymer.

[0040] In some embodiments of the present invention, preferably, R 2 Selected from ethyl, butyl, tert-butyl, isopentyl, isobutyl, isopropyl or secondary amyl. These groups can achieve the effect of end-capping the chemical structure of the polymer.

[0041] The second aspect of the present invention provides a method for preparing an aniline polymer, characterized in that the method comprises: mixing 1,3,5-triaminobenzene, an acyl halide and a diacyl halide for acylation reaction in the presence of a catalyst and a solvent;

[0042] Wherein, the acyl halide and diacyl halide have the chemical structures shown in Formula 4 and Formula 5 respectively:

[0043]

[0044] Among them, X 1 , X 2 and X 3 are each independently selected from fluorine, chlorine, bromine or iodine;

[0045] Among them, R 1 and R 2 The definition of is the same as that described in the first aspect of the present invention.

[0046] In some embodiments of the present invention, preferably, the catalyst is selected from at least one of lithium chloride, lithium fluoride and lithium bromide, preferably lithium chloride.

[0047] In some embodiments of the present invention, preferably, the solvent is selected from at least one of methanol, ethanol, ether, isopropanol, acetone, cyclohexane, tetrahydrofuran, N,N-dimethylformamide, N-methylpyrrolidone, benzene, toluene, xylene, dichloromethane, dichloroethane, pyridine and ethyl acetate.

[0048] In some embodiments of the present invention, preferably, the mass ratio of the 1,3,5-triaminobenzene, the acyl halide, the diacyl halide and the catalyst is 1:0.1:0.1:0.01-1:20:20:0.5, preferably 1:1:0.2:0.01-1:20:5:0.3. This mass ratio range can better adjust the branching degree of the polymer and the molecular weight.

[0049] In some embodiments of the present invention, preferably, the mass ratio of the acyl halide to the diacyl halide is 0.1-100: 1, preferably 1-70: 1. This mass ratio range can control the molecular weight range to the optimal range. In some embodiments of the present invention, preferably, the amount of the solvent is 200-2000g based on the total mass of the 1,3,5-triaminobenzene, acyl halide and diacyl halide per 100g.

[0050] In some embodiments of the present invention, preferably, the temperature of the acylation reaction is 70-120° C. and the time is 8-24 h.

[0051] In some embodiments of the present invention, preferably, after the acylation reaction, post-treatment is performed, including: after the reaction stops, the obtained reaction solution is precipitated into ice water, filtered and dried. The product after post-treatment can be directly used as a nucleating agent for polypropylene products.

[0052] The third aspect of the present invention provides an aniline polymer prepared by the method described in the second aspect of the present invention.

[0053] The fourth aspect of the present invention provides a polypropylene product, wherein the polypropylene product comprises a polypropylene resin, a polypropylene nucleating agent and an auxiliary agent; wherein the polypropylene nucleating agent is the aniline polymer described in the first aspect of the present invention.

[0054] In some embodiments of the present invention, preferably, the auxiliary agent is selected from antioxidants and / or calcium stearate.

[0055] In some embodiments of the present invention, preferably, the antioxidant is selected from at least one of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, tris[2,4-di-tert-butylphenyl]phosphite, β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and 4,4'-bis(α,α'-dimethylbenzyl)diphenylamine.

[0056] In some embodiments of the present invention, preferably, based on the mass of the polypropylene resin being 1 kg, the content of the polypropylene nucleating agent is 50-3000 mg; this content range can significantly improve the crystallization performance of polypropylene, reduce the spherulite size of polypropylene and improve the uniformity, thereby improving the optical properties of polypropylene products.

[0057] In some embodiments of the present invention, preferably, based on 1 kg of the mass of the polypropylene resin, the content of the antioxidant is 100-2000 mg; more preferably 1000-1500 mg. When the content of the antioxidant meets this range, the oxidation yellowing of the polypropylene matrix can be reduced during processing.

[0058] In some embodiments of the present invention, preferably, based on the mass of 1 kg of polypropylene resin, the content of calcium stearate is 100-1000 mg, more preferably 100-500 mg. Calcium stearate is used as an acid scavenger to neutralize the catalyst remaining in the polypropylene matrix during the synthesis process. When the content of calcium stearate meets this range, the product performance of the polypropylene material can be stabilized.

[0059] In some embodiments of the present invention, the auxiliary agent may optionally include a light stabilizer. The light stabilizer may be selected from, for example, at least one of poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-S-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]]hexamethylene[(2,2,6,6-tetramethyl-4-piperidinyl)imino], poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl-[(2,2,6,6-tetramethyl-4-piperidinyl)imino] and bis(2,2,6,6-tetramethyl-4-piperidinol) sebacate.

[0060] In some embodiments of the present invention, preferably, the content of the light stabilizer is 10-1000 mg based on 1 kg of the polypropylene matrix resin. When the content of the light stabilizer meets this range, the sensitivity of the polypropylene material to light can be reduced, eliminating or slowing down the possibility of photo-oxidation-reduction reaction.

[0061] In some embodiments of the present invention, optionally, the polypropylene product includes an organic pigment, and the color of the organic pigment may be at least one of blue, red, yellow and green.

[0062] In some embodiments of the present invention, preferably, based on 1 kg of the mass of the polypropylene matrix resin, the content of the organic pigment is 1-10 mg.

[0063] In some embodiments of the present invention, preferably, the weight average molecular weight of the polypropylene resin is 20,000-400,000 g / mol.

[0064] In some embodiments of the present invention, preferably, the melt index of the polypropylene resin at 230°C and 2.16 kg load is 5-40 g / 10 min. When the weight average molecular weight and melt index of the polypropylene matrix resin meet the above ranges, the nucleating agent can be dispersed more evenly in the polypropylene matrix, and the nucleating effect is better.

[0065] In some embodiments of the present invention, preferably, the polypropylene resin is selected from at least one of homopolypropylene, copolymer polypropylene and long-chain branched polypropylene, preferably homopolypropylene. The polypropylene product made with homopolypropylene as the polypropylene matrix resin has more regular units in the chain and higher crystallinity, and thus has better mechanical properties.

[0066] In some embodiments of the present invention, preferably, the copolymerized polypropylene is selected from at least one of random copolymerized polypropylene, alternating copolymerized polypropylene and block copolymerized polypropylene.

[0067] In some embodiments of the present invention, preferably, the copolymerized polypropylene is propylene and a copolymer selected from ethylene, C 4 -C 20 α-olefins, C 4 -C 20 Diolefins, vinyl cyclohexane, vinyl cyclohexene, C 4 -C 20 Alkadiene, C 5 -C 12 The copolymer is formed by at least one olefin selected from the group consisting of cycloalkadiene and norbornene derivatives, preferably a copolymer of propylene and ethylene.

[0068] In some embodiments of the present invention, preferably, when the copolymerized polypropylene is a copolymer of propylene and ethylene, based on 100 mol of the copolymerized polypropylene, the content of the structural unit derived from propylene in the copolymerized polypropylene is 50-99.9 mol, preferably 80-99.9 mol.

[0069] In some embodiments of the present invention, preferably, when the copolymerized polypropylene is a copolymer of propylene and other monomers other than the above-mentioned ethylene, based on 100 mol of the copolymerized polypropylene, the content of the structural units derived from propylene in the copolymerized polypropylene is 80-99.9 mol, preferably 90-99.9 mol.

[0070] In some embodiments of the present invention, preferably, the polypropylene product has a haze of 14-47% when the thickness is 1 mm, a clarity of 93-97%, a yellowness index of 3.2-4.9, a tensile yield modulus of 28.5-39 MPa, and a flexural modulus of 1320-1850 MPa.

[0071] The fifth aspect of the present invention provides a method for preparing a polypropylene product, the method comprising: melt-blending and molding a polypropylene resin, a polypropylene nucleating agent and an auxiliary agent to obtain the polypropylene product; wherein the polypropylene nucleating agent is the aniline polymer described in the first and third aspects of the present invention, and the definitions of the polypropylene resin and the auxiliary agent are the same as those described in the fourth aspect of the present invention.

[0072] In some embodiments of the present invention, preferably, the temperature of the melt blending is 160-260° C., more preferably 180-240° C. This temperature range can achieve the best blending effect without causing degradation of the polypropylene and additives.

[0073] In some embodiments of the present invention, preferably, the polypropylene resin, polypropylene nucleating agent and auxiliary agent can be mixed in any conventional mixing machine and then melt-blended.

[0074] In some embodiments of the present invention, preferably, the blending method includes melt blending the polypropylene matrix resin, the polypropylene nucleating agent and the auxiliary agent using a screw extruder.

[0075] In some embodiments of the present invention, preferably, the polypropylene nucleating agent, organic pigment and auxiliary agent are added to the polypropylene resin in the form of a masterbatch in which these compounds are present.

[0076] In some embodiments of the present invention, preferably, after the melt blending, pellets are collected and then stored or immediately subjected to a molding process.

[0077] In some embodiments of the present invention, preferably, the molding process includes injection molding process, extrusion blow molding process, injection stretch blow molding process, thermoforming process and compression molding or sheet extrusion molding process.

[0078] The sixth aspect of the present invention provides an application of the polypropylene product described in the fourth aspect of the present invention in at least one of the fields of automobile industry, household appliances, electronic packaging and building materials and home furnishings.

[0079] The present invention will be described in detail below through examples. In the following examples, 1,3,5-benzenetriol, hydroxylamine hydrochloride, ammonia water, and acyl chloride / diacid chloride raw materials are commercially available products from SIGMA, and the raw material 1,3,5-triaminobenzene is prepared according to the process in the following Preparation Example 1. The molecular weight (weight average molecular weight) is measured by GPC test, solvent THF, temperature 35°C, flow rate 1.0 mL / min.

[0080] Preparation Example 1

[0081] Preparation of 1,3,5-cyclohexanetrione oxime:

[0082] 3 g of 1,3,5-benzenetriol, 9 g of hydroxylamine hydrochloride and 35 mL (35 g) of ammonia water (mass fraction of ammonia: 25%) were mixed, reacted at 5° C. for 3 h, then the reaction was stopped, filtered and dried to obtain 3.8 g of 1,3,5-cyclohexanetrione oxime.

[0083] Preparation of 1,3,5-triaminobenzene:

[0084] In the presence of 0.37 g of palladium carbon catalyst (palladium loading 5%) and 50 mL of methanol, 2.0 g of 1,3,5-cyclohexanetrione oxime obtained in the previous step was reacted with hydrogen at 25° C. for 5 h. After stopping the reaction, the palladium carbon catalyst was filtered out, and the reaction solution was concentrated by rotary evaporation to precipitate crystals, which were filtered and dried to obtain 2.0 g of 1,3,5-triaminobenzene.

[0085] Preparation of aniline polymer S1:

[0086] In the presence of 0.1g lithium chloride (catalyst), 9mL pyridine (solvent) and 50mL N,N-dimethylformamide (solvent), 2.0g 1,3,5-triaminobenzene prepared in the previous step, 2.7g trimethylacetyl chloride and 0.8g glutaryl chloride were mixed for acylation reaction at 70°C for 8h. After the reaction was stopped, the obtained reaction solution was precipitated into 8 times ice water, filtered and dried to obtain 2.9g product, recorded as S1. The yield was 68.3wt%, and the molecular weight was 2450 after testing.

[0087] Preparation Example 2

[0088] The preparation was carried out according to the method of Preparation Example 1, except that 2.5 g of trimethylacetyl chloride and 1.0 g of glutaryl chloride were replaced by 2.5 g of propionyl chloride and 1.0 g of malonyl chloride. 2.2 g of product was obtained, which was recorded as S2. The yield was 54.1 wt %, and the molecular weight was 2600 after testing.

[0089] Preparation Example 3

[0090] The method of Preparation Example 1 was followed, except that 2.5 g of trimethylacetyl chloride and 1.0 g of glutaryl chloride were replaced by 2.3 g of valeryl chloride and 1.5 g of succinyl chloride. 2.4 g of product was obtained, which was recorded as S3. The yield was 57.3 wt %, and the molecular weight was 3600 after testing.

[0091] Preparation Example 4

[0092] The preparation was carried out according to the method of Preparation Example 1, except that 2.5 g of trimethylacetyl chloride and 1.0 g of glutaryl chloride were replaced by 2.2 g of 4-methylvaleryl chloride and 1.5 g of glutaryl chloride. 2.8 g of product was obtained, which was recorded as S4. The yield was 66.3 wt %, and the molecular weight was 4150 after testing.

[0093] Preparation Example 5

[0094] The method of Preparation Example 1 was followed, except that 2.5 g of trimethylacetyl chloride and 1.0 g of glutaryl chloride were replaced by 3.0 g of isovaleryl chloride and 0.5 g of malonyl chloride. 2.5 g of product was obtained, which was recorded as S5. The yield was 63.3 wt %, and the molecular weight was 3400 after testing.

[0095] Preparation Example 6

[0096] The preparation was carried out according to the method of Preparation Example 1, except that 2.5 g of trimethylacetyl chloride and 1.0 g of glutaryl chloride were replaced by 3.0 g of isobutyryl chloride and 1.5 g of glutaryl chloride. 2.4 g of product was obtained, which was recorded as S6. The yield was 57.3 wt %, and the molecular weight was 3950 after testing.

[0097] Preparation Example 7

[0098] The method of Preparation Example 1 was followed, except that 2.5 g of trimethylacetyl chloride and 1.0 g of glutaryl chloride were replaced by 2.7 g of isobutyryl chloride and 1.0 g of succinyl chloride. 2.6 g of product was obtained, which was recorded as S7. The yield was 60.5 wt %, and the molecular weight was 3850 after testing.

[0099] Preparation Example 8

[0100] The preparation was carried out according to the method of Preparation Example 1, except that 2.5 g of trimethylacetyl chloride and 1.0 g of glutaryl chloride were replaced by 3.0 g of 2-methylvaleryl chloride and 1.5 g of succinyl chloride. 2.2 g of product was obtained, which was recorded as S7. The yield was 48.9 wt %, and the molecular weight was 4700 after testing.

[0101] Preparation Example 9

[0102] The method of Preparation Example 1 was used, except that the ratio of acyl halide to diacyl halide was different, and 0.7 g of trimethylacetyl chloride and 2.7 g of glutaryl chloride were added dropwise to obtain 1.9 g of product, which was recorded as S9. The yield was 42.2 wt %, and the molecular weight was 4900 after testing.

[0103] Example 1

[0104] Preparation of polypropylene products:

[0105] 10 kg of polypropylene homopolymer (polypropylene resin, brand Y40, weight average molecular weight of 330,000 g / mol, melt index of 6 g / 10 min at 200°C and 2.16 kg load), 2.5 g of aniline polymer S1 (polypropylene nucleating agent), 3.5 g of calcium stearate and 15 g of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant) were fully mixed in a high-speed mixer and added to a screw extruder for melt blending and extrusion at 220°C.

[0106] After extrusion, the pellets were collected and injection molded to obtain test standard specimens and 1mm specimens of polypropylene products. The injection molding temperature was 220°C. After injection molding, the samples were stored in a constant temperature and humidity environment for 48 hours before testing.

[0107] Example 2

[0108] The polypropylene product was prepared according to the method of Example 1, except that the polypropylene nucleating agent S3 was selected to obtain a test standard specimen and a 1 mm sample of the polypropylene product.

[0109] Example 3

[0110] A polypropylene product was prepared according to the method of Example 1, except that copolymerized polypropylene powder (brand name: M08ETN, weight average molecular weight: 290,000 g / mol, melt index: 8 g / 10 min at 230°C and 2.16 kg load) was used to prepare the test standard specimens and 1 mm sample pieces of the polypropylene product.

[0111] Example 4

[0112] The polypropylene product was prepared according to the method of Example 1, except that the amount of polypropylene nucleating agent S1 was 10 g. The test standard specimens and 1 mm sample pieces of the polypropylene product were obtained.

[0113] Example 5

[0114] The polypropylene product was prepared according to the method of Example 1, except that the dosage of the antioxidant and calcium stearate was different, the dosage of the antioxidant was 16 g, and the dosage of calcium stearate was 15 g. The test standard specimens and 1 mm specimens of the polypropylene product were obtained.

[0115] Example 6

[0116] The polypropylene product was prepared according to the method of Example 1, except that the type of antioxidant was different, and the antioxidant was 2,4-di(n-octylthiomethylene)-6-methylphenol. The test standard specimen and 1 mm sample of the polypropylene product were obtained.

[0117] Example 7

[0118] The polypropylene product was prepared according to the method of Example 1, except that the temperature of melt blending was 260° C. The test standard specimens and 1 mm specimens of the polypropylene product were obtained.

[0119] Example 8

[0120] A polypropylene product was prepared according to the method of Example 1, except that a polypropylene homopolymer with a different weight average molecular weight and melt index was selected, specifically, a polypropylene homopolymer with a grade of T03, a weight average molecular weight of 380,000 g / mol, and a melt index of 4 g / 10 min at 230°C and a load of 2.16 kg was selected. A test standard specimen and a 1 mm sample of the polypropylene product were obtained.

[0121] Example 9

[0122] The polypropylene product was prepared according to the method of Example 1, except that the polypropylene nucleating agent S2 was selected to obtain a test standard specimen and a 1 mm sample of the polypropylene product.

[0123] Example 10

[0124] The polypropylene product was prepared according to the method of Example 1, except that the polypropylene nucleating agent S4 was selected to obtain the test standard specimens and 1 mm sample pieces of the polypropylene product.

[0125] Embodiment 11

[0126] The polypropylene product was prepared according to the method of Example 1, except that the polypropylene nucleating agent S5 was selected to obtain the test standard specimens and 1 mm sample pieces of the polypropylene product.

[0127] Example 12

[0128] The polypropylene product was prepared according to the method of Example 1, except that the polypropylene nucleating agent S6 was selected to obtain the test standard specimens and 1 mm sample pieces of the polypropylene product.

[0129] Example 13

[0130] The polypropylene product was prepared according to the method of Example 1, except that the polypropylene nucleating agent S7 was selected to obtain the test standard specimens and 1 mm sample pieces of the polypropylene product.

[0131] Embodiment 14

[0132] The polypropylene product was prepared according to the method of Example 1, except that the polypropylene nucleating agent S8 was selected to obtain the test standard specimens and 1 mm sample pieces of the polypropylene product.

[0133] Embodiment 15

[0134] The polypropylene product was prepared according to the method of Example 1, except that the polypropylene nucleating agent S9 was selected to obtain the test standard specimens and 1 mm sample pieces of the polypropylene product.

[0135] Comparative Example 1

[0136] A polypropylene product was prepared according to the method of Example 1, except that As a nucleating agent, standard test specimens and 1mm specimens of polypropylene products were prepared.

[0137] Comparative Example 2

[0138] The polypropylene product was prepared according to the method of Example 1, except that no nucleating agent was added. The test standard specimens and 1 mm specimens of the polypropylene product were obtained.

[0139] Comparative Example 3

[0140] The polypropylene product was prepared according to the method of Example 1, except that copolymerized polypropylene powder (brand name M08ETN, weight average molecular weight of 290,000 g / mol, melt index of 8 g / 10 min at 230°C and 2.16 kg load) was selected, and no nucleating agent was added. The test standard specimens and 1 mm sample pieces of the polypropylene product were obtained.

[0141] Comparative Example 4

[0142] The polypropylene product was prepared according to the method of Example 1, except that the nucleating agent selected during the synthesis was 1,3,5-triaminobenzene instead of 2.7 g p-diaminobenzene. The test standard specimens and 1 mm sample pieces of the polypropylene product were obtained.

[0143] Test Case

[0144] The haze, clarity, yellowness index, tensile yield modulus and flexural modulus of 1 mm samples of the polypropylene products of various embodiments and comparative examples were measured. The results are shown in Table 1.

[0145] The haze and clarity parameters were measured using a haze meter in accordance with the national standard GB / T 2410-2008 method; the yellowness index was measured using a yellowness index meter in accordance with the national standard GB / T 2409-1980 method; the tensile yield modulus was measured using a universal tester in accordance with the national standard GB / T 1040.1-2018 method; and the flexural modulus was measured using a universal tester in accordance with the national standard GB / T 9341-2008 method.

[0146] Table 1

[0147]

[0148]

[0149] From the above results, it can be seen that the polypropylene products prepared by using the highly branched benzamide compounds S1-S9 as nucleating agents in Examples 1-2 and 9-15, respectively, have significantly reduced haze and yellowness index, and significantly improved clarity compared with Comparative Examples 1 and 2, indicating that the use of the highly branched benzamide compounds provided by the present invention as nucleating agents can significantly improve the optical properties and mechanical properties of polypropylene products.

[0150] In addition, Example 3 selected copolymerized polypropylene as the polypropylene matrix resin, and compared with Comparative Example 3, the haze and yellow index were significantly reduced, the clarity was significantly improved, and the tensile yield modulus and flexural modulus were significantly improved; Implementation 4 increased the amount of nucleating agent, and compared with Example 1, the haze and yellow index increased, the clarity decreased, and the tensile yield modulus and flexural modulus decreased; Example 5 changed the amount of antioxidant and calcium stearate, and compared with Example 1, the clarity decreased, the yellow index increased, and the tensile yield modulus and flexural modulus decreased; Example 6 changed the type of antioxidant, and compared with Example 1, Compared with Example 1, haze and yellow index increased, tensile yield modulus and bending modulus decreased; Example 7 changed the temperature of melt blending, compared with Example 1, the yellow index increased, tensile yield modulus and bending modulus decreased; Example 8 selected polypropylene homopolymers with different weight average molecular weight and melt index, compared with Example 1, haze and yellow index increased, clarity decreased, anti-reflection effect was poor, and tensile yield modulus and bending modulus decreased; Example 9 changed the molecular weight of the nucleating agent, compared with Example 1, haze and yellow index increased, clarity decreased, tensile yield modulus and bending modulus decreased. It can be seen that the nucleating agent structure of the present invention, under a certain amount of addition, combined with other additives, can produce a good modification effect on a certain range of polypropylene matrix resins, and the optical properties and mechanical properties of the modified polypropylene resin material are significantly improved, but at the same time, it is necessary to select the appropriate types and addition concentrations of polypropylene matrix resins, nucleating agents, antioxidants and calcium stearate, and under appropriate blending conditions, the optical properties and mechanical properties of polypropylene products can be further improved.

[0151] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. An aniline polymer, It is characterized in that The polymer includes the structural unit shown in Formula 1-3: Among them, R 1 is selected from substituted or unsubstituted C 1 -C 10 alkylene, substituted or substituted non-aromatic heterocyclic group; R 2 is selected from H, substituted or unsubstituted C 1 -C 10 A hydrocarbon group, a substituted or substituted non-aromatic heterocyclic group; Wherein, the weight average molecular weight of the polymer is 400-5000.

2. The polymer according to claim 1, in, R 1 is selected from substituted or unsubstituted C 1 -C 10 Alkylene, substituted or unsubstituted C 1 -C 10 an alkenylene group, a substituted or unsubstituted arylene group, or a substituted or substituted non-aromatic heterocyclic group; and / or, R 2 is selected from H, substituted or unsubstituted C 1 -C 10 Alkyl, substituted or unsubstituted C 1 -C 10 The invention further comprises an alkenyl group, a substituted or unsubstituted aryl group, a substituted or substituted non-aromatic heterocyclic group.

3. The polymer according to claim 1 or 2, in, R 1 is selected from substituted or unsubstituted C 1 -C 10 an alkylene group, a substituted or unsubstituted phenylene group; and / or, R 2 is selected from H, substituted or unsubstituted C 1 -C 10 alkyl, substituted or unsubstituted phenyl.

4. The polymer according to any one of claims 1 to 3, in, R 1 Selected from methylene, and / or, R 2 Selected from ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, isopentyl, isobutyl, isopropyl, secondary pentyl, neopentyl, 5. The polymer according to any one of claims 1 to 4, in, R 1 Selected from methylene, and / or, R 2 Selected from ethyl, butyl, tert-butyl, isopentyl, isobutyl, isopropyl or secondary pentyl.

6. A method for preparing an aniline polymer, It is characterized in that The method comprises: in the presence of a catalyst and a solvent, mixing 1,3,5-triaminobenzene, an acyl halide and a diacyl halide to carry out an acylation reaction; Wherein, the acyl halide and diacyl halide have the chemical structures shown in Formula 4 and Formula 5 respectively: Among them, X 1 , X 2 and X 3 are each independently selected from fluorine, chlorine, bromine or iodine; Among them, R 1 and R 2 The definition thereof corresponds to the same as that in any one of claims 1 to 5.

7. The method according to claim 6, in, The catalyst is selected from at least one of lithium chloride, lithium fluoride and lithium bromide, preferably lithium chloride; The solvent is selected from at least one of methanol, ethanol, ether, isopropanol, acetone, cyclohexane, tetrahydrofuran, N,N-dimethylformamide, N-methylpyrrolidone, benzene, toluene, xylene, dichloromethane, dichloroethane, pyridine and ethyl acetate.

8. The method according to claim 6 or 7, in, The mass ratio of the 1,3,5-triaminobenzene, the acyl halide, the diacyl halide and the catalyst is 1:0.1:0.1:0.01-1:20:20:0.5, preferably 1:1:0.2:0.01-1:20:5:0.3; Preferably, the mass ratio of the acyl halide to the diacyl halide is 0.1-100:1, preferably 1-70:1; Preferably, the amount of the solvent is 200-2000 g based on the total mass of 1,3,5-triaminobenzene, acyl halide and diacyl halide per 100 g; Preferably, the acylation reaction is carried out at a temperature of 70-120°C and a time of 8-24 hours.

9. Aniline polymer obtained by the method according to any one of claims 6 to 8.

10. A polypropylene product, in, The polypropylene product comprises a polypropylene resin, a polypropylene nucleating agent and an auxiliary agent; wherein the polypropylene nucleating agent is the aniline polymer described in any one of claims 1-5 and 9.

11. The polypropylene product according to claim 10, in, The auxiliary agent is selected from antioxidants and / or calcium stearate; Preferably, the antioxidant is selected from at least one of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, tris[2,4-di-tert-butylphenyl]phosphite, β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and 4,4'-bis(α,α'-dimethylbenzyl)diphenylamine.

12. The polypropylene product according to claim 10 or 11, in, Based on 1 kg of the mass of the polypropylene resin, the content of the polypropylene nucleating agent is 50-3000 mg; Preferably, based on 1 kg of the polypropylene resin, the content of the antioxidant is 100-2000 mg, more preferably 1000-1500 mg. Preferably, based on 1 kg of the mass of the polypropylene resin, the content of calcium stearate is 100-1000 mg, more preferably 100-500 mg. Preferably, the weight average molecular weight of the polypropylene resin is 20,000-400,000 g / mol; Preferably, the melt index of the polypropylene resin at 230°C and 2.16 kg load is 5-40 g / 10 min; Preferably, the polypropylene resin is selected from at least one of homopolypropylene, copolymer polypropylene and long-chain branched polypropylene, preferably homopolypropylene; Preferably, the polypropylene product has a haze of 14-47% when the thickness is 1 mm, a clarity of 93-97%, a yellowness index of 3.2-4.9, a tensile yield modulus of 28.5-39 MPa, and a flexural modulus of 1320-1850 MPa.

13. A method for preparing a polypropylene product, the method comprising: include: The polypropylene resin, the polypropylene nucleating agent and the auxiliary agent are melt-blended and molded to obtain the polypropylene product; wherein the polypropylene nucleating agent is the aniline polymer described in any one of claims 1-5 and 9, and the definitions of the polypropylene resin and the auxiliary agent are the same as those described in any one of claims 10-12.

14. The method according to claim 13, in, The temperature of the melt blending is 160-260°C, preferably 180-240°C.

15. Use of the polypropylene product according to any one of claims 10 to 12 in at least one of the following fields: automobile industry, household appliances, electronic packaging, and building materials and home furnishings.

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