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WO2023000262A1 - 一种聚丙烯薄壁注塑料和由其制得的薄壁注塑制品 - Google Patents

一种聚丙烯薄壁注塑料和由其制得的薄壁注塑制品 Download PDF

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Publication number
WO2023000262A1
WO2023000262A1 PCT/CN2021/107879 CN2021107879W WO2023000262A1 WO 2023000262 A1 WO2023000262 A1 WO 2023000262A1 CN 2021107879 W CN2021107879 W CN 2021107879W WO 2023000262 A1 WO2023000262 A1 WO 2023000262A1
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Prior art keywords
injection molding
thin
polypropylene
less
sorbitol
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PCT/CN2021/107879
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English (en)
French (fr)
Inventor
赵文林
卢喜
黄训能
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GCH Technology Co Ltd
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GCH Technology Co Ltd
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Priority to CN202180100438.5A priority Critical patent/CN117751160B/zh
Priority to PCT/CN2021/107879 priority patent/WO2023000262A1/zh
Publication of WO2023000262A1 publication Critical patent/WO2023000262A1/zh
Anticipated expiration legal-status Critical
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D22/00—Producing hollow articles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/07—Aldehydes; Ketones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
    • C08K5/357—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene

Definitions

  • the invention relates to a polypropylene thin-wall injection molding compound, and also relates to a thin-wall injection molding product prepared from the thin-wall injection molding compound.
  • polypropylene As one of the top five general-purpose plastics with the largest production and consumption, polypropylene has the advantages of non-toxic, harmless, low cost, and easy processing. Polypropylene injection molding has broad application prospects in the fields of food packaging, medicine and hygiene, daily necessities, electronic appliances, etc. It can be used to produce plastic containers such as fresh-keeping boxes, medicine boxes, takeaway packaging products, sorting boxes, and lockers.
  • thin-wall In the field of thin-wall injection molding, thin-wall usually refers to products with a wall thickness ⁇ 1mm. Compared with large-scale injection molding and precision injection molding, thin-wall injection molding has different requirements for injection speed, material fluidity, and material crystallization speed.
  • polypropylene thin-walled injection molding materials are required to be processed and molded quickly at high temperatures, while the polypropylene thin-walled injection molding materials in the prior art are mainly processed at injection molding temperatures below 250°C It has been unable to meet the requirements of resisting mechanical shear and thermo-oxidative degradation in processing injection molding at high temperature, resulting in the defect of high haze in thin-walled injection-molded products, and it is difficult to obtain thin-walled injection-molded products with excellent optical properties.
  • the auxiliary agent used in the production of polypropylene thin-wall injection molding materials in the prior art is calcium hexahydrophthalate. Since the auxiliary agent will decompose at high temperature, resulting in the loss of haze of thin-wall injection molding products, it is difficult to prepare products, or to maintain a good haze, it is necessary to increase the amount of additives, resulting in an increase in cost.
  • an object of the present invention is to provide a polypropylene thin-walled injection molding compound with low haze and high transparency.
  • the inventors of the present invention have found through research that it is difficult to obtain thin-walled injection molded products with haze meeting the application requirements at high temperatures for existing thin-walled injection molding materials.
  • the present invention is unique, selects specific polypropylene resin materials, cooperates with specific sorbitol compounds, and injection molding at high temperatures, especially at temperatures above 230°C, such as at 230-380°C, especially at 280-380°C It can also maintain good optical properties under processing temperature.
  • the first object of the present invention is to provide a polypropylene thin-walled injection molding compound, including polypropylene resin and sorbitol compound, the polypropylene resin is homopolypropylene and/or polypropylene containing ⁇ 2wt% butene .
  • It preferably relates to a thin-wall injection compound suitable for preparing injection-molded products with a wall thickness of 0.2mm-1mm, more preferably relates to a thin-wall injection compound for preparing injection-molded products with a wall thickness of 0.3mm-0.5mm.
  • the homopolypropylene has an isotacticity greater than or equal to 96%.
  • the polypropylene resin has a melt index MFR>60g/10min (measured under the test conditions of a temperature of 230°C and a test load of 2.16kg).
  • MFR>60g/10min measured under the test conditions of a temperature of 230°C and a test load of 2.16kg.
  • the filling rate of the polypropylene resin must be greater than the cooling rate of the resin in the injection channel.
  • the choice of melt index MFR>60g/10min can meet the requirement of good fluidity of polypropylene thin-walled injection molding material at high temperature.
  • the polypropylene resin has a weight average molecular weight of 1.30 ⁇ 10 5 -1.6 ⁇ 10 5 , and a molecular weight distribution range of 6.5-9.0.
  • the inventors found that under the thin-walled injection molding conditions of high temperature and high shear, in order to ensure complete mold filling and fast mold filling speed, it is necessary to select a polypropylene resin with a lower weight-average molecular weight and a wider molecular weight distribution, but this will also cause Therefore, it is particularly critical to select a polypropylene resin with a suitable weight-average molecular weight and molecular weight distribution.
  • the weight average molecular weight of the polypropylene resin is 1.30 ⁇ 10 5 -1.6 ⁇ 10 5 , and the molecular weight distribution range is 6.5-9.0, which can meet the processability and mechanical properties of thin-walled injection molded products.
  • the polypropylene is selected from polypropylene with 0.5-2 wt% butene; more preferably polypropylene resin with 0.7-1.5 wt% butene.
  • the present inventors found that the selection of polypropylene containing a certain amount of butene chain segments, combined with sorbitol compounds, can be processed by injection molding at high temperature, and a thin-walled injection molding material with satisfactory optical and mechanical properties can be obtained.
  • the possible reason is that the above-mentioned polypropylene resin with a specific butene segment content reduces the crystallinity and at the same time helps to improve the dispersion of sorbitol compounds in the polypropylene resin matrix, so that the obtained thin-walled injection molding plastic has excellent optical properties.
  • R 1 , R 2 and R 3 are independently selected from H, C1-C6 alkyl, C2-C6 alkenyl, C1-C6 alkoxy, hydroxyl or halogen atoms.
  • Examples of said C1-C6 alkyl include but not limited to methyl, ethyl, propyl, butyl; examples of C2-C6 alkenyl include but not limited to vinyl, allyl, 1-butenyl, 2 -butenyl; examples of C1-C6 alkoxy include but not limited to methoxy, ethoxy, propoxy, butoxy, and the halogen atom is selected from F, Cl, Br or I.
  • the sorbitol compound is an alpha crystal form, and GB/T 19077-2016 is used to measure the sorbitol compound, which has the following characteristics:
  • the average particle size of the surface area is greater than or equal to 1.3 ⁇ m
  • the volume average particle diameter is greater than or equal to 3.4 ⁇ m.
  • the present inventors have found that by selecting sorbitol compounds with the specific specific surface area, surface area average particle size and volume average particle size, multiple fine crystallization nuclei can be formed in the polypropylene resin matrix to promote crystallization and refine polypropylene
  • the spherulite size of the resin can reduce the haze of the polypropylene thin-wall injection molding compound and improve its optical properties.
  • the sorbitol compound with the above specific parameters can be well dispersed in the specially selected polypropylene resin of the present invention, further improving the optical properties of the polypropylene thin-walled injection molding compound.
  • the sorbitol compound is selected from 1,3,2,4-bis-O-(3,4-dimethylbenzylidene)-D-sorbitol, 1,3,2,4-bis Methylbenzylidene sorbitol, 1,3,2,4-di-p-chlorobenzylidene sorbitol and 1,2,3-trideoxy-4,6:5,7-bis-O-[(4-propylphenyl ) one or more of methylene]-nonanol.
  • the concentration of the sorbitol compound in the polypropylene resin is 400-1500ppm, preferably 600-1500ppm.
  • the polypropylene resin containing a small amount of butene in the present invention can use a small amount of sorbitol compounds to obtain thin-walled injection molding products with excellent optical properties.
  • the polypropylene thin-walled injection molding compound also includes 2,5-diaminopyrimidine-4-carboxylate, more preferably, sorbitol compounds and 2,5-diaminopyrimidine-4-
  • the mass ratio of carboxylate is 5-10:1-2, and the 2,5-diaminopyrimidine-4-carboxylate is selected from its sodium salt and/or potassium salt.
  • Polypropylene is a semi-crystalline polymer with incomplete crystallization, especially in the rapid injection molding process at high temperature. Due to the fast molding speed, the macromolecular segment does not have enough time to adjust its structure, and the crystallization is incomplete. The crystallization area and The difference in refractive index in the amorphous region will increase the haze and reduce the light transmittance, which will affect the optical performance of the product.
  • the inventor unexpectedly found that, adding a certain amount of 2,5-diaminopyrimidine-4-carboxylate to the polypropylene thin-wall injection molding compound, the polypropylene thin-wall injection molding compound of the present invention can be injection-molded at a high temperature of 280-380°C At the same time, under the low addition amount of sorbitol compounds, the thin-walled injection molding material crystallized completely, and the optical properties not only did not decrease, but improved to a certain extent.
  • the sorbitol compound and 2,5-diaminopyrimidine-4-carboxylate are compounded according to the mass ratio of 4-6:1-1.5, and the obtained polypropylene resin
  • the obtained thin-walled injection molding compound has the best overall performance.
  • the thin-walled injection molding compound may also include one or more of auxiliary agents such as acid absorbing agent, antioxidant, antistatic agent, toner, lubricant or dispersant, which may be added according to specific needs .
  • auxiliary agents such as acid absorbing agent, antioxidant, antistatic agent, toner, lubricant or dispersant, which may be added according to specific needs .
  • the acid absorbing agent is selected from sodium myristate, sodium laurate, sodium stearate, potassium myristate, potassium laurate, potassium stearate, zinc myristate, zinc stearate, calcium myristate, stearic acid One or more of calcium, calcium laurate, zinc laurate.
  • the antioxidant is selected from one or more of antioxidant 1010, antioxidant 168, antioxidant 1790, antioxidant 626, antioxidant 3114, antioxidant DBHA, and antioxidant DBHB.
  • the compounding of antioxidant 168 and antioxidant 1010 according to the mass ratio of 1-2:1-2.
  • the lubricant is selected from the group consisting of ethylene bis stearamide (EBS), stearamide, oleic acid amide, erucamide, calcium stearate, zinc stearate, high boiling point paraffin, microcrystalline paraffin, fatty acid, PE wax one or more of these.
  • EBS ethylene bis stearamide
  • stearamide stearamide
  • oleic acid amide erucamide
  • calcium stearate stearate
  • zinc stearate high boiling point paraffin
  • microcrystalline paraffin fatty acid
  • PE wax one or more of these.
  • Described antistatic agent is selected from octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate, stearyl trimethyl quaternary ammonium hydrochloride, stearamidopropyl dimethyl hydroxyethyl quaternary ammonium nitrate, One or more of potassium p-nonyldiphenyl ether sulfonate, sodium p-nonylphenoxypropane sulfonate, dibutyl oleic acid amide, hexamethylphosphoric triamide, etc.
  • the second object of the present invention is to provide the preparation method of the above-mentioned thin-walled injection molding compound.
  • the polypropylene resin and the sorbitol compound are evenly blended to obtain a blend.
  • an acid absorbing agent such as antioxidant, antistatic agent, toner, lubricant or dispersant, and then the above blend is extruded and pelletized by an extruder to obtain a thin-walled injection molding compound.
  • auxiliary agents such as antioxidant, antistatic agent, toner, lubricant or dispersant
  • the third object of the present invention is to provide a thin-walled injection-molded product obtained from the above-mentioned thin-walled injection molding compound at a processing temperature of 230-380°C, especially a thin-walled injection-molded product obtained at a processing temperature of 280-380°C.
  • the fourth object of the present invention is to provide a sorbitol compound used to reduce the haze value of polypropylene thin-wall injection molding at 230-380 ° C, especially in reducing the use of polypropylene thin-wall injection molding at 280
  • the polypropylene thin-walled injection molding compound is as described above.
  • the invention also provides thin-walled injection molding products, especially thin-walled injection molding products with wall thickness ⁇ 1mm (preferably 0.3mm-0.5mm).
  • the polypropylene thin-wall injection molding material provided by the present invention has a haze value according to GB/T 2410 of 50% or less, preferably 45% or less, more preferably 40% or less, and most preferably 35% or less, and can be further preferably 30% or less, 25% or less, 20% or less; fog according to GB/T2410 when injecting 1mm sample or ⁇ 1mm (preferably 0.3mm-0.5mm) injection molded products at 280-380°C
  • the degree value is 50% or less, preferably 45% or less, more preferably 40% or less, most preferably 35% or less, still more preferably 30% or less, 25% or less, 20% or less, 15% or less.
  • the thin-walled injection molded product of the present invention can be obtained by known processes such as injection molding, extrusion blow molding, and injection stretch blow molding, and these molded products can be molded into desired shapes, and can be used in automobile parts, mechanical parts, food Used in resin molded products such as packaging. As a specific application, it is useful in the following applications: Thin-wall injection molded products Examples are food containers, disposable lunch boxes, crates, barrels, household products, furniture, drinking cups, lids and closures, and other injection molded products .
  • the thin-walled injection molding compound of the present invention selects homopolypropylene with a specific melt index, weight-average molecular weight and molecular weight distribution of isotacticity greater than or equal to 96%, especially a polypropylene resin containing a certain amount of butene as a raw material, Sorbitol compounds with specific physical parameters can obtain thin-walled injection molded products with low haze at high processing temperatures.
  • the thin-walled injection molding material can be injection-molded at high temperature, the processing time is shortened, and the work efficiency is increased. At the same time, the obtained thin-walled injection molding product has excellent optical properties and low haze, so the thin-walled injection molding material provided by the present invention has great production advantages and commercial value.
  • the present invention has following advantage:
  • the present invention selects a thin-walled injection-molded product prepared with a specific polypropylene resin as a raw material and a specific sorbitol compound, and can achieve better optical properties at a lower dosage of the sorbitol compound.
  • the inventor also found unexpectedly that in the compounding aid with 2,5-diaminopyrimidine-4-carboxylate and sorbitol compounds, especially sorbitol compounds and 2,5-
  • the compounding of sodium diaminopyrimidine-4-carboxylate according to the mass ratio of 4-6:1-1.5 further improves the optical properties of thin-wall injection molding products under high temperature processing conditions, especially the haze has been significantly improved reduce.
  • the thin-wall injection molding compound containing sorbitol compounds of the present invention can meet the needs of thin-wall injection molding products with different thicknesses.
  • used raw material is as follows:
  • the sorbitol compound is selected as 1,3-O-2,4-bis(3,4-dimethylbenzylidene) sorbitol:
  • Sorbitol compound A1 1,3,2,4-bis-O-(3,4-dimethylbenzylidene)-D-sorbitol, self-produced by Chenghe Technology, brand NA-98, specific surface area It is 3.75m2/g, the surface area average particle size is 1.602 ⁇ m, and the volume average particle size is 8.920 ⁇ m;
  • Sorbitol compound A2 1,3,2,4-bis-O-(3,4-dimethylbenzylidene)-D-sorbitol, commercially available product 1, specific surface area is 3.49m2/g, surface area The average particle size is 1.720 ⁇ m, and the volume average particle size is 3.529 ⁇ m;
  • Additive B calcium hexahydrophthalate, commercially available product 2;
  • Auxiliary C sodium 2,5-diaminopyrimidine-4-carboxylate
  • Acid absorbing agent calcium stearate
  • Antioxidant Antioxidant 1010, Antioxidant 168.
  • the polypropylene thin-walled injection molding materials of Examples 1-10 and Comparative Examples 1-3 were prepared by using the parts by mass of the components in Table 1-2, and the steps were as follows:
  • the thin-walled injection molding materials of Examples 1-10 and Comparative Examples 1-3 were injected into splines in an injection molding machine at 250°C to obtain Examples 1A-10A, Comparative Examples 1A-3A, and the injection molding machine was HTF90W1 of Haitian Plastic Machinery Co., Ltd.
  • the working conditions of injection molding are: injection speed 40mm/s, injection pressure 30bar, injection time 2s, holding pressure 30bar, holding time 15s, and test related performance, see Table 3-Table 4 for details.
  • Examples 1-10 and Comparative Examples 1-3 were injection-molded in a 280°C injection molding machine to obtain Examples 1B-10B and Comparative Examples 1B-3B, and the relevant properties were tested, see Table 5-Table for details 6.
  • the thin-walled injection molding materials of Examples 1-6 were injected into disposable lunch boxes with a thickness of 0.3mm in an injection molding machine at 350°C to obtain Examples 1D-6D, and the optical properties were tested, see Table 10 for details.
  • the thin-walled injection molding materials of Examples 1-6 were injected into disposable lunch boxes with a thickness of 0.3mm in an injection molding machine at 380°C to obtain Examples 1E-6E, and the optical properties were tested, see Table 11 for details.
  • the thin-wall injection molding compound containing sorbitol compounds has better haze as the thickness decreases, which meets the application needs of a wider range of thin-wall injection molding products.
  • Example 11-13 The materials formulated in Examples 11-13 were uniformly mixed in a mixer to obtain a blend, and extruded and granulated by an extruder under the same conditions to obtain a thin-walled injection molding compound.
  • the test specimens were obtained by injection molding in the injection molding machine under the processing temperature conditions of 250°C, 280°C, and 300°C, and the relevant properties were tested. The results are shown in Table 13 below:
  • Example 12 According to the formula of Example 12 in Table 12, the disposable lunch box was injection-molded at high temperatures of 350°C and 380°C in the same way, and the optical properties were tested. The results are shown in Table 14 below:

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Abstract

本发明提供了一种聚丙烯薄壁注塑料，包括聚丙烯树脂和山梨醇类化合物，所述聚丙烯树脂为均聚聚丙烯或者含有小于等于2wt％丁烯的聚丙烯，通过在上述聚丙烯树脂中加入山梨醇类化合物，在高温薄壁注塑下，可以在保持较少的山梨醇类化合物的同时，降低聚丙烯薄壁注塑料的雾度，使薄壁注塑制品具有较好的力学性能、热性能和光学性能。本发明还提供由上述聚丙烯薄壁注塑料在高温下制得的聚丙烯薄壁注塑制品。

Description

一种聚丙烯薄壁注塑料和由其制得的薄壁注塑制品 技术领域
本发明涉及一种聚丙烯薄壁注塑料，还涉及由薄壁注塑料制备得到的薄壁注塑制品。
背景技术
聚丙烯作为产耗量最大的五大通用塑料之一，具有无毒无害、成本低廉、易于加工等优点。聚丙烯注塑料在食品包装、医药卫生、日用品、电子电器等领域均具有广阔的应用前景，可以用来生产保鲜盒、医药盒、外卖等包装制品，整理箱、储物柜等塑料容器。
近年来，包装制品、塑料容器、机械器件、高精密器件等逐渐向薄壁化甚至超薄壁化发展，作为聚丙烯的一个应用最广泛的品种，聚丙烯薄壁注塑制品以一次性快餐盒、碗、盘及塑料水杯、航空杯等食品包装制品为主，其制品具有耐温、不吸水、耐腐蚀、不霉变、使用寿命长、外观美观等特点。
在薄壁注塑领域，薄壁通常指的是壁厚≤1mm的制品。薄壁注塑相对于大型注塑和精密注塑，其对注射速度、材料流动性、材料结晶速度均有不同的要求。
随着薄壁注塑领域对生产效率的进一步需求，要求聚丙烯薄壁注塑料在高温下快速加工注塑成型，而现有技术中的聚丙烯薄壁注塑料主要是在250℃以下的注塑加工温度使用，已无法满足高温下抵御加工注塑成型中的机械剪切、热氧降解的要求，导致薄壁注塑制品存在雾度较高的缺陷，难以得到光学性能优异的薄壁注塑制品。
现有技术生产聚丙烯薄壁注塑料所用助剂为六氢化邻苯二甲酸钙，由于该助剂高温下会分解，造成薄壁注塑制品的雾度的损失，很难制备出具有优良光学性能的产品，或者想要保持良好的雾度，需要增加助剂的添加量，带来成本的增加。
发明内容
针对上述现有技术存在的缺陷，本发明的一个目的是，提供一种低雾度高透明的聚丙烯薄壁注塑料。本发明的发明人通过研究发现，现有的薄壁注塑料在高温下难以得到雾度满足应用需求的薄壁注塑制品。本发明独树一帜，选择特定的聚丙烯树脂材料，配合特定山梨醇类化合物，在高温下，特别是在230℃以上的高温条件下，比如在230-380℃下，特别是280-380℃的注塑加工温度下，也能 保持很好的光学性能。
本发明的第一个目的是提供一种聚丙烯薄壁注塑料，包括聚丙烯树脂和山梨醇类化合物，所述聚丙烯树脂为均聚聚丙烯和/或含有≤2wt％丁烯的聚丙烯。
优选涉及一种适用于制备壁厚为0.2mm-1mm注塑制品的薄壁注塑料，更优选涉及制备壁厚为0.3mm-0.5mm注塑制品的薄壁注塑料。
优选地，所述均聚聚丙烯的等规度大于等于96％。
优选地，所述聚丙烯树脂的熔融指数MFR＞60g/10min(温度230℃、测试载荷2.16kg的测试条件下测定)。薄壁注塑过程中，为保证腔体充填完整，要求聚丙烯树脂充填速率必须大于注塑通道中树脂的冷却速率，在薄壁注塑高温注塑条件下，需要选用流动性好的聚丙烯树脂，本发明人发现，选择熔融指数MFR＞60g/10min，可以满足聚丙烯薄壁注塑料高温下具有较好流动性的需求。
优选地，所述聚丙烯树脂的重均分子量为1.30×10 5-1.6×10 5，分子量分布范围为6.5-9.0。本发明人发现，在高温、高剪切的薄壁注塑条件下，为了保证充模完整，充模速度快，需要选择重均分子量较低，分子量分布较宽的聚丙烯树脂，但这同时会带来聚丙烯薄壁注塑料力学性能的下降，因此，选择具有合适重均分子量和分子量分布的聚丙烯树脂尤为关键。本发明人发现，选择聚丙烯树脂的重均分子量为1.30×10 5-1.6×10 5，分子量分布范围为6.5-9.0，可以满足薄壁注塑制品加工性能和力学性能。
现有技术中，有部分原料商采用聚乙烯和聚丙烯宏观改性的方式提高均聚聚丙烯的韧性，但还是无法解决长期耐热稳定性的缺点。还有部分原料是采用丙烯单体和少量的乙烯(1-4％)共聚，乙烯单体无规、随机分布在丙烯的长链中，降低了聚合物的结晶度和熔点，改善了材料的抗冲击、耐热、抗老化等方面的性能。但是作为薄壁注塑料，综合性能还有待提升，特别是雾度等光学性能方面。
优选地，所述聚丙烯选自丁烯0.5-2wt％的聚丙烯；更优选丁烯含量在0.7-1.5wt％的聚丙烯树脂。本发明人发现，选用含有一定含量丁烯链段的聚丙烯，配合山梨醇类化合物，能够在高温下注塑加工，得到光学性能和力学性能均令人满意的薄壁注塑料。可能的原因，上述特定丁烯链段含量的聚丙烯树脂，降低结晶度的同时，有利于提高山梨醇类化合物在聚丙烯树脂基体中的分散情况，使得所得薄壁注塑料光学性能优异。
进一步地，所述山梨醇类化合物的化学通式为：
Figure PCTCN2021107879-appb-000001
其中，R 1、R 2、R 3独立地选自H、C1-C6烷基、C2-C6烯基、C1-C6烷氧基、羟基或卤原子。
所述C1-C6烷基的例子包括但不限于甲基、乙基、丙基、丁基；C2-C6烯基的例子包括但不限于乙烯基、烯丙基、1-丁烯基，2-丁烯基；C1-C6烷氧基的例子包括但不限于甲氧基、乙氧基、丙氧基、丁氧基，卤原子选自F、Cl、Br或I。
所述山梨醇类化合物为α晶型，采用GB/T 19077-2016对山梨醇类化合物进行测定，具有如下特征：
-比表面积大于或等于1.5m 2/g；
-表面积平均粒径大于或等于1.3μm；
体积平均粒径大于或等于3.4μm。
本发明人发现，通过选择具有上述特定比表面积、表面积平均粒径和体积平均粒径的山梨醇类化合物，可以在聚丙烯树脂基体中形成多个细密的结晶核，促进结晶，细化聚丙烯树脂的球晶尺寸，进而降低聚丙烯薄壁注塑料的雾度，改善其光学性能。同时，具有上述特定参数的山梨醇类化合物可以在本发明特定选择的聚丙烯树脂中有良好分散，进一步改善聚丙烯薄壁注塑料的光学性能。
更进一步地，山梨醇类化合物选自1,3,2,4-双-O-(3,4-二甲基亚苄基)-D-山梨醇、1,3,2,4-二对甲基苄叉山梨醇、1,3,2,4-二对氯苄叉山梨醇和1,2,3-三脱氧-4,6:5,7-双-O-[(4-丙苯基)亚甲基]-壬醇中的一种或多种。
所述山梨醇类化合物在聚丙烯树脂中的浓度为400-1500ppm，优选为600-1500ppm。本发明含有少量丁烯的聚丙烯树脂，可以使用较少量的山梨醇类化合物即可得到光学性能优异的薄壁注塑制品。
在本发明一个优选实施方式中，聚丙烯薄壁注塑料还包括2,5-二氨基嘧啶-4-羧酸盐，更优选地，山梨醇类化合物和2,5-二氨基嘧啶-4-羧酸盐的质量比 为5-10：1-2，所述2,5-二氨基嘧啶-4-羧酸盐选自其钠盐和/钾盐。
聚丙烯属于半结晶的聚合物，结晶不完全，特别是在高温下的快速注塑成型工艺中，由于成型速度较快，大分子链段没有足够的时间调整其结构，结晶不完全，结晶区域和非结晶区域折射率不同，会使雾度升高，透光率降低，影响产品的光学性能。
发明人预料不到地发现，聚丙烯薄壁注塑料中加入一定量的2,5-二氨基嘧啶-4-羧酸盐，本发明聚丙烯薄壁注塑料在280-380℃高温下注塑成型时，在较低的山梨醇类化合物的加入量下，制得的薄壁注塑料结晶完全，光学性能不仅没有下降，反而还有一定程度提升。
在本发明一个更优选的技术方案中，所述山梨醇类化合物和2,5-二氨基嘧啶-4-羧酸盐按照质量比4-6:1-1.5的复配，所得聚丙烯树脂制得的薄壁注塑料综合性能最优。
更进一步地，所述薄壁注塑料中还可以包括吸酸剂、抗氧剂、抗静电剂、色粉、润滑剂或分散剂等助剂中的一种或几种，根据具体需要来添加。
所述吸酸剂选自肉豆蔻酸钠、月桂酸钠、硬脂酸钠、豆蔻酸钾、月桂酸钾、硬脂酸钾、豆蔻酸锌、硬脂酸锌、豆蔻酸钙、硬脂酸钙、月桂酸钙、月桂酸锌中的一种或多种。
所述抗氧剂选自抗氧剂1010、抗氧剂168、氧剂1790、抗氧剂626、抗氧剂3114、抗氧剂DBHA、抗氧剂DBHB中的一种或多种。优选为抗氧剂168和抗氧剂1010按照质量比1-2:1-2的复配。
所述润滑剂选自乙撑双硬脂酰胺(EBS)、硬脂酰胺、油酸酰胺、芥酸酰胺、硬脂酸钙、硬脂酸锌、高沸点石蜡、微晶石蜡、脂肪酸、PE蜡等中的一种或多种。
所述抗静电剂选自十八烷基二甲基羟乙基季胺硝酸盐、硬脂基三甲基季胺盐酸盐、硬脂酰胺丙基二甲基羟乙基季胺硝酸盐、对壬基二苯醚磺酸钾、对壬基苯氧基丙烷磺酸钠、二丁基油酸酰胺、六甲基磷酰三胺等中的一种或多种。
本发明的第二个目的是提供上述薄壁注塑料的制备方法，将聚丙烯树脂和山梨醇类化合物共混均匀得到共混物，可选地，共混物中还可以加入吸酸剂、抗氧剂、抗静电剂、色粉、润滑剂或分散剂等助剂中的一种或几种，再将上述共混物 经挤出机挤出造粒，即得薄壁注塑料。
挤出造粒的工艺为本领域所熟知，《SHJ-20双螺杆挤出机操作规程》进行造粒，造粒温度为190-220℃。
本发明的第三个目的是提供一种由上述薄壁注塑料在230-380℃加工温度下得到的薄壁注塑制品，特别是在280-380℃加工温度下得到的薄壁注塑制品。
本发明的第四个目的是提供一种山梨醇类化合物用来降低聚丙烯薄壁注塑料在230-380℃注塑时的雾度值的用途，特别是在降低聚丙烯薄壁注塑料在280-380℃注塑时的雾度值的用途，所述聚丙烯薄壁注塑料如前所述。
本发明还提供薄壁注塑料制品，特别是壁厚≤1mm(优选0.3mm-0.5mm)的注塑制品的薄壁注塑料。本发明提供的聚丙烯薄壁注塑料，在230-280℃注塑1mm样片时根据GB/T 2410的雾度值为50％以下，优选为45％以下，更优选为40％以下，最优选为35％以下，还可以进一步优选为30％以下，25％以下，20％以下；在280-380℃注塑1mm样片或＜1mm(优选0.3mm-0.5mm)的注塑制品时根据GB/T2410的雾度值为50％以下，优选为45％以下，更优选为40％以下，最优选为35％以下，还可以进一步优选为30％以下，25％以下，20％以下，15％以下。
本发明的薄壁注塑制品可以通过公知的注射成型、挤压吹塑、注坯拉伸吹塑等工艺得到，可以将这些成型品成型成所需形状，并可以在汽车部件、机械部件、食品包装等的树脂成型品等中使用。作为具体的用途，在下列用途中是有用的：薄壁注塑制品实例有食物容器、一次性餐盒、板条箱、桶、家用制品、家具、饮用杯、盖子和密封品，以及其它注塑制品。
本发明的薄壁注塑料，选择具有特定熔融指数、重均分子量和分子量分布的等规度大于等于96％的均聚聚丙烯，特别是选择了含有一定量丁烯的聚丙烯树脂作为原料，配合特定物性参数的山梨醇类化合物，在高温加工温度下，可以获得雾度低的薄壁注塑制品。
由于薄壁注塑料可以在高温下注塑加工成型，缩短加工时间，增加工作效率，同时所得薄壁注塑制品光学性能优异，雾度低，所以本发明提供的薄壁注塑料具有很大的生产优势和商业价值。
与现有技术相比，本发明具有如下优点：
(1)本发明选择以特定聚丙烯树脂为原料，和特定山梨醇类化合物配合制 备得到的薄壁注塑制品，在较少的山梨醇类化合物用量下，即可达到较好的光学性能。
(2)发明人还预料不到地发现，在以2,5-二氨基嘧啶-4-羧酸盐和山梨醇类化合物一起的复配助剂，特别是山梨醇类化合物和2,5-二氨基嘧啶-4-羧酸钠按照质量比4-6:1-1.5的复配更进一步改善薄壁注塑料在高温加工条件下的薄壁注塑制品的光学性能，特别是雾度得到了明显降低。
(3)本发明含山梨醇类化合物的薄壁注塑料可以满足不同厚度薄壁注塑制品的需要。
具体实施方式
为更好地说明本发明的目的、技术方案和优点，下面将结合具体实施例对本发明作进一步说明。
实施例1-12
在实施例1-10和对比例1-3薄壁注塑料配方中，所用原料如下：
聚丙烯A1：牌号为陕西延长中煤榆林能源化工有限公司的PPH K1870-B基础料，含有丁烯的含量为1wt％，MFR为70g/10min，重均分子量M w＝1.56×10 5，分子量分布为7.0。
聚丙烯B1：牌号为洛阳石化的PPH MN60基础料，等规度大于等于96％的均聚聚丙烯，MFR为60g/10min，重均分子量M w＝1.60×10 5，分子量分布为6.5。
聚丙烯B2：牌号为广州石化的PPH S990基础料，等规度大于等于96％的均聚聚丙烯，MFR为90g/10min，重均分子量M w＝1.30×10 5，分子量分布为9.0。
山梨醇类化合物选为1,3-O-2,4-二(3,4-二甲基亚苄基)山梨醇：
山梨醇类化合物A1：1,3,2,4-双-O-(3,4-二甲基亚苄基)-D-山梨醇,呈和科技自产，牌号为NA-98,比表面积为3.75m2/g，表面积平均粒径为1.602μm，体积平均粒径为8.920μm；
山梨醇类化合物A2：1,3,2,4-双-O-(3,4-二甲基亚苄基)-D-山梨醇，市售产品1，比表面积为3.49m2/g，表面积平均粒径为1.720μm，体积平均粒径为3.529μm；
助剂B：六氢化邻苯二甲酸钙，市售产品2；
助剂C：2,5-二氨基嘧啶-4-羧酸钠；
吸酸剂：硬脂酸钙；
抗氧剂：抗氧剂1010，抗氧剂168。
采用表1-2中各组分质量份来制备实施例1-10和对比例1-3的聚丙烯薄壁注塑料，步骤如下：
(S1)将各原料按照表1-2中的配方在混合机中混合均匀，得到共混物；
(S2)将上述共混物经挤出机按照《SHJ-20双螺杆挤出机操作规程》进行造粒，造粒温度为190-220℃即得薄壁注塑料。
表1
Figure PCTCN2021107879-appb-000002
表2
Figure PCTCN2021107879-appb-000003
Figure PCTCN2021107879-appb-000004
性能测试：
将实施例1-10，对比例1-3的薄壁注塑料在250℃注塑机中注塑样条得实施例1A-10A，对比例1A-3A，注塑机是海天塑机有限公司的HTF90W1，注塑的工作条件是：注塑速度40mm/s，注塑压力30bar,注塑时间2s，保压压力30bar，保压时间15s，并测试相关性能，具体见表3-表4。
表3
Figure PCTCN2021107879-appb-000005
Figure PCTCN2021107879-appb-000006
表4
Figure PCTCN2021107879-appb-000007
将实施例1-10，对比例1-3的薄壁注塑料在280℃注塑机中注塑样条得实施例1B-10B，对比例1B-3B，并测试相关性能，具体见表5-表6。
表5
Figure PCTCN2021107879-appb-000008
表6
Figure PCTCN2021107879-appb-000009
将实施例1-10，对比例1-3的薄壁注塑料在300℃注塑机中注塑样片或注塑制品得实施例1C-10C，对比例1C-3C，并测试相关性能，具体见表7-表9。
表7
Figure PCTCN2021107879-appb-000010
表8：
Figure PCTCN2021107879-appb-000011
表9：
Figure PCTCN2021107879-appb-000012
将实施例1-6的薄壁注塑料在350℃注塑机中注塑0.3mm厚度的一次性餐盒得实施例1D-6D，并测试光学性能，具体见表10。
表10
Figure PCTCN2021107879-appb-000013
将实施例1-6的薄壁注塑料在380℃注塑机中注塑0.3mm厚度的一次性餐盒得实施例1E-6E，并测试光学性能，具体见表11。
表11
Figure PCTCN2021107879-appb-000014
对比表3中实施例和对比例可知，含1200ppm和1500ppm山梨醇类化合物的薄壁注塑料比含2000ppm有机羧酸盐类化合物的薄壁注塑料的雾度低，表明含山梨醇类化合物对薄壁注塑料光学性能具有更有利的影响。
通过表3与表5，表7的对比以及表4与表6、表8的对比可知，含山梨醇 类化合物的薄壁注塑料随着加工温度的升高，薄壁注塑料的结晶温度、弯曲模量和热变形温度在提高的同时，雾度进一步的降低；而含有机羧酸盐类化合物的薄壁注塑料随着加工温度的升高，其结晶温度、弯曲模量和热变形温度均出现一定程度的下降，雾度出现一定程度的升高。表明含山梨醇类化合物的薄壁注塑料更能满足高温的加工温度，而有机羧酸盐类化合物由于不耐高温性能，导致其对薄壁注塑料光学性能、力学性能和热性能均有进一步变劣的影响。
通过表9、表10与表11的对比可知，随着聚丙烯薄壁注塑料加工温度从300℃提高到380℃，所得聚丙烯薄壁注塑料的雾度大体呈现出先降后略有升高的趋势，但380℃的雾度仍然保持令人满意的程度。
由实施例3A-4A、3B-4B、3C-4C与实施例7A-8A、7B-8B、7C-8C对比可知，满足本发明特定参数的山梨醇类化合物，均具有较低雾度、较好力学性能和热性能。
由实施例9A-10A与实施例5A-6A的对比可知，随着均聚聚丙烯MFR的增加，在薄壁注塑料的雾度降低的同时，力学性能有所下降。表明，均聚聚丙烯MFR的增加会带来加工流动性的增强，进而使得山梨醇类化合物在基体中分散性变好，带来薄壁注塑料光学性能的改善。
由表9可知，含山梨醇类化合物的薄壁注塑料随着厚度的降低，具有更优的雾度，满足更大范围薄壁注塑制品的应用需要。
实施例11-12
按照上述表1的配方，区别在于薄壁注塑料中还加入一定量助剂C2,5-二氨基嘧啶-4-羧酸钠，各组分质量份配方如下表12所示：
表12
Figure PCTCN2021107879-appb-000015
Figure PCTCN2021107879-appb-000016
将实施例11-13配方的物质在混合机中混合均匀得共混物，在相同条件下挤出机挤出造粒，即得薄壁注塑料。分别在250℃，280℃，300℃的加工温度条件下在注塑机中注塑得到测试样条，并测试相关性能，结果如下表13所示：
表13
Figure PCTCN2021107879-appb-000017
通过表11数据可知，在山梨醇类化合物中加入一定量2,5-二氨基嘧啶-4-羧酸钠作为复配的助剂C，得到的薄壁注塑料在250℃，280℃下性能变化不大，但是在300℃的高温注塑机工作温度下，所得到的注塑样条雾度明显低于实施例4A在300℃温度下得到的注塑样条，而且力学性能也有少许提升。说明山梨醇类化合物和2,5-二氨基嘧啶-4-羧酸钠的复配发挥了协同作用，能够明显改善在高温下(280-380℃)注塑成型的薄壁注塑制品的光学性能。
按照表12中实施例12的配方，按照相同方法，在350℃和380℃的高温下注塑一次性餐盒，进行光学性能的测试。结果如下表14所示：
表14
Figure PCTCN2021107879-appb-000018
从表14数据可以看出，本发明所得聚丙烯薄壁注塑料在350℃的高温注塑条件下，雾度相比于300℃的注塑温度仍然是下降的趋势，一直到380℃雾度才开始有所增加，但仍保持再一个令人满意的程度。说明本发明提供的聚丙烯注塑料非常适合作为薄壁类的产品，比如说一次性餐盒。

Claims (13)

  1. 一种用于制备薄壁注塑制品的聚丙烯薄壁注塑料，包括聚丙烯树脂和山梨醇类化合物，所述聚丙烯树脂为等规度大于等于96％的均聚聚丙烯和/或含有≤2wt％丁烯的聚丙烯，所述聚丙烯树脂的熔融指数MFR＞60g/10min，所述聚丙烯薄壁注塑料在230-280℃注塑1mm样片时根据GB/T 2410的雾度值为50％以下，优选为45％以下，更优选为40％以下，最优选为35％以下，还可以进一步优选为30％以下，25％以下，20％以下；在280-380℃注塑1mm样片或＜1mm(优选0.3mm-0.5mm)的注塑制品时根据GB/T 2410的雾度值为50％以下，优选为45％以下，更优选为40％以下，最优选为35％以下，还可以进一步优选为30％以下，25％以下，20％以下，15％以下。
  2. 根据权利要求1所述的聚丙烯薄壁注塑料，其特征在于，所述聚丙烯树脂的重均分子量为1.30×10 5-1.6×10 5，分子量分布范围为6.5-9.0。
  3. 根据权利要求1-2任一项所述的聚丙烯薄壁注塑料，其特征在于，所述聚丙烯树脂为丁烯含量为0.5-2wt％的聚丙烯树脂；更优选丁烯含量为0.7-1.5wt％的聚丙烯树脂。
  4. 根据权利要求1-3任一项所述的聚丙烯薄壁注塑料，其特征在于，所述山梨醇类化合物化学通式为：
    Figure PCTCN2021107879-appb-100001
    其中，R 1、R 2、R 3独立地选自H、C1-C6烷基、C2-C6烯基、C1-C6烷氧基、羟基或卤原子；
    优选地，所述山梨醇类化合物选自1,3,2,4-双-O-(3,4-二甲基亚苄基)-D-山梨醇、1,3,2,4-二对甲基苄叉山梨醇、1,3,2,4-二对氯苄叉山梨醇和1,2,3-三脱氧-4,6:5,7-双-O-[(4-丙苯基)亚甲基]-壬醇中的一种或多种。
  5. 根据权利要求1-4任一项所述的聚丙烯薄壁注塑料，其特征在于，所述山梨醇类化合物为α晶型，采用GB/T 19077-2016对山梨醇类化合物进行测定，具有如下特征：
    -比表面积大于或等于1.5m 2/g；
    -表面积平均粒径大于或等于1.3μm；
    -体积平均粒径大于或等于3.4μm。
  6. 根据权利要求1-5任一项所述的聚丙烯薄壁注塑料，其特征在于，所述山梨醇类 化合物在聚丙烯树脂中的浓度为400-2000ppm，优选为600-1500ppm。
  7. 根据权利要求1-6任一项所述的聚丙烯薄壁注塑料，其特征在于，所述聚丙烯薄壁注塑料还包括2,5-二氨基嘧啶-4-羧酸钠；山梨醇类化合物和2,5-二氨基嘧啶-4-羧酸钠的质量比为5-10：1-2。
  8. 根据权利要求7所述的聚丙烯薄壁注塑料，其特征在于，所述山梨醇类化合物和2,5-二氨基嘧啶-4-羧酸钠的质量比为4-6:1-1.5。
  9. 根据权利要求1-8任一项所述的聚丙烯薄壁注塑料，其特征在于，所述聚丙烯薄壁注塑料中还可以包括吸酸剂、抗氧剂、抗静电剂、色粉、润滑剂或分散剂等助剂中的一种或几种。
  10. 权利要求1-9任一项所述聚丙烯薄壁注塑料的制备方法，包括以下步骤：将聚丙烯树脂和山梨醇类化合物共混均匀得到共混物，可选地，共混物中还可以加入吸酸剂、抗氧剂、抗静电剂、色粉、润滑剂或分散剂等助剂中的一种或几种，再将上述共混物经挤出机挤出造粒，即得聚丙烯薄壁注塑料。
  11. 权利要求1-9任一项所述聚丙烯薄壁注塑料在230-380℃加工温度下得到的薄壁注塑制品，优选在280-380℃加工温度下得到的薄壁注塑制品。
  12. 权利要求11所述的聚丙烯薄壁注塑制品在汽车部件、机械部件、食品包装等的树脂成型品中的用途。
  13. 一种山梨醇类化合物用来降低聚丙烯薄壁注塑料在230-380℃注塑时的雾度值的用途，特别是在降低聚丙烯薄壁注塑料在280-380℃注塑时的雾度值的用途，其特征在于，所述聚丙烯薄壁注塑料如权利要求1-9中任一项所述。
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